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THE MEDICAL STUDENT'S
MANUAL
or
CHEMISTRY
BT
R. A, WITTHAUS, A.M., M.D.
VBOTEWOB OF CHXMmKT Am FHTSIOS Dl TOC UJUVKMiT f OT THX ORT OT HKW TOUC ; PBOTOOl OV
uauurmi asd tozicoloot n tks ukivusjtt or acwrAu>; PBortuoa of ouMinaz
AMD TOXICOLOOT IK TBI UHTmBTTT OF VEBHOMT ; **rtnrwii Qf rSE CSKIO-
eu. Boctmn or pabu un> sxbum ; imimB or thx uaai-
OAX CHZMICAI. BOCIXTZ : FZLLOW Or THE AIOSI-
OAX ACASKMT Or KZDICDrX, ETC.
SECOND EDITION.
NEW YOEK
WTTJJAAf WOOD & COMPANY
00 & 68 Lafatvtte Place
1888
Oomtom, IBST, BT
WILLIAH WOOD fe COMPANY.
Tiiow's
PmiTtNC AND UoOKBINtHNC COMMNT
MI-9I3 Salt rwtltk St.
Vttm VOUE
The nrrangemont and classiScAtion fulopted in tho first edition hav*
been continued, <(rith the following modifications :
That portion treating of cbeinical physic? has been oontroctod, until it
contains nothing not absolutely essential to an understanding of wliat fol-
lows. This baa been done in the belief that the sciences of chemistry ami
pbjaics have each oasumod a degree of iudiWdual iniportanco in their ap-
plications to meiUcal science that they should be treated of as distinct sub-
jecta
The ohemistry of the metals has been mode to follow that of the non-
metals, in Bpito of the illogical character of such ou arrangement, because
it is believed that the student should be given as full a drilling in the
aimplcr branches of the subject as possible before ho is called upon to
face the more complex chemistry of the caibon compounds.
The fonuulffi of the acids and salts have been changed from the con-
tinental method HO,H,. NO,K. etc, adopted in tlie first edition, to that
inore generally followed in this country and iu England, H,SO„ KXO^,
etc- ; ti)e latter method being more in consonance with our system of
nomenclature.
^lat portion of the work treating of the chemistry of the carbon com-
pounds has been mnoh extended, and in great part rewritten. The prom-
inence given to Una portion of the subject the author believes to l>e justi-
fied, Dotnithstanding its intricacy and the consequent difficulty of teaching
it to medical students, by reason of the intimate connection of organic
chemistry with physiology and pharmacy, and the rapidly increasing use
of complex organic products as medicines.
B, A. W.
Kbw Tore,
Aagnttai, 1887.
lOGUU'i
In venturing to add anotlier to the already lonpr list of chemical
text-book«, tlic anthor tniatA that he may find some apology in thip,
that tlie work is intended solely for the use of a class of students
whose needs in the study of this science are peculiar.
While tlie irmiu foundations of chemical science, the philosophy of
chemistry, ninst bo tanght to and studied by all classes of stndcnts
alike, the subsequent development of the study in its details must bo
monldcnl to snit the purposes to which the stndetit will subsequently
put hid kitowled^. And particularly in tlie cnm of medical students,
in our present defective methods of medical teaching, should the sub-
ject be confined as closely as may be to the general truths of chemistry
And its applications to mcfltcal science.
In tlie preparation of this Mannal the author has striven to pro*
dnoe a work which should contain as mnch as possible of those por-
tions of special chemistry which are of direct interest to the medical
practitioner, and at the twime time to exclude so far as possible, without
detriment to a proper understanding of the subject, those portions
which are of purely technological interest. The descriptions of pro-
eeesos of manufacture are thei-cfor made very brief, while chemical
physiology and the chemistry of hygiene, therapeutics, and toxicology
have been dwelt upon.
The work has l>Ren divided into three parts. In the first part the
principles of chemical science are treated of, as well as so mncli of
chemic:d physics as is absulutely requisite to a proper nnderstsnding of
that which follows. A more extended study of phytucs is pui-jiosely
avoided, that subject being, in the opinion of the author, rather within
the domain of physiology than of chemistry.
Tlie second part treats of special chemistry, and in this certain
departnrcH from tlie metliods uauHlly followed in chemical text-books
are to be noted. The elements are classed, not iu metals and metal-
n PKBFAGB TO TEX FIB8T EDITION.
loids, a classification as arbitrary as nnecientific, but into classes and
groups according, to their chemical characters.
In the text the formula of a substance is used in most instances in
place of its name, <^ier it has been descnbedj with a view to giving the
student that familiarity with the notation which can only be obtained
by continued use.
As the distinction between inorganic and oi^nic chemistry is
merely one of convenience, the consideration of the carbon componnds
is made to follow in its logical place after that of the element carbon.
In the third part those operations and manipulations which will be
of utility to the student and physician are briefly described ; not with
the expectation that these directions can take tlie place of actual ex-
perience in the laboratory, but merely as an outline sketch in aid
thereto.
Althongh the Manual puts forth no claim as a work upon analyti-
cal chemistry, we have endeavored to bring that branch of the subject
rather into the f or^round so far as it is applicable to medical chem-
istry. The qnalitative characters of each element are given under the
appropriate heading, and in the third part, systematic schemes for the
examination of calculi and of simple chemical compounds are given.
Quantitative methods of interest to tlie phjsician are also described
in their appropriate places. In this connection tlie author wonld not
be understood as saying that the methods recommended are in all in-
stances the best known, but simply that they are the best adapted to
the limited facilities of the phjsician.
The autlior would have preferred to omit all mention of Troy and
Apothecaries* weight, but in deference to the opinions of those vener-
able practitioners who have survived their student days by a half cen-
tury, those weights have been introduced in brackets after the metric,
as the value of degrees Fahrenheit have been made to follow those
Centigrade.
R. A. W.
Buffalo, N, T.,
' September 16, 1S83.
TABLE OF CONTENTS.
PAon
PART I— mTBODUCnON 1
GsnsaAL Pbofertibs or Uatter 3
IndeBtraotibility 3
Weight a
Specifio grraTity %
Statee of matter 6
DiTiribility 7
Elrmbhts 8
Combination of Elsu ents 8
Atomic Theobt m B
Atomic and Moleculak Wsiohts 11
Valence ob Atomicity 14
Symbols— FoBMUiid—EQCATiDNB 15
Blbctboltbis 16
Acids, Bases, and Salts 18
noxenclatubb 20
Badicals S3
CfOHBTITUTION 23
Classification op Elements 2S
Physical Ciia^ctebs 27
OiTBtallization 27
iBOmorphUm 80
Dbnorpbinn 81
AUotzopy 81
Solution 81
DiffoBion S3
Specific heat 88
SpectroBoopy 88
Fotarimetiy 86
VIU CONTENTS.
PAOX
PAET H— SPECIAL CHEMISTRY 87
Ttpical Elkmbkts 87
Hydrogen 87
Oxj/gen 40
Osone 43
Water 48
Hydrogen dioxide 52
AciDnLOUS Blbmentb 64
■ Chlorine Group 64
FUumru 64
Hydrogen flnoride 64
ChiorvM 66
Hydrogen chloride 67
Compoanda of chlorine and oxygen 68
Bromine 69
Hydrogen bromide 69
Oxaoidfl of bromine 60
Iodine 60
Hydrogen iodide 61
Ozacidi of iodine 63
Sulphur Gboup 63
Sulphur 68
Hydrogen snlphide 64
Snlphnr dioxide 06
Solphnr trioxide 67
HydrosnlphorooB acid 67
Sulphnrio aoid ' 67
PyrosDiphuric add 69
Sdenium 69
T^urium • 70
NiTROQEN Group 70
Nitrogen 70
Atmospheric air 71
Ammonia 73
Nitrogen monoxide 78
Nitrogen dioxide 74
Nitrogen trioxide 74
Nitrogen tetroxide 74
Nitrogen pentoxide 76
Nitrogen acids 76
Nitric acid 76
Componnda of nitn^n with the halogens 77
Phoephanu 78
Hydrogen phosphides 83
Oxides of phoephonu 83
Phosphoms acids 83
Compounds of phoBphoms with the halogens 84
Arsenic 84
Hydrogen atseoides 86
Oxides of arsenic 86
ix
tAom
AxmhIo ftddi .,.., « 88
SolphidaBctf axtenio «... 88
Haloid oomponndA of azMDio, 80
ArMDlcal poifwiing 80
AiuJjtiaa ^.... 90
Atdimong 07
HTdragflD Uitltnoiiide 97
OxMm of utiiaoDj 97
Antiffionjr aolda 08
Obkpcide* oE nntimoojr 96
&nlphid«B of ontttnooy 00
AntimonUl polsomog 100
Annlytioal 100
BOBOK Grocf 100
Boron 100
Boron oxldo sod acids 101
CahbonObouf 101
Carbon 101
SOieon 108
Tanadiuu Ouoor 104
MuLTUDEKUU Qaoirr 104
AMi-umiciuc ELKKBim. lOiy
Gold Group 105
Ibos Group - 105
Chromittm lOQ
Maaganeit , 107
Iron 108
CompoQDda of iron 100
Salts of iron Ill
Alvhihium Gboup 1 U
Giueinivm lU
Aluminium 114
SwMlium 117
OaBium 117
Indium 117
Vbahtcu Orodf , „;. 118
LftAD Gboup .,'. 118
Bmum Gboup 1S2
Tm Group 124
pLATinnc Ghoup 12S
Bastlous Elevkxth 180
SoDiuu Gbocp 180
Lithium 180
&dium 180
Fiotaukm 185
Sihtrr 14S
Afomimium 144
Tballium Gboup ...r 144
OALrruu Gboup 147
rolsium 147
I
00NTENT8.
BtmUium 181
Barium 161
Haonesiuh Orouf 162
MoffMtium 1 68
Zine 165
Cadmium r 167
Nickel Obouf 167
COPPEK Gboup 168
Copp«r. 168
Merourjf 168
OOKPOUNDS OF Carbon 168
Momologout ieria 169
iBonuriim 170
Qamjieation of organie auittaheet 171
J^irat Series of BjfdrocarboTu 172
Haloid deriTstlTM 174
Monoatomio olcoboU 177
Simple ethen 188
HcmobMio acddB 181
Compoond ethsEB 197
Aldehydes 200
Ketones or Boetonefl SOS
UcmAminei 805
Hoiiftmides 808
Amido aoida 300
Compoandfl with other elements 219
Allflio series 931
Amylio acids and aldehj-des 234
Polyatomio eompounds 226
Seoond Beriet of SydroearboTu 828
Diatranlc aloohols 2S9
Diatomic, monobaslo aoiJs 883
Diatomlo, dibasic adds '. 240
Compound ethexB 248
Aldehydes and aohydrides 249
Amines 249
Amides 260
Compotmd areas 269
Tiiatomio alot^ols 968
Adds 265
Ethers... 265
Fats and oils 267
Third Seriea of Bydrocarbona 275
Tetratomio aloohols 876
Adds 276
Fourth Beriet of BydrooarbonM 278
Carbohydratet 282
Glnooses 282
Saocbaroses 289
AmylOMH 891
covTBsrrs,
XI
AremaUe nbstanefs ,., 280
F^lh Seria of nifdnx4jrtKmM..,„„^„ ; 807
Ucloid deriTatives '. UOO
Phenols , 80ft
Alooholi 800
Alpfaeoob 810
Aldebydea 810
Acid* 811
Amidodorivotiveft , 818
Au and duxo derivatiTe* 818
B^draxises 817
Pyridina bosw 817
Ghioolloe hues 818
Indigo Group 810
Sixth &trrU» of Egdroearbout 881
Aluobole 831
BftetUh ikriet of Hydrocarbons 883
Eighth Seritd of Bydrocat-hoiu 833
DeriTsUveit 838
Kinih SerUa of TTifdrMiir^M 891
Tenth Stria of JlgdrocarboM B24
Sintnth a*riet of UydroearboH* 834
DeriviitirM 8SS
MigktT Herift of Ilgdroearbotu 83S
Cj/ajiogtn Compoundt , 830
Gbiamdet 838
AUcatoidt 881
AibumiTundi anA g^tinoidt ...,.,.; 846
Animal erifpuUyUi 853
Animal coloring matten 854
PAET EDL— CHEMICAL TECHNICS 807
General Bules 867
BrMji^ta 868
OUaitabing 848
CoUeoUoa of gaiei ■ 8S0
Solotion 880
rredpitation, decantatlon, ato 861
ETaporatlon, dij'me, etc 808
Weighing .,.,..... 305
tfeamring ,, 806
Behemefor Analyntof Calcnii. 888
j5BA«in« far Analytit of Mintral Compounda 860
7\ai6cf8otubiUtif 874
TaiUof WeighUand Metmtrta 878
iiTDEX zrt
THE MEDICAL STUDENTS
MANUAL OF CHEMISTRY.
PART I.
INTRODUCTION.
Tue simplest deBnition of chemistry is a modification of that g^tren hy
Webster ; That brtinch of science which treats of the contpotfitton of tub-
atcnces, their chanQes in compomlion, and the lawn govemintj nuch changes.
If a bar of soft irou be beated sufficiently it becoiuoa lumiuous : if
eauaed to vibrate it emits eound ; if introduced withiu a coil of wiro
through which a galvanic current is passing, it becomes magnetic and at-
tracts other iron brought neai* it. Under all these cireumutunceH the iron
iH still iron, and so soon as the beat, vibration, or galvanic cun'ent ccasea,
it will be found with its original eharactei-s unchanged ; it has Buffore<l no
change in comnfmtion. If now the iron be hentetl in an atmosithcre of
oxygen gaa it buniH and u converted into a substance which, although it
contains irou, haa neither the appearance nor the pro[>crties of that metal
The irou ami a part of the oxygen have disappeareil and have been con-
Terted into a new mibatance, differing from either ; there has been change
in oompotUion, tliere has been chemical actvjn. Changes wrought in matter
l)y physical forces, such as light, heat and electricity arc temporary, and
hut only so long as the force is in acllnty ; except in the cjuae of duuigea
in the Btat« of aggrct^ation, as when a substance if) piUverized or fashioned
into given shnpe. Changes in chemical ooroposition are permanent, last-
ing until some other change is brought about by another manifeitlation of
obemicAl action.
However distinct chemical may thus be from physical forces, it is none
the leas united with tliem in that grand correlation whose esistcnco waa
iirst annouDced by Grove, in 1842. As, from chemical action, manifesta-
tioDS of every variety of j^hysical force may be obtained : light, heat, and
mechanical force from the oxidation of carbon ; and electrical force (rom
the action of sine upon sulphuric arid — ao does chemical action have its
origin, in many instances, m the physical forces. Luminous rays bring
alxiut the chemical decomposition of the salts of silver, and the chemical
anion of chlorine and hydrogen ; by electrical action a decom]X)sition of
many compounds into tueir constituents is instituted, while instances are
i
MAWCAL OF CHTOfTSTRT.
ftbDixlant of reactions, combinations, and decomposittona vhich requii'e a
corlain eloiration of temperature for their production. While, therefor,
chemistry in the strictest sense of the temir deals only with tbotte actions
which are attended by a change of composition in the material acted upou,
yet chemical actions are so frequently, nay uuiTereolly, affect«d by enstanjf
physical conditions, that the chemist is oblige<1 to give his attention to
the ftcience of physicfl, in so far. at leasts as it has a bearing upou chemical
reactions, to chemical phynat — a branch of the subject whieii liaa afTorded
very important evideDCfl in sapport of theoretical views originating from
purely ^emlcal reactions.
General Properties of Matter.
Indeatnictibility.— The result of chemical action is cJiango in the
composition of the substance acted upon, a change accompanied by cor-
respondiug alterations in its properties. Although we may cause matter
to assume a variety of different forma and render it^ for the time being,
inTisible, yet in none of these changes is there the smallest particle of
matter destroyed. WTien carbon is bumod in an atmosphere of oxygen,
it disappear, and, so far as wt! can learn by the senses of sight or touch,
is lost ; but the result of the burning is an invisible goa, whoso weight is
equal to that of the carlHin which has disappeare^l, plus the weight of the
oxygen required to burn it
Weight.— All bodies attract each other witli a force which is in direct
proportion to the amount of matter which tliey contain. The force of this
ntlractiou exerted upon surrounding bodies by the earth becomes sensible
as weight, when the motion of the attracted body toK*ard the centre of
gravity of the earth is prevented.
In chemical operations we have to deal with three kinds of weight :
idniolute, aj^arenl, and iipecrfic.
The Assolcte VVeioht of a body ia its weight in vacuo. It is deter-
mined by placing tho entire weighing apparatus under the receiver of an
sir-pnmp.
^^E Afpakent Weioht, OB Relative Weiobt, of a body is that which we
usually determine with our Imlances, and is, if tlie volume of the body
weighed be greater than that of tlie counterpoising weights, less than its
true weight. Every substance in a liquid or gaseous medium suffers a
loss of apparent weight equal to thai of the volume of the medium so dis-
placed. For this reason the apparent weight of some substances may be
a minus quantity ; thus, if the air contained in a vessel suspended from
one arm of a poised balance be replwtetl by hydrogen, that arm of the
balance to which the vessel is attached will rise, indicating a diminution
in weight. (See "Weighing ; Part HI.)
The Specific Weioht or St>Bcmc GiwTmr of a substance is the weight
of a given volume of that substance, as compared is'itli tlie weight of an
equal bulk of some substance, accepted as a standard of comparison,
under like conditions of temperature and pressure. The sp. gr. of solid?)
and liquids are refen-ed to water ; those of gases to air or to hydrogen.
Thus tiie sp. gr. of sulphuric arid Ix^ing 1.8, it ia, volume for volume, one
and eigbt-teutha times us heavy as water. As, by reason of their different
mteo of expansion by heat, solids and liquids do not have the same sp. gr.
at all t4*mi>eratin-e8. that at which the observation is made should always
be noted, or some atimdard temperature adopted. The standard tempera-
■
*
OENERAL PROPSKTIKS OF MATTEB.
^
tur« adopted bj some co&tiQental initers and in tho U. S. P. is 16° (69^
F. ) ; other standard tempemturea are 4*^ (39.2'' F.), tlie point of greatest
(leusitj of waUr. used by most continental writers, and 16.6° (60" F. )>
u»ed in Great Britain and to some extent in this countrj-.
Tlio determination of the npecifio weight of a substance is frequently
of great aerrire. Sometimes it affords a rapid means of distinguishing
between two mibatances similar in appearance ; Bometimcs in determining
the cjuimtity of au ingredient in a mixtoro of two liquids, as alcohol and
water ; and frequently in determining approximatelv the qoantify of sohd
matter in solution in a liquid. It is the la^t object which
we hsTS in view in delerniiiiiDg tlie sp. gr. of the urine.
An aqueous solution of a solid has a higher sp. gr.
than pure wat«r, tlie increase in sp. gr. following a
regular but iliffereut rate of increnae with each solid.
In a simple solution— one of common salt iu water, for
instance — the proportion of solid in solution can bo de-
termined from the sp. gr. In complex sohitiona, such
as the urine, the sj). gr. does not indicate the propor-
tion of solid in solution with accuracy. In the absence
d sugar and albumen, a determination of the ^, gr.
of nrine aflfords an indication of the amount of soUds
sufficiently accurate for usual clinical purposes. More-
over, as urea is much in excess over other urinary sol-
idi, the oscillations in the sp. gr. of the urine, if the
qnuntity paiiao<l in twenty-four hours bo oonBidered, and in the abeence of
albumcu luid sugar, iudicate the variations in the elimination of urea, and
oonsequently the activity of disassimilation of niti-ogcnous material.
To determine the sp. gr, of substances, different methods are adopts,
according as the subatauce is in the soHd, hquid, or gaseous state ; is in
laaw or in powder; or is soluble or insoluble iu water.
SoLCDs. — The suhUance is /wavier than iraier, inwluble in VuU Ivjuid, and
not in pojoder.^^lt is attached by a fine silk fibre or platinum wire to a
hook arranged on one arm of the btilance, and weighed. A beaker full of
pore watef is then so placed that the body is immersed in it (Fig. 1.), and
a Bsoond weighing made. By diriding the weight in air by the loss in
water, the sp. gr. (water — 1.00) is obtsinetL Example :
A ptM« «f I'&d ««itcbB tn air 88.0
AvtoMoCkkdmiiElulikWftUT.... 74.*
1
PIO. 1.
1
wo
T4
tlLWBif^gr.af iMd.
The imbstianre ia iti powder, insoluble in tmier. — The specific gravity
bottle (Fig. 2) filled with water, and the powder previously weighed and
in a separate vessel, ore weighed together. The water is poured out of
the bottle, into which the powder is introduced with enough water to
the bottle completely : the weight uf the bottle and its contents is
determined. The weight of the powder alone, divided by the loss between
tbo first and second weighings, is the specific gravify. Example :
Wel(lit of Iran fiHiw* dMd UM
Wolstit of trao AUnti ua ap. gr. hMde Blled «rith mMr 14&W
W«>clit oC ip. cr. iMataooaiAlsiaslnBitbictUid sited wUwkMr. U7.<n
Water OlaplMod bf bon MBt
■ « 7.B s ip. gr. at trao.
ftW
ofill ^
now ^M
ivcon ^1
MANCAL OP CHEMISTRT.
The gttb9iance i* lighter than water. — A BufBcient bulk of some heft^y
mbebmce, vhotte sp. gr. is known, is attached to tt and the somo method
followed, the loss of weight of the heavy subBtance being subtracted from
tho total loaa Kxample :
Xrrwttirol ol wood wetsbt 4.3IMS
AfnfOMntDftMilwclKtH lOJUf
Wodil with lewl altaehMl mrlKlw IftOIIV
WocMl •dth 1««1 klt»clMd «el«ha in HikMr &.«•>
Umtdw^tbtat eaaMtuMoa „ I.U644
IiONof wygbtollmlltmiv „ O.TIOS
I.IW •)( v^bt o( voo4 ajma
' • OJn B (p. gr, of wood.
The »t^etance ia soluble in or decomposable btj u^er. — lU npecifio gnxiby,
referred to some liquid not capable of acting ou it, is determined, using
that liquid as water is used in the case of insoluble substances. The sp.
gr. so obtained, multiplied by tlutt of the liquid used, is the sp. gr. sought,
llxample:
A pieoe of potualnin kcIkIu •-.•■• «.a*.>*Kp t.VTQ
A»9.te, tw*Ue toll of nH>t)tliB, «p, ft, O.iU, w«!gtw tttH
suao
Tim boUla irUh polalaai md oaphtfi* wlgha. Xt.lOft
to-. t«T
s 1.141 ■ t).798 s cm s fp, 0. of potiMbUp.
LfQriDs. — The sp. gr. of liquids is detenuined by the ^>ecific gravity
bottle, sometimes aUled jjicnonirfer, or by the spindle or hydrometer.
By tlie hutile, — This method is the more accurate, and, if a balance be
at hand. Is easily conducted. A bottle of thin glass (Fig. 2) is so made as
to nontAJri a given volume of water, sav 1*W c.c., at 15^ C., and its weight
is detenniiied once for all. To uho uie picnometer, it is tilled with the
liquid to be examined and weighed. The weight obtained, minus that of
the liottle, is the sp. gr. twught if the bottle contain 1000 e.c. ; ^ if 100
&c., etc. Kxample : Having a bottle whose weight is 35.35, and which
contains 100 e.c. ; filled M-itb uriue it weighs 137.91, tho sp. gr. of the
urino i.s 137.91-35.35^102.S(>x 10^ 1025.6 \Vater=1000.
Jt}j the spiniJte. — The method by the hydrometer is based upon the
fuct thitt, a solid will sink in a liquid M-hotie sp. gr. is greater tlian its own,
until it has displaced a volume of tho hquid whose weight is equal to its
own ; and all forms of hydrometera are simply contrivances to measure
the volume of liquid which they diaplaeo when immei-sed. The hydrome-
ter most used by physicifinH is tlie unnonieter (Fig. 3J; it should not be
chosen too amnll, as the larger the bulb, and the thinner and longer the
stem, the more accurate are its iudicaiiouB. The most convenient method
of using the instrument is as follows : The cylinder, which should have
a foot and rim, but no jxiuring lip, is filled to within an inch of the
top ; the spindle is then floated aud tho cvlinder completely filled with,
tho liquid under cxamlnatiou {Fig. 3). The rending is then taken at the
highest point a, where the surface of tho liquid comes in contact with
the spindle.*
' Tlie adrantopM of tbe method described over tbnt asai≪ followed oxo r Greater
fkciUly in naAing. lest-t liahilitj to atror, tfaa poamibility of ukiotc the r«adiDft ia
oimqiiQ liquids, ami the Tac-t that nadiagt are made upward. Dot downward. The
Siudlu requira to he R|ieciitl)y gradaatedf and an made bjr Baudin, of Paris, and
mer A Amend, of New YoiJl
eZNBRAL PROPERTTKS OP XATTEB.
In all det«nniDatioiis of sp. ^. the Liquid examined ehonld hATO the
temperature for vbich the iiuiniineiit is graduated, aa all Uquida expand
with heat and contract when cooled, and consequently the result Dblaiued
will be too low if tlie urine or other liquid be at a temperature above tlrnt
at which the instrument is intended to be used, oud too hif;h if below thai
An accurate correction may be made for temperature in
/\
Bunple Bolutious ; in a complex fluid like the urine, however, ibis can only
be done rouffhly by allowing l"" of sp. gr. for each 3"' C. (5.4" Fahr.) of
[Tttriation in temperature.
Qassx and VAwtits. — The specific gravitiea of gasea and Tapora are of
[great importance in theoretical cliemistri', as from them we can determine
idlecuUr weights, in obedience to the law of Avogadro (p. 14).
OoM*,— Tbi> *iMriflR piiTlUca at gwB KID oMjdiisd M follow*: A ^an Ovik of abnut 80O cc. eMadiy,
tvlBK • Mok 10 nniimolnw tonic ■*>d V mlUtmcliw In diMmMcr, uiil lUtvd with • kIhm Mopcodu ta UmI
llh Bwiciui ift TVfen^ o<r«r merconr ; hm) Allml wlUi tha w to Jnt below Out Mopcoek. TIm Mopeock
IDOweltMM: tlMtMnp««Efm.f ; tlw bMtMWlrie l yt Mu n*. I! ; wid Um hgt^bt a( IIm iiMmiri*! colomn In
to AMfc MboT* that Id tb» tnmili. A. m* dcMrahm), Mid ib» OmIe wal«1i«d. Lit P Im Uu vflgM fooHd,
Itmi T Ibe m^tits of Uil- fliwk, JuliTBUDvd oocb (or ail, Ibca
TIm Buk im then benaRht nK.ln- tb* recdvcr of »n alr-parnp. th* (tIaN Mofwocik bainc opao, fttiil lb* ftlr
I tUtmtuAaif nluwMMl kml altownl Ui enUr until Iha ku In ih* Oufc la nplM:*^ bjr air. 71m tauMmUu* f ,
)•■ lw«nvtH« prMaim H'. and the wHfflit of tk« i1iu>k niU-d <*ilh air f, ar* now Jriwinlaad. rrm tbmm
» %bm wtifSbt, K. ot ttoo st» Doeapjvmliu'yoUMm- V, in ubtatnwl by llHlaniidi:
K=P-P'+
V H'
^TT+irassf^
0.001306
Tka aph gr. nteivd to air la Fcntnil by thv lurmnta :
T.>«.wiaos
1 that nttmA to hrtUtvea bj- tha formok :
Ts « D.ooini >i o.D0nT
XAKUAL OP OBXMISTRT.
Favor*.— T%* •oKilo trnvky or npon h bM 1 lirHim I kr M^vrt iMl>ia. m Mkm : A
UfU elMi TMiri ( rig. 4) h eiM oorapMrir with Ite nU OS %«» <rlMM n|Mr 4tMtt7 la Id fas dMnali
ftBdw««h«t: ftom thii weight tkat at tha Mart 1* MhcnMal ; iteASHMv balBg th« «M||bt
»t th« nttMCWMo P. Tho ^mU iiiiboI and ««•■» u« bow la mwifj two th« ■«• braMh of
Uwapffumu (»(.»}, wMMwolcht la than dOHnatairf. TlMapp«nlM la sow UM wflh bm*-
oiuT, IIM «MUhBT opMlni M tha tiiv ot tfaa feii«ar hnwk la doMa hf tk« MMr-t>'»*b I
wtwla a^lB afllgtwd. TM apptfalaa la OH^MMid h^ * MaWUo win war Um botton 4,
taba oloaod a* tho twttom, and o cn UU tag abnt flV oa «< •■■■ Hq*d<> •rboM tefUiMt.pofarl
Uant aoA hlghar thMi thai of tha Ml i rt aa n a i ip i ri i t ii ml whan tha U^ohl baa ba«if
U> Kcciva boiling oud Iha la n uiuf emmm tofoaoporroB Iha afaUl tslia, tho banMBiCilo ■
kiKl ihc UtnptntiBW o< th* air an otaaarMd. After Um appanMo la eatfad, tte tabs tn^ I
Piu 4 »-i(b lu cMUcnbi. 14 wolgtMd. and Um tUBonnea la Iba latil «( mtrenj nhlA mdatrnt la Iho I
bntnohoK tfurtag tho h— Una dHanalaad bf braaUaar UM caDttan fub», MIm tha ■
to Um HDnlkT hfBiHh h ODHipialaly iUad, BMitlBK Um laral of HHoaf? In tha I
afaa a rtng Um dManra tnrn that paliil t» tha opanlas.
Bf tha abOT* pcocaaa ibc toUawhtg fwaota mdaHnolaad:
r = wt4gbt oC Mitataaoa ;
T = boiUBC-palBt cf oxuaal llqsU ;
( B taaijMrataie a< air ;
B a banBotrie pr mma latoood la 0* ;
k = dUhnnoa la lava! of mmarj tn two tafMKtu* of tab* ;
V m taarion of vapor ul mtnorj at T ;
m = waiffbi of BMrcoTf iMod :
9 = wa%bt irf awTvnr^r raqalnd to ftn Uio tube Fig. 4 ;
^B walgbt of la M u i Afy nnaaiiilcig la tha oa^m^iv oHw baathw.
Vroa thaM Um ^ncUk gtaWr. air k l, U oMatoad bj the <qaailaa :
D=.
PTW(U0.00WIT1ia5S
' (U * A ♦ A^ tt.oouBi [(a«-r) { 1 «^«rounsiB (T-0 1^ -r < 1 »o onns (T-oVlh^^i^MiaVj
I VIm np. gr. la tanaa of air = 1 naj ba nduoad lo ^j. gr. w fa i»l Id hjUiupn = ■, bj dividing bj O.0nfr.
States of Matter.— Matter exists ia one of three etatea ; solid, lifiuid.
and gaseous. In the solid forui tlio particles of tnattfr are comparatively
close together, aud are HCpuruted witb more difficulty tJian are Uiose of
liquid or gaseous matter ; or. iu other words, tho coheitioti of solid mattfir
is greater tlian that of the other two forms. In the liquid the particles
are less lirmly l>ound together and are capable of freer mottoQ about oo6
another. Iu the gas the mutual attraction of the particles diaappeaiq
entirely, and their distance from each other depends upon
the pressure to which tlie gas ia subjected.
The term _^uifi applies to boUi liquids and gases, the
former being designated as incojjiprevstbie, from the very
aUght degree to which their volume can be reduced by
weasure. The gases are designated as comprexs&iejiuuis,
trom the bet that their volome can be reduced by pressure
to an extent limited only by their passage into the liquid
form.
It ia highly probable that all substances, which are
not decomposed when heated, are capable of existing in the
three forms of solid, liquid, and gas. Tlioro ai-e, however,
some substances which are only known in two forms— as
alcohol ; or in a single form — as carbon ; probably Viecattse
we are as yet unable to produce artiticially a temperature
sufficiently low to solidify the one, or sufBciently high to
liquefy or volatilize the other. Since the liquefaction of
the so-called permanent gases the distinction between gases
and vapors is only one of degree and of convenience.
The passage of a substance from one form to another ia
always attended by the absorption or liberation of a defi-
nite amount of heat. In passing from the solid to the gas-
eous form, a body absorhR a definite amount of heat with
each change of form. If a given quantity of Ice at a temperature below the
freezing- p'jint of water be heated, its temperature gradually rises until
the thermometer marks O'' C, at which point it remains atotiouary until
rio-ii.
" tl
! of ice has disappeared. At that timo another riao of the
?r begins, ajid continues until 100"^ C. is reached (at 760 mni.
of barometric presaure), when the water boils, ami the thermometer re-
maioB etaliouary UDtil the lost particle of water has been converted into
steam ; after which, if the spplication of heat be continued, the thermom-
eter again rises. During these two periods of stationary' thermometer,
beat is token up by the substance, but is not indicated by the thermom-
ster or by the sensa Kut being sensible, it is said to be latcnl, a terra
'which is liable to mislead, as conveying the idea that heat is stored up in
the suVwtance as heat ; such is not the case. During the period of station-
ary thermometer the heat is not sensible as heat, for the reason that it is
sing used up in the work required to effect that separation of the par-
otides of matter which constitutes its passage from solid, to liquid or from
liquid to gas.
The amount of heat required to bring about the passage of a given
weight of a given substance fi*om the denser to the rarer form is always
the same, and the temperaltire indicated by tlio thermometer during this
passage is always the same for that substance, unless in cither case a modi-
fication l>e caused by a vivriutiou in pressure. The degree of temperature
indicated by the thermometer nhile a substance is {Missing from the solid
to the liquicl state is cjitled itri fuging-poiut ; that indicated during its pas*
sage from the litjuid tu the gaseous form, its boiling-point.
The absorption of heat by a TolatLUziug li({uid is utilized iu the arts
and in medicine for the production of cold (which is siinply the absence of
boat), in the manufacture of artificial ice, and in the production of local anios-
Jliesia by the ether-spray. The removal <}f heat from the body iu this way,
~jy the evaporation of perspiration from the surfoce, is an important fttotor
in the maintenance of the boiiy temperature at a point consistent with life.
When a substance passes from a rarer to a denser form it gives out^
liberates^on amount of heat equal to that which it absorbed in its passage
in the opposite diiection. It is for this reason that, while we apply heat
Lto convert a liquid into a vajior, we apply cold to reduce a frns to a liquid.
|JU a rule, the thermometricjil indicration is the same in whichever direction
f^the change of forra occurs ; some substances, however, solidify at a tem-
perature slightly different from that nt which they fuse.
Host solids, when heated, ore first converted into liquids, and these
into gases ; there are, however, some exceptions to this rule. Most vapors
when condensed pass into the liquid form, and this in turn into the solid ;
aoino substances, however, are condensed from the form of vapor directly
I to that of solid, in which case they are said to suUime.
Divisibility. — All substances are capable of being separated, with
greatrer or leas facility, by mechanical means into minute particles. With
suitable apparatus, gold may bo divided into fi-agmenta, visible by the aid
I of the mi('roKcoi>p, whose weight would be jooosn^iureuinr of a grain ; and
' it ia probable that whan a solid is dissolved iu a liquid a still greater sub-
division is attained.
Although we have no direct experimental evidence of the existence of
j a Hmit to this dirisibility, we are warranletl in believing that matter is not
■ infinitely divisible. A strong ai^ument in favor of this view being that,
I after physical subdivision has i-cached the limit of its power with regard to
compound substances, these may be further divided into dissimilar bodies
by chemical means.
Tho limit of mechanical subdivision ia the molecule of the physicist,
the smallest quantity of matter with which he has to deaL
4
UK
UU
■ inl
Bthe
^per
i
I
I
I
4
Tanoufl
we find that miuij ol tUem can be so decompoBeU as to yield two or
more other substaucos, diatiuct id their properties from the subetonce
from whose decotnpoaitioD tbey resoltad, and From each other. If, for
example, sugar be treated with sulphuric acid it blackens, and a mass
of churcual iK.'parated. Upon furthu: examination we hud that water baa
ftlso been produced. From this water we uia,v obtain two gaaea, diSexing
.from each other widely in their properties. Sugar is therefor made up of
carbon and the two gnaea, hydrogen and oxygen ; but it [las the properties
of sugar, and uot uiu»e of either of its constituent porta. Tliere is no
method knowu by wliich onrbou, hydrogeu, and oxygen can be epht up, as
Bugar is, into other dissimilar Bubstanoes.
An element or simple mbtUance is a Muiudance tehich cannot by any tnoton
means be ttplil up into other diisnmiiar bodies.
The number of well-characteriKed elenieuU at present known lb sixty-
six. During a few years past the discovery of other elements not included
in the above tmmher, dtTipiuvi,philippium,davyium, norwegium, and iuy>'
tunitim, has been announced.
Laws Governing the Combination of Elements.
Tlie alchemists, Arabian and European, contented themseKes in aocu-
mulnting a store of knowledge of isolated phenomena, without, as far ns
we hnow, attempiug, in any serious way, to group them iu such a manner
as to learu the laws governing their occurrence. It was not until the
Litter port of the loat century, 1777, that Wenzel, of Dresden, implied, if
he did not distinctly euuuciate, what is known as the law of reciprocal pro-
portioua. A few years later, Hichter, of Berliu, continuing the work of
,Weiuel, added to it the law of definite proportions, usually called Dalton's
first law. Finally, an the result of his investigations from 1804 to 1808,
Dalion added the law of multiple proportions, and, reviewing the work of
his predecessors, enunciated the results clearly and distinctly.
Considering these laws, not in tlie order of their discovery, but in that
of their natnnu sequence, we have :
The Law or DrrrxrrK P&oi<c>rtiox8. — lite relative weiffhts of elementary
KubMances in a amipound are defmile and invariable. If, for exBmple, we
analyze woter, we find that it is composed of eight parts by weight uf oxy-
gen for each part by weight of hydrogen, and that this proportion -exists
in every instfuice, whatever the source of the water. If, instead of deoom-
posing, or anabjzing water, we start from its elements, and by KynMesia,
cause them to unite to form water, we find that, if the mixture be made in
the proportion of eight oxygen to one hydrogen by weight, the outir©
quantity of each gas will be consumed in the formation of water. But if
au excess of either have been added to the mixture, that excess will re-
main after the combination.
Compoundg are substances made up of two or more elements united with
eacJi other in d''jinilt: proportions. Compounds exhibit properties of their
own, which difler from those of the coutititueut, elements to such u degree
that the properties of a comiHiund con never be deduced from a knowledge
of those of the constitnent elements. Common salt, for instance^ is oom-
THK ATOmO TRSOST*
of 39.32 percent of the liglit, blurali-white metAl, sodium, and 60.68
! eeut ot the greemsb-jrellow, sufEbcatiug gas, chlurioe.
A viirturv is compoted of two or more »»Mance9, eiententfi or compoutidiit
minuted in any proportion. The cliAractms of a mixture xqat be predicated
from a knowledge of the properties of ita ooastitueuta. Thus sugar and
^vaier may be mixed iu ouy propurtiuu aud the mixture will have the
iweetucss of the suRar, and will be Liquid or BoUd according as the hquid
^or solid iugredient predorainateti in quantitj.
Tub L.IW of Mi.ltu'LE PacpoRTioitB. — iVhen tico elemcnUi unite unlh each
to form vwre than one comjiouttj, the r&sttUing compounds cantaiti
ftimpie multiple proportions of one element as compared tvUh a congtant </uan-
tiiy of the nlht^r.
Oxygen aud nitrogen, for example, unite with each other to form no
teas tUau Ave compounds. Upc>n analysis we find that in theae the two
elements bear to each other the following relations by weight ;
In the first, 14 ports of nitrogen to 8 of oxygen.
Id the second, 14 poi-ts of nitrogen to 8 x 2 = IG of ox^'gen.
In the thii-d, 14 parta of nitrogen to 8 x 3=24 of oxygen.
In the fourth, 14 parts of nitrogen to 8 x 4=82 of oxygen.
In the fifth, 14 ports of uitrogeu to 8 x 5=40 of oxygon.
Tbe liiw OF Rettphocu- PnoprtRTioKfl. — The ponderahie qiutntitiee iti iMicA
«ui!«to/i«.'s unite with the same gnb^tunce f.rj)rt:Ai the reLUion, or asimjiie mxd-
tifile titertof, in which they unite with each other. Or, as Wenzel stated it,
"the weights h, b, b" of sevend bases which neutralize the same weight a
of an acu) are the same wliich will neutralize a conHtout weight a' of
, Another acid ; and the weights a, a, u ' of ditlerent acids which neutralize
tthe same weight & of a base ore the same which will uentralize a constant
weight of another base b'."
The Atomic Theory.
ISie laws of Wenzel, Ilicbter, and Dalton, given above, are simply gen-
emlize<l statementR of certain groups of facta, and, as such, cot only admit
of no doubt, but are tlie fuuutlatiuus upon which chemistry aa an exact
flcienoe is based. Balton, socking an explanation of the reason of being
of Uieae facta, was led to adopt the view, held by tbe Greek philosopher
amocrituB, that matter was not in^itely divisible. He rttnined the name
'atom {uTu/jM^ — indivisible), given by Democritus to tbe ultimate piu-ticles
of which matter was supposed by him to be composed ; but rendei'ed the
,idoa more precise by asctibiug to these atoms real magnitude and a
^definite weight, and by couaidering elementmy substances as made np of
' atoms of the aame kind, and compounds as consisting of atoms of different
kinds.
This h^'potheais, the first stej) toward the atomic theory as cntoi-tained
to-day. afforded a clear explanation of the numerical renult^ stjited in the
three laws. If hydrogen and oxygen always unite together in the propor-
tiou of one of the former to eiglit of the Latter, it is because, said I>alton,
ihe compound consists of an atom of hydrogen, weighing 1, and an atom
of oxygen, weighing H. If, again, in the compounds of nitrogen and oxy-
gen, we have the two elements uniting iu the proportions 14 : 8
U : 8x2 14: 8x3 U: 8x4 U:8x&, itia because they an
10 MAMVAL <fW
Mfvndlf eomyu m d of aa slom of luUu g ui w uftka g 14^ mitod to 1, 2, 3,
4, or 5 mtonm ai oxygen, cadt wrieliiag S. Fiulhii, Ast eompoiads do
not exist m widdi o^fneCaoDof 8 oxjgeneBta%faMBBK81i tfaowei^^
of the mdETinUe etom of oxTgCB.
One of the chief adnntegee of Deltan's h y pot h e ei i m in tte intcodne-
tioo of thia pRciae and nmple nlation between the niwuilitiLi of the em-
atitiUDte of m eom p opnd. Chendate befan Ddtoa'a d«y, in iineiiwiiii^
the resnlte of their moaijwe^ did not peog w beyond itt' iiiiiii nl ii oi the
pmeeatagB ooo^KMUion. yiprriiig tiie eotnpoKtian of fpor of tho
carboo eompoukda in pereentage^ we have :
35.0
• * ■ *
=100
14J3
^ ^
=100
* « * •
57.1
=100
# - k -
72.7
=100
Harahgaa 75.0
CAefiaotgaa 85.7
Carbonie oxide 42.9
Carfoonicaeid 27.3
Theae fignrea eonrej nothing b^ood the mae eenteeimal ennpontioD
of the anbatancea idnch they expfeaa. The cardinal point at Datton'a dia-
coferj. liea in hia tnualation of them into the simple relations:
lianbgaa. 6 3..
Oleaaotgaa 6 1..
Carbonic oxide 6 8
Carbonic acid 6 16
Dalton's hypothesis of the existence of atoms aa definite qoantities did
not, however, meet with general acceptance. Dsjy, WoUastcm, and others
considered the quantities in which Dalton had found the elements to unite
with each other, as mere proportional numbers or equivcUentSt as they ex-
presaed it, nor is it probable that Dalton's views would have received any
further recognition until such time as they might have been exhumed
from some musty tome, had their publication not been cloeely followed by
that of the results of the labors of Humboldt and of Gay Lussac, concern-
ing the vUume» in which gases unite with each other.
In the form of what are known as Qsj Lussac's laws, these results are :
/Vrrt. — There exieit a aimple relation betuxen the voiumes of gases u^ich
combine with each other.
Hecond. — There exieU a simple relation between the sum of the volumes
of the conatituerU gaaeg, and the volume of the gas formed by their union.
For example :
I Tutnina cnlorina nnlt«i with 1 ra\ata» hjdrogm to fonn S TohunM hTdrocUortc add.
1 TolniiM wij%tn unltm wlih S voluniM hfdrogea to form t volamea vspor td w*Ur.
1 vokuiM nltfugta unltai with 3 *oluniM nydiogeo to form % volainea ammonlK.
I volnnw mjKtn antte* with 1 volume nitrogen to form % vtriomei Dftrlo oxide.
1 votnma rayiteti nnltM with 3 volumea nltn^ren to fonn 9 toUudm nttrou ozlda.
Berzelius, basing bis views upon these results of Gay Luasac, modified
the hypothesis of Ihilton and established a distinction bietween the equitxi-
lenlB and alomM. The eompoBition of water he expressed, in the notetion
which he was then introducing, as being H,0, and not HO as Dalton's
hypothesis called for. As, however, Berzelius still considered the atom
of oxygen as weighing 8, he was obliged also to consider the atoms of
livdrogen and of certam other elements as double atoms — a fatal defect in
his system, which led to its overthrow and the re-establishment of the
formula HO for water.
ATOMIC AT»D MOtWTtTtAR WmOHTS,
It was reBerved to Gerhardt to clearlr establish the distinction be-
tween atom and molecule ; to obeci-rc the bearing of the discoveriea oi
Avogadro and Amp6re upon chemical philosophy ; and thus to aetabUoh
the atomic thcoTT as entertained at present.
As a result of hift investigations in the domain of organic cliemistry,
Gerhardt found that, if Daltou'H equir&lenU be adhered to, whenoTur car-
bonic acid or water is libtrated bv the dooompositiou of an organic sub-
Btance, it is invaiiablj' in double equivalents, nerer in single ones ; eJwaja
SCO, or 2H0 or some multiple Uiereof, never CO or HO. He further
found that if the equivalents C = 6, H^l, and 0—8 bo retained, the for-
ZDtdA became such that the e<iui>*alent8 of carbon are always divisiblo by
two. In fact, he found the same objections to apply to the notation then
in use that had been urged against that of Berzehus.
In 1811, Avogadro, from purely ph^-siod researches, had boon enabled
to state the law which is now knoMrn by his name, to the cflect that equal
voltana of all gases, under like conditiorut of temperature and pressure, con-
lain eqwunumbers of mol^ulfs.
In the hands of Gerhardt this law, in connection with those of Gay
Jjuflsao, became tho fouutlatiou of what is aometimea called the " new
I chemistry." Bearing in mind Avogadro'e law, we may translato tho first
three oombinations given in tho table on p. ID into the following:
r
1 moleculo ehlarlno uBlto* with t nolwtik bjtfroKCfi u* Ivm 9 BwlMal** bjdrodilnrto kcUL
1 aMloml* axnc*" nnttM witti t raolomWi hyiirocm U> torm i tnoMtmlM VApoc of miAut.
1 moMoul* ■iircc<n uniM* trltL 8 nolocuka hjdnie«a lo form > ■wtwuiJM uaiaaob.
But the ponderable quantitiea in. whicli these coiubiuatious take place
86.5 chlorine to 1 hydrogen.
16 o^gen to 2 hydrogen.
14 nitrogen to 3 hydrogen.
■And as single molecules of hydrogen, oxygen, and nitrogen are in theeo
combinations subdivided to form 2 molecules of hydrochloric acid, water,
and ammonia, it follows that thcao molecules must each contain two equal
quantities of hydrogen, oxygen, and nitrogen, less In size than the mole-
cules themselves. And, further, as in these instances each molecule con-
tains two of theite smaller quaiitJUeu, or aiwns. the relation between the
weights of the molecules must bo aluo the relation between the weights of
the atoms, and we may therefor express thu cumbinatious thus :
atom chlorine weighing 35,6 unites with 1 atom hydrogen weighing 1 ;
[1 atom oxygen weighing 16 unites with 2 atoms hydrogen weighing 2 ;
" atom nitrogen, weighing 14 luiitea with 3 atoms hydrogen weighing 3 ;
oonsequently, if the atom of hydrogen weighs 1, that of chlorine
(ha 85.6, that of oxygen 16, and that of nitrogen 14.
4
Atoznio and Molecular Weights.
Atomic Weight. — The distinction between molecules and atoms
%y be expressed by the following dctinitions :
A moieuule is the amaUest quantity of any aubitance that can exist in One
Bt^Ue.
MAVUAL 09 OHBMISTRT.
An atom ti the mnaUeat quantUy cfan dementary subdance thai am enter
into a diemioal naction.
The molecule is alw^s nude up of atonu, nptm wboae nature, num-
ber, and arrangement with r^ard to each other, the properties of the snb-
■tanoe depcmd. In an elonentaty snbstance the atoms composing the
molecake are the same in kind, and osnally two in number. In ocnn-
pound Bubstanoes they are djasimilar and vaiy in quantity from two in a
nmple compound, like hydrochloric acid, to hundreds or thousands in
more complex imbntsTirm 27te word atom can only be uaed in speaking of
an dementary body, and that only while it upamng through a reaction. The
term molecule applie* indifferenUy to dement* and compoundis.
The atoms n&we definite relive weights ; and upon an exact determi-
nation of these weights depends the entire science of quantitatiTe analyti-
cal chemistiy. They hare been determined by repeated and careful
analyses of perfectly pore compounds of the elements, and arprets the
weight of one atom, oftheelemeni at compart with the weight of one atom of
hydrogen, that being the lightetst dement known. It is also the weight of a
Tolume of the element; in the form of gas, which would occupy Uie same
Tolume, under like pressure and temperatare, as an amount of hydrogen
weighing one. What the abtohde iceight of an atinn of any element may
be we do not know, nor would the knowledge be of any service did we
possess it
The following table contains a list of the elements at preeent known,
with their atomic weights :
ELEMENTS.
A.
SymboL
R
AtomSc
Namx.
A.
Sgrmbol.
B.
AtDmic
wdgbt.
AL
Sb.
As.
Ba.
Bi
Bo.
Br.
Cd.
Ca.
Ca.
a
Ce.
CI.
Cr.
Co.
Cn.
D.
B.
Fl.
Ga.
Gl.
An.
37.03
130
74.9
186.8
306.6
11
79.963
111.8
182.6
40
11.974
141
85.467
62.4
S8.9
68.3
144.78
16S.9
19
68.8
9
196.3
H.
In.
L
Ir.
Fe.
La.
Pb.
Li.
Mg.
Hn.
Hg.
Ho.
Ni.
TSh.
N.
Ob.
0.
Pd.
P.
Pt
E.
Kh.
1
118.4
136.86
193.7
66.9
188.6
306.93
7
24
64
199.7
96.6
68
04
Cobalt
14.044
198.5
16
106.7
81
194.4
89.187
Gold
104.1
ATOXIC Ain>
<AR
BLKMENTS.— OwfAuMd:
Babidiain .
Rotbvolaia
fickudium .
iWnmm .
Snicon ....
Bilvtr
Sodlnm ...
StrouUum .
Balpbar . . .
TuiUlom .
T«lltirinn .
A.
B.
Aiaate
Kb.
85.8
Ka.
104.3
Ba.
H
Siw
1HJB
SL
88
^
107.075
5jl
29.00S
Sr.
87.4
a
St.fiM
Ti
163
Te.
128
ThaUioa.
Tborima.
Till
TUmUiub.
Tiuig>Un.
Urmtuoni.
Tttarbiam
Tltrinm..
Zioe
Ztrooniani
QyaM,
In some oases the resalts of analrsea are such as would agre« wiUi tno
nlues as the atomic weight of an elomcDt equally woU. lu tliiii cane we
can decide which is the correct \-alue by the law of Dulon^ aud l*cuL
These olisflrrera found that while the atomic weights of the eletnents Tair
greativ from each other, the sjiecl^c heats (aee p. 33) diiTer from each
other in an opposite manner, and to such an extent that the product ob*
UdiMKl br niultipl,ving the two togettier does not vary mu<m. from 6.4.
This product ia icnown as the atomic heat. ^Yhen by analysis it is not pos-
sible to determine which of two numbem is the correct atomic weight of
an element, that one is selected which, when multiplied by the spedfia
heat, gives a result most nearly approacliing G.4.
The atomic haata of boron, carbon, silicon, salpbur, and phosphonu
are subject to great varialioua, as Is showu in the following table :
SCM^
OrT«tKU[Md at - 3D •• D.lt1S L1I
OriawiiitH « 4- ia> amr aoi
CrrfUI)U«d «-(-£t8J- 0.M9 att
AiaaqilMU.
■ Olamanl
0.«5
l«l
XUMKMd
BrapUl*
I'OnplilM
■t- BO^B* 0.0«» 0.78
+ !«>> a.ai8 us
«4-1W W8W Ml
Kt - CO 0.I1M IJtt
mX + \WV lUsa SLOB
M + itT7.IF IM510 (km
amopK.
OryiUlliMd
CiyAOtMl
Onr««I»Hd
roMd
BpMtfto iMnto
bML
■t - 8B.B> o.ian sn
iit4'IA4* 0.901(9 &afl
U-{-ia>* 0.115 4.10
VtadotaKMl OjHIS a.90
SeLrvim.
OrtbotteraWo u-4- «• O.W VlII
OTtbotbocDblo kt+ »>> O.ITTI 0.0
Uiinld »t -I- IttO- Q tH T.fH
BoccnUj rwwd at 4- OS* D-Hau aw
PsocTBtnm
Y«llow ■!- T9> 0.m B.88
T«uiM Bt-t- as* o.n am
Uqatd Bt4-100* ...... 0.»t aST
Amovpliaw H+ W Q.tlO B.ir
It Will be obsorred that, aa the temperature of the aofuf element is in-
creaaod, the atomic heat more nearly approaches 6.4. It will further bo
noticed that those elements with which the perturbatione occur are those
which are capable of existing in two or more allotropic forma (see p. 81),
As in the passage of an element from one allotropic condition to nnother,
abaorption or liuerntioQ of heat always takes place, as the result of "inte-
rior work ; " it is probable that these perturbations arc duo to a coustnut
tfludenoy of the element to poas from one allotropic condition to another.
Al8<
The atomic h«ftts of those elementAij gases which have only been
liquitied by puomious cold and pressure are tolerably conatnnt nt nbtmt 2.4.
Molecular Weight. — The molecular weight of a subittance in ike weight
ita noieatie as compared teith the ueit^ht of an atom of hydrogfn. It is
so, obriotislj, tha bbiii of the wei^t« of all the atoms making np the
molecule.
A very ready means of delermuimg the molecular weigbt of any sab*
stance which we can convert into a gas is based upon Avogadro's law.
The sp. gr. nf a gaa is the weight of n given Toltinie as compared with that
of au equal volume of hydrogen. But these equal volumes contain equal
iiumbeni of molecules (p. 11), and therefor, in determining the sp. gr. of
a gas, wo obtain the weight of its molecule as compared with thnt of a
molecule of hydrogen ; and, as the molecule containa two atoms of hy-
drogen, while one atom of hydrogen is the unit of comparison, it follows
that the sp^vijic grai'Uij of a gas, muUipiied by fttvj, in its molecular teetght.
For example, tlie gas acetylene and the liquid benzene each contain
92.31 per cent of cafbon, and 7.69 per cenL of hydrogen ; which is equiv-
alent to 24 parts, or two atoms of carbon ; and 2 parts, or two atomt; of
hydrogen. The sp. gr. of acetylene, referred to liydrogen — 2, is 13 ;
its molecidar weight is, therefor, 26, and ita molecule contains two atoms
of carbon and two atoms of hydrogen. The sp. gr. of vapor of benzene is
39 ; ita molecular weight ia, therefor, 78, and ita molecule contains six
atoms of carbon and six atoms of hydrogen.
The vapor densities of comparatively few elements are known :
Yafiar Atcnle UoIkuIkt
OmiUt. wtUMU witehl.
njrdrocen IIS
OnRM.,,.. U IS 3M
ftdiibnr. «• M M
Srienlntii. SB 7» 164
TaUarbmi ISO l» «»
CblinlM. K.B MLS 71
DronlBa. 80 60 100
Ympot AUtnlo Ifdifenltr
dvMU;. Mitilit. wilsfct.
ladlne UT in au
PhMptaonM. a n IM
Atmbw ISO Ht Vki
Mtmrm 14 14 as
rotaMdnm. 89 SB 1«
CKdnlKBi B6 1» US
Monwy... lOU SU 9»
The atomic weight being, in most of the above instances, equal to the
vapor denirity, and to half the molecular weight, it may be inferred that
the molccuks of the^e elements conxist of two atoms. Noticeable <iiacrep-
andes exist in the caee of four elements. The molecular weights of
phoBphoms and arsenic, as obtained from their vapor densities, are not
double but four times as great as their atomic weights. The molecules
of phoRphoniB and arsenic are, therefor, supposed to contain four atoms.
Those of cadmium and mercnry contain but one atom.
Valenoe or Atomicity.
^^F It is known that the atoms of difTcrent elements possess difTorent
W powers of combining with and of replacing atoms of hydrogen. Thus :
^^^ One atom of chlorine combines with one atom of hydrogen,
^^fe One atom of oxygen combines with two atoms of hydrogen,
^^B One atom of nitrogen combines with three atoms of hydrogen,
^^H One atom of carbon combines with four atoms of hydrogen.
^^^ Tlie valence, atomicity, or equivalence of an element in the mturating
L potoCT* of one of its aloms as compared icith that of one atom of hydrogen*
^^L Elemeuta may be classified according to their valence into —
VAI/XKOX OR ATOMicrrr.
UoiTalent. elementH or monadR CI'
BivalGot elements or ilyada O''
Trivaleat olemeiita or triads B^"
QoadriTalent eleoaents or tetrads C"'
Quinquivnlent elements or pentads P'
Sexvalent elements or iiexads W*''
Klements of eren valence, i.e., tbom which sr« bivalent, quadrivalent,
or sexvalent, are sometimes called artiads ; those of uneven valence being
designated as pcrittsaitg.
In notation the volonco is indicated, as above, by signs placed to the
right and above the symbol of the element.
But the valence of the elemental is not fixed and invariable. Thus,
vrhilc chlorine and iodiuo each combine Trith hydrogen, atom for atom,
rtnd in those componuds are confteqtiently imivalent, uiey unite with each
oUier to form two compounds — one containing one atom of iodine and one
of chlorine, the other contmning one atom of iodine and tliree of uhlorine.
Chlorine being onivolent, iixline is obviously trivalent in the second of
these compounds. Again, phosphorus forms two chlorides, one contain-
ing three, the other tivo atoms of chlorine to one of phosphorus.
In view of these facts, we must consider, either: 1, that the valence of
an element is that which it exhibits in its mo^it saturated compounds, as
phosphorus in the pcntachloride, and that the lower compounds ore non-
saturated and have free valences ; or '2, that the valence is variable. The
first supposition depends too much upon the chances of discovery of com-
pounds in which the element has a higher vnlonce than tliat whic-Ii might
be consHlered as the maximum to-day. The second supposition — notwith-
sUindiiig tlie fact that, if we admit the possibility of two distinct valences,
we must also admit the possibility of others — is certainly the more tenable
and the more natural. In speahirig, therefor, of the valence of an element^
itw muxl not consider il ax an ahmlule qualihj of its atoms, but simply as (heir
combining poiner in tht: particular data of compounds under con»idcratioi^
Indeed, compounds are known in whose molecules the atoms of one ele-
ment exhibit two distinct valences ; thus, ammonium c^'anate contains two
atoms of nitrogen : one in the ammonium group is quinquivalent, one in
the aoid radiciU is trivalcnL
When an element exhibits different \-aleuoe8, these differ from each
oiber by two. Thus, phosphorus is trivalent or quinquivalent ; platinum
ia bivalent or qitadrivalent
y
Symlwls — Formulffi — ikiuations.
SfKBOiA — These arc conventional abbreviationB of the names of the
elements, whose jtiirpose it is to introduce simplicity and exactness into
descriptions of chemical actions. They consist of the initial letter of the
lAtin name of the element, to which is usually added one of the other
letters. If there 1>e more than two elements whose names begin vrith the
same lett-er, the single-letter Hymlvil is reserved for the commonest ele-
ment Thus, we have niue elements whose names begin with C ; of these
the commonest is Carbon, whose symbol is C ; the otliers liavo double-
letter symlxila, as Chlorine, CI ; Cobalt, Co ; Copper, Cu (Cuprum), etc
27k!*c gi/mbols do not indicate gimply an indeterminate quantUj/, but one
atom of (he corretponding clem^nL
I
If AWAi, or
Whta mora Qmd ona ttam k ^lobii ol^ tlw BBmlMr of aloiBa wfaidi it
is dciind to tadkftto » writtea «itner before tlie mnbol or, ia taBaD figures,
«fl«r and belov it ; thoa, H inHiwtei oo« atom of bjdrogtisi ; 2Q, two
Ktooa of cAloriiM ; C,. four aloma of carbon, etc
FoKVTLA-^Wfaat tba ajnbol u to tbe clement, the formnla i> to tits
eOBpouod ; hy it tbe B nm ber and kuid of attrnts of which tbe mokcntQ of
a apbatapM U made vp are ipdieated. Tbe sirapkat loDd of formala are
wbat an fcnovn as empiriad /omnia; iriiicfa indieaie oolj the kind and
mtmbsr of atoms which furm tbe com p o un d. Tboa, HCI indicataa a mole-
cole oompoeed of one atom of hjdroffeo united with one atom <A. ehlorine ;
5H,0, five molecules, each composed of two atoms of fajdnigen and one
alMD of (ixTgefi, the number of molecnles being indifated bj tfae proper
aomcrml puced before tbe formula, in wfaidi place it appliea to all the
ajvbols followmg it Som^Umce it is desired thai a nomeml shall amdy
to a psrt <A iht s-nnbols onlj, in which case the^ are endoeed in parentbe-
acs ; thus, Al, (SO.), means twice Al and 3 times SO^
For other varieties of formnlfl&, piee p. 23.
EcfTATioKa are combinatioui of fonQohe and algebraic signs so arranged
aa to indicate a ebemical reaction and its mnlta. The signs nsed are tfae
pins and eqnalitj signa ; the fonner being eqniralent to " and," and the
^^L aeeood meaning " hAve reeded upon each other and bare produced." Tfae
^^P aabatanoes entering into Uie reaction are phiced before the equ&litj sign,
^^ and the prodncts of the reaction after it ; thus, tbe equation
I "
2KHO + H^,= K,SO, + 2H,0
uaaaa, when translated into ordinnrr longnitge : two roolecnlee of pofaisb,
each oompoeed of one atom of poUutaium, one ntom of bjdrogen, and one
atom of oxygen, and one molecule of 8ulpfaaric acid, composed of one atom
of sulphur, four atoms of ox^'gen, and two atoms of hydrogen, haoe reacted
upan each other and havt produced one molecnle of potassium sulphate,
composed of one atom of solpbur. four atoms of oxygen, and tiro atoms of
potAssium, and two molecules of water, each composed of two atoms of
ojdrogen and one atom of oxygen.
As no material la ever lont or created in a reaction, the number of each
kind of atom occurring before tlio equality sign in on equation must al-
wa^-H bo the same an that occurring after it.
iSeotrolysls.
Wlien ft gahflnifl cnrrent of sufficient power is made to jmisb through
a coni[>uund liquid, or a solution of a compound capable of conducting the
current, a docompositioD of the compound almost iuTariably ensues.
The terminals by which the current is conducted into tbe liquid are
known as the poia or rlrciroden, and for this purpose are best mule of
sheets of platinum. The pole connected wUh the cnpper, carbon, or platinum
t'nd nf Ihfi fiattfiry is known a» the vonlive pole ; that connected with the zinc
fnd lu the ntr^iiiiw pole. The deoom position by the voltaic current is
kiiijwn lis elr-ctrolynus, and the liquid subjected to deeomjxwition is called
an rJrrtrohjtr,
When compounds are subjected to electrolysis tfae constituent olo-
nttmtfl arc not dinohBrgcd tliroughout the mass, although tho decompoBition
occurs at oU puiuta between tlio electrodes/ In compouuda made up of
two elements only, frinary cofitpounds, one clement is given off ftt each of
tbe poles, entirely unmixed ivith the otlier, and nlwnjB from the same pole.
Tbu8, if hydrochloric acid be subjected tx) electroI}*Hi(i, pure hydrogen ia
^iven off at the uegiitive polo and pure chlorine nt the positive pole.
In the case of oonipounda containing more than two elements, a simi-
lar decomposition occum ; one element being liberated at one pole and
the remuiuing gi-oup of elements aeporatiug lit the other. ThiH primal^
decomposition is frequently niodiliod oa to ita final products by iutorcur-
rcut chemicid i-eactiouH ; indeed, the group of elements liberated at one
I^le is rarely capable of separate existence. ^Vhen, for inatance, a aolu-
Uon of potassium sulphate is subjected to electrolysis tbe liquid in the
arm of the tube connected with the positive polo becomes odd in rcae-
tion, and gives off oxygen ; at the same time the liquid on the negative
side becomes alkaline, and gives off a volume of hydrogen double that of
the oxygen liberated. In the first place, the ixrtasaium sulphate moleoule
ia decomposed into potassium and the group HU^ :
K^, = SO, + K^
The potassium liberated at tbe negative pole immediately decomposes the
surroundiog ^vater, forming potash and liberating hydrogen ; and the group
SO, Uberatetl at the positive pole immediately reftet.s with water to form
sulphuric aoid and liberate oxygen :
K, + aH.O = 2KH0 + H, and SO. + H,0 = H^. + a
In the electrolysis of chemical compounds the different elements and
groups of elements, such as SO, in (he example given above, known as
reteidiwi 01' radicala, seem to be possessed of definite electrical characters,
and are given off at one or the other pole in preference. Those which ore
given off at the poiaiioe or platinum pole are supposed to be negatively
electrified, and are therefor known mb ci&.iro-7tetjativti or ttdduloug ele-
ments or reaidues ; those given off at the jiegative pole, being positively
eleotrified, are known as eleclro-pogitim or basi/Jou$ dements or rtixiduf^.
The following are the electrical chanicteru of the principal elements and
residues :
Euccrao-KEOATivE ob AcrotrLous.
Oxvgen.
Sulphur,
Nitrogen,
Chlorine,
loiline,
Fluorine,
Fhosphorua,
Selenium,
Arsenic,
Chromium,
Molybdenum,
Tungsten,
Boron,
Carbon,
Antimony,
Tellurium,
Niobium,
Titanium,
Silicon,
Osmium,
Residues of acids remaining after
the removal of a number of hydro-
gen atoms equal to the basicity of
the acid.
BLBOiBO-posrnvK on Bastuhth.
Hydrogen,
Potassium,
Sodium,
LiUiium,
Barium,
Strontium,
Calcium.
Magnesium,
Glucinium,
yttrium,
Aluminium,
Zirconium,
Manganese,
Zinc,
Cadmium,
IroD,
Nickel,
Cobalt,
Cerium,
Lead,
Tin,
Bismuth,
XJnuiium,
Copper,
Silver,
Mercury,
Palladiam,
Platinum,
Ubodium,
Iridium,
Gold,
Alcoholic radical8»j
18
ItANUAL OP CHEMISTRY.
Acids, Bases, and Salts.
An acid is a compound of an eJ^ro-negative element <>r residue \mlh hy-
droffen ; tchich hydrogen il can pari wUh in exchange for an eitx-tro-poeitiw
element wiilwiU formation ofahane. An acid may also be defined tm a com-
pound botiy ichch evolves xtxUer In/ it% action upon pure can»t%c potaafi or aoda.
No BubstADce which does not contain hydrogen can, therefor, be ca]le<1
an acid.
The haaiciiij of an acid in the number of replacetUtle hydrogen atoma con-
tained in its molecule. •
A monobasin aci/l is one contAining a single repUreable atom of hy-
drogen, (la nitric acid, HNO, ; a dibasir acid ia one containing two such re-
placeable atoms, as sulphuric acid, H^SO^ ; a IriOancacid in one containing
three rcploceablo bydrogeu atoms, as phosphoric ncid, H^O,. Polybatic
acids are such as contain more than one atom of replaceable hydrogen,
ffydracids are acids containing no oxygen ; oxacid* or axtfaddtt contain
both hydn^n and oxygen.
The t<?rm hane is regarded by many authors as applicable to any com-
pound body capahlo of neutralizing an acid ; it ia, howcTcr, more consist-
ent with niodeni riews to limit the application of the name tu such com-
pound sxthgtaiicen as an' capable of entering into douUe decomposition with
acids to form salts ami xcatiyr. lliey may be considered as one or moro
nioleculea of water in which one-half of the hydrogen has been replaced
by an electro-positive element or radical ; or as compounds of such ele-
ments or radicals with one or moro groupa, OU. Being thus considered
as derivable from water, they are also known as basiG hydrates. Tljcy
hare the general formula, M-, (OH),. Tliey are monatomic, diatomic, Iri-
atomic, etc., acconliug as they contain one, two, three, etc., groups oxAy-
dryl (OH).
A dotd)lfi decomposiiion is a reaction in ithich both of Ike reacting cone
pounds are decomposed to form tuxi new compounds.
Sidphobo^es, or hydro sulphides, are compounds in all respects resem-
bling toe bases, except that in them the oxygen of the base is replaced by
sulphur.
Sails are sulwtances formed by the eubstiliUion of basylous radicals or el^
menu for a part or all of the replaceable hydrogen of an acid. They are
always formeil, therefor, when bfuies and acids enter into double decompo-
sition. They are not, as was formerly supposed, formed by the union of
a metallic with a non-metallic oxide, but, as stated above, by the substitu-
tion of one or more atoms of an element or radical for the hydrogen of the
acid. Thus, the compound formed by the action of sulphuric acid upon
quicklime is not SO,CaU, but CaSO^ formed by the interchange of atoms :
and not
->
Ok
:§
it ia, therefor, calcium sulphate, and not sulphate of lime.
TLe term m/V, as ased &t present^ applies to iho compounil formed bj
) substitutioD of another element for the hydrogen of any acid ; and iii-
■8 used by some autbora, to the acida themaelves, which are con-
''Bidered aa salts of hydrogen. It is probable, however, that ereutually ihe
name will be limited to such compounds as corre3p<Hid to acids whose
molecules oontain more than two elementA. Indeed, from the earliest
timeB of moderu chemi^itry a distinction has been ob»erTed between the
h^oid Boitf, i.e., those the molecules of whose correspomling acids con-
■iftted of hydrogen united with one other element, on the ono hand ;
and the salts of the oxacids, i.r., those into whose composition oxygen en-
tez«d, on the other hand. This distinction, however, has gradually fallen
into the background, for tho reason that the methods and conditiouH of
formation of the two kinds of Balls are tistially the same when the basi/lons
tlemtni belongs to that class usually designated as metallic.
There are, however, important diflfereuoea between the two classes of
compounds. There exist compounds of all of the elements correspond-
ing to the hydrncids, binary compounds of cldonne, bromine, iodine, and
sulphur. There is, on the other hand, a large claaa of olcments which
are incapable of forming salty correupotiding to the oxacids ; no salt of an
oxacid with any ono uf the elements usually classed as metalloids (except^
ixtg hydrogen) has been obtained.
Haloid salts may be formed by direct imion of their constituent ele-
iDfiata ; oxysalts ore never so produced.
Action of Acida and Bases on Salts, and of Salts on each other.
If an aoid be added to a solution of a salt whose acid it nearly equals
in chemical activity, the salts of both acids and the free acids themsetres
will probably exist in tho solution, provided both acids and soils arc solu-
ble. Thus :
2H,SO. + 3KN0. - K,SO. -r KNO, + H,SO. + 2HN0.
■utphurtc
■uJ|ib*to.
Solptiorti:
mtrto
Mild.
If an aoid bo added to a solution of a salt whose acid it greatly exceeds
in activity, the salt is decomposed, with formation of the salt of Uio stronger
add and liberation of the weaker acid ; both acids and saltti being soluble :
H.SO, + 2C^.O,Na = Na.SO, + 2C,H.O,H
Satptantte add. fiodlam wvtBte. Boillam MilidMM. Awtia •eid.
If to a solution of a salt whose acid is insoluble in the f>otvent used, an
acid be n<ldcd capable of forming a soluble salt with the basylous element,
such soluble salt is formed and tiie acid is deposited :
H,SO. + 20..H„0,Na = hXSO. + 2C„H„0^
Sotptmilo Mdd. SodJom (Uknta. Bodbitn MlpbkML SUaricfteld.
If to a salt whose acid is volatUe at the existing temperature, an acid
capable of forming with the basylous element a salt fixed at the same
temperature be added, the Bxed salt is formed and the volatile aoid ex-
pelled. Thus, with the application of heat :
H,80. + 2NaNO, = Na,SO, + 2HNO.
BnlphBrte mU Bollum Dlmta. tMImm m^vt>•^». Nitric Mt±
p
MAKITAL OF CttEMISTRY.
^
If to a aolntion of a aalt an acid be added which is capable of forming
an insoluble ault nith the base, such insoluble salt is formed and precipi-
tated ;
H,80. + Ba(NO,). = BaSO + 2HN0
8ult>liurio ■fiU. Btdiup tUtuu. Bkrinm wlphndi, NIt/loaeld.
If to a solution of a salt whose basylou» clement is insoluble a soluble
batie is added, capable of forming n soluble soil with the acid, such soluble
salt is formed> with precipitation of the iusoluble base :
CuSO, + 2KH0 = K^. + CuH,0,
If a l)ase he added to a solution of a salt with whose acid it is capable
of forming an insoluble salt, such insuluble salt in formed and precipitated,
and the base of the orifpnal salt, if insoluble, is also precipitated :
n
BaH,0, + K,80, = BaSO, + 2KH0
BaH,0, -f- Afi.SO. ^ BaSO, + 2AgHO
Wlieu solutions of two salts, the acids of both of which form soluble
salts wttb both bases, arc mixed, the resultant liquid contains the four
sails:
^
3K.S0. + 3NaNO, = 2K^, + Na,SO. + 3KN0. + NoNO,
IVMaarium Sodinm PcUMton SmIud rotwMtoia Sodlant
nlpboM. nltnu. H>lphM«. mphMo. nlUM*. UU»t«.
I or in some other proportion.
I If BohitionH of two salts, the acid of one of which in capable of uniting
I with the baso of the other to form an insoluble snlt, ore mixed, such in-
I soluble salt is precipitated :
Ba(NO,). + Na^SO. = BaSO, + 2NaN0,
Itulaia nlmui. b™^""' MiltibUe. Biriuin ctUptiKte. aodlnn nlime.
Nomenol ature.
The names of the elements are mostly of Greek derivation, and have
their origin in some prominent propertr of the substance ; thus, phos'
pkorus, <^uk, light, and ^Uptw, to b^*. Some are of I^tin origin, as sUicon,
from gile:r. Bint ; some of Gothic origin, as iron, from iam ; and others
are derived from modem languages, asjtotassium, from pot-ash, Vcrj- little
B}-stem has been followed in naming the elements, beyond appljing the
termination itini to the metals, imd ine or on to the metalloids ; luid even
to this rule we-tind such exceptions as a metal called mangancae and a
metalloid called sulphur.
The names o( compound ttulMkniceH were formerly chosen upon the same
system, or I'uUier lai^k of system, as those of the elemcuta. So long as
the number of compounds with which the chemist bod to deal remained
small, the use of those foncifid nppellntions, conrejing no more to tbo
mind than perha[>s some unimportant quality of the substances to w*hich
they applied, gave rise to oamparaUvui^' little iiiconvemeuoe. In ihcso
later d&78» however, whc'n the Dumber of oompounds has risen liigb in tbe
thoaiaiidB, some systematic method has become absolutely uecessoi*)'.
The principle at the base of t^e ajsteui of nomenclature at preaeut uaed
is tliat the nnwe sboU tteelf convey, as fiu* as poeaible, tlie composition and
character of the substance.
Compounda couaiatiug of two elements, or of an element and a radical
only, binary compounds, are designated by compound names made up of
the name of the more electro-positiTe, followed by that of the more elec-
tro-negatire, in which the termination ide has been substituted for tbe
terminations ine, on, ogen^ yg*^n, oru*, ium. and ur. For example : the
compound of i>otassinm and chlorine ia called potassium chloru/e, that of
potaasium and oxy^u, potasnum oiide, that of potassium and pho»*
phoma, potassiuTn phosphtrfi?.
In a few inaiances the older name of a compound is used in preference
to the one which it should have under the above rule, for the reaaon that
the substance is one which is typical of a number of other substances, and
therefor deserving of exceptional prominence ; such are smmonui, KH^ ;
yeater, H,0.
Wheu, as frequently happens, two elements unite with each to form
more than one compound, these are usually dititinguished from each other
by prefixing to the last word of the namo the Greek numeral correspond-
ing to the number of atoms of the element designated by that word, as
compared with ajised number of atoms of the other element.
Thus, in the series of compounds of nitrogen and oxygen, most of
which contnin two atoms of niti-ogen, N, is the standard of comparison,
and coutMKj[Ucutly the names are as follows :
N,0 =Nitrogen monoxide.
NO ( =N,0,)^ Nitrogen rfioiide.
N,0, =Nitrogen (rioxida
N,0 (=N,OJ=Nitrogen tetroxxde.
N,Oj =Nitrogen penioade.
Another roetho4l of distinguishing two compounds of the same two
elements consists in terminating the first woni in nug, in that compound
whii;h contains the less proportionate quantity of the more electro-nega-
tive element, and in ic in that containing the greater proportion ; thus:
SO, = Sulphurous oxide.
SO,=Sulpliurtc oxide.
HgXl, (2Hg : 2Cl)=Mercurou« chlorida.
HgCl, (2Hg : 4Cl)=Mercurw chloride.
This method, although used to a certain extent in speaking of compounds
composed of two elements of Class U. (see p. 27), is used cbie6y in speak>
ing of liinaiy compounds of elements of difl'erent cJasses.
In numiuy tbe oxacids the word acid is used, preceded by the name of
the elect ro-uei^tive element other (bin oxygen, lo which a prefix or suffix
is added lo indicate the degree of oxidation. If there be only two, the
least oxidized is designated by the suffix arts, and the more ujudized by
the suffix ic, thua :
HNO, = Nitrotw scid.
HNO, = Nitrur acid.
MAWtTAL OP onmnaTRT.
If tlicro bo moro than tvo acids, formed in rpgnlar neriea, tbe least oxi-
dized is designated by tbe prefix hypo and the suffix uuh ,- tbe oext by ihe
suflSx oux ; tbe next by the suffix ic ; and tlie most higbly oxidized by tiie
prefix per and tbe suflix ic ; thus :
V
HCIO = flypochloroua acid.
HOO, = Chlorotw iicid.
HCIO, = Chloric acid.
HCIO. = i'ftrchloric acid.
Certain elements, snch as siUphur and pbosphoms, exist in acidn which
are dehred from tboae formed in tbe regidar way, and which are spedaUy
designated.
The uamei) of the oxysalts are derived 6-om those of the acids by drop-
ping tbe word acui^ chaiigiug the termination of tlie other word from ous
into ^, or from ic into tUe, and prefixing the name of the elecLn>-poaitire
element or radical ; thus :
H,80.
SvlpliBfi'iu •dd.
H,SO,
Bolplittrti: hUL
HCIO
K,SO.
FBUMtatm tlphaw.
Eao
IHifcaiam hjpoahloriW.
k
Acids whose molecules contain more than one atom of replacoablo hy-
drogen are capable of forming more than one salt with electro-nef^fative
elements, or radicals, whose valence is less than their basicity. Ordinary
pbo!)pboric acid, for iuatauce, ooutaius in each molecule three atoms of
basic hydrogen, and consequently is capable of forming throe salts by
the replacement of one, two, or three of ita hydrogen atoms by one, two^
or three atoms of a univalent element ; to distinguuh these the Greek pre-
fixoe tMino, di, and tri are useil, thus :
H KPO^ = JlTonopotas^c phosphate.
Hk,PO^ s= />ipotaa8ic phosphate.
K,P[>, = 7Wpotassin phosphate.
The first is also called dihydnjpol»8&c phosphate, and the second, hydrodi-
potassic phosphate.
In Uie older works, salts in which the hydrogen has not been entirely
displaced arc somotimes called M'salts (Incjirbonates), or and salts ; thoee
in which the hydrogen has been entirely displaced being designated as
neatrai salts.
Some elements, snch as mercury, copper, and iron, form two distinct
series of salts ; these are distinguiahetl, in the same way as the acids, by
the use of the suffix mu in the names of those containing the leas propor-
tion of the electro* negative group, and the suffix ic in those containing
the greater proportion, e.fj. :
(Cu,) SO (ISO, ; 4Cu) = Cuprous sulphate.
Cu,SO (280. : 4Cu) = Cupric sulphate.
PeSO (2S0, : 2Fe) = Ferroua sulphate.
(Fe,XSO,). (330. : iFe) = Ferric eolphate.
^
CX>N6TITtni0y. TmOAL AND ORAPIUO FORMULi&
23
Radicals.
The nameti, botftc scvlta, ffuftsalts, and oxywiXiB havQ been ftppHfil in-
fen^ntly to tuJts, audi aa tbc lead snbacctatos, vbich are coinpouniia
coataioing the normal uceUtc aud the hydrate or oxide of lead ; and to
Holtu such as the so-caUed bismuth subiiitrat^, which is a nitrate, not of
bismuth, but of the univalent railical (Bi"'0 ')'.
Hy douhie salU are meant Buch ae are formed bj the substitution of
differeut elenieuta or rAdical» for two or more atoms of roplaceuble hydro-
^^en of the acid, such as aittmouio>magnesiaa phosphate, rO.Oig" (NU,)'.
|V ^ radical, or compound radical^ is a nrm-iaiurQtea group of atom* xuhif^
' hehavex Hie an atom of an element. Such radicals are ciipnblo of passing
from one compound into another, and are sometimes, although rarely, cap*
able of separatft existence. Manth gas haa tlie composition CH, ; by act-
ing upon it in Riiitahlc way» we cud caiiao the atom of carbon, accompanied
by three of the hydrogen atouiH, to paKa into a rarietv of other compounds,
such as : (CH,)01 ; (CH.)OH ; (CH,),0 ; C^,0.(CH,). Miirsh gaa. there-
for, consists of the radical (CH,) combined with an atom of bydjrogeD :
(CHJ'H.
It is especially among the compounds of carbon that the existence of
mdicals conies into prominent notice ; they, however, ocoxur in inorganic
Bubstanees idso ; thus tho nitric acid molecule consists of the radical NO.,
combined witli the group OH.
Like the clciucuta, the radicals possess different valences, depending
always \i\toii the number of unsatisSed valences which they contain. Thus
tha radioal (CU^) is nniTaleut, because tliree of the four valences of the
carbon atom are satisfied by atoms of hydrogen, leavlug one fret! ^iilence ;
the radical (PO) of phosphorio acid is trlvaleut, because two of the live
valenoes of the phospliorus atom ore satiRfiod by the two valences of the
bivalent oxygen atom, leaving three free valences.
In notation the radicals oro usually enclosed ui brackets, as above, to
indicate their nature. The names of railicols terminate in tjt or in gen ;
thus : {CHJ = metliyl ; (CNl = cyanogen.
The terms radical and rofulue, although sometimes used aa synotiyms,
are not such in spetddng of electrical decompositions (see p. !')■ Ttius
the radical of sulphuric acid is SO, ; but when sulphuric acid u electrul^-zed
it is decomposed into hydrogen and the residxu ^O,.
Constitution. Tsrploal and Graphic Formulra.
The compotcition of a coviprmnd is Che number and inW of atom* con-
tained in ila molecule ; and xti nhawn by its empirical forrnxda.
Ti\e con*lUution of a compound i« th« number and kind of atom» and
their relalions to each oUier, toilhin il» molecule ; and it slunea hy its It/pical
or grt^ic form ula.
The choractera of a compound depend not only upon the kind and
number of its atoms, but also upon the manner in which-they ore attocheil
to each other, upon their conBtitutiou. There are, for iustjuice, two sub-
Htanoes, each having the (.-mplrLcal formula C,H,0,, one of which is a
strong acid, the other a neutral ether. As the molecule of each contains
the some number aud kind of atoms, tlio differences in their properties
{
34
MAHVAL OP CTTEMISTHT.
must bo doe to tlHerences ia the mannor in which the atoma are lixiked
In Uie BTstem of hjpuyal /ormuUe ail stibstanees are considered as being
eo constituted that their rationul fonnuL-<* may b« referred to one of three
cUbbob or trpce, or to o cooibinatiou of two of these types. These three
rlftMiee, being named after the most common subetxinco occurring in each,
are expressed thus :
Ttt b.rJMfMi
H)
eta.
eio.,
Hi
I
etc..
H.
it being considered that the formnU of any sabstAnce of known consti-
tution can be indicated by substituting Uie proper element^ or radical, for
one or more of the atoms of the type, thus :
gl(c^}o
Urdroclilorto
Mid.
AUMhftl.
XUijUunliM.
Ca>
C«khini
(80)") (00)")
k.fo. h.Jn.
SolphBrio
MikL
Typical fonnuLe are of great service in the classification of oompound
AiibstJnnces, as well as to indicate, to a certain degree, their nature aiul
the method of the reactious iuto which they enter. Thus iu the case of
the two substances mentioned above as both having the compositiou
C,H.O,, we find on eiaminfttion that one contains the group (CU,)', while
the other contains the group (C,H,0)', united to one atom of repUceable
hydrogen. The difierence m their constitution at once becomes Bp|>arent
in their typical formulis, /f^u y .- O and ^ ^' A ,- 0, indicating differ-
ences in their properties, which we find upon experiment to exist. The
first substance is neutral iu reaction and possesses no acid properties ; it
closeJy resembles a salt of an acid baring the formula ^ h i ^' '^*'
second substnnre, on the other hand, has a strongly acid reortion, and
markedly acid properties, as indicated by the oxidized radical and the
extra-radicol hydrof^en. It is capable of forming salt.& by tho substitution
of an atom of a univalent, basylous element for its single replaceable atom
of hydrogen : (C,H,0)' ) q
Na f
Althotigh typical formulm haTO been, and still ore, of great sen-ice,
many cases arisw, esiwcially in treating of the more complex organic sub-
stauoes, in which they do not sufficiently indicate the relations between
tho atoms which constitute the molecule, and thus fail to convey a proper
idea of the nature of the substance. Considering, for example, the ordi-
narj' lactic acid, we find it« composition to be C^H^O,, which, expreasetl
iO H Ol" )
typically, would be '^ ' * H. f *^*' * constitution supported by the fact
tliot
Hmoo
that the radical (C,H^O)" may be obtained in other compounds, as
/fi H Ol" t
'(if" "^'''^ constitution, howovor, cannot bo Uie true ono, because
tho first place, lactic acid is not dibasic, but monobasic ; anil, in the
nd place, tliere is another acid, called paraloctic acid, having an iden-
tical oompoaitiou, yet differing in its products of decuni position. These
dUferences iu tho properties of the two acids must bo duo to a different
4armn^merU of atoms in their molecules, a view which in supported by
the sources from which they ore obtained and the nature of their pix^ducts
of decu 111 position.
To express the constitution of snch bodies, graphic form ttim are usod,
in which the jmitition of each atom in relation to the others is aot forth.
The coDbttitutiuu of the two lactic acids would be expressed by (prapbic
ulai in this way :
/H
C-H
\H
/H
\0— H
and
/H
0— H
|\0— H
<8
O— H
CH,
H.OH
I
end
OO.OH
OnlliMrj
lacduadJ.
CH,OH
I
CH,
CO.OH
Knlulla
nrid.
H
It mnsi bo understood that these graphic formula; ore simply in-
tended to show tho rclatiTO attachments of tho atoms, and ore iu nowise
intended to cniiToy tho idea that the molecule is spread out upon a flat
surface with the atoms arranged as indicated in the diagram.
Great caro and much labor are required iu the construction of Uiese
graphic formulio, the positions of the atoms being detenuined by a cloae
study of tlio methods of funnatiou. and of the protlucts of decomposition
of the subst^mce uDcIer consideration. Naturally, in a matter of this na>
ture, there is always mom for ditTerences of opinion — indeed, the entire
atomic theory is opeu to question, as is the theory of Kmvitatiun itselt
But, whatever may be advanced, two facts caunot Ito denied : first, that
afaemistry owes its adrnncement within ttie past half-century to the atomic
theory, which to-day is more in consonance with observed facts thou any
mbotitute which can bo offeroil ; second, that without the use of graphic
formuhe it is impossible to offer any adequate explanation of the reac-
tions which WB observe in dealing with the more complex organic sub-
bUocob.
In chemistry, as in other sciences, a sharp distinction must always be
made botwocu facts and theory : tlie former, onoo observed, are immnt-
able additions to our knowledge ; the latter are of their nature subject to
change with our iiicreuaing knowledge of facta. We have every reason
tor b«lieviug, however, that the supports upou which the atomic theory
^
36 MAS^DAL or GHXMISTRY.
■
resta nre mch tihat, alihougb it may be modified iu its detoili^ ita easectial
featuiett will reimuu uiiultcrtid.
Clasalfioation of the XSexuenta.
Borztlias was the first to diride all the elemenU into twogrent
to vliich lie gave the names rnetaU and mdallaids. The mctula, being sach
BubBt&nces as are opaque, poBsees wliat is known as motallic lustre, are
good coudactors of heat and electricity, and are electro- poflitive ; the metals.
Utidn, on tlie other hand, such as are gaseous, or, if solid, do not poaseas'
uetaJlic lustre, have a comparatively low [wwer of conducting heat and
electricity, and are eloctro-nogativa
This diTision, based purely njmn pliysicnl propfrties, whicli, in many
cases, are ill-defined, baa become insufficient. Severul clemeiita fonnerly
classed under the above ruloa with the metals, resemble the metalloids in
their chemical characters much more closely than they do any of the
metals ; indeed, by the characters mentioned above, it is impoBsible to
draw any line of demarcation which ahall separate the elemeuUi distinctly
into two groups.
The classitication of the elements sfaotdd be such that each group ehall
contain elements whoso chemical properties are similar — the phjawat prop-
erties being comudered only in so far as they ore intimately connected
with the chemical (see p. 13). The arrangement of elements into groups
is not equally easy in all coses ; some groups, as the chlorine group, are
sharply defined, while the members uf utlieru dilTer from each other more
widely in their properties. The positions of moat of the more recently
discovered elements are still uncertain, owing to the imperfect state of our
knowledge of their properties.
The method uf chiKsilioation which wo will adopt, and which we be-
lieve to bo more natural than any hitherto supfgested, is based upon the
chemical properties of the oxides and upon the valence of the olf-ment*.
We abandon the division into metals and luetajloids, and substitute for it
a division into lour great dasaos, according to the natui'o of the oxides
and the existence or non-existence of oxysalts. In the first of these
classes hydrogen and oxygen are placed together, for the reason that,
lUtbongh they differ from each other in many of their properties, they
together form the bnsis of our classification, and may, for tlus and otlier
mnona, be regarded as tj/pical elements. They liotb phiy important parts
in the formation of acids, aud neither would find a Huitablo place in either
of the otlier classes. Our primary' division would then be an follows :
Class I. — T^ical etementt.
Class n,— tUevin^U whone orides unite wUh waier to form adds, never
to/orm banes. Which do noi/orfn oxi/nattH.
This class contains aU the aocalled metoUotda except hydrogen and
oxygen.
Class in. — FJlemenU whone oxides vnite toith water, some to/orm bate*,
olhei'S to/orm acidn. Which /orm oxymlls.
Class rV. — Elements u<Ao»ff oxides uniie vnth water to form bases;
never to form acids. Which /orm oxysalts.
In this class are included the more strongly electro- positive metals.
Within the classes a further sulxHviaion in made into groups, each
group oontoxmug thogao elements within tho class which have e4ujd va-
i
PHT8ICAL CHABA0TER8 OF CHSMIOAL UTTEREST.
27
wliich form correBpondinj compotmds, and whose chemical ofusrac-
ters are oLhornue tiimilar. *
For the aako of conveiiieuce the term mettd id retained to apply to the
members of CLuaes lU. and XV. ; tLd term non-meUU being osod fur those
belonging' to Claaa IL
Gaotrp L — HydrogeiL
Claaa I,
daai XL
Qaovp L — Fluorine, chlorine, bromine, iodine.
Gaocp II. — Sulphur, selenium, tellariura.
Qbocp nL — Nitrogen, phosphorus, arsenic, aotimonj.
Gbocp IV. — Boron.
Gbocp V. — Carboo, silicon.
Gnocf VX — Vanadium, niobium, tantalium.
Gaoup TIL — Molybdenum, timgateo, osmium (?).
Claas UL
Gnoup I. —Gold.
Group IL — Chromium, manganeso, iron.
GbodpIIL — Glucinium, aluminium, scandium, gallium, indium.
Qnoup IV. — Uranium.
Gdoup V. — Ijead.
Qboitf VL — Bismuth.
Oboup VH. — Titanium, urconium, tin.
Qbovp VUL — Palladium, platintun.
Gaotjp IX. — Rhodium, ruthenium, iridium.
»
Class IV.
GBorp L — ^Lithium, sodium, potassium, rubidium, ossium, silver.
Gboup IL —Thallium.
Onocrp UL — Calcium, strontium, barium.
Gbocp IV. — Magnesium, zino, cadmiimi.
Groitp V. — Nickel, cobalt.
Gboup VL — Copper, mercury.
Gboup VIL — Ytliium, cerium, ytterbium, lanthanium, didyrarnm, er-
bium.
Gboup VIIL— Thorium.
Pfayalcal Chaiaoters of Chemical Interest.
Crystallization.— Solid subfrtances exist in two forms, amnrphoug
and crysUiiline. In the former they assume no definite, shape ; they con-
duct luiat equally well iu all directions ; thcj' break irrej^ulorly ; and. if
truiiepiircDt, allow light to pass through them equally well in all diree-
tious. A solid in the crystalline fonn has a defioite geometrical slinne ;
oonducte beat more readily in some dircctiuus than iu others ; when
1
S8
UAKUAL OF OHEMISTKT.
broken, BPparates in certain directions, called ptanes of clemxige, moro^
readily than in otbcre ; and mo<liifes the oomrse of luminous rays pasuing
through it differentl^f when ihej pass in certain directions than when tljsj
pass in others.
Crystals are farmed in one of four ways : 1.) Au amorphoua substance,
y
t
i-i
Fir.. 7.
br slow and gradual modification, may aRtrnmo the crystalline form ; as
vitreous araeitic trioxide (^. u.) paases to tlie crystalline variety. 2.) A
fused fioltd, on cooling, cryatallisee ; as bismuth. H.) Wlien a solid is sub-
liraMi it is usnally< condensed in Uie form of nrystols. Such is the cofie
with araeuic trioxide. 4.) The usual method of obtaiuing crystals is by
the evaporation of a solution of tho substance. If the cvnporation bo slow
and tbc solution at rest, the ciystals are large and weU-detiue<l. If the
crystals separate by the sudden cooUng of a hot solution, espedaUy if it
be agitated during tlie cooling, they are small.
Most crystals may bo divided by imaginaiy planes into equal, aymmet'
rical halves ; such planes are called planes (>/■' si/mmeiry. Thus in the
crystalB in Fig. 7 the planes ab alt, acac, and lie be are planes of symmetry.
Mlien a plane of symmetry coutaius two or more equivalent linear
directions passing ttirougb the centre, it is called the princijxit plane of
gtjmmetn/ ,- as in Fig. 8 the plane ^ab, containing the equal linear direc-
tions aa and bb.
Flo. ft.
Any normal erected upon a plane of symmetry, and prolonged in both
directioDfl until it moots opposite parts of tho exterior of the crystal, at
equal distances from tlie plane, is called an axv( of symmeiry.
The axis normal to the principal plane is the pnncipal axis. Thus in
Fig. 8, 00, 66, and cc are axes uf syuuuoti-)-, and cc is the principal axis.
Upon the relations of these imaf^ary planes and axes a cl£is&ification
of all ciTstalline forms into six syKtt-mm has been l>ase<i.
L Tim Cmac, Kbocl-ui, ok MoNOHrrBio Svbtcm. — The crystals of this
a/atom have three equal axes, aa, bb, cc. Fig. 7, crossmg each other at right
angles. The simple forma are the cube ; and ita <lehvat.ive8, the (k'tafuutroji,
ttlrahciiron, and rhombic dodecahedron. The crystala of this system exjHUid
equally in all directions when heated, and are not doubly refracting.
IL ■ The IIiOUT fAjHARE I'MSMATIC, l*nUMIDAL, t^ADRATtC^ Tetraookal,
OR DiMETRic Stoteh contoins thoae ciystols having three axes placed at
right angles to each other — two as aa and bb. Fig. 8, being equal to each
other and the third, eo, either longer or shorter. The siuiple forma are
the right square prism and the right nquare based octaiiedron. The crj'stals
of this system expand equally onJy in two directions when heated ; tlicy
re-
■ —
c _j,:>i
A
t
<
1
1
1
1
— -- |-
i
"^ A 1
rio. «.
refract light doubly tn all directions except through one axis of single re-
fractioa
in. The Rhoi(bohi:dr.\l or Hexagonal Ststkk includes cnyatalB liar-
ing four axefl^ three of wbicli aa, aa. aa, ]6tg. 9, are of eti\iH\ leii(^1i and
cross each other at 60'^ in the same place ; to which piano the fourth axis,
oc, longer or shorter than the others, is at right angles. The simple forms
are the regular itix-sided priem, the rvgular dodecahedron, the rhombohedron,
and the tealenohddron. These crystals expand equally in two directions
when heated, and refi-urt li^ht singly through the principal &\\a, but in
other directions refract it doubly.
IV. l^HE RiioMBtc, KioHT pRisMATio, OB TnrMrrHio SvsTEM. — The axes
of crystolH of i\nn syHtem are three in nunil>er, all at right angles to eacli
other, and all of unequal lenj^h. Fig. 8 represents crystalB of this system,
supposing aa, bb, and cc to he unequal to each other. Tlio simple forms
are the right rhombic octahedron^ the right rhombin prigm. the right rectangu-
lar octahedron, and the right rectangular prutm. The crystals of this system,
like Uiose of the two following, have no true principal plane or axis.
V. The Obliqcte. Monosthmetmo, or Mo^totxnno SYsnnj. — The cr>'8tals
of this system bare three axes, two of which, aa, and cc, Fig. 10, are at
30
3(A1«UAL OF CHIi:M13TKT.
right anp:le8 ; iho third, bb, is perpendicular to one and oblique to
other ; Uiey may be equal or all unequal in lengtli. Tlie aimple forms are
Me oblique rectangiUar and obUqiie Thtmilnr prOim and ociakedron.
VI. Tm "DaoBLx Obuqcx, AsnmrrBic, Tbicunic. ob Anouthio HraTEH
containn crjetola hanDg three aies of unequal length, czx)aBing each other
Fio. 10.
at angles not right angles ; Fig. 10, oo, hi, and cc being unequal and tho
angles between them otlier thou 90°.
The cnstals of the fourth, fifth, and sixth systems, when heated, ex- 1
pand oqumlv in the directions of their three axes ; thej refract light doubly
except in two axes.
BBcoNDABr FoBMs.— Tlie crjstals occurruag in nature or produced arli-
floiaUy liave some one of the forms mentioned above, or some moditication
of thofw fnrmR. These modificntJons or aefondanj /orms may be produced
by symmetricallv removing the angles or edge^, ur both angles and edges,
of the primary forms ; tlms, by progressively removing the angles of Uie
cube, the secondary forma shown in l*ig. 11 are produ<^.
It sometimes happens in the formation of a derivative form that alter*
Date faces are excessively developed, producing at length entire obUtei-a-
tion of tlie others, as shown in Fig. 12. Such cr}'stnls are said to be
^
[ hemihedrxd ; they can be developed only in a system having a principal
^m axis.
^P IsouoRPuisM. — In many instances two or more substances crystallize in
^^ forms identical with each other, and, in moat cases, such substances re-
semble each other in their chemical constitution ; they ore said to be
Fio. 11
w
P1XV9ICAL CHABACTBB8 OF CHEHIOAL INTEREST.
inmorphoiig. Thia identity of crratalline form does not depend no maoh
upon the nature of the elemeuts Ibemselves, as upon the structure of the
molecule. The protoxide and peroxide of iron do not orystalUzo in the
some form, nor can they bo aubstituted for CAch other in reactions with-
,t radically altering the properties of the resultant compound. On tlie
othflT hand, all thnt class of Bolts known as alums are isomorphuun ; not
only arc their crystals identical in shape, but a crystiU of one alum, placed
in a saturated solution of another, grows by regular depoeition of the
d upon its surface. Other alums may be subsequently added to the
orystal, a eection of which will then exhibit the variouB salta, layer upon
layer.
DtMORpmBsc — Althongh most substances oryBtallize, if at all, in one
simple form or in some of its modi ti cation a, a few bodies are capable of
,«aBuming two crystalline forma belonj^g to different bystems ; such ore
id to be dimorphous. Thus, aulphur, as obtainctl by the evaporation of
its solution in carbon diaulphide, forms octobedra belonging to the fourth
, aysteta ; when obtained by cooling melted sulphur, the cr^'stols are obli()Ue
prisms, belonf;^nK to the fifth sytttem. Occasional instances of trimar-
phitim, of the formation of crystals belonging to three different systems
oy the same substance, are also knowTi.
AujoTBonr. — Dimorphism apart, a few substances are known to exist
in more than one solid form, These \arictios of the some substance ex-
hibit dUXerent physical properties, while their chemical qualities are the
same in kind. Such modifications are said to be alloiropic. One or more
allotropic modlGcatioua of a substance are usually crystailine, the other or
others amoi-phons or vitreous. Sulphur, for example, exista not only in
two diiiiorphmis \-arietio8 of crystals, but also in a third, alloiropic form,
in which it is flexible, amorphous, and transparent Carbon exists in
three allotropic forms : two crystalline, the diamond and graphite ; the
third amorphous.
In passing; from one allotropic modification to another, a substance
absorbs or gives out Iieat.
Solution. — A solid, liqui(L or gns is said to dissolve, or form asoiution
with a liquid when the two substances unit« to form a homogeneous liquid-
Solution may be a purely physical process or a chemical combination.
In »xmple or phytncal solution there is no modification of the proi>ertie9
of Uio solvent and disaolred substance, beyond the liquefaction ; the latter
can be regenerated in its primitive form by simple evaporation of the
former ; and the act of solution is attended by a diminution of temperature.
In ct^emioal aoiution the properties of both solvent and dissolved are more
or leas modified ; the dissolved substance can not be obtained from the
•olution by simple evitporation of the solvent, unless the compound formed
he decomposable, with formation of the original substance, at the tempera-
ture of the e^-aporation. The act of chemical solution is attended hy on
tievoHon of temperature.
The amount of solid, liquid, or gns which a liquid is capable of dissolv-
ing by simple solution depends upon tbc following conditions :
1. The nature <^ the notoent and sidwtance to be dissolved. — No rule can
be given which will apply in a general way to the solvent power of liqnids
or Uie solubility of substances. Water is of all liquids the best solvent of
most substances ; in it some substances are so readily soluble that they
absorb a sufiiciency from the atmosphere to form a solution ; as calcium
chloride. Such substances ore said to be deliouescent. Other substances
are insoluble in water in any propoition ; as Dahum sulphate. Hemen-
H
32
MANUAL OP OnEMISTBT.
tary HiibBtamn>fl lire insoluble, or Bparingly soluble, in wntcr. Substanoes
rich in carbon are insoluble in walt-r, but stilublo in organic liquiile.
2. Tiie temperature has a marked influence on the solubility of a sub-
stance. As a rule, water (lissolTea a greater quantity of a solid eubatanoa
as the temperature is increased. This increaao in solubility ia diCTerent in
the case of diHercnt soluble subfitauces ; thus the iucrcBse in solubility of
the cklorideB of barium and of potassium is directly in proportion to the
increase of temperature ; the solubility of sodium cliloride is almost
imperceptibly increuaed by elevation of temperature ; the solubility of
sodium sulphate increases mpidly up to 33" {9VA F.), above which tem-
j>eraturo it again diminishes.
The s(ilti)>ilitT of gases in vater is the greater the lower the tempen^
tore and the higher the pressui*e-
The aiuuujit of a subetniice that a given quantity of solrcnt is capable
of disBolving at a given temperature is fixe<l. A solution containing as
much of the dissolved substance as it i» capable of dissolving is said to be
iaturu(fd ; if made at high temperatures it is said to be a hut eaturtUed,
and if at ordinary temperatures a cold saturatrd itttlution.
If a hot saturated solution of a salt be cooled, the solid is in most in-
stances separated by crj*atallization. If in the cai*e of certain substances,
such as sodium sulphate, however, the solution bo allowed to cool while
tmdisturbed, no crystallization occurs, and t-he solution nt the lower tem-
perature contains a greater quantity of the solid than it could dissolve at
that temperatiu-e. 8uch a solution is said to be sujnTsaiuraied. The con-
tact of particles of solid mnterial isith the surface of a supersaturated so-
lution induces immediate cr^'stallizatiou, attended with olevatioii of tem-
perature.
3. The pretence of other substances already dtssoloed. — If to a saturated
solution of potassium nitrate, sodium chloride be added, a further quan-
tity of potassium nitrate may be dissolved. In thiit case there is double
deoomposttion between the two sidts, and the solution contains, besides
them, potassium chloride and sodium nitrate.
4. The presence o/a second sotwnt. — If two solvents, a and 6, incapable
of mixing with each other, be brought in contact with a substance which
both are capable of dissolving ; neither a nor b take up the whole of the
substance to the exclusion of the other, however greatly the solvent power
or bulk of tlie one may exceed that of tlie other. The relative quantities
taken ui) by each solvent is iti a <:onstant ratio.
Dmtision of XiiqiiidB — Dialysis.— If a liquid be carefully floated
upon the surface of a second liquid, of greater density, with wluch it ia
cai>aWc of mixing, two distinct layers will at first be formed. Even at
perfect rest, mixture will begin immedintely, and progress slowly until
the two liquids have tiij/utted into each other to form a single liquid whose
density is tlie same throughout.
Substances diflfer fiom each other in the rapidity with which they dif-
fuse. Substances capable of crystallization, crifstailoidtt, are much more
diffusible than those which are incapable of crjstalliiuilion — cvUoids.
If, in place of bringing two solutions in contact with each other^ they
be separated by a solid or semi-solid, moist, colloid layer, difliision takes
place in the same way through the interposed layer. Advantage is taken
of this fact to separate CT}'stalloida from colloids by the process of dialysis.
The mixed solattons of crystalloid and colloid are brou<:ht into the inner
vessel of a dialyser. Fig. 13, whose bottom consists of a layer of moist
parchment paper, while the outer vessel is tilled with pure water. Water
4
Specific Heat. — E({tial Tolumos of different Rubstancea at the saiue
tempemturc conUin flitToreutftmouiita of heat. If t^ro equal volumes of
the same liquid of different teinpei-alurea be mixwi together, the resulting
mixture liiui a temperature wliich id tlie menu between the temperaiurea
of the orijjinal volumes. If one litre of water at -k" bo mixed with a Htre
at 38', the resulting two litrps will Imve a temrwrdture of 21'. MirfAirea
of equal Tolunies of different substances, at different temperatures, do not
liftve a temperature which is the mean of the original tetuperatures of ita
conatitucnta A litre of water at 4'^, mixed with a litre of mercury at 38^,
forma a mixture whose temperature is 27**. Mercury and water, therefor,
difier from each other in their capacity for beat The aoiue difference
exists iu ft more marked degree between equal vxighta of dissimilur
bodies ; if a pound of water at 4 ' be agitated with a pound of mercury at
70°, both liquids will luive a teui|>erature of f>7\
The amount of heat required to raise a kilo of water 1'' iu temperature
is a detiuite quantity. The sjj^'cijic heat of any Hubstance is the aiuuunt of
heat rc<juired to raise one kilo of that substance 1° in temperature, ex-
pressed in terms having the amount of heat required to raise a kilo of
water V aa unity.
Spectroscopy. — Light in pAssing through a prism is not only re-
fracted into a different course, but is also decomposed or dispersed into
different colors, which make up a tcpecirnvfi. A apoctrum ia one of three
kinds: 1.) Continuous, consisting of a continuous baud of colors: red,
onuge, yellow, green, blue, indigo, and violet. Such spiectra ore pro-
duced by light &om white-hot solids and liquids, from gas-liglit, candle*
light, lime-light, and electric light. 2.) liright-lirie sqievtra, composed of
bright lines upon a dark ground, are produced by glowing vapors and
gases. 3. ) AbtarjAion vpectm consist of continuous speotra, crossed by dark
uoes or bands, and are produoe<l by light passing tlirougb a solid, liquid,
or gas, capable of absorbing certain rays. Examples of bright-line and
absorptioD spectxa are ahowu in fig. 14.
Pto, II.
liofer's lines, the moat distinct of wbich are deingnat«d by letters (No. 1,
Hg. 14).
The Hpectroftcope oonfdBta of four essential parts : lal, the slit, a. Fig.
M ; u linear opening between two accurfltelj struight and parallel knife-
PHYSICAL CHAllACTKRS OF 0H1EM10AL nfTEREST.
edges. 2d, the collimoting lens, h; b, bicouvex Ions in whom principal
focus Uie Blit is placed, and whose object it is io rendor the rays from the
alit parallel before they enter the prism. 3d, the prism, or prisms, c. of
dense glasii, usually of 60'^, and so plar«d that On refracting edge is paral-
lel to tbe slit 4th, an observing telescope, d, so arrangeu as to receive
the rays as they emerj^ from the prisms. Besides these parts spectro-
acopes are nsuidly titt«d with some arbitrary graduntiuu, which serves to
fix the location of linos observed. In direct vision spectroscopes a com-
pound prism is used, so maile up of prisms of different kinds of glass that
the emerging nty is nearly in the same straight line as the entering ray.
As the spoctra produced by differout substonuos are characterized by
Fta. li.
the positions of the lines or bands, some means of fixmg their location is
required. The usual method coiitiists in determining their relation to the
principal Fraunhofer linoa As, however, tlie relative positions of these
lines var}' with the nature of the substance of which uie prism is made,
although their jxisitiou with regard to the colurs of tbe spectrum is fixed,
no two of the arbitrary seales use*! will give the same reading.
The most, satisfactory method of stating the positions of linen and
bands is in wave-lengtbs. The lengths of the waves of rays of different
di^jrees of refrangibihty have been csrefuUy determined, the unit of
neasuremcnt being the ieuth-metre, of which 10** make a metre. The
waro-lengtha, = A, of the principal Fraunhofer lines, arc ;
A 7604.00
a 7185.00
B 68(57.00
C C562.01
D 5893.12
E 5269.13
b 6172.00
P 4860.72
4307.25
H 3968.01
H, 3033.00
The scale of wave-lengths can easily be used with any spectroscope
having an arbitrary scale, with the aid of a curve constructed by interpo-
lation. To constnict such a cnr\'e, paper is utted which is ruled into square
inches and tenths. The ordinntes ore marked with a scale of wave-lengths,
and the abscisses with the arbitrary ocalo of the instrument Tho posi-
tion of each principal Fraunhofer tine is then carefully determined in
terms of the arbitrary scale, and marked upon the paper with a x at the
MAirUAL 07 CHXMISTBT.
point where the line of its vm^-e-length and (hat of its poeition in the ar-
bitrary scale crose each other. Through these x a ourre is then drai\ii
as regularly aa poaaible. In noting the position of on abaorption-band,
the poaitioD of its centre in the arbitrHT^' sciile is observed, and it« value
in wave-lonpths obtained from the curve, which, of course, can only be
used vcith tht^ Bcale and prism for which it has been mode.
Polarimctry. — A my of light paiiaing from ou« mediimi into another
of difiereiit density, at an angle other than 90'" to the plane of separftliou
of the two media, is deflected from its course, or vfracU-d. Certain sub-
stanoea have the power, not only of deflecting a ray falling upon tliem in
certain direcUous, but also of tlividing il into two rays, which are pecu-
liarly modified. The sijlitting of Uie ray is termed double refraction, and
the altered rays are said to be polarized. When a ray of such polHrized
light meets a mirror held at a certain imgle, or a crystal of Iceland Bpar
peculiarly cut (a Nichol's priam), also at n certain angle, it is extinguished.
The crystal which produces the polarization ia called the polarizer, and
tliat which produces the extinction the analt/zer.
If, when the polarizor and analyzer are so adjusted as to extinguish a
ray patting through the former, certain substances arc brought between
them, light again passes tlirough the analyzer ; ami in order again to pro-
duce extinction, the analyzer must be rotateil upon the axis of the ray to
the right or to the left. Substances capable of thus influencing polarized
hght are said to bo opIiccUhj ocdir. If, to produce extinc^tion, tlie analyzer
is tumefl in the direction of tlte hands of a watch, the substance is said to
be dextroffyrous ; if in the opposite direction, hrvogifrvug.
The distance through wluch the analyzer must be turned depends upon
the peculiar power of the optically active substance, the length of the
column interposed, the concentration if in solution, and the wave-length
of the original i-ay of light The specific rotary poiaT of a substance is
the rotation produced, in degrees and tenths, by one gram of the sub-
stance, dissolved in one cubic centimetre of a non-artive solvent, and ex-
amined in a column one decimetre long. The specific rotary power ia
determined by dissolving a known weight of the substance in a given vol-
ume of solvent, and observing the angle of rotation produced by a column
of given length. Then let p = weight in grams of the Hul>stance con-
tained in 1 U.C. of solution ; I the length of Llie column in decimetres ; a
the anglo of rotation obsened ; and [a] the specific rotary power sought,
we have
a
H - -■
pt
In most instnimonta monochromatic light, corresponding to the D line of
the solar spectnim, in used, and the speci&c rotor)' power for tliat ray ia
expressed by the sign [a]t,. The fact that the rotation is right-handed
is expreoaed by the sign -t- , and that it is left-bauded by the sign —.
It vUl be seen from the above formula that, knowing the value of \a] o
for any given substance, we can determine the weight of that substance
in a solution by the formula
a
p= .
[a]i) X I
The polarimeter or sarcharometer is simply a peculiarly constructed
polarisoope used to detenuino the value of a
J u
ce
4
AiTHOtKiH, in a strict sense, hydrogen is ref^orded by moat chemists as
the one and only typ«-clement — that whose atom 18 the unit of atomic and
molBQulAr weights — the im|>ortmit part which oxygen plaj-a in the forma^
tion of those compouada whose nature forma tlie b^is of our clasHLficjitiont
its acid-forming power in organic compounds, and the dififerencca existing
between its properties and tho»« of the elements of the sulphur group,
with which it ih uauallr cLiHseil, warrant us in separating it from the
other elements and elevating it to the position it here occupies.
HYDROGEN.
Symbol = 11 — Univaif.nt — Atomic uvig/it—\ — Mnfecular fceight=:2 —
8p. grr. = 0.0G'J2«A*— fiiff lii$v toeighs 0.0896 grani-^ —100 cubic vtches
wei^A 2. 14i)B (/raiVia I — 1 gram ineaifiiren ll.id lilres-f — 1 grain meaitures
4G.73 cubic iitchet J — Name derived from ^&iff> = vxUer^ and yorow = Ipro-
duoe — Diacooered bi/ Cavendish, in 1766.
OoctnotEKCB. — Occurs free in volcanic gaaea, in fire-damp, occladed is
meteorites, in the gases exhaled from the lungs, and in those of the
Btomach and intestine. In combination in water, hydrogen sulphide, am-
jnoniooal compouuda, and in many organic Bubstanoea.
FbsPABATioN.— (1.) By electrolyais of water. H la given off at the nega-
tive i»le. Utilized when pure H is required.
*Air= 1. WbeD the np. ^. b referred to H = 1, A li replaced bjr H.
I Ak 0' 0. ftod 700 mm. b»roni«tric pcwnure.
} At GU* P. ud 30 iuchos Iwr. ptNOTura.
MAKITAL or CHEMISTRT,
J
(2.^ Bj the diaassocintion of water at Tery high temperatures.
(3.) By tho decompositiuii of Tvater bjr certain meUkla The allcAlioe
metals decompose water at the ordiiiar}' temperature :
2H,0 = aNaHO
W«tar. SixUtuB
4- H.
Some other metals, such as iron and copper, effect the decompoeitiou
only at high temperaturea :
3Fe, + 8H,0 = 2Fe,0, + 8H,
(i-) By dooompoaition of water, passed over red hot ooke :
C + 2H,0 = CO. + 2H,
Ovboo. WM«i. 0«rbcKi<lloxtd«. Hj4n|*ft.
or at a higher temperature :
2H,0
Wstrr.
= 2C0 +
OvbaB RHWiaxidir.
2H,
(S. ) By deoompoaition of mineral acida, in the praaence of water, by
zinc and certain other metals :
Zn + U,SO, + xH.0 = ZnSO, + H, + rKfi
ZItko. Solpliiulc Mid. WaU*. Zlttc n]|itMM. UjAtogaa. Wat«r.
What pai-t the water pl&ya in the reaction ia still a subject of discus-
aiou ; it is probable that ita action is rather physical than chemical.
Chemically pure zinc, or ziuo whoso surface has bocu coated with an alloy
of zinc and mercury, does
not decompose the acid un-
less it formH part of a gal-
Tauic battery whose ciicuit
is closed. The zinnt of
galvauic baiterieti are there-
for coated with the ulioy
mentioued — are aninlga-
mated — to prevent waste
of zinc and acid.
This methot.1 is reeorted
to for obtAiniu); U ; the gaa
so obtained is, however,
contaminatefl with small
quantities of other gaees,
hydrogen phospliide, sul-
phide, and arsenide.
Hydmnn, dartian dkizlde, )wdr»
RVB iwphkM, and oUier paM prwroovd
(tr tlM Mthw ol a OquJd npen a mIU
FIb*. ISaiul IT.
I (HM aboot l)Tec^li>
Hatild^ rwifant b tcont uam co Ubw InrndnoMl bf Itw taao^
_ Id wlUk It. Th* vMh-bottiM aco partlaUjr fllted wttb wM«r
Tba aifpsniUK. Pin. IT, haa tfaa adnataf* «r iMlBf tSwrt iMtfy f<r
oiMapw. wbm it la ctoaed ttin InUnial iiiwaow dav**an tba lrr«l c(
ttaaUqald In Alnlbtb*hv«-af fankvaKlaM, and Ibo adlon Is uTratcd.
PRoneBrnn. — PhyxiaU. — Hydrogen is a colorless, odorless, tasielcsa
gas; 14.47 times lighter tliau air, being the lightest Hul>stiincc kuown.
The weight of a litre, 0.0896 gram, ifi called a crUk {xpi&ij = borloyconi).
ng.u.
■>artliiy t— ipwtarM.a>aba»t|«ip>w<lBOiwcfttalfl>M«cifappaimm»rtioi>tn FIb*. ISaiul IT.
Tb(i Mild nMwtal k plMxd In tlw taaartootOe (Flit- 1SX or ov«r a htrer at bnkan
tiHtra thkk In Um boeito A (Vto. m. A*
Utw.Fta.»: «rtli*bot(lo8,Fi(.n. hBIM wlUklt.
to anwt an liqnld or aolld UNpaHtjr.
NM : wbMi UM rtofNuck la opMi tbe gaa oacapa^ wbm it U ctoaed ttin InUnial pra
I
^
It is almost insoluble in water and alcohol In obedience to the law : The
diffanibditij of tim ga9f» farwat inverseJy as the square roots of their dcti^ities,
it is the most ra{)idl)' diffusible of gaaen. Tho rapidity with which this
diffu^oD takes place rcoders the use of h^ilrogeu, which has beon kept
for oven a short time in
ffaa-baga or gasometers,
dangerous. At - UO" (-
329" F.), under a press-
ure of 650 Rtmnspher««, it
forms a eteel-bluo liquid.
Certuiu mf tjdb huve the
power of abeorbinff large
quantities of hydrogen,
which is then said to be
ucditdfJ. Palladium ab-
aorba 376 volumes nt the
ordinary temperature ; 643
voh. at 90° (11W° F.), and
626Yolfl.al245''(473'F.).
The occluded gas is driven off by the application of heat, and poaeeaaea
great chemioal activity, similar to tliat which it has when in the noaoent
state. ThiH latter quulity would Heem to indicate that the gaa ia contained
in the mcUd, not iu a mcro physical staU) of condensation, but in chemical
combination.
Chemicaf. — Hydrogen exhibits no preat tendency to combine with other
elements at ordinary tt>mi>bmtureB ; tiie only one with which it conibiueu
uuder such ciroumHtauces is chlorine, and then only under the influence
of hght It does not Bupiwrt combustion, but. when ignited, bums with
a (lale blue imd very hot muue ; the result of the combination being water.
Mixtun^ of hydrogen and oxygen (in the proportion of 2H to O) explode
violently on the approach of llame or by the passage of the electric spark,
the exploBion being caused by the sudden expansion of the vapor of water
formed, under the iufluence of the beat of the reaction. Hydrogen alao
unites with oxygen when brought in contact with spongy platinum.
Many compounds containing oxygen give up that element when heated
iu an atmosphere of hydrogen :
Kw. IT.
CuO + H. = Cu
Cimrtc oxUU. Qjrdrocw- Oonpw,
+
h;o.
Wmmt.
I
The removal of oxygen from, a conipoutid is called a redticlion or deoxi-
dcUion.
At the instant that H is liberated from its compounds it has a deoxi-
dizing power similar to that which ordinary H poesesHes only at elevated
temperatures. The greater energy of U, and of other elements as well, in
this ruucent state, may be thus explained: free H exists in the form of
molecules, each one of which is composed of two atoms. At the instant
of ita liberation from a compound, on the other hand, it in iu the form of
individual atoms, and that portion of force required to split up tho mole-
cule into atoms, neoessory when free H enters into reaction, ia not re-
quired when the gas is in the nascent state, and consequently a less addition
of force in the shape of heat is required U> briug about the reaction.
In its physical ajid chemical jirojMirties, this element more closely re-
sembles those nsually ranked as metJils than it doRS those forming the
class of metoUoids, among which it ia usually placed ; Its conducting power,
4
4
40
MAMrAL OF CirEMlSTRT.
its appeamncA in the liquid form, as well ag Ita relafioD to the aciJa, which
may be coDHidered as aolts of H, tend to separate it from the luetalloids.
Analtticat. C1LUUOTE&8. — (1.) Burns with a faintly blue flame, vhich
deposits water on a cold surface brought in contact with it; (2.) Mixed
with oxygen, explodes on cootact with flame, producing water.
OXYGEN.
Sf/mboi =r O—Bivaletit — Atomic wi(}ht = IC ; molecular iraiffht ^ 32 —
ap. </i: - 1.10563 A (calculated ~ 1.1U8S) ; 15.95 H ; *p. .tt. 0/ liq>iid =
0.9787— Ono litre toeighi 1.4300 grams = 16 criths— 100 cubic incheM vy^fjh
3427 graint — Name derioed from 6$iq = arid, aud ytn'dnt = I produce — X'l*-
covtreii by Mayow m 1674 ; rV'ducovered by Prientley in 1774
OoocKBCESCK — OxygoQ is the most abnndant of the elements. It exlsla
free in atnioRpheric air ; in combination in a great number of substascea,
mineral, vegetable, and auimaL
PaepAiuLTioit. — (1.) By heating certain oxides :
2HgO
Ifcrmrie oxld*.
2Hg
+
This was the methoil used by Priestley ;
produce 5.16 litres of oxygen :
100 grams of mercuric oxide
35IuO.
ItangKitHB dins Ida.
TrimM^aitUr U-UDildaw
The black oxide of manganese is heated to redness in an iron or clny
retort (.Scheeie. 1775) ; nnd ItlO f^-ams viold H.51 litres of oxygen.
(2.) By the electi-olysis of water, acidulated with sulphuric acid, O is
given off at tlie puKitive pole.
(3.) By the aetiou of sulphuric acid upon certain compounds rich in O :
mongaDCse dioxide, potassium dichromate, and plumbic peroxide :
2MnO, +
lCftD8«n«w dioxide
2H,S0,
Baljibarie «eid.
s 2MnS0. +
2H,0
Wuar.
100 grama of manganese dioxide produce 12.82 litres of O.
(4) By decomposing Ii,SO. at n red heat, 2H,SO, ^ 2SO,+2H,0+O,.
(6.) By the decomposition by beat of certjiin salts rich in O : alkaline
permanganates, nitrates, and clilorates.
Tlie best method, and thiil usu;illy adopted, is by licating a mixture of
potassium chlorate and manganese dioxide in equiil partii, moderately at
nrbt and more strongly toward tbe end of tlie reaction. At the end of the
operation tbe manganese dioxide remains, apparently unaltered, and it is
probable that during the action it goes through a series of oscillating oxi-
dations and deoxidatious, which t;d£e place nt a lower temperature than
that re<}uired for tbe decompositiou of the chlorate alone.
Tlio chlorate gives up nil its (27.26 litres from 100 grai
according to tbe etjuation :
2KaO.
PataaiBBi ctiluntv.
' grains of the salt),
2KC1 +
roUMlua cUotid*.
OXTOBW.
The operation mny be contlucted in tlio apparatus shown in Fig. 18, or,
' on H lur^o scale, with a copper or iron retort,
pQorERTiKs. — I'hi/Kwal.—OxyQen ia a colorless, odorless, tasteleea gas,
Terjr m)arin^l7 soluble in water, somewhat more itolublo in absolute slco-
'"lol. ft liquefies at — IW (229'' F.) under n presam-e of UOO utmoBpheies.
CJjewitmi.— Oxygen is cbwactorized, chemically, by the stronj^ ten-
dency Tvhich it exhibits to enter into combination with other elements, only
one of which m known, i.e., fluorine, that doen not form an oxygenated
compound. With motjt elements it uuit^s dii-t;ctly, especially at eWated
temperatures. In many instances this union is attemled by the appear-
anee of Ught, and always by the extiicalion of heat. The luminous uuiou
of O with another element couslitules the familiar pheuomeuou ofcomhnS'
tion, and is the principal source fi'om which we obtoiu uo-cuUed artilicial
Via. i&
and light A body is said to bo cojnbii»iil^e when it is cnpable of so
energetically combining with the oxygen of tlie air as to liberate light as
veil as heat. Gases are said to be suf/porters of c*)mbui>tiun, when com-
bustible substances will unite with them, or wiui some of their constitu-
ents, Uie union being attended with tlie njipeiiranoe of heat and bght.
The distiuctiou between combustible subst&nccs and supporters of com-
bustion is, however, one of mere convenience ; the action taking place be-
tween the two flul>staiicea, one ia as much a i»aity to it as the other. A
t'et of ur bums In an atmosphere of coal-gtis as readily as a jot of coal-gas
>ums in air.
The compounds of oxygon — the oxides — aro divisible into three
groups :
1. Anhydrides—oxides capable of combining with water to form acide.
Thus Hulphuric anhydride, 30,, unites with water to form suiphuric acid,
H.SO..
The term "anhydride" is not Umitod iu application to binary com-
^pounds, but applies to any substanco capable of combining with water to
form an acid. Thua the compound C.H.O, is known as acetic anhydride,
I
UANUAL OF CnXJflSTBT.
because it nombinPB with water to form aceiic aoid : C,H,0, + H,
SC^H^Oy (See coni{K)ut]d6 of arscnie and sulphur, p. 88.)
2. Jiasic oxides oro Buch as combino witli water to form basea. Thus,
calcium oxide, OaO, unites with water to form calcium bjdrate, CaH,0,.
8. Saline, ne\Ural, or indifferent oxides are such ob ore neither acid nor
baaic in character. lu some iustaucea they are easeuUally neutral, as in
the cose of the protoxide of hydrogen or water. Id other cases they ore
formed by the union of two other oxides^ one basic, the other acid in qual-
ity, such aa the red oxide of lead, Pb,0,, formed l>y the union of a mole*
cule of the acidulous ]>eroxide, PbO,, with two of the basic protoxide,
PbO. It ia to oxides of this character that the t«rm " saline " properly
applipK.
The procosa of respiration i^ very similar to combustion, and as oxygen
gas is the beat supporter of combustion, so, in the diluted form in which
it exists in atmospheric air, it is not only the best, but the only supporter
of animal respiration. (See carbon dioxide.)
Anai-tticu. CHAKAcreBs. — 1.) A glowing match-stick bursts into fliune i
li-cc uxygeu. 2.) Free O when mixed with nitrogen dioxide produoea a
brown gaa
OZONE.— AIXOTROPIC OXYGEN.
n
Air throupfh which dischargea of Btatio electricity have been paasei
and oxygen obtaiuetl by decorapoiiitiou of water (if electrodes of gold
platinum be used), have a peculiar odor, somewhat resembling that of s
phur, which is due to the conversion of n part of the oxygen into ozone.
Ozone has not been obtained fi-ee from oxygen ; indeed, the highest
degree of conceotrntiou which has been reached docs not exceed ten per
cent of ozone. Thus diluted, ozone is produced : 1.) By the decomposi-
tion of water bv the battery. 2.) By the slow oxidation of phosphorus in
damp air. 8.) '^y the action of concentrated Hulphiiric acid upon barium
dioxide. 4.) By tlie passage uf silent electric dlachargea through air or
oxygen.
]bi the preparation of ozonized oxygen the beat results are obtained by
poBsing a i^ow current of oxygen through an apparatus made entirely of
glass aud platinum, cooled by a current of cold water^ and trareraed by-
the inmible discharge of an induction coil.
Under the most favor/ible conditions hitherto attained, the nearest ap-
proach to pure ozone ha.s been ten parts in one hundred, the remainder
being unaltered oxygen.
When oxygen is ozonized it contracts slightly in volume, and when tlie
ozone is removed from ozonized oxygen by merciny or potassium iodide
the volume of the gas is not diminiithed. These facts, and the great chem-
ical activity of ozone, have led chemists to regard it as condensed oxygen ;
the molecule of ozone being rcprcsouU^d thus (OOO), while that of ordi-
nary oxygen is (00).
Ozone is very sparingly soluble in water, insoluble in solutions of acids
and alkalies. In the presence of moisture it is slowly converted into oxy-
gen at 100" ^212" F.), n change which takes place rapidly and completely
at 237" (459 F.). It is a powerful oxidant ; it decomposes solutions of
jMtassium iodide with formation of potassium bydntte and liberation of
iodine ; it oxidizes all metals except gold and platinum, in the presence
of moisture; it decolorizes indigo and other organic pigments, and acts
rapidly upon rubber, cork, and other organic sut^tancea.
n
49
AxALmcju. Chabactebs. — 1.) Neutral litmus paper, impregnated with
fiolutiuu of potaasiuni iodide, is tamed blao when exposed to air coutaiu-
iug* osone. The mine litmus pnper without iorlide is not otTected. 2.)
Muigaiioua sulphate Bolution is turned brown by ozone. 3.) Solutions of
Ihallous salts are colored yellow or brown by ozone.
When inhaled, air containing 0.07 gram of ozone per litre causes in-
tense coiyjA and hrcroopty^is. It is probable that ozone is by no means
as coustajit a constituent of the atmoapberQ an was formerly supposed.
(See Hydrogen dioxide.)
Compounds of Hydrogen and Oxygen.
Two are known — hydrogen oxide or water, H,0 ; hydiogeu peroxide
OP oxygenated water, H,0,.
Water.
H,0~Molecular weight — 18 — Sp. gr. = 1 — Kapor denailg = 0.6218 A
— ComponUion. discooorcd by FrieiUley in 1780.
OocosBBMCB. — In ottorganized nature HO exists in the gaseous form in
atmospheric air and in Tolcanic gases ; in the liquid form very abundantly ;
and as a solid in snow, ice, and bail
As water of cri/ntaUiiatioii it exists in definite proportion in certain
crystals, to the maintenance of whose shape it id necessary.
In the organizetl world H,0 forms a constituent part of every tissue
and fluid.
FutiMATios. — Water is formed : 1. By union, brought about by eleva*
lion of temperttture. of one vol. O with two vols. H.
2, By bumiug H or Hubstances coutaining it in air or O.
8. By heatitig organic substances cotit^iiniiig H lo reduess with rupiic
oxide, or with other substances capable of yielding O. This method of
fonoation is utilized to determine the amount of U contained in organic
^^ substances.
^B 4. When an acid and a hydrate react upon cacli other to form a salt :
" fror
I
H,ao.
+ 2KHO
K,SO. +
2H.0
WXM-.
fi. When a metallic oxide is reduced by hydrogen :
CuO
Cnprto oxlch).
HrdTOKCti.
On
Oopfwr.
H.O
Wu0.
*
6. In the reduction and oxidation of many organic substances.
Pure H,0 is not fouwl in nnture. When required pure it is separated
from suspended matters by filtration, and from disaoWed substances by*
HisUlltttion.
Properties. — Phjsicai. — With a barometric pressure of 760 mm. H,0 is
solid boluw 0' (32 r.) ; liquid between 0" (32' F.) and 100' (212' F.) ;
and gaseous above 100^ (212^ F). When 11,0 is enclosed in capillary
tubes, or is at complete rest, it may i>e cooled to —IS'' (6" F.) without
solidif^'ing. If at thi.i teuipenituro it bo agitated, it solidifies instantly
and the temperature suddenly rises to 0° (32 F.). The melting-point of ice
is lowered 0.0076*' (0.0136° F.) for each additional atmosphere of pressure.
I
The boiling-poiiil is subjcci to fprenier Tariations ib&n the freezlog-
poiDt It 18 the loTver as tbe pressure is diminished, and the higher oa it
is iDoreaaed. Advantage in taken of the re(luce<1 boiling-point of ttolutions
in Tacoo for the separation of substoucea, such as cane sugar, which are
injured at tbe temperature of boiling H,0. On the other bond, tbe in-
creased temperature that may be imparted to liquid H,0 under pressure
is utilized in many proceasefi, in the laboratory and in the arts, for effecting
solutions and chemical actions which do not take place at lower tempera*
iurea. Tbe boiliL^'-poiut of H,0 huUlinK solid uinlter in solution is higher
than that of pure U,0, the dejrreo of increase depending upon the amount
and nature of the substance ditwolvMl. On the other hand, mixtures of
H,0 with liquids of lower boiUug-poiut boil at temperatures less than 100"
(212° F.). Although the conversion of water into watcr-gua t«kcs pkce
most actively at lOO** (212** P.), water and ice evaporate at all tempera-
tures.
Water is the best solvent we ha\iB, and acts in some instances as a sim-
ple solvent, in others as a chemical scJvcnt.
When a solid abaorba sujficienl water from the air to form a soitttion it is
taid U> deliquesce.
Qaaes are more soluble in cold than in hot liquid*. Hydrogen forms on
exception to this rule, being equally soluble in all temperaturea.
The ftolidiiidy of a gan in water varies directly as the pregettre.
In most caneu wlids are ntore soluble in hot than in cold Uguidti.
When a liquid contains aa mttch of a di^Uoed sid»ttance asitis capaiUe O)
heading at the exi&ting temperi^urt^ ti is gaid to he naturaled.
Solutions of certain aalLu, Haturuled at high temperatures, may be
cooled without depositing any of the sidt ; they are then superscUnrated,
and oontoin more of the dissolved substance than they could take up at
the lower temperature.
A saturated solution of one substance in H,0 is often capable of dis-
solving considerable quantities of another substance, and of then becom-
ing capable of taking up a further quantity of the tirst substance.
The power of H,0 to dissolve guses iucreu^cH with increase*! pressure.
FutK, resins, and, in general, organic substances containing a largo
number of carbon atoms, are insoluble in H,0.
Vapor of wnt^r ia colorless, transparent, and invisible. Sp gr. 0.C284
A or 9 H. A litre of vapor of Avater weighs 0.8064. The latent heat of
vaporization of water is 63G.5 ; that is, as much heat is required to vapor-
ize 1 kilo, of water at 100° as would suffiiie to raise 63G.5 kilos, of water
1° in temperature. In passing from the liquid to the gaseous state, water
expands l,(iUG times in volume.
Chemical. — Water may be shown to consist of 1 voL O and 2 vols, H,
or 8 by weight of O and 1 by weight of H, cither by analysis or synthesis.
Analysis is the reducing of a compound to tin constilHeni dements.
Synthesis is the formation of a compound from its elements. A partial
synthesis is one in which a complex compound is produced from a simpler
one, but not from the elements.
Water may be resolved into its constituent gases : Ist. By electrolysis
of acidulated water ; H being given off at the negative and O at the posi-
tive pole. 2d. By passing vapor of H,0 through a platinum tube hcalc<l
to a wbitcneas, or through a porcelain tube heated to about 1,100°. 3d.
By the action of the alkaline metals. Hydrogen is given ofT, and the me-
tallic hydrate remains in solution in an excess of H,0. 4th. By passing
vapor of H,0 over red-hot iron. Oxide of iron remains and H is given otL
^
WATER.
45
tntcT combinoB with oxides to form new compounds, somo of which
ids aud others baneH, known as hi/iiraies.
A hydrate ia a compound JormcJ by ike jvplacement of part of the hydro-
l^^n of loalcr by another eiement or radical.
^B Tho hjdiates of the electro-negative elements and radicals ore adds ;
^Hoiost of ihoHB of the electro-positive elements and radicals are iMmc hydrvUes.
^F^ A compound capable of combining wUh vxUer to form an acid is called art
^^tnhj/dride,
^F Certain substancos, in assuming the crrstalline form, combine with %
^■definite projmrtiou of water, which is known as u^tUer of crynialli2aiion, and
^^vhoae presence, although uucessury to the moiut^^uance of certain physical
characters, such as color and crystJdlino fonu. does not modify Ihtir chem-
ical reactions. In many instances a portion of the water of ciTstalh/jition
may be driven off at a comparatively low temperature, while a much higher
tem|3erature is required to expel the i-cmaiuuer. This latter is known as
toaler of con^ituHoa.
The symbol Aq (Latin, aqua) is frequently used to designate the water
of crystallization, Uie water of constitution being indicated by H,0. Thus
MgSO^ H,0 + 6 Aq represents magnesium sulphate with one molecule of
water of constitution and six molecules of water of cr^'stallizatiou. We
feonsider it preferable, however, as the distinction between water of crys-
tallizotion and water of constitution is only one of degree and not of kind*
to use the symbol M\ to designate the siun of the two ; thus, IfgSO, +
Crystals which lose their water of crystallization on exposure ia air are
said to i-ffiorexce ; those which do not are said to be itermanenl.
Water decomposes tho chlorides of the second class of elements (those
of carbon only at high teinperatiires and under pressure) ; while the
chlorides of the elements of the thirtl aud fourth classes are either insolu-
Plile, or soluble without decumiw^itiou.
Natthal Wateqs. — Water, as it occurs in nature, always contains solid
and gaseous matter in solution, and frequently solids in suspension.
Natural waters m.-iy be classified, according to the nature and quantity
of foreign matters which they contain, into potable and unpolable waters.
To the tii-st class belong rain-water, snow- and ice-water, spring-water
P (fresh), river-water, lake-water, and well-water. To the second claas belong
■tugnant waters, sna-water, aud llie waters of mineral springs.
Hain-tcater is usually the purest of natural waters, so ^ aa dissolved
solids are concerned, containing very emitll quantities of the chlorides,
solpboteB, and nitrntos of sodium aud ammonium. Owing to tho large
surface exposed during condensation, rain water contains relatively large
quantities of dis.Holv&l gases — oxygen, nitrogen, and carbon dioxide ; and
sometimes hydrogen sulphide and sulphur dioxide. The absence of car-
bonates and the presence of nitrates and oxygon render rain-water particu-
larly prone to dissolve lead wlien in contact with that metal. In sunuuer,
rain-water is liable to become charged with vegetable organic matter sus-
pended in the atmosphere.
lae-u)Qier contains very small quantities of dissolved solids or gases,
which, during freezing, remain in great part in the unfrozen water. Sus-
pended impurities are imprisoned in the ice and liberated when this is
melted.
MfUed Bnmc contains about the some proportion of fixed solid matter
u rain-water, but a less proportion of ammonioral Halts and of gases.
^ring-wtUr is ruin-water which, having percolated through a
I
HAWTTAL OF CHKMISTKT.
of Uie earth's crust (in which it may also have been Bubject«d to preiiaure),
has Uecoaie charged with solid auil gascoaa matter ; var^'ing in kind and
quantity according' to the nature of the ntrata tlirough which it has perco-
lated, the duration of contact, and the pressure to which it was subject'
during such contucL
Spring-waters from igneous roots and from the older sedimentarj for-
mations nrc frosh and sweet, and any spring-water niay be considered such
whose temperature ia less than 20"^ {GS" F. |, and which does not contain
more than 0.4 gram uf yolid matter to the litre (28 grainiiper gal.) ; pro-
Tided that a largo proportion of the solid matter does not consist of salts
having a medicinal action, and Uiat sulphurous gases and sulphides are
nhsent.
Artesian wells are artificial springs, produced by boring in a low-lying
district, until a pervious layer between two impervious strata is reached ;
the outcrop of the system being in an adjacent elevated region.
Jiiver-ualer is a mixtxu'e of rain-water, spring-water, and the drainage
water of the district through which the river flows, to which snow-water,
ice-water, or seiv-water is sometimes added. The water of a river flowing
rapidly through a granitic, region is, unless polluted by man, bright, fresh,
and highly aerated ; that of a stream flowing sluggishly through rich al-
luvial land, is uuat^rated, and rich in dissolved and suspended solids.
Tlte amount of dissolved solids in river water increases with the dis-
tance from its source. The chief sources of pollution of river-water ai*e by
the discluirge iutu them of the sewage uf towns and cities, or of the waste
prodocta of factories.
/vUT7-(fo/»T is an acc.nmulation of river- and rain-water. As the waters
uf lakes i\xe kept in constant agitation both by the wind and by the cur-
rent, they become to a great extent purified from organic coutaniino-
tioa
Welt'tmter may be very good or very bad. If the well be simply a res-
ervoir dug over a spring, and removed from sources of con tain inution, it
has all the characters of fresh spring-water. If, on the other hand, it be
simply a hole dug in the earth, tiie water which it contains is the surface
water which has percolated through the thin layer of earth corresptuiding
to the depth of the well, and is consequently worm, unaSrated and charged
with organic impurity.
Wells dug near dwellings are very Hable to become charged with the
worst of contaminations, animal excreta, by their titration through the
soil, either by renson of thR fracture of the house-dnun or otherwise.
Imjtiiutibb in Potable Wateks. — A water to be fit for drinking pur-
poses should be cool, Uinpid, and odorless. It should have an agreeable
taste, neither flat, salty, nor sweetish, and it should dissolve soap rea<Iily,
without formation of any flocculent precipitate.
Although it is safe to coudemu a water which does not possess the
above chanicters, it is by no means safe to regard all waters which do pos-
sess tliem 08 beyond snapicion. To determine whether a water is potable
it must be more carefully examined as to the following constituents :
Tofal solids. — The amount of solid material dissolved in potable waters
varies from 5 io 40 in 100,000; and a water containing more than the
latUT quantity (28 groins per gall.) ia lo be condemned on that account
alone.
To ilrtrnnlnit tha qimnUl? oT tuUI solM* W cv. d the flltmeit watar an mparatod to iIijimmi In « pre-
rkinriy *ei)!h««l ptoifmiin ih»h. o.w ih* wi»W-b«ih, TbtKllah «ith thcoonulocd dr? raridoe li oootod In
* dtvkrkKH- •nrl »|aiii welichail. Tba loenMa lo wrl«hl, ntittlptJtd \>f 4,0(111, give* Um toUl Mllite ta puM
pcrlin.OV0.
4
d
Bardnegs.— The greater part of the solid mnlter disBolverl in natural
iraterv conBJBta of the salta of (Calcium, acpompanied bj* less quimtitiea of
the aalts of magneBium. The calcium oolt is usually the carbonalc or the
sulpbftte ; aometinies the cbloriifo, phosphate, or uitrate.
A vater oontaining an excess of calcareous salt is said to be hard, and
one not no charged ia said to be «o/i[. If the bardnesa be due to the pres-
enoe of the carlmtiate it is lemnorart/, if due to the sulphate it is perma-
nent. Calcium carbouate is Eumofit iusolublc iu pure M-atcr, but in the
preeenco of free carbonic acid Uie more soluble bicarbonate is disaolveil,
but on the water boiufr boiled, it is decomposed with precipitation of the
carbonate if the quantity exceed 0.6 gram per litre. As cAicium sulphate
is held in solutiun by virtue of its own, albeit sparing, solubility, it is not
deposited when the wat^'r is boiled.
An accurate determination of the quantity of cnlcium and magnesium
salts in watef ia rarely required ; it is, however, frequently desirable to de-
termine their quantity approximately, the result being the degree <^
hardnew.
b
b
For thia i w r p u w k ■alntlno ofwaii nt Imntm utrmKili (■ nvtolni'l. TMm b omAv h]r dtoK<1*lBg 10
■BM of ftlf-drfad, wMte Cunito icap, <rat luut ilitn ahftvlnK*, In m llm of dlloM •k)<>tta( (*p, at. <I.MU|. To
l.lIgranMot Miv, twcntly tOMd <»lciiiRi clilorldo tn » litre of nur. •radUntMl wllb W cc of wUer uxl
tteHif MiliiuiMiMldad ontila iwraMant laUirr teprudoead oa agnstkiiL If II o.c. •■! >o«|> lotutiun li«*»
!■•■ aaHl k haaUw Draper Uimfth ; U « tcrvaUtr or Ibm ijuaatUy Iwra twen ulil«I It niiuL bo iMiicianUalnl
or ADntod hi prapocuon to Uie exoM* or i^rieaof. Tbe wmp aaTnUiMi miMt not Imi fiturod, boi. It Lnrtild,
mvM. b« riwlnn Mfora iMlnc*
To (MMmliM Uio lurdnM*, 10 e.r. at tba «raUr to ba tsrtod *n ptaicvd In « g l MP to)p«c»ii bottk ftt
IM S.B. B^MotCT, Ud Ui« Map aalutkut icr*diwlly Kililnd frucii k burrtM. Attrr ttuib MhlltKin uf Matp roIb-
Una tb« boltia b ■!!*>«■. Mid ktlowml Ui Ue ninn It* iddr flv<^ mlnntM. Tbl* U ooaUnned nntU at Um end of
*w »h«te»* latli^ mmIim tnnw the ntufniwof the I1i)iild tn thebnttla. Atthla dm* the hariiw^ liln-
(HcaMdbT Dwamnbvraf cc ol «mi> KOntJnn addod. mmaaoae. Uioon tboo 16 cc «t WMp WlaMoa M*
added KM OqalA In itM tntCM Biwt ba dUnt4»d wtth 70 ilci. of dMUt«d watM.
A pood drinking-water should not have a hardness ot more than fifteen.
CUnru/f-if. — The profinnce of the chlorides of tlie alkaliue metals, in
quantities not Hutltfueut to 1>e detectable by the taste, ia of no importance
j>er «e ; but in connection with the presence of organic impurity, a deter-
mination of the amount of chlorine aflfords a ready method of indicating
the probable source of the organic contamination. As vegetable organic
matter brings with it but small quantities of chlorides, while animal
contaminations are rich iu those compounds, the presence of a large
amount of chlorine servos to indicate tliat organic impurity is of animal
origin. Indeed, when time presses, as during an epidemic, it is best to
rely upon determinations of chlorine, and condemn all waters containing
more than 1.6 in 100,000 (one grain per gallon) of that element.
For Ihd deUrodnUlMi of «htoriiw two anlnllooaaro rtqntr«d: a anlutlan of •flmr nl£t«t«<-(MiMlnliir4 *9
ttnn»inTllir«; aftronsatriuttonof poMaviDTnohromatc. One hnndnd o.c of tb« water an ptaoaJtn a
iiMkw attth aoMRtl at Uh* ctaromaw aolntkiR ta c^namantcab) a dlaUn«t j«lkM oulor. U Ui« rvacUon b«
Mid It U ntidand naatral iM-yMntte alkaline br Uwaddttkw ot auJlwm oartwaf aolnUan. Ttavaitvar aula.
Dmi |a mam ■IkHnd in Sow in tnma m bniwtta, drap In diom dnffng oMutaBi afttaUnii, nnlll a/tatet raddMi
Uagtt p a a iaifc At thto ttaiw the buratM nadlDc h taMa ; eWb cfl. at rilvcr ■olntkui added nftmaam 0.01
of cbtelM ptr Utt«
Organic MtUtfir. — The most serious of the probable contaminations of
drinking-water is that by organic matters containing nitrogen. When
tbeee are present in even moderate quantity, and when, at the same time,
the proportion of chlorine is greater than usual, the water lias been con-
timinated by animal ex<Ti*i?ta and contains, under suitable conditions,
the causes of disease, be they germs or poisons.
Of tlio methods suggested for the deterniination of the amount of or
ginie matter in natunil waters there is unfortunately none which is easy
48-
MAUL'AL OF CHEVISTBT.
o{ Bpjdicntion and at tho same time reliable,
resiuts is Vianklyu'a process :
That wliich yieida tlie
TiM followinii antathnui am ivintrH : a. If lule 1>t dt<aal*iiv VO )[***"■ of potaslBm hrinita utd
ffmuKof poCM«ltiiiipena»ng*nu«la* litre o(«Mcr Tbeaohtuoti labelled don b> aboat ?n cc, oovUd.
■lidlinRi«UU>Uaflcl(tultmlkbTtlM*>d<Utioi)Of lKU«l<lUUUmIw»tor. ». .VM*<«r'« ratptnl. »KmiDa«l
potowdBM lodkla ■ait 18 grmaia at mercuric diUriiJu w diaul^td in 600 c-c. ot water by lh« Mid ol hru and
■gltatliua. A aoM, wuimMd Mrialion ot tnnmna ctJurUle U ttaen aildcd, ilrafi bj drop, until tharfid pr»-
tiidlMc wbldi li t»TBMl U no h<BR«r ndiMolvnl on metxMxiaa : tflO cruBa of poumimm hjilrale arc tbeo dl^
Mdvcd in Ui* liquid, ta whkb a *ll(rlit «xmm «( nwrourio clila«U>> wdntlM) la AiMlljr adikot, and Um balk d
Um wlwla maid* S9 toklUio with wator. TlMwIntlnn i< allows lo alaiid, drcanlML «ImI pnacrT«<l In omd-
|iM«l7 AIZkI, wcU-abifiiiend butUea, c. SkmOaril )tt.lHUi>>in nfurnmi^niit. Tbu Utvagerut ihtm laBiaidabjr
ditantvlns S.1& namB of amnumlum ctikiridii In a UU« ot irairr. Ttic wcoJter. \if BilKlng on* vohuBs of tba
■trongir with tw volnniM o( wawr. Tba taU«r outtiaiu O.OUOOI gnm vt atnnioDla In each co , and ta Uw
ooa uacd in tba dnmnlnatlacuk th« •bangf-c aolailon irrvlnc t<a\y tar Ita onnrnifcei prepaiaUoo. d. A
taturattt»MiM»i*9/tt>Mum oarfttmMa. «. DUtttttd <MWr. TbcmMilla Uilidoftba dMlUaU. lOU cc at
wbicb muat fuA ba |Htro*pUblr CtJorad in ten nUntM bjr lb« ad4LtioB vt S ixc uf Kaailn*a twig«nt.
TbctattlBiraf aaratarbeoBdnictalaalotlDwa: BatfaUlnof Uw watar lo bataMcd (befm taking tha
aamplfi, tiM dmnifohn ar otbar *»,»\ containing Um wato- nuK ba thflaooililj ahahni) I* IntiodncMl. t^ •
fnniML into a lubttUtad N«ort awnble of hukUnc ntim Utn. tf ibe waur b« add, 10 cc. of tfap aoliiUon oi
BodiniB CBrtwiuUa d ara addad. Unvinc oooMcWd tli« iHntt with a LlcMC< oaod>UBr. Iba joint Mine
made Ugbt \>j a fawUnf ol noMMwd IUwr-pat<«t, ttia «Bl*r l« nuda to boU aa aoon aa jitnlbla if anriviiic
Um ikuM at a BnwNn bnmcr btaagbt vlOM w iLa tiottam uT tbi> aaltnl returi. Tha ttna flO clo. of dbdlUala
an ooOMtad In a arllDdrinl vmmI uf fdMr glaM, abent an locb In illaaictiTF. Ttw toUowtBC 180 an. ■>«
eoltected btmI thrown awaj, %tUT which tba dra U withdrawn VThUe tlM>w an pa«riBg met, Uw dnt BO
cc. an Naailariaad (efaM U-fra), and th* reault, pliu one-third an uuoh affftln, la tba aaMtoit of tnm aai-
uoiiin cMitolMd la (b« halfUira of wum.
Wh«B 90D cc. haw diatlUud orer, all Uw fnv MnatoBla hm* hrai nitnorett. aad 11 now mnalni to deciiai'
poa* Iba OlinntO material, and dMnrminc Uw amoont u( anuuoala furned. To rflori thla, M &«. of tha
pwaayanata aolutlop a aw added thrmgb UielonDol tfr thaeoatmlaal tba rattn. wtaUdl la iti^Mn. <(c^
pand, and atpOn bealad. Tba dlaUUalo U n^nr c<i1lKt«d ia aeiarato portlooa of 60 && aMh, Id (laM oylliw
dan. nntU 8 wdi lurttoaa ha** b«*w euUaotad. lliaaa an tbvB WMntaJj' 3IaiBl«ctaad aa MIowa ; 3 cm. uT
Iha Saadv reagent arr added to tha mniila ot W 0.0. ol dIMitlala : ll aniBmBla ba uraaiiH, a jrllow or
DmwD cnlor witl be pradnooA, dark In prnportion totb>q.iBMiltoolBinn«BilB prraant. Into another oylln-
dar a Klvan qaaiiUty of Uia Maodanl wtntlca of aiBBumla r ta aliowsd la dtnr nrm a bnratta ; oiOBirti a-aur
U added to mate th« hoDc ap to 6U c.o.. aod ibaa t c.a of Nt^cr l a agum . Thia crllodra. aad Uiai -xm .
talnlug Ih* 60 cc ot Naaalarlaad dtaUUnta^ an th«n ptaoad ddm bf ttOt npon a Utact ot vrhtta paper ami
ihrlr ouToT eianitftul. U tho ahoda ot ootar In tba twoo}llndcn> ba ^KKf/v tba Mma, tba BO C.& ol ftMlllala
oontnlii thu mtni! lUDoiir.t iiT ammonia aa Ibe qiiacUt)' td aUndard aolBtlaa of awmoaia uaed. If ibe uuhm
bo dlfTiTrnt in Inlmaltj, anotbvr oaaipariaBD.CTliDdar murt ba arnuvwd, oalng mora ur ham ot the atandatd
a(d»tiuo. ■■ the drx compMiaou-cyUiidcr wai liKbter or darker than tho ribtillau. When tba ptonw aim].
larltj- o( ahadoa haa l>aan aOalncd, the nnmber of cubic ornitlmMrr^ ot thn uao<lard fojHtloa naed la dotar>
odnad bj Ibarandlngon tba mtrotta; Tbia prooM^ wbioti. wUb a llliJv practko. U nallbor dlttGuli twc
ladloaa, la to be rajMtad wilb the flr*t BO cc ot dlaUUals and witb lb« tltroe turtlvna of 80 cc aaoh, dia-
tOled anor tbo adiUtlnn ot tba parmaniranaCB aoladon. If, for uaamph^ It niiuliad 1 c.o. uf itandanl aula-
Hon in NfMleftUnc Ibe Brat fiflr.e., and for Um othon U cc, 1 Jl 0.0., andO.Hc.c., tbo tolkiwlai b tba »■
■mt and tbt lanal tnatbud ot TeoocdiDK It :
... .01
... .Wd
on
.015
.ooi
.us
fna ammonia [wr litre .OSAmllller.
.ou
AlfaamlDoU ammoabt par llti* IMnllllcr.
If n water yield no albuminoid ammonia it is organically pure, even if it
contains much free ammonia and chlorides ; if it contnina n-om .02 to .06
miiligranis per litre, it ie Htill quite piu"© ; when tlie albuminoid ammonia
reaches 0.1 milli^. yxtr litre the wat^r ia to be looked upon ivith Ku»pi-
nion ; and it ia to be condemned when the proportion reaches 0.15. ^Yhen
free ammonia is also present in considerable quantity, a water pelding
0.06 of albuminoid ammonia is to be looked upon with suspicion.
Poisonoua MeiaU. — Those most liable to occur in drinking waters ara
iron, copper, and lead, and of these the last is the most important.
The power possessed by a water of dissolving lead vftriea materially
with tho nature of the substances which it holds in sohition. Tlie pres-
ence of nitrates is fevorable to the solution of lead, on iuBuence which is,
however, much diminished by the simultaneous presence of other salts. A
water highly char^'cd with oxygen dissolves lead readily, especially if the
BietAllio surface be so exposed to the action of the water as to be alter-
Sfttely acted upon by it and by the air. On the other hand, waters con-
taining carbonates or free carbonic acid may be left in contiKt with lead
with comparative impunity, owing to the formation of a protective coating
i
WATKR.
40
of tlie insoluble carbonate of lead on the snrfnce of the metal. TUIh iloea
not apply, however, to wat«r charged with a largo excess of carbon dioxide
under prpssure. Of all natural waters that uioirt liable to couUimiuatiou
with lead is rnin-wntor; it containa animonium nitrate with venp- small
quantities of otbur aalt^ ; and it is hi<^hl}' aerated, hut contains no car-
bonates and com pn rati Tel V small ijuautitief* of cariHiu dioxide. Obvioiialy,
therefor, rain-water should neither be collected from a leaden roof, nor
stored in leaden tauktt, nor drnidi after having been long in contaot with
lead pi|>e8. As a rule, the purer the vra,ter the more Hable it is to dissolve
load when bronght in contact with that metal, especially if the contact
cciir when the wator ia ut a high temperature, or when it lasts for a long
iriod.
To determine the power of water for dissolvinff leiul, take two tntnlileTS
the water to be tested ; in one place a piece of lend, whoso Burfucti baa
Bcraped brif^ht, and allow them to stiud tweuty-fotir hours. At
end of that time remove the lead and pass sulplmretted hydrogen
llxrouf'b the water in buth tumblers ; if the one wliinh contained the metal
bccotne perceptibly darker titan tbo other, the wat«r lum a power of dis-
>lnng lentl such as to render its contact with surfaces of that metal dau-
erous if prolonged beyond a abort time.
To test for the presence of poisonoiia metals, solution of ammonium
-Solphjdrate is added to the water contained in a porcelain capsule. If a
A color be produced, which is not discharged on addition of hydro-
luric add, the water is contaminated with lewd or copper.
Fir gnar.tlutlvs (I«Linnln*tlaa«. MhittocM contnlnlDX koown qoMtUliaaof tlic potooooiw tnetal* %n OMd :
' iron *.'Jn gnma nt fautou* auj|<CtBCa m m titra of watar ; tor <»pt»r 8.93 imuD* ol cuprlc Hil|iti«to tu U«
• : amUlortmit I.M imtiQ of tnxl ■ntalaloUioUtrD. Oimi a.c oI ni«li MliiUDa cuntaimU.OUl grwm ot
I flurbtL 1^ wa thu wilulkMiM 100 e.c ufUie wativU) ba tortxl «biI IOU o.c. of pure wnterare pUiJBllo
lain tatMiitaik lo eaA lA whtch Mitnn ATa^MHiiom inilTihf«tT»te la thai wldnl. Tho apprnfirtaie lUnO-
]en U th«Q ■Uftvoit to fl(iwlnb>(h*<«iMnl»<w)Mintnitth«piin>wntcr, ontll chu khiulo of cetor
to dt* MBW M (hiU uf U)» IV]alil la tli« •liUivt oinul*. Th« tVRtU Kardliw U Uiia due sivm
M( oIoMiUfnuiu of Ui« tOBlsl ill * IUr« at wftlct.
Suspended solul^. — Most natural waters deposit, on standing, more or
leas solid, insoluble materi^iL These substAuces luive been either sus-
pended mechiinically in the water, which dp|Kjait8 them when it remains
at reit, or they have been in solution, and are depoHited by becoming in-
soluble as the water is deprived of carbon dioxide by exposure to aii' and
by rebof from pressure.
Tbc tnapBa4itA putlclwi akoulil bH ao B wtrt Uy NilMldnMM In » ixMkal sImm, and riMnrid Im ■cuniuad
nrtw w p m itaiHy for lo-' funna ut wlwl wirt ^'^»U l ito Ufe. Tba qiuniltjt of MUfmuhvl •olkbladfunnlDvl
Df pTT-'-rr k litre ot tho airbbl water ihronnh > drtoil umI wwlnboil OltiT, wUcH with the raUocMO itoinrit,
illl ^Kln ilrWl aiul <i«lgli«L Th» lUBorMia) bvtwowii Urn two woiglita ia ttau iia%ht at Mj^Kaiktl Ruttor tn
^BlNortb«w>t«r.
rurijioation ofi^cUer. — The artaiicial means of rendering a more or less
contaminated water fit for use are of five kinds : 1. Distillation; 2. Subsi-
ience ; U. Filtration ; 4. Precipitation ; 5. lioiling.
The method of diatUlation is used in tlie hd>oratory when ii v&ry pure
rater is desired, and abo at sea upon steamships, uud even on saiUng ve»-
bIs upon occasion. Distilled water is. however, too pure for continued
B, being liard of digestion. nn>.l flat to tlie tjisto from the absence of
'gases and of solid matter in solution. When circumsbincea oblige tlie use
of such water, it should be Agitateil ^nth air, and should be chargeil with
inorganic matter to the extent of about 0.&3 grum euoh of calcic bicartwn-
ale and sodium chloride to the litre.
Purification by »uhAule.nci: is adopted only aa an adjunct to precipitation
ind Ultratiou, and fur the sepamtiuu uf the heavier particles of suspended
'mfttter.
MANCAL OT CHEMISTRY.
The iiloftl procpss otJiUration consists in the RPpnration of all parlicles
of susi>euded matter, without anv alteration of such substaucos as are held
in solntion. lu tbe Bltration of potable waters on a lar{,'0 scale, however,
tlie more minute particles of suspeDded matters are only paj-tially nepar
rated, while, on the other hand, an important rhiuigc in the dissolved
inaterialu takes place, at least in certain lands of ttltors, iu the oxidation of
organic matters, whether in solution or in saspeDsiou. In the filtration of
large quantities of water it is passe^i through sand or charooal. or through
both substances arranged iu alternate luyeru. Filtration tlii-ough chared
is much more effective than that IhruugLi aaud, o^'ing to the much greater
activity of the oxidation of uitrogenize<l organic matter in the former case.
Prfvipiiatuin prooeBses are only adapted to har<l waters, and are de-
sigued to separate the excess of calcium salt, and at the naiue time a con-
•siderable quantity of orgauic matter, which is nicchnnicnlly carried down
with the precipitate. The method usually followed consists in the addi-
tion of lime (in the form of lime-water), in just su£Bcieui quantity to
neutralize the excess of carbon dioxide present in the water. The added
limo, together with Uie calcium salt naturally present in the water, is then
precipitated, except that small portion of calcium carbonate which the
water, fre«l from carbon dioxide, is capable of dissolving. To detenuine
when sufficient hme-water has i>een added, take a sample from time to
time during the addition, and test it with solntion of fiiker nitrate until a
brown precipitate ia formed. At this point cease the addition of lime-
water and mix the ItmBd w^ater with further imrtions of the hard water,
until a sample, treated with silver-nitrate solution, gives a yellowish in
place of a brown color.
The purification of water by hoUing can only be carried on uywn a smell
scale ; it is, however, of great value for the softening of temporarily hard
waters, and for the destruction of organized impurities, for which lattejr
pnmose it should never be neglected during cutbrei^s of cholera imd
typhoid, if, indeed, water be drank at all at such times.
31iNER.\£. Waters. — Under this head ai-e classed all waters which are of
therapeutic or imlnatrial value, by reason of the quantity or natuie of the
diH.solved solids which they contain ; or which have a teuipcratui'o greater
than 20'^ (CS^Foh.).
The composition of mineral waters varies greatly, according to the na-
ture of tlie strata or veins tliruugh which the water piUtses, and to the
conditions of pressure and previous composition under which it is in con-
tact with these de|Kiaita
The substances almost universally present in mineral waters arc : oxy-
gen, nitrogen, carbon dioxide ; sodium carl>onate. bicarbonate, sulphate
and chloride ; c-alcinm ciirlHinate and bicarbonate. Of sulwtanceB occasion-
ally present the most important are : sulphydric acid ; sulphides of sodium,
iron and magnesium ; bromides and iodides of sodium and magnesium ;
calcium and magnesium chlorides ; carbonate, bicarbonate, sulphate, per-
oxide, and crenate of iron ; ailicnt<»8 of sodium, calcium, ningnesium, and
ii-on ; aluminium salts ; salts of lithium, caiaium, and rubidium ; free sul-
phuric, sihcic, arsenic, and boric acids; and ammoniacal salts.
Although a sliarply <letined classitication of mineral waters is not pos-
sible, one which is useful, if not accurate, may bo made, based upon the
predominance of some cunatituent. or constituents, which impart to the
water a well-defined therapeutic value. A classitication which has been
generally adopted is into five classes :
L AcidiUous waters ; whose value depends upon dissolved carbonic acid.
.1 ..t
They contain but small qaontiiies of soluU, principallj tho biearbonatoa
of sodium and calcium and sodium diloride.
Q. Alkaline vxUers ; which contain notable quantities of the carbonates
r or bicarbonates of sodium, potaBsium, lithium, and calcium, eufficiont to
I communicate to them an alkaline reaction, and frequently a soapy taste ;
«itber nntumlly or after c:>cpult(ion of carbon dioxide by boiling.
HL Chali/becUe uxiters ; which contiun salta of iron in greater propor-
tion than 40 miUigrams per Utre (2.8 grains per galL). They conUin fer-
rooa bicarbonate, sulphate, crenate, and apocrenate, calcium carbonate,
sulphates of potas«iura, soilium, calcium, inagneaium, and aluminium,
notable quantities of sodium chloride, and fre<]ueutly small amounts of ar-
Benic. Thev have the taste of iron and are usually' clear as they emerge
from the earth. Those containing ferrous bicarbonate deposit a sediment
on standing, by loss of carbon dioxide and formation of fen*ouB carbonate.
IV. Saiine uxUcrs ; which contain neutral salts in considerable quantity.
The nature of the salts which they contain is eo direrso that the gi'oup
may well be subdirided ;
a. Chlorine uxUerg ; which contain large quantities of sodium chloride,
accompHiiied b,v less umuunts of the chlorides of potassium, calcium, and
mngnebiutu. .Some ore so rich in sodium chloride that they are not of
service as therapeutic agents, but are evaporated to yield a more or less
pure salt Any natural water containing more than 'A grams per litre (210
grains per gall) of sodium chloride belongs to this class, provided it do
not contain substances more active in their medicmal action in such pro-
portion as to warrant ita claHsifi cation elsewhere. Waters containing more
thau 15 grama per litre (1,050 grains per gall.) are too concentrated for
internal administration.
fi. Sulphate Mxiierx are actively purgative from the presence of consider-
able proportions of the sulplmtea of aodinm, calcium, and magnesium.
Some contain largo quantities of sodium sulphate, with mere tmees of the
calcium and magnesium salts, while in others the proportion of tlie sid-
phatea of magnesium and calcium is as high as 30 grams per litre (3,100
grains per gall.), tu 20 grams per litre (1,400 grains per giiU.) of soditua
sulphate. They vary much in concentration ; from 6 grama (3-30 grains
per gall.) of total solids to tho litre in some, to near 60 grams per litre
(4,2C^ grains p^T gall.) in others. They have a salty, bitter taate, and vary
much in teuijienittu-c.
y. Bromine an'l iodine icaiers are such as contain the bromides or
iodides of pota.ssiiim, sodium, or magnesium in sufficient quantity to com-
municate to them the medicinal properties of those salts.
V. Si^phuroHtt toalerm ; which bold hydrogen sulphide or metallic sul-
phides in sulution. Tliey have a diiiogrecuble odor and are usually n'ann.
Hiey oontaiu 0.2 to 4 grams of solids per liti-o (14-280 grains per gall.).
Phtsiolooioal. — Water is taken into the Iwdy Iwth as a liquid and as a
constituent of every article of foo<l ; the amount ingested by a healtliy
adult being 2.25 tu 2.75 litres (21^ to 3 quarts) per diem. Tlie greater tbe
elimination and the drier the nature of tho food the gi'eater is the amount
(of HO taken in the liiiuid form.
Water is a constituent of every tissue and fluid of the body, varying
from 0.2 per cent, in the euumcl of the teeth to 99.5 per cent, in the per-
^iration and saliva. It constitutes about 60 per cent of the weight of
the body.
The consistency of the various parts does not depend entirely upon the
relative proportion of solids and H,0, but is influenced by the nature of
L
OS MATfDAL OF OHEMISTBT.
the BoUds. The blood, although liquid in the ordinary scnso of the term,
oontains a less proporttoDiU amount of H,0 than does the timnie of the
UdDevs, and about tae same proportion as the tinue of the heart Although
the bile and mucus ore not ns fluid as the blood, the^ coutalu a larger
proportion of 11,0 to solids tbnn does that liquid.
Water is discliars'ed by the kidneys, intestine, sliin, and pulmonary
Bur&ioea. The quauUty diachargod is greater than that ingested ; the
excess being formed in the body by the oxidation of the H of its organio
ooDBtitaeiitft.
Hydrogen Dioxide.
Sijdrogen peroxide — Oxygenaled voter,
H,0, — Molecuiar weight = 34 — Sp. gr. = 1.456 — Discovered by 7%fti-
ard in 1818.
This substance may be obtained in a state of puritj by accurat«lj fol-
lowing the pn>ceas of Th^'uard. It mny also bo obtained, mixed with a
large quantity of H,0, by pnfwiing a rapid current of carbon dioxide
through HO holding hydrate of barium dioxide in HUKpension — BhO,H,
+ COj :rr BaCO, + H,Oj. It is also formed in small quantity during the
slow oxidation of many elements aud compounds, such as P, Pb, Zn, Cd,
AJ, alcohol, other, and tlm cssenoea.
The piu-e substance is a colorleHS, syrupy liquid, which, when poured
into H,0, sinks under it before mixing. It has a flisngrceable, metallic
tasta, somewhat resembliug that of tartar emetic. IrVhon taken into the
month it produces a tingling sensation, increases the 6ow of saliva, and
bleaches the tissues with which it comes in contact. It is still liquid at
—30" ( — 22^ F.). It is verj- unstable, and, even in darkness and at ordinaxy
temperatures, is gradmUlv dficompoaed. At 20^ (68' F.) the decomposi-
tion talces place more quickly, and at 100'' (212'' F.) rapidly and with ef-
fervescence. The dilute BubsUnce. Iiowever, is comparatively stiible, and
may he boilod and even distiUed without Buffering dc>coni posit ion.
Hydrogen peroxide acts both aa a reducing and an oxidizing agent.
Arsenic, sulphides, and sulphur dioxido are oxidized by it at the expense
of half its oxygen. When it is brought in contact with silver oxide both
substances are violently decomposed, water and elementary silver remiuii*
ing. By certain substanoos, such as gold, platinum, and charcoal in a
state of fine divhtion, libric, or manganese dioxide, it is decompoaed with
evolution of oxygen ; the decompoamg agent remaining unchanged.
The pur© substance, whou dcoompoeed, yields 475 times its volume of
oxygen ; the dilute 15 to 20 volumes.
h\ dilnto solution it is used aa a bleaching agent and in the renovation
of old oil-paintings.
As^LVnrAL CnAHAfmna. — 1. To a solution of starch a few drops of
cadmium iodide aolution are added, then a small quautity of the fluid to
he tested, and, dually, a drop of a solution of ferrous sulphate. A blue
color is produced in the presence of hydrogen peroxide, even if the solu-
tion contain only 0.05 milli^rnini per litre.
2. Add freshly prepartxl tincture of guaiacum aud a few dropsi of a cold
infusiou of malt A blue.color— 1 in 2,000,000.
HTDBOaSN DIOXIDB. 53
3. Add the liqmd to be tested to mixed solutions of ferric chloride and
potaaaiam ferricyaoide (which ahoald have no blue tinge). A blue color
—1 in 10,000,000.
4. Add to 6 ca of the liquid sulphuric acid, iodide of zinc, starch-paste,
2 drops of a two per cent solution of cuprio sulphate, and a little one-half
per cent, solution of ferrous sulphate, in the order named. A blue color.
Atmosfhebio Htdbooen DioxniB. — Atmospheric air constantly contains
small quantities of hydrogen dioxide, which is also present in rain-water
and in hail, and in less proportion in snow and hoar-frost The amount
present in rain-water varies from 0.008 to 0.499 miUigram per litre
(0.000454 to 0.028 grain per U. S. gallon), according to iSxe direction of
ue wind and the season of the year. It is more abundant with equa-
torial than wiUi polar winds, and more abundant in summer than in winter.
54
OP OHEMISTBl
CLASS H— ACXDULOnS TTT.TnvrTTTJTrH
£!uacsrr8 azj. or wuoaK HrDRATEa aue Acids, and which do not fobh Saints
WITH THE OIAOID6,
I CHLORINE GROUP.
"Pvcomsz. CnLORDis. Bbohins. Iodikk.
The elements of this group aro uuivalont. With hydrogen they form
add compounds, composed of one Tohirae of the element in the gaseous
state with one volume of hydrogen. Their hydrates are monobasio adds
when they exist (tluoriue forms no hydral«). * The 6rst two ore gase«, the
third liquid, the fourth soUd at oi-dinary temperaturea They are known
as the halogens. The ixlations of their compounds to each otlier are shown
in the following table :
C1,0 C1,0, C],0,
— — W
HCIO
HBrO
mo
HCIO,
mo.
gfifao-ic ftdd. Uoocutd*, TtUixldo. Tocnuldc. Hypo oua keid. -otu Bcld.
HCIO, HCIO.
HBrO, HBrO.
mo. mo,
■l« Kid. P«r-lc Kid.
FLUORINE.
Symbol = V—Atomic weight ~ 19 — DvKowred by Sir H. Davy in 1812.
Although many attempts have been made to isolate this element, it has
probably never been otitained in the free state, unless the colorless gas
obtained by G. J. and Th. Knox, by tlie decomposition of mercury fluo-
ride oud of hydrofluoric acid in vessels of fluor-spar was the element.
Fluorine forms compounds with all the other elements except oxygen.
Hydrogen Fluoride.
Hydrofluoric acid = HF — Molecular weigki — 20.
Hydrofluoric scid ts obtained by the action of an excess of aulphurie
add upou fluor-Bpttr, with the aid of gentle heat : CaFl, + H.SO, =
CaSO, + 2HF. If a solution be desired, the operation ia conducted in a
platinum or lead retort, whose })eak is connected with a U-8liai>ed receiver
of the same metal, which ia cooled and rontains a small quantity of water.
The aqueous acid is a colorless liquid, highly acid and corrosive, and
having a penetrating odor. Gi-oat caro must be exercisod that neither the
solution nor the gas come in contact with the akin, as they produce pun-
ful ulcers which heal with difficulty, and also constitutional symptoms
which may last for days. When the acid has accidentally come iu contact
with the skin the part should be washed mth dilute solution of potash,
and the vesicle which forms should be opened.
CULOBUrS.
55
Both tbe gaseons acid And its solution remove Uie Eilica from glass, a
property utilized in etching upon tLat RtibBtance, the pArtti upon Trtiic}] no
action ia desired being protected hy a coating of wax.
The presence of iluorine iu a comiwund ia detected b^ reducing the
ftubetance to p«wder. nioisteiung it with sulphuric acid in a. platinum cru-
cible, over which is placed a slip of glass prepared na above ; at the end of
half au hour tlu> wax is removed from the glass, which will be found to be
bed if tlie substance examined contained a ^uuride.
CHIjORINEI.
I Syir^fol=C\ — Atomic v:eight= Z5.5—Molecuhriveight =71 — ^. yr.=
f 'J.4fi0'2 A — One hire tceighH 3.17 gramg — 100 t'ufeiV; inches uvigh 76.3
I j/rairui — Jvame deritxdfrom xku^po^ ~ t/eUowidi-</retnt — Didcovered by Schecle
in. 1774.
r OocfKRESt^B. — Only in combination, moat abundantly iu sodiuu chlo-
ride.
Pbeparatiox. — (1.) By heating together mnngancBe dioxide and hydro-
chloric acid (Scheele). The rieoctiuu taked place in two stages : manganic
chloride is tirst formed according to the equation : MnO, 4- 4HC1 =
MuCl. + 21i,0 ; ani) is subsequently decomposed into manganous chlo-
ride and chlorine : MuCl^ = MnCl, + CI,.
Tlti» and idinHAr di«t>Uuiui m tuoMXtj oiuitui-lnl Id >a ikgijisrBltiii mich >■ tliat shown In Fitc- Ift. Tha
ewtkmwftrc revr) A i «rhlrh oa a Mtiall arale mMf l>" rrjilnrr.l hy a. c'-aas llflKk t !• Cwi-i ihinli Allal wttlt
tanp* of BuagkM^- iliiuiulo erf tbc dM ol bud-oau, and ailjiuud Id iLe wmur-batit ; hjilracblorlc aoU U
A
aV
^
Jv
■^
Ji^
3:
•^er^NTS
:i.
J Ib dmnnrh tb* ntatrtnbe and tbo bMtti ImbML Tb* dlamMca^ gM U oaaaed to bobbl* ibfHvh
IbemkllqMomvof w*l«tlnS,btb«idrladbrp*Maf*<lv«1b«nBflMBU<tfc»IdUBChk>rld»lflC, and
to Ocalljr oallacted 1^ il tij Ia wiB iint at «tr In th* vMari D.
VhmUia viHtl A tuM bBniaie hall flilnl with liquid UUIicMt todoaBnLllin Kilutinn ut iiMiisaiMRi* cUo-
rUc, wa«h Iho mwLlnlniE nxlOa <rlUi watf^r knd hngln sn«w. A kOo, at oidda rMitii SGT & llOn uf CI.
(2.^ By the action uf mangatieHe dioxide upon hydrochloric acid in the
presence of sulphuric acid, monganoub BulpUato being also formed : MnO, +
MAKTAL OF OHEMISTRr.
2H01 + H,SO. = MuSO, ■*- 2H,0 4- CI,. The Bonie qoaniity of cUorine is
obtaiued as in (1), villi tho use of haUtfao amount of hydrochloric acid.
(3.) By heating n mixture of one part each of mauBuieae dioxide and
Aodiiita chloride, with three porta of solphuria add. Hydnxblorio acid
and sodium bidphslo mv finit fonueil : H^SO, + 2NttCI = Na,SO, + 2HC1 ;
imd the acid is immediately decompoaed by oiiber of the roaotions indi-
cated in (1 1 and (2), aooonling as Hulphuria acid ia or is not present in
excesB.
(4.) By the action of pofaasiura dichrotnate npon hvdrochloric acid ;
potiissimn and chromin chlori^les being ulso formed : K,dr,0, + 1-lUCl =
yKCl -f Cr,Cl. + TH.O + 3C1^. Two parta of powdered dichromate are
heated with 17 p:ui» of acid of sp. gr., 1.16 ; lOO grams of the aalt yield-
ing 22.5 litres of CI.
(5. ) When a hlow OTolution of C\, extending orttr a conwilemble perioil
of time, ia detured, aa fur ordinary diaiufection, moiHteued chloride of lime
ia exposed to the air. the caloiuia luTiochlorit^ bcin^ decomponod by tho
atmospheric carbon dioxide. If a mora rapid evolution of gaa be desired,
the chlorirle of lime is moistened with dilute hydnxddorio acid in place of
with water.
PitopEUTiKs, — Phynical.—X grconish yellow gas, at tho ordinary tempera-
ture and pressure ; it has a penetrating ochn*, and ia, even when hiphlj'
diluted, Tory initating to the respiratory pasKBges. Being soluble in H < *
to the extent of one Tulumo to three volumes of the solvent^ it must uo
collected by displacement of air, ns shown in Fig. lU. A saturated oquc*
ouB solution of CI is known to chomists as ckiorina ti-ater, and in phar-
macy as aqua chlori {V. S.), Liquor ckiori (^r.); it sliould bleach, but
not redden, Utniua paper. Under a pressure of 6 atmospheres at 0" (32"'
F.), or 8^ atraosphorea at 12" (53'^.fi F.), CI lioromeaau oilv, yellow liquiil,
of 8p. gr. l.;W ; ami boihng at — 83.G° (— 28°.5 F.),
Chi'micai, — Chlorine exhibits a great tendency to combine with other
elements, with all of whinh, except F, O. N, and C, it unites directly, fre-
quently witii evolution of light as well aa heat, and sometimes with an ex-
plosion. With H it combines slowly, to form hydrochloric acid, under the
influence of diffaso daylight, and violently in direct simlight or iu highly
actinic artificial lighta. A candle bums in CI with a faint flame and thick
smoke, itsH combining with the CI, while carbon becomes free.
At a red boat CT decomposes H,0 rapidly, with formation of hydro-
chloric acid. Tlie same change takes place slowly under the influence of
sunlight^ hence chlorine water should bo kept iu tho dark or in bottles of
yellow glass.
In tlie presence of H^O, chlorine ia an active bleaching and diainfectr
ing agent It acts as au indirect oxidant, decomiioHiug H,0, the nascent
O from which then attacks tlie coloring or odomus principle.
Chlorine is readily fixed by many organic substances, either by addi-
tion or substitution. In the flrst iiiHtaiice, as when CI and oletiant gaa
unite to form ethylene chloride, tlie organic substance simply takes up one
or more atoms of cliloriue : C,H, + CI, = C,H,C1,. In the second ius^Dce,
as when CI acta upon marsh gas to produce methyl chloride : CH^ CI, =
CH.Cl -t- HCI, each sulmtitute^l atom of CI dispLices an atom of H, which
combines with another CI atom to form hydrochloric acid.
Hydrate vf chlorine, 015H,0, is a yellowish green, crystalline subsUnoe,
formed when CI is pjissed through chlorine water cooled to 0" (32° F.). It
ia decomposed at lO"" (oO' F.).
A»Ai.TxicAL CiLuucTuca. — i^Jeo p. 62.
HrDBOGSJr CULOBIDK.
57
Hydrogen Chloride.
ffjfdrocMoric Aoid. — Muriatic Acid. — Acidum ffydroohhricum {V. S. ;
rr.i— HCl— Jfotocutor vieighi = 3G.5— ^ jr., 1.259 A^A litre iveighs
.62113 i/ram,
OoctrRKDicK. — ^In volcanta gases And in tho gostido juice of the mom-
CBtfABATiON. — (1.) By (be direct union of iU consUtueot elements.
(2.) By the action of sulphuric acid upon a chlorido, a siilpliate bciug
at the same Ume formed : H SO. ^ 2NaC:i = Na^SO. + 2HC1.
Ilua iB Lbo reactiou by which the UCl used iu the iirfs ia produced,
^flither an a separate industry or as ou iucidental product iu Leblauc'ii pro*
for obtaiuiog sodium carbonate (q. v.).
(3.) Hydrocluoric acid is aiso fonited in n great number of reaetiooB,
05 wheu CI IB Hubbtitulcd iii uu urgauic cuupuuiid.
pAurcm'iEs. — Phymxd. — A eolorl&ba (^jts, acid iu reaction and tuste, bav*
inp a aliarp, poDetnUinpf odor, nnd producing great imtation when in-
It beconiea liquid umler a pre«8uro of 40 atnioapheres at 4 ' (30*
T.). It ia very tioluble iu H,0, one volume of which diasolveii 480 vulumee
of the goa at 0^(32'' F.).
Chemical, — Hydrochlorio acid is neither combustible nor a Rupporterof
combustion, although certain elements, such as K and Na, burn iu it^ Ik
foruia white clouda on contact with uioibt air.
S'furnoN or Hti>rochloiuo Acid. — U id iu the form of aqueous solution
that thia acid is usually c-mplayetl in tbo arts and in pharmacy. It ia,
hen pure, a colorleusi U<)uid (yellow when impure), acid in tnate and
Uoa, whose ap. gr, and boilijig-puint vary with the degiee of concen-
,tion. When heated, it evohes HCl, if it contain more than 20 per
cent of that gas, and H,0 if it contain Jess. A solution containing 20
per cent, boils al 111^ (2;i2^ F.), is of sp. gr. 1.009, has the coiupoaitiou
UCl + HH,0, aud ilistils uncliauged.
CommercuU. muriatic acid is a yellow liquid ; sp. frr. about 1.16 ; con-
tains 32 per cent. HCl ; oud contains iron, sodium chloride, luid nnieiucBi
compounds.
Amdum hydrochhricum is ft colorless liquid, containing small quantities
of impuritiea. It contains Sl.OjMrcent HCl and itasp. gr. is 1.16 (U.S. ;
Br.). Tlie dilute acid is the abovo diluted with water. Sp. gr. 1.049 =: 10
Kfier cent HCl (U. S.) ; up. gr. 1.052 ~ 10.5 per cent HCl (Br.).
^y C. P. (cbemicali;/ pure) avid is usually the bame oa the strong phormo-
^^ oeutical acid and far from pure (sec below).
I Hydrocliloric acid is olasse^U along with nitiic and suli^uric acids, as
I one of the tlirec gironrj mineml qcuI». It is decompoaed by many elcmenta,
^^ with fonuation of a chloride niid liberntion of hydrc^en : 2HC1 ^ Zn =
^^kZnCl, + H,. With oxides nnd hydmte« of elements of the third and fourtli
^■fdasBM it fintera into double decomposiuon. forming H,0 and a cliloride :
CaO + 2HC1 = CaCl, + H,0 or CaHp + 2HC1 = CaCl, + 2H,0. Moat
of the metallio chlorides are soluble in H^O, those of Ag. Pb, and H|; (ous)
b»ng exceptions. The ohlorides of the non-metala ore decojuj^raasd on
ooDtnct with H,0.
Oxidizing agents decompose HCl with libernlion of CL A mixture of
hydrochloric and nitric acids in the proportion of three molecules of the
former to one of the latter, is the avidutn nitrohydrocidoricum {V. S. ; Br.)t
fi
MANUAL OF CHKtflSTRT.
or aqita reffia. The latter aame alludes to its poviei of disaolTiii^ pol^
by combmatioD of the uosceiut CL which it liberates niUi that luelol to
form the soluble auric chloride.
lMFVBmEa.^A chcmicallT pure solution of thia acid is exceedingly rare.
The impurities usually present are : Suli/lturotu ac>i>/— bydrogeu sidphide
is given off when the acid is poured upon zinc ; ifulphuric acid — a white
precipitAte is fonned with barium chloride ; Chlorine colors the acid yel-
low : Leo/i gives a block colur when the acid is treated with hyflrogea
sulphide ; Iron — the acid gives a red color with ainmooiutii sulphocyouate ;
Anenic — the method of testing by hydrogen sulphide is not sufBcieut.
If the acid is to be used for toxicologicol analysis, a litre, diluted with half
as much US), and to whicii a small quautity of potassium chlorate lias
been added, is evaporated over the wnterbaUi to -100 cc. ; 25 c.c. of sul-
phuric acid are then added, and the evaporation continued until the li(|uid
measures about 100 c.c. This is introduced into a Harsh ap}>aratua and
must produce no mirror during ou hour.
AsALmcAL CaARACTEiii — Sco p. 62.
ToxicoLOOY. — Poiiom attd corrtmves. — A ptdaon is any »ul»tance which,
t^r absorption into the blood, produces death or serious bodily harm,
A convince ia a mtbstattce capable of producing death by its chemical
action upon a tissue toUh which U comes in direct contact, without absorptiua
by the blond.
Under the above definitions the strong niinend acids act as corroaiTdfl
rather than as poiwns. They produco their injurious results by destroy-
ing the tissues with whieli thpy come in contact, and will cause death a»
surely by destroying a liu-ge Hurface of skin as when they ore token into
the stomach.
The object of the treatment in corrosion by the mineral acids is to
neutralize ttie acid and convert it into a hannless hoIL For this purj>ose
the beut agent is magnesia (magacsia ustaj tiuspcudcd in a small quimtity
of water ; or, if this be not at hand, a strong solution of soap. Chalk and
the carbonates and bicarbonates of sodium and potassium should not be
given, as they generate large volumes of gas The scrapings of a pla»*
tered wall, or oil, are entirely useless. The stomach-pump, or any attempt
at the inLi-oductiou of a tube into the on'sophagus, is not to be thought of.
Compounds of Chlorine cmd Oxygen.
Three compounds of chlorine and oxygen have been isolated, two be-
ing anhydrides. Tliey are all very unstable, and prone to sudden and vio-
lent decomposition.
CBuumNi: MosoxmB — C1,0 — 87 — = hypochhrous anhydride or oxide, it
formed &a a blood-red liquid by the acUon, below 'iO*^ {^W F.), of dry CI
upon precipitated mercuric oxide : HgO + 2C1, = HgCl, -|- C1,0.
On contact with H,0 it forma kypochlorous acid, HCIO, which, owing
to its instabihty, is not used industrially, although the hypochlorites <^
Co, K, and Na are.
CHUtance TaroxroE = chlorous anhydride or oride, C1,0, — 119 — is a
yellowish-green gas, formed by the action of dilute nitric acid upon potas-
sium chlorate in the prcseucG of arsenic trioxide. At 50° (1*22" F.) it ex-
plodea It is a strong bleaching nj^-ent; iw very irritating when inhaled,
and readily soluble in H.0, the solution probably containing cfdorous acid,
HCIO^ * •
CaLoarsE TmtoxiDE = chlorine peroxide, CLO,— 135— is a violently ex-
plosive body, produced by the action of Hulpnuric acid upon potosBiom
cbJormte. Btlow — 20"^ ( — 4" I''-)) it is an onuige-colured IJqmd ; aliove
tiiat temperature, a yellow f^as. There ia no corrcspondijig hydrate
known ; and if it bo brought in contact with an alkaline hydrate, a mix-
ture of chlorate and chlorite is formed.
Besides the above, two oxacids of CI are known, the anhydrides cor-
responding to which hJave not been isolated.
CnLOBio Acid — HCIO, — 8-4.5 — obtained in aqueous solution ns a
rtronfjly acid, yeUowish, syrupy liquid, by decomposing ita boriimi salt by
the proper quantity of sulphuric iicid.
FEacaioftio Acid — HCIO^— 100.6 — is the most stable of the series. It
IB obtained by boilin;^ pota^um chlorate with hydrofluosilicic acid, de-
canting the cold fluid, evaporating until white fumes appear, decanting
from time to time, and finally distiUing. It is a colorless, oily liquid ; i;p.
^. 1.T82 ; which explodes on contact with organic substances or charcoal
BROMINE,
Syvihot — Br — Atomic weight = 80 — Molecular leeighi = 160 — Sp, or.
of liquui — 8.1872 BiO°i of vapor = 5.52 A—Freenmf-pmrU = — 24 .6
(-12M r.)~BoUing-point - (i3^ (I45<'.4 /'.)— ^o»?k? derived from j8poJ/*(«
= a ttench. — Diacovered by Baiard in 1826— -ffrcnnum {D. S. ; Br.).
OoouBBESCK. — Only in combination, most abundantly with Na and Mg
in sea-water and the waters of mineral spriiign.
• FHEPAah'no:f. — It la obtained from the mother liquors left bv the evap-
oration of sea-water and of that of certain mineral springs, and from sea-
weed. These are mixed with sulphuric acid and manganese dioxide and
heated, when the bromides are decomposed by the CI produced, and Br
distila
PBOPsmes. — Phijsical. — A dark re<1di8h brown liquid, volatile at nil
temperatures above — 24'*.5 (— 12°.l F.); giving off brown-red vai>ors
which produce great irritation when inhaled- Soluble in Water to the
extent of 3.2 parts per 100 at 15° (59' F. ) ; more soluble in alcohol, cajbou
disulphido, chlorofomi, and ether.
Chemical. — The chemical characters of Br are similar to those of CI,
but IfHti active. With H,0 it fonus a crj-stalline hydrate at 0° {32° F.) :
Br. 5H O. Its aqueouH solution is deoumpused by exposure to light, with
formation of hydrobromic acid.
It is highly poisonons.
AxALvncji. CuAiucTEKs. — See p. 62.
Hydrogen Bromide.
TTtjdrohromic acid — Acidum hydrohromicuvi dU. (U. S.) = Uur — Jfo/e-
etdarwcight — SlSp. yr. — 2.71 A— A litre tveiyks 3.63 grama — Liquefiet
a* - 69" (-92*.2 F.)— Solidifies at - 73" {-09^4 F.).
Pbspabation. — This substance caimot be obtained from a bromide as
HQ is obtained from a chloride. It ia produced, along with phosphorous
acid, by the action of H,0, upon phosphonis tribromide : I*Br, + 3H,0 =
H,PO, + 3HBr ; or by the action of Br ujion paraffine.
im/AL OF OUESUSTKT.
Pbopbbtrs. — A Rolnrlefis gaa ; proiluoeii vrinte fumea with moutt air ;
acid in taate and reuctiou« and roadil; soluble iu H,0, with which il loi
a hydrate, HBr2U,0.
Its rhcmicnl properties are sizuikr to those of the oonrespondiDg CI
compound.
AatALmuAL. — See page S'i.
I
Qxaolds of Bromine.
No oxides of brominn ara known, alLhough three oxacids oxist. either
in the free stato or as aoltfi :
Uvi^BBouous Al'u> — HBrO — 07 — lb obtoioed, in aqueoua solution, hy
the action of iiv upon mercuric oxide, silver oxide, or ailver nitrate. M'ben
Br is added to concentrated solution of potassium hrdrate, no hjpobro-
mite is formed, but a mixture of bromato and bromide, having no decol-
orizing? action. With sodium, hydrate, however, sotlium bypobrouite is
foriuLMl iu solutiou ; luid tiuch a eolation, freshly prepared, is used iu Enop's
proppss for determining m"oa (q. t.).
Bittmtit: Aril) — HBrO, — 1211 — haH only been obtained in aqneona solo-;
tton or iu combiuation. It is formed by deouiujioKiiig barium bromattf]
with an equivftleut quantify of Ruli»huric acid : Ba (BrO,), + H,SO, =
HBrO, -h BoSO,. Iji combination it ia protluced, along with the bromidei^
by Uie actiuu of Br ou caustic potaswi : 3Br. + 6KH0 = KBrO, + 6£Br
+ 3U,0.
pEnniwMic Aca>— HBrO^ — 145 — ia obtained on a oomparatively stable,
oily liquid, by the decomposition of perchloric acid by Br, and concentrat*
in^ over the water-bath.
It ifi noticeable in this connection that, while HCI and the chlorides
are more stable than the corresponding Br comjunnda, the o:nrgen com-
pounds of Br are more permanent than those of C'L
IODINE.
Stfmboi ^1— Atomic toeiyhl =127 — Molffcxdar inei^A/ = 254 — 8p. gr.
ofswiiA = 4 948 ; of mpor - 8.716 ^— /\tfw ai I13».ti (236^5 F.)—lMlg
at 175 ' {347" /!)— Aiime derived from wA/f = i.iolit — Dixeover^ by Ihur-
toia in IBll—Iodum {U. 8.; Br.).
OoccBBENCE. — In Combination with Na, K, Ca, and Mg, in soft-woter.
the WAtera of mineral springs, maiiue plants and animals ; ood-liver oil
OODtains about 37 parts iu 100,000.
i^EPutvTios. — It is obtaine<l from the aahoa of sea-weed, called k^ or
varvch. These are extracted with H,0, antl the solution evaporfttea to
small bulk. The mother liquor, aeparateil from the other salta which
ctystallizo out, contains the iodides, which arc decomposed by CI, aided by
heat, and the libomtcd iodine condensed.
PwiwcnriEs. — Phyricat, — Blue-gray, crystaUino scales, liaving a metallic
lustre. Volatile at all tempeiatures, the vniKir having a nolot color and a
peculiar odor. It is sparingly soluble in 11,0, which, however, dissolves
larger quantities on sUuidiug over an exceaa of iodine, by reason of the
formation uf hyilriodic acid. The pre»euco of certain salta, notiibly putaa*
Blum iodide, increase the solvent power of U,U for iodine. The Liq. lodi
HTJJBOOEN lODroX.
61
chic
Comp, (V. S). (Li/J- Todi, Br.) in f»o1ution of potaiwintn iodide containing
free iodine. Verj- soluble in alwjbol ; Tinct. iodi ( V. S. ; Br. ) ; in ether
chloroform, beuzo], and carbon disulphide. With tho three laBt-noiucd
iBolvents it forms violet sohitionH, with tlie others brown Bolntiona
(jhemvxU. — In its chomicnl characterB I resembles CI and Br, but is leas
live. It decomposes H,0 ulowly and is a weak bleuching and oxidizing
^ent. It docomposos hvrlrogen snlphido with formntion of hydriodio
»cid and libemtion of sulphur. It doee not combine directly with oicygen,
but does with ozone. Poliissium hydrate solution diHSolvt-B it, witb for-
mation of i>otassium imlidc and some bj*poiodito. Nitric acid oxidizes it
to iodic acid. With ammonium hydrate solution it forms tlie explosive
nitrogen iodide.
IwritmEs. — Nfm'VclatUe aubstancen remain when the I is volatilized.
H'a^tT sepflratea as a distinct layer when I is lUssoWed in ciirbon disulph-
ide. Cyanogen iodide appears in white, aoicular crystals among the rn,-s-
tals of sublimed I when half an ounce of the subetanco is heated over the
-water-bath for twen^ minutes, in a porcelain caiwule, covered with a
Hat-bottomed dask tilled with cold water. The last named is the most
serious impurity as it is actively poisonous.
ToxiooLOGT. — Taken internally, iodine acta both as a local irritnut and
as a true |K)ison. It is disL-harged iia nu alkaline iodii.le by the uiiiie and
I>cn»piration, and when taken iu large cjuontity it appears in the faxes.
The poison should be removed as rapidly as posaililo by tho use of the
E-^^^-y^h-pmnp and of emetics. Farinaceous substances may also be given.
JALTTIOAL GilAKACTBBD.— See bcloW.
_ L
Hydrogen Iodide.
Hydriodic acid—Bl— Molecular weight = 128—^. gr. 4.443 A.
kr
pRWARATtos. — By tlie deoornposition of phosphoroua triio<lidD by water :
8H.O = H.PO, + SHI. Or, in solution, by pasaiiie hydrogen sulph-
e through water holding iodine in suspension : H,S + I, = 2HI 4 S,
pRor-ERTiER. — A colorless gas, forming white fumes on contact witli air,
and of strong acid reaction. Under the influence of cold and pressore it
rms a yellow liquid, which flolidifioa at —56" (—67° F.). Water dissolves
to tho extent of 425 volumes for each volume of the solvent at 10° (fi()°F.).
It is irartly decomposed into il«i elements by heat. Mixed with O it u
decomposed, even in the dark, with foneatiou of H,0 and liberation of L
Under the influence of sunlight the gas is slowly decoroposed, although it«
solutions arc not so affected, if they l>e free from air. Chlorine and In-o-
mine decompose it, with liberation of iodine. With many metala it forma
iodides. It yields up its H readily and is usod in organic chemistry as &
source of that element in the nascent state.
AxALTTicAi. Chaiucters. — Ghixieixe, BnomNC, ASD Iodise, asc tbzib Bi-
XABT CoMPOPKDs. — Chlorine. — (1.) Color.
(2.) Odor.
(3. ) Is dissolved by solutions of the alkaline hydrates, to which it com*
nnicates bleaching powers.
(4.) With sUver nitrate solution it gives a white ppt.^ soluble in NH
HO. insoluble in HNO^
Brifmine, — (1.) Color of liquid and vapor.
62
MATTTTAt OT OHEMISTBT.
(2.) Chloroform or carimn disnlphide, when shaken with solution of
Br, assume a ^'elluw or brown color.
(3.) Colors starch pasto yellow.
Iodine, — (1.) Color of vj^tor, '
(2.) DisBolvesi in chlorofonn and carbon disnlphide with a liolet color.
(3.) Colors Btarch-pn&te deep violet-blue, the color disappearing oix
beating' and returning on cooling.
Chloridfs. — (1.) With AgNO^ a white ppt, insoluble in HNO,, readily]
soluble iu NH HO.
(2.) With Hg,(NO.)„ a white ppt, which turns black with XH.HO.
Jiromide*. — (1.) With AfrNOj, a yellowish- white ppt,, insohible in H|
NO,, sparingly snluble in NH,H0,
(2.) Witb chlorine water, a yellow color, and when shaken with cfaloro-|
form the latter is colored yellow ; or colors starch-paste yellow.
/fWirfa*.— (1.) With AgNO^ a yellowish-white ppL, insoluble in HNO^
almost insoluble in NH,HO.
(2.) With fuming HNO„ a yellow color, and when shaken with chloro-
form lie latter ia colored violet ; or colors starch-paste dark blue,
(3.) With PdCl^ a dark brown ppt
Oxacids of Iodine.
The best known of these are the highest two of the series— iodic and
periodic acids.
Iodic Acm — -HIO^ — 176 — is formed as an iodate, whenever I is dis-
solved iu a solution of an iilkalino hydrato : I, + GKHO — KIO, -t- SKI -|-
3H,0 ; as the free acid, by the action of strong oxidizing agents, such as
nitric acid or chloric acid, npon I ; or by passing CI for some time throug'h
H,0 holding I in suspeusiuu.
Iodic acid appears in white crystals, decomposable at 170* (338° F.)»
and quite soluble in H,Oj the solution Imving an acid reaction, and a bit-
ter, astringent taste.
It is an energetic oxidizing agent, yielding up its O reatlily, with sejiia-
ration of elementary I or of Bi. It is used as a test Tor the presence of
morphine {q. v.).
Peiuowc Acid — HIO, — 192 — is formed by the action of CI upon an al-
kaline solution of sodium iodale. Tlie sodium salt thus obtained is dis-
solved iu nitric acid, treated with silver nitrate, and the resulting alver
periodate decomposed with H,0. From the solution tbe acid ia obtmned
in colorless cr}'8tal», fusible at 130'^ (26t>^ F.), very soluble in water, and
jeadily decomposable by heat
IL SULPHUR GROUP.
ScLPHUR — Seleshtv — Tellubitjm.
The elements of this group are bivalent With hydrogen they form
comixiuuds composed of one volume of the element, in the form of *va]ior,
with two volumes of hydrogen— the combination boiug attended with a
condensation in volume of one-third. Thoir hydrates are dibasic adda
I
Symbol = S — Atomic wetyAi ~ 32 — Molecular xceight = 64 — Sp. gr. of
vapor ^ 2.22 A— /Vw« at lU' (237.2" l\)—Boih at 447.3° (837° P.).
OocuBRErccE. — Free iu crystaUine powder, large cr^stola. or amorplious
in Tolcanic regions. In oombuution m sulphides aud sulpliates, uid tn
albuminoid RubHtAucea.
pREPAaATios. — By purification of the native sulphur, or decora postti on
ot pi/rU':ii, natiirul sulphides of iron.
Cnide avlphur ia the product of a fimt distillation. A second diBltlla-
tion in more perfectly constructed flpparotus yields vjined mlphur. Dur-
ing the firat part of the distillation, whito the air of the condensing cham-
b^ is still cool, the vapor of S is suddenly condensed into a fine, crystal-
line powder, which is Jlotocn of eulphur, sulphvr tublimatum (U. «S.).
Later, when the temperature of the condensing chamber is above 114^ the
liquid S collects at tiie bottom, whence it is drawn off and cast into sticks
of roll aulphur.
pROPEBTiEB. — Phtjifiait. — Sulphuf is usually yellow in color ; at low tem-
peratures, and in minute aubdivision, as in the precipitated mill' of sulphur,
gulphnr prwcipUatum {U. S.), it is almost or quite colorless. Its taste and
odor are faint but characteristic. At 114" (237".2 F.) it fuses toathin yel-
low linuid, which at 150^ -ICO^ (SOa^'-SaO" F.) becomes thick and brown ; at
330''-»40'' (626 -^>42^2 F.) it again becomes thin and light in color;
finally it boils, giving offbrownisb-vellow vaimr at a tenq^nUurc variously
stated between 440^ {H'ir Y) and *44«' (838''.4 F.). If heated to abovit
400* (752" F.) and suddenly cooled it is converted into plagtic siilphur,
which may be moulded into any desired form. It is insoluble in water,
sparingly soluble in nnilin, phenol, benzol, benzine, and chloroform ; read-
ily soluble iu protochloiido of eulphur and carbon disulphide. It ia di>
morphous ; when fused sulphur crystallizes it does so in oblique rhombic
prisms ; its solution in carbon disulphide deposits it on evaporation in
rhombic octahedra. The prismfltic variety is of sp. gr, 1.95 and fuses at
120' (248" F.) ; the sp. gr. of the octahetW is 2.05, aud its fusiug point
114*^.5 (238' F.). The "prismatic ciystals by esposure to air become
opaqne, by reason of a gnwlual convei*sion into octaliedra.
Chemical. — Sulphur unites readily wiUi other elements, especially at
high temperatures. Heated iu idr or O, it bums with a blue flame to sul-
phur dioxide, SO,. In H it bums with formotion of hydrogen sulphide,
H^S. The compounds of S are similar in constitutioD, and to some extent
in cliemical properties, to those of O. In many organic substances S may
replace O, as in sulphocyanic acid, CNSU, corresponding to cyanic acid,
CNOH.
UsBB. — Sulphur is used principally in the msnufncture of gunpowder ;
also to some extent in making sulphuric acid, sulphur dioxide, and matches,
and for the prevention of fungoid and parasitic growths.
HAMVXL Of CimnaTttT.
| » oJuU of Ihe d eo uw i poJU P u
8; IB aolotian ID the
iy in ^BiQ ^—iitifj in tke
of
oT tfaeintas-
OtfpBUO
nw *p''"*g* * flDa
ttae.
FkirjuuTioif.— (L) Qy dtz««t uuob of tin ekneais ; eilfaes' by faoaisig
S in H^ or ^ pMmg H tlmaefa mottea 8.
(3. ) Bj the actioa of n«neiit H apaa vn^dmzic mad. if tha mixture 1i»*
eooM bested. <8m Hvrii test lor anemc)
(3.) By Ami fc^/i #rf Hfl nprm M ^ ^ it mt^mm fa JM.IiJ.^iU ■ Bh ft -f Wfl ^
2SbCL + 3H^
(4) Bv tM setion of dihito s iUfcifk sad non ferrDos ■nlphide :
(+ H,SO, = Fe80, + HJi
(n.) Bt tbe actioa of HCl npon esLoiimi ■ulpbide : QiS + SHa =
nt> r rn rr. iiii nn n i am I, ni hin Mitninii. ni tl n«dll«»KM vtili«BM*^«|v«^
IHuM Ml^ til
m. M
« hitlta riR. tn. «n> <lli>d errnm In eonUot wfth tlto mlphldvi whan tbi* HafetKik t* opwirt,
t" :i "' "1 ■ 'DlhfuvichlhafnBtMlnbvr. a Ukwuh-bottloiMrtlj lllM with wnlfr.
i>t«lnan«thv nd m hjrOroKDn MlpMA* ffra«niwi (mu It idkj b* ««<
In II" m wrwn raqnlnd fot toxtootoflQil MuJjrBiA tHamii alwmrab*
laiFii'i iij iCTt'liirti I ill I'l [ni- r\|r;4ir'iillB, Vl^, ID.
pROpRBTim. — Physical. — A colorlees gas. liaviug the odor cff rottoD eggs
and ft diiguatitig toetc ; enlnblo iu H,0 to tho o:&teiit of 3.23 parta to 1 at
Iti" (69" F.) ; Bolublo in alcohol. Under 17 atmospheres pressure, or at
— 74" ( — ior.a F.) at tho onlinary preaaure, it liquefies; at — 85,6*-
( — 122° F.) it forma white co'stols.
iical. — Bums in air with fomifttion of sulphur dioxide and wnter :
2H.S - 30, = -280, + 2H,0. 1/ the supply of oxygen be deficienU H„0 in
formed and sulphur liheratod : 2H,S + U,=2H.O + S,. ilixtures of H,S
(uid air or, O explode ou coutact with flame. Solutions of the gas whcu ex-
poaed to ftir becomo oxidized with deposition of S. Such solutious should
he inade viUi boiled H,0 and kt^pi in bottles wliich ore oompktely lilled
and well corked. Oxidizing agents, CI, Br, and I I'eniove its H with depo-
sition of S. Hydrogen sulpliido and sulphur dioxide mutually deeoui|>oBe
each other into water, pentathionio ncid and sulphur : 4SO, + 311^ —
2H,0 + H S,0. + S,.
When the goa ia passed tlunugh a solution of an alkaliue hydrate ita
S diaplaces the O of the hyilrate to form u sutphydrnte : H.S -t KHO ~
H,0 + KHS. Witli solutions of metallic salts H,.S usimllv relinqoiKhes its
8 to tbe met«l : CuSO. + H.S = C»H + H^SO,, a iiroj^rty which renders
il of great Toluo in analytical chemistry.
AsALVTiOAL CHAftAOTDM — Hifdrogcn sulphide. — (1.) Blackens paper
moistened i\-ith lead acetate solution. (2.) Has an odor of rotten egpi.
.SV//tAtiycx.~-(l.i Heated in the oxidizing flame of the blowpipe, give a
bine fliuue and odor of SO,.
(3. ) 'With a mineral acid give oC H.S (esoept solphidea of Hg, Au,
and It).
I'sraioioarcAi.. — Hydrogen sulphide in produced in the intestine by the
deoompoaition of albuminous substauces or of taurochlorle acid ; it also
FiU- S2.
occars soraetimea in nliAcesaes, and in the urine in tubereulnaia, rariola,
and cauoer of tlie bladder. It may also reach the bladder by difi'uiuon
from the rectum.
TonooLooT. — An animal dies almost immediately in an ntmoaphere of
pure H,8, and the diluted gas is still rapidly fatal. An atmosphere con-
taining one ))er cent may be fatal to man. although individuals habituated
to its presence can exist in an atmosphero coutfiining three jwr cent. Kren
when hifihly diluted it produces a condition of low fever, and care ia to be
taken that the air of laboratories in which it is used shall not become con-
taminated with it. Its toxic powers arR due primarily, if not entirely, to
ita power of reducing and combining with the blood-coloring matter.
Tlie form in which hydrogen sulphide generally prodiicea deleterious
effects ia as ft eoustituenl of the gases cmanntllig from sewers, pririea,
burial Taulta, etc. These give rise to cither slow poisouing, as when
sewer gases are admitted to sleeping and other apartments by defective
plumbing, or to sudden puisoniug, as when a person enters a vault or
other locftUty containing the noxious ntmosjihere.
Tlie treatment should consiiit in promoting tlie inhalation of pure air,
ariifipiiU respiration, cold aflusions, and the administration of stimulants.
After death the blood is found to be dark in color, and gives the spec-
trum shown in Fig. 22, due to 8ulpha?mogtobin.
Sulphur Dioxide.
■
Sutphurous oxide, anhtfdride or acid — Acidum gulphuronum (V, S.
I1r.)--tiO^—Mol^itar mnghi = 64—.%. gr. of oai= U.213 ; of liquid =
1.45— JJtrtfa al - 10" (14= F.) ; aUidifiea at - %^ {- 103° /:). '
OooTHBSitcK. — la Tolcanic gases and in aolation in somo miiifiral walanL
Pkepahjition. — (1.) By bumiup S in air or O.
(3.) Bj rowrfiDg iron pjntett in n rnrrent of air.
(3.) I>uring ibe comuiutiaa of coal or coal-gaa contaimng S or ita
oompouucls.
(4.^ By heating milphxirio acid ivitli copper : SH^SO, + Ca = CqSO. t
2H,0 + SO
(6.) By Leatijig Bulpburic acid with cbartoal : 2H,S0, + C = 2S0, +
CO -i- 2iio.
Vlieii tiie ^tM is to be used as a disinfectant it is usually obtained by
reactinu (1) ; in milphuric acid {ariories (2) is useil; (3) indicates the
method iu wliich atmospheric 80, ia chiefly produced ; in the labora-
tory (4) is uaetl ; (5) is the process directed by tho U. S. and Br. Pbar-
mncopiriias.
PaopisTtiH. — Pftt/sical. — A Lolorleiut, bull&>catLng gtia, luviiig a disagree-
able and persistent taste. Very soluble iu U,0, which at 15' (39 F.)
dissolves about 40 times its volume (see below) ; also soluble in alcohol.
At — 10" (14 F) it funus a colorless, mobile, transpai-eut liquid, by
whose rapid evupomtiou a C(dd of — Go'' ( — 85* F.) is obtained.
Oiemic-it. — Sulphur dioxide is neither combustible nor a supporter of
combustion. Heated with H it is decomposed : SO, 4- 2H^ = S + 2H,0.
With liiiscent hydrogen H,8 ia formed : SO, + 3H, =: H.S -t- 2H,0.
Water nut only dissolves Uio gas but combines with it to form the true
BulpIiuroHH acid, H^SO,. With solutions of metallic hvdrates it foi-nis
metallic sulphites : SO, + KHO = KHSO, or SO, -i- 2KH0 = K SO. +
H,0. A hydrate having the oompoaitiou H.SO^ 8U,0 has been obtained
as u crj-stiJhno sohd. fusible at + 4" (3fl^.2 F.).
Sulphur dioxide and sulphurous aciil solution are powerful reducing
■ments, being tljemstelves oxidized to sulphuric acid : S0,^ H,0 4- O =
H SO. or H SO, 4 O = H,SO,. It reduces iiitrie acid with formation of
sulphuric acid and nitrogen tetroxide : SO. -r 2HN0, = H,SO, + 2N0,.
It decolorizes organic pigments, without, however, destroying tlie pig-
ment, whotte color may bo rcatore<l by an ulk:di or n. stronger acid. It
dcstrovs U,S, aoting in this Instance, not ns a reducing, but ns an oxidiz-
ing agent : 4S0 + 3H,S = aH,0 + H,S,0, + S,. With CI it eombines
directly mider the influence of sunlight to form tulpkuryl chloride (80,) "
d^ Sulphurous acid is dibosia
AxALTTiCAL CHAaACTEiw — ( 1. ) Odor of burning sulphur.
(2.) Paper ranistene^l with starch-pnste and iodic acid solution turns
blue in air containing I in 3.01K) of SO,.
Sutt,hile».—{\.) With HCi give off SO,.
(2.) With Zu and HCI give off H,S.
(3.) With AgNO, ft white ppt , soluble in excess of sulphite. When
the mixture is boiled elemeutmT Ag iK depoHited.
(4.) With 13q(N0,) a while ppt, soluble in HCI. Solution of
added to this solution forms a whil« ppt, insoluble in ooids.
a
BULPHURIO AOII>.
67
Sulphur Trioxide.
Sulphuric oxide or anhydnde — SO, — 3folecuhr tceight — 80 — 5^. gr.
1.9o— fuses at 18.3^ (65<* F.>— i?oii*t at 40^ (114.8° F.).
pREPuuTios.— (1.) By unioD of SO, and O at 250''-300'* (482*-572''
P.) or in preeenco of spongy platinum.
f (2.) Hy heating sulphuric acid in presence of phoFiphono anhTdride :
^fi,SO, + P,0, = HO. -r 2HP0..
(;i.) By hoatint,' ilry sodium pyrosulpknte : Na,S,0, = Nft,S0, -f SO,.
(4.) Bj- heating pjrosulphuric acid below 100^ (212" F.) in a retorfc
fitted with a receiver, cooled by ice and salt : H,S,0, = H,SO, + SO,.
PuopKHTLEa. — White, silky, odorless cr\'sta]H which give off white fumes
in damp air. It unites with H,0 with a hissing soimd and elevation of
temperature to form snlphtirio acid. When dry it doea not redden Utmas.
Oxacids of Sulphur.
H,SO, Hydrosulphuroue acid.
H,S0, Sulphurous acid.
H.SO, Sulphuric acid.
H,8,0, Hyposulphiwous acid.
H,S,0, Pyroaulphurio acid,
H,S,0, Dithionic acid.
H,8,0. Trithionic acid.
H.8.0, Tetrathionic acid.
H.8.0. Pentathionio acid.
Hydromilphuroufl Acid— H,SO,— 66.
le on nnstable body only known in solution, obtained by the (lotion of
Ktoc upon solution of sulphurous acid. It is a powerful bleaching and
deoxidizing agent
Sulphuric Add.
Oa of VUrtol—Acidum Kutphxtricum {U. &; Br.)— H,SO.— 98.
pBffuuTKW. — (1.) By the union of sulphxir trioxide and water : SO, -f
H,o = H,ao..
(2.) By the oxidation of SO, or of S in the presence of water : 2S0, 4-
2H,0 + 6, - 2H,SO, ; or S. 4- 2H,0 -f 30, = 2H SO,.
The mauufscture of H,S0, may be said to be the basis of all chemical
industry, as there are but few processes in chemical technology into some
part of which it does not enter. The metboil followed nt present, the re-
sult of gradual iroproTement, may be divided into two stages : Ist, ttie
formntion of a dilute iicid ; 2d, the concentration of this pro«.luct.
The first port is carried on in immense chambers of timber, lined with
lead, and fumislips an acid having a sp. gr. of 1.55, and containing 65 per
c^nt of true Hulpburic acid, H,SO,. Into these chambers SO,, obtained
by burning sulphur or by loaMtiog pyrites, is driven along with a large
Cxccas of tiir. In the cliambers it comes in contact ^nth nitric acid, at the
expense of which it is oxidized to H,SO,, white nitrogen tetroxide (red
fumes) is formed : SO. + 2HN0, ^ H,SO, f 2X0,. Were this the only
resctioDi the dispoaal of the rod fumes would present a serious diffi-
4
MAWTTAL OF CHEMISTRT.
■
And the amount of nitric add consumed woulJ be Tery greal A secoml
reartion occiini betireen the red fumes and H,0, which ia injeoletl iii the
forui of steam, br which nitric acid and uitrugen diuxide are produced :
3X0, + tl,0 = iZHXO, + NO. The nitrogen dioxido in turn combinea
witb O to prodnoe the tetroude, which then regeneratea a further quan-
tity of nitric acid, and so on. This aeriea of reactioua ia made to go on
cuntinuoasly, the nitric acid being constantly re^jreucrated, and aciting
luurely as a carrier of O from the air to the SO^, in such manner that the
sum of the reactions may be represented by the equation : 2S0 -f 2H,0
- a = 2H.S0..
Tbc ncid in tillawed to collect in the chambeis until li baa the ap. gr.
laa, when it is drawn off. lliia chamber acui, although used in a few in-
dutttrinl proceseea, is not yet strong enough for moat purposes. It is con-
ceulrated, first by eTBporatioo in Ludlow loulen pons until its sp. gr. reaches
1.T4G ; at this point it befiius to act upon the lead, and is (raustetred to
platinum stills, where the coocentration is completed.
TABiKma, ^-Sulphuric acid ia met with in several conditjona of ooDoen-
tration and parity :
(1.) The commercial oil of vitriol, larj^y uaed in nuiuufacturing pro-
ceases, is a more or less deeply colored, oily Uquid, varj-iug in sp. gr. from
l.H'A'A to I H42, and in concentration fi*om 93 per cent to 99k psf oent of
time H^SO..
(2.) C. P. acid = Actdum aulpliuricum, U. S. ; Br., of sp. gr. 1.84, col-
orles.s and comparatively pure (aee below).
(3.) Glacial valphuric turul Is a hydrate of the cumpoHttion H,SO_,HO,
sometimes called biiijfdraicd tsatphuric acul, which cr)'atiillixeu in rhomuic
prisms, fusible at + 8°.a {47^. 3 F.) when an acid of B]*. gr. 1.788 is cooled
to that temperature.
(i.) Ar.. sulph. dil. {U. S. ; Br.) is a dilute acid of sp. gr. 1.06D and
ooutaining bet^voen i) and 10 per cent, H,SO, (U. S.), or of sp. gr. 1.094,
containiti-^ (wtween 12 and 13 per cent, H,SO^ {Br.).
PaoPKBTiEs.— /'Ayrficat — A colorless, hearv, oily liquid ; sp. gr. 1.842 at
12^ (53".6 F.) ; crystallizes at lO'.S {50=*.9 F.) ; boihi at 338 (040 .4 F.),
It is odorleKi. iiiteniW'ly acid in taste find reftctii>n, and highly cori-osive.
It is non-volatile at ordinary tempomtureB, Mixtures of tiie acid «-ith H^O
have a loner boiling-point and lower sp. gr. as the projxniion of H^O iu-
cretiBos.
Chemioal. — At a rod heat vapor of H,S0. is partly dissociated into SO,
and H,0 ; or, in tho prosonco of plntinuai. into .S0,.IL0 and O. When
heated with S, 0, P, Hg, Cu, or Ag, it is reduceil, with formation of 80,.
Sulphuric acid has a givat tendency to absorb H,0, tho uuion being
attended with elevation of tempcmture, uicrease of bulk and diminution
of sp. gr. of the arid, and contraction of volume of tho mixtm-e. Three
pirts, by weight, of acid of sp. gr. 1.842, wiieii mixed with one part of
HO produce an elevation of tempemture to 130° (26fi'^ F.^, and the pe-
sulting mixture occupies a volume ^ less thiiu the sum of the volumes of
the constituents. Strong H^HU, is a good desiccator of air or gases. It
should not ho loft exposed in uncovered vesfiels lest. 1>y increase of volume,
it overflow. AVlien it is to bo diluted with H,0, the acid should be added
to tho H,0 in a vessel of thin ginss, to a\'nid the projection of particles or
tho rupture of the vessel. It is by virtue of its affinity for H,0 that H^ISO,
chars or dehydrates organic substances. Sulphuric acid is a powerful di-
basic acid.
lurcBiTtEs. — The commercial add is so impure that it is only fit for
mAna£ictxiring and tlip coftrsest cltemical uses. The so-called C P. acid
may furtlier cunLain : Lead ; becomes cloudy wben mixed with 10 times
ita Tolnme of H,0, if tho quantity of Pb be mifficient; the dilute acid pivcs
a block color with H,S. SaiU ; leare a fixed residue when the acid ib
•^'QporatcKl. Sulphur dioxide ; gives oflf H,S wheu tho acid, diluted with
au equal Tolumo of H,0, comes in contact with Zn. Carbon; comuiuui-
eakta a brown color to the acid. Arnertic ; is very frequently present.
Wben flie uad is to )>e used for toxicolngitvd luialvsis, the test by H,S is
not sufficient ; tho acid, diluted with au equal volume of H,0, is to be in*
troduci-d into a Mareh appurutus, in which no vi»ible dtain lihould be pro-
duced dm-ing an hour. Oj^cs ofiii(ro{f€n ; are almost invariably present ;
tbey coimnnnicate a pink or red color to pure bnicine.
ANALTTia\i. CHARACTEaa. — (1.) Barium chloride (or nitrate) ; a white ppL,
insuluble iu acids. The ppt., dried and heated with charcoal, forms likiS.
which, with HCl. gives off H,a
(2.) Plumbic acetate forma a wbit« ppt, insoluble in dilute acida
(3.) Calcium chloride forma a white ppt, cither immediately or on di-
lution with two volumes of alcohol, intKilulJe in dilute UCl ov HNO^
ToKicouJOY. — Sulphuric acid ia an active conosive and may be, if
taken in Kuflicient quantity iu a highly diluted Htjite, a true poison. The
oOQoentrated »cid causes i)eatb, either within a few hours by corroBion and
porforation of the walla of the Rtnmaoh and (esophagna, or, after m:uiy
weektt, by starvation due to destrurtiou of the gaatric mucous membrane
and <'losnro of the pyloric orilice of the atonuich.
The treatment is the same as that for conosloD by HCL (See p.
68.)
it
Pjrroaulphurio Acid.
I
ming tndpliuric aHd — XonVtauKn oil of vitriol ^ DJeuiphuric ftv-
c'raU—U.S.O^—ifoiec-ular weight = 17S~Sp. gr. = L9— fioiis at 52. ''2
(I2G^ r.).
pRCPARATiON. — By distilUng dry ferrous sulphate ; and purifloation of
the product by repeated crvstalhzatiouu and fuaions, uutU a substance
fusing at 35^ {dB" P.) is obtaintnl
pBOPEnriES, — The commercial NorUhausen acid, which is a mixtui«of
H,8,0, with excess of SO,, or of H,SO^, is a brown, oily liquid, which
boilB below 100" (212'' F.) giving oS SO, ; and is aoUd or liqtud aoooitliDg
to the temperature.
SELENIUM.
I Symbol = Se — Atomic uvigiU = 79.5 — MoleeiUar weight = 159 — -fjj. gr.
I ^ aolid = 4788 ; o/ vapor = 6.68^ — Name from <rt\j^ = moon — Dia-
I covered by Jierzdim in 1817.
I *'
■ aooom
1 oompo
A rare elemeni, occurring in combination with Cn, Fe, Ag and Hg and
aooompauying S. It is capable of exit>tiu<; in three allotropic forma. Its
oompouuda ore anular in conatituU^n to thoae of 8.
St/mbol = *te— Atomic ivright = 128 — Mokcuhr iivight — 256 — Sp. gr.
ff gotitl = 6.25; of vapor = Q.QA — Name from tellua = earth — Dw»vered
in 1782 by JliUler.
\ One of t}ie leoai commoa of the elemeuts, it occura free and com-
bined with Bi, Fb, Ag, <Sh, Hi and Avl It ia solid, hns a metallic lustre,
fuses at about 600*^ (932° F.). Its compounds ore similar to those of 8e
andS.
L.
HL NITKOGEN GROUP.
KiTBOOKR — PuoepaoBua-rABSEHio — AymioKT.
The plementfl of this proiip are either trirnlent or quinquivnipnt. Wit
hydrogen they fonu uon-ncid coiupouuds composed of one volume of the
riement in the gaseous state with three rohiraea of hydroj»en, the union
being Httendml with a coudensiution of volume of one-half. Their hr-
dratvB are acids containing one, two, three, or four atoms of replaceable
hydrogen.
Bismuth, frequently classed in this group, is exr-lnded, owing to the
existence of the nitrate Bi(XO J . The relations existing between the
oomjiouuds of the elements of tins group are shown in the folIo%viDg table :
NH., N.O.NO,N,0^ NO^N,0,. - — — _ HKO,
PH,. - -P.O.. -PA- H,TO..H.PO., H^., H.P,0, HPO.
AbH,, — — A8,0„ — As.O.. — H.AsO., H.AsO., H.As.O,, HAsO.
SbH^ — — Sb.O., — Sb,0^ — — H.SbO,. H.Sb 0„ HSbO,
Hjd- MoB' ni- Trl- TtAt- Fear. Hypa-ou -tmim Ortlio In P}-m-b Mot* Ic
ikta, ovUhk oztdai, o«ld«. ozkU. oxld«. mM. kU. vM. mdd. tuM.
NTTROGEN".
fe\2oie — Sjjmhnt = N — Atomic weight — 14 — Molrtr^ttar it^ight = 28 — Sp,
: 0.9701 — One litre weighs 1.254 yruma — Xame from vlrpca- = nilre,
wtirtf = source; or from d, privative {c*^ — life — Discovered by Mayow in
^ 1669.
™ OccuREESCK. — Free iu atmospheric air and in volcanic gaaee. In com-
bination in the nitrates, in ammoniacal compounds and in a great num-
H ber of animal and vegetable substnnces.
H PsEP-YHATius. — (1.) By removal of O from atmospheric air, or by burn-
ing P in air, or bv passing air slowly over red hot copper. It is contam-
inatod with CO„H,0, etc.
(2.) By poaaing CI through exceis of ammonium hydrate solution.
If ammonia be nut maintained iu excess, the CI react-u n-ith the ammonium
chloride formed, to province the explosive nitrogen chloride.
(3.) By boating ammonium nitrite : or a mixture of ammonium chlo*
ride and potassium nitrite.
Phopebties.— A colorless, odorless, tasteless, noucombusiible gas; not
a supporter of combustion ; ver^* sparingly soluble in water.
H It is very slow to enter into combination, and most of its compounds
I
NITEOGKIf.
n
toe verr proDe to decomposition, which may occur explosiTely or slowly.
Kitrogen combines directly with O under the influence of electric dw-
charges ; and witli H under like conditions and iudii'ectly dui*iug the
^ deoompoatiou of oitrogeuized organic Kub&taiices.
Nitrogen is not iioisouous, but is incapable of supporting respiration.
Athosfhebic Ain.
The alchemiets considered tiir as an element until Mayow in 1669
demonstrated its complex nature. It waa not, however, until 1770 that
Priestley repeated the work of Mayow ; and that the compound nature of
air and the characters of ita constituents were made generally known by
tlie labors (1770-I7ttl) of l^estley, Rutherford, laToisier and Cavendish.
The older chemists used the terms pat and air aH R_\-nonymous.
CoKKisrrio!!. — Air in not ft chemical compound, but a mechanical mix-
ture of O and N vnib smaller quantities of utlier gases. Leaving out of
eonsideiatiott alwut 0.4 to 0.5 pt^r cent, of other gases, au* couaista of
20.i)3 O and 7y.07 N, by volume ; or 23 O and 77 N. by weight ; pro-
portons which vary but veri' slightly at different times and places ; the
extremes of Uje proiwrtion of O found having been 20.908 and iiO.DOO.
That air is not a compound is shown by the fact that the proportion of
its constituents does not represent a relation between their atomic weights
or between any multiples thereof ; aa well as by the sulubihtv of air in
water. Were it a comiwuud it would have a definite degree oi solubility
of its own, and the dissolved gns would have the same composition na
when free. But each of its constituents dissolves in H,0 according to its
own solubility and air dissolved in H,0 at 13° (SB".! F.) consists of N and
O, not in the proportion given above, but in the proportion Go. 27 to 84.72.
Beaidca these two main constituents, air contains about 4-5 thous-
andths of ita bulk of other substances : va])or of water, carbon dioxide,
ammouiacal compounds, hydrocarbons, ozone, oxides of nitrogen, and
solid particles held iit suspension.
Vapor of water. — Atmospheric moisture is either visible, as in fogs
and clouds, when it is in tlie form of a finely divided liquid ; or iuviiiible,
OS vapor of water. The amount of H,0 which a given volume of air can
hold without precipitation varies according to the temperature. It hap*
tttdns rarely that air is as highly charged with moisture as it is caps*
vie of being for tlie existing temperature. Tlie difference lietween the
^ttmotmt of water which the air is capable of holding at the existing tem-
perature and that which it aetiiolly docs hold is its ffuHiou vf boIu-
ration, or hi/ffromeiric slate. Ordinarily air contains from t>B to 70 per
cent, of its possible amount of moisture ; if the quantity be less than
this the air is too dry and causes a pitrcheil Bcusiitiou and the senbe of
" Ktuflliness " so common in furimce-henlcd house's ; if it be greater, evapor-
ation from tlio skin is impcdc<i and the air is oppressive if warm.
The actual amount of moisture in air is deieriiiined by pustdng a knonn
Tolnme through tubes filled vrith calcium chloride ; whoso iucrense in
weight reproaents the amount of H,0 in the volume of air used. The frac-
tion of saturation is det«nniijed by instruments called hygromeien, iiygro'
KOp&f or peyckrameterif.
Carbon flu.>xide. — The quantity of carbon dioxide in free air Tuies from
8 to 6 parts in 10,000 by volume. (See Carbon dioxide.)
Ammoniacal ccmrjwuruib.— Carbonate, nitrate, and nitrite of ammon}
MA37!TAL OP CKRMISTRY,
occur in small qunntity fO.l to 6.0 pnrte per million of NH,) in wr, eu
products of the decomposition of nitrogenised organic Bubstances. They
are absorbed and iwHitnilatfHl hy planta
Nilric and nitrouji acUls, usually ill cumbinatiou wUb ammouiuui. are
produced eitber by tb© oxidation of oombuMtible subetances conlainiii*,' N,
or by direct union of N and 11,_0 durinf,' discbarges of atinoBphehc electricity.
Bain-WMter fuUin;^' during tbuiider-Kbowers has be«in found to coDtoin as
much as 3.71 per million of HNO,.
SuipJturic and sulphurotix mi'df oc^iu" iu combiuatiou with NH, in
the air over cities and manufacturing diBtriots, where Lhey are prodnced
by tlie oxidation of 8 esisting in
coal aud cohI-^hb.
IJ;/drocarf>oTVt hare been de-
tected in the air of cities and of
Bwampy places, in small quantities.
Solid parties of tho most di-
Terse imture ai-e lUwayy present in
air and W-ponie vimlile in a beam
of sunlig^ht Cliluride of iodium
isabuost always ptfscut, always in
the nei;j:hboriiood of salt water.
Air iKsntains myriads of frenus of
vegetable organisms, mould, etc.,
which Are propagated by the trans-
portation of these germs by air-
eiirreiits. Whether or no certain
diseases are thus propagntetl by
germs or poisons ; and wlietlier
low forms of organized beings cau
or cannot make their ap]M:anuice
without the intrwluction of germs
are questions, both sidt>s of which
are supported by nt^tive piirtisans,
and concerning wbtrh little or
nothing is known with certainty.
The continued inhalation of air containing large quantities of solid par-
ticles in suspension may cause severe pulmonary disorder by mere uiecbaui-
cal irritation, and npart from any ]ioiaonous qiudity in the Hubstonce ; sucli
is the case with the air of carpeted ball-rooms, and of the worlishops of
certain trades, fumitm*o pobshers, metal-filers, etc.
AtmwiAotto awt li MA oaUMtod t>T ma Inlnan-at mi«li u I* thvwn In Fig. 13. A dMc of tfala bIiw* U
IHHWrt apUB Utv ptala *. vrer the «anl1 oTtmttiit <u A. md Hm luwvc aarfao* molAned vUh k nlxtan ot
•qnal |Mrtt ot wbMt ftwl gtyoBrln, tha opcolng (1 1* uonaoDMil skh mi ■aplnrtar. Alter otic or roan cnUo
mntna of air Iwra bMu dimwn thmuicb Uiu TtMrmii, Um thin g^m ^ rt^Mihil wxl Uui ilctnua munlfnd
■iHnMM|4fBl|]ri
FiS. &
W ffr.= Q.iiS^A~lAqw/im at -40" (-40° F.)~BoiU at - 33^7 (-
I F.)—8(itid\Jiei at -75° { - 108" F.)—A lUre vxiyha 0.7656 fframa.
Amino nia.
PnspABATioirs, — (1. ) By union of nascent H with N.
(2.) By decomposition of organic matter containing N, either
taneously or by destructive distillation.
-Sp.
28*. 7
span*
NITUOGKN MCNOXTDE.
73
(3. ) B5 heatmg a mixture of dry slacked lime with ammomum chloride :
2NH CI + CoH^O, = CaCl, + 2H.0 + 2NH,.
(4 ) By heating solution of ammonium hydrate : NH.HO = NH, + H^O.
PnopBKiTBs. — Phtjsiciil. — A colorless giw, having a pimgent odor and an
acrid ta8t«. It is Terr soluble iu H^O, 1 volume of which nt O'^ (32' F.)
iaaoWes 1050 vok. NH. imd at 15- (59" F.), 7l'7 vok. NH . Alcohol
id ether also dissolve it readily. Liquid ammonia is a coloriees, mobile
ftiid, ased in ice machines for proilucii.^ artificial cold, the liqaid absoi*b-
ing a great amount of heal in TolatiHring.
Ciiemicttl. — At a red heat ammonia is decompoBed into a mixture of N
and H, uccupyin;^ double the volume of the original gas. It is similarly
decoojjKHiod bv the pi-olongod passago through it of discliarges of elec-
tricity. It is not readily combustible, yet it burns in an almosphere of
>0 with a yellowish Hame. Mixtures of KH, with O, nitrogen mouoxide,
or nitrogen <lioude, explode on contact with flame. Water dissolves am-
monia with eteTation of temperature and pro1>nbIy ^th formation of
ammonium hydrate, NH,HO (q, t.J. It combines directly with acids to
producti ommouium salts, without Heparutiou of hydrogen. (See Ammo-
mom.)
Nitrogen Monoxide.
iroua oTide — Latightui/ t/as—Nilro'ien proloj.-uIc — tT,0^ — Motei'tdar
= 44—^. <?r. = l,527i— fiJK^A at -100° (—148^ r.)—Ji<niM at
(—124" F.)-~IH9coventd in 1776 by PrumtUy.
pKEi'AttATioM. — By heating ammonium nitrate : (NH jNO, = NO + 2
H,0. To obtain a pui'o product there should be uo ammonium cliluride
'present (as an impurity of tlio nitrate), and the heat should be applied
gradually and not allowed to exceed 250® (482' F. ), and the gas formed
should be piisaed through wouli-bottles containing sodium hydrate and
ferrous tmlphnte.
PaoPKirrtBiL — Physical. — A colorless, odorless gas, having a sweetish
tast« ; soluble in H_0, more so in alcohoL Under a pressure of 30 atmo-
spheres, at 0° (32' F.), it forms a colorless, mobile liquid, which, when
dissolved in carbou disulphide and evaporated in vocuj, produces a cold
of - 140' (-220" F.)
Chemical. — It is decomposed by a red heat and by the continuous
of electric sparks. It is not combustible, but is, after oxygen, tlie
it supporter of combustion known.
pHYsroLOtiic.vu — Although, owing to the roodinesa with which N,0 is
decomposed into its constituent elements, and the nature and relative pro-
portions of Uieso elemenla, it is capal>le of maintaining respiration longer
ihan any gas except oxygen or air ; uu animal will Uve for a short tmie
only iu an atmot^phere of pure nitrous oxide. Ai\Tjen inlmled, diluted with
air. it produces the effects first observed by Davy in 1790 : fii-st an exhil-
arBtion of spirits, frequently accompanied by laiigliter, and a tendency to
iiiUBCulnr activity, the patient sometimes becoming aggressive ; afterward
there is complete auscsthesia and loss of oonsciousuess. It has been much
n«6d, by dentists ei^iedally, aa an antesthetic in operations of short dura-
tioD, and in one or two instances anieathesia has been maintained by its
too for nearly an hoar.
A solutiou in water uuder pressure, containing five volumes of the gas,
is sometimes used for internal administration.
J
Nitroyen Dioxide.
Nxiric oruie— NO— Moiecular toeighi = 30— Sp. gr. = 1.039^— i>i»-
covered by Sales in 1772.
Pbepabation. — By the action of copper on moderately diluted nitric
acid in the cold : 3Cu + 8HN0, = 3Cii{NO,) + 4H,0 + 2NO ; the gas
being collected after diBplacement of air from tiie apparatus.
Paun^BTiEa. — A colorfesa gaa, whoso odor and taste ore unknown ; xery
sparingly soluble in H,0 ; more Boluble in idcohol.
It combines with O when uiixed with that ^'as or with air, te form the
reddish-brown nitrogen tetixtxide. It is absorbed by solution of ferrous
sulphate, te which it communicates a dark brown or black color. It ia
neither oouibuistible uor a good supporter of combustiou> although ignited
C and V continue te bum iu it, anil the alkaline metals, when boated in it^
combine with its with lucaDdeaceuce.
Nitrogen Trioxide.
Atirous anhydride.— Nfi,— 16.
ECaa not been obtained in a condition of purity. A mixture of 95
I>er cent, of N^O, with 5 per rent, of N^O may, however, bo obtained by
dccompoHiug liquetied nitrogen tetroxide with a small quantity of H,0 at
a low temperature : 4N0, + H,0 = 2HNO, + NO,. This ia a dark
indigo-blue liquid, which, boiling at about 0^ (32 F.), is partly decom-
posed.
Nitrogen Tetroxide.
Nitrogen peroxide— Ili/ponitric acid — Nitroug ftimea — NO — Jfofct
idoj- weight = 4fi— .-fe. gr. = 1.58J {ai IBi^Cj—JloUs at 22' (71 .G /'.
—SoUdifiets at T (15^8 F.).
pREPARATio:ff. — {1.) By mixing one Tolume O with two volimies NO;
both dry and ice cold.
(2.) By heating perfectly dry lead nitrate, being alao produced :
2Pb(NO.), = 2PbO + 4N0, -*- O..
(3.) By dropping stroug nitric acid upon a red-hot platinum sur&oe.
PROPEfiTiEs-^When pure and dry it is an orange-yellow liquid at the
ordinary' temperature ; the color being darker the liigher the temjierature.
The red fumes which are produced when nitric acid ia deeoiupoaed by
starch or by a metal consist of NO, mixed with N,0,. It dissolves in nitric
acid, forming a dark yellow liquid, which is blue or green if N,0, be also
present. With SO, it combines to form a solid, crystalline compound,
which is somotimoa produced in the manufacture of li,SO.. aud kuowu aa
kad chamber crygiah. A small quantity of H,0 decomposes it into HNO,
aud N,0j, which latter colors it green or blue ; a lai-ger quantity of H,0
dbcompoaea it into HNO, and NO. Bv buses it is trauaformed into a
mixture of nitrite and nitrate : 2XO, -^ 2KH0 = KNO, + KNO, + H,0.
It is an energetic oiydant, for which it ia Inrgelv used. AVith certain
organic substances it dues not behavu aa an os:ydant, but becomes
SriTHOQBS" Acn>s.
ru
tainted w an nmvolont radical ; thus \ni\x benzol it forms nitro-bcnzol :
.(NO,).
lusiouLOoy. — The brown fumes given off during many piXKessefi, in
which nitric ncid is decomposed, are ilangerous to hie. All auch opera-
tions, when carried on on n small scale, ns in the laboratory, should bo
conducted under a hood or some other arrangement, by which the fumes
are carried into the open air. When, iu industrial processes, the Toluine
of gas formed becomes such as to bo a nuisance wheu discharKod luto
the air, it shouhl be utilized in the manufacture of U,S<\ or absorbed by
H,0 or an alkaline solution.
An atmoHpbcre contaminated with brown fumes is more dangerous
itban one coutouilng Gl, as the preseuce of tlie latter is mure iramedi»t<:ly
'annoying. At first there is only coughing, and it is only two to four
hount later that a ditficulty in breathing is felt, death occurring iu ten
to Eftetoi hours. At the autopsy the lungs are found to be extensively
diaontanized and tillod vtith black lliiid.
Even air containing small quantities of brown fumes, if breathed for
a long time, produces chronic disease of the respiratory organs. To
prerent such nccideuts, thorough ventilation in locations where brown
nimes oro liable to bo formed is imperative. In cases of spilling nitric
acid, safety is to be sought in retreat from the apartment tmtiJ the fumes
hare been replaced by pure air from without
(66" F.)
Nitrogen Pentozide.
Nitric anhydride~N,0.—Moiecular weight = 10»— /W<« ai SO'
—Itoih ai iT (U6\6 R).
Pbepabation. — (1.) By decomiwaing dry silver nitrato with dry CI in
an upparatuB entirely of ghiaa : lA^NO, + 2C1, = 4AgCl + 2N,0, + O,.
(*2.) By removing water fi-om fuming nitric acid with phosphorus pent-
oxide : 6HN0, + P,0, = 2H,1'0. -I- 3N,0,.
pBOpERnia. — Prismatic crystals at temperatiuva above BO* (86° F.). It
is very unstable, beinfj decomposed by a heat of CO* (122* F.) ; on contact
with H^O, 'nith which it forms nitric acid ; and even spontaneously.
Most substances which combine readily %\ith O, remove that element
Arom N.O..
Nitrogen Adds.
Iiggaa known, either free or in combination, corresponding to the
tfaree^mlcs containing uneven numbers of O atoms:
N.O -f H,0 = 2HN0— Hyponitxous acid.
N,0, + H,() - 2HN0,— Nitrous acid.
N,0. + H,0 ^ 2HN0,— Nitric acid.
Hyponltrous acid — HNO — 31— Known only iu combination. Silver
hypunitrite is fui lued by reductiun of sodium nitrate by nascent H and de-
coiiipoftition with silver nitrat*.
Nitrous acid — HNO.^ — 47 — has not been isolated, although its salts,
the nitrites, ore welldehued cuupuuuds: MNO, or M"(XOJ,.
Aqua/ortui — Hydrogen nitrate— Jcidum nUricurr^ XT. S. ; Br, — HNO,
—63.
Pbepak-ition. — (1.) By the direct union of ita constituent elementa
nnder the influence of electric dischargeti.
(2. ) By the decompoeition of ad aUuihne nitrnto by stronp H,SO.. With
modfrat-e lieat a jrortion of the acid is libtTJited : 2NaN0, + H,SO, =
NbHS(), -r N'&NO, + HNO,, and at a higher tenipemture the remainder
is given off: NuNO, + NiiHSO. ^ Na,80. + HNO,. This is the reaction
UBed in the manufacture of HNO^
VAaiETna. — Vommttrcial — a yellowiah liquid, very impure, and of two
degrees uf concentration : vingle aquafarlnf ; gp. gr. about L25 = S9f
HNO, ; and JouUe aqua/ortiv ; «p. pr. about 1.4 = G4^ HNO,.
Fuminrj—fk reddish yellow Uquid, moi-e or le83 free from impuntics ;
ehargeil with o^sides of nitrogen. Sp. gr. about 1.5. Used as an oxidiz*
ing agent
C. P. — a colorless liquid, sp. gr. 1.522, which should respond favorably
to the leete given below.
Acidum mtrin-um, C. 8. ; Br. — a colorleBs acid, of m. gr. 1.42 = 70;(
HNO,.
Avidum nitricum dilutum, V. S.j Br. — the last mentioned, diluted
with H,0 to Btt gr. 1.059 = 10;^ HNO, (£7. &), or to sp. gr. 1.101
^ IT.WK HNO. (Br.).
Puoi'£itTi£s. — J'hyaicai. — The pure acid is a colorless liquid; sp. gr.
1.522; boila at 86'' (186^8 F.) ; soUdities at— 40= (— 40" F.) : gives off
white fumes in dtuiip air ; and has a strong acid taste and reaction. The
sp. gr. uud boiling-point of dilute acids vai'v with the couceutration.
li n stroug acid be distilled, the boiling-point graduollv rises from 86°
(18«^8 F.) until it reaches 123^ {253°.4 F.). when it remains constant,
the ap. gr. of distilled and diHtillnte being 1.42 ^ 70,^ HNO,. If a weak
acid be taken originally the boiling-point rises until it becomes stationary
nt the same point
Cht^iU-al. — WTien expoaed to nir and light, or when heated to redness,
HNO, is decompoacd into NO, ; H,0 and O. Nitric acid is a valuable
ox}'dant ; it converts I, 1', S, C, li, and Si or their lower oxides into
their highest oxideu ; it oxidizes ami destru^vs most organic substances,
although with some it forms products of substitution. Most of the
metals dissolve in HNO, as nitrates, a portion of the acid being at the
some time decomposed into NO and H,0 : 4HN0, + 3Ag = SAgNO,
+ NO -f 2H,0- The 8o-cftlled "noble metals," gold and piftliniim. ore
not disBolved by either HNO, or HCl, but di88t>lTe as chlorides in
a mixture of the two acids, called aqua ri'ffia. In this mixture the two
acids mutually decompose each otlier aooording to the etjuatious : HNO,
+ 3HC1 = 2H.0 + NOCl + CI, and 2HN0, -t- GHCl = 4H.O +
2N0C1, + CI, with formation of miroxyl chl'-ride, NOCl. and hichloride
NOCl, ; and nascent CI ; tlie lost named comhiuing with the metal.
When HNO, is decomposed by zinc or irun or in the poi-ouscup of a Grove
battery, NO, and NO, are formed and dissolve in the acid, wbich is colored
dark yellow, blue or green. An acid bo charged is known as nt/nwo-ni/nc
acid. Nitric acid is monobiuiic.
luPCBirnB. — Oxides of Niirogen render the acid yellow, and decolorize
J
pofaminm permaD^nnte when ailded to the diluto tutict Sulphuric acid
pnxluces clouJiucas when BaCI, is atlJed to the acid, diluted with two
rolames of H,0. Chlorine, iodine cause a white ppt. with AgNO,. Iron
gives a red color when the diluted acid is treated with aniraonium sulpho-
cranate. Saiin, leave a fixed reaidue when the acid is eTajmrati'd to drj*-
ness on platinum.
AxALTTicAL OHAiuicrrEits. — (1.) Add au equal volume of ecu cent rated
H,SO,. cool, and float on the surface of the mbcturc a solution of KeSO,.
The lower layer becomes gradually colored brown, black or pnrple, be-
giuuin}{ at the top.
(2.) Ikiit in a test-tube a small quantity of UCl ooutiuuiDg enough
Rulp)niidi;^'otir arid to roiumunicatt? a bhip color, add the sunjiected solu-
tiuu and boil again ; the color is digchiirged.
(3.) If acid neutraluM with KHO, ovajKiratG to dryness, add to the res-
idue a few drops of ]i,80, and a crystal of bmcine (or some sulpbanilio
ncid) ; a red color is produced.
(4.) Add H^SO, and Cu to the suspeetAd liquid and boil,- brown fumes
appciLT (best visible by looking into the mouth of the teat-tube).
The nbuve np))earancee are cansed by frc>e nitric aci>1, but if the testa
be conducted as diroctetl a nitrate, if present, is decomposed with libera*
tion of the ncid.
All neutral nitrates are soluble in H,0 ; aomo so-called basic salta are
insoluble, as bisrauthyl nitrate : (BiO)NO^.
Toxiaii/Kn*. — Although most of the nitrates are poisonous when taken
intenialiy iu sufHcicntly largo doses their action seems to be due rather
to the motfll than to the ocid raiiical. Nitric acid itself is one of the
most powerful of oorrosiveB.
Any auiuml tissue with wliich the concentrated acid oomen in contact
i) immediately di>)integrated ; a yellow stain, afterwanl turning to dirty
Ijrownish, or, if tlie action l>e prolonged, an eschar, is formed. When
taken iutenially its action is the same as ujKfn tlie skin, but, owing to the
more immediately important function of the parte, is followed by more
serious results (udIprs a brge cutaneous surfaoe be destroyeil).
The ^irmptoros following its ingestion are the same as those produced
by the other mineral at-ids, except that all parts with which tlio acid Irna
come in contact> including romiteU shrods of mucous membrane, are
colored yellow. The treatment is the same ns that indicated when SO,H,
or HCl have been token ; Le. neutrallxation of the corroaiva by magueaia
or au ftlhflli.
Compotinda of Nitrogen ^yith the Halogens.
Nitrogen chloride — NCI, — 120.5 — ^is formed by the action of c:Eces8
of CI upon NH or an ainmoniacal compound. It is an oily, light yellow
liquid ; &)). gr. i.G53 ; has been distilled at 71" (159^.8 F.}. When heated
to %" (UOl'^.B F.), when Bubjeoted to concussion, or when brought iu
coutact with phosphonis, alkalies or greasy matters it is decomposed,
with a violeut explosion, into oue volume Nond tlu-ee volumes CL
Nitrogen biomido— NBr,— 254— has been obtained as a reddiah
brown, B^TUpy liquid, very volatile, and resembling the chloride in it«
propertieH. by thi action of potassium bromide upon nitrogen chloride.
Nitrogen iodide — Nl, — 395 — When iodine is brought in conUict
with ommouiom hydrate solution, a dark brown or black ^^vder, highly
\
78
VATVUAL or 0HEUI9TBT.
explosive when dried, is formed. This sulxitAnce varies in composition
According to the conditions under which tlie action oocxira ; sometimes
the ioilide alone is formed ; nuder other circumstances it is mixed with
compounds containing N, I and H.
PHOSPHORUS.
Symbai = P — Atomic weighi — 81 — Molec^dar weight ~ 124 — ^. gr. of
txipor = 4.2904 A — Xame fnmi ^wc = light, ^Mpw = Ibear — Discovert by
Brandt in l(J6l>— /'Ao^/Aori« (f. .S. ; Br.).
Occi^HBEscE. — Only in combination ; in the mineral and vegetable worlds
as phosphates of Ca, ilg, Al, Pb, K, Na. In the animal kingdom as
phoHphates of Ca, Mg, K and Na, and in organic combination.
PEEi'AB.\Tins. — From bone-ash, inwhicli it occurs aa tricalcio phosphate.
Throe parts of bone-osli are digested n*ith 2 parts of strong H SO,, di-
luted «vith 20 volumes U,0, vrhen insoluble calcic sulpliate anfl the hoIu-
blo monocaicic plioaphate, or "superphosphate," are formed : Ca,(PO )
+ 2H,S0. = H Ca(P0.), + 2CiiSO,. The solution of superphosphate
is filt<ircd off and cvaix^rated, the residue is mixed with about one-fourtli
its woip;ht of powdered charcoal and sand, and Hie miituie heated, first to
redness, finally to a white heat, in earthenwnre retorts, whoeo beaks dip
under water in suitable receivers. During the first part of the heating
the monocaicic phosiilmte is converted into metapbosptiate : CaH,(P0,),
= Ca(P0,), 4- 2H,0 ; which is in turn reduced by the charcoal with
formation of carbon monoxide and lil>emtion of pbospboruB, while the
calcium ia combined as silicate : 2Ca(P0.), + 2SiO, + 5C. = 2C^iO
+ lOCO + p..
Tlie crude product is purified by fusion, finit uuder a solution of bleach-
ing powder, next under ammoniacal water, and finally under water contain-
ing a amnll quantity of sulphuric acid and potassium dicbromnte. It is
then strained through leather and cast into sticks under warm water.
PuoPEitTiEs. — Physical. — Phosphorus is capable of existing in four allo-
tropio forms :
( t. ) Ordinarif, or yellow varielr/, in which it usually occurs in commerce.
Tliis is a yellowxMh, iranalucid solid of the couaiateucy of wax. Below 0"
(32^ F.) it is brittle; it fusee at US (Ul .7 F.) ; and boils at 2W
(554' F.) in an almosphero not ciipiiblc of acting upon it chemicallv-
Its vapor is colorless; sp. gi*. = 4.JJ\— 65 H at 1040" (11)40^ F.). It
volatilizes below its boiling-point, and water boiled upon it gives off steam
charged with ita vapor. Expusod to air it gives off white fumes and pro-
duct's ozono. It is luminous in the dark. It is insoluble in water; spar-
ingly soluble in alcohol and ether ; soluble in ciLrbou disulphide, una ui
the fixed and voktile oils. It crystallizes on evaporation of its solutions
in octahodres or dodecahednc. Sp. gr. 1.K3 nt 10° (50** F,).
(2.) ^V^i!to phofphorus is formed as a white, opaque pellicle upon the
surface of the ordinary variety wktu this is exposed to liglit under aerated
water. Sp. gr. 1.515 at 15 (59'' F.}. When lused it reproduces ordin-
ary phosphorus without loss of weight
(3.) Black varietij is formed when ordinary phosphorus is heated to
70' (168" F.) and suddenly cooled.
(4. ) Red variettf is produced from the ordinar}- by maintaining it at firom
210'' (464'' F.) to 2H0^ {oiG' F.) for two or three days iu an atmosphere
J
puospnoBus.
79
of carbon dioxide ; and, after cooling, waehing out the unaltered yellow
phoBphoruB tvith carbon diitiilphide. It U also formed upou tbe surface
of tb« yellow varibty when it is exposed lo direct sunlight
Jt is a reddish, o^lorless, tiistelcMH solid, which does not fume in air, nor
disBolre in the eokeots of the yellow variety, ijp. gt. 2. 1. Heated to 500^
{9B2'' F.) with lead, in the absence of air, it diHsoWes in the molten metal,
>m whioh it aepnrat«0 on cooling in violet black, rhoiubohedra] crrstals,
8p. gr. 2.a4. If prepared at 250^ (482° F.) it fuses below that temper-
aliire, and at 260 ' (500" F.) is transformed into the yellow vaiiety which
icUstila The cr^stAllino product dooe not fuse. It is not luminous at
'Onlinary temperatures.
Chemical. — The most prominent property of P is the readiness with
which it combines witli O. The yellow variety ignites and bums with a
j bright flame if hcntod in air to 60" fliO^" F.)."or if exposed in a finely
divided state to air at the ordinary temperature ; with formation of P,0 ;
P,0^ ; H,PO, orH,P0,accxmlinpft8 is present in excess or not and accora-
ing AS the air is dry or moist Tbe teiu{}erature of it^iition of yellow P is
[•o low that it must he preserved uudcr boiled water. By directing a
cnrreni of O upon it P may be bunial under H,0, heated above 4^°
(XlS* F.). Tho rod variety combines with O much less readily and may
be kept in contact with air witliout danger.
The luminous appearance of yellow P is said to be due to the formation
of ozone. It does not occur in pure O at the ordinary temperature, nor
in air under jfressure, nor in the absence of moisture, nor in tho presence
of minute quantities of carbon disulpbide, oil of turpentine, alcohol,
ether, naphtha, and many gases.
Yijllow phosphorus bums in CI with formation of PCI, or PCI, accord-
ing OS P or CI ia present in excess. Botli yellow and red varieties com-
bine directly witli CI, Br. and 1
Phosphonia ia not acted on by HCl or cold H,80.. Hot H,SO oudizea
itwithformuUoQof pho.(iphoi-ousix>idaudsulpburdioxido: P^ + GlI,SO^ =
4H,P0, + GSO.. Nitric acid oxidizes it violently to phosphoric acid and
nitrorjen di- andti-tr-oxides: 12HN0, -i- 1\ = 4H^. -^ 8NO, + 4NO.
Phosphorus is a reducing a<reiit Wlieu iuunersed in cupric sulphate
ftolution it becomes covered with a coating of metallio copper. In silver
^nitrate solution it produces a black deposit of silver phosphide.
ToxicoLuoY. — The red variety differs from tlie other allolro|)io forms of
phosphorus in not being i>otaonous, probably owing to its inaolubiHty,
and iu being little liable to cauao injury by burning.
Tho burns produced by j'cUow jihospUonis are more serious than a
like destruction of cutaneous siirr^ce by other substances. A burning
lont of P adheres tennciously to the skin, into which it burrows. One
tho products of tho combustion ia metaphosphorio acid tq. v.) which,
' ig absorbed, gives riso to true poisoning. Bums by P ahould be
Gvaahed immediately with dilute jnrelle water, liq. sodte chlorinate, or
'solution of cldoride of lime. Tehow P shoiUd never bo allowed to come
in contact with the akiu, except it be under cold water.
y<mow P ia one of the most insidious of poisons. It is taken or
administered usually h.s "ratabjuio " or mat^h-hends. The former is fre-
quently »t)U"ch ]KiHto charge*! with phosphonia ; the latter, in the ordinary
sulphur match, a mixture of potassium chlorate, very fine sand, phos-
phorus, and a coloring matter. Tho svmptonis in acute pbosphoius-
|.poisoning appear witli greater or 1ph.h rapidity, according to the dose,
id the presence or absence iu the stumach of substances which favor its
I
MANUAL OF CHEMISTKr.
abftorption. Their appeirjince inny bo delayed for days, but as * nik
tliey npp^ar within a few houra A diaagreeable garlirJcy titste in the
moutb. and li(>at in the stomach are first observed, the Intter f^raduAUj
deTelopinfT into a buniinfir pain, acoouipjiiiied by voraitin(;f of dark-colored
miUer, which, when ahiUtcn in the dart, is phosphorescent ; low tvm}K;ra-
ture and dilatation of the pupihi. In some caacs death follows at this point
Rnddenly, without the appearftncc of any fnrthar marked fsymptoma ;
asuallj, bowerer, the patient raUica, aeema to be dcdng well, untol tnid-
deuly jaundice mitkes its appearance, accompouied by retention of urine,
and frequently dcHriuni, followed by coma and death.
There is no known ohemical anli<3ote to phoHphorua ; the treatment ia.
therefor, limited to the remoTal of the uuabaorbed portions of the {wisou
by the action of on umoiiCj zinc sulphate or apomorphio, as cxpeditiou&ly
Pio. Jl.
aa posailile, and the administration of oil of turpentine — the older the oil
thu better— OS a physiolo^ieal antidote. The use of fixed oils or fats ia to
be nvoide*!, as they favor the absorption of the poison by their aolvent
action. Tlie pro^iows in verj- uufaTorable.
As commercial phosphorus ia usually contaminated with arsenic, the
eflfecte of the latter sulwtoiice may also appeor in poisoninjif by Uie former.
Anali/j>iit. — When, after a death supposed to be caused by phosphorua,
chemical eridence of the existence of the poison iu the body, etc., ia
desired, the investigation must be made as soon after death as possible,
for the reason that the element is rapidly oxidized, and the detection of
the higher stajres of oxidation of phospboruB is of no vnluo as evidence
of the administration of the element, because they are normal constitu-
euta of tlio body and of the food.
The detection of ciomcutoi-y phosphorus in a systematic toilcological
tnaly«i8 is connected with that of pruBsic ncid, nloohol, ether, chloroform,
nod o1h«r vfilatile poiscns. Thtt Ruhstarires umler examination arc diluted
with H,0, ncidulated with H,30„ and heated over a saud-bath in the tlask
a (Fig- 24). This flnsk is connected with a CO, gonerator, b, whose stop-
cock ia closed, imrl with a Liebig's condenser, c, whicli is in darknena (the
operation is best comlurted in a dark room) and so placed as to deliver the
diatiUate into the tlask <l. The odor uf the distillate is noted. In the piea-
ence of P it is uaiuUly alliaceous. The contlenser is also obser\-ed. If at
the point of greatest condensatioii a faint, lutniuoua ring Im obaerved (in
the absence of ail reflectiona), it ia proof {wtiilive of the presence of uuoxi-
dized phosphorus ; the ubsenoe, however, of that poiaou is not to be in-
ferred from the absence of the liiniinoua rin^ (see above). If thia fail to
appear when one-tbird the fluid contents of the daak a have diHtUled over,
the tiotideust r h Jisconuected at c, and ill its place the alworbing ajiparattie,
Fi«. 96).
Fip. 25, partly flilpd with a neutral solution of silver nitrate, ia adjusted
by a rubber tube attached at y, and a alow and constant etreain of CO, is
caused to traverse the apiMuiitus from b. If during contiuuation of the
distiUation no black deposit ia formed in the silver solution, the absence
of P may be inferred. If a black deposit be formed, it must be further
examined to determine if it be silver phosphide. For this purpose the
apparatus shown in Fig. 2f> is used, in the bottle a hydi-ogcu ia gen-
erated from pure Zn and H SO,, the gas passing through the <lrying-tube
b, filled with fragments of CuCl,, and out through the platinum tip at c ;
d and « are pinch-cocks. When the apparatus is filled with hydrogen, il
is cltiaod until the funnel-tulie/ h thrcp-fjimrters filleil with the hquid
from a ; then ff is closed imd d opened, and the black silver deposit, which
has been collected on a filter and washed, is thrown iutoy ; t* is then
slightly opene<l and the escaping gas ignited at c, the size of the flame
being regulated by t;. If the dcjwsit contain P the flame wilt have a green
color; aud wben examined with the spectroscope will give the BpecLrum
of bright bands shown in Fig, 27.
Chronic jihosyhorux i>i)Uionint/, or lAtinfer dxmaef, occurs among opera-
tives engaged in the dipping, drying, and packing of phosplionis matches.
Those onpfage*! in the munufacturc nf pbosplionis iUrlf are not bo affected.
Sicklj women and cliildren ore most Bubject Uj it The cause of the iUaea»e
lifta been ascribed to the preeeucc of arseutc, and to the formation of oxides
of phosphorus and ozone. The prop^ss of the disorder is slow, and its
cuhuinating manifeatation ia the doHtruction of one or both maxilhu b;
necrosia.
rw, ST.
The &cquency of the dim^ose may be in some de^jrrec dimintahed bj
thorough ventilation of the 8)iop6, by frequent washing of the face and mouth
with a weak eoUition of sodium carbonate, and by exposing oil of turpen-
tine in saucers in the worksliops. None of these inothodB, howerer, effect
a perfect pretention, which can only Ik attAiued by the aubstllulion of the
red variety of phosphorus for tlie ycUow in this industry.
Hydrogen Phosphides.
Gftfieotis hydrogen phosphide — Phoi^}homa, Phraphamine — PH,—
S4 — A colorlefffi gati, having a strong olUoceous odor, which is obtained pure
by decomposing phosphonium iodide, PH.I, with H^O. Mixed with H and
vapor of l*,H, it is pro<lnce«l as a Hjjontaneously intiammabto gas, by the
action of hot, concentrated Bohition of potassium Ijydrate on P, or by de>
criiuiH>silion of calcium phosphide by HO. It is hi^lily poisouous. After
death the bluod is found to be of a dark violet color, and to have, in a
great measure, lost it* power of absorbing oxygen.
Liquid hydrogen phosphide — P,H, — 6(i — is the subRtanrc whose
vapor coniiniiTiirates to PH its property of igniting on contact with air.
It is Bcparattfd by pnsaing the spontaneously inflauunablo FH, through a
bulb tube surroiuiiied by a freezing mixture.
It ia a colorlesa, heavy liquid, which ia decomposed by exposure to
Bunhght or to » temperaluro of 30" {SG^* F.).
Solid hydrogen phosphide — P.H, — 12G — is a yellow solid, formed
when I\U, is dt'cum|>oscd by suuliglit It is not phosphoresoeut and
only ignites at lUO^ (320" F.).
Oxides of Phosphorus.
Two are known : P,0, and P,0,.
Fhosphorufl trioxlde — Phofj^horom arihydndr — P^O, — 110 — is
formed when P ia burned in a very liniitetl supply of perfectly dry nir or
O. It is a white, flocculent aolid, which, on esposuro to air, ignites by the
heat developed by its union with water to form phosphorous acid.
Phosphorus* pentoxlde — fAospftwnc anhydride— P,0. — 142— ia
formed when P is burned in an excess of dry O. It is a white, florculent
solid, wliich bus almost oa great a tendency to combii:e with H,0 as has
P,0,. It absorbs moisture rapidly, deliquescing to a hijrhly acid liquid,
containing, not orthophosphohc, but metaphosphoric acid. It is used as
n drying agent.
4
njrpcnihcMplMNU Mid H|PO,. I rmpboapboric MiU BAOi
Fbovtwraw add UtE^t- MoUpIw^liorUi «cM BFO|.
Pk«|iboriaBrid... B,ro,. |
Their basicities are as follows : H,PO, is monobasic ; H^PO, Is dibasic ;
U,I*0. in tribauic ; H.P.O, is telraboaio, and HPO, is monobasic.
HypophosphorouB aoid— H,PO,— GG—is a crvatalline solid, or,
more usually, a etronglv ncid, colorless srnip. It is oxidized hy air to a
mixture of H.PO. aiid H,PO,.
Phosphorous acid — HjPO,^S'2 — is formed by decomposition of
phosphorous trichloride by water : PCI, + 3H,0 ~ H,PO, -|- 3HCI. It is
a higlily acid Hvrup, is decomposed by beat, aud is a strong reducing
agent.
Orthophosphorio acid — Common, or tribasir, phogphoric acid —
Acidum phoffphoTxcum, V. S. : itr. — H,PO, — 98 — does not occur free in
nature, but is widely disseminated in combination in the phosphates, in
the Uiree kingdoms of nature.
It is prepared : (1) By converting bone phosphate, Ca,(PO,)„ into the
corresponding lead or Imrium salt, Pb (PC).)^ or Bft,{POJ,, and decom-
posiog the former by H S, or the latter by H,SO,. (2) By oxidizing P by
dilate HNO, aided by neat. The operation should be conducted with
caution and beat gradually applied by the sand-bath. It is best to use
red phosphorua This is the process directed by the U. S. and Br. Pharm.
The conueutrated acid is n. colorless, transparent, syrupy liquid ; still
contoioing H,0, which it gives off on exposure over H,SO,, leaving the
pare acid in transparent, deliquescent, prirtniatic crystalR. It ia decom-
posed by heat to form, Tinit, p^Tuphosphorio acid, then metaphosphorie
add. It ia tribosic.
If mode from arsenical phosphorus, and commercial phosphorus is usu-
ally arsenical, it ia contaminated vn.t\i arsenic acid, whose presence may
be recognized by Marsh's test (q. v.). The acid should not respond to the
indigo and ferrous sulphate testes for UNO,.
Akalvticai- Ch.ib\cter8 or the Ortbophosphateh,— (l) With ammoniacal
Bolution of silver nitrate, a yellow precipitate. (2) With solution of am-
rooniam molyhdate in HNO,, a yellow precipitate. (3) With magnesia
mixture,* a white crystalline precipitate, soluble iu acids, insoluble in am*
monium liydrato.
Pyrophosphorio aoid— H,P,0, — 178. — Wben orthophosphorie acid
(or liydro-dis)i>Iic phoHphale) is maintained at 213° (415".4 F.), two of its
molecides unite, with the loss of tbe elements of n molecide of water :
2H.PO, ^ P/> H^ I H.O. In form pyropbosphoric acid.
Metaphosphorie acid — Olaciai pho^orta acid — HPO, — 80— is
formed by beating H.PO, or H.P O, to near redness : H.PO. = HPO, +
CH,0 ; or H.P,0, - 2HP0, + H,0. It ia usually obtained from bone
phosphate; this is first converted into ammonium phosphate, which is
Ohlf
* Hade hy illsBolTtnj; 11 pt«. crTntAlllzedrnft^Minm Rh1ort<1e amlSd pts. ainmonlDm
ohlortdfl in IflO pta. trtUT, adding 7U pt& dilat« amniviiiain li/dmUt aud illttfriug aftvr
Ivo d&f &
*
It is n white, glassy, Iransparcnt itolid, odorlesB, and add in taste and
reaction. Slowly deliquescent in air, it is verj* soluble in HO, although
the solution takes place slowly, and is accompiuiied bv a peculiar crackling
sound. lu coustitutiou and basicity it resciubleB HXO,.
Actios or the I'liosmATBa os thk Bcokomt. — The nalts of ortho-
phoRphoric aciil are important conntituenta of animal tiaeues, and give
rise, wbeu taken Lutenialiy in reastmitble duties, to no untovrard symptoms.
Hie acid itself may act dclctcriously by vii-luo of its acid reaction, ifpta-
and pyro-phosphorio acids, even when taken in the form of neutral salts,
have a distinct action {tlje pyro being the more active) upon the motor
ganglia of the heart, producing diminution of the blood-pressure, and, in
comparatively small doses, death from ceasatiGU of the heart's action.
^H Compounds of Phospbonis vrith the Halogens. ^^^
^^^ Phosphorus trichloride — PCI, — 137.5 — is obtained by heating- P in
a limited Bui)ply of CI. It is a colorless liquid ; sp. gr. l.til ; bus an irii-
tating odor ; fumes in aii- ; boils at 16" (ICU" I'.). Water decomposes it
with formation of H,PO, and HCl.
PhoBphonis peataohloride — PCl^ — 208.5 — is formed when P is
burnt in *■ xcesw of CI. It in a Ht,'lit ytUow, a-yataUine solid : gives offirri-
tfltiiig futuea ; and is decuuiptvsc-d by H,0.
Phosphorus oxychloride^POCi, — 153.5 — is formed by the action
of a limited quantity of H,0 on the peutachloride : PCI, -f H,0 = POCl,
-f- 2HC1. It irt a colorless liquid ; sp. gr. 1.7 ; boUa at llO' (230" F.) ;
aud aoliditiea at -10" { + W P.).
With bromine P forms compounds similar in composition and prop-
erties to the chlorine coniiKiundH. With iodine it forms two compounds,
PI, and PI,. WiUi fluorine it forms two compounds, PP, and PF^ the
former liquid, the second gaseou&
ARSENIC.
SyvOsA = As — Atomic weight = 76 — 2folecular iceighi — 300— .Sjp.
gr. of Kolid = 5.75 ; of wpor = 10.G.4 at 860' (1580* F.)—Xame from,
Aptrtvucof ^= orpimeTit.
OccnEfua<c£. — Free in small quantity ; in combination aa arsenides of
Fe, Co, and Ni, but most abundantly in the sulphides, orjnment and
real^u', and in arsenical iron pyrites or mispickel.
Pbet.ulvtios. — (1.) By heating mispickel in clay cylinders which com-
municate with slieet iron condensing tubes.
(2.) By heating a mixture of arsenic trioxid© and charcoal ; and puri-
fying the pi-odnet by resublimation.
PBOi-iiHTiE*. — Physiaii. — A brittle, steel gray solid, having a metallic
lustiu At the ordiuary pi-essure, aud without contact of air, it volatilizes
■without fu-^ion at 180^ (251j" F.) ; under strong pressure it fu-ses at a dull
red heat Its vapor is yfillowinh, and ha.s the odor of garlic. It is insolu-
ble in H,0 and in other liijuida unlewi chemically altered.
Cht^mical. — Heated lu air it ia converted into tlie trioiide and ignites
Homewbnt below a red heat In O it bums with a briiliants bluish white
light In dry air it ia not altered, but in the presence of moisture its sur-
face becomes tarnished by oxidation. In HO it is slowly oxidized, a
It comV)ines readily with CI,
With H it only eomWnea
Wiirni, concButnited H^SO,
g>rUon of the oxide (lisaolving in the water,
r. I, and 8, and with mcwt of the metals,
when that elciuent is in the nasceut state.
is decomposed by Aa with forrantion of ISO, ; As,0, and H,0. Nitric acid
is readily decomposed, giving up its O to the formation of arsenic acid.
With hot HCl, ai-aeuic tricliloride is fonn&L Whoa fused witli potassium
hydnit«, lu-bcuic iii oxidized, U is given off. and a mixture of (wtassium ar-
aeiut« and arsenide remains, which by f^ater heat is converted into arsenic,
w^cli Tcdatilizea, and pobk>8iuiu arbeuute, which remaina
■
Compounds of Arsenic and Hydrogen.
Two are kuowu : the solid Aa.H (?), and tlie gaseous, AsH,,
Hydrogen aiBeoide — Ar^niuretted or arveneit&J hydrngcn = Jrsenui
— A-nenamine — AsH — iMecxUar loeight—lH — Sp. ^. ^^ 2.61(5.-1 — lAqite-
JUfeat -Ai)" (-40' F.).
Formation. — (1.) By the action of H,0 npon an alloy obtained by fusing
together native sulphide of antimony, 2 pta. ; cream of tartar, 2 pta ; and
srsenia trioxido, 1 pt
(2.) Bv the action of dilute HCl or H^SO upon the arsenides of Zn and
Su.
(3.) Whenever a reducible compound of arsenic is in presence of
naacent Imlrogen. {See ^L1^ah test.)
(1 ) By the action of H,0 upon the arsenides of the alkaline metals.
(5.) By the combined action of air, moi.*itnre and organic matter npon
ical pigments.
PsopEimua. — Physical. — A colorless gas : having a strong ftUiaoeoua
odor ; soluble in 5 vols, of HO, free from air.
Chemical. — ^It ia neutral in reaction. In contact with air and moisture
its H is slowly removed by oxidatiou, and elementary Aa deposited. It is
also decompot»cd into its elements by the pafi^igo through it of lumiiioua
electric dischar^'eB ; an>l when subjected to a red heat. It is not acted on
by dry O at ordinary temperatures, but a mixture of the two gases cou-
tainiug 3 vols. O and 2 vols. jVhH, explodes whca heated, forming As^O,
and H,0 ; if the proportion of O be less, elementary .4.8 is dep<tsited.
The gas burns witJi a greenish tlame, from whioh a w^hite cloud of ar-
senic trioxide arises. A cold surface held nl>ove the flame Ik-coidcs coated
witli a white, crystalline de{>osit of the oxide. If the flame be cooled by
the introduction of a cold sui-face into it the H alone is o.\idizeil and ele-
mentary As is deposited. Chlorine decomposes the gas explosively T\ith
formation of HCl and arsenic trioxide. Bromine and iodine behaie simi-
larly, but with less violence.
All oxidizing ngonts dccomi>osc it readily ; H,0 and arsenic trioxide
being formed by the leas active oxidants, and H,U and arsenic acid by the
more active. Hohil potaaaiuiu hydrate decomposes the gas partially and.
becomes coated with a dark deposit which seems to be elemeuUu'y ar-
senic. Solutions of the alkaline hydrates absorb and decompose it ; B is
given off and an alkaline nrsenite remains in the solution. t^Iany metals,
when heated in AsH., decomi>oBe it with formation of a metallic arsenide
and liberation of hydrogen. Solution of silver nitrate is reduced bv it ;
elementflrj- silver is deposite<l, and the solution contains arsenic trioxide.
Althongh H.^S and AsU. decompose each other to a great extent, with
formation of arsenic trisulphide, the latter gaa is capable of existing, to
86
HAKUAL OF CUEMISTRT.
some extent at least, m presence of the fonuer. Hence in making H,S for
use in loxicological analysis niateiials &oe from Aa mubt be used.
Coxapounda of Arsenic and Oxygen.
Two are known : A«,0, and Aa,0,.
Frobablj the gray gubatance formed by the action of moist air on ele-
mentAry arsenic is a tower oxide.
Arsenlo trioxide—Arsenious auht/dridf—WhUe arsenic — Araenic —
Anenious acid — Acidum arseitioitum, V. S.; Hr. — As,0, — 108,
pREPABATiox.— (1.) By roosting tbo native sulphides of arsenic in a cur-
rent of air. '
(2.) By burning arsenic in air or oxygen.
PsoPERTnES. — I'hijMcal. — It occurs in two distinct forme: crys/allhed or
"powdered," and vUreoit:^. \\'hen freahly fused, it Hpjxyirs in ciilorleas
or faintly yellow, ti-anaparent, vitreouB masses, having uo visible crystalline
structure. Shortly, however, these masses become opaque u\)ou thu surfoco,
and present tlie appearunco of porcelain ; this change, which is due to the
substance assuming the crystnlline form, slow^ly progresses toward the
centre of the maKS, which, however, remains vitreous for a long lime. The
change is attended by the slow libemtiou of heat, and, if it be made to take
place more rapidly, n faint lijrht is visible in obsciuity. Wlien arsenic tri-
oxide ia sublimed, if the vaixu-s be condensed upon n rool surface, it is
dejxistted in the form of brilliant octahedral crystals, which are larger oiid
more perfect the nearer the tt'mi>erature of the condensing surface ia to
ISO" {'SMi^ K). The crystalline variety may be converted into the vitreous
by keeping it fi">r some time at a tempernture near its point of volntilizalion.
The taste of arsenic trioxide is at first ftiintly sweet, aftenvard acrid,
metallic, and nauseating. It is odorless ; in aqueous solution (see below)
it has a faintlv acid i-eaction. The sp. gr, of the vitreous variety ia 3.786 ;
that of Uie rrysUtline, 3.680.
Its solubility iu water varies with the temperature, the method of
making the solution, the presence of foreign substances and tlie natm-c of
the oxide :
1 ,000 parts of cold diittillnd water, ift«r
Btaiiding 34 hours, disaolved
1,000 pftTbi of twiling wnt^r |iouri>d on
(\iu oxidv, Mild allowed tu stand for
34 hours, disHolved
l,(HlO]iartEof eriUi<rboiU>dfDroni> hour,
thtf qufltititj beiiiii kepi miifonn by
lli» atidilioii of lioiliiig wBlor fnim
time to tituf). and filtered fmm«dl-
alely, diwolved.
Traaapuvat focal,
1.74 parts.
10.13 puis.
ft4.5 parts.
Opaitaa fona.
Vmit
I CTTM,
aUlIM
1.IQ ports. I 2.0 parts.
5.4 parts.
76.0 parts.
15.0 paru.
87.0 parts
i
The vitreous vnriety is more soluble than the crysrtollino, but by prolonged
boiling the cryslidliue is converted into the vitreous, or, at all events, the
solubility of the two forms Iwoomes the same. The solution of tlie nys-
tallixed oxide in cold Hi) is always very slow (the vitreous oxide dissolves
more rapidly), and coutmues for a loug time. If white arsenic be throu'U
C0Sn*0UNI>8 OP ATlSEyTC AND OTVOKN.
^
npon coKl H,0, only n portion of it Rink<i, the remaimlar floating upon ihe
surface, notwithstoudin^JT ita high speciiic grunty. Thi» is duo to a ropul-
aioD of the H,0 from the surfaces of the cr^st^ds, which also accounts, to
some extent at leasts for its slow sohition. Even after BeTerol daya, cold
H,0 does not dissolre all the oxide with whicli it ia in contact. If one part
of oxide be digested with 80 purtu of H,0, at ordinary temperatures for
serei'al days, the resulting solution contains i\ ; with ItJO ports H,0, j\jf ;
with 240 pnrls. ,1;, ; with l.OlMJ parts H,0, ,,Va i and even when 10,000 or
100,01)1) ptirtx of HjO are used, a porttou of the oxide remains undissolved.
Arseuious oxide which had remained in contact with cold H^O iu closed
Teasels for eighteen yeai-s, dissolred to the cxtout of 1 port iu 54 of H,0,
or 18.5 parts in 1,000, which may be given as the maximum solubility of
the crystallized oxide in cold water. The power of H,0 of holding the
acid in solution, ouce it is dissolved, is not the same as its power of dia-
Bolving it. If a concentrated solution be made by boiling U,0 upon the
oxide and filtering hot, the filtrate may be evnptoratcd down to one-half its
original bulk withont depositing any of the acid, of which titis concentrated
fluid now cuotains as much as one part in sis of H^O, or lti6.6 ports per
1,000. If a hot solution of the acid bo allowed to cool, the solution will
contain 6-J.5 parts per 1,000 at 16^ ((J0".8 1-'.}, and 50 parU per 1,000 at 7''
{U\6 F.)
The solubility of the oxide in alcohol varies with the strength of the
spirit and the naiiu^ of the oxide, the vitreous variety being more soluble
in strong than in wpak alr-ohni, while the contrary is the case ynih the
cr^'stAlline, as is shown in the following table :
1 nnnf«rt>.iu-jH> AleoholU AToihnlM' AloobnliU Abtolus
i,iiuniwtsai>»iv« MiyiroMiL ISpurewnt. Mi«rwnl. kloobcd.
r^v— .111™* ««-)■** "^ '**''■) I* N" 1* *• ^ W «
xTrKMiUMUKM^ At th# tR.uiBirpaiou , 4».m «,5i a.n u.ia
TItieMi oKhfa Kt la* (3ft* P.J B.04 &.40 10. a)
The preaonco of the minenJ acids and alkalies, autmouia and ammoni-
acal saIU, alkaline carbonates, tartaric acid, and the tartrates, increases
the solubility of .irseiiic trioxide in water. It ia leas soluble in duida con-
taining fats or extractivo or other organic matters (the various liquid
articles of food), than it is in pure water.
In chfimico-Iegol cases, in which the question of the solubility of arBeuio
is likely to arise, it must not be forgotten that the rpiiintity of Aa^O, which
a person may unconsciously take in a gireu quantity of lluid ia not limited,
under certain circumstances, to that which the fluid is capable of dissolv-
ivj ; a much greater (pmutity than this may bo token while in suspcnaion
in the liquid, especially if it be mucilaginous.
CHEutcAi,. — Its solutions are acid in reaction and pro1>ably contain the
true arsenioua acid, H^AsO, ; they are ucutmlized by bases with formation
of ar»enUe9. Solutions of sodium or potassium hydrate dissolve it with foi*-
mation of the corresponding arsenite. It is readily reduced, with sepa-
Tation of As when heatml with hydrogen, cjirbon, or potassium cyanide,
and at lower temperatures by more active reducing agents. Oxidiziug
agent«, such as HNOj. the hydrates of chlorine, chromic acid, convert it into
arsenic pentoxido or arsenic acid. Its solution, acidulated with HOI and
boiled iu presence of copper, deposits on the metal a gray film composed
of an alloy of Cu and \a.
Arsenio pentoxide — Anenw anhydride — Ag^O^ — 230— is obtained
by h^Ating araenic acid to redness. It is a white, amorphous solid, which,
when exposetl to the air, slowly absorbs moisture. It is fusible at a dull
Arsenious acid ~H,AsO,— 126 — is suppoeed to exist in aqaeotu
solutions of the trioxide, although it has nut been fiepftrated. Goire-
spondiiig to it are iiunortiuit aaltfi, colled amenites, which lutve the genestl
fornjiilii- HM .AiiO,, IDI AaO^ H.M' (AsO J,.
Orthoaraeoto a.cid -Arsenic acid — H.AsO^— 142— is obtained by
oxidiziug Ae.O, with HNO, in the presence of H^O : Aii,0 + 2H,0 ■*■
2HNO, = 2H,AkO, -h NO,. A similar oxidation is abo effected bjf CI,
atjua regiu uud other oxiuanto.
A B^Tupy, culorlees, etronglT acid Boluiion is thus obtained, vhioh. at
15* (59° F.) beeoinP8 semi-solid from tho formation of transparent ciy&tals
containing 1 Aq. Theae crystttlH, nbich are vt:ry soluble and deliquescent,
lose their Aq. at 100° (212° F.) and form n white, pasty mass oomi)osed of
minute white, anhvdrous needles. At higher tempsraturefl it is oouverted
into H.As,0„ HA^„ and Aa.O .
In presence of nascent H it is decomppsed into H,0 and AsH,. It
is reducible to BL,A80, by SO,. If H,S bo passed through solutions of
arsenic acid or of an araenato, the first portions of the gas reduce tlie
arecuicid compound to the lower state of oxidation, while S separates ;
nftem-ant the arsenious acid is decomposed, with fonuation of arsenic
trisulphido.
Like phosphoric acid, arsenic acid is tribaaic ; and the arsenates re-
semble the phosphates in composition, and in many of their chemical and
physical properties.
'PyroarBenic add— H,Aa,0, — 266. — Arsenic acid when heated to
160* (3*20* F.) is converted into compact masses of pyroorsenic acid :
2H,AaO, — H.ASjO, + H^O. It is very prone to revert to orthoarsenio acid
bv taking up water.
Metarsenio add— HAsO — 124.— At 200°-206° 1392^-403' F.) Ab,0,
U.gmdually loses &,0 to form nietarseuicacid: H.As.O, =2HA80, + H,0.
It forms white, pearly ci-yatjils, which dissolve readily in H,0 wiUi regsn-
eratiou of H^O,. It is monobasic.
Compounds of Arsenic and Sulphur.
Arsenic disulphide — Red sulpkide of are/'n-tc—Hfinlgar — Red orpiment
—Ruby itulphur^Sandarach — As^S, — 214 — occurs in nature in tronsluoent,
ruby red crystals. It is also prepared by heating a mixture of As^O, and
S ; OS BO obtained it appears in brick-re<l mosses.
It is fusible, iuHolulile in 11,0, but soluble in solutions of t^e alkaline
sulphides and in boiling solution of potassium hydrate.
ARSXinCAL COMPOUNDS UPON THB ANIMAL ECONOMT.
Arsenic triBidphide—Orjiiment—AuTipigmetJlum — YeUow Kulphide
of anvnic — King's ^/om— As,8,— 24(> — fmruni in nature in hrillinnt
golden yellow Oaken. Obtained by paasing H,8 ttirough an acid solution
of A8,0. ; ur by heating a mixture of Aa oud S, or of Ab,0, and S in
equivnlc-Dt proportiona.
When formed by prpcipiifttion it is n lemon yellow powder, or in
orange yellow, cryRtalliue iiiat»e« wlien propared by mibliniatiou. Aluost
insuluble iu cold 'li,0, but sufljcientl^y sohible in bot H,0 to commnnioate
to it n distinct yellow color ; by amtiuucil boiUng with H,0 it is decom-
|K»ed into H,S and As^O,. lusoiuble in dibit* HCl ; but readily soluble
lu aolntious of tbc olk^ine hydi-atea, carbonates, and aulphideb. It vola-
tilises when Leuted. * .
Nitric arid o\idixen it, forming H,AbO, and H,SO,. A mixture of HCl
and potassium chlorate htm tlie same vffwt It correepoude in constitution
to Ajb,0,, and, like it, nifiy be regarded as an anhydride, foi*. nlthougb
•olpbanienioua arid. H^AaS,, baa not been separated, the snlplioi'senitea,
prro- and ineta-Hulphnrseiiites are well-characterized coroponnda,
Arsenic pentasulpbide — A9,S, — 310 — is said to have been formed
by fasiuf; a mixture of Aa.S. and H in proper proportioue, ns a yellow,
fuaible solid, capable of sublimation in absence of air. There exist well^
defined sulpharsenates, p}TO- and meta-sulpharsenates.
^.
Compounds of Arsenic vritii the Halogens.
I
AxBenic trifluoride — AsF, — 132. — A colorless, fuming liquid, boiling
at G3" (145'' F.). obtained by dititilliug a mixture of Aj8,0^ H/JO, and
tluorapor. It attacks glass.
Arsenic trichloride — AsCI,— 181.5. — Obtained by distilling a mix-
ture of Aa^Oj, H S(.)^ auJ NaCl, u-sin-j a well-cooled receiver.
It is a colorless hquui, boils at V.i-i' ('273'^ F.), fumes when expnsed to
the air, and voUtilizes readily at tempemlures beluw ita boiling-point. Ita
fomiAtiau must bo avoided iu processes for tbo chomico-legol detection of
arsenio, lest it be volatilized and lost It is formeil by the ot^tinn of HCH,
even when comparatively dilute, upon As,0, at the terapcratture of the
water-batli ; but, if potoasium diluntte be lulded, tlie trioxide in oxidized
to arsenic acid, and the formation of the chlonde thus prevented. Arsenio
trioxide. when fused with so«lium nitrate, is converted into tKniium arsenate,
which is not vulatilo ; if. however, small tiuantitios of chlorides bo present,
As CI, is formed. It is highly poisonous.
Arsenic Lribrotnide — As Br, — 315. — Obtained by ulding powdered
to Br, and distilling the product at 220'' (428" F.). A solid, colorlcea,
body, fuses at 2U^-2o" (G8 -77» i'.), boila at 220" (428" F.),
and is decom|K)sed by H,0.
Arsenio triiodide — Argenii ioilidum, U.S. — ^Aal, — 456. — Formed by
adding As to a solutiou of 1 iu ciu-bun diiiulpludo ; or by fusing together
As and I in proper proportions. A brick-red solid, fuaible and volatile.
Soluble in a large (pinntity of H,0. Docompoaed by aamall quantity of
H,0 into HI. Aa,0^ H,U and a residue of AsX-
Action of ATBenical Corapotmds upon the Animal Economy.
The poisonoiuj nature of many of the arsenical componnds bas been
known trom remote antiquity, and it ia probable that more muidera have
been committed b; Oxeir use than bj thnt of all olber toxic subetacces
cumbiucd. Even at the present time — notwithatontling the fact that, ena-
piciou once aroused, the detection of arsenic in the dead body ia certain
and comparatively easy — criminal arbeuical poisouing la BtiU quite com-
mon, especially in nu-nl districts.
The poison is usually taken by the mouth, but it has also been intro-
ducod by other channels ; the akin, either uninjured or abraded; the rectum,
ragina or male urethra. The furuis in which it has been taken are : (I.)
ElemetUary arsenic, vrliicli is not poisonous «o long cu it remains such ; in
contact with wator, or T^ith the snliva, however, it is converted into an
oxide, which is then dissolved, and, 1>eing capable of absorption, produces
the rliarar tens tic effects of the arsenical cofupounda Fly jiaper is coated
with a paste coutainiuj* As, a portion of wtiich has been oxidized by the
action of air and moisture. (2.) J/yiirogen arsenuie, the most actively
poisonous of the inorganic comj>ounds of arsenic, has been the cause of
several accidental deaths, amonj? others, Uiat of the chemist Gehlen, who
died in consequence of having inhaled a few bubbles of the gan while ex-
perimenting upon it In other coses death has followed the inhalation of
hvdrogen, made from zinc, or sulphuric acid contaminated with arsenic.
(S.) Arsenic trioxUie is tlie compound most frequently used by criminals.
It has been given by every channel of entrance to the circulation ; in somo
instancfis concealed with great art. in others merely held in ausjwnsion by
stirring in a transparent fluid given to an intoxicated jKirKon. If the poison
have been given in quantity, and undissolveii, it may be found in the
stomach after death in the form of eight-sitled crystals, more or less
worn by the action of the solvents with w)iich it has come in contact.
The lethal doso is variable, death having occurred fiom two and one-
lialf grains, and reooveiy having followed the taking of a dose of two
ounces. It is more active when taken fasting than wheu taken on a full
Btomuch, in which latter case all, or nearly all. the poison is frequently ex-
pelled by vomiting, before there lias been time for the absorption of more
than a small quantity. (4.) Potassium arsenite, the active substance in
" Fowler's solution," itltLougb largely used by Iho laity in nuUarial districts
as an ague-cure, has, so for as the records show, produced but one ease of
fatal poisoning. (5.) SfHiium areenita is sometimes n.sed to clean metal
vessels, a practice whose natural results are exemplilied in the deatli of an
individual who drunk beer from a pewter mug so cleaned ; and in the
serious illness of 340 children in an Kngliah institution, in which this
material hful been used for cleaning the water-boiler. (G.) Amenicacid
and flnwrmi/^jf.— The arid itself hns, so fnr a.^ we know, been directly fatal to
no one. The cases of death and iUnesa, however, which have been put to the
account of the red auiliu dyes, ai-e not duo to them directly, but tc arseni-
cal residues remaining in them as the resnlt of defective processes of
manufacture. (7.) SulphideJt (^ ariteiuc. — Poisoning by these ia generally
due to the use of orpiment, introduced into aiiiclea of food as a coloring
matter, by a combination of fraud and stupidity, in inlstjxke for turmeric.
(8. ) The anmiicai ijreens. — ^Scheele's green or eupric arsenite, and Schwein-
furth green or cnpric aceto-metarseiiite (the latter commonly known in
the United States na Piuis green, a name applied in Europe to one of the
aniline pigments). Theao snbstanoee, althuugh rarely adminiaterd vvith
murderous intent, have been the cause of death in a great number of
cases. Among suicides in the lower orders of the population in large
cities, Paris green has been the favorite.
The arsenical pigments may also produce disastrous i-esults by "acci'
PRSCAtnPIOWB ni cases of suspected POISONUrO.
ut ; ' by being iocorporated in ornainentAl pieces of confectlouerj ; by
uig used iu Uio dyeiug of textile fabrics, from which they may bo easily
bb«d off; aud by being used in the manufacture of wall-paper. Many
tftuoes of chronic or subacute arsenical poisuniug have resulted from in-
halHting rooms hung with jjuper whoue whitetj, reds, or greena were pro-
duced by arsenical pigmenta. From such pnpca* the poison in disseminated
in the atmosphere of the room in two ways : either aa on impalpable
powder, mechanicaUy detached from the paper and floating in ttie air, or,
oa Fleck has ahown, by their Jeoompoeition, and the conse<juout ditTuaiou
of volatile arsenical compounds in the air.
The trcaimerU in acute nreenical poisoning ia the Bome, whatever may
be the form in which the itoison has been taken, if it have been taken by
the mouth. Tbo £rst iudicatiou ia the removal of any unabaorbed poison
from the alimentary' canal. If vomiting have not occurred from the
effects of the toxic, it should be induced by the administration of zinc sul-
phate, or by mechanical meana. Tlie atomach-pump sliould not be use<l
less the case is seen soon after the taking of the poison. When the
mach lias beou emptied, the chemical antidote is to be odminiutered,
ith a view to the transformation iu tlio stomach of any i-emaining arseni-
cal compound into tiie insoluble, and, therefor, innocuous ferrous arsenate.
From recent exj^ericnoes. it would ueem that the prepiu-ation knciwn as
" dialyzed ii-on " is very efficacious ; failing this, ferric hydrate must bo
pored extemporaneoualy, aa when dry or not recently prepared it has
lO longer the power of (X)mbiumg with the arsenical compound. To piv-
pore this substuuoe a solution of ferric sulpluite, Lio. ferri tfrsiiipitaiis
(C. S.) — Liq. ferri j>^rsutphatis (Br.), is diluted with three rolumcs of
iter and treated with at^ua ommocirp in slight excess. The precipitate
led is coUecte<l upon a mualiu filter and washetl with water tmtil the
are nearly tastelesa The contents of the filter — t'erri oriJum
(rat»m (U. 8.), Furri jferoxidum humidum (Br.) is to be given moist in
repeated doses of one to two teaspoonfuls, tmtil an amount of the hydrate
equal to 20 times the weight of white arsenic token has been adminis-
tered.
^^ii
Hbre
cautions to be taken by tho Physician In oases of suspeoted
Poisoning.
P It will rarely happen that in a case of suspected homicidal poisoning
by arsenic, or by other poisons, tho i>hywcian iu charge will be willing or
competent to conduct the chemical analysis tipon which probobly the cou-
▼iction or acquittal of the arciised mil uuiinly depend. Upon his knowl-
edge and care, however, the success or futihty of the chemist's labors
depend in a groat mooeure,
It is, as a rule, the physician who first Buspects foul play; and, ivhile it
is ondoubtetlly hia duty to avoid any public manifestation of his suspicion,
it is just OS certainly his duty towani his patient and toward the community
to iiatisfy himself as to the truth or falsity of his suspicion by the applica-
tion of a simple test to the excreta of the i»atient during life, the result of
which may ouuble him to prevent a crime, or, failing that, take the first
Step towunl the punishment of the criminal
In a ca»e in which, fi-om the symptoms, the physician suspects poison-
ing by any substance, he should himself test the urine or fwccs, or both,
.Vid govern hia treatment aud his actions toward the patient, aud thoae
HAirUAL OF OBSMISTBT.
»
Borroun^liiig the patient, by the results of his examiDfttion. Should the
ca»e term mate fatally, he shonM at once commnnicflte his suspicious to the
prosecuting officer, and require a poBt^nortem investigation, which shoulJ,
if at ail poaeible, be conducted in the presence of the cheiuist who is to
conduct the anaijais ; for, be the phreiciau as skilled as he may he, there
are odors and appearances, obserrable in many cases nl the oix'niiif^ of the
fomly, full of meaning to the toxicological chemist, which are fphetneral,
and whose beariti({ upon the case ia not readily recognized by thooe not
thoroughly experienced.
Cases frequently arise in which it is impoBsible to hrinp the chemist
upon tJie ground in time for the autopsy ; in such caseH the physiciaii
should remember that that portion of the poison remaining In the alimEHt-
ory tract (we are 8[»eaking of true jwisous) is but the residue of the <loee
in excese of that which has been necessary to produce death ; and, if the
processes of elimination ha^-e been active, there may remain no trace of
the poison in the alimeutary canal, while it still may be delectable in
deeper-seated organs. Moreover, the finding of poison in the stomach
alone would not, at the present time, be sufficient to procure conviction
of the criminal, who might raise the question as to whetner the poison was
not iujecte<l by some iikalicioUH person into that viscuii after death.
For these roaaons it is not sufficient to send the Btomach alone for an-
alysia ; the chemist should also receive the entire intestinal canal, at least
oue-half the liver, the spleen, one or botii kidneys, a piece of muscular
tissue, the braiu, and any urine that may i*omain in the bladder, llie
inteatinal canal should be removed and sent to tlie chemist u-ithoitt having
been opened, and with Ugatm-es enclosing the contents at the two ends of
the stomach and at the lower end of the iuteutiue. The bralii and alimen-
tary caual are to bo placed in separate jars, and the other viscera in another
jar together ; the urine in a ^-ial by itself. All of these reeaelB are to be
new and clean, and are to be tjosed by new corka, or by ^ass stoppezit, or
covers (not zinc screw-capti). which are then coated nith {toi-affiue (nat
sealing- wax), and so fastened with staings and seals that it is impossible
to open the vessels without cutting the strings or breaking the seals. If
the physician fnil to obsene theae precautions, he has jii-obubly made the
breach in the evidence through which the criminal will escape, and has at
the outset defeated the aim of the analTsis.
Analyiical Characters of the Arsenical Compounds.
^
Arsenious CoinpoundB. — (1 ) HjS, a yellow color in neutral or
alkoliito h()uid8 ; a yellow ppt in acid liquids. The ppt dissolves in boIu-
tions of the alkaline hydrates, carbonates, and sulphydnitea ; but is scarcely
affected by HCl. Hot HNO, decomposes it
(2.) AgNO,. in the presence of u little NH.HO, gives a yellow ppt
This test is best applied by placing the neutral arsenical solution in a
porcelain capsule, abiding neutral solution of AgNO,, and blowing upon it
over the stopper of the NH,HO bottle, moistened with that reagent.
{3.) Cu!SO^ under the same couditious as in {'2) givee a yellowish green
ppt
(4.) A small quantity of snHd As^O, is placed in the point a of the tube.
Fig. 28 ; above it at 6, a splinter of recently ignited charcoal ; 6 is first
heated to redness, then a ; the vapor of As.O, pasbing over the hot char-
coal is reduced, and elementary As is deposited at e in a metallic ring.
ATTALTTICAt CltABACTEBS OF ARSE!nCAt COSTPOTTNDS. 93
Th* tube is then cut between 6 and c, tho larger pi«oo Iwld with d unper-
mort ud heated at c; the depotiit is TolaUUzod, the oilor of garlio ia
obaecTsd, aud bright, octahedral crystahi appear in the cool pai-t of the
tub«.
(6 ) Reinach test. — The suspected liquid is acidulated with one-sixth its
bulk of HCl ; strips of electrotype oo|^r are immoreed in the liquid,
which is boiled. In the preeence
of an arsenious compound a gray
or bluiah deposit is foruied uikid
the Cu. A similar deposit is pro-
duc<*d by other subfitances (Hi,
Sb, Hg). To complete the test
the Cu is removed, washed, and
dried between folds of filter- 5*=^
paper, without remoTing the de-
poait. The copper, with its ad-
herent film, is rolled into a c^'lin-
der, and introduced info a dry
piece of Bohemian tubinj^, about
^inch in diameter nnd six inches
long, which is held at tho tmnle
shown in Fig 2ft and heated at
the point containing the copper. If the deposit consists of nrnenio fl whitd
depout is foruied at a, which eontaius biilliaut specks, aud when examined
with a magnifier is found to consist of minute octnhcdnil crystals, Fig. 30.
The advantages of this test are : it may be nppHed in the presence of
orgranic matter, to the urine for iuatauco ; it ia easily conducted ; and its
positive results are not mislead infj^, if the text be t-urrieti to completion.
These advantages render it tho most suitable method for the physician to
use, during the life of the patient. It should not be used n/lcr death by
the phjrsician, as by it copper ia intr(Mluce<l into the substances under ex-
aininatiou, wliich may subsequently interfere seriously with the analysis.
Tlie purity of the Cu ami ilLl must be proved by a blank testing before
ttse^ Reinsoh's test is not as delicate as Marsh's, and it does not react
when the arsenic is in the liigher stage of oxidation, nor in presence of
oxitUzing agents.
(6.J Marah't tesi is based upon the formation of AsH, when a reducible
Fio. s&
FM.II.
compound of arsenic ia in presence of nascent H ; and the subsequent de-
composition of the arsenic^ gas by heat, with separation of elementary
arsenic.
The apparatus used (Fig, 31) consists of a glass flask Q; of about II
94
nXWAL OP CCTEMTSTBT.
(5 fl 3 ), throupli tlie cork of which pasa a fimnel-tub<> c, and a right aii{;l«
bulb-tube /). The latter U coDo^cUd with a tube d, filled with fragments
of ciilciam chloride ; which in turn connects with the Bohemian glass tube
gg, who«e middle third is bent into a spiral (Fig. 32), The other end of
Fio r;].
yj; is bent downward, and dips into a solution of silTor nitrate in the test-
tube _/*. Tlio coiled portion of gg, which is to be strongly heated by a
large Bunsen burner, is supported by a coarse wire gauze and enclosed in
a sheetiron chimney e.
The flask a is first charged with abont 25 gmms (6i 3 ) of pure granu-
lated rinc, which has been in contact with a diluted solution of pUtinic
chloride for half an hour and then wtujhed. The ap^uirutuH ia tlien con-
ncctcd iu such a luouuer that all joints are gas-tight^ and the fiwnel-tube
c about half filled with H,SU,, diluted with an equal bulk of H,0, and
cooled. By opening the t)tupcx>ck tlie acid is
brought in contact with the zinc in sniall
qimntities, in such ft iminuer that during the
eutire testing bubbles of gas pass throngh/.
at the rate of (i0-8(>iier ininiit*. After fif-
teen minutes the Bunsen burner is lighted
and the heating coutiuuetl, during evolution
of gas from zinc and H.SU,, for an hour, At
the end of that time, if no atain have formed
in g lieyoiid e, then zinc and acid may be
considered pure and the suspected solution, prepiured as described on
page 98, introduced slowly through the funncl-tubo.
If arsenic be present in the substance examined, a hair-broi^-n or graj
deposit is formed tn the cool part of r; beyond e ; at the some time the con-
tents of / are darkened.
To distinguish the stains produced by arsenical compounds from the
similar ones produced by tmtimony the following dilTereucea are noted :
fm. as.
ATTALTTICAT. CITARACTEIta OF ARSEjnCAT* COMPOUXBg.
TAtf Arttnieat Stain.
. — >Is fartlicr removiwl from tVie
ht«d portion of tbe tube, and. it mall
'In qa&ntitj, is double—the tnt hair-
brown, Um aeoood it^el-gray.
Hecarut. — Vulatiliwft readily when heat-
ftd in an atmoapheio of hydro^u. heitiK
depontod fartlK^r nloog in the tobe. The
cecapinff ^as hu the odor ot ^orlio.
Third, — Whi-n caiitmniilj' hc-utod in ft
carrent of oxygen, brilliant wbit« octahe-
dral cryittslfi of nrM'iiiu trioxlile are de-
posited farther oIod; in the tube.
Fmirth. — Instautly »ohible in aolulaon
of aodiitm hypochlorite.
^V/W. — Slowly di«olved by wlution of
ammotiiain lulphydratc ; more rapidly
wh«n warmed
Sixlh. — The lolation obtained in 5
Jeavea. on cTaporation over the vrat«c-bath,
a brifbt yellow resldae.
lUi. — The residue nbtaine<] in (I in
io aqua acniuoui:e, but insoluble
Ironhlorio ncid.
jhtK. — la Holuble in warm idtrlo add ;
•nlatioii on e«apnnitii>i) yieldu a white
[xeaidtie, which tanu brick-red when moUt-
I«De<t wilb Bilver nitrate nolutiou.
iV'iriM. — Ii notdLsiiolTed by a aolution
of fttannoaa chioride.
Th* AntimooitU Stain.
PirMt. — Is qnito near the heated por-
tion of tha ttibe.
iSflcowrf. — Requires a much highor toui-
peraturo for ite TolatilisBtioa -, f uiie« bofore
voIatiliuu(f. EBca|>ing %a!^ boa uu idlia-
ceons odor.
Third. — No uryetals fonnod by haalJiig
in oxygon.
Fourth — Tneiiiluble in aolntJon of no-
dium hypochlorite.
Fifth. — Diaxolvex qnldcly in solution of
ammooiom milpbydrate.
StttK—The flolQtioa obtabed in 5
laaTea.on BTaporattou over the wat«r-bath,
an orange-red reiidue.
•Sri-tiM.— The raaidue obtained in i<t
inaolubla in a<iua ammooio, but Holnbla
io hydrofibloric iictd.
Eighth. — Id itolnble in warm nitric acid ;
thn Rolution on i^vniionitioii yielda a whito
reddne, which in not colored when moiat-
eued with silver nitralu solution.
Ninth.^~\y\aK\yv» alowly iu solution ot
Bt£i>unoua chloride.
Flo. 8S.
If, however, tbe process dcscriljed on p. 98 have been followetl, there
can bti uo ouUmou^ in the liij^uid which would coutain areouic, if present.
The eilver soiution in /is tested for nrsenious acid by floAtin^ upon its
surface a layer of diluted NH,HO soluliun, which, in the preBence of
arMnic. producea a ycUow (not brown) bond at the point of juuction of tlu
two liquids.
In place of bonding the tube gg' downward, it may be bent upward
itnd drawn out at g. If the esraping gaa be then ignited, tfae heating of
the coil being discontinued, a white dejKiait of As,U, may be collected on
a glass sur^^ held ab^i^x the flame ; or a brown de^iosit of olemontar}' Ab
upon a cold, poroelaio surfaee held in the flame.
(7.) Frezeimui' and von Ii<Ana ieM. — The sulphide obtained in {1) is
dried and mixed with 12 parts of a dry mixtui'C of 3 pts. sodium carbonate
and 1 pt potu»iium cyanide, and the mixture brought into the tubo. Fig.
8S at k. The npparntua is then connected as in the figure and tilled with
CO, which is allowefl to pass through It in a eknr current from a. Tlia
tube is Lbeu heated to redness at ic, when, if arsenic bo present, a gray
deposit is formed at / ; which has the characters of the arsenical stoiu
indicated on p. i^7.
Absekio CovKiuinw. — (1.) H,3 does not form a ppt in neutral or alka-
line solutions. In acid tiolutiona it first reduces the arsenic to on
ar^nious comix>und, which is then decomposed with precipitation of tho
yellow Aa,S .
(2.) AgNO^ under the same conditions as witli the orseuious com-
pounds, protluces a brick-red ppt of silver arsenate.
(3.) CuSO, under like circumstaucea produoes a blaiafa>green ppt.
Antenio compounds behave like arsenious compounds with the tests 4,
6 and 7 for the latter.
Method of Analysis for Mineral Poisonfl.
In eaaee of suspected poisoning a systematio coui'se of analysis ia to be
followed by which the preueuce or absence of aU the more usual poisons
con be determined.
In ttw K«rrh int m1n«ml fn|«m« (wa •l^tnlilii, p. WM) the flnt atcp Is Uia ilntmrtlnm vt ermntc wMf
Ur. Tu thi< vTiil th» m«[«rliil ti> (m «umkn«ri. If ttryxM, U Utlntud with H^ : nnA if unJld ii (])v)<l«<l inU
■irudl rl«.^« Mill nutpcnJol In H^O. Aboet ■',(, th« Tn]nmf> of miiMiilnud UCI uid m, komU quuitiif ot
pouMium dUoiaW «ni aildal luid lbs niUtan heotMl ov(-r n mtuiMwtli Is a p o rwU I n cn|«a>n. i'i>liu»ititi)
oMonlc In mimII ituuitldeiv kuil. If uMnwarr, IICl, luv ^Idwl fntni Uom to Ums, irhtta Ui* mismra b
ooeuioiuilljr atlrrv] and lump* of tolld niMttv cniaJuKl wiHi » ll*tt«n(d KlMBitMl, tinUl lb« naw hu • nnl-
lOta tlKbt joUow ctiUrr. U tb« \\t^v^a iaaA\ (tronaly «f CI. CO^ U pMMd thimiet) IL Wbm tlw nlar of CI
lift* illMppraml, th« IkiHld Ik nitemi aiitl tho tvi>1<Iiil' oiuhm] with not mtcc. U « (leiXMlt fomi on hnUm
Itwllqakl is aitaln Bluml. Tlic-rlmr iklcmranj wmHliiiiuik If itrangljr ■eld, mrmpartlallp nwitfillMj wtui
■ndltilB (nrtK>ni>t«' ^ml tVMUJ w|i \\ W^ -. Ibr gmi bi-iag |>nunl tdowljr dlrutiKli Vam liifiiU for almit half.Bti'
bnar Ht % tlm^. nt lnt«rv>l< C4 4-11 h-MT*. durinit X d<i}'s ; liio vtm^l hoinf mil mrfeo'l dnriiv tho InUrraL
Tlw |]T«dt'li''l« formal, wblch cnar contain Bo,A^ Sb. il|r. Pt\ Bi «rCi>, mcinllwtod on* UMrklid wwbcd
Willi lltOciiiUirjiitt BntMlLijiMiitlljr of lltSi nnUl tTio KOAblnff* f&ll M Biro \imjtuum oIooiIImm wbea
iNtltd. ■cUulalnl with If ^(>, nnd iruttwl «iUi (ihcr iiltntc
SolBtt'in Dt •nimoniiim •iilphj^ilnt* U luldn) to Ihr |inv]|)itnh) on ttw flltar. whirh b thtsi KSitlMid
wttli wst«r. Th« •oliitlon p*«alnK thmnnh may ronialii An. Kli. RrmkICu: th<>n>Uae m the Blbcr fA)
BUf «Mil«fD Ht, Vtt. Vk uiil Ou. TtM nhukia Ii ovftpontcd over tb* WMtrr-lMiB to drrncM, and tlM rMMM
muMnMd «iUi fiitnbi«HNOM driail, iiwiIk—biI trtth Hf^ Mod (tifwl wv^Tal tlin<«, nnd ibon, *n«r nwntml-
Iwlliwi Bllfi oniatlo nda, Aiiwl irlCh ■ nfartnn ot MdUun oariwoata and nllralp. tuiUI It (a aulurliaa, nr roa-
mlM only a blainli, gmnlw dacioaM. dip hcM hHntl ■lowly Incinwari. Tho nxikd raHclon c>f funnot U
dlMolvttd In a «na11 qaanH^Mwiinn HgO, luid CCf 1* jibmmI thmntch ihn uliittnn, whrihirit be ekaror
chKidy. Tba tolatloa. tf not pariWtljr clear. I* flhored. Any dipoak rMaln«d by the lltTrr (lii may otiutn
So, Sl>er Co. TbalUtlBM U attonsly addulaiod with U^HU^, and clowly ovapontad luwl heawd, wlUi
BiMiUon u< man BJBO| It ntm fmwj, until abandaat w%Ua lUDMam ilvan oS. Hm conlod nwLdsp, wUdl
tR*y onataln An. la dlaaolvad la H,0 and intnuliiGnil into Iba Hanli apparataa wbM oold.
Tlwt rwldtia B, If bkch. h ilIwnlvM In luic KOaH oDil the njlnllun trateil for On. If It be whltf. It In
tnitad with tbe alter In a pofnrliiln<-raHb1(> ; fnixxl uith pcUtiuiiini cjanlilc; anil waahnl irlih lijO.
The ratlilo* b extracted witfa warm IICI ami (ho tirjhiiltm (--tfrl for !*n. I( any naldap remain tt U
«nr«c4<4 with UCltowhIohB fawdropaof H^iri, hK^c be#n atWInl. and tho aolaUMl MCad bw 8b.
Thr rvtdna A. aftai wa^tnit. 1« boiled wiih HNn^ 4ilulod with li,0 and flUand. Tbafilttnlc Ulaatad
bjr Cb, hi and fb. TtM raMne. U any, U lia<c«0 tar tfy aiid Fb.
Synibol = Sb {Latin, gtUnum) — Atomic uxight = 120— ifo/ccu^ir weigJtt
- 240 (?>— % gr. = &.IU—Fiae» at 450* (642° F.).
OocxsRKSOE. — Free in small quanti^ ; prmcdpally in the trUulphide.
Pbepabatioh. — The native sulphide (black or crude antimony) is roasted
and then reduced by heating with charcoal The commercial antimony so
obtained may be puriiied by fusiug a mixture of autimouy, IC pta.; native
sulphide of antimony, 1 pt ; and dry sodium carbonate, 2 pts. iVficr cool-
ing, the bntton ih jxiwdered and fused ^rith 1^ pts. aodium carbonat« and
1^ ferrouti sulphide. The antimony is again separated, powdered, and
fused with sodium carbouatti ood a small quantity uf aodium nitrate. Each
fusion is maintained for an hour.
PBopEitTus. — Physical. — A bluisb-gray, brittle solid, baTing a metallic
readily cr>*stulHzable ; tasteless and odorleas ; volatilizeu at a red
eat, and may l>e diatillcd in on atmoHpbere of U.
Chemical. — Is not altered by dry or moist air at ordinaiy temperatures.
When sufficiently heated in air it bunis with formation of Sb^O^, as a whitei
crystalline soUd. It also combines directly with CI, Br, I, S, and many
itallic elements. It combines witti H under the some circumstances as
« As. Cold, dilute H,SO, does not affect it ; the hot> concentrated
neid forms with it antimoiivl sulphate, (SbO),SO, and SO,. Hot HCl dis-
Holves it when finely divided, with evolution of H. It is readily Dxi<li::ed
by UNO,, with formation of H^SbO, or Sb,0,. Aqua regia dissolves it as
SbCL or .SbCl,. Stjlutions of the alkaline bydrates do not act on it.
I The element itself does not form aalta with the osidea. There are,
f however, coniiiounds, formed by the substitution of the group aniimonyl
I (SbO), for the basic hydrogen of those acids. (See tartar emetic.)
I u
fusion
^Ktuatre
^'lieat, a
I
Wh*
crys
■ioet
^^ nrid
Hydrogen Antlmonlde.
Antimoniuretted hydrvgen — Stibamine — Stibonia — SbH, — 123. — It has
not been obtained in a condition of purity, but is produced, mixed with H,
when a reducible compound of Sb is in presence at nascent H.
It is a oolorlees, odorless, combustible gas, subject to the some decom-
positions as AsH, ; from whicli it differs in being by no means as poisonous,
and in its action upon stiver nitrate solution. The arsenicid gas acta
npon the silver salt according to the equation : GAgNO, + AyHj + 3H,0=
tiMNO, +■ H,As0,-f 3jVg,, and the precipitate foi-med is elomentaiy silver,
vhile H^AsO, remains in the solution. In the case of SbH, the reaction is
'SAgNO + SbH,^3HK0,+ SbAg., all of the Sb being precipitated in Uie
blaick silver antimonide.
I
Compounds of Antimony and Oxygen.
Antimony trioxide — Antimonom anhydride— OTidf. of antimony —
AtUimonii orfdum {U. S. ; Itr.) — Sb O^ — 288 — ocmu*a in nature; and is
propnred artificially by decomposing the oxychloride ; or by heating 8b in
air.
MAmJAX OP OHSHISTRT,
It is im amorphous, insoluble, tasteless, mlorless powder ; white at
ordinarv temperatureR, but jellow when liented. It (uses readilv, aud ma}*
be dlBtilled iu ubseiico of oxygen. Heated Id air it biirna like tinder and
is oonverted into Sb O^.
It is reduced with sepomtioD of Sb when heated with charcoal or in H.
It ia also readily oxiiUzed by HXO, or jK^tatwium permau^^auate. It dia-
fiolvea iu HCl as SbCl, ; in NoMlwusen Bulphurio acid, from which solu-
tion briUiaut crystalline plates of antinionyl pyroeulphate, (SliO),3,0^
aeparnte ; and in Roliitions of tartarie acid and uydropotassiu tartrate (see
tartar emetic). Boiling aolutions of alkaline hjdratea convert it into anti-
nionic acid.
Antimony pentoxide^.-lnyinionic n»Ai/rfn>ff— Sb,0^ — 320— is ob-
tained by bpatinp nietiintimonic acid to dull rednesa. It is an amorjiLoua,
tasteless, odorless, pale lemon-yellow colored solid ; very sparingly aoluble
in water and in acids. At a rod heat it is decomposed into Sb,0, and O.
Antimony antimoniate — Tniermedia/e oride — Diantimonrc tetror-
ide — Sb,0 — d04 — occurs in nature, and is formed when tbe oxides or hy-
drates of Sb are stronr^ly heated, or when the lower Btagee of oxidation or
the sulphides are osiiliKed by HNO,, or by fusion with sodium nitrate. It
ia insoluble iu H,0 ; but is ilecomposed by HCl, hydropotamiu tartrate and
potash.
Antimony Acids.
The normal antimonons acid, H.SbO,, corresponding to HiIH)^ is un-
known ; bat the series of antimonic acids : ortho — H,SbO|, pyro— H,Sb^O„
and mot:i — HSbt),, i» complete, either iu the form uf suits or iu tliat of the
free acids. There also exists, in its sotlium soltj a derivative of the lacking
Butimnnoiii6 add : metaniimonou» acid, HSbO,.
Tiie compound sometimes used in medicine nnder tlie name toasted
dittphorttic antimony is potassium metantiuionate, united with an excess of
the pentoxide -. 2iiSbO„ Sb,0,. The hydropotassic p^Toantimonate,
K,H»Sb 0,.6.\q ia a valuable reagent for the sodium compounds. It is
obtained by calcining a mixture of one part of antimony with four parts
of potassium nitrate and fusing the product with its own weight of potas-
sium carbonate.
Chlorides of Antimony.
m
Antimony trichloride — ProlocJdoridff or btiUer of antimont/SbCl,
— 22(J.5— ia obtained by passing dry CI over an excess of SKS, ; by dis-
solving Sb.H, in HCl ; or by distilling mixtures, either of Sb,S, and mer-
curic chloride, or of 8b and mercurio chloride, or of nntimoDvl pyrosul-
phale and sodium chloride.
At low temperatures it is a solid, crystidUnc body ; at the ordinaiy
temperature a yellow, semi-solid mass, resembling butter ; at 73\2 (164"
F.) it fuses to a yellow, oily liquid, which boils at 223*" (433^.4 T.). Ob-
tauied by solution of Sb.S, in HCl of the usual strength it forms a dark
yellow solution, which, when concentrated to sp. gr. 1.47, constitutes the
l/iq. Anlimonii chloridi {Jlr.).
It absorbs moisture from air and is soluble in a small qunntity of H,0 ;
^ith a larger quantity it is decomposed with precipitation of a white
stn-pmoM OP ATrmfOKT.
99
powder, pwnJer of Algarotk, whoM compositiou is SbOCl if cold H,0 be
used, and Sb.OCi if the H,0 bo boiling, lii H,0 containing 15 per cent
or more HCl, SnCl, is soluble without decorapwition.
Antimony pentaoUorido — SbCI^— 2^1.5— is formed by tbe aotiou
of Ci iu excess upon Hb or hibCl, and purified by distillation in a current
of CI
II 18 ft fuming, colorless liquid, which solidifiea at —20' (—4° F), liifl
solid fuaing at —0" (21". 2 F.). It ftbi.torba moisture from air. Witb a
amiUJ nuontitj of H,0, and by evaporfttion over H,SO., it forms a hjdrate,
SbClg4H,0, which appears in tranHpiirent. deliqiieHeent cr^-stals. With
more H,0 o cryataUine oxychloride, Sb(K_"l,, is formtd ; and with a still
greater quantity, a white prei^ipitatc of ortboantimonio acid, U^SbO^.
SulpMdes of Antimony.
Antimony trisulphide — iSenquisuIphide of antimony — Black antimony
— Aniimonii stdphtdnm (f' 5.) — Antimonium nigrum (fir.) — Sb.S, — 386—
is the chief ore of antimony ; and is formed when H...S in passed througlt
a solution of tartar enielic.
The native stUphide is a ateel-^^ray, crystalline solid ; the artificial
product an oran^je red or brownish-red, aniori^liouH powder. The crutit^
antimony of commerce m iu conical loaves, prepire<l by Bimple fusion of
the native Hulphidu. It is soft, fusible, readily pulverized, and him a bright
uetallie lustre.
Ueatf-d in air it is decomposed into SO and a brown, vitreous, more
or less transparent moHS, composed of varying pro])ortious of oxide and
oxyaulphides, known as crocus, or liver, or glans of antimant/. Sb,S, ia an
anhydride, correspooding to which are saltB known as Kiitphantinionifes,
having the general formula M'^HSbS,. If an exceBs of So S^ be boiled
with a solution of potash or aodo, a liquid is obtaiued which coiitjUim an
aUtttlinc Bulphflutimouite and an excess of Sb,S,. If this solution be filtered
and decomposed by an acid while still hot, an orange-coloi"ed, amorphous
precipitnie is produced, which is the ajilivioninm gufphuraltim {C S.; Itv.)
and consi«ts of a mixture iu ^Tii-j-ing proportions of Sb,S, and Sb,0,. If,
however, the sohition be allowed to cool, a brown, voluminous, amoiphous
precipitate seijaratea, which consists of outimouy trisulphide and ti-iuxide,
potassium or sodium sulphide, and alkaline Bulpliimtimonito in varying
proportions ; and is known as Kermes mlnrral. It' now the solution from
which the Kermes h:iH been separated, be decomposed with H.SO,, a red-
disli-yellow substance separates, which is the goltlfn sulijhuret of antimony ,
and oonsistfi of a mixture of Sb„S, and Sb,S,. The precipitntfl obtaine«i
when H,S acta upon a solution of an imtimouiol compound is, accordinc to
circumstances, Sb,S, or Sb,S^ mixed with free S. By the action of HCl
on SI\H , H,S is produced.
Antimony pentasulphide. — Sb^S. — 400 — is obtained by decom-
posing an alkaline sulphantimouate by an acid. It is a dark orange-r«d,
amorj^khnu-s [towdcr, readily soluble in solutions of the olkaliefl and alkaline
sulphides, with which it forms eulphantimnnaies.
An oxysulphide, 8b,S^O., is obtained by the action of a solution of
•odium hyiHj»uIphite upon Sb CI, or tartar emetic. It is a fine, red pow-
used as a pigment, and called aniimoni/ cinnabttr orantimony vermilion.
I
or CHEiaSTBT.
Action of Antimony Compounds on the Economy.
The compounds of antimonj ore poisonous, and net with (rreater
less energy as they are more or less soluble. The compound vhidi
roast frequently the caune of antimonial poiaoning is tartar emetic (q. tJ
wbicli boB caused death in a dose of half a grain, although recovery hi
followed the ingestion of half an ounce in sevenil iiistancca Indeed, tl
obancefi of recovery seem to be better with large than with small doses,
probably owiii^ to the more rapid and complete removal of the poison by
vomiting with large doaca. Antimouials huve been sometimes crimiually
ndujinistercd in small and repeated doaee, the victim dying of cxhanstion.
In Kuch a cise an examination of the urine will reveal the cause of the
trouble.
If vomiting have not occurred in cases of acute outimonial poisoning
it should be provoked by warm water, or the stomach should be evacuated
by the pump. Tnnnin in some form (decoction of oak bark, cinchona,
nntgalls, tea) should then be given with a view to rendering any remain-
ing poison insoluble.
Medicinal autimonials are very liable to contamination with arsento.
Analytical oharaoters of Antimonial Compounds.
(1.) With H,S in acid solution, on oraugo-red ppl., soluble in NH,]
and iu hot HCL
(2.) A strip of bright copper suspended in a boiling solution of an Sb
compound, acidulated with HCI. i.s coated with a blue-gray de[>o«iL This
deposit when dried {on the cupper) and heated iu a tube open at both
ends yields a white, a morphoiut RuhMmate (see No. 5, p. 95).
(3.) Antiraouinl compounds yield a deposit by Marsh's test, similar to
that obtained nith arsenical compouuds> but difTeriug in the particulars
given above (see No. 6, p. 97).
If, in cftees of suspected poisoning, the exominatifln have been con-
ducted aa directed on p. 98 any &b present ta sejmrated during tlie fusion
with sodium nitrate and carbonate, and the subsequent solution and 6Ura-
tiou, 50 completely that As and Sb cannot be mistaken for one another.
IV.— BORON GROUP.
BORON
Svniliol — B — Atomic iceigkt =^ 11 — Molecular \ceigl\t = 22 (?) — Isolated
by Vavy m 1807.
Boron constittttea a group by iteelf ; it ie Irivalent in all of its com-
pounds ; it forms but one oxide, which is the anhydride of a triliasio acid ;
and it forms no compound with H.
It is separable in two allotropic modifications. Amorphous boron is pre-
pared by decomposition of the oxide, by beating with metallic potassium
or BOilium. It is a greenish-brown powder ; sparingly soluble in H,0 ;
iufusible and CApable of direct union with CI, Br, O, H and X.
CrystaUued borun is produced when the oxide, chloride or lluorido is re-
CARBOK.
101
duced by Al. It crystullizea in qaadratio priams ; more or lees trauB-
parent, and varying in color from a £aiut yellow to deep garuet-rcd : veiy
nwd ; "P* P*- ^'^ ^^ burns when atrongly Iieatod in O, and readily in
CI ; it also combines with N, which it is capable of remoring from XH, at
a lUgb temporatore.
Boron trioxide.
Boric or bomcic anhydride— "Bfi^ — 70— is obtained by heating lioric
acid to redness in a platinum vessel It is a transparent, glass-like mass,
osed in blowpipe analysis under the name viireoui boric acid.
Borio Aoidfi.
Orthoborio acid — Boric or boracic add — addum ftoWcwm {V, S.)—
H,BO, — 62— orcurB in nature ; and ia prq^ared by slowlr decomposing a
boiling, ooncentruted solution of borax witli an excess uf H,SO,, and al-
^lowing the acid to crvHtallizc.
It forms brilliant cryiitAlIine plates, unotnous to the touch ; odorless ;
^Blightlv hitter ; soluble iu 25 parta H,0 at 10" (50" F.) ; soluble in alco-
fboL ita aolutiuu reddeiia litmus but turns turmeric paper brown. When
jits a(|ueouii aolutiou ia distilled a portion of tkc acid passes over.
If H,IX), be heateil for some time at HO'* (176-^ K), it loses li,0 and
ia converted into metaboric acui, HBO,. If maintained at lOO** (212° F.)
lor several (hiys it loses a further quantity of H,0 and ia converted into
pyroboric acid, H,15^0,, whose sodium salt is borax.
v.— CABBON GROUP.
Cabdcin — SaiooK.
je elementa of this group are bivalent or quadrivalent. The satura-
ted oxide of each is the anhydride of a dibasic acid. They ore both com-
bustible, and each occurs in three allotropio forms.
CARBON.
Symbol— C — Atomic weight = 12-~Molacuiar toeight = 31 (?).
OocuBBE!(oB. — Free in its three allotropic forma : The diamond in
oetahedral crystals ; in alluvial sand, clay, sandstone and conglomer-
ate ; graphite, iu amorphous or imperfectly crvMbUline forms ; amorphotts,
in the different varieties of authnicitc and bituniinouB coal, jet, etc. In com-
bination it is very widely distributed iu the so-called orf^anic substances.
I'nopEBTUta. — Diamond. —The cri'stals of diamond, whieh is almost pure
carbon, are usually colorless or yellowisli, but may be blue, green, pink,
brown or black. It is the hnrdeat substance known, and the one which re-
fracts tight tlie moat sti-on^'Iy ; its imlcx of refraction ia 2.47 to 2.75. Tt is
very brittle ; a bad conductor of heAt and of electricity ; sp. gr. 3.50 to 3.65.
When very Btrongly heated in vacuo it swells up and lb converted into a
black maae reeembuug coke.
Orapiiite U a form of carbon almosi as pore as the diamond, capable
of crystolUziii;; in hexaj^oiitil piniefi ; 8p. nr. 2.2 ; dnfk gray iu cotor ;
opfMjuc ; soft enough to bo scrat^iied by the nail ; and a good couductoE
of electripitT- It in aisn known an blanl' lead or plumbago. It has been
obtained tuliiicuUIy by allouin^ molten cast-iron, troutaiuiug an excess of
carbon, to cool Btowly, and dissoKing the ii-on iu UCl.
Amorjihous carbon is met with in a great variety of forms, natural and
artiBciat. in .ill of wltirh it is black ; ap. gr. 1.6-2.0 ; more or less porous ;
and a conductor of electricity.
Anthracite coal is baixl and dense ; it docs not flame when buruisg ; ia
difficult to kindle, but giTes great heat with a suitjible drauglit. It cou-
tains KO-!K) per cent, of cjirlion. Bituminousi cool differs from anthracite
iu that, when burning, it gives ofl* gases which produce a flame. Some
.Tftriefiea oi'e quito soft, while others, such OBj'et, ore hard enough to assume
a high polish. It is usually compact in texture, and ver}" frequently con-
tains impressions of leaves and otlier parts of pliuita. It contains about
7a per cent of carbon.
Charcoal, carbo lifjni, U.S.,]a obtained by burning woody fibre with an
icsofficient »up|)ly of nir. It is Ithttle and Ronorous ; has the form of the
wood from which it was obtained, and retains all the niinei-al matter present
in the woody tisauo. Its sp. gr. ia about 1.57. It has the power of con-
densing within its pores odorous snlMtanccs and large quantities of gases ;
90 volumes of ammonia, 55 of hydrogen sulphide, 9.25 of oxygen. This
proj^erty is taken advantage of in a variety of ways. Its power of absorb-
ing odorous bodies renders it valuable as a disinfecting and lilteiing agent,
and in the prevention of putrefaction and fermentation of cei'tain liquids.
The efficacy of charcoal as a tUtering material is due also, in a great
measure, to llie oxidizing action of Uie oxygen condensed in its pores ;
indeed, if charcoal be boiled with dilute HCI, dried, and heated to redness,
the oxidizing action of tbe oxygen, whieh it thus condenses, is very ener-
getic.
Lamp'Uack is obtained by incomjilctc combustion of some resinous
or tarty substance, or natui-nl fr-ia, the smoke orsont from which it directed
into snitable i-ondcnging-chambers. It is n light, amorphous powder, and
couUiua a notnblo (quantity of oily and tori-y material, fi*oui whieh it may
bo freed by heating in a covered vessel. It is used in the manufacture of
printer's ink.
dike is the substance remaining iu gas-retorts after the distillatioD of
bituminous coal in the mjuiufacture of illuminating gns. It is a hard,
gra_>'ish subsUmce, usually ver>' poi*ous, dense, imd sonorous. Mlien iron
retorts are used, a portion of the gaseous products are decomposed by
contact with the hot iron sui-face. upon whicli there is then deposited a
layer of verj' hard, comp-ict, grayish carbon, which is a good conductor of
electricity, and fumi»hi.-4 the best material for miUiing the carbons of gal'
xivnic batteries and the points for the electric Ugbt it does not form
when gas ii* maile in clay retorts.
Animal rhircmt is obtained by calcining animal matters in closed vea-
eels. If ijrepm-od fi-om bones it is known as ft&ne-blucir, curfto anivutlin,
t". S.; if fiom ivoi-y. ironj block ; the latter is used as a pigment^ the for-
mer as a decolorizing agent. Bones yield about (tO per cent, of bone-black,
w^hich contains, besitles carbon, nitrogen and the phosphates and other
mineral aubstanL>G» of the bones. It possesses in a remarkable degree the
power of absorbing coloring matters. When its decolorizing power is lost
by satui-ation with pigmentary bodies, it may be restored, although not
com}^ete]y, by calcination. For certaiu purposes purified animal charcoa],
Lc, freed from mineral matter, ixiii>o animtUU purijicatuu, U. S., la re-
quired, and IB obtained bj extracting the commercial article with HCl and
mflluBg it thoroughly ; its decoluriziug power ia dimiuisheil by this treat-
ment Animal charcoal had the power of removing from a solution certiun
ojotalliue substances, notably the alkaloids, and a method has been sag-
gestedfor separating these bodies from organic mixtures by its use.
All forms of carbon are insoluble in any luion'n liquid.
Chemical. — AM forma of C combine with O at high temperaturea witii
light and beat. The product of the union is carbon dioxide if the supply
of air or O be sufficient ; if O be present in hmitovl quantity cjurbon mon-
oxide is fonned. The affinity of C for O reiiilers it a valuable re^lucing
agent. 3lany metallic oxides ore reduced when heated with C, and steam
is decomposed when paase<l over red-hot C : H,0 -f C = CO -f H,. At^
elevated temperattiree C aldo combines directly with 8, to form carbon
disulphide. With U carbon also combines directly under the influence of
the voltaic ara
Foil Coupomms or Carbon see paob ItiS.
SILICON.
JS^in&oI=Si — Atomt'e toeigkt = 2H — Molecular utfiV;^ = 56 (?)— jWftxnjCTvrf
by Davy 1807 — Name from «Aex=Jlint.
Also known as siiicium ; occurs in three allotropic forms : A'm<rrphou»
tilicon, formed when silicon chloride is passed over heated K or N^a, is
III dark brown powder, bea\*ier than water. When heated in air it bums
[with a bright dame to Lhu dioxide. It dissolves in potash and in hydro-
[fluoric acid, but is not attacked by other acids. Oraphiioid sUuwt is ob-
[tained by fusing potassium fiuosilicate with aluminium. It forms bexag-
[onal plates, of sp. gr. *2.4d, which do not bum when heated to whiteness in
'O, but may be oxidized at that temjjerature by a mixture of potassium
chlorate and uitrute. It dissolves slowly in alludine solutions, but not in
-«cid8. Cryiftailiud mticon, corresponding to the diamond, forms rryfitalline
rseedles, which are only attacked by a mixture of nitric and liydrolluoric
acids.
HiUcon, although closely related to C, exists in nature in but few com-
I pounds ; it bus been caused to form artificial combinations, however,
'irhiob indicate its possible capacity to exist in substances corresponding to
those comjiounds vulgarly known as organic, e.g., tiUciichtoro/orm and
tUidbromo/oriii, SiHCl, and SiHBr,.
Hydrogen Biliclde — SiH,— 32— is obtained as a colorless, insoluble,
spontaneously intUmmable gas, by passing the current of a galvanic baU
tety of twelve cells through a soluaou of common salt, using a plate of
aluminium, alloyed with silicon, as the positive electrode.
Silicon ohloiide^SiCl, — 170— a colorless, volatile liquid, having an
.irritating odor ; sp. gr. 1.52 ; boila at 59° (138*^.2 F.) ; formed when Si is
treated to redness in Ci
SLliolo oxide— SHioic anhi/dride—SilexSiO^ — 60— is the most im-
portant of the cntniwunds of silicon. It exists in nature in the different
fTarietiea of quartz, and in the rocks and sands couUiining that mineral, in
fete, camelian, flint, etc. Its purest native form is rock cryslai ; its by-
HAKUAL OF CHEMISTRY.
(Irates occur in the opal, nnd in solution in natural wat«rs. When citb-
tallizeil it is fusible n-ith difEculty ; wheu hcatod to redness nitli the alJca^
line carboDAteB it forms nittcatefi, irhich soHdif}* to glaRH-Iike niasaes on
cooliuR. It unitfls with H,0 lo fomi a numlxu* of atid hydmtea. T}ie
norma! bvilrale, H.SiO , baa not been isolated, allLough it proU'ibly exisO
in the solution obtftiiieil by a<ldiDj,'an excess of HCltoasoIotioii of sodiam
silicat*. A gelatinous hydrat*. Bohihle in water and in acids and alkalies,
is obtained by adding a small quantity of UCl to a concentrated solution
of sodium »ilicat«.
Hydrofluosilioio acid — H.SIP, — 144— is obtained in solution by
gassing the gaa disengaged by gently heating a mixture of equal parts of
uorspar and pounded glass, and 6 pts. H„SO„ through water : the dis-
engagement tubo being protected from moisture by a layer of mercuiy.
■It ie used in analysis as a test for K and Na.
VL VANADIUM GliOUP.
YaNANUII — NiOBIUlI — Taxtalvv.
TlwalaBaitaef tUiVOBp itambla UmhuI Um N gmtp, bol an bum dldlBCtlr qnadrinlent -, par.
tkakriy Kb ud liL
Tto»dhiin— T— ai,8~«tenitaiil,(iT»i«ni«iB maUl; *t> gr. = U : whldi tomw k wr1«i o< (isldM ttml^K
loUMMof M. NoMlnof T w«kaiavD, tii»M:uo(Ttudjri(VO)4MiuuBen)ttc ud *j« ued In ttw o»nii>
fMitura nf kniltriD black.
NiobmiD— Nb— '>!-■ briihi, ftMl-fm/ lavUl ; ap. gr. T.W ; which bnnw Id klr bi HbaO^ uid In CI lo
Tinalom— T»— lt d dbm H j I— mtile* Sli In ite cbemial cbancWn.
VIL MOLYBDENUM GROUP.
UoLVBnEKUU — TcNOOTei — OsMWVK.
The pndlion oT UiU grronp 1* doubtful : mid tl U pnjbKbk' that the luwcTOsltk* wfC bo foDBi) lob«t«*to
tnrfiar^itvr: la «htufa cam thHtrruuiitliODHI bi' tmiaffTrmrl tc th« thinloUM.
M«l]rb«loniuB^Mo— U6.fi -• brittle whits meal Ttao ooailo U<>U|. mo^tdK onAydrUs, ennbtOM whh
li-O lofonn anambor of adda; tlM amiooaUini MUtoIvnavf whwlt u immI m a nac«Dt tor PO,II); wnb
wfilch It turja» a ooolusaw ortd. pAotUumot^baie ocW. naad h » TMir«it tor tba alhalDiiila.
T<incatan-H'o(^>»— W— lKl.b-B laard. tiriUla idbuI; ap. p. IT.I. The oxiil.?. WU„ l-nglti: €ti)t^
drMe, U a yallaw ixrwdar. ranBLng with R_n Hvcnl Mdd hjrciraia; one of whi/^h. m^iaiiitgtlie actd, h
luad u a ttal tor tti« allMloM*. u an alan tfia ouniMala aWwImwHk! ana fiAoapAMan^aMc; aeU*. Ttwun
Inpraitnatvil wllb aurflum tunifUaU tm nrndi-md cataAaBunabla.
OaoUain— Oa— IBHJt -oocnni In n->inh!niulfin v\ih tr la Pt orw; oombnctlnlp ami readllf oxMlaad lo
Oi<>t. Thia oxtda^ tmown aa aamie itcM. formi oolorleM erjNala, aolnblo In H,U. which idva otC liiUmt^j
(iTlUUlntf vapora. U t* aied aa a rtftioiog at^sui t>r hUtologUU, and aUo Is dcoul pncttca.
I
TRON a ROUP.
105
CLASS m.— AMPHOTERIC ELEMENTS.
£e21CBSTS WB06B OxnuB Uktte wrrn Wateii, soke to fobm
OTHEBS TO rOKM AcUW. WbiCH FOBM OXYSALTS.
Basisi,
I. GOLD GROUP.
GOLD.
JSymiKrf = Au (AUHUM)— Atomic v»ight = 196,2— Molecular uieighi^
, 392.4 (?)— ^. ^. = 19.258-19.367— /u#e« at 1200' (,2192'' F.).
Tills, the oul}' member of the K'ruup, forma two series of compoucdB ;
in ODe, AuCl, it is imivaleut ; in tJtio other, AuCI,, trivalcut Its bydrate,
auric acid, Au (OH)., coiTespond? to tbe oxide Au,0,. Its oxystdtA are
nxiHtable.
It is yellow or red by reflected lisht, green by transmitted ligM,
rcddifih-purple when finely divided ; not verj' tenacious ; softer tlum sil-
Ter ; rei-y malleable and ductile. It is not acted on by H,0 or air at any
temjierature, nor by any single acid. It combines directly witli 01, Br, I,
P, ah, xVs, and U^^ It dlsHolves in nitromuriatic acid as auric chloride.
It is oiidize<l by alkalies in fusion on contact witli air.
Aurio ohlbride— Cf*/rf /ruWon</e—AuCl,— 302.7— obtained by di»-
•olving Au In aqua regia, e^-aijonitiug at 100^ (212' F.), and purifjiiig by
crysUiilization from H,0. Deliquescent yellow prisms, ver)- soluble in
11,0, alcohol and ether ; readily decomposed with Reparation of Au, by
contact with P, or with reducing agents. Its solution, treated with the
chlorides of tin, deposits a purple double Blaunato of Sn and Au, called
" purple of cassius. With nlludino chloridea it forms double chlorides,
chlorauratex {auri et sodii chtoridum, U.S.).
Analytioal Cbaractera.
(1.) With H^S, from neutral or acid solution, a blackish -brown ppt
in the cold ; insoluble in HNO, and HCl ; soluble in acjua re^a and in yel-
low NH HS.
(2.) With stannous chloride and a lititle chlorine water, a purple-red
ppt., insoluble in HCl.
(3.) With ferrons sniphnte a brown deposit, which assumes the lustre
of gold when dried and bumishexl.
n. mON GROUP.
( CnBOMiTM— Masgaxese — Ibon.
The elements of this group form two aeries of compounds : in one they
are bivalent, as in Fe'Cl, or Uu'^^ while in the otiier they are quad-
i
livalent ; but when quadnrfllent the atoms do not enter inta oombia&tioa
taa^y, but grouped two together to form a hexavalcntuuit I | I , u in
(Fe,)"C1,. (Cr,)"0,. They form several oxides ; of which the oxide MO,
is on anhydride, corresponding to which are acids and salts ; most of the
other oxides ore basic
CHROAIIUM.
Symbol = Cr — Mamie weighi ?= 62.4 — Sfol^rrular wnght — 104.8 (?> —
Sp. gr. — 6.8 — DiscovcTvd by Vmiqudin, 1707 — Name from p^puyia = color.
The element is sepftr&te<l with difficulty by reduction of its oxide "by
charcoEd, or of its chloride by sodium. It is a hard, crystalliuo, almost
infusible metal. Combines with only at a red heat ; it is not attacked
by acids, except HCl ; is readily attacked by alkalies.
Chromio Oxide ~6Vft(yuioxu/«, or green oxide of chromium — Cr,0, —
152.8— obtAiued, amorphous, by calcining a mixture of potassium dichro-
mate and starch, or, crystolliKed, by heating neutral potassium chromate
to redness in CI.
It is green ; insoluble in H,0, acids, and alkalies ; fusible with diffi-
culty, and not decomposed by heat ; not reduced by H. At a red heat in
air, it combines with alkaline hydrates and nitrates to form chmmatea. It
funna two serieH of salts, tlie terms of oiie of which are green, tliose of the
other «oleL The alkaline hydrates separate a bluish green hydrate from
solutions of the green salts, and a bluish violet hydrate from those of the
violet salta.
Chromium green, or emerald gmen, is a green hydrate, formed l)y de-
composing a donble borate of chromium and potassium by H.O. It is
used in the arts as a substitute for the arsenical greens, and is non-
poisonous.
Chromio Anhydride— J(-«/«m chromicum {U. 5.)— CrO, — 100.4— Is
formed by docompoRing a solution of potassium dichromate by excess of
H,SO, and crystallizing.
It ciysUUlizes in deliquescent crimson prisms, very soluble in H,0
and in dilute aluuhol. It is a powerful oxidant, capable of igniting strong
alcohol
The true chromic acid has not been isoUted, but salts are known
which correspond to three acid hydrates: H.CrO, = chromic acid;
H,Cr O, = dichromic acid ; and H^Or,0,„ = trichromic add.
' chlorides. — Two chlorides and one oxychlonde of cbromiam are
known. C'hromouK chloride, CrCl,, is a white solid, soluble with a blue
color in HO. Chromic chloride^ (Cr,)Cl^ forms lazge, red crj-stab, in-
soluble in H,0 wiion pure.
Sulphates. — A violet sulphate crystallizes in octahedrn, (Cr)^(SO,),
+ 15 All, and is very soluble m H,0 ; at 100^ it is converted iuto a yreen
salt, (Cr) (SO,), + 5 Aq. soluble in alcohol ; which at higher temperaturea
is converted into the red, insohible, anhydrous aaXt Chroiuic stilnhate
forms double sulphates, containing 24 Aii, with the alkaline sulphates.
(See Alums.)
H
MANOAITBSB.
107
Analytical Charaoters.
Chbomous Salts. — (1.) Potash, a brown ppt.
(2.) Ammonium hydrate, greenish white ppt
S3. ) Alkaline sulphitles, black ppt.
4.) Sodium phoaphatv, blue ppL
Chboujc iJ<s. — (1.) Poto^, ^rreen ppL; an excess of precipitant
forms a green aolaiion, from which Cr,0, 8epArat«a on boiling.
(2.) Ammonium liy'lmtf, preen iKli-gray ppt
(3.) Ammouium sulphytlmte, grccniah ppt.
CintoiiATEa — (L) H,S in acid solution, brownish color, changing to
green.
(2.) Ammonium ftutphyclrate. frreeuish ppt
(3.) Barium chloride, yellowish ppt.
(4.) Silver nitmto, browi»iah-red ppt, soluble in HNO, or NH.HO.
(6.) Lead aoetato, yellow ppt, soluble in potueb, insoluble in acetic
acid.
Actioa on the Economy.
Chrontir anhydride oxidizes oi'gonic substances, and is used as a caustic,
Tlie rJiromfd*^», especially potaiifrimn dichroraate {q. «.), ai*e irritants,
and have u diatiitctly jx>iisouous action an well. Workmen handling the
diohromate are liable to a form of chronic poisoning.
In acute chroroiuro-poisonlng, emotion and subsequently magnesium
carbonate in milk, are to be given.
MANGANESE.
St/mbol = TSn— Atomic wei^hi — 5i — Moiecuiar weighi — 108 (?) — S^.
^. = 7.138-7.206.
A hard, grayish, britUo metal ; fusible with diiGculty ; obtained by
'< ledaction of its oxides by C at a white heat It in not readily oxidized by
cold, dry air ; but is mii^erticinlly oxidized when heated. It decompoaea
H,0, hberating H ; and diHMjlven in dilute acids.
Compounds of Manganese.
Oxides. — IdanganeBe forms six oxides or compounds representing
them : Mntujanoun oxiiie, JLiO ; manganow-ifuingaiiit: oxide, Mn,U, ; wan-
ganicoxidfi, Mn,0, ; permanganic oTtrfr, MnO,, Mid permanganic anht/f/ride,
Mn,0„ aie known free. Mamjanic anhydride, MnO,, has not been iso-
lated. MnO and Mn,0, ore basic ; Mn,0, and MnO, are indiOerent oxidee ;
and MnO, and Mu,0, oro aubydrides, oorrosponding to the nianyanates and
permon^naleti.
pEauuNOAXio Oxide. — ifanr/aws^ dioxide, or black oxide — Mangani ojci-
dtim nigrum (U, S.) — JUmutoneaii v.r. nig. {^r.)—MnO,~86— exists in
nature ha pyrolnnilf, tlie pi-incipal ore of manganese, in steel gray or
bruniiiah-bhick, imperfectly cr^-Btalline masses.
MANUAL OF CHEMISTRf.
At ft red heat it loses 12 per cent, of O : 3MuO, = Mn,0. + O, ; and at
a white heat a further quantity of O is given ofT: 2Mn,0. = GSluO + 0^
Heated with H,SO, it gives ofl" O and fonns manganona sulphate : 2MnO.
+ 2H SO. = 2M11SO. + 2H,0 + O,. With HCl it vields raanganoufl chlo-
ride, HO and CI : UaO, + 41iCl - MnCL + 2H.0'+ CL. It is not acted
oa bv lL\0,. •» — . ^
Chlorides. — Two chlnridea of Mn are known : manganou* chhride,
HnCl^ a pink, deliqiicsc^eut, Boluble salt, oc<nirring, mixed with ferric
chloride, in tlie waste liquid of the preperatiou uf Ci ; and manganic cftloride.
Salts of Mangraiiese.
Manganaee formfi two series of salts : Mcmganoug salts, ooutaining Mu";
and numtfonui mlU, contiiininp (MnJ" ; the former are colorless or pink,
and soluble in water ; the lutter are unstable.
Manoaxocs Scu'Kate, — Mangaui mdphaa (U. S.) — MnSO,+ nAq — 160
-hnl8— IB rornievl by the acUon of H H<), on MnO,. lielow 6* (42*.8 F.) it
crystallizes with 7 Aq. and is isooioriihouH with ferrous sulphate ; between
T'-flO" (44^6-68^ F.) it forms crj-stols with 5 Aq, and is isoniorpbous with
capric sulphate ; between 20''-30 ' (fiS^-Sfi" F.) it crystallizes with 4 At).
It is rose-colored, darker as Uie pn)})i>rtiou of Ao iucnfases, scduUe in
HO, intuduble in alcohol With the alkaline sulpuateii it forms double
salts, with ti Aq.
Analytloal Characters.
M-uJOAKOUf). — (1.) Potaah, white ppt., turning brown.
(2.) AlkaUne carbonateti, white pptji.
(3.1
*
Ammouium sulphydrate. lletdi-eolored ppt, soluble in aeicls, spar*
ingly Bohible in excess of precipitant,
(■4.) Potassium ferrocyonide, faintly reddish wliite ppt, in neutral solu-
tiou ; soluble iu HCl.
(6.) Potassium cyanide, roso-colored ppt, forming brown solutioa with
esceas.
MxsaAina — (1.) H,S, ppt of sulplmr.
t Ammonium sulphydratc, flesh-colored ppL
Potassium ferrocyanide, greenieh ppt
Potassium fen-icyanide, brown ppt.
Potassium cj-anidc, Ught brown ppt.
jaANATEs — are green sidia, whose solutinns are only stable in pres-
ence of excess of alkali, aud turn brown wLeu diluted aiii.1 iioiduliited.
PERM.woANATEs^form Tod Bolutjons, which are decolorized by SO^, other
reducing agents, and many organic substances.
moN.
Symbol ~Te (PBRRUM)— .^/omwj M«'y?i( = 55.0— Jfo/coiZor wtt^
= 111.8 ?— .9p. ^. = 7.25-7.9 Fustx at 1600° (1912° ¥.)—Nmie front Out
Saxon, ireu.
OocCBiiKSCE. — Free in small quantity only in platinum ores and me-
teoritea As Fo,0, in rc-ii htvmafif.e and tpecular iron ; as hytb-ates of
Fe,0, in brown hcurnalite and oolitic iron ; as Fe,0, in nmgnetic iron ; as
4
COMPOUNDS OF IHON. ^^^^ 109
*
FeCO, in spathic irnn, c/oy ironstone and hog nra ; and as FeS, in pvritee.
It is also a constituent of most soils and clajs, exists iu many nuuerol
vmteza, and in the red blond pigment of animals.
PBLKPARAnus. — In working the ores, re<luriion is 6r«t effected in a blast-
wnwioc. into which eitcnmate layers of ore, coal, and limestone are fed
im the top, wliile air in forced in from below. In the lower part of the
famsce CO^ is produced at the expense of the coal ; liigfher up it is r&-
dnoed by the iucandesceut fuel to CO, which at a still higher point reduces
the ore ; the fused metal so libei-atcd collects at the lowest point uu<ler a
layer of kIivi, and is drawn off to be cast as pi^ iron. This product is then
purified by biuiung out impurities, in tlie process known as puddling.
Pure iron is prepared by reduction of ferrous chloride or -of lerrio
oxide by H at a temperature approacliing ix^duoss.
Vawktiks. — Cost iron is a brittle, white or grar, crystalline metal, con-
sisting of Fe 89-90;* ; C 1-4. 5:^ ; and Si, P, S, aiid Mn. As pig iron, it
is the product of the blost-fumace.
li'roughi or bar iron is a fibrous, tough metal, freed in part from the
impurities of cast iron by refining and puddling.
Sted is Fe combined' with a quantity of C less than that existing in
cut, and greater than that in l^ iron. It is prepared by cementation ;
vhicb consists in causing bar iron to combine with C ; or by the Ilfissemer
method ; which, as now used, fionsists in burning the C out of molten cast
iron, to which the proper proportion of C is then added in the shape of
epiegel cinen, an iron rich in Mu and 0.
The purest forms of commercial iron are those nsed in piano-strings,
the teeth of carding machines, and electro-magnets ; known as jutft iron.
Reduf.'Cfl inm — Ferrnm rfffurtuvi (U. S.) — Fcr. r*ulactnm (J?r.)— ia Fe,
more or less mixed w-itb Fe iL), and Fe,0,, obtained by heating Fe,0, in H.
PnopETiTiEs, — J'h\j!n*al. — ^Pui'o iron is silver-white ; quite soft ; crystal-
lizes in cubes or octaliedra. Wrought iron ia gray, luuxl; very tenacious;
■rous; quite malleable and ductile; capable of being welded ; highly
agnetic but only temporarily so. Steel is gray ; very hard and brittle if
tempered^ soft and tenacious if not ; prrnianently magnetic.
Chemical. — Iron is not oltei'ed by drj- air at the ordinary temperature.
At a red heat it is oxidized. Iu damp air it is converted into a hydrate ;
iron ruit. Tinplate is sheet iron, coated with tin ; galvanized iron is coated
with zinc, to preserro it from the action of damp air.
Iron unites directly with CI, Br, I, S, N, P, As, and Sb. It disaolrea in
HCl as ferrous chloride, while H is lilwmted. Heated with strong H,SO,,
it gives off SO, ; with dilute H,SO,, H is given off and ferrous sulphate
formed. Dilute HNO, dissolves Fe, but the conccntj-ated acid renders it
ssicc, wheu it is not dissolved by cither concoutrated or dilute HNO„
til the passive condition is destroyed by contact with Pt, Ag or Cu, or
liy beating to 40' (104* F.).
Compounda of Iron.
Oxides.— Three oxides of iron esist free : FeO ; Fo,0, ; Fe O,.
FERBors OxvDE— Protoxide of iron — FeO — 71.9 — is formed by beating
Fe,0. in CO or CO,.
FzBBic Oxide — Sesmtioxide- or peroxide of iron — Colcothar—Jew^^B
rouge — Venetian reti — Pe,0,^ — 159.8 — occurs in nature (see above); and ia
formed when ferrous sulphate is strongly heated, as in the manu&u:ture of
110
jijTosiili>lnirir aoid. It U a rwldish, amorphous solid, is a weak base, and
iH (lecumpQsed at a white heat into O and l''6,0,.
MjtaxKTto OuD£ — Black oxide — Ihri oxidum magnetirum {fir.) — Pe,0,
—231.7 — is the naiural iMdvtone, and ia fonued by the action of wr or
Rteftm upon iron at high temperatures. It ia probably a compound of
ferroua arid ferric oxides (FeO, Fe,0,), as acids produce with it mixtures
of ferrouii and ferric salta.
Hydrates. — FEnRors. — Wlicn a solution of a ferrous suit is decom-
posed by an alkalins hydrate, a greenish white liydrate, FoH,0,, is de-
posited ; which rapidly abaorlw O from the air, with formation of ferric
hydrate.
FmRic. — When an olfcali is added to a solution of a ferric salt, a brown,
gelatinous precipitate is formed, wliirh is the normal f err ir hytiralf, (Fe),
H,0, = Ferri peroxidum hiftiralum {U. S.) ; Fer. jicrox. humidum (Br.).
It is not formed in the presence of fixed organic acids, or of sugar in suiB-
cient qunutity. If preaerred under H,0 it is portly oxidized, forming an
oxyhydrate which is incapable of forming ferrous arsenate with As^O,.
If the hydrate (Fe,)H.O be dried at 100" (212« F.). it Imbs 2H,0,
and is converted into (Fe,)Oy ^fiv which is iha £hri peroxidam hydrtttum
(■Br).
If the normal hydrate be dried in vacuo it is oonTortod into (Fo ,),H^O^
and this, when boiled for some houni with H,0, is converted into Uie ctilr
loid, or miHliJird hi/tirate (FeJH O, (?), which is brick-red in color ; almost
insoluble in HNO, and HCl ; CTves no Prussian blue reaction, and forms a
turbid solution with acetic acid. If recently precipitated ferric hydrate be
dissolved in solution of ferric chloride or acetate, and aubjected to dtalyuis,
almost all the acid pasnes out, leaving in the dialyzer a dark-red soluUon,
which probably contains this colloid hydrate, and which is instantly coag-
olatcd by a trace of H,SO,, by alkalies, many salh^ and by beat {dial\fKd
iron).
Febric Arm— H,Fe,0.— Neither the free acid nor the oxide, FeO,. are
known in the free state ; the/ernite^, however, of Na, E, Bo, Sr, and Oi are
known.
Sulphides. — FEBBoraSnuHmE— /Ve^osMfpAttfoq/'iron. — PeS — 87.9— is
formed :
(1) By he^iting a mixture of finely divided Fe and S to reducsa;
(2) by pressing roll sulphur on white hot iron ; (3) in a hydrated eondi-
uon, Fe8, H,0, by treating a solution of a ferroua salt with an alkaline
sulphydrate.
The dry sulphide ia a brownish, brittle, magnetic solid ; insoluble in
H,0. soluble in acids with ovolutioii of H,S. Tlie hydrate is a black i>ow-
der, which alwwrbs O from the air, turning yellow, by formation of Fe^O,.
and libGrntion of S. It occura in tito foeces of persona taking ulmlybeate
waters or preparations of iiou.
Ferric Sulpiode — Sfsqmsuiphid.e — Fe,S, — 207.8 — oecnrs in natuj^ in
copper pijrih's and ia formed when the disulplitde is heated to redness.
Ferbio Disui-pinDE — FeS, — 119.9 — occurs in the white and ifdloxc Mar-
tial ptfrites used in the manu^ture of H.SO.. When heated in air it is
deoomposed into SO, and mnffurtic pitritfs: aFeS, 4- 20, — Fe,S, 4-2SO,.
Chlorides. — Fkrroi-s Cmi^^iTtw—PnAochhridf. — PeCi — 129.9 — is pro-
duced : (1) by passing drv HCl over red hot Fe ; (2i by heating ferrin
chloride in H ; (3) as a hydrate. FeCl,, 4H,0. by disaolving Fe in HCl.
The anhyiii'oua compound is a yellow, cryjitalliTie, volatile, and very solu-
ble aolid ; the liydrated is in greenish, oblique rhombic prisnis, deliquefi-
SALTS OF IBOW.
oent anrl rerr aohible in H,0 and alcohoL VTheu heated in air it is con-
veried into ferric cliloride and an osycLloride.
Fkbhio CuimiiDE—&ifquUhlw-ide—Pervhi(iiride~Fcrrichhridum {U. S.)
— ^Pe CI.— 3*24.8— is produced in the anhTdroua form by beating Fe in
CI Aa a hydrate, Fe,CI,,4H,0 or Ke,Cl,6H^O ; it is formed : (1) by bo-
lutiou of the niihytlroua conipoimd ; (2) by aiseolvinp Fe in aqua refjia ;
(3) by dissolTing ferric hydrate in HCH ; (4) by the acUou of CI orof HNO,
on solution of ferrous eldoride. Jt ia by the kst method that the pharma-
ceutical product ia obtained.
The anhydrous con)]>ound forms roddish-Tiolet, crystalline platea, very
deliqaescent. The hydrates form yellow, nodtdar, imperfectly crTStalUne
mannrn, or rhombic plates, very soluble in HO, soluble in alcohol and
ether. In solution it ia converted into FeCl, by redueinp affeuts. The
Li^./tTT-i chlvridi {V. S.) rz Lvf. fer. ptrchloridi {Hr.) is an atfueous solu-
tion of this compound, containing excem of acid. The Tiiicl. fer. cMor. ( U.
S.) and Tmrt. JW. jMn-chl. {Hr.) are the solution diluted with alcohol ; and
contain ethyl chloride and ferroua chloride.
Bromides. — Fcaaoos Bbouide — FeBr — 21o.9 — ia formed by the ac-
tion of Br on excess of Fc in presence of H,0.
'Wtaaac Bbomidb — Fe,Br, — 591.8— is prepared by the action of excess of
Br on Fa
Iodides.— FERROC8lomDB—/'errtiorftV/Mm (6'. .% ; /?r.)—FeI,— 309.9—
is obtained, with 411,0, by the action of I upon exceaa of Fe in the pre-
sence of warm H/X When anhydrous, it is a white powder ; hydiated, it
is in green cr>-fita]8. In air it is rapidly decomposed, more eionly in the
presence of Bugnr.
Fekbic Iopide— Fe,I, — B73,8 — is formed by the acUon of excess of I
on Fe.
Salts of Iron.
Sulphates. — FEnaora Scjuiute — Protomilphate — Green vitriol — Cop-
pgrag—Ftfrri sulj,hm [U.S.; Wr.)— FeSO. +7 Aq— 1G1.9 + 12G— ia
formed: (1) bv oxidation of the sulphide, Fe^S^ formed in tbo manu<
factnre of H,SO, ; (2) by diasoh-iug Fe in dilute H,SO,.
It forms green, etilorescent, oblique rhombic prisms, quite soluble in
H,0, insoluble in alcohol It loses 6 Aq at ICtll^ (212° F.) {Ferr. mlph,
exiruxvius V. S.y. and the hut Aq at about 300° (572° F.). At a r«d heat
it is decomposed into Fe^O^, SO and SO,. By ex|K>8ure to air it ia grad-
nallT converted into a basic feme siUphate, iFe,)(S0,),,5Fe,0,.
Frrbic Sclphateb aic quit« numerous, and are formed by oxidation of
jlerrous sulphate imder dijfl'ei-ent condiliona The normal (sulphate, (Fc,)
||S0,),, ia formed by treating solution of FeSO with HNO,, and evaporat-
ling, after addition of one molecule of H,SO^ fi>r each two molecules of
'FeSO,. The Liq.fer. terMtlphatU (U. S.) contains this salt It is a yel-
lowish-white, amorphous solid.
Of the many ba-vin ferri<: tfiilphiUes, the only one of medical interest is
Jf^otiseri! nail, 5(Fe,)(30,), -t- 4Fe,0,, which exists in the Li(^. ferri aubaul-
phaliJt (U. fi) and Litifrr. pt^muiftiiaii^ {fir.). Its solution is decolorized,
and forms a white deposit witli excess of U.S0,.
Nitratea— FcanoLM NrriuTK — Fe(NOj,— 179.0 — a greenish, unstable
salt, fonned by double decompotiitiou between bariimi uitaitti and ferrous
flulpbate ; or by the action of HNO, on FcS.
FsBBic Nn-RATSB. — The norntal niira^tf— (Fe,)(NOJ,— 153.8— ia ob-
I
tuDecl in aolutlon by disBoIving Fe in HNO, of «p. gr. 1.115 ; or by dis-
solving ferric hjdmte in HNO,. It therefor exists in the Liq.frrri rtUmtis
{U. &). It crj-stallizes in rhombic prisms with 18 Aq, or in cubes with
12 Aq.
Sfsrcral basic nitrates are known, all of whieli ore unorrstallizftble. and
by their presence (as when Fe is dissolved in HNO, to saturatiouj prerent
the crystallization of the normal salt
Phosphates. — TBira»i»ocs PnosPHATE—Pe,(PO,),— 357.7. — A white
precipitAt«, formed by adding disodic phosphate to a solution of a ferrous
salt, in presence of sodium acetate. By exposure to air it turns blue ; a
part being cooTertotl into ferric phosphate. The ferri phoi*phas {Ifr.), is
such a mixture of the two salts. It is insoluble in U,0 ; sparingly solu-
ble in HjO containing cartwnic or acetic acid.
It is probably tlua phosphate, capable of turning blue, which some-
times occurs in tho luugs in phthisis, in blue pus, and iu long-buried
bones.
Fbbbic Phosphate — {FeJ(PO,), — 301.8 — is produced by the action of
an alkaline phosphate on fenic chloride. It is soluble iu HCl, HNO,,
citric and tartaric acids, iusolublo in phosphoric acid and in solution of
hydroaodic phosphate. The ferri p/iiufphaii {C S.) is a compound, or mixt-
ure of this salt with disodio citrate, which is soluble iu water.
There exist quit« a number of basic forric phosphates.
Fbkric Pyrophosphate— (Fe,),(P,0,), — 745.6 — is precipitated by d&-
compositioD of a solution of a ferric compound by aodinm pTrophoAphate ;
an excess of the Nii salt dissolves the precipitate when wanueil, and, on evap-
oration, leaves scales of a double salt, (Fe.) (P,0,)„ Na,(P,0,), -h 20 Aq.
The ferri pyrophosphoK (6'. S.) is proljably a mixture, or compound (?)
of ferric pyrophoBphate, trisodic citrate, and ferric citrate.
Acetates. — Feki:ol;!1 Acct-vte — ^Fe(C H,0,), — 173.9— is formed, by de-
composition of ferrous sulphate by c^cium acetate, iu soluble, silky
needles.
FEBRrc AcBTATEs. — The normal salt, (FeJ(C,H,0,),, is obtained by
adding slight excess of ferric sulphate to load ncctato, and dccontiug aft^
twenty-foui* hours. It is dai'k red, uncrysfAllizable, very soluble in alco-
hol and in H^O. If its solution be heated it darkens suddenly, gives off
acetic acid, and contains a basic acetate ; when boiled it loses all its acetic
acid au<i deposits feme hydrate ; when heated in closed vessels to 100^
(212'' F. ), and treated wi^ a trace of mineral acid, it deposits the modified
ferric hydrate.
Ferrous Carbonate — FeCO — 115.9 — occurs as an ore of iron, and is
obtainftd in a hydntt^d form by adding an alkaline carbonate to a ferrona
8ftU. It is a grecuidh. amorphous powder, which, on exposui-e to air, turns
red by formation of ferric hydrat^c ; a change which is retarded by the pres-
ence of sugar, hence the addition of that substance in the ferri carbonat
saccharaias ( C. S. ; Br.). It is iusoluble in pure H,0, but twjluble in H,0
contaiuiug carbolic acid, probably as ferroui hicarbon^e, H^e(CO,)^ in
which form it occurs in chalybeate waters.
Ferrous Lactate— Fflrri lartm ( V. .S^)— Pe(0,HpJ^-f 3 Aq— 233.9 +
54 — is formed when iron fiUngs are dissolved iu lactic acid. It crystAllizea
iu greenish-yellow ueodks ; soluble in H,0 \ iusoluble iu alcohol ; penniir
nent in air when dry.
Ferrous Oxalate— /J-rri oxdas {V. S.)— PeC,0, -f- Aq— 143,9 -I-
36— is a yellow, cr)-»tulline powder ; sparingly soluble in H,0 ; formed by
dissolving iron IJliugs iu solution of oxalic acid.
Tartrates.— FERRorfl Tabtratb— PeC,H O, + 2 Aq— 203.9 + 36.—
A wbile, crTatalliiie powder ; formed b^ dissolviijg Fe in hot concen-
trated eolation of tartaric acid.
Ferric Tartrate— Fe,(C,H,0,), + 3 Aq— 555.8 + 54.— A dirty yel-
low, amorphous mass, obtained by dissolving recently precipitated ferric
liydmtc in tartaric ncid aolution, and evajwrating below 50° (122*' F.)-
A nnmber of double tartrates, containing the group (Fe,0,)" aro also
known. Such are : Ferrico-ammojiic tarirate =fen'i et ammonii tartrott
(C &), (C,H.Oj,(Fe,0,), (NH.) -f 4 Aq, and FcTrico-potamc tartrate =
ferri et potoiuni tartras (U. 5.).iC.H^0 ),(Fo,0,)K,. They nrc prepared by
disBolTing recently precipitated feme hydrate in hot Bohitions of the hy-
droMdliahne tartrate. They only react with ferto- and Bulphocyanides
after addition of a miuerul acid.
Citrates.— Febbjc CmiATE— /Wrt cilras (U. &)— (Pe,}(C,H^O,), +
Aq — 181^.8 H- 108 — is in gamet-colore*] scalea, obtained hy dissolving fer-
ric brdrate in solution of citric acid and evaporating the solution at about
G0'J140^ F.). It losea 3 A(j at 120^ (248" F), and the remainder at ISO'*
(302*' F.). if a small quantity of ammonia be atlded before the evapora-
tion, the product consists of the mod\jiM citrate z=. ferri et ammonii ciiras
{U. S.\ which only reacts with potoHsium ferrocyanide after addition of
HCL
The Tftrions citrates of iron and alkaloids are not definite conipounda.
Perrlo Ferrocyanide— /V»A-fflflji ^>fu^— (Fe,),(FeC.N,), + 18 Aq—
859.3 + 324 — iti a dnrk blue precipitate, formed when j>otasaiuin ferrocy-
anide is added to a ferric salt It ia insoluble in H,0, alcohol and dilute
adds ; soluble in oxalic acid solution (blue ink). Alknlifis turn it brown.
Ferrous Feirioyanide— T^imbH/fj* Wu^ — Fe,(Fe C„Nj,) + nAq —
691.5 + n 18 — is a dark-blue substance produced by the action of potiis-
siura ferricyauide on ferrous salta. Heated in air it is converted into
Prussian blue and ferric oxide.
Analytical CharaoteTs.
PcRiotrs. — Are acid ; colorless when anhydrous ; pale green when by-
drated ; oxidized by air to basic ferric coiu})ouuds.
{ 1.) Potash : greenish-white ppt ; insoluble in excess ; changing to green
or brown in air.
(2.) Ammonium h^-drate : greenish ppt; soluble in excess ; not forlned
in presence of luumouiacal salts.
(3.) Ammonium sulphydrate : black ppt.; insoluble in excess ; soluble
in acitls.
(4.) Potassium ferrocyanide (in absence of ferric salts) : white ppt;
turning blue in air.
(5.) Potassium forricyanide : blue ppt; soluble in KHO ; insoluble in
HQ.
Ferric — Are acid, and yellow or hrown.
(1.) Potaab or ammonium hydrate : voluQiinouB, redbrown ppt; insol-
uble in excess.
(2.) Hydrogen sulphide : in acid solution ; milky ppt of Bulphnr ;
ferric reduced to ferrous compound.
(3. ) Ammonium bulpbydrate : block ppt ; insoluble in excess ; soluble
in acids.
lUXVAL 07 CnfUtSTRT.
(44 Pofasaium ferrocvanide : dork-blue ppt ; insolnble inHCH ; soluble
inEHO.
(5.) PotosBium Bnlphocyanate : dork red color ; prcrented bj tariaricor
citric acid ; discharged by mercuric chloridfl.
(6.) Tannin : blue-black color.
m. ALTJMINItJM GROUP.
GLOcnauM — Aunaxwu — SoAXDaii — Qaluuv — Ixnrou.
I
Ttus group ia placed in the third class by virtue of the existence of
the alumiiiates, and of the relattoua between the compounds of these ele-
mentH and some of those of the previous group. They form, however,
but one series of compounds, corresponding to the ferric, containing the
group (M,)''. No acids or salts of the mombers of tlie group, other than
aluminium, are kuowii ; jet their resemblances in other points are euch as
to forbid their separation.
GLUCDnUM.
Symbol = Gl or Be {BeryUium)— Atomic vteighi = 9—^. gr. = ZL
A »nt •temrat neenrrtw la Uw WMnU and tMrjl TIm maUl i«MnaliU> Unntatun aoA Itt eoO'
iamnrtarMHDbIattiaMotAI.uA, la ■omorMitwU.UMM at kg. lu Mlntik mIU an nraet la tMtotTAacv
ALUMINIUM.
Symbol = Al — Alomic weight = 21^Molecular iceiykt = 65 (?) — fp. gr.
~ 2.5G-2.67— /•WW* at about 700° (1202" F.)-Namc from alumea = alum
—Discovered by Wiihler, 1827.
OccTRHEvct— ExceedtDgly abundant in the clays aa silicate.
pREPui\Tiojr. — (1.) By deoompostng vapor of aluminium chloride by Na
or K (Wohler).
(2.) Aluminium hydrate, mixed with sodium chloride and charcoal, ia
heated in CI, by which a doable chloride of Na and Al (^2NaCl Al^ClJ ia
formed. This is then boated with Na, when Al and NaCl are pr(xluced.
(The industrial process.)
PaopEBTiEiJ. — Phf/sical. — A bluish-white metal ; hard; quite malleable
and ductile when annealed from time to time ; slightly magnetic ; a good
oondnotor of electricity ; non-ToIatile ; rery hght, and' exceedingly sonor-
oos.
Chemical. — It ia not affected by air or O, except at very high tem-
peratures, and then only RiipeiUciAlly ; if, howerer, it contain Hi, it banis
readily in air, forming aluminium silicate. It does not decompose H,0 at
a red heat ; but in cunluct with Cu, Ft, or I it does so at 100 (212^ F.).
It combines directly with Bo, Si, CI, Br, and L It is attackol by HCI,
gfuieoua or in Bohition, with evolution of H, and formation of Al,Cl,. It
disBolves in alkaline solutions, with formation of aluminates, and li)>ei'ation
of U. It alloys with Cu to form a golden yellow metal (aluminium bronze).
SALTS OP ALUJaKITTM.
115
Compounds of Aluminiiun.
Aluminiiuu Oxide— Aiumim — A1,0, — 102— oocxu-s in nature, nearly
pure, AS corundum, emery, ruby, sapphire, and ttrjtaz ; and U formed arti*
fidaDy by calcining the hydrate, or ammonia alum, at a reil beat.
It is a light, wliite, odorless, InsteJesa powder ; fuees with, difficulty ;
and, ou cooling, solidifies in very hard crvstals. Unices it have been
heated to bright redness, it combines witli"H,0, with elevation of tem-
perature. It is almost insoluble in ncidK ftml alkalies. H,SO,, diluted with
ui equal bulk of H^O, dissolvex it slowly aw (Al,)(HO J,, I'^isod potash and
soda combine with it to form alumloates. It is not reduced bv charcoaL
Aliiminiuro Hydrate — Aluminii hydraft {U. 5.)— A1,H/0, — ISti— is
formed when a solution of an aluminium salt is decomposed by an alkali,
or alkaline carbouitte. It constitutes a gelatinous mass, which, when
rtried, leaves on amorphous, translucid mass ; and when pulverized a wliite,
tasteless, amorphous powder. AVhen the liquid in which it is formed con-
tains coloring matters, these are carried down with it, and the dried de-
poeitA are used ns pigments, called taken.
When fresldy precipitated, it is insoluble in H,0 ; soluble in acids and
solutions of the fixed alkalies. When dried at a temperature above 50"
(122* F. 1, or after 2-4 hours contact with the mother liquor, its solubihty is
greatly diminished. With acids it forms salts of aluminium ; and with
alkalies, alumiuntes of the alkaline metal. Heated to near redness it is
decomposed into A1,0, and H,0. A soluble mollification is obtained by
dulyaing a solution of AljH,0, in Al^CI,, or by heating a dilute solution
of aluminium acetate for 24U hours.
tated aluminium hydrate in potash solution. It forms white crystals
Tery soluble in H^O, insoluble in alcohol ; caustic and alkaline. By a large
quantity of UJ3 it is decomposed into aluminium hydrate and a more
aUudine salt, K,A1.0..
Sodium Ai.trMnjATi. — The aluminate Na Al O, is not known. That hav-
ing the composition Na^^O, is prepared by heating to redness a mixture
of 1 pt sodium carbonate and 2 pts. of a native ferrugirions aluminium
hydrate fbeauxite). It is insoluble in H,0. and is decomposed by carbonic
amd, with precipitation of aluminium hyrlrate.
Aturmniuni Chloride— Al.Cl, — 267 — is prepared by posaLng CI over
a mixture of A1,0, and C, heated to redness ; or by heating clay in a mix-
ture of gaseous HCl and vapor of CS,.
It cr^-Btallizes in colorless, liexogonal prisms ; fusible ; Tolatile ; dell-
quoBcent ; ver%' soluble in H,0 and in olcolioL From a hot, concentrated
aolntion, it separates in prisms Mnth 12 Aq.
The disinfectant called chloralum is a solution of impure A1,C1,.
Aluminii 8tiipha» {U. S.)—(Ai^){SO.)^ +
by dissolving A1,H,0, in H,SO, ; '
ally) by heating clay with H,SO..
I Aluminium Sulphate
I Aq— 342 + 324— is obbiinpd b
I ally)
I very
Salts of AlnTfiiniiim.
18
or (industri-
II crystallizes with difficulty in thin, flexible plates ; soluble Ju H^O ;
very eparingly soluble in alcohol. Heated, it fuses in its Aq, which it
116
KAIOrAL or CIIEMISTBT.
gradnally losea up to 200* (392" F.). -when a white, am(»phon8 powder,
(AJ J(SO,)^, remains ; this is decom|>o8C(l at a red heat, leaving a residue of
pure alumina-
Alums — are dntible snlphatee of the alkaline metals, and the higher
au]phat«3 of this or the preceding group. When crjatallizetl, thev have
the genemi formula : (M,)'*(SO.)., B'.SO, -^ 24 Aq, in which )>f) luav Ixj
(Pe A (Mn,). (Or,), (Al,). or (GnJ ; and R. may bo K„ Na^, ltb„ Cs,. Tl,. or
(NH,)^ Tiiey are isoraor|>houB with each other.
Alumm {C. .V.)— Al,(SO.)^ K,SO, + 24 Aq— 516 + 432— i« manufact-
ured from " alum ehalo.'* and is fonucd wheu Bolutions of the sulphates
of A) and K are mixed in suitable proportion.
It cTTstallizes in large;, transparent, re^ilnr octahedra ; liaa a aweetish,
astringent tast«, and is readily uuluble iu H/). Heated, it fuaea in its
Aq at 92* (197*'.6 F.) ; and gradually loses 43.5 per cent, of ita weight of
H,0 as the temperature rises to near redness. The product, known as
hurni alum = alumen exsiccalum { U. S.), is (Al),(SO,)„ K,SO , and is slowly,
but completely soluble in 20-30 pts. H,0. At a bright reil heaf^ SO, and
O are given off and A1,0, and potassium sulphate remain ; at a higher
temperatare, potassium aluminate is formed. Its soluHona are acid in re-
actiim ; dissolve Zn and Fe vrith evolution of U ; and dejKJsit A1,H,0,
when treated with ammonium hydrate.
Alumen (/*r.)— Al,(S(y„(NHJ.l50, + 24 Aq— 474 + 432— is the com-
pound now usually met with as aJiim, both in this country and iu Ungloud.
It differs from potash alum iu being more solublo in H,0 between 20"'-80'"'
(GB^-SC** F.). and leas soluble at other temperatures ; and in the action of
heat upon it At *)2-* (I97^« F.) it fuses in its Aq ; at 205** (401" F.) it
loses its ammonium sulphate, leaving a white, hygroscopic substance, very
slowly and iucompletol; soluble iu H,0. More strongly heated, it learee
ftUimina.
Silicates — ^are very abundant in the different varieties of day. ffM-
n»r, a\h\X'\ lahra>lnriU\ mwirt, etc. The clays are hydrated aluminium
Silicates, more or less contamioated with alkaline and earthy salts and
iron, to whieh last certain clays owe their ciolor. The purest is kat^xn^
or porcelain clay, a white or grayish powder. They are largely used in
the mauufucturo of the different varieties of bricks, terra eotta. pntt«ry,
and porceliin. A>ireirnii is made from the purer clays, mixed with sand
and feldspar ; the former to prevent shrirkage, the latter to briug the
mixture int^ pirlial fusion, aud to render the product translucenL The
fashioned articles are subjected to a first baking ; the porous, baked clay
is then coated with a glo^iv, usually composed of oxide of lead, sand, and
salt. During a second baking, the glaze fuses and coats the article with
a hard, impermeable layer. The coarser articles of pott^ery are glazed by
throwing sodium chloride into the fire ; the salt is volatilized, and. on con-
tact with the hot alumiuium silicate, deposits a coating of the fusible so-
dium silicate, which hardens on cooling.
Analytical Charaotera.
{\.\ Potash, or acda ; white ppt ; soluble in excess.
(2.) Ammonium hydrate : white ppt.; almost insoluble in excess, es-
pecially in presence o^ ammoniacal salts.
(3.) Sodium phosphate ; white ppt ; readily soluble in KllO and Na
HO, but not in NH.llO ; solublo in mineral acids, but not in acetic acid.
makujll of chemistry.
IV. UBANIUM CfBOUP.
URANIUM.
MfmAot B Dr-Jjombt te^tght s S|8.»-^, gr. = 18.4— i)McaMr«tf hg Xl^rMk {1T8B>.
ntoBlMn«Rt to BwaOj cImmiI wUb P« and Cr, or w'Ut N| boiI Co^ It ilow bM. homvtm. tam
pxmdtfvMrabUBtf tfeebvnn: it fnmii ■ mwitm wt wmll ifaJaart ■mnriiM anrl * uMlMof compnttk •€''
ndkal MntnyirUO/- Btaailaid ■doUaoaaf IttMMtaUof allnUi «m UMd furlhuqiuu)UuUT«iM««lB>>
V. LEAD GROUP.
I£AI>.
Symbol =■ Pb (PLUMBUM) -,4f<>wuV uWjW = 20G.9~.Wjf«*iJ far
wewAi = 413.8(?)— % ijr. = 1 1.446— A*(«^« a^ 326' (617^ F-}— .Vttmt- /njm
Leo^l is uaiinlly cloased vrith Od, Bi, or Cu and Ug. It differs, how-
ever, from Bi in being biTaleni or quadrivalent, but not trirnlent. and in
forming no compouuda resembling those of biuniuthyl (BiO) ; from Cd, in
the nature of ita O compoiinds ; and fi-om Cu and H^ iu formiui; no com-
pounda similar to the mercurous and cuprous salta Indeeil, tlie nature of
the Pb compoiuida ia Bucb that the element ia beat rlaiwe*! in a group br
itself, which finds a place in this duaei by virtue of tbe exiuteuoe of potaa-
sium plumbote.
OocnRBS]«:& — It« most abundant ore is galima, FbS. It also occurs in
ichito lead ore, PbCO,, in angie^fite, PbSO., and in horn Imd, PI>C1,.
PhEPAB^Tios. — Galena ia first roaated with ii little lime. The mixture
of PbO, PbS, and PbSO,, so obtained, is strongly heated in a reverberatorr
furnace, when SO, ia driven off The impure vx}rk lead so formed is puri-
fied by fusion in air and removal of tlic film of oxides of Sn and Sb. If
the ore be rich in Ag, that metjil is extracted by taking advantage of the
greater fusibility of an alloy of Pb and Ag, than of Pb alone ; and subse-
quent oxidation of the remaining Pb.
Pbopzbties. — Phymcul. — It is a grayish white metal ; brilliant upon
freshly cut surfaces; very Hoft and pliable : not very midleable or ductile ;
crj'stallizGH iu octaliedra ; a poor conductor of electricity ; a botU;r con-
ductor of heat. "When expanded by heat it does not, on cooling, return
to ita original volume.
Chrmiffil. — 'Wlien exposed to air it is oxidized, more readily and com-
pletely at liigh temi>eratures. The action of H,0 on Pb varies with the
conditions : Pure unai-rated H,0 has no action upon it. liy the combined
action of air and mnit;tiire I'b in oxidizoil, and the oxide dissolved in the
ELOt leaving a metallic surface for the continuance of the action. The
solvent action of H,0 Ujwn Pb is increased, owing to the formation of
basic salts, by tlie presence of nitrogenized organic siibatancesv uitnttes,
nitrites, and chlorides. On the other hand, carbonates, sulphates, and
phosphates, by their teudenc}- to form insoluble coatings, diminish the
corroding action of H,0. Carbonic acid in small quantihr, especially in
presence of carbonates, tends to ])reserve Pb from solution, while H,0
highly charged with it (soda water) dissolves the metal readily. Lead is
dueolved, as the nitrate, by IDiO,. U^-SO, when cold and moderately con-
COMPOUNDS or iMiA, 119
eantiBted, docs not affoet it ; but, when heated, disaoWes it the mora
readily as the acid is more coQceDtrated. It ih attacked by HCI of sp. gr.
LIS, eapecially if heated. Acetic acid dittaolves it aa acetate, or in Uie
praeoioe of CU^ convfirta it iuto white lead.
Oompounda of Lead.
Oxides. — ^LsAO Monoxide — Pr<ttoxide — Massticot — LUharge—Plumlnori-
dttm {V. S. ; Br.) — PbO — 222.9 — ia prepared b^ heatiiifjr Pb or its carbo-
nate or nitrate in air. If the product have been fused, it is lHhargi' ; if
not, nuxsgicot. It fonns coppfr-colorurl, mica-like plates, or a jellow pow-
der ; or crrstallizeii from ita »oluUon iu soda or potash in white, rhombic
dodeeiihedni, or iu roee'Colured cubee. It fuses near a red heat, aud rcla-
tilizes at a white heat ; sp. gr. 9.277-9.5. It is Bparingly soluble in H,0,
forming an alkaliue solution.
Heated in air to 300'^ (572^ F.) it is oxidized to minium. It is readily
reduced by H or C. With CI it forms FbCI^ and O. It is a strong base ;
dcoomposee alkaline salts, with liberation of the alkoU. It (hssolvee in
HNO, and in hot acetic acid, as nitrate or acetate. M'hen ground up with
oils it sajxinilies the glycerin ethers, the Pb combining with the fatty acids
to form Pb soaps, one of whicli, l<'ad olcatf, is the ewplastrum piunibt
( C. S. ; lir. ). It also oombiucs with the alkalies and earths to form fAum'
bitea. Cairium plumhUe, CaPb.O,, is a cn|-KtalUne salt, formed by heating
FbO with milk of lime, and uaetl in Holutioii an u liair-dye.
pLrMJioao-FLDUBic OxiDK — Jicd oxide — Minium — lied lead — Pb,0, —
684.7 — is prepared by hentiug moasicot to ^00'' (572° F. ) inair. It ordinarily
has the composition Pb,0,, and has been considered as ccmposed of PbO^,
SPbO : or as a basic lead salt of plumbic add. PbO.Pb, PbO. An orange*
colored variety ia formed when lead carbonate is healed to 300° (572" F.),
It is a bright red powder, sp. gr. H.(j2. It is conterted into PbO when
airongly heated, or by Uic action of reducing agents. £X0, changes its
color to brown, dissolving PbO and leaving PbO,. It is decomposed by
HCI, with formation of PbCl,, H,0 and CL
Lead Dioxide — Pertfxtde, or jnuv oxide, or brown oxide, or binoxide of
lead — Pluiid}ic anhydride — PbO,— 238.9— is prepared, either by dissolving
,the PbO out of red lead by dilute HNO„ or by passing a current ol CI
^Ihrou^'h H.O holding leo*l carbonate in suspension.
It is a dark, reddish-brown, amorplious jxiwder ; sp. gr. 8.903-9.190 ;
iuBoluble in H,0. Heated, ib loses half its O and is converted into PhO.
It is H Tidiiabic uxiduut. It absorbs SO, tO form PbSO^. It combines
with oilialiea to form jAumbatfs, Jii^PbO,.
PLrMnic Acm^P'bO.H ■ — 256.9— forma cryatalbne platen, at the + elec-
trode, when alkaline solutions of the Pb salts ore decomposed by a weak,
current.
Lead Sulphide— Gafcna—PbS — 23S.9— exists in nature. It ia also
fonneil by direct union of Pli and S ; by heating PbO with S or vapor of
CHj ; or by decompofdng a aolution of a Pb salt by H,S or an alkaline eul*
I^de.
The native sulphide is bluisli-gray, and has a metallic lustre ; sp. gr.
7.58 ; that formed by precipitation is a black powder ; sp. gr. 0.924. It
flnses at a red heat and ia portly BuljliniC'd, partly converted into a siibsul-
hphate. Heated in air it is converted iuto PbbO^ PbO an(l SO^ Heated
in H it ia reduoorl. Hot ECNO, oxidizes it to PbSO,. Hot HCI ooiiT«rtg
it into PK;1,. Boiling H,S0, converts it into PbSO, and 80,.
Iiead Chloride— PbOl,— 277.9 -ifl formed by the action of CI upon
Pb at a rod heat ; by the action of boiliug UCI upon Pb ; and hy double
doootnposition between a lead-salt and a chloride.
It crj-stollizea in plateR, or heiagonal needles ; Bparingly soluble in
cold H,0, lcK8 Holulite in H^O containing HCI ; more soluble iu hot H,0,
and iu coucentrateU HCI.
SoTcnU oxvcblorides are known. Caasel, Faiii, Verona^ or Turner's j/el-
/owisPbCI ji'bO. •
I*ead Iodide— Plf«m 6* indidum{U. S. ; Br.) — Pbl^ — 460.9— is de-
posited aa a bright yellow powder, when a solution of jMtassium iodide is
oddod to a solution of a Pb salt. Fused in air it is converted into an
oxyiodide. Light and niotstiu« decompose it, with liberation of I. It ia
almost insoluble in HO, soluble in solutions of ouuuuuiuu chloride, so-
dium hyposulphite, alkaliuo iodides, and potosL
Salts of Lead.
Nitrates.- LKAi>NrrEATE— P/umMmVnw— (C S.; ^.)— Pb(NO.),—
830.11—18 formed by solution of Pb or of it« oxides in excess of HNO^
It forms anhrdrous crystals ; soluble iu H,0. Heated, it is decoiupused
into PbO ; O^nud NO,.
Besides the neutral nitrate, basic lead nitrates are known, which eeem
to indiCAte the existence of nitrogen acids similar to those of phoepborus ;
Pb,(NO,)^ — orthonilraie ; and Pb,N,0,— /)yrontOa/tf.
Lead Sulphate — PbSO — 302.9 — is formed by the action of hot, con-
ccDtrated H,SO, on I'b ; or by double decomposition between a sulnliate
and a Pb salt in solution. It is a white powder ; almost insoluble in H,0 ;
soluble in conceiitrnted H,SO, from which it la deposited by dilution.
Lead Chromate — Chrome yeWo»t'— PbCrO, — 323.3— is formed by de-
composing Pb(NO,), -with potassium cbromate. It is a yellow, amorphous
powder ; insoluble in H.O ; soluble in alkiiliee.
Acetates. — Nei'tiul Lwd Ai^ktatk — Sail of Sat urn — Sugar of Lead —
riumbi acetas {U. S. ; ^r.)— PbfC^^O,), + 3 Aq— 324.0 + 54-i8 formed
by dissolving PbO in acetic acid ; or by exposing Pb in contact with acetic
acid to sir.
It crystallizes in lai-ge, obliciue rhombic prisma, sweetish, with a metal-
lic nfler-tftste ; soluble iu H,0 and alcohol ; its solutions being a<'Jd. In
air it efHorosces, and is superficially converted into carbonate. It fusee
at 75^6 (167^9 F.) ; loses A*), and a part of its acid at 100^ (212^ F,),
forming tlio sesquibaaic acetate; at 280** (536° F.) it enters into true
fusion, and, at a slightly higher tomperat\ire, is decotaposed into CO, ;
Pb, And acetone. Its aqueous solution dissolves PbO, with formation of
basic acetatea
Sexbasio Lead Agitate— Pb(C,H,0,)OH, 2PbO— 728.7— is the main
oonstitueut of GunlanVa extract = Liq. ptumbt ttntxu^aiin (V. S. ; Br.), and
is formed by boiling a solution of the neutral acetate with Pb in fine pow-
der. The solution becomes milky ou addition of ordinary H^O from foi"-
nintion of the sulplmte and carbonsto.
Lead Carbonate — PbCO — 2(>0.9— occur? in nature as cerusnle ; and
ia formed, aa a white, insoluble powder, when & uolution of a Pb com-
I
ponnd is deoompowd by tui alkaline carbonate, or by pasetng CO, (lirough
a Bolation oontaining Pb.
The ptunU?! carbonaa ( U. S. ; Br.), or white lead or ceruse, is a basic car-
bonate, (PbCOJ,, PbHjO, — 774.7 — mixed with varring proporiioue of
other basic carbonates. It is usuaIIt prepared by the actiou of CO, od a
solution of the subacetite, prepared by the action of acetic acid on Pb and
PbO. -It ia a heavy, white powder ; insoluble in H,0, except in the pre-
,8eDce of CO, ; soluble iu acids with oflervcBceuoe ; and decomposed by
heat into CO. and PbU.
Analytical Characters.
(1.) Hydrc^ea sulphide, in acid solution : a block ppt ; insoluble in
aUiaJiue sulphides, and in cold, dilute acids.
(i.) Ammonium aulphydrate : black ppt ; insoluble in excess.
(3.) Hydrochloric acid : white ppt ; in not too dilute solution ; solu-
ble m boiliii^jr H,0.
(4.) Ammouium hydi-atc : white ppt. ; insoluble in excess.
{5.) Potash ; whit* ppt ; soluble in excess, especially wlien heated.
(6.) Sidphiiric acid : white ppt ; insoluble in weak acids, soluble in
solution of ammonium tartrate.
(7.) Potassium iodido : yeUow ppt ; eporiugly soluble in boiling H,0 ;
Bolable in large excess.
(8.) PotASMium chromate : vellow ppt ; soluble Iu RHO solution.
(9.) Iron or zinc separate the clement from solutions of its salts.
Action on the Economy.
All the soluble compounds of Fb, and Uiose which, although not solu-
ble, arc rtadily convertible into soluble compounds by H,0, aii-, or the
digestive fluids, am actively poisonous. Some are also injuriouB by their
local action upon tiHsue^ with which tliey come in contact ; such are the
acetate, and, in lesa degree, the nitrato.
The chroim form of lead intoxication, juxiiUer'g cotic, etc^ is purely
poisonouH, and is produced by the continue<l absorption of minute qium-
titics of Pb, cither by the skin, longs, or stomach. The acute form pre-
sentA aymptoms referable to the local oa well as to the poisonous action of
the Pb salt, aud is usually catised by the iugestiou of a single dose of the
acetate or carbonate.
Metallic I'b, although probably not poiaonoua of itself, causes chronic
lead- poisoning by the readiness with which it is converted into compoimds
tumble of absorption. The sources of poisoning by metallic Pb arc : tlie
contamination of drinking water which has been in contact with the metal
(see p. 48) ; the use of articles of food or of chewing tobacco which has
been packed iu tln-foU containing an excess of Pb ; the drinking of beer
or other beverages which have been in contect with pewter ; or tbe hand-
ling of the metal and its alloys.
Almont all the compounds of Pl> may produce painter's colic The
oorbonate, in painters, ai'tists, oianufuctureraof white lead, and iu persons
Bleeping in newly paintdl rooms; the oxides, in the itinniifftc.>tiii-os of glass.
pottery, sealing-wax, and litharge, and by the use of leod-glfized potteiy ;
by other compoimda, by the inhalaLion of the dust o{ cloth factorioe, and
l>y the U8C of lead hnir-tlyes.
Acute lead-poiaoniiig is by no means of as common occnrreDoe as the
chronic form, and usi^y tenninates in recovery. It ia caused by the
ingestion of a single large dose of the acetate, subaoetate, carbonate, ci
of red lead. In such cases the administration of magnesium sulphate
is indicated ; it enters into double decomposition with the Pb salt to form
tbo insoluble PbSO..
lisad once absorbed is eliminated verj* slowly, it becoming fixed by
combiuatiou with the albuminoids, a form oi combination which ia ren-
dered soluble by jxitaasium iodide. The channels of elimination are by
the perepii-ation, uriue, and bile.
In the aualj'sia for mineral poisons (see p. 96), the major part of the
Pb is precipitated as PbS in the treatment by H S. The PbS remain*
upon the filter after extrocUou with ammonium sulphydrate ; it is treatad
^^ith warm HCL wlaoh decolorizes it by transforming the sulphide into
chloride. The Pl)Cl thus formed ia dissolved in hot H,0. from which it
crystoUizea on coolmg. The solution still coutiuns PbCl, in sufficient
quantity to respond to the testti for the metaL
Aitliough Pb is not a normal constituent of the body, the cvcry-day
methods by which it may be intro«luced into the economy, and the slow-
uesa of its elimination are such as to render the greatest caution neces-
fwuy in cU-awing conclusions from the detoction of Pb ia the body after
death.
>X BLSMUTH GROUP.
BISMUTH.
Symbol = Bi— Atomic weight = 201.5^Mokcular weight = 420 {?)—%
gr. - 9.G77-9.935— /■««» at 368" (514\4 >'.).
This element ia usually classed wiUi Sb ; by some writers among the
metals, by others in the phosphorus group. Wo are led to clo&s Bi in
our third doss, and in a group alone, because : (1) while the so-called
salts of 8b are not salts of the elmneut, but of the radical (SbO)', antimonyl,
Bi outers into saline combiuatiou, not only in the radical bi^muthyl (BiO)',
but also as an clement ; (2) while the cximjwuuda of the elements of the
N group in which those elemcute ore quiuquivaleut are, as a rule, more
stable thou those in which they are trivalont, Bi is triTiUent in all its
knoxrn compounds except one, which is rery unstable, in which it is quin-
quiralent ; (3) the hydrates of the N group ore strongly acid, and their
corresponding salts are stable and well de&ned ; but thoee hydrates of Bi
which are acid ai*e but feebly so, and the bismuthates are unstable ; (4)
no compound of ]}i and H is known.
^L OcCDBBSKCB. — OccuTs priucipaUv free, slso as Bi.O, and Bi.S,.
^^B PBOPBrnaa— Crystallizes in brilliant, metaUio rhombohedra; bard and
^^ brittle.
I It is only superficially oxidized in cold air. Heated to redness in air, it
I becomes coated with a yellow film of oxide. In H,0 containing CO. it
I forms a crystalline siibcnrbonote. It combines directly with CI. Br, and L
I It dissolves in hot H,80^ aa siilplmte, and in HNO, as nitrate.
^^^ It is usually contaminated with As, from which it is b^t purified by
I by
BBMIITH,
beaUn^ to redn«fiB a mixtare of powdered bismuth, potasuum carbonate,
•oap. and charcoal, under a iayor of obarcoal. After an hour tho uiibti ia
coolMi ; the button is eeparated and fused until its suriaoe begins to be
coated with a Tellowiah-brown oxide.
CompouDds of Bisznutb,
Oxides. — Four oxidoa are known : Bi^O, : Bi,0, ; Bi,0^ ; and BLO^.
formed by heating Bi, or ita nitmte, carbonate, or hrdrate. It ia a pale
vellowj iusolublo ]X)wder ; ep. gr. 8.2 ; (usee at a red beat ; soluble in UCl,
ilNO, and H,SO, and in fused potaeh.
Hydrates. — Bismuth forms at least four hydrates.
BisMCTHoca HrDRATE — BiH,0, — 261 — ia formed as a white precipitate
when potash or ommuuium hydrate is added to a cold solution of a Bi
salt. \Vbcn dried, it loeea H.O and ia converted into bismuthyl hydreUe
{BiO)HO.
&BiniTHic Actd — (BiO. )HO--2ri9— ia depoaite<l ns a red i>owder when
CI is passed through a }>uiling sohition of jMitauh, holding bismuthous hy-
drate in suspension.
pYROBiRMT-Tinc Acni — H.BLO, — 536 — is a dark brown powder, precipi-
tated from Bulution of biinnutb nitrate by potassiuiu cyanide.
Bismuth Trichloride — HinnwUhmus tAryndf — BiOl, — 316.5 — ia
formed by heating Bi in Cl ; by distilling a mixture of Bi and merctuic
chloride ; or by diJidUiug a solution of lii in aqua regia. It is a fumble,
Tolatile, deh(iuetic«nt solid ; soluble in dilute IICL On contact with H,0 it
ia decomposed with formation of himiuihyl chloride (BiO)Cl, or pearl xoh'iU.
Salta of Bismuth.
Bismuth Nitrate— B1(N0,), + 6 Aq— 390 -h 90— obtained bydissolv-
ing Bi in HNO,. It erystaltizes in laoTje. colorlesa prisma ; at 160'* (302'^ F.),
or by contact with 11,0, it ia conv^ted into biamuthyl nitrate ; at 260°
(500* F.) into Bi,0..
Salts of Biamuthyl.
Biamuthyl Nitrate — TrutnUrot*; or i^ubmtmte of bismuth — F7ate
vihUe—Bu^mnthi guhnitroA {U. S. ; /yr.)~- ^BIO)NQ,H,0— 30fi— is fonued
by decomposing a solution of Bi(NO,), with a large quantity of H,0, It is
a white, heavy, faintly acid powder ; soluble to a slight extent in H,0
when freshly precipitated, the solution depositing it again on staudiug.
It is decomposed by pure H,0, but not by H,0 containiog yip ammonium
uitrnte. It usually contjiins 1 Aq, which it loses at 100° (212 F.).
Bismuth siibuitrato, as well as the stibcarl>onate, is Inible to contam-
ination with arst>oio, which accompanies bismuth in its ores. Tho method
for sepaniting this <iaugerouH impurity, directed by the British Pharmaco-
poeia, ia mnru perfect tlmn tliiit usually followed in this country, llie
metal is (imt purified by fusioo with jwtjissitim nitrate, whiuh dissolves
^any arseuiu present in the form of sodium antenite, and tiio puriJ&od metal
124
UAKCAL OP CfTEMISTRF.
ie then converted into nitrnte b^r eolution in UNO^ and ibis in t\irn into
Bubnitrato bj de<?ompoeition Mith a lai'ge volume of H,0.
Tbe maximum amount of arsenic which ha» beon found in CDmmeroi&l
biaiuuth Guboitrate is ono-tcnth of one per cent.
To detoct the presence of arsenic, tJie subuitmte (or subcarbouale) is
boiled for lialf an hour with an equal weight of pure iKMlium CArbonate,
di^olred in ten times itti weight of U,0. The solution is tiltered ; tbe fil-
trate evapoi-ated to divncsa ; the i-csiduo strongly heated ; and, after c«k>1-
ing, cautiouBly decomposed with strong H^SO,. The mass is tbou gradu-
ally heated, during stirring, until dense nhit« fumes are given ufT. The
oooled residue is tmolly treated nitli water and tbe liquid introduced into
ft Marsh Appiirattis. (iSee page 93.)
Blsmuthyl SubcartKjnate — tiiitmvlhi Sfibcarbonax {C. S.) — Bismuthi
raiixmajt {//r.)^(BiO),CO,H.O — S30 — is a white or vellowisli, ninoq>hoitH
powder, formed when a solution of an alkaline carbonate is added to a
solution of Bi(NO,)^. It is odorleus and tasteless, and insoluble in H,0
and in alcohol
When heated to 100" (212* T.). it loses H,0 and is eonvertfid into
(BiO]pO,. At a higher temperature it is further decomposed into Bi,0,
audCO^
Analytioal Characters.
(1.) Water : white ppi, even in presence of tartaric acid, but not of
HNO.. HCI. or H,SO..
(2.) Hydrogen sulphide : black ppt; insoluble in dilute acids and iu
olkaliue sulphides.
(3.1 Animonium stilphydiute ; black ppt. ; insoluble in excess.
(-1.) Potash, soda, or ammonia : whit« ppt; insoluble in excess^ and m>
tartaric acid ; turns yellow when the htjuid is boiled.
(5.) Potassium ferrocyanide : yellowiah ppt.; insoluble in HCL
(6.1 Potassium ferricyauido : yellowiali ppt.; soluble in HCL
I Infusion of galls : orange ppt.
I Potassium iodide : bron-n ppt.; soluble in exuesa.
) Reacts with Reiuach'a test (</. v.), but gives no sublimate in the gl
Aotion oa the Economy.
Although the medicinal compounds of bismuth probably are poisonous,
If taken in sufficient qunntity, the ill eflfects oseribed to them ore
most, if not all case». r(tfenibh> to conbuniniition 'witli arsenic. Symptoi
of arsenical poisoning have not only been fre<|ueutly observed when thftj
Bubnitrato boa bceu token internally, but also when it has been used as ■
cosmetic:,
\Mieu preparations of bismutli are odTniniafered, the alviue discharges
contain bismuth sulphide us u dork browu powder.
OF TtW.
Vn. TIN GROUP.
TlTASICM. ZlBCOSTTM. TlJT.
Tt ftutl Sn are bivalent in one aeriefl nf compounds, SnCl,, and quaJri-
Talent in another, SnCl,. Zr, so far hs known, is always quadnralcnt.
Each of these elements fonnn an ncid (or aalta conespomlm[;r to one) of
the composition U3XO„ ant] & eeries of oxrsalt« of the composition M"
TITANIUM.
Sgmbot ±± Tl— jllofMc uMffil = <S-4p. ffr. = 5.8.
Oerara In (4a7««ii>1 Iroa ana kixl m TIO, In wvnaJ mliwMU. Tttantc itnAgilrU*, T1(V ta ft white, tn-
«ilDh1<-. InfnaCblr pcmtlpf, iumI lit iha maniifarairr oranUolkl tMCh: dlMolvntntaDMl £HOk« pDt««liinL
ttteBBU' Tfuniiim ruinHriMrvwHljr wlDi K, wblcti It ftUoTtM ftoo air wbcn bMtod. VtimllH, i>n«M*rt
WCT mt-btft Tl'>« It U d«coRii»x-l with fciriDMlMt oC Ibt riolal oltiMi^ TtN^, Anotlur oaav>Minai uf TL
ZIRCONIUM.
Oecora ta ttiooa Mtd hrsdaUt. lu oxid*. Hreema, ZiO*. U & wfal(« powdoi. Inwilabhi Id kho. Bubw
tBtmOM and aoi altarMl bj rapoMm u air, tt U umJ in pencil* to i«i>Um Uum Iu tbo cnleUun ligtil,
TIN.
Sgmbol = Sn (STANNUM) — Atomic vxighe = 111. 1 —Molecular
weight = 235.4 (?)—»/>. gi\ - 7.285-7.293— JV«t« ai 228° (442''.4 F.).
OcccBaKHOB. — As tinfUojte (SnO,) and in slrcam tin.
I'bcpaiutiom. — The comtaerciol mottd is prepared by roasting tLo ore,
extracting with H,0, reducing the residua hj heating with chm\M:)al, and
refining.
Pure tin is obtained by dissolTing the metal in UCl ; filtering; erapo-
rating ; dissolving the residue iu H^O ; decomposing with anunonium car*
bonat« ; and reducing the oxide with charcoal.
Pbupertieh. — A aoitf malleable, bluisli-white metal ; but slightly tena-
cious ; emits a peculiar sound, the tin-cry, when bent. A good conductor
of heat and electricity. .-Ur affects it but little, except when it is heated ;
more rapidly if Sn be alloyed Tv-ith Pb. It oxidizes slowly in H,0, more
rapidly tu the presence of sodium chloride. Its presence with Pb accele-
rates the action of H,0 upon the latter. It dissolves in HCl as SnCl^. In
presence of a small quantity of H,0, HNO, converts it into metastaunic
acid. Alkaline solulious dissolve it as uietastannates. It combines directly
wiUi CI. Br, I, S, P. and Aa
Tin plates are thin sheets of Fe, coated with Sn. Tin foil consists oi
tbin laminiB of Sn, frequently alloyed ynih Pb. Copper and iron vessels
ore tinned, after brightening, by contact with molten Sn. Pewter, bronze,
bell metal, gun metal, britannia metal, speculum metal, type metal, solder,
and fusible metal contain Sn.
Compounds of Tin.
Oxides. — SrAjiNors Oxide — Protoxidf.SiiO — 133.7 — obtained by
heating the hydrate or oxalate without contact of air. It is a white, amor-
phous jHiwder, soluble in acids and iu hot concentrated solution of potash.
It abtiorbs O readily.
«
i
J
MAWCAL OF CHEMISTRT.
STASino OsjDE — Bintxriile of tin — SnO, — 149.7— occura native as tin-
stone or itumt'^te, and is formed when Sn or SnO is heated in air.
Hydrates.— St .u»-Noir« Htdr-*te — SnH,0, — ir>L7— isawhite precipitate
formed by alkaline hydrates and carbonates iu Bolutious of SuCl,.
•Stanxic Acid — H,SnO, — 167.7 — is formed by the action of alkaline hy-
drates on RolutioDs of SnCI,. It dissolves in solutions of the lUknline
hydrates, forming stannaiea.
ilETAWAKxic Acid— H,Sn,0 — 7GC.5— is a nbite, insoluble powder,
formed by acting on Sn with HNO,.
Chlorldea— -Stakxocs CaixttaoE — Protnchloride — Tin crystals — SnCl,
+ 2 Aq— 188.7 + 86— is obtained by dissolving Sn in llCl. It crystalliEes
in colorless prisms ; soluble in a small quantity of H,0 ; decomposed bj a
largo f]uantity, unless in the presenee of free HC'l, with formation of an
oxychloride. Lnnes its Aq at 100" (21*2" F.). In air it is transformed into
stannic chloride and oxychloride. Oxidizing and chloriualing agents con-
vert it into SnCl,. It is a strong reducing agent.
5yr.*NNin Chwrihe — liichloride — Liquid of I.U»ivius — SnCl, — 259.7- — by
acting on Sn or Snt'I, with CI, or by henting Sn in aqua regia. It is a fum-
ing, yellowiali liquid ; 3p. gr. 2.28^ boils at 120" (248' F.).
Analytical Gharaoters.
Stahsous.— (1.) Potash or soda: white ppt ; soluUe in excess; the
solution deposit Sn when boiled.
(2.) AmmoniuiD hyilmte : white ppt. ; insoluble in excees ; turns olive-
brown when the liquid is boiled.
(3.) Hydrogen wiilphido : dork brown ppt ; soluble in KHO, alkaline
sulphides, and hot H,0.
J4.) Mercuric chloride: whit« ppt ; turning gray and black.
(5.) Auric chloride : purple or brown ppt., in presence of small Quan-
tity of EL\0,. x-r f H
(6. ) Zinc : deposit of Sn.
STA5NI& — (1.) Potash or ammonia : white ppt ; solulile in excess.
(2.) Hydrogen sulphide ; yellow ppt. ; soluble in alkalies, alkaline Bul-
phides, aiAl hot HCl.
(3.) Sodium hyposulphite : yellow ppt when heated.
VUL PLATINUM GROUP.
Paluuiium. Pl&tinux.
IX. KHODIUM GROUP.
Bhodiuk Ruthentctm. Ibidiuil
The elements of these two groups, together with osmium, ore usually
cloKfled as "motais of the platinum orea." They all form hydrates (or
mlts representing them) baring acid properties. Osmium has been re-
moved because the relations existing between its compounds and those
of molybdenum and tungsten are much closer than those which they ex-
hibit to the compounds of these groups. The separation of the remaining
PLATINUM.
Syrnhol = Tt—Atomic teeight = 19i4— IWeeu/ar ioeight = 388.8 (?)
^-Ip. ^. = 21.1-21.6.
OcxmiHKNCB. — Free and alloyed witli Ob, It, Pd, Rh, Ru, Fe, Pb, Au,
Ag, and Ou.
Pbopkbtibs. — The compact metal baa a silvery lustre ; softens at n
vhite heat ; may be welded ; fuses with difficulty ; hifjhly malleable, ductile
and tenacious. Spongy plntinum is a grayish, pomua mass, formed by
beating the double chlonde of Pt and KH,. Platinum biatrk ig a black
.powder, formed by dissolving Ft Gl, in solution of potash and heating with
alcohoL Both platinum black and platinum sponfje are capable of condens-
ing large quantitieti of gas, imd act as indirect oxidants.
Platinum is not osidized by air or O ; it combines directly witb CI, P,
As, Si, 8, and C ; is not attacked by acids, except aqua rcgia, in which it
dissolves as PtCl,. It forms fusible alloys when heated with metals or
reducible metallic oxides. It m attacked by mistores liberating CI, and by
contact with heated phosphates, uilicatca, hydrates, nitrates, or carbonateii
of tbe alkaline metals.
Platwic C'HiiOiUDK — Tetrachloride OT pfTch!oride of platinum — PtCl^ —
33G.1— is obtained by diaaolviiiK Pt in aqua regia, and evaporating. It
crystallizes in very soluble, deliquescent^ yellow needles. Its soIuUon ia
used as a test for compounds of KH, and K.
PALLADIUM.
Symbol = PA— Atomic weight = 105.7— J/u/«;u/or iveight = 211.4 (?)—
tp. gr. =11.5.
A white metnl resembling Pt in appearance, but usually exhibiting a
'reddish reflection. It ia harder, much lighter, and more rentlily fusible
than IH. It dissolves in HXO, as Pd(NO,)^ It possesses the property
of ocduding gases, notably hyth-ogen, in a much more marked degree
than any other metal One volume of pallndium condeuaea 040 volumes
of hydrogen at 100° (212° F.).
RHODIUM.
Byinbol = Vh— Atomic weight = lOiA— Molecular rceight = 208.2 (?)—
'•p. pr.= 11.4.
A hard, malleable, while metal, insoluble in ai]ua regiiL Ita com-
pounds arc mostly red, whence its uaiue, from poiw, a roes.
128 HANUiO. 07 OHEHISTBY.
RirrHENIUM.
Symbol = Ru — Atomic weight = 104.2 — sp. gr.— 1L4.
A hard, brittle, very difficultly fusible metal, not diBSolved by aqua
regia, occurring in Bmall quantity in platinum ores.
IRIDIUM.
Symbol = Ix— Atomic weight =192.7 — sp. gr.= 22.8.
A bard, brittle metal which occurs in nature in platinum ores, and
aUoyed wiUi osmium. It is not attacked by aqua regia. It is used to
make an alloy with platinum which is less fusible, more rigid, harder,
denser, and less readily attacked chemically than pure platinum.
XITALTTTCAL CnARACTKBS.
199
CLASS IV.— BASYLOUS EHJBBiEENTS.
Tii.rvtsm tbosb Oxides Unite with Water to form B.\sBa ; mtTER to
rOHM AcUkL WhXCU IfOBM OxiMAUrS.
L SODIUM GROUP.
larami — Sodium— PoTAaHUM. EmuDnm— Cisron — SiLTia.
Each of the elomenta of this group forms a HiDgle chloride, M'Cl, and
,ane or more oxides, the louBt stable of which hau the composition M' O ;
tiiey are, therefor, univalent Tlieir hydrates, MHO, are more or leaa
and liave rnarkciUj basic characters. .Silver resembles ihe other
embera of the group in chemical propertien, although it does not in
lyncal chmcten.
LXTHIUIkl.
Sifmbol ^^^JJ. — Afomio weight = 7 — 3^ecuiar iceiffht ^ 14 (^ — Sp. gr.
0.689— Fuww at ISO" {356" F.)—Dm:Qveretl by Arfoedson in 1817—
'anc/rom. Ai'tfcuic = stonj.
OccuHBXNce. — Widelj diatributed in small quantity ; in many minemla
and mineral waters ; in the ash of tobacco and other plants ; in the milk
and blood.
FBOPKRma. — A silver-white, ductile, volatile metal ; the lightest of the
•otid elements ; bums in air with a erimBOu flame ; decomposes 1I,0 at
ordilUDT temperatures, without igniting.
liltnituu Oxide — Li^O — 30— is a white solid, formed by burning li
in dry O. It dissolves slowly in HO to form litUinm hydrate — LiHO.
Uthium Chloride — LiCl — i'h.5 — crystalhzes in dehqueacent, reg*
ular octabcdra ; very soluble in H,0 and in alcohol.
Idihium BTomide—LUhii hromidtim {i'. .S'.)— LiBr — 87 — is formed
by decompoiUDg litbiutn nulpltate nith potaaaium bromide ; or by satur-
ating a solution of Hi3r with lithium carbonate. It crystallizes in very
dehqtiesoent, sohiblo needles.
Lithium Carbonate— /.i/An carbnnan {U. S. ; 7?r.)— IJLCO,— 74 — is
a white, sparingly soluble, alkaline, amoriihous powder. With uric acid
it forms hthium urat« {q. v.).
Analytloal Characters.
(1.) Ammonium carbonate : white ppt. in concentrated solutions ; not
in dilute solutions or in presence of ammoniAcal salts.
(2.) Sodium phosphate : white ppt. in nentrn) or alkaline solution ;
soluble in adds and in solutions of ammoniacal salts.
MATTCTAI, 07 CHEMISTBT.
(3.) It colore Uic Bunsen flame red ; anil exlubite a spectrum of tiro
lines-^ - 6705 and G1U2 (Fig. 14, No. 4).
SODIUM.
8i/mbol = NR (NATRIUM)— ^/omic wei^W = 23— Jfofecu/ar weight.
= 46 (?)—.%). gr. — 0.972— /'itsea at 06".6 (204*'.l F.)—Dufcovered bg Davy,
1807.
OccTRRKSCE. — Ab chloridfl vfirf ftbiindantly and Tridely distribnted ;
also as carbouute, iiitruU;, milphuU^, boraU>, etc.
pREP.in.vnoN. — By hcatiug a mixture of (Irj' sodium carlxmatc, duUk, and
charcoal t*> whiteness in iron retorte, connected with suitable condensers
in which the distilled metal collects mider a layer of coal naphtha.
Pifl>pEimE8. — A Htlverwhite metal, rapidly tamiuhed and coated with a
yellow film in air. Waxy at ordinary tempcraturea ; volatile at a white
heat
In air it is gradually oxidized from the surface, but may be kept in
closed vessels without the protection of a layer of naphtha. It decomposes
H,0, sometimes explnsivelr. Bums with a yellow tlame. Combioetf di<
recUy with 0% Br, X S^ P. As, Pb, antl Sn.
Compoundfi of Sodium.
Oxides. — Two oxides are known : Sodium monoxide — Na,0 — agrayifib-
white mass ; formed when Na is bnmt in dry air, or by the action <rf Na
on NoHO. Sodium dioxidi- — Na O, — a white solid, formed when Na is
heated in dry air to 200^ (392*^ F.).
Sodium Hydrate— C'aitrtte »oda—Soda {U. S.) — Soda raugtica (Br.) —
NaHO — 4(>^i8 formed : (1) when H^O is decomposed by Na ; (2) by de-
compoainp eodic carbonate by calcium hydrate : Na,CO, + CaH,0, = CO,
Ca + 2NftH0 (soiia by lime); (3) in tbe saiiie manner as in (2), using barium
hydrate in place of hme (soda by Larj'ta). It frequently contains con-
siderable quaiititiefl of Aa.
It is nn opftqne, white, fibrous, brittle soUd ; fusible below redness ; sp.
gr. 2.00 ; ver>- soluble iu H,0, forming strongly alkaline and caustic solu*
tiona {noda hje and liq. sodtje). When exposed to air, solid or in solution, ■
it absorbs H,0 and CO, and is converted into carbonate. Its solntioiu
attack glass.
Sodium Chloride — Cwnmon sail — Sea salt — Table salt — Sodii cltloridum
{V. S., Ilr.) — NaCl — 58.5 — occurs very abundantly in nature, deposited in
the solid form aa rod- salt ; in solution in all natural niiters, especially in
sea and mineral epriug waters ; iu suspension in the atmosphere ; and as
a constituent of almost all animal and vegetable tissues and fluids. It iB
formed in an in6nit« variety of chemical reactions. It is obtained from
rock salt, or from tbe waters of the sea or of saline springs ; and is the
source from which all the Na compounds are usually obtained, directly or'
indirectly.
It crj-stallizoB in anhydrous, white cubes or octahedra ; sp. gr. 2.078 ;
fuses at a red beat, and crystallizes on cooUug : sensibly volatile at a white
beat ; quite soluble in H,0, tbe solubility varying but slightly with the
OMPOCXDS OF SODTtTM.
lempsrntura. Dilute solntions yield puro ice on freezing. It is precipi-
tated from concentrated solutions by HCI. It i8 insoluble in absolute
alcohol ; sparingly soluble in dilute spirit. It is decomposed by U.SO
with formntion of HCl and sodium sulpliftte ; 2NaCl + H,t>0, = 2UC1
+ Na.SO..
Phtsiolooical. — Sodium chloride exists in ererj' animal tissue and
flnid. and is present in the latter, especially the blood, in tolerably con-
stant proportion. It is introdnceil with the foo<l, eitliftr as a constituent
of tlie aUmentary substances, or as a condiment. In the Inxly it serres to
aid the phenomena of osmosis and to niuiutoin the solution of the albu-
minoids. It is probable, also, that it is decomposed in the gastric mucous
membrane with formation of free hydrorhloric: acid.
It is discharged from the economy by all the channels of elimination,
notably by the urine, when the supjily by the food is maintained. If.
howe\'er, the food contain no salt, it ttisappears from the urine before it is
exliauatcd frtim the blood.
The amount of CI (mainly in the form of XaCl) voided by a normal male
adult in 24 hours is about 10 grams (151 grains), corresponding to 1G.5
grams r2ijS grains) of NaCI. When nora^al or escessire doses are talfen,
the amount eliminated by the urine is less than that taken in ; when amall
quantities ore tokou, the elimination is at first in excess of the supply.
The hourly elimination iucrcAsea up to the seventh hour, when it again
diminishes. The amount of NaCl passed in the urine is less than the
oormal in acute, febrile discuses ; in intermittent fever it is diminiiilied
during the paroxysms, but not during the intervals. In diabetes it is much
increased, sometimes to 29 grams {H8 grains) per diem.
Qitantiiatioe fietermination of rhlnruiex in tirine. — The process is based
apou the formation of the insoluble silver chloride, and upon the formation
of the brown silver chromatc in neutral htjuids, in the absence of soluble
chlorides. The solutions reipiired are: (1) A solution of xihvr nitrate ot
known strength, made by dissolving 29.075 grams of pure, fused silver
nitrate (see p. 143) in a litre of water ; (2) a wltUion of neutral potassium
cJtromab!.
To conduct the determination, 5-10 c.c. of the urine are placed in a
platinum basin, 2 gruus of sodiuui nitrate {free from chloride) are added ;
the vhole is evaporated to dryness over the water-bath, and the residue
heated gradually until a colorless, fused mass remains Tliis, on cooling,
is dissolved in H,0, the solution placed in a small beaker, treated with
pnre, dilute HNO, to faintly acid reaction, and neutralized 'nitli calcium
corbonat^. Two or three drops of the chromate solution are added, aud then
the silver solution from a burette, during constant stirring of the liquid in
the beaker, until a faint reddish tinge remains permanent. Each c.c. of
the ailver solution used represents 10 miUigrams NaCl (or 6.065 milligrams
CI) in the amount of urine used.
Example. — 5 o.a urine used ; G c.c. silver solution added ; 1,200 c.c.
urine passed in 24 hours : •'•——^ — x 1,200 = 14.4 grams NaCl in 24
hours.
If the urine contain iodides or bromides, they must be removed by
acidulating the solution of the residue of incineration with SO,H,, remov-
ing the iodine or bromine by shaking with carbon disulphide, neutralizing
the aqueous solution with calcium carbonate and proceeding as above.
Sodium Bromide — Sodii bromifium (U. S.) — NaBr — 103— is formed
bj dissolving Br in solution of NaHO to saturation ; evaporating ; calcining
132
MANUAL OP CITEMISTRT.
at doll redness ; rediBaolviDg ; filtering ; and crystalliziog. It crTstaUizoi
in anhydrous cubes ; quite Boluble in U,0, soluble in nleohoL
Sodium Iodide — Sftftii uxiuium {V. -S'.)— Nal— 150 — ia prepared by
heating togetiier H,0, Fo, and I in fine powder ; filUtring ; adding an
eqairalent quantity of Etodium mtlpbate and some Blacked lime ; boiHng ;
decanttnET and eTaitomttng. Orjstallizea in anh^rdrous oubee ; fery sol-
uble iu H.0 ; tiolublo in aloohoL
Salts of Sodium.
Sodium Nitrate— ChMo or C?n7t aaUpatre—Sodii m'trait {U. S.) — SodiB
tii/'"a8 (Br.) — NaNO, — 85 — orcure in natural dep«>Kit« in Chili and PeriL
It er;)*dt&Uize8 in anhydiuuH, deliquescent rboubobedra ; cooling mid aome-
wliat bitter in taste ; fusee at 310^ (SiK)'' F.) ; vcr>- soluble in 1J,0. Heated
with ajiO, it is deMimposetl, jielding H^O, and hydrosodio sulphate :
H,SO, + NuNO, ^ HNaSO, -f HNO,.
Sulphates.— UiiDiiuMuLiic Scu-uate — Aciff Kodium snlphaie— Bvtuiphaif
— HNaSO —1*20 — ciTHtallizes in long, four-sided prisma ; i» uiiHtable and
deeomi»08cd bv air, H^O or alcobol, into H,SO. and Na,SO,. Heated to
dull leduesa it is converted into i"Miium pyronuiphale, Na^S^O,, correspond-
ing to Nordhnai4oi) sulphuric aoid.
Some SiTLPHiTE — Se.utrtU sodium niUphote — QUxuber'n saU—Sodii aiUphat
{C. S.y—SKHia: »nljihatf (fir.)— Na^SO, — n Aq — 142 -f « 18 — occurs in
nature lu Bolid deposits nud iu soUitiou iu uaUiral waters. It is obtatnod
pnucipallv as a step in the manufacture of the oarbonate by the action of
H^O. on XaCl.
It crystallizea vith 7 Aq, from saturated or supersaturated solutions at'
5« (4X* F,) ; or, more usuaJiy, with Il> Aq. As usually met with it is in
large, colorless, oblique rhombic prisms -nith 10 Aij ; which effloresce in
air and gradually lo»e all their Ac|. It fuses at 33^ (0I^4 F.) iu its Aq,
which it gradually loses. If fused at 33'^ (i)1^.4 F.) and allowed to eool,
it remains liquid in sftpt^jtaiuraied aolotion, from which it is deposited, the
entire mass becuiuing solid, ou contact with a KUUkU particle of Kolid mat-
ter. It dissolves in HCl with oonsiderablo diuiiiiutiou of temperature.
Pm'sioLooiciL. — The neutral sulphates of Na and K seem to exist in
small quantity iu all animal tiH.>nies and tluids, with the exception of milk,
bile, and gastric juice ; certainly in the blood ant) urine. They are partially
introtluced with the food, and partly fonutd iis a result of the metamor- *
pbosis of those constituents of the tissues which contain H \a organic
combination.
The principal elimination of the sulphates Is by the urine. All the
sulphuric acid in the urine is not in simple combination with tlie olkiiline
metals: a considerable amount exists in the form of the alkaline salts of
conjugate, monobasic ether acids, which on decomposition yield an aro-
matic organic compound. The amount of H,KO. discharged by the urioQ
in 24 hours, in the form of alkaline sulphates, is from 2.5 to 3.5 grama
(3K.5 -54 grains) ; that eliminated iu the salts of coujagate acids, 0.617 to
0.094 gi-am (i).5-1.5 grains).
Sodium Sulphite -.SWn suiphw (C. .s'.)-Na.SO, + 7 Aq— 126 +
12G^is formevl by passing SO, over crystallized Ka^CO,. It crj-stallizea
in efflorescent, oblique prisms ; quite soluble iu H^O, forming au alkaline
solution. It acta as a inducing agent
1
Sodium Hyposulphite— iStxiu hi/posuiphig (U. .S".)— Na^Sp. + 5 Aq
— 158 + 90— is ubiainetl hy JissolvinB H m hot couoentraUid aolution of
Na,80,. ftntl crrstallizing.
It funua itu-ga, uolorlesH, efflorescent prienna; fuses nt 45^ {113'* F.);
vetj soluble iu H,0 : insoluble iu olcobot Ibi Holutiuns precipitate alu-
minft from solutions of Al salts, wiUiout procipitatinf;; Fc or Mn ; they diA-
solre miiny compounds inBoluble hi H,0 ; cuprous Imlmte, iodides of Pb,
Ag and Hg, sulphates of Ca and Pb. It act« aa a disinfectant and auti-
SUioates. — Quite a mimlier of eilicat** of Na are known. If silica and
Ka^CO, be fused together, the residue extracted with H.O, and tlie solution
fffaporated, a traospareut, gluse-like muss, soluble in worm wuter, remainB ;
this ia golitble g/oM or icater gltutti. Kxpos(;d to air in contact with stone, it
becomoH insolublu, and foruiit an impermeable coating.
Phosphates. — 'I'niwmr l^nospiUTB — liagic nodium pAospWe— Na,PO,
-^ 12 Aq — 1G4 -f 21t» — is obtained by abiding NnHO to disodic phosphate
fiolutiou and crvstalliziug. It forms six-sided prisms ; quite soUible in
H,0. \iB solution is alkaline, and, on exposure to air, abtwrbs CO, with
fonnation of HNa,PO, and Na,CO,.
Dwouic Phohphatb — flydrih-disodic pAotpAote — Neutral aodinm phofphale
— Phosphate of nofla — 5w/ii phottpluvf ( I7i S.) — Soda phosphaa (Br.) — HNa,
PO, -+- 12 Aq — 142 ■* 2IG-— is obtained by converting tricalciepbospliate
into monocnicic phosphate and decomposing that Bait with sodium car-
bonate : Ca(PO,H,), ■+■ 2Na,CO, = CaCO, -^ H,() + CO -*- 2HNa,lX)..
Below 30" (86*' F.) it crvatallizts in oblique rhombic prisms with
12 Aq ; at 33' (91^.4 F.) it cnst/tUizus with 7 Aq. The salt with 12 Aq ef-
floresces in air and mrts with 5 Aq ; au'l is verj- soluble in H,0. The salt
with 7 Aq is uot efllurescent and less soluble in H^O. Its solutions ai'e
faintly alkaline.
MoNOfionic Phosphate— /1m/ wdium phosphate — H,NaP0.4-Aq — 120
-f- 18:— ctystjUlizes in rhombic prisros ; forming acid solutions. At 100°
(212^ F.> it loses Aq ; at 200" (^2^ F.) it is converted into acid pifropho»-
phaUs. Na^,l\0, ; and at 204° (399^2 F.) into the mtrtapAospAafe, NaPO,.
PcTTsiOLOOicu,, — AU the sodium phosphites exist, aocompanied by the
corresponding K salts, in the animtil economy. Tlie disodic and dipotas-
sic pho«phatea are the most abundmit, and of these two tlie Conner. They
exist in every tissue and Huid of the body, and are more abundant in the
fluids of the oamivorn than in those of the herhivora. In the blood, in
which the Na salt pi-orlomi nates iu the plasma, and the K salt in the cor-
puscles, they sen-e to maintain an alkaline reaertion. With stritrtly vege-
table diet the proportion of phosphates iu the blood diminishes, imd that
of the carbonates (the predominating salts in the blooil of the hcrbirora)
iDoreoses.
The nmnosodic and inonopotassic phosphates exist in the urine, the
farmer prudomtuating. and tu their presence the acid reaction of that
fluid i» largely iluo. Tliey aie produced by decomposition of the neutral
salts by uric aciil The urine of the herhivora, whose blood is poor in
phoHphjitos, is alkaline in reaction.
The greater part of the phosphates iu the body are introduced with
the food. A portion is fnrmorl in the economy by the oxiTlation of phos-
phoiizc-d org;uiic wuhstances, the lecithins.
Diaodio Tetraborate — Smhum pi/robfjrafe — Borate of fOfiium — Bomx
—Ttnf'ol—S'wtii borrut{r. .S'.)— //omx (/M) — Na,B,0, + 10 Aq-202 4-
180 — is prepared by boihng borucic acid with Na^CO, and cryatalliziug. It
■
MAWUAt OP CHBMISTBT.
crcatollizea id hexAj^onal prisms with 10 Aq ; permanent in moist air. but
effloreticent in dry air ; nr tn regubir oetakeilni wttb 5 Aq, ]>ennanent in
dry air. Either form, when heated, fuses in its Aq, swells cousiderablj ;
at a red he»t becomes ouhydrous ; and, on cooling, lonves a tronsparoDt,
glass-like mass. When fused it is cftpable of dt88olving mnnpr metnllio
oiideH. forming rariously colored maaeea, hence ita uae oa a mix and in
blow-pipe aualvKiH.
Sodium Hypochlorite — NaClO — 74.5 — only known in aolntion —
JAq. sodtx chloratir (U. S. ; Hr.) or, Lalnrraque'e tolutwH — obtained by de-
composing a Holittiou of chloride of lime by Na,CO,. It la a valuable
source of CI, and is used as a bleaching and disinfecting agent
Sodium Manganate— Na^MnO, + 10 Aq — 164 -}- ISO — faintly col-
ored crystals, forming,' a green tjolution with H^O — Coiidyn green duin-
fectaut.
Sodium Permanganate— Na,Mn,0. — 282— prepared in the aame
way as the K salt {q. v.), which it resembles in its proi)ert7e8 It enters
into the composition of Condy'sjiuid, and of *' ciUorozone" which contains
Na^Mn.O. and NaClO.
Sodium Acetate— 5odu acetaa {U. R)—Sod(jeaceUvt (i?r.)— NaC,H,0,
+ 3 Aq — 82 + 54 — ^crj-stollizes in large, colorless prisms ; acid and bitter in
tasl« ; quit« soluble in H/> ; soluble in alcohol ; loses its Aq in dry air,
aud absorbs it again from moist air. Heated with soda lime, it yieida
miuTih gas. The anhydrous salt, heated with H,SO,, yields ghiciol acetic
acid.
Carbonates,— Three ai-e known : Na,CO, ; HNaCO,, and H,Na,(CO J^
SoDic C.uuwNATE — Xcutrat <ar6oiia/e— 5oJu — Sal isoda — Wanhiity itoda —
Soda cruataU—^odii carbotuis {U. S.) — S(Mits earbonoi (/ir.)— Na,00, + 10
Aq — 106 + 180— industrially the most important of the Na compounds,
is manufactured by Leblanc's or Solvuy's processes ; or from cryolite, a na-
tive fluoride of Na and Al.
Lebhuic's process, in its present form, consists of three distiucl pro-
cesses : (I.) The conversion of NaCl into the sulphate by decomposiUos
by HjSO,. (2.) The conversion of the sulphate into carbonate by ueating
a mixture of the sulphate with calcium Mrbonate and cliarcoah The pro-
duct of this reaction, kuowu aa iilaci: bail »xia, is a mixture of sodium
carbcmate with clmrcoal and calcium sulphide and oxide. (3.) The puri-
fication of the product obtained in (2). The boll black is broken up, dis-
integrated by steam, and lixi\-iated. The solution on evaporatiou j'ields
the toda aaii or aoda of commerce.
Of late years Leblanc'e prooesa has been in great part replaced by
Solvay's method, or amTnonia jj/vctrss, which is more economical and yields
a purer pro<luct. In this process sodiiuu chloride and umiuouium bicar-
bonate react upon each other, with protluction of the sparingly soluble
sodium bicarbonate aud the very soluble ammonium chloride. The sodium
bicarbonate is tlien simply collected, dried, acid heated, when it is deoom-
poeed into Na,CO„ H,0, and CO^
The anhydrous carbonate, Sodii carhonasf exsiccaiwi ( U. S.), Na,CO„ ia
formed as a white powder by calcining the crystals It fuses at dull red-
ness and gives off n little CO,. It combines with and dissolves in 1^0
witb elevation oJ temperature.
The crystalline sodium carbonate, Na,CO, + 10 Aq, forms large rhom-
bic crystals, which effloresce mpidly in dry air ; fuse in their Aq at 34
(93-'.2' F.) ; ore soluble iu H,0, moat abundantly at 38" (100^.4 F.). Tl»
solutions ai*e alkaline in reaction.
The
Htpbosodio Cabbonate — Mono«odic carbonaU — Bicarbonate of soda —
JUM oorfeonate of Koda — Vichy mil — Sodii bicarhonas — (L*. S,) — Sodce hi-
earhanea (Br.) — XaHCO, — 84— exists in soluUuu iu many mineral waters.
It is obtained by the action of CO, upon tho diaodio sail in tbs presence
ofH,0.
It cTk-fltAllizes in rectanf^ular prisms, anhydrous aiid permanent in dry
■ir ; in damp air it gives ulT CO, and is converted iutu the KeHquicarbunate,
N»,H.(COJ„ When boated, it gives off CO and H,0, and leaves the
diK>dic carbonate ; quit« soluble in wat«r ; atrave 70° (158^^ F.) the eolu-
tioD gives off CO,. The solutions are ulkaliue.
Fhtbiological. — The fiict that the carbonates of Xa and K are almost
invariably found in the ash of animal tissues and fluids, is no evidence of
their existence there in life, as the carbonates are produced by the incinera-
tion of the Na and K saltn of organic acids. There is, however, exceUent
indirect proof of the existence of tho alkaline carbonates in the blood, *
J of tlie Iierbirora, in the urine of the herbivora at all times, and
in that of the comivora and omnivora when food rich in the salts of the
organic aciils, with alkaline metals, iu taken. The carbonates in the blood
are both tho mono- and disodio and potassic ; and the carbonic acid in tho
plasma is held partially in simple- solution, and partly in combination iu
the mouometaUic carbonates,
Analytical Charaoters.
(1.) Hydrofluosilicic acid : gelatinous ppi, if not too dilute.
(2.) Potassium pyroantimonate : in neutral solution and in absence of
fttotols, other than K and Li : a white flocculeut ppt. ; becoming crystal-
line on standing.
(3.) Periodio acid in esceas : white ppt., in not too dilute solutions.
(1.) Colors the Buusen fltune yellow, and ahowa a brilliant double line
at X = 5895 and 5B»9 (Fig. 14. No. 2).
POTASSIUM.
Symbol = K (KAUUM) — Atomic weight = 39 — ifolecuiar weig?U =
78 (?>— Sp. gr. = 0.865— /'««ts at 62'.5 {1W.5 F.)—IMgcovert'd b>j i>awy,
1807 — Names from pot ash, and iiali = asbea (Arabic).
It is prepared bv a process similar to that followed in obtaining Xa ;
'is a eilver-wlute metal ; brittle at O'' (32' F.) ; waxy at 15^ (59° F.) ; fuses
at 62^6 (144°.5 F.) ; distils in green vapors at a red heat, condenaiiig in
cubic crystals.
It is the oidy metal which oxidizes at low temperatures in dry air. in
which it is rapidly coated with a white layer of oxide or hydrate, and fre-
quently ignites, burning with a violet Aame ; it must, tlierefor, 1>e kept
under naphtha. It decomposes HO or ice with great energy, the beat of
the reacuou igniting tho hberoted H- It combines with C'l with incao-
deuencc, and al»o unites directly with H, P, Aa, Sb, and Su. Heated in
I CO. it is oxidized and liberates C.
CompoundB of Potaaslum.
Oxides Three are known : K,0 ; K,0, ; and K^O,.
Potassium Hydrate — i'utat^h — Putaaaa — Common aiu»tk' — Pottan
{U. S.)~Potamx cauOica {Br.) — ^KHO — 5C— is obtained by a prooewi siini-
Ibt to tliat used in monufaottiring KaHO. It in purified bv solution in
atculiol, evaporation and CusioD in a silver basin and ca&tiug^ in silver
moiUila — jiotagh by alcohiU : it is tbeu free from KCl and K^SU,, but eon-
tains small quautitiesof K,CO, and fi-cquently As.
It is usuaUj met with in cylindrical sticks, lund, wliite, opaque, and
brittle. Tbe KHO by alcohol has a bluistitinire and a Binoutlier mirftice than
tbe cummon; Hp. gr. 2.1 ; fuses at dull redness ; i» freely soluble in H,0,
formiuf; a stron^^ly alkaline and caustic liquid ; less eolnble in aloobot In
air, solid or in Bolutinn, it absorbB U,0 and CO,, and ia converted into
K^OO,. Its aolutiona diaaolve CI, Br, I, S, and P. It decomposes the am-
mouiacrd salts with lilwratiou of NH, ; and the aalts of many of the
metula, with fonuation of a K salt oud a metallic hydrate. It diasolvee the
albuminoids ; and> when heated, dcroniposeii them with formation of lencin,
tyroain, et«. It oxidizes the carbohydrates with formation of potasHium
oxalate and carbonate.
Sulphides.— Five aie known : K,S, K,.S„ K,S„ K,S^, and K,S. ; also »
Bulphy.lrate : KHS.
PuTAKsritM MuNoauLPHtDE — K S — 110 — Is fonued by the action of KHO
on KHS.
PoTARsriM DiaTTi,pini)R — KjS^ — 142—18 an oran go-colored solid, formed
by exjxmiii^' an alcoholic oolution of KHS to the air.
PoTAasiiM Thisulfhuse — K,S, — 174 — n bixuvuiah-yellow mass, obtained
by fuBinfj together K,CO, and S in Uie pmportiou : *4K,C0, + 108 = SO.
K, + 3K,S, + 4CO,.
PoTAKSH'M PKNTAStTLMiinB — K,8, — 238 — Ih foniicd, OH a bn>wo mass,
when K CO, and H are fused together in the pi-oporliou : 4EL,CO, -f 1(JS
= 400, -t- :^K,S. -t- K,SO..
Liver of ttulphur — M/Hir sulj^urui — potagsH stJphuntuni ^U, &; Br.) — is
a mixture of K,S, and K,S^.
PoT^ssI^w Sr-LPHVDBATE— KHS — 72 — is formed by saturating a eolation
of KHO with H,S.
Potassium Chloride — Sal diycsthnim Sylvii — KCl — 74.5 — exists io
nature, either pure or mixed with other cblorideB ; principnlly as carnaUile,
KCl. M({CI + 6 Aq. It crystallizes in oidivdrcuu, pennauent cubes, sol-
uble in H,0.
Potassium Bromide— Po/a&*ii hromidum {T\ S. ; lir.) — KBr — Hfl —
is formed either by decoropoaing ferrous bromide by K,CO,, or by disi-
Bolving Br in solution of KHO. In the latter case the bromafe formed is
oonveiled into KBr by calcining the product It crystallizes in anhydrous
cubes or tables ; has a sharp, sidty ti^te ; very soluble in H,0, H^iariugly so
in alcohol It is decomposed by CI with liberation of Br.
Potassium Iodide — I'otassii wiUiuyn {C. S. ; Br.) — KI — Ififi — is ob-
tainefl by satui-ating KHO sobition with I, evaporating, and calcining the
resulting mixture of iodide and iodate vrith charcoal. It frerjuenlly con-
tains iodate and coi'bonate. It cryiitallizeH in cubes, tmnspareut if pure ;
permanent in air ; anhydrous ; solulile in H () and in alcohol. It is de-
composed by CI, HyO, ami H\0 , with Uberntiou of L It combines with
other iodides to form double iudidea.
OP POTASSnTK.
137
Salta of Potassium.
PotasBluzn Nitrate — Nilre — Saiipetre — Potasixiiniirfat{U. S.) — Pottuso!
itiinu {Hr ) — KNO, — 101 — occurs iii uaturo and is produced arUficioUysB
tt rabult of tbo (lecoinpotnitian of nitrogenizod or^nnic RuLstauces. It is
usually obtained by deconipoaing native NaNO, bv boiling solution of K,
CO, or KCl.
It cr>'BtalUze8 in six-sided, rhombic prisms, grooved upon the surface ;
soluble in H,0 with depression of temperature ; more soluble iu H,0 con-
taitiing NaCl ; very sparingly soluble in aloohol ; fuses at 350 {(102° F.)
ritbout decomposition; givea off O and is converted into nitrite below
Tedoess ; more etrou^ly heated, it ia decomposod into N, O, and a mixture
of K oxide& It is a valuable oxidant at high temperatures ; heated vrith
it deflagrates.
Gunpowder la an intimate mixture of KNO, with S and C, in such pro-
>rtion that the KXO, yielils all the O required for the combusliou of the
uda
Potassluin Chlorate — Fotatrsii chIorwt{U. A'.) — PotasittE chloras {Hr.) —
KCIO,— l:2ii.."i— iH prtpiirwl: (1) by passing' CI thixjugh a solution of £H0;
(2) by passing ^^ over a mixture of mill: of lime and KCl, heated to 00°
1140^ K). It cnr'stallizea in tronaparent, anhydrous plates; soluble in
B O ; Bparinglv soluble iu weak alcohol
' It fuses at -iOO* (752" F.). If further heated it is decomposed into KCl
■nd i>erchlorate, and at a still hi;.'lier temperature the percldorate is de-
composed into KCT and O : 2KC1(), = KCIO -f KCl + O, and KCIO =
KCl + 20,. It is a valimble source of O, and a more active oxidant tnan
KSO,. Wlien mixed with readily oxidizable substances, C, S, P, sugar,
tauuiu, resins, etc., the mixtures explode when subjected to shock. With
strong H.SO^ it gives off C1,0,, an explosive yellow gas. It is decomposed
ffcy HNO.with formation of KNO., KCIO,, *and liberation of CI and O.
Htistetl with HCI it gives off a mixture of CI and C1,0., the latter acting
as an energetio oxidant in Kolutions in which it is generated.
Potassium Hypooblorite — KCIO — lK)."i — is formed in Bolution by
imperfect aalur.itiou of a cuoled Sfjlution of KHO with hypochluroua aciil.
An impure solution is usetl iu bleaching : JaoeUe ttrafer.
Sulpfaates.— PoTASBic Shu^jite — IHjyotamr siilphaie — Potasgii vuljfixas
(f. S.)-— fWosscF Hulphas {fir.) — K^BO, — 174— occurs native ; in the ash of
many plants ; and in sohitinn in mineral waters. It crystallizes in right
rhombic prisms ; hard ; permanent in air ; salt and bitter in tasto ; soluble
tnBLO.
annfOPCfrxBRtcHrrLTBKTK—Sfonopotamice^Uphate — Addnulphate — KHSO^
— 13G — is formed as a by-protlnct in the manufacture of HNO . When
heated it loses H,0, and is converted iuto the pt/rosulphaU; K,S,0„ which.
At a higher leinporature, is decomposed into K,SO, and fiO,.
Potassio Sulphite — IhpoiaKnr vulphiin — i'oimvii sidphis {U. S.) —
K^SO, — 158 — is formed by saturating solution of KCO^ with 80^ and
evaporating over H,SO,. It crjutallizen in oblique rhombohedra ; soluble
in H,0. Its solution absorbs O from air, nith formation of K,SO,.
Potassium Diohromate — iiichromiite of poia&h — PotiiMtn tnchromas
(U. S,)—PolasacB bickroman {flr.)—K,Cr,0,— 294.8— is formed by heating
a mixture of chrome iron ore with KNO,, or K,CO, in air ; cxtnicting with
H,0 ; neutralizing with dilute li^SO, ; and evapomting. It forms large,
reddish-orango colored prismatic crystals ; soluble in H,0 ; fuses below
138
HAmJAL OF CHEUISTBT.
redness, and at a higher toTDperatore is decomposed into O, potueiiiiD
diromate, and sesquioxide of chromium. Heated with HCI, it givea off CL
Potassium Permanganate— /'t<fa*WH /jfrr/uoHpanojf {C. .S.)— /'otoawr
permangaiuu {Ur.) — K Mu,0^ — 314 — is obtained by fusing a mixture of
mouganeBe dioxide, KHQ, aud ECIO,, and evaporating the solution to
crjatallizatiou ; K,MnO, aud KCl tiro first formed ; on boiling with H^O
the mangaunte is decomposed into K,Mn,0, and KHO and MnO,.
It cri-atollizes in dark prisms, almost black, with greenish reflections,
which yield a red powder wheu Uruken. Soluble in H,0, coiumimicating
to it a red color, even iu very dilute solution. It is a mostTalunblo oxidia-
iog agent. With organic matter its solution is turned to green by the for-
mation of the maugonate, or deposits the brown sescjuioxide of manganese,
according to the nature of tlio urgmiic substance ; in some instances the
reaction takes place best in the cold, in others under the inliuenoe of heat ;
in some better in acid solutions, in others in alkaUne solutions. Mineral
reducing agents act more rapidly. Its oxidizing powers I'euder its solu-
tions valuable as ilisicifectants.
Potassium Acetate — VoUjmU acetaa {V. S.) — PotasacB acetag (Sr.)—
KC,H,0, — 11(J — exists in the aap of plants; and it is by its calcination
that the major port of the carbonate of wood ashea is formed. It is pre-
pared by neutralizing acetic acid with K,CO, or KHCO,.
It forms crystalline needles, deliquescent, and very soluble in H,0 ; less
soluble in nicohol. Its Kolutions are faintly lUkaline.
Carbonates— Ft/rASSiu C\iuioxATK—Salt o/' tartar — Pearl oak — Ptitasii
carboiias {L\ S.) — Fotas^-w carOouas {ltr.)—K^<U). — 138 — exists in mineral
waters and in the animal economy. It is prepared industrially in an impure
form, known us fxtiash or jtearlash, from wood ouhes, from tlie molaHses of
beet-sugar, and from the native Stassfurth chloride. It is obtained puie
by decomposing the monopotassic salt, puritied by several recrvstolliza-
tions, by heat or by calcining a potassium salt of an organic acid. Thus
cream of tartar, mixed witli nitre aud heated to redness, yields a black
mixture of C aud K^CO^ called black Jiux ; ou extracting which with H,0,
a pure carbonate, known as soU of tartar, is dissolved.
Anhydx'oua, it is a white, granular, deliquesceiit, very soluble powder.
At low temperatures it crystaUizea with 2 Aq. Its solution is alkaline.
HvDaopoTAssio CAB^osiTK^Monopotaasic carhonntc — Jlicarhonate — Potai-
8U bicarhonas (C. S.) — Polani^ai bicarbonaB (Br.) — HKCO, — IQO— is obtained
by dissolving K,CO, in H,0 and saturating the Bolution with CO,. It
crystallizes in oblique rhombic prisms, much leas soluble than the carbon-
ate. Ill solution it is gradually converted into the dii)otassic salt when
heated, when brought into a vacuuin, or when treated with an inert
gas. The solutions are alkaline in reaction and in taste, but are not
caustic.
The substance used in baking, under the name saJieratue, is this or
the corresponding Na salt Its extennive use in some parts of the
country is undoubtedly in great measure the cause of the prevalence
of d^'Spepsin. When used alone in bodying it " raises " the breail by
decomposition into carbon dioxide and dipotaasic (or disodio) carbonate,
the latter producing disturbances of digestion by its strong alkaline reao-
tion,
Hydropotasslo Oxalate — 3Ionopot'jAnc oxalate — Biiwxalatr of Potafh
^HKC O^— 128^form9 traiispAi"ent, soluble, acid needles. It occurs,
along with the 'jtuuintj-alatf, HKC.^0,, Hj.C,0,-|-2 Aq, in mif of lemon ov salt
ofaurmi, used in straw bluaching aud for the removal of ink-stains, etc It
I
i
I
K
closelv resemblea Epsom Bali tn appearance, and has been fatally mistaken
fur it.
Tartrates. — Pot,ui«ic Tabtratr— ZHpo/ttMic tartrate — SotuNe tartar—
Keiitrai tartrate of potash — folasgii tartras {U. S.) — Potaxxtn lartrax (fir.) —
KfC,H,0^ — 2*26 — ia prepared hy ueutraliziu^ the Lydroputodsic aalt witli
potaaeiuin carbonate. It forms a white, crystalline povrder, very soluble
in H,0, the solution being dextrogyrous, [a]^ =^ + 2S\i8 ; soluble in
alcoboL Acids, even acetic, decompose its solution with precipitation oi
the monopotaasio ealU
HYDitopoT.\ssio Tarteate — Mojiojwtassic tartrate — Cn-am of tartar — Po-
tassii bUartfXiM {C. S.)~PotasatE bitartraa (Br.)— HKC,H O,— 188.— Dur-
iug the fermcutation of (^niije-juict', as the prupurtluii of olcohul increases,
crystalline crusts collect in the cask. These constitute the crude tartar or
argol of commerce, which is comp<^9ed, in great part, of monopotasKic t^ir-
trate. The crude product is purified by repeated crvstallizatiou from
boiling H,0; digesting the purifietl tartar with Hd'at 20^ (68" F.) ;
vashing with cold H,0, and crystallizing from hot H,,0.
It cryfrtallizea in hard, npaque (translucent when pure), rhombio priamB,
which bare an acidulous taste, and are very sparingly soluble in H,0, atiU
leas soluble in alcohol. Ita solution is acid, and dissolves many motallio
oxides with fonnation of double tartrates. When boiled with antimony
itrioxide, it forms tartar emetic.
It is used in the household, combiueil with iiionoHodic carbonate, in
baking, the two substances reacting upon each other to foim Itochelle
salt, with liberation of carbon dioxide.
B&KOtQ-i^wDRitH are now largely used as substitutes for yeast in liie
manufacture of bread. Thcii* action is based upon the decomposition of
HNaCK)j by some salt having an ooid reaction, or by a weak acid. In ad-
ditioD to the bicarbonate and flour, or corn starch (added to render the
bulk conveuient to handle and to diminish the rapidity of the reaction),
" ley contain cream of tartar, tartaric acid, alum, hydrochloric acid, or acid
ihosphatea Sometimes ammonium sesquicarbon&te is used, in whole or
part, in place of sodium carbonate.
Hie reactions by which the CO, is liberated are :
1. HKC.H.O,
U)'<tro[MUiMla
uruMv.
2. H,C.H.O,
Tvlam: aciil.
-}- NaHCO
-f. 2NaHC0
catbonau.
NaKC.H.O, +
Sodium poUAtltun
NaC,H.O, +
H,0
W*ur.
a Al,(SO,),.K,SO,4-6NaHCO, = K,SO, -f 3Xa,S0, + A1,H,0, + fiCO..
[TfttaMihiiTi itlmMi
MAmTAt OF OHBJnOTRT.
6. HCI + NaHCO. =
Mid. auboaml*.
7. NaH.PO, -H NaHCO.
8. 2A1.(S0.). + 3[2((NH.LCO,)COJ +
AJniiilnlam Asmonluo
wl|)bAUB. aMqaSowtMiiiMe.
NaCl + H,0 + CO,.
Sodltun Water. Oubon
chlovlda. diiuUd*.
= NtHPO. + ILO -
MmMc
ptumfitmlm.
6H.0 =
2Al,H.O, +
AltunlDbuin
fajrdntc
OkrtMxi
C(NH.)m
Amnamma
Na 1 is tho reaction wLich takes place when cream of tartar and
or a bRidiig^-powder compose*! of those BubstancoR, are used in laVit
Tlie w>ltil product of the reac^tiou iti Roohelle Holt No. 2 in that wbi
occurs between turtiiric acid and eoda, and is but seldom utilized. Nu. 9
is thiit between burnt potoasium alum and soda. It is not utilized at
present, as the aniiuoniuui alum is more economical. Non. 4 tuid 5 ore
tbofie which occur in olmn baking-powders, the burnt omniouia alum be-
ing onhydruuti ammonium aluminium sulphate, or oluuiiuium sulphate, ac-
cording to the degree of heat used in its manufacture. The soUd residues
of the reaction ore so<lic sulphate and aluminium hrdrate. No. 6 is a re-
action very httle used, on'iug to the inconvenience of hautUing a liquid, to
the too rapid action of tho substances upon each other, and to the danger
of ininxlucing arsenic with the acid. No. 7 is used to a certain extent^
and has the adTantage that the solid residue of the reaction is a normal
constituent of tlie botly. No. 8 is occasioutdly utilized aa an odj uuct to No.6.
In our opinion, while jeoat ia to be prt-feired to any bakin ^'-powder,
an alnm-powder is in no way more liable to produce disturbances of
digestion than one comjxjunded of creiun of tartar und soda. Referring
to Equation 5, above, and taking tbo amount of powder generally used,
35 grains per pound of bi^ad, it will be seen that that amount of ]>owder,
contJiining 9.26 grains of aluminum sulphate, when neutralized during
baking, produces 11.5graiu8of Glauber's salt, 4.24 gtatns of aluminium
hydrate, and 7.12 grains of carbon dioxide. On tho other hand, a cream
of tartar powder to produce, according to reaction above, the same quan-
tity, 7.12 grains, of cai*bon dioxide, forms at the same time 38.9S grains of
Bochelle salt Assuming that one to two pounds is the avenigo amount of
bread consumed by nu adult in twenty-four hours, there can be but little
choice between taking on the one Iinnd 4.24-8.48 grains of alumina and
ll.u-23.0 grainB of Glauber's salt; and on the other hand, 33.98-67.9ti
grains of Itochelle salt. Indeed, thpre is mni*e danger to be apprehended
from the tendency of repeated small dt>sea of Rochelle salt to render the
urine alkaline and tlius favor the forniation of phosphatic calculi, than
from any Bup})ose<l deleterious action of aluminn, whose local action, even
in considerable doses, is that of a very mild astringent, and whose ab-
sorption is very doulttfuL
SonnTM PoTAsertrM TAimuTE — Rochelle soU — Sei rft? geignelte — Potassii et
sodii tartraa {('. S.)—S(xfa tarlarata (//r.)— NaKC,H,0, -t- 4Aq— 210+ 72
— is prepared by saturating hydropotasaic tartrate with sodium cjirbonate.
It crystfUlizos in largo, transparent prisms, which effloresce superficially in
dn' air and attract moisture in damp air. It fuses at 70-80'- (158 '-176°
F.), and losiea 3 Aq at 100^ {212^ F.). It is soluble in H^O, the solutions
being doxtrogyrous, [aj„= +29 .G7,
Ml
K
PoT*sSTrx*A>rrTMnNTL Tabtrate — T'arlarited antimony — 'Hirtar eniftic —
Anttmonn et tH^iasiih tartraa (('. fj.) — AiUimonium tariiwatiim (Br.) — (SbO)'
KC,H O,— 323 — is prepai-ed by boiling a mixture of 3 pta Sb,0, and 4
pts. HiiC.U.O, in H,0 for an hour, filtering, and allowing to crystallize ;
when required pure, il niunt be made from pure materinlA.
It cryataUizeH in tianspareut, soluble, right rbombic octahedra, which
torn white in air. Ibt Bolutioim are acid in reaction, have a nauseating,
metallic taste, are IrBTogjTona. [a]^ ^ +15fi*.2, and are precipitated by
alcohol. The cnrBtals contain ^ Aq, which they lose entirely at 100" (212°
K), and partially by exposure to air. It is dccouipuitcd by the idkalica,
albalino earths, and alkaline carbonates, with precipitation of Sb^O.. The
Srecipitate is redisBolred by excess of soda or potanli, or by tartaric acid.
[CI, H,SO. and HNO, precipitate correspanding antimonyl compouuds
from solutions of tartar emetic. It converts mercuric into niercurous
chloride. It forms double tartrates with the tartrates of the alkaloids.
Potassium Cyanide — Po/o.'wii cyanidum (C S.) — KCN— 65— is ob-
tained by heating a mixture of potasHium ferrocyanide and dry K^CO, oa
Ions u efferreaccuoo oontiuues ; decanting and crystallizing.
It is usually met with in dull, white, omorphous masses ; odorless
when dry. it has the odor of hydrocyanic acid when moist. It is doliquea-
cent, and very soluble in H,0 ; almost iiiiMduble in alcoliol. Its solution
ia acrid, and bitter in taate. with an oftcr-taste of hydrocyanic acid. It is
Teiy readily oxidized to the cyonote, a property which renders it vahinble
ai a reducing agent. Solutions of KCN dissolve I, AgCl, the cyanitles of
and Au, aud many metallic oxides.
It is actively poisonous, and produces iU elTects by decomposition and
Uberation of hydrocyanin ncid (q. v.).
Potassium Ferrocyanide — Telloic prutaiate ofpotaah — PotcLssiifer-
•yanidum {V. S.) — Potaasce prumas Hava (lir.) — K,[Fe(CN),] + 3 Aq —
7.y + 54. — This salt, the source of the other cyanogen compounds, is
manufoclured by adding organic matter (Wood, bones, hoofs, leather, etc.)
and iron to K,CO, in fusion ; or by other procoBsoa in which the N is ob-
tained from the residues of the purification of coal-gas, from atmospherio
air, or fi'om ommonincal compounds.
It forms soft, flexible, lemon-yelluw crystals, permanent in. air at ordi-
nar>' temperatures. They begin to lose Aq at 60° (I-IO'^ R), and become
oubydrouB at IftO" (212" F.). Soluble in H,0 ; insoluble in alcohol, which
precipitates it from its aqueous sohition. When calcineil with KHO or
Bk,CO,, potassium cj-aniile and cyanate aie formed, ami Fe is precipitated.
Heated with dilute H^SO,, it yields on insoluble white or blue salt, potas-
sium sulphate, ntid hydrocyanic acid. Its solutions form with those of
many of the mobUUc saltfl insoluble fcrrocyanides ; those of Zn, Tb, and Ag
are white, cuprio ferrocyanide ia mahogany-<'-oloi-ed. ferrous feirncyanide is
blnbh-wbit«, ferric ferrocyanide (Prussian blue) is dark blue. Blue ink
a solution of Prussian blue in a solution of oxalic acid.
Potassium Ferrlcyanide — lied prtimate ofpotoHh — K,Fe,(CN)„ —
57.8 — is prepared by acting upon IJie ferrocyanide with chlorine ; or,
better, by heating the white residue of the action of H,SO. upon potassium
feiTocyonide. in the preparation of hydrocyanic acid, with a mixture of I
vol. FTNO, and 20 tola H,0 ; the Wfwr product is <ltgested with H,0 and
potassium ferrocyanide, the solution filtered and cvapor.ited.
It fonns red, oblique, rhombic prisms, almost insoluble in oloohoL
With solutions of ferrous salts it gives a dark blue precipitate, TumbuU'n
MATTTTAL OF CITEMTSTRT.
Anftlytioal Characters.
(1.) Platinic ehloride, in preseBoe of HCl : yellow ppt.; orystaUice if
slowly formed ; sparingly soluble in H,0, much less so in alcohol
(2.) Tartaric acid, in not too dilute solution : white ppL; aoluhle in al-
kalies and in concontratcd acids.
(3.) tiydroflaofiilicic acid : translucent, gelatinons ppL; forme slowly;
soluble in strong aDiaUea.
(4) Perchloric acid : white ppt; sparingly soluble inH,0; insoluble
in alcoboL
is.) Pho8i)homolybdic acid : white ppt.; forma slowly.
6.) Colors the Bunsen dame violet (the color is only obserrable
through blue glass in presence of Na), and exhibits a spectrum of two
bright lines : A = 7860 and 4046 (Fig. 14, No 3).
Action of the Sodium and Potassium Compounds on the
Economy.
The hydrates of Xn and of K, and in a leas degree the carbonates, dis-
integrate aiiiuial tissues, dead or li^'ing, with which they come in contact,
and, by virtue of this action, act as powerful caustics upon a liYing tiaaue.
Upon the skin they produce a soapy feeling and in the mouUi a soapy
taatc. Like the oindii, they cause deatti, either immediately, by corrosioti
or perforation of the stomach ; or secondarily after weets or months, by
closoro of one or both openings of the stomaob, due to thickening, conse-
quent ujMn inflammation.
The treatment coneists in the neutralization of the alkali by an acid,
dilute vinegar. Neutral oils and milk are of service, more byrcoaon of
their emollient action than for any power they have to neutralize the
alkali by the formation of a soap at the teui])erature of the body.
The othet compounds of No, if the acid be not poisonous, are without
deleterious action, unless taken in excesfiivo quantity. Common salt has
produced paralysis and death in a dose of half a pound. The neutral salts
of K, on the coutrarj-, ore by no meana without tnie poisonous action
when taken internally, or injected subcntaneously in sufficient quantitie-s ;
causing dyspntea, convidsions, arrest of the heart's action, and death. In
the adult human subject, death has followed the ingestion of doses of ; as,
- 3 j. of the nitrate, in several instances ; doses of 3 ij* - S ij- o' the sul-
pliiaLtre hare also proved fstaL
Omtbiint-'Sim^l = 0*— Atomic tttieM = littft; kniBabldlniB— .'^imtftrt/^ Bh—AUmtc weiglit := StA
— «« twa IV* elenwnU, OlatnTBrad In ISBU by KirvbuA mad Hnliani wbll« fXftinlniRK «p«ctrOK«[4c»Il; Uw
Mb of K fvrlnt tTMrr. Tbry inl«l In vrrf midl i|Dantnt]r In ltpldd>liU. Tlxej cOfnbla* wlUi O Uul dMXn>
pott II)0 e>«D mcR raerit*'Uc«ll/ tti«ii iIom K, fomtlnf stionglir Kllnlltti! brdimte^
SILVER
Symbol = Ag (ARGENTUM)—^ /omic vxiohf = 107.0 — Moiecular*
weight = 216 (?)— .*^>. gr. =^ 10.4-10.54— ibises at 1.000" (1,832= F.).
Although silver is usually classed with the " noble metals," it diflers
from Au and Ft widely in its chemical characters, in which it more oloaely
resembles the alkaline metals.
AKALYTIOAI. CHARACTErW.
143
When pure Ag is required, coin silver is dieeoltetl in HNO, nnd the di-
luted solution precipitated with HCI. Thfl silvpr rhlorirle is wftBh<?d until
the wofihingB no longer precipitate witli ttiWer nitrate ; and reduced either
(1) by suspending it in diUitc H SQ^ in n platinum Imsin, with a bar of puro
Zd, and washing thoroughly ait^r complete reduction ; or (2) by niix-
ing it with chalk and cljarcoal (AgCl, 100 parts ; C, 5 porta ; CnCO,, 70
ports) and grudually introducing the mixture into u red-hot {■nicible.
Silver ia a white metal ; very malleable and ductile ; the best known
conductor of heat aud electricity. It is not acted on by pure air, but is
blackened in air onntaining a trace of H,S. It combines directly witli CI,
Br, I, S, P, and As. Hot H,SO^ dissolves it as Bulphnte, and HNO, as
nitrute. The caustic alkalies do not affect it. It alloys readily with many
metals ; its alloy with Cu is hanler than the pure metal.
Oxides. — Three oxides of silver m-o known : Ag,0, Ag,0, and Ag^O^
Sn,VKB MoNoxiDR — Profojride — Argenti oxidum — (t'. A'.,- Jir.) — Ag^O—
231.8 — formed by pi-ecipitating a solution of silver nitrate with iHjtaah.
It is a brownish powder ; faintly alkaline and very slightly soluble in H,0 ;
strongly basic. It readily gives np its oxygen. On contact with ammo-
nium hydrate it forms a fulminating powder.
Chloride^AgCI — 143.4— fonned when HCI or a chloride is a<ldej to
a solution containing silver. It is white ; turns violet and black in sun-
light ; volatilizes at 2fi0* {r>00* F.) ; sparingly soluble in HCI ; soluble in
solutions of the alkaline chlorides, hyposulphidea, and cyanides, and in am-
monium hydrate.
Bromide — AgBr ; and Iodide — Agl — are yellovrish precipitates, formed
by decomposing silver nitrate with potassium bromide and itMlideu
Argentic Nitrate— ylrvyen/i nitran {C. S. ; /?r.)—AgNO,— 109.9— is
prepared by dissolving Ag in HNO„ c%'aporating, fusing, and recryslalliz-
mg. It crystallizps in anhydi-ous, right rhombic plntes ; solublt* in H,0.
The solutioDH are colorless and neutroL In the pi'eseuce of organic matter
it turns black in sunlight.
The salt, fuserl and cast into cyHndriciU moulds, constitutes litrutr caus-
tic, tapin infei-naliit ; argenti nitran f am (V. A'.). If, during fusion, the tem-
perature be raised too high, it is converted into nitritCi O, and Ag ; and
if sufliciently heated leaves pure Ag.
Dry CI and I decompose it, with liberation of anhydrous IINO^. It
absorbs NIL to form a white solid, AgNO„HNH„ which gives np its Nil,
when heated. Its solution is decomposed very slowly by H, mth deposi-
tion of Ag.
Argentic Cy^xdAe— Argenti cyanidum. {U. 5.)— AgCN— 133.9— is
prepared by patwing HCN through a solution of AgNO,. It is a white,
tasteless powder ; gradually tunis brown in daylight ; insoluble in dilute
acids ; soluble in ammonium hydrnte, and in solutiuna of ammoniacal
salts, cyanides, or hyposulphites. The strong mineral acids deoompose it
with liberation of HCN.
Analytical Charactera.
(1.) Hydrochloric acid: white, docoulent ppt ; soluble in NH,HO;
insoluble in HNO,.
(2.) Potash or soda : brown ppt ; insoluble in oxcoss ; soluble in NH,
HO,
(3.) Ammonium hydrate, from ueuti'al solutions : brown ppt ; soluble
iu excess.
144
MAKITAL Oy OIULUISTBV.
(4.) Hv(lrof];en milphide or ammooiuiQ sulplivdnito : Uack ppt ; in-
soluble io NH.Ha
(5.) Potassium bromido : ypllnwisli-wbite ppL ; insoluble in acids, if
not in great exocsB ; Huluble iu NH,HO.
(f>.| I'otos&iuin iodide : same as EiJr, but the ppt is losB soluble in
NH,HO.
Action on the Eoonomy.
Silver nitrate acts both lonally as a corrosiTe, and 8}'atemically as a tnis
poiaou. It£ local action is due to its decouipi^sitjou by coutact witb organic
Bubetances, resulting in the separation of elementaiy Ag» wboae depoeitaOQ
causes a black stain, and lilKo^tiou of free HXO,, ^liich acta aa a caustic.
When absorbed, it causes uerruus sjmptoms, referable to its poisonoua
action. The blue coloratiou of the sldii, ol>8crved in those to whom it is
adminifltered for some time, is due to the reduction of the metal under the
combined influence of light and organic matter ; eRpedally of the lattor, as
the darkening is observed, although it its less intense, in internal organs.
In acute |x>i8ouiug by silver nitrate, sodiimi chloride or white of egg
should be given ; and, if the case be seen before the symptoms of
are far advanced, emetics.
AMMONIUM COMPOUNDS.
The ammoniuni theory. — Although the radical ammonium, NH^,
has probably never been isolated, its existence in tlie ammoniacal com-
pounds ia almost universally ailmitted. The amniouiuiu hypothesis is
based upon the following Enets : (1) the close resemblance of the anmic
acal salts to those of K and N« ; (2) when ammonia gas and an acid
come together, they unite, unlhoiil libpra/wn of hydrogen, to form an am-
moulacal aolt ; (3) the diatomic anhydrides unite directly with dry am-
monia with formation of the ammonium salt of an anudo acid :
SO, + 2NH, = SO.(NH^(NH.)
Sotpbor trioxlde. Amraonlk. Ammoninin ralpbaautW.
(4J when solutions of the ammoniacal salts are subjeeted to electrolynB^
mixture having the composition NH, 4- H is given o£r at tbe negatiN-e pole ;
(6) amalgam of sodium, in contact with a concentrated solution of am-
monium chloride, inrreaseH much in volume, and is converted into a light,
soft mass, having the lustre of mercurj-. ITiifi ammonium amaigam is de-
composed gradually, giving off ammonia and hydrogen in the proportioi
NH, -t- H ; (6) if the gases NH, + H, given off by deAimposition of tin
amidgam, exist there in simple solution, the liberated H would have the^
ordinary properties of that element ; if, on the other hand, they exist
combination, the H would exhibit the more energetic affinities of an de-l
lent in the nascent state. The hydrogen so liberated is iu the uoacent
CompoundB of Amni" "*^'"! .
Ammonium Hydrate — Caustie ammonia — NH,HO — 35 — has nerer
been isolated, pn>bably owing to its tendency to decomposition : NH HO =
1^, + H,0. It is considered as exiatiug iu the ao-called aqueous solutioua
SALTS OP AMMONITBf.
145
of ammonia Theee are colorleas liquids ; of leas ep, pr. than H,0 ; BtroiiKly
nlkaUne ; anrl Imving the taitte and odor of aintiionia, which gas they give
off on exposure to air, and more rapidly when heated. They are neutralixed
by Bcid«, with elevation of tompemturo and fonnation of oiniiiomiwal Halta
The Aqua ainmonuF (f. S.) and Liq. Ammonke {lir.) are such eolutiona
Sulphides.— Four are known : (NH,),S ; (NHJ.S, ; (NHJ,S. ; and
(XH.),S. ; aa well as a sulphydrate (NH,)Ha
AifMojfnni SiiuHTDinTE — NH^HS — 51 — is formed in solution by satu-
ntisg a Bohition of NH^HO with H^S ; or anhydrous by nuxiiij» equal
Tolumee of dry NH, aud dr>- H^S.
The anhydrous compound is a colorless, transjMiront, volatile and
soluble solid ; capable of subHmation without deeomposition. The solution
when freshly prepared is eolorlesa, but soon becomes vellow from oxidation
and fcjrmatiou of ammuniuiu disulphide and hyposulphite, aud finally de-
posits sulphur.
The sulphides and bydrosulphide of ammonium are also formed during
the decomposition of albaminoids, and exist in the gases formed in burial
vaolta, Mwera, etc.
Aininonluni Chloride — Sal ammoniac — Ammomi cMoridum {V. S. ;
Br.) — NH,C1 — iKl.3 — is obtained from the ammoniacal water of gas-
works. It is a traualucid, tibrous, elastic solid ; salty iu taste, ueutral ir)
reaction ; volatile without fusion or decomposition ; soluble iu 11,0. Its
solution is neutral, but loses NH, and becomes acid when boiled.
Ammonium chloride exists in small quantity in the gastric juice of the
sheep and dog ; oIho iu the perfipiration, urine, saliva, and tears.
Atomonlum Bromldo — Ammonii bromidum {C. S.) — (NH^)Br — 9H
— is formed either by combining NH, and HBr ; by decomposing ferrous
bromide with NH.HO ; or by double decomposition between KBr aud SO,
(NH ),. It is a white, granular powder, or crj'stallizea iu largo prisms,
whicli turn yellow on exposure to air ; quite soluble in H,0 ; TolatUe wiUi-
out decomposition.
Ammonium Iodide — Ammomi ivdidum (U. S.) — NHJ — 145 — is
formed by union of equ:il volumes of NH, and HI ; or by double decom-
position of IU and (NHJ,SO,. It crystAlIizes in deliquescent, soluble
cubes.
Baits of Anmioniuxn.
Ammonium Nitrate — Ammonii nilrm {U. S.) — (NHJNO, — 80 — is
prepared by neutraHzing HNO, with ammonium hydrate or carbonate. It
eryst&Uizes iu flexible, unhy<lrouB, six-sided prisms ; very soluble in H,()
with considerable diminution of temperature ; fuses at 160" (302^ F.), and
decomposes at 210' (-tlO^ F.), witli formation of nitrous oxide : (NHJNO,
= N,0 + 2 H,0. If the heat be suddenly applied or allowed to surpass
260° (482° F.), NH„ NO, and N,0 are formed. WTien fused it is an active
oxidant.
Sulphates—AMMOMo Sitlphatb — Diammonic sulphaie — Ammonii »«/-
phag (U. S. )_(NH,),SO,— ia2— is obtained by collecting the distillate from
amixiureof nmmouiacalgasliquorand lime in H,SO,. It farms anhydrous,
soluble, rhombic crvstals ; fuses at 140" (284" F.), aud is decomposed at
200^ (302" F.) intoNH, and H (NH.)SO..
Hydro.uimonic Sulpoate — Momt-ammnnic aulphat''. — ftisulpAate nf ammo-
nia— H{NH), SO —US^i^ formed by the action of H,SO. on (NH,),SO,.'
It crystallizes in right rhombic prisms, soluble in H,0 and olcoLoL
MANUAl. OK CmCMlKl'ICT.
AmTnonluin Acetate — (NHJC,H,0,— 77— is formed by saturating
noetic acid with NH„ or with ammonium rarbonat«. It is a white, odo^
very soluble solid ; fuses at 8t>' (186^8 F.), nnd gvrea off NH, ; then
Eficfitic ncid, luid finallr acelainidc. Lir^. ammonii acetatia— ^piriX of Mm-
\dererug is an aqueous Rolution of this salU
Carbonates. — Smmwcui Cariioxxte— />uBnmoiiiccor6«iate — NeutrtdatO'
monium lyirfx/nate — (NHJ^CO,4-Aq — 96 + 18 — baa baen obtained as a
vhit« crj*stntliDe solid. ^ air it is rapidly decomposed iuto NIL uikI
(B(NH.)CO..
Htdboauuunio Cakhosatk — Mfmoammonic rarhonate — Acid cari»nale
*o/ammonia — H(NH,)CO, — 79 — is prt-jjored by (Kitamttng a solutioD of
KH,HO or ammonium scsquioarboDnto with CO,. It crrstaUizea in large,
rhombic priHrna ; quite soluble in U-0. At tiO" (140'^ F.) it is deoompond
iuto NH, and CX),.
Ammonium bisguiCAiiDOSATB — Sal volatile — Preston salts — Ammonii oar-
honas {U. S.)--Ammmia! carbonas (Br.)— (NHJ.H (CO,),— 254— is pre-
pared by heatinff a mixture of NH.Cl and chalk, and condensing the pro-
duct. It crygtallizes in rhombic prisms ; has an ammoniacal odor and an
.alkaline reaction ; soluble in HO. By exposure to air or by heating ita
Bolutiou it is decom[>oaod into H,0, NU.. and H(NH.)CO,.
Analytloal Characters.
fl.^ Entirely volatile at liigh tcmporataroe.
(2.) Heated with KHO, the ammoniacal componndfl g;iTe off NH
cogniznble : [a) by changing nioist red litmua to blue ; (6) by itA otloi' ;
fc) by fonning a white cloud on contact with a glass rod moistened
[a
With platinic chloride : a yellow, crystalline ppt
^i^
(4.) Witli hvdro-sodic tartrat«, iu moderately concentrated and neutral
solatioQ : a white, or^-etnUino ppt.
Action on the Economy.
Solutiona of tlie hydrate and carbonate act upon animnl tieaues in the
same way as the corresponding No and K compounds. They, moreover^
disengage NH,, which causes iuteuiw d^^-spuuia, irritation of the air pa»-
sage^ and suffocation.
The treatment indicated in the neutralization of the alkali by a dilnti«
acid. Usually the vapor of acetic acid or of dilute HCl moat be admiais'
tered by inhaiatioii.
TL THALLITTM GROTJP.
THAiaJXJM.
»p- ffr.= Il.S-llJ-nuM Of SI* (Sn* r.y-DUeamtnd
armboi = Tl—Aiomie »tlgitt = xnLT
crookt* (lafu).
Xnn elMasDC, Int abtaln«4 f ram tkc dejxMHa In Aooof ntphDloaeld futertw fn vlijcli pfrnmtnm
Ui« HMti wan BMd. I( rconOM Tb tii «p|K*T»no« aod tn plirXcttt ptoj/unlM, Imt dUBtn MiUnlf tran
Ihmk almMit In ita OlMBatel CttUncrUn. n llwrobln An Lb being uniralrnt Hnd toivolnil, bat OiOtn
fna ll^ and raMatUra tka ■IIuUm maiahilB bshia nadllT OcMbnl, in rmniiii^ nlunu, and tn formlncnoMM
hfdnto. !■ dtlhra tnm tba alkBlla* netak tn lie UmQIo asninuiiiU, which cuiUln Tl'" It li cbftnuUr-
iMd n* c K W0PP*0lly bj • brtgitt tr^ma llM-A a S84a
COMPOriTDS OF OALCrUM.
147
IIL CAIXJIUM GROUP.
Metals of the AlJtaiine Earthn.
CALdUK — Steokttum — Babium.
The memboTB of this gronp are brraleiit in aH their compounds ; each
forms two oxidM : HO and MO. ; each forms a hydrate ha
marked baeio chamcten.
CALCIUM.
vin^
weU-
Symbol = C9i— Atomic weight = 40— ^fotccular vxight = 80 (?) — ^ gr.
L984 — Discovered by Davy in 1808 — Name from calx = lime.
OocuTB only in eombinfltion, ha limestono, marblfi, chalk (CaCO,) ;
aelenite, alabaat«r (CibSO,), atid niauy other lainenUs. In bones,
«gg-«bellB, ojat^r-shells, etc. , as Oa,(PO.), and OaCO,, and in many vegetable
strQctares.
The element is a bard, yellow, very doctilo. and malleable metal ; fum-
ble at a red heat ; not senrably volntile. In liry nir it is not altered, bat ia
converted into CaH,0, in damp air ; decomposes H,0; bums when heated
iaair.
Compotmdfi of Calcium.
i
^■^ Oalcinm Monoxide— t»«it'ifc lime — Lime — Calx {V. S. ; Br.) — CaO —
^^G^is prepared l>v hpiiting a native cftrbonate (limestone) ; or, when ro-
qnired pure, by heating a carbonate prepared by precipitation.
It occurs in while or grayiHli, amui-plioua moeaes ; (nlorleas ; alkaline ;
caustic ; almost infusible ; sp. gr. 2.3. With H,0 it gives off great heat
and is converted into the hydrate (sla/^hing). In air it becomes air-nUu-l^dj
&llij]g into a white powder, having the composition CaCO^, CaH,Oj.
Caloium Hydrate— A'^cXvrf lime—Caldtt htjdras (//r.)— CaH^Q, — 74
— ia formed by the action of H^O on CaO. If the quantity of H,0 used ba
one-third that of the oxide, the hydrat* remains as a dry, white, odorleaa
powder; alkaline in taste and reaction ; more soluble in cold thim in hot
H,0. If the quantity of H,0 be greater a creamy or milky liquid remains,
cream or mili: of lime ; a solution holding an eicess in suspension. With
a sufficient quantity of H,0 the hydrate ia dissolved to a clear solution,
which is lime uxiter — lAquor calcis (C. H. ; Br.). The solubility of CaH,0,
is diminished by the presence of alkalies, and is increased by sugar or
mannite : Liq. catr. saccharattts {Br.). Solutions of CaH,0, absorb CO,
with forniution of a wliite deposit of CaCO,.
Calcium Chloride— Co/ca chloridum (T. .*?. ; 5r.)— CaCl,— 111— is
obtained by dissolving marblo io HU : CaCO + 2HCI = CaCl, -^ H,0 +
CO^ It is bitter ; deliquescent ; very soluble in H,0 ; crystallizes with
6 Aq, which it loses when fused, leaving a white, amorphous mass ; used
M a drying agent.
Chloridb op loiSEr—Bl^aching powdtv — Calx chlorata {V. S. / Br.) — is a
mixture composed chiefly of Ca(!I, and calcitim hypochlorite Ca(ClO), ; pre-
pared by passing CI over CaU,0,, maintained iu exceau. It is a graj-ish
MAKUAL OF OHKMISTKT.
white powder : hitiw and acrid in taste ; nnluble in cold H.O ; decoropoaed
by boiling H,0, and by the weakest acids with lil>eration of CL It is de-
composed by CO, with fomiation of CaCO,, and lil>eration of bypochloroos
uid, if it be moist ; or of CI, if it be dry. A Tslaable diBinfectaoL
Salts of Calcium.
Caloluxn Sulphate — CaSO, — 13G — occurs In nature as anhydrite ;
and with *2 Aq iu gypmim, alaltatfler, ed^nUe ; and in solution in natural
waters. TVrni aiba is ground gypsum. It cirstalUzes with 2 Aq in right
rhombic prisms ; Hparin{»ly- soluble in H^O, more soluble in H.O oODtainm^
free acid or thlorides. \Vben the hvilrated salt (j,;yp«uin) is hcat«d to 80^
(170" R), or more rapitUy botweon"l20^-130" ('24H -266' F.), it loses it»
Aq and is converted into a white-, opacjue niBsa ; which, when ground, is
pia^lfrr-of-Parit.
The netliiig of plaster when mixed with H^O, is due to the conrersiou of
the anhydrous into the crystalline, hydrsted salt The ordinary- plastering
should never be used in hospitals, as, by reason of its irret^ilarities and
porosity it soon becomes saturated witli the transferrers of septic disease,
be thoy f^erms or poisons, and cannot be thoroughly puriBed by disinfect-
antA. Plaster sumoes may, however, be rendered dense and be highly
polished, so as to be smooth and impermeable, by adding glue and almn,
or au alkuliiie silicate to the water used in mixing.
Phosphates.— Three are known : Ca,(PO,), ; Ca,(HPO,)^ and Oft(H,
TiucAUTic Pbosphatk — TViltanc or neutral pbosphcUe — Rone phomhaUi —
Calcii pho^has jmtcipitatuii (U. S.)— CWci> j^lioifjihaa {/?r.)— Ca^(POJ, —
310 — occurs in nature in soils, pusjio, copnilite*, phosphorite, In all plants,
and in every animal tissue and fluid. It is obtained by dissolving bone-ash
in HCl, filtering, and precipitating witliNH.HO; or by double decompoai-
tion between CaCI, and an alkalino pliosphatc. When freshly precipitated
it is gelatinous ; wlien dry, n light, white, amorphous powder ; almost in-
soluble in pure HO; soluble to a slight extent in H,0 containing am-
monincal salts, or NaCl or NaNO,; readily soluble in dilute acids, even in
H,0 pliarired with cwbonic acid. It is decomposed, by Ji,SO, into CaSO.
and Cn{H,POjj. linne-asOi is an impure fonn of Cau(PO,),, obtained by
calcining Imiics, and used in the manufuctui-e of P and of superpfaoephata
DiCAU-ic PaitspHATK— Ca^(HPO,), -(- 2Aq— 272 + 36 — is a ciystalline,
insoluble salt ; furnied by double decomposition between CaCl, and HNa,
PO in acid solution.
MosocALcic PnoBPHATB — Add ralrium phoitphate — Supt^hnnphafe nf
Hmc — Ca(HjPO,), — 234 — exists in brain tissue and in those animal liquias
whoso reaction in acid. It is also formed when Cft,(PO,), is dissolved m au
acid, and is nmnufsrinred, for use as a manure, by decorapoHing bone-ash
with HjSO,. It crjstallizes in pearly plates; very soluble in H,0. Its «>
lutions are acid.
PmrsioLOQicAi-— All three calcium phosphates, accompanied l>y the cor-
responding Mg salts, exist in the animal economy. The tricalcic salt occurs
sn all the solids of the body and in all fluids not having an nrid reaction,
being held in solution in the Inttt-r by the presence of chlorides. In the
fluids it is present in very small quantity, except in the milk, in which it is
comparatively abundant ; 2.5 to S.ftrt parts per 1,000 in human milk, and
1.8 to 3.87 y&xta per 1,000 in cow's milk ; conatitutiug about 70 per cent
L
guulSb of caloittm.
149
of the a&b. The bones contain about 35 parts of orpuitc matter, combined
with 66 partit of mineral material The average of human bone-iuih ia :
Ca,(PO,),— 83.89 ; CaOO,— 13.03 ; Ca, combined with CI, Fl and or'Tanio
Bcida— 0.35 ; Fl— 0.23 ; CI— 0.18. The arerago quantity of Ca.(PO,|, in
male adult bones is 57 per cent ; that of CaCO,. 10 per cent, ; and that of
M;;,(PO,),, 1.3 per cent In paUioIogical conditions the composition of
bone is mudided us shown in the following table :
Aj(ALVBS8 op Bonis.
In 100 pmn*.
IMsddB ptuMphan . . .
OUdan aaoThHL
Pildtinn «wbo(ut*
IMawpwde pbMphAM.
OUwMlb.
OitBalonati«r.,,„
• ladudad Ui Crtoilok pb<M-
plMla.
I^r™
I*
ill
66.1
10.1
i.a
K.8
4^
111
4BJ8
».1B
n,H
■'iM
a.ra
met
^8
it
<1H
4. IB
63.81
1^
1.M
OHO
in
»M0
[ai.itj
*
o«
Nl 1«
nou
8. 4.-1
o.in
san
N
4I.<tl
use
I. OS
I.™
49. n
fl
IO.M
La
vt.»
4.n
in
o.«
TV.W
T
a
I
The teeih conrast largely of Oa,(POJ, ; the dentine of human molars
taining 66.72 per cent, and the enamel 89.8'2 per cent
From the uriiie, tricalcic phonphate is frequently deposited, either in
the form of an amorphous, granuhu" sediment, or as colculL The divalcic
salt occiu* occasionally in uriraiy sedimentR, in the form of needle-
ehape<l crystals arraugetl in rusetteji, and also in uriunry calculi. The
monooalcic salt is always present in acid urine, constituting, with the cor-
responding magnesium salts the eorthtj jtho.->phrtie!t. The total elimination
of H PO^ by the urine is about 2.75 grams {42.5 grains) in 24 hours ; of
which two-thinls ore in combiiuition witli Na and K ; and oue-third with
Ca and Mg. The hourly elimiaation follows about the same variation 08
that of the chlorides. The totid elimination is greater with animal tliau
with vegetable food; is diminished during pregnancy; and is ubovo the
normal during excessive mental work. iTie elimination of earthy phos-
phates is greatly increased in osteumolacia, often so far that they are iu
excess of the alkaline phosphates.
8o long as the urine is arid, it contains the soluble acid phosphates ;
when the reaction becomes alkaline, or even on loss of CO by exjxianre to
air, the acid phosphate is convprted into the insoluble CaJrO,),. Alkaline
urines arc for this reason almost aln-ays turbid, and become clear on the
addition of acid. It is in such urine that phosphatic ealciiU are invariably
formed, usually about a nucleus of uric arirl or of a foreign lHidy. If the
■Ucalinity be due to the fonnation of ammouia, the trimognesic phosphate
is not formed, but ammouio-magnesian phosphate {q. u.).
Quantitntivp. determirwtinn of pho^yhat^x in urine. — A proeera for deter-
mining the quantity of phosphates iu urine is based upon the fonnation
the insoluble uranium phoephat«j and upon the production of a
I
IdO
MAKUAL OF CmEMlSTBT.
brovn color wlieo a Bolution of a uraiuiun salt in broaght in odd-
tact witli B sulutiuu of p<jluaiuLmi ferrocjanidc. Four sulutioiui are n-
quired : (1) a aiandard sottUivn v/* dinodic phogphcU':, made bj diAsolTing
l().08/> grama of orTstoUized, non-efflorencea HNa,PO^ in H,0, ajxl diluting
to a Utre ; (2) an acid yolution of notiium acelate, zn&de by diwolTing 100
ffranu sodium acetate iu H,0, adding 100 c.c. glacial acetic add, and
dilutiDg with 11,0 to a litre ; (3) a etrong solution (^ potassium femcy-
anidn ; (4) a standard aolulion o/'urtmium acettUf, made bv dissolving 20,3
grams of yellow unuiic oxido in glacial acetic acid, and diluting witb H,0
to caarly & litre. Solution 1 Bcrvcs to dctcrumie tbu true streDgth of this
solution. OS follows : 50 c.c of Solution 1 are pliced in a beaker, 5 c.c. of
UoIutioQ 2 ore addod, tlie mixtura heated ou a water-bath, and the uranium
solution griKlually uddeil from a burette until a drop from the beaker pro-
duces a brown color when brought in contact with a drop of the ferrocy*
anide Bnhition. At this ptiint the reading of the burette, which indicates
the number of c c of the uranium solution, corresponding to 0.1 — 1\0^ is
taken. A quantity of H^O, deteruiineil by calculation from the result thug
obtained, is then added to the remaining uranium solution, such as tu
reader eacb c.c. equivalent to 0.005 g^m P,Q^.
To determine tne total phiffpftaies iu a urine: 60 c.o. an» placed in a
beaker, 6 c.c. sodium acetate solution are added ; ilie mixture ia heated
oo the water-bath, and the ui-anJum solution delivered from a burette tmtil
a drop, removed from the beaker and brought in contact with a drop of
ferrocyanide solution, produces a brown tinge. The burette rea^g,
uiultiplteU by 0.005, gives the amount of P,0^ iu 50 cc urine; and this,
multiplie<l by ^^ the amount of urine passed in 24 hours, gives tiie daily
ebminntion.
To determine the '«r//n/ ;>'t'"7Via^d, a siimple of 100 cc urine is ren-
dered alkaliue with NM^iO aud t>et aside for 12 houi-s ; the precipitate is
then collected upon a tilter, washed with aramoniocal water, brought into
a beaker, dissolved in a umiUI quantity of acetic acid ; the solution diluted
to 50 c.c. with U,0, treated with 5 cc sodium acetate solution, and ttie
amount of i'fi^ determined as above.
Calcium Carbonate — CaCO, — 100— the most abunJant of the
natural compounds of Ca, exists as limestone, caiaqjor, cfiaU:, marhle, Ice-
land j*p(ir, and arragonite ; and forms the basis of corals, shells of Crustacea
and of mollusc^ etc.
Tlie precipitated chaik — Caicii carbonas pnecipitata {U. 8. ', Sr^) — is pre-
pared by precipitating a solution of C'aCl, with oiie of Na,CO,. Ptf^red
ehalk — CrvUi ptw/jfifata {C'. <S'. ; Br.) — is native chiilk. pm-ined by grindin g ,
with HO, dihiting. allowing the coarser particles to subside, decaotuflH
the still turbid liijuid, collecting, and drying the liner particles ; a proc^^H
known as elulriatwn.' '
It is u white powder, almost insoluble in pure H,0 ; much more soluble
in H,0 containing carbonic aciii, the solution being regarded as containing
hydrocalcic carhonaf^, Hj.Ca(CO,),, At a re<i heat it yields CO, and CoO. ,
It is decomposed by iicids with liberation of CO,,
Puraiui/wicAU — Calcium carbonate is much more abundant in the lower
than in the higher forms of animal life. It ocouru in the egg-shells of
birds, in the boneH and teeth of all animals ; in solution iu the saliva and
urine of the herbivoro, and dejKisited in the crystalline form, as oioiiihs, in
the internal ear of man. It h depoaited pathologically in calcitications, in
parotid calculi, and occaaioDally in human ui-iufiry calculi and sediments.
Caloium Oxalate — OxtUate of /ime— CaC.O,— 128 — exists iu the
BARIUM.
151
flftp Of many plants, and is formed as a. white, ciratalliiie procipitato, by
doable decnni})08ition Imtween a On aalt and sn tUkalitie oxabite. It is in-
sohible in H,0, acetic ucid« or NH^HO ; soluble m the mineral adda and
io solution of H,NaPO,.
P&TStOLooR^AL. — Calcium oxalate is taken into the body in vegetablo
food, and ia formed in the economy^ wliere ita production ia intunaiely
oonnaoted with that of uric acid.
It oocura in the mino, in which it ie increased in quantity when large
amounts of regetable food are taken ; when sparkling wines or beers are
indulged in ; and when the carbonates of the alkies, lime-water and
Wuiou-joice, are adniiuisteretl It is deposited as a urinary sediment in
the form of small, brilUant octahedral having the appearance of the backs
of square letter-envelopes ; or in dumb-bella. It is usually deposited from
acid urine, and accompanied by crystals of uric acid. Sometimes, bow-
ever, it occurs in urines uudergoiug alkaline fermentatiou, iu which case
it is ac-companied by cTy»tals of ammonio-magnesian phosphate.
The renal or venical calculi of calcium oxalate, known as mulberTy cal'
cidi, are dark brown or gray, very bard, occmrioually sniooth, generally
tuberculatc-d, soluble in HCl witliout cfTervesceuce ; and when ignited, they
blAokeo, turn white, and leave an alkaline residue.
ft
Analytioal Characters.
(1.) Ammonium snlpbydrate : nothing, unless the Ca salt bathe phos-
phate, oxalate or lluurtde, when it forms a white ppt.
(2.) AUcolino carbonates : white ppt ; not prevented by the presence
of ammoitincal Halta.
{ft. ) Ammonium oxalate : white ppL ; insoluble in aoetio omd ; aolubla
in HCl, or nXO,.
(4.) Sulphuric acid: white ppt., from solutions which ore not too
dilute ; vety sfKiringly soluble in H,0 ; insoluble in alcohol ; soluble in
sodium hyposulphite solution.
!5.) Sodium tuugstate : dense white ppt, even from dilute solutions.
G.) Colors the tlame of the Bunsen burner reddish-yeilow, and exhib-
its a spectrum of a number of bright bandH. the most promineut of which
Bhre : A = G2G5, G202, til81, GOU, oB82, 5'J33, 5543. and 5517.
JU rtnMol, Ml M ftbnndMit M Ba, oomrrlaK priiwlpdr in tte niBindi Mr»iWton<w fCO,Sr1 sad c^^
HNrfSO.flr). lUMMnpoandartMHnble tboMbf Oi mad IU. Ibnhrale 1« OMd !■ ■wkinic ml arc.
Aaalrttad ABTMtnu— (1.) &«hftn*IU»B«*rtthkUuJiiM>OMtMBMMMtd POt>U,U. {t.) CalchimnU-
t: •■fell* lift. Whkh telM rivwif ; anwlaratad by ■adlUtwi of ^MboL (8.) Tbv ?r cumiwuada coloc
Iwn— Hum nd, or. m* Bt—»eii Ibimigh Unn ||hw. purula or nma wlor. Th* Kt lUiaa giro « mtm-
ffTRONnUM.
t= Sr— Jtonifo teflffht = ta.4—^. (pr. = IH.
pteM
UMUuiiMa
IiaaMjlMnl^atwfaiebttonottpraailiiHtvB: '*.=
im,«OB«,«0a,«NT.
BARIUM.
Symbol = Bti— Atomic wfvjhl = VAfi.S—MoIeouIar twi'^ft/ = 273.6 {?)-^
gr. = 4.0 — Discovered by Davy, 1808 — Namefrtrnx fiapv^ = heavy.
Oocurs only in combination, principally as heavy spar (BaSO,) and
te (BaCOj. It i.q a pale yellow, moUeablo metal, quicaly oxidized
air, and decomposing H^O at ordinary ieutperatures.
I
Oxides. — Babiuh Mokoxide — BaO — 152.8 — ia prepared by calaniug
the nitmie. It is a gra^iab-wlate or white, amorpbouB, oanstic solid. In
air it absorbs moisture hihI CO,, and combineft with H,0 aa does CaO.
Babitiic Dioxu>e — BaO, — 168.8 — la prepared by hetiting the mouoxide
in O. It is a grayish-vvhitc, amorj)hous sulid. Heated in air it ia dooom-
liaO, = VieX) + O. Aqueous acids diasolre it with formation of a
ic salt and H,0,.
rlum Monohydrate — Cattntic baryta — BaH^O, — 170.8 — is prepared
by the ootion of H,U ou BaO. It ia a white, amorphous eoUd, soluble in
H,0. Its aqueous solution, bort/la vxUer, is alkaline, and abaorbe GO, with
formatiou of a whito deposit of BaCO^.
Barium Chloride— BaCl, + Aq— 207.8 4- 3G-is obtained by tieab-
ing BaS or BaCO, with HCl. It crystallizes in prismatic plates, pcnua-
nent in air, soluble in H,0.
Salts of Barium.
Barium Nitrate — Ba(NO,), — 260.8 — is prepared by neutralizing
HNO, with BaCO,. It forms oclahedml crystals, soluble in H,0.
Barium Sulphate— BaSO,—2it2.8— occurs in nature as heavy ipar
and is formed na an aiuorjihou-s, white jxiwdor, iiisohible in acids, by
double decomposition between a lia salt ami a sulphate in solution. It is
insoluble in H,0 and iu acids. It is used as a pi<(Dient, permanent white.
Baritun Carbonate — BaCO, — lafi.S — occurs in nature as teiUierU^,
and is formed by double decomposition between a Ba salt and a carbonate
in alkaline soluttou. It ia a heavy, amorplious, white powder, insoluble in
H,0, soluble with effervescence in acids.
Anal3rtioal Characters.
Alkaline carbonates ; white ppt.,in alkaline solution.
Sulphuric acid, or calcium sulphate : white ppt ;
insoluble
VS.) Sodium phosphate : white ppt ; soluble in HNO^
(4.) Colore tlie Bunscn flame greenish -yellow, and exhibits a f^>ectnim
of seTcral lines, the most prominent of wluch are: X ~ 6106, 6044, 5681,
5636.
Action on the Economy.
The oxides and hydrate act as corroHivea by virtue of their alkalinity,
and also aa true poisons. All soluble conipcmnds of Ba, and those which
are readily converted into soluble compounds in the stomaeh, are actively
poisonous. Soluble sulphates, fuUuwf?d by emetics, are indicated as anti-
dotes.
TV. lUGNESIUM GROUP.
MaOKESIW ZlMO — C&BHItTM.
"Each of these elements forms a single oxide — a corresponding basic'
drate, oud a eehes of solta in which its atoms are bivalent.
MAGNESIUM.
r
Symbol = Mg — Atomic wW'/ft/ = 24 — Molt^culur vxig^ = 48 (?) — &}.
=: L7&— /\w« 0/ 1000" (1832^ F.)— ^>««'i'<^'^ ^y ^"V- 180a
Occurs aa corboDato in doiomUeoT magnesian limentone, and as silicate
in mica, asbestos, soamtotie, mt^rtchaum, laic, and in other miuerala It also
aocompanies Ca in the forms in which it is found in the animal and vege-
table worlds.
It is jirepiu-ed by heating its chloride with Na. It is a hard, light, mal-
leable, ductile, white metiU. It bums with gi*ent brilliiuicy when heated in
lir (mngTieKiuni light), but may l>e dittlilled iu H. It decom[>i)»e8 vaiior of
H,0 whf:n heated; i-educeu CO, with the aid of heat^ oud oom bines du^ctly
with CI, 8, P, Aa, and N. It d^eolves in dilute acids, but is not affected
1^ alkaline solutions.
Compoiizids of Magneaiuxn.
Magnesium Oxide — Calcined vtagnesia — itxagi^Ma {U. S,; Br.) —
MffO— 40— is obtained by calcining the cArbonate, hydrate, or nitrate.
It is a light, bulky, tastelesH, udorlesH, aiu(>r[>hoiiti, white jiowder; alkaline
iu reaction ; almost insoluble iu H,C} ; readily soluble without eScrreeceooe
in acids.
Magnesium Hydrate — MgH,0, — 58 — occurs in nature, and is
formed when a solution of a Mg salt is precipitated with exoessof NaHO in
abeencc of ammoniacal salts. It is a hea^y, white powder, insoluble in H,0 ;
absorbs CO,.
Magnesium Chloride — MgCl — 05 — is formed when MgO or MgCO,
is dissolved in HCl. It ia an excoediuj^ly deliquescent, eulitblo substance,
which is decomp(^se<l into HCl and MgO when its aqueous solutions are
evapoiBted to dimness.
r
Salts of Magnesium.
Magnesium Sulphate — Ef>fiom mlt — S^dliiz salt — Mtrnteni sulphtu
{U. S.)—Maifnemr. sulphur (^r.)— MgSO + 7 Aq— 120 + 12G— exists in
solatiou ill Hea- water and in the waters of many miiicnil springs, especially
those known as hitler mtierit. It is formed by the action of H,SO, on Mg
00,. It crystallizes in right rhombio prisma ; bitter ; slightly efferres-
oent, and quite soluble in H,0. Heated, it fuses and gmduidlv loses 6 Aq
up to 132' ('26fl^.ti F.) ; tlie last Aq it loses at 21(r (410'^ F.).
Phosphates. — Basemble those of Ca in their constitution and proper-
ties, and accoiu[jatiy them iu the situations iu which they occur in the ani-
mal body, but in much smaller qa-intity.
Magnesiiun also forms double phoHphates, constituted by the substitu-
tion of oue atom of the bivalent metal for two of the atoms of basic hy-
drogen, of a molecule of phosphoric acid and of an atom of au alkaline
aiew, or of an ammonium group, for the remaining basic hydn^gen.
Ammonio-Maonesun Puospuate — Triple phosph^ — Mg{NH jPCX -f 6
+ 108— is produced whoa an alkiuine phosphatvuud NH,HO are
134
KANUAL OF CHEMISTBT.
added toa boIuUod cotitaining M(^. Wlioa heated it is coDverted iuto mng-
nesinm pyrophosphate Mg,P,0,, in wbioh iorm H,PO, uid Mg are nsually
weighe^iin (juoiititntive aualyaia
In the nhne, olkaUno phogphAtes and maf^esium salts are always
preaent, and oonaequentlv when, by decomposition of nreo, tiie urine be-
comes sdkaliue, the couJiUoos fur the formation of this compound are
fulfilled ; oud boiu^ practically insoluble, eBpeciaUy in the presence of
uoees of phosphates and of aiomouia, it is depositexl in cr^'stala, usually
tabular, sometimes feathery and stellate in form. When it is formed in
the bladder, in the presence of some body to serve as a nuclcua, the
crystallization takes place upon the nucleus and a fuaible calculus is
producf'i.
Carbonatee. — Magkesiuv Gabbokate — Keuirat carbonate — ^MgCO, — 84
—crista natiTc in mn/fneitite, and, combined with CaCO,, in dolomitn. It
caoDot t^ formed, like other carbonates, by decompoBing & "hlg salt vith
an alkidiue carbonate, but may be obtained by passing CO, through H,0
holding tetnuut^cneaic tricnrbonat« in Busponaiou.
TmMAGSEMo DicARnoMATE— (MgCO,),iytgH,0, + 2 Aq— 226 -+- 36— ii
formed in small crystals when a solution of MgSO^ is precipitated vith ex-
oeaa of Na,CO, and the mixture boiled.
TBTEABCAosEaio Tricabbosatk— Ma'f/t'jt-ia alba — Magncb-ii carfconos (f7. S.) —
Magneifi^ carbonan {Hr.) — 3(MgC0.}MgH,0^-ha Aq—:il0 + 54— occurs in
commerce in lif^liti white cubes, composied of a powder which ia amorphous
or partly cryatidline. It is prepared by prccipttetiug u «olution of MgSO,
wiUi one of Na,CO, ; if the precipitation occur in cold dilute solution*
(Maf^nesifS carboiias /u;l'w, Jir.), very little CO, is given off ; a li^dit^ bulL7
pi*ecipitate falls, and the solutiou contains magnesium, probably in tho
form of tho bicarbonate Mg(UCOj), ; this solution, on standing, deposits
crystals of the carbonate, MgCO, + 3 Aq. If hot concentrated solutions
be used and tho liquid then Iwiled upon Oie precipitate, CD, is given ofl^
and a denser, heavier precipitate in formed, which varies in comjxwifion
accordiug to tlie length of time duniig which the boiling is continued,
and to tho presence or absence of exctss of sodium carbonate. The
phannacenticftl product frequently contains 4{MgCO,),MgH,0, + 4H,0,
or even 2(MgCO,),MgH,0, + 2H,0. All of these compounds are very
S])aringly soluble in H,0, but much more soluble in 11,0 containing am-
moniacol salts.
Analytical Charaotem.
J
(1.) Ammonium hydrate : voluminous, white ppt from neutral solu-
tions.
(2.) Potash or soda: voluminous, white ppt fix>m warm solotiooa;
prevented by the presence of NH, salts and of certain organic substances.
(3.) Ammonium cai-bonate : slight ppt from hot solutions ; prevented
by the presence of NH, salts.
(4.) Sodium or potassium carbonate : white ppt, best from hot^ soln-
tion ; prevented by the presence of NH, compounda
^5.) Disodic phosphate : white ppt. in hot, not too dilute sohitions.
(6.) Oxalic acid : nothing aloue, but in presence of NH,HO a white
ppL; not formed in presence of NH^Cl or salts of NH^.
COUPOUXDa OF ZINC.
1B5
ZINa
Symboi = Zn — Atomic weight = ^O—MoUcular weight =. B49 — fJp.
ffr. = 6.862— 7.21&—/'u«tf8 at iW {779° F.}—I>uiiil^ ai 1040^ (1904° K).
Occurs prinoipnllj in adamine (ZnCO,) ; and Uendf. (ZnS) ; also ua
oxide and aUicate ; uever iree. It is tieparuted from its ores by calciuing,
routiug. and di<)tiIIjttioii.
It is a bluisli- white metal ; c^staUioe, grannlar. or fibroua ; quite mal-
leable aiid ductile when pure. The commercial metal in uauallv brittle.
At 130*-150" (266''-802'' F.) it is pliable, and becomes brittle again abore
2CK)-'-210- (39^°-410* F.).
At 500° {'J32' F.) it bums in air with a creeaiah-wbite flame, and givea
offauowy white flakes uf tlie oxide (lana phuosophica ; nil album; painpho-
tix). In moist air it becomes coated witli a film of hydrocarbonaie. It de-
oompoBes steam vhea heated.
Pure HjSO, and pure Zn do not react together in the cold ; if the acid
be diluted, however, it dissolves the Zu with evolution of U and formation
of ZuyO,, in ilie pre&ettce of a traoo of l*t or Cii. The commercial met&l
diaaoWea readily in dilute H^SO,, with oTolution of H and formation of
ZnSO,, the action being accelerated in preaence of Pt, Cu, or As. Ziuc
surfaces tboroughly coated with a kyer of an amrdgaui of Hg uud Zn luo
only att^tcked by ti,>SO, if they form part of closed ^vimic circuit ; heuce
tha zincs of ^'alvanic Imtterioa are protected by amalgamation. Zinc alao
decompoBeu UNO , HCl, and acetic acid.
When required for toxicological analysis, zinc must be perfectly free
from As and sometimra from P. It is better to test samplea until a pure
one ia found than to attempt tbe purification of a contaminated metal
Zinc Burfacea are readily ottuckfd by weak organic acids ; Tcssela of
galoanized iron or stutet zinc should therefor uever be used to contain arti-
elaa of food or medicinea.
r ^
Compounds of Ziuo.
Zlno Oxide— ^inci oxidum {U. S.; Mr.) — ZnO~S0.9~i8 prepared
either by calcining the precipitated carbonate, or by burning Zn in a cur-
rent of air. An impure oxido, known as luUy, is deposited in tJie flues of
zinc furnaces and in those in which brass is fused. When obtained by cal-
cination of Uie carbonate, it forms a soft, white, tasteless, and odorless
powder; when produced by buxuiug the metal, it occura in light, volumi-
nous, white maascA Itis neither fusible, rolatile, nor deronipoRable by heat,
and is completely insoluble in neutral solventa It dissolves in dilute acids,
with formation of the oorresponding salts.
It is used in the arts as a white )>igmcnt in place of lead carbonate, and
is not darkcnoil by 11 K
Zinc Hydrate — ZdH,0, — 08.9— is not formed by union of ZnO and
H,0 ; but is produced wlieii a solution of a Zn salt is treated with KHO.
Frealdv prepared, it ia Tery soluble m alkalies and in solutions of NH,
aaltfl. "
Zinc Chloride- Bu«tT ofnnc—Zmd chloridnm (U. 8. ; 5r.)— ZnOI,
4- Aq — 135.9 + 18— is obtainoil by dissolving Zn in HCl ; or by heat-
It is a soft, white, very deliquescent, fusible, volatile mass ;
Tcrj solublo in H,0, Bomevrhat less so in alcohol Its solution has a
buminfT uietAllio UrttA ; destroys Tegetuble tissnes ; dissnlves silk : and ex-
erts a fitrong ilchydratiiif^ action upon organio substances in geuend.
lu dilute solution it is used as a <^li!jiufectant and antiseptic {BurneU'n
Jiuid), as a presorratiTe of wood and as an embalming injection.
Salta of Zlno.
ZIno Sulphate — White cilriol—Zinci sulphas {U. S. ; J5r.)— -ZnSO
H-nAq — 1G0.9 t-nI8— is formed when Zu.ZnO.ZnS, or ZdOO, is dissohea
in dilute<l H,SO,. It crystalHsws beIo\v 30^ (86^ F.) with 7 Aq ; at 30*"
(86" R) with G Aq ; between 40^-50" (104°-122° F.) with 5 Aq ; at 0°
(32° F.) from concentrated acid solution with 4 Aq ; from a boiling solu-
tion it is precipitated by concentrated H,SO, with 2 Aq ; fi-om n saturated
solution at 100" (212^ F.) with 1 Aq ; aud anhydrous when the salt with
1 Aq is heated to 238» (460^ F.).
The salt usually met with is that with 7 Aq. which Is tn large, colorless,
four-sided priiitns ; effloreacent ; very soluble in H,0 ; sporiugly soluble in
weak alcohol. Its solutions have a strong, styptic taste ; coagulate albumin
when added in niodenite ({uantily, the coagulum dissoUHng in an excess ;
aud form iusulublo precipitates with the tannins.
Carbonates. — Zmc Carbonate— ZnCO,— 124.9— occurs in nature as
calamine. If an alkaline carbonate be added tn a solution of a Zn salt, the
neutral carbonate, as in the case of Hg, is not formed, but an oxycarbo-
nato, nZiiCOj, »ZnH,0, [Zinci carbonas {C S.; Br,)}, whose composition
varies with the conditions under which it is formed.
Analytical Characters.
(1.) Hydrate of K, Na or NH^ : white ppt., soluble in excess.
(2.) Carbonate of K or Na : white ppt,, in rtl>!>eiice of Nli, salts.
(8. ) Hydrogen sulphide, in neutral solution : white ppt. In presence
of an excess of a luiueral acid, the formation of this ppU is prevented un-
less sodium acetate be also present
(4.) Ammonium eulphydmte : white ppt, insoluble in excess, in
KHO, NH,HO, or acetic acid ; soluble in duut« mineral acids.
(5.) Aiiunonium carbonate : white ppt., soluble in excess.
(6.) Disodio phusplmte, iu absence of NU, suits: white ppt., soluble
in acids or alkalies.
(7.) Potassium ferrocyanide : white ppt, insoluble in HCL
Aotlon on the Economy.
All the compoonds of Zu which are soluble iu the digestive fluids be-
have as true poi^ns ; and solutions of the chloride (in common use by
linsmiLhs, and in disinfoctiu;^ fluids) have also well-marked corrosive
properties. >\'hcn Zu compounds are talcen, it is almost iuvariably by
mistake for other substances : the sulphate for Epsom salt, and solutions
of tlie chloride for various liquids, gin, fluid magnesia, i-inegar, etc.
Metallic zinc is dissolved by Holutions containing NaCl, or organic
acids, for which reason articles uf food kept in vessels of galvanized iron
COBALT.
157
become contaminatdd with zinc compouncls, and, if eaton, prodace more
or less inteuae s^oiptomB of intoxicatiou. For the same reason materials
intCDded for analjeis, in cases of uupposed poisoning, thovM never be
liacted in Jan closed by zinc caps.
SjfmM = Cd—Atomic weight = Ul.S—MolectUar teeight = llLS^Sp.
jp. =8.604— />«« at 227=.8 (442^ F,)^Iioil* at 860" (1580* F.).
A white metal, malleable and ductile at low temperature, brittle when
heated ; which accompanies Zn in certain of its orca It resembles zinc
in itA physical as well as its chemical cliaracteni. It a used in certain
fusible alluvs, and its iodide is used in phulography.
Ak-M-ttic'L CnABACTEBs, — Hydrogcn sulphide: bright yellow ppt; insol-
uble in NH.HS and in dilate acids and alkalies, soluble in boiling HNO.
orHCL
V. NICKEL GROUP.
Nickel — Cobalt.
These two elements bear some resemblance chemically to those of the
Fe group ; from which they difl'er in forming, so far an known, no com-
pounds Himihir to the ferrates, chromates, and manganates. They form
cxanpounds corresponding to Fo,0,, but those corresponding to the ferric
series are either wantiDg or exceedingly unstable.
NICKEL,
Symbol = JUi~Atomic vxight = 58 — Sp. gr. ^ 8.637.
Occurs in combination with S, and with S and As.
It is a white metal, hard, slightly magnetic, not tarnished in air,
Oeman silver is an alloy of Ni, Cu, and Zn. Its salts are green.
Analytioal Charaoters.
L) Ammonium snlphydrate : black ppt ; insoluble in excess.
(2.) Potash or soda: apple-green ppt, in absence of tartaric acid;
insoluble in excess.
(3.) Ammonium hydrate: apple-green ppt. ; soluble in excess, form*
ing a violet solution which deposits the apple-green hydrate when heated
with KfiO.
COBALT.
Symbol = Co — Atomic uxight = 68.9—% gr. = 8.5-8.7.
Occurs in combination with As and S. Its salts are red when hydrated,
and usually blue when anhydrous. Its phosphate is used as a blue pig-
ment
155
MANUAL OF CICEMTSTRT.
Analytical Charaoters.
n.) Ammoniam enlphjdrate : black ppt. ; inBoluble in exoesa.
(2.) Potash: bluo ppt. ; turns rod, slowly in the cold, quickly wlieu
heated ; not formed in the cold in presence of KH, Raits.
(3.) Ammonium hydrate: blue ppt,; turus red in absence of air,
green is iU presence.
VL COPPER GROUP.
COPFSB — TiSXBCVVt.
"Each of these elements fozms tvo series of compoonds : one oontaioi
I ;l or (Hg,)" which are designated
by the terminntion otta ; the other contains compounds of single, bivaleut
atoms Cu" or Hg", wliieh are designated by the termination ic.
COPPER.
Symbol = Cu (CUPRUM)— ^(omic weiqht = 6S.1— ^o^eritZor iceighl
= 127 (i)—Sp. gr. - a91-l-8.952— /•««« at 1U91'' (1996" F.).
OooDHRKiCB. — It is found free in crystals or amorphous masses, some-
times of great size ; also a sulphide, coj/jmt pyrites ,- oxide, ruby ore and
biaek oxide ; and basic carbonate, maiackife.
PaopKRiTES. — J'hysicai. — A yellowish-rod metal; dark brmim when finely
divided ; vnry malleahle, ductile, and tenacious ; a gooil conductor of beat
and electricity ; haa a peculiar, metallic taste and a characteristic odor.
Chemkal. — It is imaltered in dry air at the onlinary temperature ; but
when heated to rwiueas is oxidized to CuO. In damp air it becomes
coated mth a brownish fibu of oxide : a given film of boaic caibonate ; or,
in salt air. a {?i-een film of boaio chloride. Hot n,SO, dissolves it with
formation of CuSO^ and SO, ; it is dissolved by hDJO, with formation of
CuJNOJ, and NO ; and by HCl with liberation of H. Weak acids form
with it soluble salts in presence of air and moisture. It is dissolTed by
NH.HO, in prosoneo of air, with formation of a blue solution. It combines
direcUy with G, frequently with light
Compounds of Copper.
Oxides. — Ccpnous Oxwe— Suboxide or red ojcide o/" copper— (Cu,)0 —
142.4 — is formed by calcining a mixture of (OuJCl, and Na,CO, ; or a
mixture of CuO and Cu. It is a red or yellow powder ; permanent in air ;
sp. gr. 5.T49-G.093 ; fuses at a red heat; eaaUy reduced by C or H.
Heated in air it ia converted into CuO.
CnPBio Oxide — tiinoride or UaHc oxide of copper — CuO — 79.2 — Is pre-
pared by heating Cu to dull redness in air ; or by calcining Cu(NO,), ; or
by prolonged boiling of the Uquid over a precipitate produced bj heating
SALTS OF COPPER.
150
* Mlution of a capric Boli, in presence of glucose, with KHO. Bj the lusi
BUtfaod it is sometimes protluced in IVommor 8 test for sugar, when an
etoaaavo quautity of CuSO h»a liecn iwecl.
It is a black, or dark reddish -brown, Bmorjjhoua solid ; readily reduced
by C, H, Na, or K at comparatively low temptrnturoa. When liortt*^! ■with
organic Rubstancee it gives up its 0, coDrerting the C into CO, and the H
into H,0 : 0,H.O + 6CuO = 6Cu -f- 2C0 + 3HjO ; a property which
rendws it ratuable in oi^anic analysis, as uy heating a known wcig}it of
organic substance with CuO and W€if»hing the amount of CO, and H,0
produced, the percentage of C and U may be obtained. It dissolres in
acids wiUi formation of solta
Hydratea.— CtrpBOTO Htthmtr— (Cu),H,0, {?>— lGO.-t(?)— ieformcd as
a yellow or red powder when mixed solutions of CnSO and KHO are
hentad in presence of glucose. By boiling the solution it is rapidly dehy-
drated with fonnation of (Cu,)0.
Cppric Hvdrate — CuH,0^ — 97,2— is formed by the action of KHO
upon solution of CuBO,, in abeence of reducing agents and in tbe rold.
It is a bluiali, amorphous powder ; very unstable, and re^idily dehydrated,
with formation of CuO.
Sulphides. — Ci^Mocs SixpBiDE — Subxvlpkide or proiogtilphide of copper
— Cu,S— 15H.4 — occurs in nature as cojiper glance or chaic<aine, and in
many double sulphides, pi/riifjt.
CnpRiG SruHifE — CuS — 95.2 — is formed by the action of H,S or of
NH^S on solutions of cupric salts. It is almost blat^k when moist,
gnanuh-brown when dir. Hoi UNO, oxidizes it to CuSO, ; hot HCI
copTWta it into CuCl,, with separation of S, and formation of E.S. It is
spatui^y soluble in NH.HS, its solubility being increased by the pres-
ence of organic matter.
Chlorides. — Cwaoua Chloridie — SubcMoride orprotorhloride — (Cu,)Cl,
— 197.4 — is prepared by heating Cu with one of tiio chlorides of Hg ; by
diflsolving (Cu,)0 in HCI, witbont contact of air ; or by tho action of
reducing agents on solutions of CuCl,. It is a heavy, white powder ;
turns violet and blue by expoeui-e to light ; soluble in HCI ; insoluble in
H,0. It forms a cryst-alhznblo compound with CO ; and its solution in
HCI is used in analysis to absorb that gas.
CuFKic CuLuiUDt — Oiloridc or (ieutof-hhride — CuCl, — 134.2 — is formed
by dissolving Cu in aqua regia : if the Cu be in excess, it reduces CuCH, (o
(Ca^)Cl,. It crystallizes in bluishgreon, rhombic prisms with 2 Aq ; deli-
qneecent; very soluble in H,0 and in alcoboL
Salts of Copper.
Cuprio Nitrate — Cu(NO,),— 187.2— is formed by dissolving Ca.
OuO. or CuCO. in HNO,. It crystallizes at 20»-2o' (G8°-77° P.) with
8 Aq ; below 20" (GS"* F.) with G Aq, forming blue, deliquescent needles.
Strongly ht?ated, it is convert**! into CnO.
Cupric Sulphate — Blue vitnol — Blue stove— Cupri sulphas {U. S.; Br.)
—CuSO. + 5 Aq— 150.2 -f 90—18 prepared: (I) by roasting CuS ; (2)
from the water of copi^er mines ; (3) bv exposing Cu, moistened with di-
lute H,SO,. to air ; (4) b>- heating Cu with H^SO..
As ordinarily crj-atJiilized, it ia in fine, blue, oblique prisms ; fiolabic in
H-O ; insoluble in alcohol ; efflorescent in dry air at 15" (59* F.), losing 2
Aq. At lUO' (212'' F.) it still retains 1 Aq, which it loses at 230° (446'*
HAjnTAL OF cnzmsTRT.
F.), leaving a whito. iimorpbous powder of the anhydrouB salt, which, on
taking up H,0, resumes its blue color. Its solutioos are blue, add,
styptic, aud metallic in taatfl.
NMieii NU,HO is ajlded to a Bolntion of CnSO,, a blaiah-wlnte predp-
itute fuUs, which reclisaolves iu excess of the alkali, to form a deep blue
eolution ; strong iilcobul floated over tho surface of this solution separates
long, riglit rhombic prisms, baring the composition CiiS0,,4NH, + H,0,
whiob are very soluble iu H,0. This solution couatitutes ammonio-
fuiphate of copper or aqxia aapphirina.
Araenite-^Schede's green—Mineral green — is a mixture of cuprio
arsenitc and hyilnite ; prepared by adding potassium arsenite to solution
of CuSO,. It is a grass-grceu powder, insoluble iu H,0 ; soluble in
NH HO, or in acids. Exceedingly poisonous.
BcHWEixFTBT (iRKEs — MUiit gTVt'n oT Paris green — is the moat frequently
used* and the most dungerous of the cupro-arscuical pigments. It is pre-
pared by adding a thin paste of neutral cupric acetate with H,0 to a boil-
ing solution of arsenious acid, and continuing the boiling during &
further addition of acetic acid. It is an insoluble, green, czystamoe
powder, baring the composition (C H,0,),Cu + 3(A3,0,Cu). It is decom-
posed by prolonged boiling in 11,0, by aqueous solutions of the alkalies,
and by Uie mineral acids.
Carbonates. — The existence of cuprous carbonate is doubtful. Cu-
pric carbonate— C\iCO, — exists in nature, but has not been obtained ai^
tificially. Dirupric carbonate — CuCO,,CuH,0, — exists iu nature as malo'
chttc. When h solutiou of a cupnc salt is decomposed by an alkaline car-
bonate, a bluish precipitate, having the composition Cu00^OuH,O, 4-
H O. is formed, which, on drying, loses H,0, and becomes green ; it is
used oa a pigment under the name mineitii green, lyicupric carbonate —
Settquicarbonate ofcojyper — 2(CuC0,),CuH,0, — exists in nature na a blue
mineral called azurUe. or mottjuain blue, and ig prepared by a secret po-o-
oess for use as a pigment known as Uue ash.
Aoetatea. — Cumuc XcerxTt— iMacataie — Cryiihdxo/ Venu» — Cupriace-
ta* { r. S)— Cu(0,H,O,), + Aq— 181.2 -t- 18— is formed when CuO or Ter-
digris is dissolved in acetic acid ; or by decomposition of a solution of
CuSO by Pb(C.H,OJ,. It crystallizes in large, bluish-green prisms,
which lose their Aq at UO" (284" F.). At 240'^-2G0^ (464°-500* R) Uiey
are decomposed with liberation of glewial acetic acid.
Basic Acfn-ATia — Verdigris — is a substance prepared by exposing to air
piles composed of alternate layers of grape-skins and plates of copper,
and removing the bluish-green coutiug from the copper. It is a mixture,
in rarying proportions, of three different substances : (C^,0,) CuH,0 -t-
5 Aq ; [(C,H.OJ.CuJ,.CuH.O, + 5 Aq ; and (O.H.O.).Cu.2(CuH,0,).
Analytloal OharaoterB.
CcpBODS — ore very uostable and readily converted into cupric com-
pounds.
il.) Potash: white ppt ; fuming brownish.
2.) Ammonium hydrate, iu absence of air : a colorless liquid ; turns
blue in air.
*juPBH>— are white when anhydrous ; when soluble in H,0 they form
blue or grcpu, acid solutions.
(1.) Uj-drt^eu sulphide : black ppt ; insoluble iu KHS or NalJS; spar-
Acnow ow THE kconomt.
infrlv solable in XH,BS ; solithle in bot concentrated HNO, and iu
KCN.
(2.) Alkaline snlphydrates : same as H,S.
(3.) Potash or soda: pale blue ppt ; insalublo in esceas. If tbe Bolu-
tioo be heated over tlie ppt, the latter coutracta and turns block.
(4.) Ammonium hydrate, in small quantity : p«Uo blue ppt. ; in larger
quantity, deep blue Roliition.
(5.) Potassium or sodium carbonate : grceniah-btue ppt. ; insoluble in
excess ; turning black when the liquid is boiled.
(G.) Ammonium carbonate : piUe blue ppt ; soluble vrith deep blue
color in exoess.
(7.) Potastdom cyanide : grceaisb-yellow ppt ; soluble in excess.
(6.) Potassium fcrrocvanido : cbcstautr-brown ppt. ; insoluble inwealc
acids; decolorized by Kllo.
(9.) Iron is coated with metidUc Cu.
*
Action on the Economy.
Tbo opinion, until recently universal among toxicolof^ts, that all the
compounds of copi>er are poisonous, has been much modified by recent
reaearchea. Certain of the copper compounds, such as the sulphate, hav-
ing a tendency to uunibiiie with albuminoid uitd other animal subataucea,
pioduee symptoms of in-itatiuu by their dii-cct local action, when brought
in contact with the gastric or intentinal mucous membraue. One of the
characteristic symptoms of such irritation is the vomiting of a greenish
matter, wliich develops a blue color upon the addition of NH,HO.
Cases are uot wanting in which severe illness, and even deatb, has
followed the use of food which has been in contact witii imperfectly
tinned copper vessels ; cases in which nervous and other symptoms re-
ferable to a truly poisonous action have occurred. As, however, it has
aldo been sliowu that non-irritant, ptir't copper compounds may be taken
iu considerable doses with impunity, it appears at least probable that the
poiaoaoua action attributed to cupper is due to other substaucca. Tlie
tin and eolder used in the manufacture of copper uteusils contain lead,
and in some coses of so-called copper-poisoning, the symptoms have l>een
such as are as consistent with lead-poisoning as with copper- poisoning.
Copper is also notoriously liable to coutominutioiii with arsenic, and it ie
by no means improbable that compoiuida of that clement are the active
poisouous ogeuts lu some cases of supposed copper-intoxication. Nor is
It improbable that articles of food aUowed to remain e:tpoBed to ail' In
copper vessels ahould undergo thgse peculiar changes which resnlt in the
formation of poisonous substances, such as Uie8auaago> or cheese-iwisous,
or the ptomaines.
The treatment, when irritant copper compounds liave been taken,
should consist iu the admiiiiiilrutiou of white of e^g or of milk, with
whose albuminoids an inert compound is formed by the copper salt. If
vomiting do not occur Kpontoneously, it should be induced by the usual
methods.
The detection of copper in the viscera after death is not withont
interest, espepially if nraonic have been found, in which case its discovery
or non-discovery enables us Ui differentiate between poisoning by the ar-
senical greens and that by other arseuical compounds. The detection of
mere traces of copper is of no sigmficancc, because, although copper is
I
d
MAWTTAl OP CHKSnSTRT.
not ft pliTBioIorrica] ronstituent of the body, it U aImo«tt innimblT pres-
ent, having beea talteu with the food.
Pickles and canned vegetables are sometimes intentionnllT grtened by
the addition of copper ; this fraud is rendilj detected by inserting a large
needle into tlie pickle or otlier vegetable ; if copper be present the steel
will be found to be coated with copper after half an hour's contact
MERCURY.
Symbol = Ug (HYDRARGYRUM)— Atomic vxight = 199.7 — Ato-
Ufnilar weight = 199J— SjKgr. of tiqaiit = IS.MB; of vapor = 6.97~FuaeM
at -38°.8 (-37*.9 F.)~JimU at 360^ (662^ F.).
OcciTBBiifCE. — Chie6ja8 cinnabar (HgS) ; also in small quantitj free and
as chloride.
PKK]MK.^no!(. — The commercial product is usually obtained by simple
distillation in a current of aii- : HgS + O, = Hg + bO,. 1/ rcquirtd pure,
it niuHt be freeil from other motals by diBtillstion, and aptatioD of the re-
distilled product with mercuroua nitrate solution, solution of Fe,Cl^ or
dUtiteHNO,.
PaopKBTiE& — Phyncal. — A bright metallic liquid ; volatile at all tempera-
tures. Crystallizes in octahedra of sp. gr. 14.0. When pure it rolls over
a smooth surface iu round dro[}B ; the formation of tear>shaped drops in-
dicates the presence of impurities.
Cbemioai-— If pure it is not altered by air at the ordinary temperature,
but if contaminate<l with foreign .metals its surface becomes dimmed.
Heated in air it is oxidized superficially to HgO. It does not decompose
H,0. It combines directly with Cl, Br. I and S. It alloys readily with
most metals to form amaltjamn. It amalgamates with Fe and Pt only
witli diflicuity. Hot conceotratrd H,.S<), dissolves it vrith evolution of SO,
and formation of HgSO,. It dissolves iu cold HNO, with forrantion of a
niti-atc.
Elementary mercury is insoluble in H,0, and probably in the digestivs
liquids. It enters, however, into the fonuation of three medicinal agents ;
hydrargyrum cum cnla (C. S, ; Jir.) : maam hydrar\pjri (U. S.) = uilula
hydraryt/riiBr) ; and unguetUum hyiirargtfrU C S.; i/r),all of which owe
their effimcy, not to the metnl itself, but to a certain proportion of oxide
pro<luced during their mannfacture. The fact that bkie mass is more
active than mercury with clialk is due to the greater pn)portion of oxide
contaiued iu the former. It is alao probable that abaoiption of vapor of
Ug by cutaneous euriaces is atteuded by its conversion into HgCl,.
Compounds of Meroury.
Oxides. — MEBmMTTfl Oxipe — Protoxide or black oride of mercvry —
(Hg,)0 — 415.4 — is obtained by adding a solution of {Hg,)(NO,), to an
excess of solution of KHO. It is a browiiisli- black, tasteless powder:
very prone to decomposition into HgO and Hg. It is converted into
iHg,)Cl, by HCl ; and by other acids into the corresponding mercurous
salta
It is formed by the action of CaH^O, on mercurous compounds, and ex-
ists in black wuh.
OOMPOUNDS OF MEUCURY.
163
HisccBIC Oxide — Bed, or binoxide qfm'*rcur}/ — Hydrargyri oxidum Jla-
vum (t" .S*. ; ^r.) — Hydrargyri oxidum rubrum ( U. S. ; Br. ) — HgO — 215.7
— is prepared hj two methwls: (1) by calcining Hg(NO,), »a long as
brown fumes are giTen off (Bydr. oxid. rubr.) ; or, (2) by precipitatiup n
solution of a morcuric salt by excess uf KHO (ffydr. oxid.Jlantm). The
produote obtainerl. although the earao in oompositioD, differ in phyeioal
chaxKcters and in the activity of their chemical actions. That obtained by
(1) is red and crj-stalline ; that obtained bv (2) is yellow and amorphous.
The latter is much the more active in ite cbcmical and medicinal actions.
It is very R|>aringly solnble in H^O, the solntion having an alkaline re-
action and a nietollic taste. It Rxtsts both in solution and in STispenition
in yellow icaahf prepared by the action of CaH.O, on a mercuric compound.
Exposed to light and air it turns black, nioro rapidly in presence of
organic matter, giving off O and liberating Hg : HgO — Hg + O. It
decomposes the chlorides of many motallic elements in solution, with for-
mation of a metallic o\ide and mercuric oxychloridea. It combines witJi
alkaline chlorides to form soluble double chlorides, called chhrmnercuralet
or chtorhyirar gyrates ; and forms simitar compounds with alkaline iodides
and bromiilffs.
Sulphides. ^3lEacDBOD8 S[n.pHa)B — (Hg,)S — 431.4 — a very unstable
compound, formed by the action of H,S on mercxirous salts.
BfESctnuo SuLPHTOE — lied sulphide of mercury — Cinnabar — Vermilion —
ffytfrarcjyri ftuMiidtim rubram (U. 8.) — ^HgS — 281.7 — exists iu nature in
amorphous red masses, or in-red crystals, and is the chief ore of Hg. If
Hg and S be ground up together in the cold, or if a solution of a mercuric
■all l>e completely decomposed by H,S, a black sulphide is obtained,
whieb is the v£f/iio/j« minemlis of the older pharmaoisls.
A red sulphide is obtained for use as a pigment {vennUipn), by amtot-
ing for some hours at 60" (14(>- F.) a mixture of Hg, S, KHO, and H,0.
It is a fine, red powder, which turns brown, and finally black, when
heated. Heated bi nir, it bums to 80, and Hg. It is decomposed by
Btmiig H,SO.. but not by HNO. or HCl.
Ctilorides. — Mei«thoi's Chijdiiwk — I'ratochloride or mild chloride of mer-
cury — Calomel — Hydrargyri chloridum mita (U. S.) — Hydrargyri subrhlori-
dum (fir.) — (Hg^)Cl, — 470.4 — is now principally obtained by mutuid
decomposition of NaCl and (Hg,)SO,. Mercuric sulphate is first obtained
by beating together 2 pts. Hg and 3 pts. H SO, ; the product is then
cnuaed to combine with a quantity of Hg equal to that first used, to form
{Hg,)SO, ; which is then mixed with dry NaCl, and tho mixture heated in
glflis vessels, connected with coudeusuig choiubers ; 2NaCl + (HgJIiJO,
= Na,SO. + (Hg,)Cl,.
In practice, vari-ing quantities of HgCI, ore also formed, and must be
removed from the product by washin}:; with boUed, distilled H,0 until the
washings no longer precipitate with NH,HO The presence of HgCl, in
calomel may Ira detected by the formation of a black stain uimn a bright
iron Hurfa<!e, ImmerBed in the calomel, moistened with alcohol ; or by the
production of a black color by H^.S in 1 1 ,0 which lias been in contact with
and filtered from calomel so contaminated.
Calomel is also formed in a number of other reactions : (1) by the ac-
tion of CI ui>on excess of Hg ; (2) by the action of Hg upon Fe^Cl, ; (3) by
the action of HCl, or of a chloride, upon (Hg,)0, or upon a merrurous
salt ; (4) by the action of reducing agents, induding Hg, upon HgCI,.
Cuomei cr}*stallizeB in nature, and when sublimed, in quadratic prisma.
When precipitated it is deposited as a heavy, amorphous, white powder.
164
MANUAL OF OaXVlSTBT.
faiiiUT yellowish, and prodmnng a }rellowiflh mark when mbbed upon a
dork 8urfac«. It auhUmes, without fusing, between 420"* and 5(t0'' {liiti-
9<:t2'' F.), is insoluble in cold U,0 and in alcohol ; uoluble in 'boiliiiti; H,OU)
the extent of 1 part in 12,000 ; when boiled with H^O for some time, it
Bufiers partial decomposition, Hg in depoRite<l anil HgCl diflaohes.
Althouf^h Hg,C'l, ia iuBoloble in H,0, in dilute HCl, and in pepeiB
solution, it is dissolveil at the body temperature in an otjueuuti oolutiun of
pepsin acidultited with H('l.
Wlien exposed ti> light, calomel becomes yellow, tlien Rraj, owin^ to
partial decomposition, with liberation of Hg ami furmaUou uf UgCl,:
(HgJCl, = Hg -t- HgCl,. It is converted into HgCl, by CI or aqua regia:
(HgJCl, + CI, = 2HgCl^ In the presence of H,0, 1 converte it into »
mixture of H^n, and Hgl^ (Hg )C1, + I, = HgCl. + HgL. It ia also
converted into HgCl, by HCl and by alkaline chlorides : (Hg,)Cl, ~ HgCl,
+ Hg. This change occurs in the etomach when calomel is taken inter-
nally, and that to snob an extent when Lac^ quantities of NaC^l is taken with
tlie food, that calomel cannot be used in naval practice aa it may be with
patienta who do not subtnst npon Halt proviHiuua. It is converted by HI
into (Hg,)I,: (HgjCl, t- 2KI = 2KC1 f (Hg,)I, ; which is then decomposed
br exoesa of KI into Fig and Hgl,, the latter dissolving; (Hg),I, = Hg +
Hgl,. Solutions of the sulphates of Na, K, and NH, dLssolve notable
quantities of (Hg,)Cl,. The hydrates and carljouatcs of K and Na decom-
pose it with formation of (Hg)0: (Hg,)CI, + NaCO, = (Hg,)0 + CO,
+ 2NaCl ; and the (Hg,)0 so formed is decomposed into UgO and Hg.
If alkaline chlorides be idso present, they react upon the HgO so pro-
duced, with foi-mation of HgCL.
SlKnctrnwi Cnr^RinR — FercMoride or bichloride of mercury — Corroiiio$
tubiimate — llijtirargyrichloridxtm ccrrosimim [C. .S.) — Hydrargyri perchlori'
dum (/yr.)— HgCl, — 270.7 — is prepared by heating a mixture of 5 pts. dry
H(j80, with 5 pts. dry NaCI, and 1 pt MnO, in a glass vessel communi-
cating with a condensing rJiamber.
It crystullizes by sublimation in octahedra, and by evaporation of ita
solutions in flattened, right rhombic prisms; fuses at 265° (509' F.). and
boils at about '290'' (.'ifiii^ F. ) ; soluble in HO and in nJcohol ; very soluble
in hot HCl, the solution gelatinizing on 4»Muiiig. Its aoluiious have a dis-
agreeable, acid, styptic taste, and arc liighiy poisonous.
It is easily reiluced to (Hg.^Cl, and Hg. and its oqueona solutionn are
•o decomposed when exposed to light ; a change which is retanled by the
presence of NaCl. Heated with Hg it is converted into (Hg,)Cl,. When
dry HgCl, or its solution is heated with Zo, Cd, Ni, Fe, Pb, Cu, or Bi,
those elemcnh) remove part of all of its CI, with separation of (Hg,]Ct, or
Hg. Its solution is decomposed by HJi with separation of a yellow sulpho-
chloride, which, witli an excess of tlie gas, is (Ninverted into black Hg8. Ik
is soluble without decompouitton in H.SO,,HNO,. and HCl. It is deeom-
poscd by KHO or NaHO, with sepoi-ation of a brown oxychlorido if the
alkaline hydrato bo in limited quantity ; or of the orange-coloreti HgO if
it \ye in excess. A similar decomposition is effected by CaH,0^ and Mg
H,0, ; which does not, however, take place in presence of an alkidiuu
ohlorido, or of certain orgnnic matters, such as sugar and gum. Many
organic substances decompose it into (Hg,)Cl, and Hg, especially under
the infjuenco of sunlight Albumen forms with it a white preci|atate,
which is insoluble in H,0. but soluble in on excess of fluid albuineu and
in solutions of alkaline chlorides. It readily combines with metallie
chlorides, to form soluble double chlorideti^ called dUorvmercumtes or chlor-
A
BALTS OF MERCURT.
165
k]fdrtxrgyrate9. One of theee, obtained in flattened, rhombic piisms, b^ tbe
enolitij,'^ of a bulling solutioD of HgCI, and KU,Cl, has the conipoRitioD
HgCl,, 2(?^,C1) 4- Aq, and was formerly known aa sal alembroOi or sal
mfpterUice.
IbsctmAinfOKnnt Chlorihk — Mercury ckioramidide — In/imble whUe
pnnptifitr — Ammoniaied mervuri/ — Htjdrargyrum ainmonialuni [U. S. ; Br.)
-^TfH HgCl — -251.1 — is prepared by mldiut^ a ehghl excess of NH,HO to
a solution of HgOl,. It is a white powder, insoluble in alcohol, ether, and
oold H,0 ; deoompoBBil by hot HO with sejiaration of a heaTy, yellow
powder. It is entirely volatile without fusion. The fusible ttJiUe precijA-
taU is formed in small crystals when a solution containing equal ports of
HgCl, and NH,CI is decomposed by Na,CO^ It is mercurdiammonium
ddoriiie, NH,HgCi,NH,Cl.
Iodides. — Mbbcubul's Iodide — I^rotoiodide or yeiiow iodule — Bydrargyri
iodidum viride (U. S. ; lir) — HgJ, — G53.4— is prepared by grinding to-
gether 200 ptA. Hg and 127 pts. I with a little alcohol until a green
paste is formed. It is a greenish -yellow, amorphous powder, insoluble in
H,0 and iu tUcohoL When heated it turns brown and volatilizes com-
pletely. When exposed to light, or even after a time in the dark, it is de-
oomposed into Hgl, and Ug. The same decomposition is brought about
instantly by KI ; more Hlowly by solutions of olkiiline chlorides and by
HCl when heated. NU,UO dissolves it with sepamtiou of a gray pre-
cipitate.
MzHCiTKio Iodide — Biniodide or red iodule — Uydrargyri iodidum ndrrum.
{U. S.; Br.) — Hgl, — 453. 7 — is obtained by double decomposition between
HgCl, and KI, core being had to avoid too great an excess of the alkaline
iodide, that the soluble potassium iodhydrargyrate may not be formed.
It is Hpariiit^ly auluble in H,0 ; but forma colorless solutions with
alcohol. It dissolves readily in many dilute acids and in solutions of am-
moniacal salta, alkaline chlorides, and mercuric salts ; and in solutions of
alkaline JoJideH. Iron and cop|M)r convert it into (HgJI,, then into Hg.
The hydrat«8 of K and Na decompose it into oxide or oxyiodidc, and com-
bine with another portion to form iodhydrargjTates. which dissolve,
NH.HO separates from its solution a brown powder, and forms a yellow
uolutiou which d(.'|K)sits white flocks.
CyanldOB.— iLutci'BioCvANmE — Uydrargyricyanidum ( C S.) — Hg(CN),
— 251.7 — is best prepared by heating together, for a quarter of on hour,
potasidum ferrocyuniJc, 1 pt ; HgSO., 2 pt& ; and H,0, 8 pts. It crystal-
iizee in quadraoguUr prisms ; soluble in 8 pt& of cold 11,0. uiucli less
eolnble in alcxihol ; highly poisonous. When heated dry it blackens, and
is decomposed into (OX) and Hg ; if heated in presence of H,0 it yields
HON. Hg, CO., and NH,. Hot concentrated H.SO., and HCl, HBV, HI,
and H,S in the cold, decompose it with liberation of HON. It is not d&-
oompoiied by alkalies.
Salts of Meroury.
Nitrates. — There exist, besides the nonnul nitrates : (Hg,)(NO,), and
Hg(NO.),. tlireo basic mercurous nitrates, tliree basic mercnric uitnitee,
and a mf^rcnroso-nierruri*: nitrate.
Mercceoiw Nituatb— (Hg,)(NO.), -r 2 Aq^523.4 + 86 — is formed
when excess of Hg is digested with HNO^ diluted with <) vol H,0 ; until
abort, prismatic crystals separate.
166 MANUAL OP CHKm.STRT.
It effloresces in air ; fuses at TO'' (168" F.) ; dissolves in a Bmnll qoantitv
of hot U,0, but with ii larger qtmntitr in dccomposetl with septtatioo ol
tlie yellow, basic trimejvaru: niimte, Hg(NO,)^ 2HgO -f- Aq.
DmEaccEous Nn-EATt— (Hg,)(NO.}^,Hg,,0 -f Aq— 938.8 -f IS-is
formed by actiug upou the prout-diug salt with cold H,0 luilil it turns
lemoD-yeUow ; or by extracting with cold H,0 the residno ol evspomlioo
of the product obtained by acUng upon excess of Hg with conceutntol
HNO^
TBiHEiicfBors NrnuTE— (HgJ,(NO,)„ Hg.O + 3 Aq— 1462.2 + 5*-
is obtained in large, rhombic prisms, when excess of Ug is boiled vith
HNO,, diluted witii 5 pta. H,0, for 5^6 hours, the loss by evapontioD b*>
iug uiado up from time to lime.
Uencmic NrnnTE—Hg(NOJ,— 323.7— is formed when H^ or HgO
ia dissolved in excess of FTXO^, luid the solution evaporated at a gentle
heat A syrupy hqiiid is obtained, which, over quick-Hme, deposits largt^
doliquesueut crysttUH, haviug the coupoeittou if[U;{(NOJJ + Aq, wlule
there remains nn \mcrystallizable liquid, HgfNO,), + 2 Aq.
This salt is soluhle in U^O, and exists in the Liq. hydrargyri itifratH
(6*. S,), Liq. hydrargyri nitralig acidus {Br.) ; in the volumetno atandani
solution used iu Ling's process for urea ; and probably iu citrine oinlnmi
— (Jug. hydrar. nitratls (C S. ; Jlr.).
Dimebdtbk: NrriuTK^Hg(NO,),, HgO + Aq — 689.4 — is formed wli«
HgO is dissolved to suturatiou in hot HNO„ diluted with 1 voL H,0; um!
crvittalltzes on cooUug. It is decomposed by li,0 into trimvrcuric nitraU,
Hg{N().),. 2HgO. and Hg(NO,).
Hi:x\mi:iu;l'iuc Nitkatk — Hg(NO,),, 5HgO — 1402.2 — is formed as a red
powder, by the action of H,0 on tiimcrcuric nitrate.
Sulphatea— MxHCuaocs .Si:i.pH\TE~(Hg^)SO, — 495.4— is a white, ery»-
talline powder, farmed by gently heating together 2 pts. Hjj and 3 pta
H.80,. and ctiusing the product to combine with 2 pts. Hg. Heated with
NttCl it forms (HgjCl,.
Meiuxrio Splphate — ffydrat-gyri aiUpha* (Hr.) — HgSO_^ — 295.7 — is ob-
tained by heatiug together Hg and H,SO, ; or Hg, H,SO,, and HNO^. It
is a white, crystidliuo, anhydrous powder, which on contact wiQi ^O ti
decomposed with formation of trimercun'c sulphatu, Hg>SO,, 2HgO ; a yel-
low, insoluble powder known as lurpelh nwieral = ilydrargyn tsuitsulphas
Jlavua {U. S.).
Analytloal Obaraoters.
MERcmons.— (L) Hydrochloric acid : white ppt.; insoluble in H,0 and
iu Bcida ; turns black with NH,HO ; when boiled with HCl, deposits Hg,
while HgCl, dissolves.
(2.) Hydrogen sulphide: black ppt; insoluble in alkaline sulphy-
drates, in dilute adds, and in KCN ; partly Bohible in boiling HNO .
(3.) PotusU : black ppt; insoluble in excess.
(4.) Potassium io<llde : greenish ppt: oourerted by excess into Hg,
whirh is deposited, and Hgl„ which dissolves.
Almtcriuc. — (l.| Hydrogen sulphide : black ppt If the reagent be
slowly added, the ppt. is first white, tben orange, finally black.
(2.) Ammonium sulphydrate : black ppt; insoluble iu exoees, except in
the presence of organic matter.
(!).) Potash or soda : yellow ppt ; insoluble in excess.
ACmON ON THB 3B0OKOMT.
(4.) Ammoniam hydrate: white ppt; soluble in great exceas and in
lations of >'U, 8alt&
f 6. ) Potaasium carbonate : red ppL
(6.) Potosmiun iodide: jellow ppt, rapidly turning to salmon color,
llien to red ; eatdlT soluble in excess of Kl, or in great excess of mercuric
salt.
(7.) Stannous chloride, in Bmall quantity ; white ppt; in larger quan-
tity gray ppt.; tmd when boiled, deposit of globules of Hg.
Action on the Economy.
I Mercury, in the metallic form, is without actioo upon the animal econ-
omy eo loug as it remains such ; on rontoci, however, with olkoliDO chlo-
rides it in coorerted into a soluble double c^liloride, aud tluH the more read-
ily the greater the degree of subdinsiun of the metoL The uiercuriols
insoluble in dilute HCl are tHao inert until they ore converted into Holuble
1; oom)xiunda.
Merruric rhlond(<, a substance into which many other compounds of
Hg are converted when taLeu into the titomach or a^ijilied to tJie akin, not
onlv has a distinctly corrosive action, by virtue of its tendency to unite
with albuminoids, but when absorbed it produces well-marked poisonous
effectR, somewhat similar to those of arsenical poisoning ; indeed, oning to
its corrosive action and to ita greater solubiUty, aud more rapid absorp-
tion, it is a more dangerous poison than Art„0,. In poiaoning by HgCl,,
the ayniptoms begin sooner i^ter the ingestion of the poison than in arsen-
' ical potsuning, aud those phenomena referable to the local action of the
I toxic arc more intense.
The treatment should consist in the ndminiRtration of white of egg, not
in too great quantity, and the removal of the coiu^mund formed, byemesia,
before it lias had time to redissolve iu the alkaline chlorides oouUined in
the stomach.
, Absorbed Hg tenda to remain in the system in combination with albu-
minoids, from which it may be set free, or, more ])roi>erlv, brought into
I soluble combination, at a period quit« removed &om tne ^te of last ad-
I ministration, by the exhibition of alkaline iodides.
Mercury is eUminated principnlly by the saliva and urine, in which it
may be readily detected. The fluid in faintly acidulated with HCl. and in
it is immersed a short bar of Zu, around which a spiral of dentist's gold-
foil is wound in such a way aa to expose alternate surfaces of Zn and An.
After '^4 hours, if the saliva or urine (Viiitain Hg, the Au will be whitened
by amalgamation ; and, if dried and heated in tlie dosed end of a small
gUBB tube, will give off Hg. which condeuKCR iu glabules, visible with tlw
aid of a magnifior, i^ the cold part of the tube.
168
KAirrAL OF CHEMI9TKT.
COMPOXmOS OF CARBON.
Organio Substanoes.
In tlie seventeenth and eif^il«enth centuries, chemistn had o1
that tboro uiight bo extracted from ouiinol aud vegetable htMliiui substances
which (.lifTerutl lutK-h in ilicir prui>ertieB fruiu ihuBe which cuuld be ob-
tjuned from the mineral world ; Bubataucos which burned withuut leav-
ing a reaitlue, and many of which were subject to the peculiar change*
wrouglit by the procesaea of fenueututioa und putrefaction. It was not
until the beginuui^ of tho present century, however, Lhot chemistzy was
dindcd into the two aoctions of inorganic and organic.
In the Intter clAsa were included all auch subotances as OTisied only in
the organized bodies of animals and vegetables, and which seemed to be
of n different essence from tliui of miuend bodies, as chemi^itii had been
unable to produce any of the«e organic ^ubstimces by artificial means.
Lat«r in the history of tho science it was found that these bodies were all
made up of a very few elements, and that they all contained carbon.
UmcUn at this tiiuo proposed to consider as organic substuuces all such aa
contained more than one atom of C, lua object in tlius limiting the mini-
mum number of atoms of C being tlist substances containing one atom of
C, such as carbonic acid and maruh-gns, were formed in the mineral king-
dom, and consequently, according to ihen existing views, could not bo con-
aidered as organw. Illogical as such a distinction is, we find it still adhered
to in text- hooka of ver>' recent date.
The notion that organic substances could only be formed Irf some mys-
terious agency, manifested only in orgnniwtl beiug», was fiualiy exploded
by the labors of Wohler and Kolbe. The former obtained urea from am-
monium cyaiiiite ; while tlie latter, at a subsequent jieriod. formed acetic
add, using in its preparation only such unmistakably mineral subetauces as
coal, sulphur, aqua regia, and water.
During the half-century following Wohler'a fii-st syutliesia, chemists
have succeeded not only iu making fi'om mineral materials many of the
substances previously only formed in the laboratorj- of nature, but have
also produced a vast number of carbon compounds which were pi'cnously
unknown, and which, so far as we know, have no existence in nature. At
the present time, therefor, uv mwU conxidtr ax an <trganic nuhslance any
compound coniaimtig carbon, whatever may be i(s origin and u-haietxr its
pn^feriieK. Indeed, the name orgaruc is retained merely aa a matter of
convenience, and not in any way as indicating the origin of tliese com*
pounds. Although, owing to the great numlwr of tlie carbon compounds,
it is still convenient to treat of tliem as fonning a section by themselves,
tlieir relations with the compounds of other elements is frequently very
close ; indeed, within the past few years, compounds of silicon have been
obtained, which indicate the poysibiUty that that element is capable of
forming series of compounds as interesting in numbers and ^tuiety as
those of carbon.
Nevertheless, there arc certain peculiarities exhibited by C in its com-
ponxidB, which are not possessed to a like extent by any other element.
HOKOtOOOTTS SERTES.
169
ud wbicli render the study of organic subatancea peculiarly iDteresting
lod profiUble.
Ill tUe study of tbo compounds of the otUor olemenfa, we Lave to deal
with a small number of flul>8tance8, relatively speaking, formed by the
union witb each other of a large number of elements. AVith the organic
ubetances the reverse is the cose ; for. although compouudii have been
formed which contain C along with each of the other elemonta, the creat
majority of the organic Biibstancea are made up of C, combiiicii with a
very few other clementa ; H, O and N occurring in them moat frequently.
It ia chiefly in the study of the coibou compounds thiit tvu have to deal
wiUi rft'iii-<U» (s«o p 23). Among mineral substancea there are many
whose molecules consiat simply of a combination of two atoms ; among
organic substances there is none which does not contain a radical : indeed,
organic chemistry lioa been defined as "the chemistry of compound
radicaU."
The atoms of carbon possess in a higher degree than those of any other
element the pow^er of uniting vnih. each other, and iu so doing of inter*
changing valences. Wore it not for this property of the C atoms, we could
have but one saturated compound of carbon and hydrogen, OH,, or,
expressed graphically :
H
H-C-H
i
There exist, however, a great number of such compounds, which differ
from each other by one atom of and two atoms of U. In these substances
the atoms of may be considnrod aa linked together in a continuous chain,
their free valeuoeit being satisfied by H atoms ; thus :
H H fi H
H
H H
1
H— C— H
H— C— C-H
1
H
^^
[_C_C_C— 0-1
iu
If now one H atom be removed from either of these combinations, we have
a group poseeaeing one free valence, and consequently univalent. The
deoompoeitjona of those substances show that they contain such radicnls,
and that their typical formuhc are :
OH,
H
]■-
^■i-
]■■
'•^\-
Homologous Series.
It win be ohaerved that these formula) differ from each other by CH„
or some multiple of CH,, more or loss. In examining nurabors of organic
substances, which arc closely related to each otlier in their properties, we
find that wo can arrange the great majority of them in Bcries, each term
of which differs from the one bok>w it by OH. : such a series ta called ao
170
MAKFAL
homoloffouM seriei. It will be readily unrlerntood that such an arnuig^
ment in aerieB \t>AiXy bcilitatea Uie romembering of the couipoaiUoD ol
organic bcKlies. In the following table, for extuuplo, aro giveu the ntn-
ratcil hTdroL'orboDS and theii* more imniediut« derivatives. At Ui6 head
of each VBrtical column is an algebraic formula, which is the geikmi
formula of the entire series below it; n being equal to the nuzneticil
position in the series.
HouoLooous Skbob.
cartedK
Alcobolii,
AlikfardM
AeUa,
nmmn,
CnD^+|0.
CaUa.0.
C&H^O^
CbU^
CHi
CH.O
00,H,
Q.H.
0,H,0
cn.o
C.O.H*
0»H.
O.H,0
cu.o
O.O.H.
CH.O
C4Bt«
O.H„0
c.n.o
C.OtH.
CH.O
001,,
C.H,.0
(;.u,.o
C*0,H,.
CA.0 ■
C.H,.
o.n..o
C,II„0
C.O.H.,
1
CtH..
C.Hi.O
c,u>.o
CO.H..
«
o,n..
C.H„0
C.H,«0
C.O.H..
0^.4
C,H,iX>
<\0.H..
0„IT„
O.JtnO
C,.0,H,.
OmH..
0,.H..
0,>0,H„
0,.H„
«■!'«■■
0,.Q,«
CifOiHit
But the arrangement in homologous series does more for us than thia,
Hie properties of substances in the same series vary in ro^aikr gradation
ooooniing to tlieir position in the series ; thus, in the series of alcohols in
the above table, the boiling-points of the firat six are. 66.5.°, 78.4°, 96.7°,
m.7'', 132.2^, 153.0* ; from which it wUl be ticen that the boiling-point
of any one of them can be determined, with a maximum error of '.i , Igr
taking the moan of those of its neighbors above and below. In this way
we may prophecy, to some extent, the properties of a wanting member in
a series bcfoi-e its discovery. The terms of any homologous series must
all have the same constitution, i.e., their constituent atoms most be sim-
ilarly arranged within the molecule.
Isomerism — Metamerism — Polymerism.
■h oth^^
Tux> subetances are said to be isomeric, or to be itomeres of each
when tht^yhave the mame centettimal compotitioiu If, for instance, we analyze
acetic acid and metlijl formiate, wo nnd that each body consists of C, O
and H, in the following proportions :
Carbon 40
Oxygen 53.33
Hydrt^n (J. 67
100.00
24 = 12
32 = 16
4= 1
This ttimUarity of centesiual composition may occur in two ways : the
two subsUiuces may eoub coutoin iu a moleuule tbe i>aiue numberB of each
JoikI of titom : or one may contain in each molecule the same kind of atouiB
u the otlier, but iu a higher multiple. Iu the aboTe instance, for example,
each substance may have the compusitiou C,H,0, ; or one may have tlint
fonuula and the other, C,H,,0^ or C^ O, x 3. In the former coae the
Bobgtances ai-e said to be metameric, in the latter polymeric. Whether two
■ulistances are metameric or polymeric can only be determined by aacer-
taiuiiig the weights of their molecules, which is usually accomplished by
determiniug the sp. gr. of thcii- vapore (see p. 14).
'Ilie ep. gr. of the rapor of acetic acid is tbe same as that of methyl
formiate, and, consequently, each Hubatonco is made up of molecules,
each couUiiuiiig C,H,0,. But the two subataucea differ from each other
greatly in their properties, and their differences are at once iudicated by
their trpioal or graphic formuLe :
(CAO^jO ana <^h0};}0;
or graphically :
CH, H
and I
OOH COOCH,.
i
Ctasslfioation of Organio Substances.
Aa the compounds of the other elements may be divided into clasaes,
such HH Hcidt), bases, saltH, etc., according to their chemical fimctiuiis, the
compounds of cai-bon also arrange themselves into certain well-defined
groujie, called by the Fi-eneh chemists fiinrtions — a term which it would
be wbII to introduce into qur own nomenclature. The properties of the
fuuctiuna of organic subatancea do not depend, like those of other com-
{K>imds, upon the hud of atoms of which they are compused, but rather
upon the arrangement of the atoms within the molecule ; and in thia point
vc find the most prominent distinction between organic and mineral sub-
stancf>8- Arsenic, for instance, is potBonous in whatever form of chemicid
oombinutiun it may be, provided only that it can be rendered soluble, and
therefor capable of absorption. Carbon, oxygen, and hytlrogen, on the
other hand, combine with each other to form KubHtances lumng the most
diverse action upon the economy — tlie fats and sugai's, ordinary arlicios of
food, on the one hand, and substances having such marked toxic powers
us ether and oxalic acid, on tlie other — the differences between tbe prop-
erties of the two substances dejieuding eutin'ty upon the numbers and
positions iu the molecule of the same kind of atuma.
i
4
179
MAKUAL OF CnSMTSTBY.
SITUBAIED HYDBOOAKBOMS AND THMR DEBiyATIVIS.
FIRST SEHIES OF HYDROCAJRBONR
A hydrocarbon xa a compound of carbon and hydrogen only. li it tatv-
rated when <dl the valences of all the constUuent alomti are tafUJied.
Thfi hydrocarbooa of this aeries at present known are the ftdlowing :
Mum.
vttori bj^rido. . ,
lYomrt fafdrUa..
Balyl brdrtd*...
Am^lbj^rUe....
li«i>'l hrdnd* . .
UaiMylhydrUA...
Octyl h^ariilo ..
FocoMilft.
OB.H
0,H,II
C,ll,II
C»U„H
c;,M„H
C,II„H
SpsdAc
gnvltjof
UqHU.
BoOInc*
potat.OoB
DWUal 0* 9-
fi <WU M lb* Bf*-«t*
a.n« at IB* n«*-iis>
Kami'.
BpMlSe
mtvtqruC
tmitfiL
ttgndt.
K<Hvl bTdrido.... C.B|*H 0.741 at 1»*
D«»lhydrid«.....|Cr,«H,,HU.7BT mt !«■
nMlaerihrrirUe..Ci,H,,H 0.700 u 18*
DodMTl br(M<1«.. 0,|BuHO.m M tO"
iTMOMTl ti3<lrld«..:c,»ll„lI0.>tK> M tS*
iTotrMMTl hyilr.do C,.HhH MR* »t ItT
{■WUdM^lbrJrM* C,tH|,U O.tW mL lb*
HenwtMiyl hjilride 0,«llnHi
They form an homologous aeries whose general forrauU is C^m - ti
and are kuowu as i>aruffine» from their stahility (paruni =: little, affinis s
affinity). Their couutituliou is expressed typically by the formate
^*^* \t [ ' and the radicaia G.Hm 1 1* o' which they are the ht/dridea, arc
designated as the nulicals of the monoatomic iilcohols.
Corresponding to tho hi};;bcr terms of the series (those above the
third) there are one or more isomeres, which may be arranged in four
rlasaea ( I. ) The mirmal or regularly formed serir-B, in which each C atom
is linked to two other C atoms. (2.) Those in which one Catom is linked
to three others. (3.) Those in which two C atoms are each linked to three
otherB. (4.) Those in which one C atom is linked to four others. The
constitution of these aeries is explained by the graphic formulffi :
(1-)
(2.)
(3.) •
(*.)
CH.
CH.
CH,
CH.
f.
1
fl-C-CU,
H-C-CH,
H,C -C-CH,
k
1
H-C— CH,
1
CH,
Ah.
1
CH.
iH.
1
OH,
b
1
CH,
GH,
-
CA.
CH.
CH.
C.H..
As all of these compounds are saturated they are incapable of bciuj^
modified by addition, i.e. by the simple insertion of other atoms into the
i
PltlST SZtEIIES OP H T DTIOCA EBONS.
!f!
molecule ; the; may, however, be modified by sfubtitituiion, Le. by the re-
nujviU of one or mora of thoir atoms aud the subsLitutiou Iberefor o( an
itom or atoms of different kind.
BCethyl hydride^ iletham — Manh^gati — lAgM carburetted hijdrogen —
Fire-damp — CH, — 16 — in giveu ofl" ia swampa as a product of decomposi-
Uoa of vegetable matter, in coal miues, aud iu the giueu isauiug from
the earth in the ncinity of petroleum deposits. Coal-gas eontaijiH it in
the proportion of 36-50 per cent. It may be prepared by strongly heat-
ing k mixture of sodium acetate with sodium liydrate and (juicklime.
It is a culorlesd, odorless, tasteleaa gaa ; very sparingly soluble in H,0 ;
sp. gr. 0.5511A. At high tempomtures it is deeonipysed into C and 11.
It bums in air with a pale yellow rtame. Mixed with air or O it explodes
Tiolently on oontact with flame, producing watei' and carbon dioxide ; tho
latter constituting the a/ier-damp of miuerii. It is not affected by CI iu
the dflffk, but under the influence of diffuse daylight ono or more of tho
H atoma are di^laced by an equivalect quantity of CI. In direct sunlight
the substitution ia accompanied by an explosion.
Petroleum.— Crude petroleum differa iu composition and in pbyucal
properties in the products of different wells, even iu tho same section of
country. It varies in color frora n faintly yellowish tinge to a dark
brown, nearly black, with greenish reflections. The ligbter-coloreil varie-
ties aie limpid, and the more highly colored of the couKiuteiu-i^ of thin
rip. The sp, gr. varies from 0.74 to 0.92. Crude petroleums coutalu
the hydro^rbonn mentioned in the list on p. 172 (the first of the
•eries, iHiing found iu the gases accomj>anying petroleum, is aL>o held iu
solution by the oil under the pressuro it supports in natural pocketsj, be-
sides hydrocarbons of the oletine series, and of the benzol series.
The crude oil is highly inttunmable, usually highly colored, and ia pre-
pared for its multitudinous uses in the arts by the processeM of distillation
and refining. The distillatioa is usually so oonduoted as to divide the
product into four ports:
jn^UM «p. ffr.D.TDB-IS-im
gamatmm ■(■.cr.U.TW- B-W
ihimUiif irtt Bp. gr. 0.Y88— W<
JtMUw um and touM IS-IOlC
^^ The naphtha, orpetroleum ether, is further separated by distillation into
f^otlier proilucta : Ithigolinr, a highly infkmmable liquid ; ap. gr. about O.GO.
I which boils at about 21" (70'' F.). It is used to produce cold by its
rapid evaporation, but its low boiling-point and inflammability render its
n^e dangorouji. Qtuiolitu: ; sp. gr. alwut 0.(J3-0,Gl ; boils at about 76"
, (170" F.).
/it-mine or bemolin.-j, sp gr. about 0.73 ; boila at about 148' (298' ¥.),
and is largely used in the arta as a solvent. It must not bo confounded
with benzol or benzene, C,H, (q. v.).
The most important proiluct of petroleum is that portion which distils
almve 183" (3(U' F.) and whic^h constitutes Icernserw.^ and other oils used
for burning in lamps. Au oil to be safely used for burning iu lampa
should not "Hash," or give off inflammablo vapor, below 60' (140* F.J;
ani should not bum at tempor.\ture« below 65'. 6 (150° F.).
' From the re-nidue remaiuiug after tho separation of tho keroaene, n
variety of other products are obtained. LnbricaUn>j oils, of too high boil-
j ing-point for use in Inmps. Pamjhnf, a white. cri-Htalline solid, fnsible at
I 45'-<!.")' {113°-149'^ F.), which is used in the aria for a variety of pur-
poiM^s formerly served by wax, such as the manufacture of candles. In the
iboratory it ia very osoful for coating tho glass stoppers of bottles, and for
otlier purposes, as it is not. affected by ncids or by alkallM. II is odori
U&l«lesB, iuHoluble id H,0 aud in cold alcohol ; aoluble in boiling alcol
and iu etber, fatly aud vulutilo oils, and mineral oils. It is also obtained
by the distillation of cortain varieties of coal, and is found in nature in
ff>9*il vnx OT ozocerite.
The products knoTrn aa vtufline, petrotaium (U. S), coamcitTie, etc.,
i\'liich are now »o largely used in pharmacy and perfumery, are mixtures
of paraffine and the heavier j>eiroloum oils. Like petrolcora itself ita
vanouB commercial dehvatiTes are not definite compounds, but mixturai of
the hydrocarbons of this aeries.
Haloid Derivatives of the Farafflnea.
By the action of 3^ upon the paraffinea, or by the action of HCl,
HBr or HI upon the corresponding hydrates, compounds are obtained in
which one of the H atoms of the hydrocarbon has been reulacetl by in
atom of a, Br or I : C,H. 4- Br, = C JI.Br + HBr, or C.H.OH + HO
= C^jCl f- H,0. These compounds may be considered as the chloride^
bromides or iodides of the alcoholic radicals ; and are known aa haloid
ethers.
AVhon CI is allowed to act upon CH., it replaces a further number of
H atoms nntil tlnnlly carbon tetrachloride, CCl,, in produced. Consider-
ing marsh gas aa methyl hydride, OH,,H, the first product of Bubstitution
ia methyl chloride, CH,.C1 ; the second monochlormelhyl chloride. CH^Cl
CI ; the third dichlonueihijl chloride, or chloroform, CHC1,C1 ; and the
fourth carbon teirarhhride, ('CI,,
Similar ilerivHti%-<>s are formed with Brand I and with the otiier hydro-
carbons of the scries.
Methyl chloride— CH,C1 — 50.S — is a colorless gaa, slightly solo-
ble in H,0, and having a sweetiKh taste luid odor. It Ia obtained by dis-
tilling togetlier H.80,, sodium chloride and methyl ochohoL It nmy be
condensed to a hqnid which boils at —22* (— 7^.6F.). It bums with a
greenish flame. Heated withpotassiumhydrateit is converted into methyl
ucobol
Monoohlormethyl ohloriAe~-^fethene chloride — Ihctdoromethane—
MethijU'iifi (•/(/.rriV/'-— CV(/orrt)Hrr/ii/Z— CH,C1,C1— 85— is obtained by the
action of CI upon CH,C1 ; or by shaking an alcoholic solution of udoro-
form with powdered sHnc and a little ammonium hydrate. In either caw
the product must be purified.
It is a colorless, oily liquid, boils at 40*^2'* (104*-107<'.5 F.) ; ep. gr.
1.30 ; its odor is similar to that of chloroform ; it is very slightly soluble
in H,0 ; and is not iufiammablc. Like most of the chlorinated dcrirutives
of tlus scries, it is possessetl of amesthetjo powers. Its use as an aaR«-
thetic is attended with the same (if not greater} danger aa tliat of chloro-
form.
Dlohlonuethyl chloride — 3fethenyl chloride — fbrmt/l chloride —
Trichhron\ethane— Chloroform— ChloroformumiO. &, flr.)— CHC1„C1—
120.5 — ia obtained by heating in a capacious still, 35—10 litres (0-1 1 gall.)
of H,0, adding 5 kilos <^11 lbs.) of recently slocked lime aud 10 kilos (22
lbs.) of chloride of hme ; 2.5 kilos (2.^ qts.) of alcobol are then mldod and
the temperature quicklv raised until the product begins to distil, when
the fire is withilrntm, heat being again applied t<^\var<1 the end of the
reaction. The crude chloroform bo obtained is purified^ Urst by agitaticMd
with H,SO, tlipn hv mbdng -with alcobol and rooentlj ignited potassium
carbonate, and diutUling the mixture.
It is a colorless, volatile liijuid, biiviug a strong, ^reeable, ethereal odor,
and a sweet ta8t« ; sp. gr. 1.497 ; very sparinglv soluble in H,0; miscible
with alcohol and etherin all proportions ; boils 'at BO^.H (141°.4 ¥.), It is
a good solvent for man,T substances insoluble in H.O, such as pbos-
phoma, iodine, fat«, resins, cnoutchouc, gutla-percba and tLe alkaloids.
It ignitos with difficulty, but burns from a wick with a snioky, red
Bame, bordered with green. It is not acted on by H,8(3,, except after long
contact, when HCl is given off. In direct sunlight CI converts it into OCl,
and HCl. The alkidies in aqueous solution do not act upon it, but when
heated with them in alcoholic solution it is decomposed with formation of
chloride and formiate of the alkaline metal, ^\^len perfectly pure it is not
altered by exposxire to light ; but if it contain compounds of N, even in
very miuuie quantity, it is gradually decomposed by aohur action into HCl,
01 ood other substances.
IupcBiTiES.—./1/roAoJ, if present in large amount, lowers the sp. gr. of the
chloroform, and causes it to fall through H,0 in opiique, pearly drops. If
present in small amount it produces a green color with ferroua dinitrosul-
phide (obtained by acting on ferrous chloride with a mixture of potassium
nitrate and ammonium hydrosulphide). vtWeAyrfe produces a brown color
when CHCl, containing it is heated with litjuor potasaio. ffi/drochlvric
acid reddens blue litmus, and causes a white precipitate in an aqueous
solution of silver nitrate shaken with chloroform. Methyl and empyten-
tnalic compounds are the most dangerous of the impurities of chlorofurm.
Their absence is recognized by Uie following charactci'S ; (1.) When the
chloroform is shaken with an equ.il volume of colorless H,SO,, and allowed
to stand 24 hours ; the upper (chloroform) layer should bo perfectly color-
less, and the lower (acid) layer colorless or faintly yellow. (2.) When a small
quantity is allowed to evaporate spontaneously, the last portions should
have DO pungent odor, and tbe remaining film of moisture should have no
taste or odor other than those of chloroform.
AsALmcAL Cn.uiACTEB.9.^(l.) Add a little alcoholic solution of potash
and 2-^1 drops of aniline and warm ; a disagreeeble odor, resembling that
of witch-hazel, is pr(Hluce<l.
(2.) Vapor of CHCl,, when poRScd through a red-hot tube, is decom-
posed with formation of HCl and (.'!, the former of which is recogniz-ed by
the production of a white ppt., soluble in aniuionium hydrate, in iiu aci<1
solution of silver nitrate. Tliis test does not afford rehablo residts when
the substance tested contains a free acid and chlorides
(3.) Dissolve about O.OI Om. of fi uaphtliol in a small quantity of KUO
solution, worm, and add the suspected liquid ; a blue color is pro-
duced.
ToxiooLooY. — The action of chloroform varies as it is taken by the
stomaoh or by inhalation. In the former case, omng to its insolubility,
but little is absorbed, and the principal action is the local irritation of
the mucous surfaces. Becovery has followed n dose of four ounces, and
death has been caused by one drachm, taken into the stomach. Chloro-
form vapor acts much more energetically, and seems to owe its potency
for evil to its iwralyzing influence upon the nerve-centres, notably upon
those of the heart. Wliile ptn-sons putVering from heart disease are particu-
larly susceptible to the pai'alyzing ctTept of chloroform vapor, there are mnny
eases recorded of d^iith from tbe inhalation of small quantities, properly
dilated, in which no heart lealon was found upon a post-mortem examines
MAirUAL OF OHEBOSTBT.
11 ur
lion. Chlorofonu is apparently uot altered lu tlie system, and 13 eUmi-
&atcd with tbo expired air.
No chemical aatidote to chloroform is kitown. When it haa been
Rwallowed, the stumacb-pump and etneticH ure iudienled ; when UkcTX by
iuhalatiou, a free ciiculalion of air should be estnblisUed about the face;
urtifieiol respiration And tlie apphcation of the induced current to the 8id«
of the neck should be resorted to.
The nature of the poiaon is usually revealed at the outop^ by iU
peculiar odor, which is most noticeable on opening the cranial and tho-
racic cavities. In a toxioological analysis, chloroform is to be sought tor
especially in the lun<ra and blood. These are placed in a flaak ; if
neutralized with sodium carbonate ; and subjected to distillation at
tcmpcmturo of the water-both. The Tapora are passed through a tabft
difficultly fusible gla»( ; at first the tube is heated to redness for about an
inch of its len^^th, and test No. 2 applied to the issuing gas. The tube is
then allowed to cool, and the distillate collected in a pointed tube, from
the point of which any CHCl, is removed by a pipette and tested according
to Nos. 1 and 3 above.
Carbon tetraohloride — Chlorocarbon — CCl, — 154— ia formed by the
prolonged ai'tion, in sunlight, of CI upon CH^Cl or CHdl^ ; or more rapirUy,
by passing CI, charged witli va|iur of carbon disulphide, through a red-bot
tuhe, and purifying the product
It is a colrtrless, oily hmiid, insoluble in HO ; soluble in alcohol and
in ether ; sp. gr. 1.50 ; boiJa at 7H'^ {ITl'A F.). Its vapor ia decomposed
at n red licat into a mixture of the dichloruie, C^Cl^, trichloride, C CL, and
free CI.
Methyl bromide — CH,Br— 95. — A colorless liquid; spL gr. 1.664;
boiU at 13' (53. i' F.); formed by the combined action of P and Br 00
methyl hyilnvte.
Dibromom ethyl bromide — Methenyt bromide — /brmt// bromide—
Bromofortn — CHBr,, Br— 263— is prepared by gradually adding Br to a
cold solution of potassium hydrate iu methyl alcohol, until &e liquid
begins to be colored ; and rectifj-ing over calcium chloride.
A odorless, aromatic, sweet liquid ; sp. gr. 2.13; boila at 1.'>0'*-IS3''
(302''-806' F.); solidifies at -9" (15^8 F.); sparingly soluble in H,0 :
soluble in nlcohol and ether. Boiled witli alcohoUo potash it is decom-
posed in the same way as id CHCl,.
Its physiological action is similar to that of CHCl,. It occurs aa ac
impurity of commercial Br, accompanied by carfxni letrai/romide, C'Br,.
Methyl iodide— CH^I— 142— a colorlew* liquid, sp. gr. 2.237 ; boils
at 15* (113" F.); burns mth difficulty, producing violet vapor of iodine.
It is prepared by a process similar to that for obtiuning the bromide ; and
is used iu tlie nuiliue industry-.
Diiodomethyl iodide^Methenf/l iodide^Formyi iodide— lodt^orm—
f'tdoformnm, U. S. — CHI^I — 394. — Formed, like chloroform and bromofonu,
by the combined action of potash and the halogen upon alcohol ; it is olao
proiluceil by the action of I upon a great number of oi^auic substaiices,
and ia nsualiy prepared by heating a mixture of alkaUne carbonate, H^O,
I and ethylic alcohol, and purifyiug the product by recry stall ization from
alcohol
Iodoform in a solid. cr\'stallizing in vellow, hexagonal plates, which
melt at 115=-120° (^239^-248^ F.). It may be Bublimcd. a portion being
dmioniposed. It is insoluble in water, aci<Is, and alkaline solutions : solu-
ble in alcohol, ether, carbon diaulphide, and the fatty and essential oils :
MOirOATOMIC ALCOHOLS.
177
flA^fcdutiona, when exposed to the light, undergo deeompositioD and
nmuiDe a viulet-red color. It hiks a swtet taste and a peculiar, penetrating
odor, reseuibliug, when the vapor is larf^ely diluttd with air, that irf
aiflron. ^Vhen heated with potnah, a portion is decomposed into foruiiate
and iodide, while another portion in carried off unalt^tred n-ith the aqueous
V ipor. It coiitaiiis !>6.7^ of Us weight of iodine.
Ethyl chloride— //yt/rot-Woric or muriatic rtAer— C,H,C1— 64.5.— A
colorleaa, white, ethereal liquid; boija at H" (6l".8 F.) ; obtained by
passing gaseous BCI through otbylio alcohol to saturation and distilling
over the wator-bath.
Ethyl bromide — Hrjdrabromic dher — C,H^Br — 103. — A colorless,
ethereal liquid; boils at 40".? (105°.3 F.) ; obtained by tlie combined
action of P and Br on cthylic aloohoL
Ethyl iodide— Hi/fiiiodic eihir — C,H,I— 156 — is prepared by placing
absolute alcohol and P in a vessel surrounded by a freezing mixture and
gradually adding I ; when the action bnii ceased, the liquid is decanted,
distilled over the watcr-batb, and the distillate washed and roctifiod.
It is a colorless liquid ; boils at 72^.2(102^ F.) ; hasapowerful, ethereal
k odor ; bums with dimculty. It is largely used in the omliue industry.
MONOATOMIC ALCOHOLa
SEaiaa 0,3^^,0.
The follQwing is a list of the terms of the primary aeries which hare
been studied, and their prouiiucut physical protK>rtieu.
Nbhw.
Hatbrl hjdrat*.
Ethyl hjrdntte
Prop;! hjdnta
Bat7l bydrata
A107I hydrate
Hflzyl bydraM
Haptyl bydr&ie
Octyl bydrst«
Noayl hydrate
Deoyl hydrate
CetylhjdniU
(Jeryl hydrate
Kyric^l bydrmt*
nmplriaU
tunitiUa.
polnt.
Builinff-
point.
SpocUo
CH.O
CH.
H
, ,
08" .0
D.SU
C.H.0
o.n.
H
..
7r.8
O.0O9S
C.H.O
O.n,
H
..
96".7
0.890
0,H,,0
H
llV.7
0.»'I7
CJIifO
H
-20*
II12*
....
C«K|,0
CiHi*
H
ISO*
0.880
OiH,«0
0.H,.
H
l«6*
-. - •
C,H„0
H
IM'
a > V «
CH]/)
C.H„
H
304*
....
C.HiaO
0..H,.
H
■0
....
> f • •
0,*H„0
0,JI„
H
40-
. • • •
CdHmO
H
■0
7ft'
....
....
0„H4,0
H
86*
MXUTAL or oiTEsn.rmT.
The name alcohoi, formerly applied ovXy to the Bubsttfioe ncnr pqh
ularlj 60 called, bns gradually come to bo used to designate a Urge cIm
of important bodiea, of which vinic alcohol in the repreHentatire. These
substances are mainly characterized by their power of euteriug into
double docompCHutiou with acids, to form ueuti'al compoundB, called remt-
povnd elker$, water being at the same time formed, at the expense of bolii
alcohol and acid. They are the ht/dratea of hydrocarbon mdicaU, and n*
such retevfdjU the metailic hydrates^ while the compound titherv are the coun-
ter parts of the nvetaUic toin :
(C.H,>[0.<C.H.0)Jo=(Cj^j0}|0.H|o
Bthfl hTdmtc
AoettoKld.
EULftMMM*.
Wktw.
g|o+(c."-0)lo=(c.n^)}o,+ |{}o
taydral*.
AMIicMld.
Ih«— torn
Water.
As the metallic hydrates may be considered as formed by the union of
one atom of the metallic element with a mimher of proups Oil , coare-
gponding to itn valence, so the alcohols are formed by union of an nnoxi-
dized radical with a uumberof groups OH', equal to or less than the noia-
ber of free valencee of the rodicaL When the alcohol contains cue Oil,
it ia designated as monoatomic ; when two, diaiomic ; wheil three, Iri-
atumic, etc
The simplest alcohols are tliosc of this scries derivable from the
satumteil hydrocarbons, and liaii-ing the general fonnula C.Hj„^.jO, or
C,n,„^,OI!. They may be forrae<l synthetically : (1.) By acting upon the
corresponding iodide with potaBwium hydrale : C,!! J 4- KHO = KI + C H^
on. (2.) From the alcohol next Ijclow it in the series, by direct audi-
tion of CII„ only, liowever, liy a succession of five reactions. {3.) By the
action of H,SO and H^O upon the corresponding hydrocarbon of the se-
ries CM,..
The saturated monoatomic alcohols are, however, not limited to one
corresponding to each alcoholic radical. There exist — corresponding to the
higher alcohols^a number of substances having the same centesim^ com-
position and the same alcoholic properties, but differing in their ph3r8ical
characters and in their products of decomposition and oxidation. These
isomeres have been the subject of much careful study of late years. It
has been found that the molecules of methyl, ethyl, and other higher alcCH
hols are made up uf the group (CH,OH)' united to H or to C»H,,+^, tlius :
cn,ou
n
CH.OH
CH,OH
Mrth;] KlceboJ.
Bthf 1 •IqoIwI.
Prapjl ftlmba).
and all monoatomic alcohols containing this group. CH,OH, have been
desiguated as i>r\marrj alcohols. Isomeric with these ore other bodies,
1tOT70ATOMTO ALCOHOLS.
17ff
vhxch, in place of the group (CH^OH)', contain the gronp (CHOH)", and
duitinguiahed as secondary alcohoU. Thiiu we huve :
cu.
(CHOH)"
(CH,OH)'
0.H.O
Pttmarj
piopjl aioohoL
And further, other isomeric snbetances ore known which contain the
group (CX>H)"', and which are called tertiary alcohols, thus :
(CH,OH)'
O.H.,0
T
(CHOH)"
C.H..0
SMondvy uiylk
■louhid.
(C,HJ-{60H)"'
in,
0.H..0
Ttftkrjr uofllo
cii,oa
1
CH.
COH
COOH
BthjF) klootwt
Btbjrt »ldel)]rd«.
AotUoBCU.
The alcohols of these three chieses are distinguished from each other
principaUjby their products of oxidation. The primary olcoholR yield bj
'' oxidation, first an aldehyde and then an acid, each containing the same num*
bcr of C atoms as the alcohol, and formed, the aldehyde by the removal of
H, from the gronp (CH,OH), and the acid by the substitution of Ofor H,
in the same group, thus :
pKs the case of the seoondary alcohols, the first product of oxidation is a
kriane, containing the same numWr uf C atoms as the alcohol, and formed
He tertiary aloohols yield by oxidation ketones or acids, whose molecules
contain a less number of C atumu than the alcohol [rum which they are
dorivod*
But the complication does not end here ; isomeres exist corresponding
to the higher alcohola, which are themseWcs primary alcohols, and coutiun
^^he group (CU,OU)'. Thus there exist no less than sovcn distinct sub-
r
CHOH
in.
ikoboL
Prater I kotoiw
OrMMOBCb
180
M^
rAL OF CHEMTSTBT.
stftDcen, all harinp the centesimal composition of nmyl alcohol, C.H,,0,
the proportics of alcohols ; and theoretical conaidenitions point to tlifl
prolHible existence of im ei^^hth. Of these eight eubbtanoes, (our ure pri-
mary, three secondary alcohols, and the remaining one a tertiary alcohol
As each of these bodies cont&init the group of atoms characteristic of the
elaaa of alcohol to which it belongs, it ia obvious that the differences ob-
Mrred in their properties are due to difTerences in the arrangement of
the other otoms of the molecule. Experimental evidence, which it would
require too much space to discuss in this place, has led chemists to ascribe
the following formulm of constttutiou to Uiese isomeres.
rnniary amylic alcohois :
CH,-CU,— CH,— CH,-CH„OH
Konokl unjUa mh^thfil.
g^^H-CH-CH.,OH
AoUva aiBjUa kkolMl ot tfrBMmlAUoa.
cn.JH:>"-cH..OH
0H,\
CH,— C-CH„OH
trnkmnm.
Secondary amylio alcohol* :
Distil jrl cuMnoL
CH,— CH— CH;/^^^'^^
Metbjl- propyl cktUimiL
CU.\Sh''>CH,OH
CH,/^" /
Motbjl-Uopfopyt cuMnot.
Tertian/ artiylic alcohol .•
CH.\
CH— C.OH
CH»-CH,/
Methyl hydrate— CarWnoi — PyroTyHcmirit — Wood tcpirii — CH,H(
—82 — may be formed from marali-gas, CH^H, by first converting it into
the iodide and acting upon this >vith potassium hydrtite : CH,I + KHO ==
KI + CH,H0. It is usually obtained by the destructive distillation of
wood. Tlie crude vxxtd vinfirjar so produced is a mixture of acetic acid
and methyl alcohol with a variety of other products. The crude Wnegar,
■epvated (roui tarry products, is i-edietilled ; the lii'at tenth of the distil-
MONOATOMIC AtOOHOlA
181
hte 18 treatetl with quicklime and again distilled ; the distiUato treated
with dilute H,SO, ; decanted oud again distilled. The product, Htill quite
impure, is tho vkhxI aioahoit v>ood 7iap/Uha, or pyroxylic gpirit of conuDcroe.
The pun hjdrate can onlj be obtained b^ deoompoaiug a crystalliue cum-
pound, such aa methyl oxalate, and rectifying the product until the boiling-
point in constant at (J6".5 (151°.7 F.).
Pure methyl alcohol ia a colorlccui liquid, having an ethereal and alco-
holic odor, and a sharp, burning tasto ; sp. gr. 0.814 at 0^ ; boila at Ctl°.5
(151^7 F.) ; bums with a pule rtame, giving legs heat than that of ethylio
alcohol ; mixes with water, alcohol, and ether in all proportions ; is a good
solvent of resinous substauecs, aud also diasolrea sulphur, phosphorus,
potash, and soda.
Methyl hydrate in not afiected by exposure io air under onlinarj cir-
cumstances, but in the presence of platinum-black it is oxidized, with for-
mation of the corresponding aldehyde and acid, formio acid. Hot HNO,
decomposes it with formation of nitrous fumes, formic acid and methyl
nitrate. It ia acted upon by U^« in the game wav as ethyl alcohoL
The organic acids form methyl ethers vith it With HCl under the in-
fluence of a galvanic current, it forms an oily substance having the com-
poftition C,U,C10.
Methfjlateti npint is ethyl iJcohol contaiiiiug sufficient wood spirit to
render it unfit for the manufacture of ardcut spirits, by reason of the dis-
gusting odor and taste which crude wood alcohol owes to cei-tain empy-
renmatic products which it contains. Spirits bo treated are not subject
to the heavy duties im|xiHed upon ordinary alcohol, and are, tlierefor,
largely used in the ai-ts and fur the preservation of anatomical prexHurationa.
It contfuns one-ninth of its bulk of wood naphtha.
Ethyl hydrate — Ethylic alcohol— M^yl carbinol — Vinic tUcohoI — Air
cohoiSpirits ofiviiie—CflBO—^G.
I^fiEpAOATios.— Industrially alcohol and alooholio liquids are obtained
from substances rich in starch or glucose.
The manufacture of alcohol consists of three distinct processes : Ist,
the conversion of starch into sugar ; 2d, the fermentation of the saccharine
liquid ; 3d, tlie seimrfttion, by distillation, of the alcohol formed by far-
mentation. The raw materials fur the first process are mall aud some sub-
stance (grain, potatoes, rice, corn, etc.) containing starch. Malt is barley
which ha» been allowed to germinate, and, at the proper stage of germina-
tion, roasted. During this growth there is developed in the barley a
peculiar nitrogenous principle caileil diasta»f.. The starchy material is
mixed with a suitable quantity of malt aud water, and the mass maintained
at a temperature of GG^-TO' (IIS^-ISS" F.) for two to three hours,
during which the diastase rapidly conTciis the starch into dextrin, and
in turn into giua/ae.
The saccharine fluid, or wort, obtained in the first process, is drawn otE,
led, and rjetut is added. Aa ft result of the growth of the yeast-plant> a
complicated series of chemical cliangea take place, the princi{>al one of
whi<ui is the Kplitting up of the (glucose into carbon dioxide and alcohol:
C^,,0. - 2C,H,0H + 2CO,. There are formed at the same time small
quantities of glycerin, succinic acid, and propyl, butyl, and arayl alcohols.
An aqueous fluid is thus obtained which contains 3-16 per cent, of
alcohol ; this is then BC])arateU by the tliird process, that of ^listillation
and rec'tiScation. The apparatus used for this piiri>ose has been so far
perfectofl tliat by a single distilltttion an alcohol of i>0-!}5 per cent can
be obtained.
uuu
^^us
Wool
k
183
makUal op CnSUlSTBT.
1
In iMjine oaseR alcohol is prepared from fluids rich in glncofle. such sa
gr^B-juice, molaeaes, aymp, etc ; in such casea the first proceoa becomei
nnneeesaazy.
Commercial ftlcohol alwars eonijiins If^O, and when pure or t^Moluk j
alcohol is re<iuired, tlie cominercial proiluct mufit he mixed iiith some by-
groecoptc solid substimce, micb aa qiiiokliine, Irom which it is distilled
aftor having; romaiupd in coutact twwily-four hours.
Fbimentation. — This term, derired from fervsere = to boil, was origi-
nally applied to alcoholic fennentation, by reason of the bul>btin<^ of the
Mcduiriue liquid caused by the escape of CO, ; subsequeutly it came to be
applied to all dccompoeitioos similarly attended by the escape of gas.
At present it is used by many authors to apply to a number of betero*
geneoua processes ; and some writers diatinguish between " true " and
"false " fermcntatiou. It is beat, we believe, to limit tbe application of
the term to those decompositions designated as true fermenUUioiM.
Fermtmlatimi i* a d^^rompointion of an organic mibgtance, produced bjf the
procesgej; of nutrition of a low form of animal or vegetable tife.
The true fermeuta are therefor tUl mtjanixtfd Jjeings, sucti as torula oer a- n
UMtrt", producinjf alcoholic fermentation ; penifUUum glaitcum. produda^H
lactic acid fermentation ; and mtjcudenna of^ii, producing acetic acid U^^^
mentation.
The false fermentations are not produced by an or<fauizod body, h
by A soluble, unorganized, nitrogenous subBtanco, wliose method of acti
is as yet imperfectly understoixl. They may be, tlierefor, designated
the term cryptolysis. Diastase, pepsin and ttypein are cryj)tol}/tea.
PnorsnTna — Alcohol is a thin, colorless, transparent Uquid, baring
spirituous odor, and a sharp, burning taste ; sp. gr. O.SOOS at 0", 0.7939 at
16° (69^ F.) ; it boils at 78^5 (1"3=.3 F), and has not been eoUdified ; at
temperatures below —90'^ ( — 130'^ F.) it is viscous. It mixes with water
in all proportions, the union being attended by elevation in temperature
and contraction in volume (after cooUng to the original temperature). It
also attracts moisture from the air to such a degree that absolute alcohol
only remains such for a verj- short time after its preparation. It is to this
power of ftttmcting 11,0 thatalnohol owes its prpsorvative i»ower for animal
substances. It is a very useful solvent, dissolnng a number of gaaos,
most of the mineral and org&tiic acids and alkaltis, most of the chlorides
and carb<:inat€3, some of the nitrates, all the sulphates, essences, and resins.
Alcoholic solutions of fixed medicinal subBtances are called tincturtt ; those
of volatile principles, fpirUs.
The action of oxygen upon alcohol varies according to the oonditionB.
Umler the influence of energetic oxidants, such as chromic ucid, or, when
alcohol is burned in the air, the oxidation is rapid and coiujilete, and is
attended by the extrication of much heat, nnd the formation of carbon
dioxide and water: C,II,0 f- 30, -2CO -( 3H,0. fixtures of air and
vnpor of alcohol cxploilo upon contact witli flume. If a less active oxidant
be tued, such as plalinumblaok, or by the action of atmospheric oxygen a t
low temperatures, a simple oxidation of the alcoholio radical takes plaodH
with formation of acetic arid ^^^ | O -^ O, =^'^'h [ O (- H,0, a reaction^
which is utilized in the mamifacturo of acetic acid and vinegar. If the
oxidation be still further hmitecl, afdehi/tit! is formed : SC^H^O + O^ =
2C,H.O + 2H^0. If vapor of alcohol be passed through a tube tilled with
platinnm sponge and heated to redness, or if a coil of Lealetl pbtiuum
wire be introduced into im atmosphere of alcohol vapor^ tbe products of
!
J
MOKOATOMIC ALCOHOLS.
183
oxidation are quite numerous : among them aro water, ethylene, aldehyde,
acetylene, airbou monoxide, and ucctal. Healed jjlutinum wire introtluced
into vajjor of alcohol continues to glow by the heat resulting from the oxi-
dation, a fact which hiui been utilized in the thermocautery.
Chlorine and brumiac act energetically upon alcohol, producing n num*
ber of chlorinated aud brominatcd derivatives, the fiual products beiu^
chloral and hromal (q. v.). If the action of CI bo moderated, aldehyde and
HCl are first pn^duced. Io<liuo arts quite slowly in tlie cold, biit olil solu-
tiona of I in alcohol (tr. iodine) aro found to contain HI, ethyl iodide, and
other imperfectly studied |)roduct». In the presence of an alkali, I acta
upon alcohol to produce loiloform. Potassium and sodium diBSolvo in
alcohol willi evolution of H ; upon cooUn*;, a white solid crystjillizeH. which
is tlie double oxido of ethyl and the idkiiline metid. Nitric acid, aided by
a gentle heat, acta violently upon alcohol, producing nitrous other, brown
fumes, and producU of oxidation. For the action of otlier acids upon
alcohol Bee the corresponding ethers. The hydrates of the alkaline metals
dissolve in alcohol, but react upon it slowly ; the solution turns bron-n and
contAius an acetate. If alcohol be gently heated with HNO, and nitrate of
mlver or of mercury, a gray precipitate falls, -which ia Bilver or naercury
fulminate.
Vjuiunna, — It occurs in diffci-cnt degrees of concentration : absolute
.ohot is pure alcohol, UH,0. It is not parehasablo an<l must be made
as required ; the so-called absolute alcohol of the shops is rarely stronger
that 98 per cent Alcohol {V. A'.), ep. gr. 0.820, contains 94 per cent by
volume, and yiArUuH fecliJiciUus (lir.), sp. gr. 0.838, coutoioa 84 |)er cent
^This ia the ordinary rectified spirit used in the arts. Alcohol lOlutum ( U, S,)
iSpirittig tenuior (Br.), Hp. gr. 0.920, used in the preparation of tinctures,
mtaias 53 per cent It ia of about the some atrcngth as iho proof spirit
of commerce.
Ajt-u-mcAi. Ch.\hacter8, — (1.) Heated with a amall quantity of Bolution
of potassium diehromato and H.SO., the liquid ii.s»ume.H im emerald-green
color, and if the quantity of C,H,0 be not very small, the peculiar fruity
odor of aldehyde is developed.
(2.) Warmed and treated with a few drops of potash solution and a
small c|uantity of iodine, an alcohohc liquid deposits a yellow, crystalUue
ppt of iodoform, either immediately or after a time.
(3.) If HXO, be abided to a liquid containing C,H.O, nitrous ether,
recognizable by itsoilor. is given ofT. If a solution of mercurous nitrate mth
excess of HNO, be then added, and the mixtui-e heated, a furtlier evolu-
tion of nitrous ether occurs, and a yellow-gray deposit of fulminating mer-
cury is forme<i, whitrh may be collected, washed, dried and exploded.
(4) If an alcoholic liquid be heated for a few moments with H,SO, di-
luted with H,0 and distilled, the distillate, on treatment with H SO, and
potAsaiiim pennangonate, and afterward witli Ro<lium h^'posulphite, ^nelds
ftldebydc. which may be recognized by the production of a violet color
with ft dilute solution of fuchsin.
None of the above reactions, t^il-m fdngly, is characteristic of alnohoL
AcnoK OS TBH EooKOMY. — lu a concentrated form, aUfohol exerts a do-
faydniting action upon animal tissues with which it comes iu contact ;
causing coagulation of the albuminoid constitucnta. When diluted.
ethylii^ alcohol may be a fooil, a medicine, or a poison, according to the
dose aud the condition of the jjerson taking it When taken in oxceaaive
do«M» or in largi> doses for a long time, it produces symptoius aud
oharaoteristic of pure alcoholism, acute or chxxsnic, modilled or
184
MAJniAL OF CUEUI&TRT.
aiiTgraTftted hy those produced by other subeianceB, sooh aa mdjI q1(^
which accompMiy it in the nlcohaUe. fluids imetl as boTerages. Takes
modenitA qn.-m titles, with food, it aids digestion and produces a seuse
comfort and exhihiratioD. Ah a medicine it is the most valuable
Klimuluuta.
Much has been vrittcn eoDooming (ho itiluo of aloobol as a food,
it hate any riiloe as such, it is as a producer of heat and force by ita os-
idatioQ in the body ; experiments have failed to &how that more than it
email pcix<eiitage (16 per ceut iu 24 hrs.) of medium doses of alcohol is-
gesied are eliminated by all channels ; the remainder, therefor, disappean
in the body, as the idea that it can there " accumulate " ia entirely unlen-
nble. That some part should be climiuitted unchanged ia to be expecte^H
from the rapid diftusiou and the high volatility of alcohol ^|
On the other hand, if alcohol be oxidized in the body, we should ex-
pect, iu the absence of violent muscular exercise, on increase iu tempera-
ture, aud the appearance iu the excreta of some product of oxidation of
alcohol: aldehyde, acetic acid, carbon dioxide, or water, while the elimi-
nation of nitrn^enous excreta, urea, etc., would remnin unaltered or bo
diminished. \Miilo there ia no doubt ttiot excessive doses of alcohol pro-,
duce a, diminution of body temperature, the experimeutal evidence coi
oeroiug the action in this direction of moderate doses is conflicting
incomplete. Of the products of oxidation, aldehyde has not been detect
in the excreta, and acetic acid only in the intestinal canal. The elimi-^
nation of carbonic acid, as such, does not seem to be increased, olthuugli
positive iufonnation upon this point is wanting. It acetic acid be pro-
duced, tliis would form an acetate, wliich in turn would he oxidizeil to n
carbonate, and eliminated as such by the urine. The elimination of water
under the induence of large doses of alcohol is greater than at other times:
but whether this water is pro<Iuced by the oxidation of the hydrogen of
the alcohol, or ia removed from the tissues by its dehydrating action, ia ai^^
open question. ^|
While physiological experiment yields only uncertain evidence, thl^l
experience of arctic travellers and others shows that the uro of aloohol
tends to diminish rather thui^ increase tlie capacity to withstand cold.
The experience of athletes and of military comiuandera is that intense
and prolonged muscular exertion can be best perfomie<l without the use
of alcohol. The experience of most literary men is that long-continued
mental actiWty ia more difficult with than without alcohol.
pro-
coi^H
In cases of acute poisoning by alcohol, the stamach-pump and catheto^J
should be used as ciu-Iy us possible. A plentiful supply of air, the col^^
douche, and strong cofl'ee are indicated.
Alcoholic Beverages. — The variety of beverages in whose prepara-
tion alcoholic fentieutntion plays an important part is very great, and the
products differ from each other materially in their composition and iu their
phyaiologicjd action. Tliey may be diridcd into four claesos, the claaeifi-^
cation being based upon the sources from which tliey are obtained an^H
upon the method of their preparation. ^^
I. — Those prepared by the fermentation of malted grain — 6t'er«, ales,
andporterft. ^h
n. — Those prepared by the fermentation of grape juice — urines. ^^
m. — Tlioso prepared by the fermentation of the juices of fruits other
tlian the grape — ciditr, fnnt-viiws.
IV.— Those prepared by the distillalion of some fermented saccharini
liquid — ardent ^lirittt.
MONOATOinO ALCOHOLS.
185
Beer, ale, and porter are aqueous infusions or decoctions of malted grain,
fermented and flavored with hops ; they contain, therefor, the soluble con-
•titueutft of the grain employed ; dextrin and glucose, produced during
tlie maltinf^ ; alcohol and carbon dioiide. proiluced during the fcruien-
tation ; and the soluble constituents of the flavonng nmtt;rial. The al-
coholic strength of malt liquors vudes &um 1.5 to 9 percenL Weiss beer
contains 1.5-l.y per cent.; lager, 4.1-4,5 per cent. ; bock beer, 3.88-
6.23 per cent ; Ix>ndon jwrter, 5.4-(i.!» per cent. ; Burton ale. 5.9 per
cent. ; Scotch .'Ue. 8.5-9 per cent Molt liquors all contain a considerable
quantity of nitrogenous uuittriiU (0.4-1 per cout. N), and succinic, lactic,
and acetic acids. The amount of inorganic material, in wliich tho phos-
pbfttea of pota»uura, Rodium, and magnesium predominate largelv, Tories
from 0.2 to 3 per c«nt The sp. gr. is torn 1.014 to 1.033.
The at^l alterations of malt lii^uors are numerous and varied. Sodium
earbonate is abided with the double purpose of ueutrahzing an excess
of aoetio acid and increasing the foam. The most serious adulteration
cODsista in the introduction of bitter principles other than hops, uud nota*
Wj of strycbuiuo, cocculus indicus (picrotoxiii ), and picric acid.
H^iHfeiare produce<l by the fermentation of grape-juice ; in the case of
red wines tho marr, or raauis of skins, seed and stems, is allowed to remain
in contact witli the miixf, or fermenting juice, until, by pitxluction of al-
cohol, the hquid dissolves a jxirtion of the coloring-matter of tho skins.
A certain projwrtion of tannin is also diasolTed, whose presence ia neces-
sary to prevent itlriiujinesg. Sweet wines are proiluced from must rich in
glucose and by arresting tho fermentation before that sugar has been com-
pletely decomposed. Dry wines are obtained by more complete fermen-
tation of must leas rich in glucose. Tortario acid is the predominating
acid in grape-juice, and as the proportion of alcohol iucreaseH during fer-
meataliou the acid potassium tarirate is deported.
Most wines of good quality improve in flavor with age, and this im-
proToraent is greatly hasteiietl by the process of pa»teurimj, which oon-
sists in warming the wine to a temperature of G0° C. (140^ F.), without
contact of air.
Li^hl icines are tho!^e whose percentage of alcohol is less tlian 12 per
cent In this clusa are included the clarets, Suuternes, Rhine, and Moselle
winea; chAmpagues, Hurgnmlies, tlie .Vmericau wines (e.^cept some varie-
ties of California wine! Australian, Grtek, Himgarion, and lUdian wines.
The champagnes and some Mo)H;Ue •wiutm are sparkliug, a quality
which is commuuicatei^ to them by bottling them before tho fermentation
is completed, thus retaining the carbon dioxide, which is dissolved by
virtue of the pressure wliich it exerts. When properly prepared they are
agreeable to the palate, and asdist the digestion ; when new, however,
they are liable to L-ouimuuicate their fermoutatiou to the contents of the
stomach and thus soriounly disturb digestion.
Of tho still wines, the most widely use^l are the darets, Vinum rubrum
(U. S.), or red liordean.t wines, and the hoci's, Vinum album (tJ. S.), or white
Rhine, Moselle and American wines. Tho former are of low alcoholic
strength, mildly astringent, and contain but a small quantity of nitjogen-
OUS material, qualities which render them particularly adapted to tjibln
uae and as mild Ktimulants. The lUiinc wines ore thinner uud mure acid,
and generally of lower alcoholic strength than the clarets. The Burgundy
end Rhone wines are celebrated for their high flavor and body ; they are
not strongly alcoholic, but contain a large quantity of nitrogenous ma-
terial, to which they are indebted for their notoriety as dovclopora of
166
MANUAI. OF CITKMISTRT.
goat. Otir nfttire American Tines, partictOarlir tfaoee of the Ohio Tallef
aad of Califomm. are yearly iniproriog in flaTor and quality ; Uiey men
closely resemble the Uhino winea and Sautemes than other Koropeoii
Ti-ines.
Heavij wines ore those vhoae alcoholic strength is greater than 12 per
cent, UHuiilly 14 to 17 percent; they include the idierrieH, ports, ^ladcinu,
Marsala, and some ColifomtA winc«, and are all the products of vrarm
chmatea. Slierry ia an amber-colored wine, gi-own in the sotaUi of SpaiB,
Vinum Xcricum {Br.). Marsala closely resemblea aherr}' in Bppeanuioe;
aod is frequently Bubstitutcd for it Fort is a rich, dark red wine, grown
in PortngaL
The adulteration of wine by the addition of foreign subatances is
coniiued iduiost entirely to their nrtilicial coloration, Ttrhich is produced by
the most various Bubstonc**, indigo, logwood, fnchsine, etc. The addi-
tion of natural cunBtituenta of wines, obtained from otlier Rcmrces, and the
mixing of different grades of wine are, howeter, extensively practised.
Water and alcohol are the chief 8ubHt.'inced bo addetl ; an excetts of the
former may be detected by the taste, and the low sp. gr. after expulsion of
the alcohol. Most wiiiea intended for eiport are fuTtiJied by tlie uldiliou
of alcohol ; when the Hl<x>holic Hpirit nsetl is free irmn amyl idcohol, and ia
added in moderate quantities, titero can be no serious objection to the
practice, espeoially when applied to certain wines which, without sach
treatment, do not bear tronsijortation. The mixing of fine grades of wine
with thoHe of a poorer quality is extensively practised, particularly with
ohompagues, clarets, ani.1 Burgundies, and is perfectly legitimate. The
snme cannot be said, howevrr, of the manufacture of factitious wine,
either entirely from materials not produced from the grape, or bv con-
oonverting white iato rod wines, or by mixing wiuoswith coloring matters,
alcohol, etc., ix\ produce imitations of wines of a different class, an indus-
try which flourishes extensively in Normandy, at Bingeu on the Kbine,
and at Haiubui;;. The wiuca 8o produced are usually heavy wines, port
tsA aheiry so-called.
CHder ia the feiinentod juice of the apple, prepared verr much in the
Bome way as wine is from gi-ape-juice, and containing 8.5 to (.5 per oont of
alcohol It is very prone to acetous fermentation, which renders it sour
and not only unpalntahle, but liable to produce colic and diarrhoea with
those not hardened to its use.
Spirita are alcoholic beverag&s, prepared by fermentation nnd distilla-
tion. They differ from beers and wines in contMuing a greater propor-
tion of alcohol, and in not containing any of the non-volatile consUtueuts
of the grains or fniits from which they aie prepared. Ucsides alcohol
and W!itcr they contain acetic, butyric, valerianic and cpnanthio ethem,
to which they owe their flavor ; Bonietimcs taunlu nnd coloring matter
derived from the cask ; amylic alcohol remaining after imperfect purifica-
tion ; sugar intentionally added ; and caramel. It is to the last-named sub-
stance that all dark spirits owe their color ; although, after long keeping
in wood ft nnturally colorless spirit ossimios a straw color.
Tlie varieties of spirituous beverages in common use are :
Brandy, spiritus fini gallici (U. 8., Br.), obtained by the distillation
of wine, and nmnufactured in France and in California and Ohio. It is of
Bp. gr. 0.929 to 0.934, is dark or light in color, acconling to tbo qiumti^
of burnt sugar added, and contains about 1.2 per cent of solid matter.
American vhtskcy, tpirilua frumenti (U. S.), prepared from wheat, rye,
barley^ or Indian com; has a sp. gr. of 0.922 to 0.937 and contains O.I to
MOJTOATOMIC ALCOHOLS.
187
N^
0.3 per cent.of soUda. Scotch and Truth ichutkie*, colorlefu npiritB diBtUled
from fermented graius : ap. gr. 0.915 to 0.920, baviu;;; a peculiar amokj
flBTor producocl by drying tho mnlt«d grain by ft pent fire, Oin, alfio die-
tilled fntiii malted groin, sp. gr. lVJ\i(i to 0.944, flavored with juniper, and
sometiiucs fraudulently with turpentine. Hunt, a spirit <Ht4tiUod from
molasses, and varying iu color and llaror from the dark Jamacia rum to llie
colorless St. Croix rum. The former is of Bp. gr. 0.914 to 0.926, and con-
tains one per cent of Botid matter.
Liqueurs are spirits sweetened and flavored with vegetable aromatics,
and frequently colored ; ani^^Uc is flavored Avitb auisecHl ; abvirUhe, with
wormwood ; curofoa, with orange peel ; Irir^hioa&ter, with cherries, tho
aUraes being cracked and the spirita distilled from the bnrised fermented
fruit; kiimmel, with cummin and comway seeds ; inanuchino, with cherries ;
iioyeau, with poach and apricot kernels.
Propyl hydrate— W/ii// carbmnl —lYimanj propyl alcohol — C,H,OH
—60 — 13 produce*!, along with ethylic alcohol, duiing fermentation, and
obtained by fractional diHtillftUon of marc brandy, from cognac oil, huile di
marv (not to bo confouiuled wilh oil of wine), an oily matter, possessing
the flavor of inferior brandy, which Beparatfts from ranrc brandy, distilled
at high temperatures ; and from the reindneti of monufticturo of alcohol
from beet-root, gniiu, molasses, etc. It is a colorleBs li(iuid, huH a hot
alcoholic taste, and a fniity odor ; boils at 90.7" (206M F. ); and is mts-
ciblo with water. It has not been put to any use in tho arts. Its intoxi-
cating and poisonous tictiouK ore greater than those of ethyl alcohol. It
exists in small quantity in cider.
Butyl aloohcOs— C H,OH— 74.— Of the four batyl alcohols theoret-
ically possible three are Known to exist :
i*rtmarij nonnal butyl alcuhol— Butyl alcohol of fcrment(Uion — Prtjpyl
carbinoi — CH, — CH, — C'll,— CH^OH — is formed in small qimntities during
alcoholic fermentation, and may be obtained by repeated fractional dis-
tillation from the oily liquid left In the rectification of vinic alrohnl. It
is a colorlesB liquid*; boils at 114^.7 (SSS^.S F.). It is more actively poi-
sonous than etliyl or methyl alcohol.
Secondary butyl alcohol; ethyl-methyl OBrfcinof— CH, — ^^f'.NciIOH
CH,/
A liquid which boils at 99' (210*.2 P.),
cn,\
1\Ttianj butyl alcohol ; trimethyl carbinol, CH — COH— o crystalline
CH./
•olid, which fuses at 20*-25'' (68°-77° V.). and boils at 82^ (179°.6 P.).
Amylio alcohols — OH,, OH — 88.— Of the eight amyl alcohols theo-
retically po-wible (Bee p. 180) seven have been obtained. Tho aubatance
usually known as amylic alcohol, poloio finril, fuml oU, alcokot amylicum
(Br.), is a mixture in varying proiwrtiona of the two primary alcohols ;
^N^H-CH -CH.OH and ^^^'-^^^'^^-CH.OH ; the former dif-
fering from the latter iu that it deviates the plane of polarization to tho left
( [a}„ = —i'^.'Mi') : in its boiling-point being U^ (:!'*. U F. ) lower, and in
the greatf^r holubiHty of the amy]-flti]p)iate of l>arium obtaineil from it
It is formed during alcoholic fermentation of glucose in greater abun-
daoce than any of the alcohols other than the ethylic. Owing to its high
boiling-point, it is in great part retaine<I in the oily material which collects
in the still during the rectiflcation of alcohol and spirits ; a portion, how*
ever, passes over and is removed by subeequeut treatment (see below). It
188
UAKTTAL OF CRESnSTRT.
is obtained from tho last milky producla of roctiGcation or ftlcohoUe fliudi
made from grain or potfttoes ; these are shaken with H,0 Lo remove «XLj\
alcohol, the supeniutant oily fluid ia decanted, dried by contact with Wd
calcium cldorido, and dintilled ; that portion which paaaea over betvMn
128° and 132' (2C2'.'U269^C F.) being coUected.
It is a colorlesa, oily liquid, has an acrid taste and a peculiar odor, at
first not unpleasant, aftcmard nauseating and provocative of severe liwd-
ache ; it bolla at 132' (269.6 F.) and crvslullizea at -20" {4^ F.) ; sp. gr.
a8184 at 15° (5* F.) ; it mixes with alcohol and ether, but not with water.
It burnt! difllcultly wiUi a pale blue flame.
When exposed to iiir it oxidizes very slowly ; quite rapidly, however, in
conlact with platiuimi-block, forming voleriauic acid. The same acid,
along with otber Bubstancen, is prruliiced by the action of tho more power-
ful oxidanla upon amyl idcoboL Chlorine attacks it cuergeticuUy. formicg
ftmyl chloride, HCl, and other chiorinatcd dcrisntivea Sulphuric acid
dissolves in aniyl alcohol, with formation of amyl-sulphuric acid, SO,
(0,H,,)H, corresponding to ethvl-aulphuric acid. It iUbo forma similar
acula with phosphoric, oxalic, citric, and tartaric acidii. Ita etliera, when
diaaolved iu ethyl alcohol, have the taat« and odor of various fruita, and
ai^e used in the prepuration of artiflctal fruit- essences. Amyl alcohol is alao
used in onolyaisas a solvent, particularly for certain olkaluids. and in phar-
macy for tho urtilicial pn>ductiou of valerianic acid and tho vnleriauatea.
Ita vapor, when inhaled, produces severe headache, a sense of suffo-
cation, gtddineRs, and, in large doeea, death. The liquid, taken internally,
especially when iu alcoholic solution, is much more actively poiaonous
than eMiylio alcohol. Even in very dUute solution it produces the rapid
intovication, and Rovere headache and vertigo, which are prominent efleets
of inferior whiskey.
To free tipirita of amy] alcoboi to de/anetaie them, advantage is usually
taken of the absorbent power of freshly burnt wood charcoal, which is
either placed in the still or mode into a filter, through which the spirit is
passed after lUatUUiition, or, preferably, the vajxir from the still is made to
pass through a layer of charcoal before condensation. Spirits properly
freed of fusel oil give off no irritating or foul fumes, when hot ; tliey are
not colored red when mixed with three parti^ C^H^O and one part strong
H.SO, ; they are not colored red or black by ammoniocol silver nitrate
Bolntion ; when 150 parts of the spirit mixed with 1 port potash, dis-
Bolved in a little H,0, are evaporated down to 15 parts, and mixed with on
equal volume of dilute H,SO^, no offenBive odor sliould be given ofT.
Cetylhydrate—(7»!/i//tV.vj^ro/(rV—i:/;iai—C„H„OH— 242— is obtained
by tlio a-ipimilicatimi of spermaceti (ita pidmitic ether). It is a white crys-
talline Bolid; fusible at 4»^ (120'.2 F.) ; insoluble in H,0 ; soluble in
alcohol and etJier ; tasteless and odnrleas.
Ceryl hydrate— C„H„OH— 896— and Myrieyl hydrate— C„H„
OH— 438— lu-e obtAined as white, crystalline solids : the former from
China wax ; the latter from beeswax, by saponification.
SIMPLE ETHHRS.
Oxiniis OP Alooholiu Radioai^ or tes Series C^Hj.f,.
The term etiur was originally applied to onyvolatilo liquid obtained by
the action of an acid upon an alcohol,
TfiG itimple ethers are the oxidex of Ihe ahoholic radicals. The; bear tho
SIUPLS: XTH7CRS.
ie relation to the alcohols ihnt the oxides of the basylona eleraentA benr
their hrdratea :
BUi«l OKlda
(kloohol.)
When the two alcoholic r»Iic.al» are the same, as in the above instance,
the ether is designated as simple ; when the radicals are difierenl, as in
methrl-ethyl oxide, /-i i| [ Oi they ore called mixed ethers. '
CM )
Methyl oxide — „„* [ O — 40 — isomeric with ethyl alcohol, ia ob-
tained by the action of H^SO, nnd boric acid upon methyl alcohol, or by
the action of silver oxide on methyl iodide. It is a colorless gas ; .has an
ethereal odor ; bums with a pale flame ; liquefies at —36° (— 32°.8 F.);
and boUs at -21**<-6°.8 F.) ; is soluble in H,0, H,SO. and ethyl alcohol
Btbyl oxide — Efhylic ether— JCtfter — Suiphurw ether — jEtiicr fortwr
(C. S.)—.Wier puru3 (/''-.)— q'§' { O— 74
pREPiLBATiOH. — A mixture is made of 5 pts. of alcohol, 90 %, and 9 pt«.
of concentrated H^SO,, in a vessel mirrouaded by cold H,0. This mixture
is introduced iuto a retort^ over which is conveuieiiLly arranged a veusel
from which a slow stream of alcohol can be made to enter the retort.
Heat is applied by a sand-bath, and the addition of alcohol and the heat
are so regulateil that the temperature does not rise above llO"* (284° F.).
The retort is connected with a well-cooled condenser, and the process con-
tinued until the temperature in the retort rises above the point indicated.
It is important that the tube by which the alcohol is introduced be drawn
out to a small opening, and dip well down below the surface of the liquid.
The distillate thus obtained contains, besides ether, alcohol, water, and
gases resulting from tlie deconijiosition of the alcohol and H,80,, notably
80,. It is subjected to a first purilicntion byshakingwitliH^O cuutaiuiug
potash or Itmo, decanting the supiTiiutuut ethor and redistilUng. The
pro<luctof this process is "washed ether," or ivCher (U. S.). It is still con-
t&mtnatpd with water and alcohol, and when desired pure, as for protluc-
ing an:ttHlhesia and for processeH of analyms, it is subjected to a second
purification. It is again shaken with HO, decanted, after separation,
shaken with recently fused calcium chloride and newly burnt liino, with
which it is left in contact 24 hours, and from which it is then distilled.
It was known at an early day that a small quantity of H.SO, is capa-
ble of converting a large quantity of alcohol iuto other, and tbat at tlie
end of the process the H,HO, remains in the retort unaltered, except by
secondary reaction& A metaphysical explanation of the process was
found in the assertion that the acid acted by its mere presence, by cotalyei^,
as it was said ; in other words, it acted because it acted, a very ready but
a very feminine method of explaining what is not understood, which is
still invoked by some authors as a covering fur our ignorance of the ra-
tionale of ci>rtain chcraioo-physiological plienomena- It was only in 1850
that Alex. WilliamBon, by a series of ingenious experiments, determined
the true nature of the process. In the conversion of alcohol into ether,
an intermediate substance, sulphoriuic acid, is olteruately formed at the
expense of the alcohol, and destroyed with formation of ether and regen-
190 ^^^^^^TKATtfjAL OW OITEMISTRY.
eralion of H^SO^. At firat H^SO. and alcohol net upon each ofbor, neHt-
cule for molecule, to form H,0 and Bulpbovuiio acid : *^ [ ^ "^
^ j O, = ^ I O + CX [ O,. Tbo new acid, ui tsoon &6 fonaed,
reacts with a second molecule of akoUol, with regeneration of H,SO, and for-
mation of ether : cX[o, + *^'^l^ = ^'}*^- + c'u*!*^-
Tlicoretically, therefor, a given quantify of H,SO, could conveit an
unlimited amuuut uf alcohol into ether. Such would al&o be the case in
practice, were it not that the acid gradually becomes too dilute, by admii-
turc with the 11,0 formed during the reactiou, and at the same time b
decomposed b}* ttccoudary reiu:tiou». into which it enters with impurttiei
in tlie iilcohol ; causes wliich in practice limit the amount of ether pro-
duced to about four to five times the bulk of acid used.
PoopEBTiEa — i'hifavxd, — Ether is a colorless, hmpid, mobile, highly
refracting liquid ; it has a sharp, burning taste, and a peculiar, tenacknu
odor, characterized as ethereal. Sp. gr. 0.72U nt Vl".^ (54°.6 F.); it boik
at 'WS) (94 .1 F.), and crystallizes at -31° (-SS'^.S F.). Its tcnaon
of Tapor is very greats especially at high temperaturea ; it should, therefor,
be stored in strong bottles, and should be kept in situations protected
from elevations of temperature. It is exceedingly volatile, and, when al-
lowed to evaporate freely, absorbs a great amount of heat, of which prop-
erty advantage is token to produce lo«d ouiiratheuia, the part being he-
numbetl by the cold produced by the rapid evaporation of ether sprayed
upon the surface, \Vftter dissolves one-ninth its woiglit of ether. Ktliylic
and methylic alcohols are miscible with it in tdl proportions. Kther is
an excellent solvent of many substances not soluble in water and alcohol,
while, on the other hand, it does not dissolve many substances soluble
in those fluids. The resins and fats are readily soluble in ether ; the
salts of the alkaloids and many vegetable coloring matters are soluble in
alcohol and water, but insolublo in ether, while the free alkaloids are
for the most part soluble in otiier, but insoluble, or very sparingly soluble,
in water.
Citemical. — Ether, whether in the form of vapor or of liquid, is highly
inflammable : and bums with a luminous flame. The vapor forms with
air a violently explosive mixture. It is denser than air, through which it
falls and ilifFuKeH it«elf to a great distance ; great caution is therefor re-
quired in handling ether in a locality in which there is a light or fire,
especially if the fire be near the floor.
Pure ethpr is neutral in reaction, but, on exposure to air or O, espe-
cially in the light, it }>ecomeB acid from the formation of a snmll quantity
of acetic acid. H,HO, mixes with ether with elevation of temperature
and formation of sulpnovinic acid ; sulphuric anhydride forms etliyl sul-
phate. HNO , aided by heat, oxidizes ether to carbon dioxide and acetic
and oxalic acid& Ether, saturated with llC'l and distilled, yields ethyl
chloride. CI, in the presence of II-O, oxidizes ether, with formation of
aldehyde, acetic acid, and chloral. In the absence of H,0, however, a
series of pr»>lucts of substitution are produced, in which 2, 4 and 10 atoms
of H are replaced by a corresponding numl>er of atoms of CI. Tliese
substances in ttini, by substitution of nlcDliolio nuhcAls, or of atoms of
elements, for atoms uf CI, give rise to other derivatives.
k
MONOBASIC ACmS.
ini
AcmoK OS THE EaoNoxT. — Ether ia largely used in medicine for pro-
duciug oDODstUvaia, either locally by diiuiuuliou of temperature due to ita
rapid evaporation^ or generally by inbalation. When takcu in overdoee
it cauwa death, iUthou<;li it iw by nu means as hable to give riise to fatal
aooidaiita aa in cluurofunn. Patients aulTeriiig from an ovenliMte nmj. in
the vast majority of cases, be reauacitatwl by artificial respiration and the
induced current, one pole to be applied to the nape of the neck, and
tlae other carried across the body just below the anterior attachments
of the diaphragm.
In cases of death from ether the odor is generally well marked in the
clothing and surroundings, and especially on openini^ the tlioracic cavity.
In the analysis it ia sought for in the blood and lunga at the same time
09 chloroform (q. t.j.
b
MONOBASIC ACIDS.
SEnm C^.O,.
Aa the higlier terms of this series are obtained from the tais, and the
lower terms are volatile liquids, these acids are sometimes designated as the
votetUefoUif acida. The known terms ore :
imU
PrBpUaole Mcld . . .
8017 fit Mrid
Talwteiikiaiald...
Cmvt%*e MM
(iMnUiyUa mM.
O^itrlw BreM . . . .
fWMgiiolcacki..
OlIKtCMia
Fonnalft.
Fudne-
B'-Utnc-
1
jolnt.
IH^nL
oiin^H
!•
100*
C,U,UiH
ir*
tifl
C,II.O,U
l«i
C,H,0,H
-V
l»J
'»•
in
11H
ch;o^
tis
c,H„o5i
u^
«w
C,ll.,OB
1!C
an
17*
Nainr.
Futmulft.
potnL
MyriJttcMdd
I'almitlc Mill
MMv«rla«tUd . ..
StMitoMhL
Anahte add.
o„n„o,H
C,.H„0,H
C,«II>|0,U
Ci, H,^.U
CtaUMO^H
C,oH,,0,U
0„H„0,H
c„n„o,K
O„M„0,H
ae*
KotUar
polaL
Although formed m a Taricbr of ways, these acids may be considered as
being derived from the primary monoatomic oloohols, by the substitution
of O for H, in the group CH,OH :
CH,— CH,— CH,— CH,— CH„OH
Nomial unfile kleotuil.
CH,-CH,-CH,-OH.-C0,0H
NonBtl vftkrfaiitlo add.
Considere<1 tvpically, the substitution of O for H, occurs in the radical :
H ) C U'o 1
'h" i ^ — * H 1 ^' *"'^ communicates to tlie radical electro-negative or
aoid quabtiea
Formic aoid— HCO.OH — ir>— occurs in the acid secretion of red
anta, in the stinging hairs of oertain insects, in the blood, mine, bile,
Crspiration, and mitscular Huid of man, in the stinging- nettle, and in the
iTes of trees of the pine family. It is produced in a number of reactions ;
by the oxidation of many orgnnic substances : sugar, starch, tibrin, gelatin,
albumin, etc ; by the action of potash upon chloroform and kindred
li)2
MANUAL OF COKMISTBT.
^
botlicg ; "h^ the artloD of mLienJ octdB in hydrocjauic ncid ; daring the
ffiiueutrilion of diftlxjtic urine ; bj the direct union of carbon monoiiiU
aitd wnter ; by the deoompositiou of oxalic acid under the i&flaence of
gljceriu ftt aU>ut 10)" (212^ F.)-
It is n culorle^u litiuid, having ad acid taste and a penetrating O(]or ; it
acts as aTDBicant ; it boils at lUO' (2!2" F.), and. when pure, crjstallizoait
0^ (32^ F.). It is miscible with H,0 in all proportions.
Tho mineral acids decompose it into H,0 oud carbon monoxide. Oxuli^
ing ageutj} convert it into U,0 and carbon dioxide. Alkaline hydrates
decompose it with formation of a carbonate and liberation of H. It ads u
a reducing agent with tlie salts of the noble metals,
Aoetlo add — Acetyl hydrate — llydrij(fen acetate — Pyrolign&n9 add—
Addum aceiicum (C. S. ; J5r.)— CH,CO.OH~G0.
Fonunov. — (1.) Bj tlte oxidation of alcohol :
CH,CH„OH + O, = CH.CO.OH + H,0.
S2.) By the dry distillation of wood.
3.) By the deoompoHitiou uf natural acetates by mineral adds.
(4.) By the action of potash in fusion on sugar, starch, oxalic, tartaric
citric acids, etc.
(fi.) By the decomposition of gelatin, fibrin, casein, etc., by H,SO^ and
manganese dioxide.
(6.) By the action of carbon dioxide upon sodium methyl : CO, + Ns
CH^ C,H,0,Na ; and decomposition of uie sodium acetate so produced.
The acetic acid used in the arts and in pharmacy is prepared by the
destructive distillation of wood. The products of the distillation, which
vary with the nature of the wood used, are numerous. Charcoal rcmiuns
in the I'etort, while the distilled product cousista of an acid, watery liquid*;
a tarry material ; aud gabcuus products. The gases are curl>on dioxide,
carbon monoxide, and hydi-ocarbona ; thpy are sometimes used for illu-
minating purjKMfpR, but arc usually directed into the furnace, where they
serve as fuel. The tar is a mixture of cmpyreumatic oils, hydrocarbons,
phenol, oxyphenol, acetic acid, ammonium acetate, etc.
The acid water is very complex, and contains, besides acetic acid,
formic, propionic, butyric, valerianic, and oxyphenic acids, acetone, napb-
t)uLlene, benzene, toluene, cumeue, crcaaote, methyl alcohol, and metliyl
acetate, etc. Faiiiolly freed from tar by decantatiou, it still contains about
20 per cent of tarry aud oily material, and about 4 per cent, of acetic
acid ; this ia the crtuh pyroUgneom acid of commerce.
The cTude product in subjected to a first purification by distillation ;
the first portions ore collected Bcparatcly aud yield metliyl alcohol (q, v.) ;
tho remainder of the distillate is the disiillcd pyrviiyt'coua acid, used to a
limited extent as an antiseptic, but principally for tho manufocture of
acetic acid and the acetates. It can only be freed from the impurities
which it still contains by chemical means ; to this end slacked lime and
chalk are added, at a gentle heat, to neuthdlzation ; the liquid ia boiled
and allowed to settle twenty four hours ; the dear liquid, which is a solu-
tion of calcium acetate, ia decanted and evaporated ; the cjdcium salt ia
conTerte<l into sodium acetate, which is then purified by calcination at a
temperature below 330" ^026" F.), dissolved, filtered, and recrystollized ;
tho salt is then decomposed by a proper quantity of H.HO,, and the liber-
ated acetic acid separated by distillation.
The product so obtoiued is a solution of acetic acid in water, oontain-
MONOBASIC ACIDS.
m
kg 36 per cent of imc acetic acid, and beiug of sp. gr. 1.047, U. S. (the
acid of tiie Br. Ph. is weaker — 33 per cent. C,H O,, and ep. gr. 1.014).
Pure acetic acid, kno^ra ait glacial aceHc acid, acidum aatiuyum glaciaU
(U. S.), ia obtained by decomposition of a pure dry acetate by heat
Pbopebttes. — Acetic acid is a colorless liquid. Below 17° (62''.0 F.),
wfaen pure, it is a crystalline solid. It boils at 119'' (24C^.2 R) ; ep. cr.
10801 at 0" (32° F.) ; its odor ia penetratinff antl acid ; in contact witn uie
skin it destroys the epidenuia and causes vesication ; it mixes with HO in
all proportions, the mixtures being less iu volume than the sum of the
Tolames of the constituents. The sp. gr. of tbo mixtures gra<lnally in-
CTBase up to that containing 23 per cent of H,0, after which they again
diminish, aud all the mixtures containing more tJban 43 per cent, of acid
are of higher sp. gr, than the acid itself.
Vapor of acetic acid bums with a pale, blue flame ; and ia decomposed
at a red heat It only decomposes calcic carbonate in the presence of H,0.
Hot H,SO« decomposes and blackens it, SO, and CO, being given oE
Under ordinat7 circumstances CI acts upon it slowly, more actiToly under
the influence of sunlight, to produce mtmnciiloracftic acid, CR^CICO.OH ;
dwhtoracelic acid, CHC1,C0,0H ; and trichloracetic acid, CCl.CO.OH. The
last named is an odorless acid, strongly veHicant, crvstulline ttolid ; fuses
at 46' (lir.8 F.) and boils at 195^-200^ (383^-392' F.).
AsALTTic.u, Chajuctees. — (1.) Wftmieii with SO,H, it blackens.
(2.) With Milver nitrate a white ctystalline ppt, partly dissolred by
beat; no re^luction of Ag on boiling.
(3. ) Heated with H,SO, and C JH.O, acetic ether, recognizable by it«
odor, is giTen ofll
(4.) When on acetate is calcined with « small quantity of As,0, the
foul o«lor cacodyl oxide ia developed.
(5.) Neutral solution of ferric chloride produces in neutral solntionB of
acetAtes a deep red color, which turns yellow on addition of free acid.
Vtne^^ar is an acid liquid owing its acidity to acetic acid, and hold-
ing certain fixed and volatile sulwtanpps in solution. It is obtained fi'om
nme liquid containing 10 jiev cent, or less of alcohol, which ia converted
into acetic acid by the transferring of atmospheric oiqrgen to the (doohol
during the process of nutrition of a jyeculiar vegetable ferment, known na
mycoderma aceix^ or, popularly, as mother of tnnegar. Vinegar ia now
manufactured principally by one of two processes— the Gerumn method
and that of Pasteur. In the former, tbe alcoholic fluid, which must also
contain albuminous matter, is allowed to trickle slowly through barrelB
containing beech-wood shavings;, supported by a perforated fidse bottom.
By a suitable arranp^eraent of holes and tuben, an ascending current of air
is mode to pass through tlie barrel. The acetic ferment clings to the
shavings, and under its influence acetiflcatlon takes place rapidly, omng
to the large surface exposed to tbo air. In Pasteur's process, the ferment
sown upon the surface of the alcoholic liquid, contained in large, shallow,
ered vats, from which the vinegar ia drawn off alter ncetification haa
n completed ; the mother ia collected, washed, and used in a subsequent
operation.
Tlie liquids from which vinegar is made are wine, cider, and beer, to
which dilute alcohol is frequently added ; the most esteemed being that
obtained from white wine. Wine vjnajitr has a pleasant, arid taste and
odor ; it consists of wator, acetic acid (aliout 5 per cent.), potassium bitar-
trate, alcohol, acetic ether, glucose, malic acid, mineral salts present in
wine, a formontescible, nitrogeuized substance, coloring maitor, etc. Sp.
tot
MAKVAL Of CHBM18TRT.
gr. 1.020 to 1.025. Wlien evaporated, ityieldfl from 1.7 to 2.4 perocnt
of solid residue.
Viucf^ars made from alcoboUc Ucgutds other tliau wine contain nopo-
tAseium bitartrat«, cont&in less aootic acid, and have not the aromAtk
odor of wine vinegar. Cider vinegar is of sp. gr. 2.0 ; is yellowish, liastn
odor of apples, and yields 1.5 per cent, of extract on eTaparution. Bea
vinegar is of 8p. gr. 3.2 ; has a bitterish flavor, and cm udor of eour be«r;
it leaves 6 per cent, of extract on evaporation.
The ])rincipal aduUeraiumit of ^iimgar are ; xiUithuric acid, which pro-
duces a bhick or bruwn color when a few drops ui the vinogar and aoue
fragments of cano-suf:^ arc evaporated over the miter-bath to dzTiKM.
WtUeTt *n excess of whicli is indJcaterl by a low power of saturation of tbe
vinegar, in the absence of mineral acids. Two parts of goo<l wine vioegii
neutralize 10 porta of sodium carbonate ; the same quantity of cider Tine-
gar, 3.5 parts ; and of beer vinogar, 2.5 parts of carbonate. Pj/rtdigntoui
acid may l>e detected by Uie creosote-lite odor and taste. Pepper, capti'
cum, and other acrid stibstances, are often added to communicate fictitious
strength. In vinegar so adulterated on acrid odor is perceptible after
iieuti^ization of tlie acid with sodium carbonate. Copper, zinc, lead, and
tin frequently occur in vinogar which hoit been in contact with those elfr-
meuls, either during the i>i'oc:ess of manufacture or subsequently.
IHstilletl vineijar is prepared by distilling vincgoi' in glass vessels ; it
containit none nf the tlxed ingredients of vinegar, but its volatile conslitn-
euts (acetic acid, water, alcohol, acetic ether, odorous principles, etc), and
a small quantity of aldehyde.
Wlien thT acetate of copper is distilled, a blue, strongly acid liquid
[JOHses uver ; this, upon rectifi cation, yields a colorless, mobile liquid,
which boils at 56' (132^.8 F.), 1ms u pecuhai- odor, and is a mixture of
acetic acid, water, and acetone, known as radicai vinegar.
Toxiooi/jnT. — When taken internally, acetic acid and vinegar (the latter
in doses of 4-5 fl. 3 ) act as irritants and corrosiTes, causing iu some in-
stances perforutiou of the stomach, and death iu G-15 hours. Milk of
magr^esia should be given as ou anliJotc, with tlie \-iew to ueuti-olizing
the acid..
Propionic acid— C.H^CO,OH — 74 — is formed in many decompoai-
tions of organic suhetances : By the action of caustic potussa ujmn sugar,
starch, gum, ami ethyl cyanide ; during fermentation, vinous or acetic ; in
the distllliitiun of wood ; during the putrefactiun of peas, beans, etc ; by
the oxidation of TJonnal propylic olcnhtjl, etc. It is best prepared by
heating ttbyl cyanide with potash until the odor of the ether has disap-
peared ; the acM is th<jn liberated from its potassium compound by H,s6,
and piiriQed. -^i^-o^f^ :> (L<^ \C'^'*'^fi/:{.^-^ fi^.
It ia n colorless liquid, sp. gr. 0.996, does not stftdify at —21*' f — B'.S F.),
boils at 140' (284* l'\), mixes with water and alcohol in oil proportions,
resembles acetic aoid in odor and taste. Its salts are soluble and cry»-
tallizable.
Butyric aold— C.H,00,OH— 88— has been found in the milk, per-
epimtion, muscular fluiil, the juices of the spleen and of other glands, the
urine, contents of the stoma<'h and large iiiteatiue, fn-cee, and guano ; in
certain fruits, in yeast, in the products of decomposition of many vege-
table substtuiees ; and iu natuml waters ; in fresh butter in small quantity,
more abundantly in Ibat wliich is rancid.
It is formed by the atttion of H,SO^ anil manganese dioxide, aided by
heat, upon cheese, starch, gelatin, etc ; during the combustion of tobacco
MONOBASIC ACroS.
195
{as lunmonium butyrat.e ; by the action of HNO, upon oleic acid ; (luring
the putrefacLioB of fibriji and other ttlbumiuoids ; during a peculiar fei^
mentation of glucose and starchy matoi-iul iu the prosenoe of casein or
gluten. This fermentation, known as the btitjric, takes place in two
Ma{^; at Brst the glucose is converted into lactic acid: C,H,^0, =
2(C H,OJ ; and this iu turn is decomposed into butvric acid, curlx>u di-
oiide, and hydrogen : 2C,H,0. = O.H.O, + 2CO. +2H,.
Butyric acid is obtained from the animal charcoal which has been used
in the purification of glycerin, in whicji it exists as calcium butyrate. It
ia also formed by subjecting to fenucutation a mixture composed of glu*
cose, water, chalk, and cheese or ghiteu. The calcium butyrate is de-
composed by H,SO,, and the butyric acid separated by distillation.
Butyric acid is a colorlesss mobile liquid, baring a disagreeable, per-
sistent odor of rancid butter, and a sharp, acid taste ; soluble in isuter,
alcohol, ether, aud methyl alcohol ; boils at 164° (327°.2 F.), distiUing
unchanged ; solidifies in a mixture of solid carbon dioxide and ether ;
op. gr. 0.074 at 15* (59<> F.) ; a good solvent of fats.
It is not acted upon by H.SO, in the cold, and only slightly under the
influence of heat. Nitric acid dis^ves it unaltered in the cold, but on the
apphcation of heat, oxidizes it to succinio acid. Dry CI under the influence
of sunlight, and Ur under the influence of heat and pressure, form pro-
ducts of substitution with butyric acid. It readily forms ethers luid salts.
Butyric acid ia formed in the Intestine, by the process of fermentation
mentioned above, at the expense of those portions of the carbohydrate
elements of food which escape absorption, and is discharged witii the
faeces as ammonium butyrate.
Isobutifric acid, an isomere of butyric acid, which boils at 152* (305*^.6
F.), has a}so been found in human fa>ces. It corresponds to iaobutyl
alcohol
Valerianic adds — C.H.CO.OH — 102.— Corresponding to the four
primary amylic alcohols, there are four amyUc or valerianic acids :
t CH,— OH,— CH,— OH — CO,OH. IL ^"^CH— CH,— CO.OH.
in. r»r ^"'^^CB—CO.OK. IV. Ch!— C— CO,OH.
cu,/
CH.— OH,/
L Normal valerianlo aoid — Butyl/ormic acid — Propyfacctic add—
is obtained by ilie oxidation of normal amyho alcohol. It lb an oily liquid,
boils at 1H5^ (365" ¥. ), and has an odor resembling that of butyric acid.
IL, in Ordinary valerianic aoid— Deijjitinic acid—Fhticenic acid —
Jaovcdcric acid — Impropyl acetic acid — Jsobutylformic acid — Acidum valeri-
onicum (Br.). — This acid exists in the oil of the porpoise, and in valerian
root and in angelica root. It is formed during putrid fermentation or
oxidation of albumieoid substances. It occurs in the urine and fsocee in
typhus, variola, and acute atrophy of the liver. It is also formed in a^
Tariety of cliemical reactions and notably by the oxidation of amylic alcohol.
It is prepared either by tlislilling water from valerian root, or, more
economically, by mixing ret'tilied amyUc alcohol with H,SO„ adding when
cold, a Rolution of potassium dichmmate, and distiUing after the reaction
has become moderated : the distillate is neutralized nith sndium carbon-
ate ; and the acid is obtained from the sodium valerianate so produced, by
decomposition by H,80, and rectification.
HjiiriTAL OF COKUISTBT.
Tho proportiefl and nature of the acid differ according to Uioae of tiu
Bmyl alixihol from which it is obtaiued. The active alcohol yielda the acid,
^g* yCH. — CH, — CO, OH, which is itself optically active ; which fomu an
UDei78t4dlizablo and exceedingly soluble barium salt, and whose boiling-
point is 173". 5 (344°.3 F.). The inactive alcohol yields by oxidation tk
**^*^ CH.— CH* /*^ — CO.OH, which is optically inactive ; whose harium
■alt is readily crystAlIizable and soluble in water to the extent of 18 pads
in KM) ; and wboae boiling-point is 174'^,5 (34t;'^ F.).
The acid obtained from valerian root is identical with the add obtained
by the oxidation of optically inactive amylic ulcohoL The artificial product,
being obtained from the commercial mixture of active and inactive alcohols,
is a mixture in different proportionB of the two acids mentioned above.
The ordiuary valerianic acid is an oily, colorless liquid, bavins a pene-
trating odor, and a almrp, acrid taste. It soUdifies at — IG'' (3^.2 F.); boils
at 173 -175^^ (3-43^4-347 F.); sp. gr. O.J)343-0.94fi5 at 20" (68" F.);
bums with a white, smoky flame. It dissolves iu 30 parts of water, and in
alcohol and ether in all proportions. It dissolves pbonphoruB, campher,
and certjiiu resins.
IV. Ti-imethi/l acetic acid — PivaHcactfl — is a crj^stalUne solid, whichfuaes
at 3r».5° {%' F.) and boils at 163°.7 (326. 7'F.); sparingly soluble in
HjO ; obtained by the action of cyanide of mtircury upon tertiary bu^l
iodide.
Caprolo aoidfl—Zferv/*cor*rf»—C.H,,00,OH^116.— There probably
exist quite a number of isomeres having the composition indicated above,
aome of which have been prepared from butter, rocoa-oU, and cheese, and
by decomposition of amyl cyanide, or of hexyl alcohoL
The acid obtained from butter, in which it exists as a glyceric ethtt,
ia a colorless, oily liquid, boils at 305° (401' F.); sp. gr. 0.931 at 16" (69''
F.); has on odor of perspiration and a sharp, acid taste ; is very sparingly
Bolublc in water, but soluble iu alcohoL
(Enanthyllo aoid — /Irplf/tia acid — 0,H„CO,OH— 130 — exists in
spirits distillfKl from rice and maize, and is formed by the action of HNO,
on fotty substances, especially castor oil. It is a colorless oil ; ep. gr.
0.9167 ; boils nt 21*2" (413".6 F.).
Caprylio add — Octijlic acid — C,H,,CO,OH — 144 — accompanies
caproic acid in butter, cocoa-oil, etc It is a solid ; fuses at 15** (59'' F.) ;
bods at 236' (467" F.i; almost insoluble in H,0.
Pelargonlc &cid~Nonylic ocu/— C.H„CO,OH— 158.— A colorless oil,
Bolid below 10' (50" l-'.); boUs at 260* (500" F.); exists in oil of garaninm,
and is funned by the action of HNO, on oil of rue.
Caprlo €LOid ~ Vecylic acuf— C,H„CO,OH— 172— exisU in butter,
eocoa-oil, etc., osnociatod with caproic and caprylic acids in their glyceric
ethers, and in the residnes of diBtillaiton of ficfltch whiskey, as amyl
capmte^ It is a white, cr}-stalliuo solid ; melts at 27°.5 (Sl'^.o F.); bous
at 273" (523^4 F.).
Xjaurio aold — LaxtroHearic acid — C„H„CO,OH— 200--i8 a eolid,
fnsible at 43*^.5 (110*^.3 F.) obtained from laurel berries, cocoa-butter, and
other vegetable mis.
J/yrmficactd— C,,H„CO,OH— 22R.— A crystalline soUd, fusible nt 64*
(129^2 F.); existing in manv vegetable oils, cow's butter, and s]>ermacetL.
Palmitic acid— AVAaltc'oarf— C,,H CO.OH— 256— existain palm-oil,
in combination when the oil is &eah, and free when the oil ia old i it also
COMPOUND BTHEBS.
197
Bnlen into the composition of Dearly all animal and vegetable fata. It is
olrfninetl from the fats, palm-oil, etc, by saponification witb caustic ixitaiaa
and !tub8£M|u«nt decompoaition of the soap by a utrong aoid. It is also
formed by the action of cauBtic potanh in fiLiiou upon cetyl alcohol (ethal),
•ad by the action of Uio samo reu}<cut upon oleic acid.
Pfdtuitic acid is a white, crystaUiue aohd ; odorless ; tasteless ; liRht^r
than H,0, in whicli it is insoluble ; quite soluble iji alcoliol and in ether ;
iusoa at 02 (143''.0 F.); tUstils uiichan-jted with vapor of water.
Margaxic aoid — C,,H„CO,OH — 27H— foruitrly supposed to exist as
ft glyoeride in all fats, solid and hquid. What had boon taken formargaric
asid vaa a mixture of 90 per cent, of palmitic and 10 per cent, of stearic
acid. It is ubtaiued by the action of potassium hydrate upon cetyl cyiuud«,
as a white, crystallino body ; fusible at 53". 9 (140" F.).
Stearic add— C„H„CO, OH— 284— exists as a glyoeride in aU soUd
fata, and in many oils, and also free to a limited extent.
To obtain it pure, the fat is saponilied with an alkali, and the soap
decomposed by HCl ; the mixture of fatty acids is dissolved in a huge
quantity of olcobol, and the boihng solution partly precipitated by tlie
addition of a concentrated solution of barium acetBte. The precipitate is
collected, washed, and decomposed by HC'l ; the stearic acitl wliich sepa-
rates is washed and recnstalhzcd from alcohol. The process is repeated
until the producit fuses at 70' (ITiS" F.).
Ihire stearic acid is a colorless, odorless, tasteless soUd ; fusible at 70°
(158" F.)^ unctuous to the touch; insoluble iu H,0 ; very soluble in
iloohol and in ether. The alkaline stearates ore soluble in H,0 ; those of
Oa, Ba, and Ph are insoluble.
Stearic luid j>almitic acids exist free iu the intestine during the diges-
tion of fats, a portion of which is docomjxised by the action of the pan-
creatic secretion into fatty acids and glycerin. The aame decomposition
also occurs in the presence of putrefj-ing albuminoid subetancea.
Arachlo acid — C.,H,,C0,OH— 312— exists as a glyoeride in peanut*
oil (now largely used as a substitute for olive-oil), in oil of ben, and in
small quantity in butter. It is a crystallina solid, which melts at 75°
(le?" F.).
COMPOimD KTHERa
As the alcohols resemble tho mineral bases, and the organic acids re-
Mmble those of mineral origin, so the compmnd ethers are similar in con-
stitulaon to the salts, being formtd by the double decumporition vf an alcohol
iuith an acid, mOicral or or<fanic, as a salt is formed by double decouipoei-
tion of an acid and a mineral base, the radical playing the part of an atom
of oorreeponding valence.
£thyl nitrate— MArw «A«f^J,jg' J O— 9L— A colorien liquid ; hu
• nraetiMto tad bitter flAcr^ute; ^ gr. till stir <G3=.6F.); boils at
85^ (IBS' PJ ; gives off es|daKT8 vapon. Prepared br ^liirtilling b mix-
tore of HNO, aad C^.O in the ytaeiiu e o( urea.
Ethyl nitrite— A'iCrost elfcer^J^ [• O— 75-ia best preporad by
diractiag the nitroas faiiiee» produced hj the aofckm of starcL ou HXO,
ondcr tite ipJhwiK^ of href, into alcohol, *'^*****'"«*^ in & rc-tort connected
vitb A well-cooled TeQexrer.
It is a yelknriab liquid ; hu an apple-Hke odor, and a aharp, sweetiak
taste; Bp.gr- 0.941 ; bodkat IB"" (G4^4F.) ; giruoff infianuDaUc rapor ;
tezy Bporin^^r solnble in H,0 ; readilj soluble in aloobol and etber.
Warm H.O deoompowa it into C,H,0 ; HNO, and NO. Alkalies de-
oompoae it into malate and nitrate ot tbe aikAline element It ia ener>
Sticallj attacked by H,SO,, H,S and the alkaline snlphidea. It is Hable
apootaneoos decomposition, eqiecially in the presence of H,0» into NO
ft&d nulio acid.
Ita vapor rapidly prodocee aiawtltfaitt ; it ia, boweTer. oseil only in aleo-
hoUo solutian : Sj'inius atheris nitron (U. S., Br.), wUicb also coDtaioi
aldehyde. Owing to the presKUce of the last-named substHuce, and to
the presence of H,0, the spirit is very liable to become acid, either from
tbe fonnation of acetic acid by the oxidation of the aldehyde, or from the
decomposition of the ether under the influenoe of H,0, a change which
rendent it unfit for use in many of the prencriptious in which it ia fre-
quently used, especially in that with pot^eium iodide, from which it Hber-
atea iodine. The presence of free acid may be detected bj efferreeceDce
when the spirit is shaken with hydrosodic carbonate. Ita acidity may be
oonected 1^ ahaking with potassium cArlionate, and decanting, prorided
it does not contain H,0.
Ethyl aulph atea.— These are two in number: {C.UjHSO^— Ethyl'
suiphuric, or sulpkovinio acid ; (O H^),SO, — Ethyl-eulphaie—tiulphuric ether.
SO,)
ErrHYi/-8ULPiJuuio Acid— (C^,) >- O, — 126 — ^is formed as on interme-
diate product in the mnnufncture of ethylic ether (q. t.).
Pure ethyl -Hulphm-ic acid is a colorless, syrupy, highly acid liquid ;
ap. gr, 1.316 ; soluble in water and alcohol in all proportions, insoluble in
ether.
It deoompoeea slowly at ordinary tempeTntnres, more rapidly when
heated. "When heated alone or with alcohol, it Welds ether and H,SO..
Wben heated with H,0, it jHehls alcohol and 6,30.. It forms crystal-
line fwdte, known as «u!phomnai*'s, one of which, sixlium gulphovinate,
(C,H^)Na80^ hoe been used in medicine. It is a white, doliqueaoe&t solids
J
COMPOCXD ETUSRS.
either crTstalliBe with lAq., or gmnitlar and tmli^clrous ; soluble in H,0.
Ita flolutioa should give no precipitate with boriuiu chloride.
SO I
Etuyl Splwute — ,„ n\*\ ^t — 154— the truo sulphuric ether, is ob-
tained by passing vapor of SO, into pure ethylic ether, thoroughly cooled.
It id a colorless, oily liquid ; has a shai-p, biu-niug taste, and the odor
of pcpperiiiitit ; ap. gr. 1.120; it cannot be distilled without decompo*
ntion ; in coutuct witli H,0 it in decompuaed vith formation of sulpho-
Tinic acid.
By the action of an excess of H,SO, upon alcohol ; by the dry distil-
Ution of the sxdp ho vitiates ; and in the last stages of manufacture of ether,
a yelloxvish, oily liquitl, having a penetrating odor and a sharj), bitter taete,
isiormed ; IhisisstwW or heavy oii of wine, oud its ethereal solution ia Oleum
oHkereum (U. S.). U soema to be a mixture of ethyl- sulpliate with hydro*
oarbona of the Berie.s 0„H,„. On contict with H,0 or an alkaline solution,
it is decomposed, sulphoviuic acid is farmed, and there separatea a color-
less oil, of sp. gr. 0.917, Ijoiliug at 2S0° (536^ F.), which ia lighi oil of wine.
ITiia oil is polj-meric with ethylene, and ia probably cetene, C,^H„ ; it is
sometimes called etiurine or etherol.
C R O )
Ethyl acetate— ^ceitc ether — .Ei'ner aceticua {U. S,) — % i, f O—
88 — is obtained by distilling a mistuie of Bodiuin acetate, alcohol and
H,BO, ; or by passing carbon dioxide through an alcoholic solution of
potaaainm acetate.
It is a colorle&s liquid, baa on agreeable, ethereal odor ; boils at 74*
(I65^2 F.) : 8p. gr. (I.K9 at 15^ (5!)^ F.) ; soluble in fi pts. water, and in
all proportions in methyl and ethyl alcohols and in ether ; a good solvent
oleseeuoea, resins, eautharidinc, morphine, gun-cotton, and, in general, of
substances soluble in ether ; bums with a yellowish white flame. Chlor-
ine acte energetically upon it, producing products of substitution, varying
according to the iuteuaity of the light from C^H^Cl^O, to C\C1,0,.
Aiuyl nitrate — n h ' i ^ — 133— obtained by distilling a mixture of
HNO And amvlic alcohol in the presence of a small quantity of urea. It is
acoloVlees, oify liquid ; sp. gr. 0.094 at lO"" (50'' F.) ; boils at 148" (298''.4
F.) with poi-tiul decomposition.
Amyl nitrite~.1mj(i nUra ( t; 5.)— ^,^^1 O— 117— prepared by
directing the nitrous fumes, evolved by the action of NO H upon starch,
into amyl alcohol coutuimx.1 in a retort heated over a water-uath ; purifying
the distillate by washing vrith on alkabne solution ; and rcctifving.
It is a slightly yellowish liquid ; sp. gr. 0.877 ; boils at 95'^ (20^=* F.) ;
its vapor explpdes when heated to 260" (500° F.) ; insoluble in water;
soluble in aleohol in all proportions ; vapor orange-colored. ^Ucoholio
solution of potasli decomposes it slowly, with formation of potassium ni-
trite and oxides of ethyl and ainyl. When dropped upon fused potash, it
ignites and yields potassium valcriiniate.
Amyl nitrite is frequently impure ; its boUing-poiut should not vary
more tiian two or three degrees from that given above.
C H O I
Cetyl palmitate — Cetine—'^ ^ Y O — 480— ia the chief oonatiU
uent of gpennaceti ■= ceiacenm. (U. S., Br.). This la the concrete portion,
obtained by expression and cr^'stollization from alcohol, of the oil con-
tained in Uie cranial sinuses of the s^ierm-wbale. It forms white, crystal*
I
200
HAJfUAl. or CHKMISTBT.
line pUtea ; fuaible at 49' (120^2 F.) ; alightW unctaons to the touch ;
tMteIes8, and aliuuijt odurleiui ; inaolable in water ; soluble in alcohol and
ether ; burns with a bright floiue. Besides uctiue, it cuutuius ethers not
only of palmitic, bat also of stearic, nirristic, and Uurosteatic ncidB ; and
of the alcohols : teOial, C. H„0 ; meUMl, C,.H_0 ; «U*ai, C, JL.O ; and
aiethai, C„H„0.
Mellssyl palmltate — ife/i«nn—",Ji. I O— 676.— Beeswax con-
sists mainly of two substancea ; cerotic acid, C,,H^O,OH, which is aoluble ia
boiling aleuhol, oud melissyl jialinitate, insoluDle in that liquid, united vith
minute quantities of subsUuiL-eti which comuiuuicate to the wax its color
and odor. Yellow wax mclte at G2^-G3* (14:j .G-X45" .* F.) ; after bleach-
ing, whi(^ ia brought about by exposure to light, air, and moisture, it does
not fuse below G6" (XflO'^.S F.). China imx. a while substance resembling
Bpermaccti, is a vegetable product, coiittiatiug chieily uf ccrt/l ce roiiUe,
AIJ>£iHYD£S.
SEBim C.H^O.
PonDio aUabTd* CRfO.
AMUoKlil^yih) CLH,U.
lIuplMiio ttUvliyite 0,H,0.
Bh^ttIi) oldalnda 0,11,0.
tMbntima MUnhrd* 04H|0.
TttlMtaaki aMrtrds 0»H„a
CavruLo aldal»da C,H„0.
tBnmUiyllo ■kUbrd* C,B,«0.
Oprrtlc aMehrri* ......0»Ut/>^
ramlUe «hl«hTd«. ....€,«a««0.
It will be remembered tlmt the moopbaaic acids are obtained from the
aloohola by oxidation of the radical :
BthrUknbol.
(C.
AaattauM.
These oxidized radiwda are capable of forming compounds aimilor in con-
atitution to thoue of the non-oxidized radical There are cldoridee^ bro-
mides, and iodides ; their hydrates are the acids, ^ "^ H !' ^ ~ acetic
(C H O^ 1
acid ; tiieir oxides are known aa anhydrides, /q'w^Q) ^ ~ acetic anhy-
dride ; and their hydrides are the aldehydes ' *^h = acetic aldehyde.
The name aldehyde is a corruption of alcohol dehydrogenatum, from the
method of tlieir formation, by the removal of hydrogen from alcohol
The aldehydes aJl contain the proup of iitoms (COH)', and their con-
stitution may be thus graphically indicated :
COH
CH,
PivptonfaiakMijda.
ALDSnTt^
201
They are capable, by fixing H,, of regenerating the alcohol ; and, by
filing O, of formiug the conesiJoncUug acid :
COH
I
CH.
CH,OH
i
CO.OH
iMtfOMOU.
C.H,0
Aoetlo aldehyde — Acettjl hydride — '^'"^ f — ^44— ie formed in all
reftctioDS in which alcohol is deprived of H without iuti'oduction of O. It is
^■■repared by diittilUng from a (vipJtcioim retort, connected with a well-oxjled
^^nidenser. a mixture of Il.SO,, G pts. ; H,C), 4 pUk ; alcohol, 4 pta. ; and
F powdered muuganeMO dioxide, 6 pt& The product is redistilled from cal-
cium chloride below 50' (l^a'* K). The aecond distillate is mixed with
two Toluni^H of ether, cooled by a freezing mixture, ami saturated with tin:
XH, ; there Heporate cryatala of ammonium Oicvlyiitif, H,0, NH,, which
are waahed with ether, dried, and decompoued m a dtstilling ai)i>arniuH,
j! over the water-bath, with the proper quautily of dilute li,^0, ; the dinLiUato
' it Anally dried over calcium chloride aud rectilied below 35^ (95^ F.).
I Aldehyde ia a colorless, mobile liqui<l ; has a strong, miffbcating odor ;
•p. pr. 0.790 at 18" (64".4 F.) ; boils at SI" (69^.8 F.) ; soluble iu all pro-
portions in water, alcohol, and ether. If perfectly pure, it may bo kept
unohange^l ; but if an excess of a^'id have been nsp-d in its preparation, it
. gradually decomputie:^. When heated to 100° (212° F.), it is decomposed
I into water aud crotuuic nlcleliydc.
In the presence of nascent II, aldeliydo takes up U, and regenerates
alcohoL CI cxmvertsit into acetyl cUoride, C,II,0, CI, aud other products.
Oxidizing agents <juickly convert it into acetic acid. At the ordiuary tem-
perature H,.SO, ; IlCl ; and SO, eouvert it into a solid subetnnce called
I paraltMtyih, C,H„0, {?). which fuses nt 10.5' (50M) P.) ; boils at 124*
' (2o5'^.2 F.), and is mure soluble in cold than in wiirui water. ^Iieu heated
\ with potassium hydiiite, aldehyde becumea bi'own, a brown resin separates,
I and the solution coutiuns potassium formiat« and acetate. If a vateir
I Bolutiun of aldehyde bo treated, first witli NH, and then with I [,8, a aolid,
' cr^'shUUue base, thialdiae, 0,0, NS,, separates. It ah^o forms crystalliue
compounds with the olkaliuo bisulphites. It decomposes solutions of
silver nitrate, separating the silver in the metallio form, and under condi-
tions which cause it to adhere etroufrly to glass.
. Vapor of al<lehyd6, when inhaled in a concentrated form, produces as-
1 pbyxia, even in comparatively small quantity ; when diluted with air it
I ia said to oot as au anaesthetic. Wlien taken iuteruidly it causes sudden
I and deep intoxication, and it is to its presence that the first prodncis of
the distUlation of spirits of inferior quality owe in a great measure their
rapid, deleterious acLiou.
hydride — adoral — ^'^^'g { —
Triohloraldehyde — Tfichloracetyl
147.5— is one of the final products of the action of CI upon alcohol, and ia
obtained by paseing dry CI through absolute alcohol to saturation ; apply-
ing heat toward the end of the reaction, which requires several hours for
lis completion. The liquid soparatGa into two layera ; the lower is removed
aod shakeu with au etjual volume of concentrated U,SU, and again allowed
to B4:'parate into two layera; the up^K^r is decanted; again mixetl with
H.SU^ from which it in distilled ; tliu disliUule iu treated with quicklime^
202
MANUAL OF CHEUISTBT.
from which it is again distilled, that portion which passee over beiwMBl
and 99* {20r.2-21U .2 F.) btinK coUocied, It sometimes happens
chloral in contact with U^SO^ is converted into n modification, insoluble in
U,0, known as metacMnral ; when this occurs it is washed with H,0, dned
and heated to 180'' (356" F.), when it is converted into the soluble variety.
which distilB over.
Cliloml is a colorless liquid, unctuous to the touch ; has a penetrating
odor and an acrid, catutiu tosto ; ep. gr. 1.502 at 18° (tU^.4 F.) ; boils at
91.4''{201^9F.) ; very soluble in wat«r, alcohol, and etlier ; dissolves CI, |
Br, I, S and 1*. Its vapor is highly irritating. It distils without alteratdoo.
Although chloral liaa not been obtained bj the direct substitutioa of
CI for H in aldehyde, its reactions show it to bo an aldehyde ; it forms
crystalline compounds with the biMdphites ; it reduces solutions of silver
nitrate in the presence of XH, ; NH and H,S form with it a componnd
similar to thialdine ; with nascent ll it regenerates aldehyde ; oiidiziM^
agents convert it into trit^.hloracetir acid. Alkaline solutions decompose i|^|
with formation of chloroform and a formiate. ^H
With a siitall quantity of H,Ochloi-ul forms a solid, crystalliDe hydrate,
heat being at the same time liberated. This hvdrate has the compositii
C\HCl,n,H,0, and its constitution, as well as that of chloral itself i^
cated by the formulm :
OH, oca, CO.
6ho cho C]
jud«hr<u.
{cbUnl).
;h(oh).
CiUffnl kydraie— Chloral {U. S.) — is a white, crystalline solid ; fuses
57" (IW.G F.) ; boUs at DH" (208°.4 F.). at which temperature it suffra-s
jiartial decomposition into rhloral and 11,1) ; volatilizes slowly at ordinary
t«jmpemtures ; is very soluble in H^O ; neutral in reaction ; has an ethereal
odor, and a sharp, pungent taste. Concentrated U,SO, deoomposea it
with formation of chloral and chiaraiide. HNO, converts it into trioblor-
acetic acid. When pure it gives no precipitate with silver nitrate solution,
and is not brow-ncd by contact with concentrated H^SO^.
Chloral also combines with alcohol, with elevation of temperature, to
form a solid, crystallino hodj— chloral alcoiiolate : CCl, — CH^f V. « «
Actios op CmjoaM, TJtdbatr noN the Ecoxomy, — Although it was the
ready dccompo»itioa of chloral into a formiate and chloroform which first
suggested its use as a liypuotic to Liebreich, and ulthouRh this decompo-
sition was at one time believed to occur in the body under the influence
of the alkaline reaction of the lilood, more recent investigatiouB have shown
that the formation of chloroform from chloral iu the bloo*l is, to say the
least, highly improbable, and that chloral has, in common with many
other chlorinated derivatives of this series, the property of acting directly
upon the nerve-centres.
Neither the urine nor the expired air contain chloroform when chloral
is taken internally ; when taken in largo doses, chloral appears in the urine.
The fact tliat the action of chloral is prolonged for a longer period than
that of the other chlorinated derivativea of the fatty series ia probably due,
in a great mcaeure, to its less volatility and loss rapid elimination.
When taken in overdosei chloral acts as a poison, and its use as sun
KETOJfBS OR XCVtOVTS.
SOS
U rapidly tncreasing as acquiuatance with xtn powers becomes more widely
disseminnted.
Xu chemical outidote ia known. The treatment bhould be directed to
the removal of any chloral remaining in the stomach by the stomach-pump,
and to the maintenance or restoration of respiration.
In &tal cases of poisoning by chloral that substance may be detected
in the blood, urine, and contents of the stomach by the following method ;
the Liquid is rendered Btrongly alkaline with potassium hydrate ; placed
in a flask, which is warmed to 50°-60° (122''-140'' F.), and through which
a alow current of air, heated to the same temperature, is made to pass ;
the &ir, after bubbUtig through the liquid, is tested for chloi-oform by the
methods described on p. 113. If affirmative results nro obtained in this
testing, it remains to determine whether the chloroform detected existed
in the fluid tested in ita own form, or resulted from the decomposition of
ckkjral ; to this end a fresh portion of the suspected liquid is rendered acid
and tested as before. A negative result is obtained in the second testing
when chloral is present.
Bromal —
C.BrO
Hf
— 281.^ — A colorless, oily, pungent liquid ; ep. gr.
3,34; boils at 172° (341°.6 F.); neutral; soluble in H,0, okohol, and
I ether. It combines with 11,0 to form bromal hydrate, CBr,,CIl(OU),;
large transparent cnrstala ; soluble in H,0 ; decomposed by alkalies into
bromoforui and a fonuiate. Produces anueathesia without aloep ; very
I poABOnouft.
^ Aia
KETONXIS OR AOETONIIS.
Semes O^n.,0.
Although the aldehydes are not acid in reaction, and are not usually
regarded as acida, there exist substances kconii as ketones or acetones,
which may be regarded as farmed by the substitution of on alcoholic radi-
cal for the II of uie gronp COH. 'fhesB substances all contain the group
of atoms (CO)' ', and their constitution may be represented graphically thus :
IMm«li)rl IcalQiM
(■CBtOU*).
6E.
the first being a symmetrical irf.lone and the latter a ■non-n/mmetricoL The
ketones are isomeric with the aldehydes, from which they are distinguiahe<1 :
1st, by the action of U, which produces a primary alcohol with an alde-
hyde, and a secondary alcohol with a ketone ;
COH
cirou
im, + H,
= L
in.
in.
204
UAnrAL OF CHEMISTRY.
CH, CH.
CO -I- H, — CH,OH
CH, CH,
2d, 1)^ tLe action of O, which uiutea directly with an aldehyde to produce
the correHpondiiig ucid, wUile it causeu the dianiption of the molecule of
the ketone, \nth fommtiou of two acids :
COH CO.OH
CH, + O = CH,
CH, cn.
I CO.OH CO.OH
r^^'n -^ in.
AwtoBO.
Vtaenloadd.
iAidoBcU.
Dimethyl ketone — Ac^one — Aoeiylmelhylide — Puroaceiic el
/CH
ipirit — CO;f ^g" — 58 — la formed as one of the products of the dry dis-
tiUation of tlie ooetatee ; by tlie deoompontion of the vapor of acetic acid
at a red heat ; by the dry distillation of tnignr, tartaric acid, etc.; and tu
a number of other reaclioua. It ia obtained by diutilling^ dry calcium
acetate in an eorthcuwure i-etort at a<lull red heat; the dj»tillat«, col-
lected in a well-cooled receiver, is freed from II.O by digestion with fused
calcinm chloride, and recti^ed ; tboHe portioua being collected which poM
over at 60° (140° F.). It is also formed iu large quantity iu the preparation
of aniline.
It ia a Umpid, colorlesa liquid ; sp. pr. 0.7921 at 18° (64^4 F.) ; boils at
56" (132°.8 F.) ; soluble in U,0, alcohol, and ether ; hasa peculiar, ethereal
odor, Olid a buruiuf^ taste ; ia a good Bolvcnt of reaius, fate, camphor, gun-
cotton ; reathly iuttammablo. It foiins cr^'stolline compounds with the
alhahuc bisulpliites. CI and Br, in the presence of alknlies, convert it into
ohlorofonn or bromoform ; CI alone produces with acetone a number of
chloriiinteil produclH of subfttitution. Certain oxidizing ngenta ti-aimforn^H
it into a mixture of formic and acetic acida ; others into o:mhc acid. ^|
Acetoue has been found to exist in the blood and urine in certain
pathological conditions, and notably iu diabetes ; the peculiar o<lorexbal
by diabetica is produced by tliis BuUstanee, which has also been consid
by »ome autliors as being the cause of the reapinitory derangements
coma wliich frequently occur in the Last etagee of the disease.
That acetone exists in Uie blood in such c-ases la certain ; it is not
tain, however, that its presence produces the condition designated as
aceloncemia. It con hardly bo doubted that the acetone thus existing in
the blood Li indirectly fonDe<) from diabetic sugar, and it is probable also
that a romplex acid, known aa etht/ldtacetic, C,H,0,H, ia formed as an i
termediute producL
MONAU1KB6.
203
MONAMINES.
lie monamines aro subfltoncea vliich ma^ be considered as being de*
from oue molecule of KH, hy the substitutiuu of one, two, or three
>bolic rndicaU for one, two, or thre« 11 atoms. They ore designated
imaru, gecondanj, and tertiary, according as thej contain one, two, ex
alcoholia radicals :
H
N_H ll—on,— OH,
U H
<prun«r7>.
H
I
N— CH,— CH,
H,-OH,
I
<0,H.),HN
DMkTtemlM
(•OOOOdM^).
CH,— CH.
N— ClI— CH,
CH,— OH,
(C,H,).N
TriMlntaiBliw
They are also known as compomid ammonias, and reaemblo ammonia ia
their chemical properties ; unittng with acids, witliout eliminatiOD of JU^O,
to fonn salts resembling those of ammoniam. They also combine with
U,0 to form ffuaiemart/ ammonium hydraieg, similar In coustitutiou to am-
monium bydrat*. The alkalinity and solubility in HO of the primary
monamiuea are greater than those of the sccondan-, and those of the seoond-
ary greater than those of tho tertiary. Their chlorides form sparin^y
soluble comj)Ounda with platinic cliloride.
The primary mouoniincs are formed by tbo action of potassium hydreUe
ipon the corresponding oyanic ether ;
CNO,C,H. + 2KH0 = NH,.CJI, + CO.K, ;
Bthjrt «yMMt«. PoMnti. Bthylantlnu. IMteMltun
by heating together an alcoliolio solution of ammonia and an ether :
HI
C.HJ + NH, =^
Erbfl AmnonU. Hrdilodlo
lodldo. add.
NH„0,H.;
BtbrlMnlH«,
or by the action of nascent H upon tho cyanides of the olcohoUc radicals :
CN,CH, + 2H, =
Uotbll CTmolJa. Bjdtognn.
NH.,C.H..
BthyUmlni^
Bui
■^di
Hie secondary monamines are formed by the action of the iodides or
bromides of the alcoholic radicals upon tlie primary monominea.
The tertiary monaraines are produced by the distillation of the hy-
drates or ioiliden of the qnnt«mary ammoniums, or by the action of the
iodides of the alcoholic railirals upon the secondary roonaniines.
It is obvious from the ftlwTe aescribcd properti(>8 of thpse aiibstancesi
lint they are true alkaloids (see p. 331), among which also belong thej
diomiuGB and triamines (see |>. 249).
Methylamizie — Mulhylia — „• 'r N — 31 — ia a colorless gas ; hoa
by, anunoniacal odor ; in^mmable ; ia the most soluble gas ks'*'
MANUAL OF CHJEMISTBT.
iao
Tolnme of H,0 diasolving 1,154 Toliimea of methylitt at 12'.5 {54^5 F.);
the solution U strongly aikuUnc! azid caustic.
Tiie a(]ucous solution poftaeaeea the odor of the gas, and is highly
klistic and nlkoline. It netttralizes the acids witli fonn&tion of meUi}i
)niuni salts (e.r?., CH,H,N,XO,= mcthylaimuouiuui uitrate), viach
for the most port crjBtallizuble and very soluble in H,0. Its cLlu^
[•urate crystallizes in benntiful golden -ye) low needles, soluble in water,
ftlcohol, and ether. Its clilorophitinat« cryatoUizce in golden-yeBow sctka,
Boluble tu wat«r, insoluble in alcohoL
See triincthylaminc, below.
Vimethylaraine—Dimdhx/Ua—^^^'^l N— 45— is a liquid below 8'
(46^4 F.) ; has an auununiacol odor, and is quite soluble in H,0. IIcod-
slitQtes about &0 per cent^ of the commercial trimcthylamiuc, which &bo
oontains 5 to 10 per cent of triraethylamine, the remainder being a miit-
ure of monnraetliylamine, iaobutylamiue, and propylamine, ha chloro*
plaliiiate forma long needles.
St'o ti'imethylamiue, below.
Trimetbyiamine — Tiimefki/Iia — (CHJ,N— 59 — is formed by
action of methyl iodide upon NH,, and as a product of decomposition ol
many organic substances, il bc-tng one of tlie products of the actioa of
potash on many vegetable subst«uice«, alkaloids, etc. It also occun oat-
urolly in cod-liver oil. ergot, chenopodium, yeast, guano, human urine, the
blood of the calf, and many flowers.
It is an oily liquid, having a disagreeable odor of tluh ; boils at 9'
(48°.2F.); alkaline; soluble in H,0, alcohol, and ether; iuflummablc. It
kfiombines with acids to form salts of trimethyl ammonium, which are
■(Bryetallizable.
Trim ethyl amine boa long been known to exist in the pickle in wluch
herrings havo been piTserved. More recently it has been found to be
an Lm|>ortant product of putrefactive changes iu fish, starch-paste, brain-
tissuo, muscular tissue, and other albuminoid substuuces, being accompa-
nied by lesser quantities of monometbylamine, dimethylamine, etbylamise,
and diethylamine, as well as by other peculiar alkaloidnl bodies. It Las
also been observed accompimylug more active alkaloids in blood-serum,
etc., which have served for the culture of various bacilli. (See choline
and neurine, helnw, and ptomaines, p. 343.)
Its chloruplatiiiate cr^-Biallizes in ocLahedra, insoluble in alcohol.
The commercial trimethylamine, •obtained by the dry distillation of
distiUery-iva-ste, contains but /f per cent of the substance whose some
it boars, (^co dimetbylamiuo, above.) It Las frequently been mistaken
by writei-s upon materia medica for its isomer© propylamine,' » jj' J N,
which lUiTers from it iu odor and in boiling at 50° (122'' F.). Its chloride,
under the names chioride of propiilamia, of secalia, o/eecalin. Las been used
in the treatment of gout and of rheumatism.
Tetramethyl anunonium hydrate — (CH,).N,OH— 91.— This sub-
stance, whoso c-onstitiition is simihir to that uf ammonium hydrate, is
obtained by decomposing the coiTOspondtng iodide, (CHJ,NI. formed by
the actionof melhyliodide upon trimethylnmine. It is a crystalline solid ;
deliquescent ; very soluble in H,0 ; caustic ; not volatile without decom-
position. It attracts carbon dioxide from the airland combines with acids
to form crystnlliz-'ible wdta
The iodidu is said tu exert on action upon the economy similar to that
of curare.
MOVAUISEB,
£07
Choline — TrimeOitfloxethylammonium hydrate —
(CH CH - -OHl r^>^^~^*^>*^*^» — 121— is a quaternary monammf
nitini hydrate, containing three nietbyl groups and oue etliyleue hj'droiic
(oxetbyl) group. It dom not occur in the nornial body in the Iroe statfi^^
out is niilely disseminated as a component part of an exceedingly irapor-'
tent class of substances, the lecithins (see p. 273). It is also obtained
from bile and from the yolk of eggs. It is one of the earliest products of
cadaverit: putrefaction, resulting, in all probability, from decomposition
of the lecitliina.
Choline has been obtained ByDtLeilcally by the action of a concen-
trated Roltilion of trimethylamine upon ethylene oxide, or upon ctliyleuflj
chlorhydrin. "When heated, it splits up into glycol and trimethylamine.
It appears aa a thick svTup, soluble iu H^O und in alcohol, and strongly
alkaline io reaction. Even iu dilute atjueous solution it prevents the coag-
ulation of Albumin and redissolves coagulnted albumin and tibiin. It is
ft strong base; aftrncts carbon dioxide from the air: forms with HCl a
salt* soluble in alcohol, which crystallizes in plates and needles, very much
resembling in appearunce tliose of cholesterin. Its chloroplatiiinte is puri-
fied with difficulty ; its chloraurato readily. Solutions of its chloride dif-
fer in their behavior with nlkaloidol reagents from those of neuiine in
forming no precipitate Ais-ith tannic acid, and iu forming a voluminous
vhite precipitate with phosphomolybdic acid, which becomes crj'stalline
on standing.
Administered hypodermically to animals it causes muscarine-lilce intox-
ication, although much less intense m its action than either that alkaloid
rne urine.
Am aniline — Trimeihyloxethylideneammanium kydrat^^
(OT — CHOH) I '^S^^ = C,H.,NO,— 121— is an isomere of choline, exist-
ing along with muscarine (see below) in Agaricu» mmc<trivA. By oxidation
willj HNO, it yielila muscarine.
Muscarine— j^^^^ . I N,OH = C,H,.NO,— is a substituted tctra-
methjlommonium hydrate closely related to choline and amanitine, fi-Qva
«i former of which it may be obtained by oxidation.
It occurs in nature iu Jgarivitit muncarius, und is produced during pu-
factive deconiposition of albuminoid substances. Its formation under
such circuiristauces is of great iinpurtauco, not only by reason of its ac-
tively |K)isonous qualities, but for the reason that, with the exception of
the amines alvive niontioned, it is the otdy alkaloid formed during putre-
faction which is known to be a product of the vegetable world us well.
The free alkaloid occurs iu very deliquescent, irregular crystals, or, if
not perfectly dry, a colorless, odorless, and tasteless, but strongly alkaline
syrup; readily soluble in oil proportions in woter and iu alcohol; vei^
sparingly soluble in chloroform ; insoluble in other. It is a more powerful
base than nmnionium hydrate, forming an alkaline carbonate and neutral
salts with other acids. When decomposed it yields trimetliylan>ine. Its
platinochloride crrstallizes in octahedm. Its chloride forma colorless,
brilliant, deliquescent needles.
When adiiiinjsternd to animals, muscarine causes increased secretion of
saliva and tenrs ; vomifing ; evacuation of freces, at first solid, later liquid ;
contraction of the pupils, almost to the extent of closure ; diminution of the .
rapidity of the pulse ; interference with respiration and locomotion ; grad-'
uaJ sinking of the heart's action and respiration ; and death. Atropine
mmili Om Mtioo of :
'Mteb^ud
and dimhushefl its intensit j vben olm^T
I !-NOH = (
(<
Keurin^—Drimethylvinylammonium hydrate,
no, u K sabstanoe neurlj rdated to choline, and long confoonded witb it,
jnppoaed hj Liehreicb to exist in the brain. The name bodv is ooe at
>tbe alkaloida produced hy tluf putre&ction of mascubir tiasoea^ and is en-
rdowed with poiaonoua qualitieo, resemldiiig, bot leaa iatezne than, tfaose
i«f iniWQimne.
Another cadareric allcaloidt related to neurioe and prodaced under
atnular couditiona, i» a dianiiiie ; nfvrvline, C,H,,N^
UONAMIDES.
Thwn bodiea differ from the amines in containing oaygenaUd, or odd
tjadicala, in place of alcobobo radicala. Like the ominea, Uiey are diiiait^e
into pri$nanf, ttcondaryy and leriiary. Thej are the mtrides of the add
radicala, as Uie amines are the uithde« of the alcoholic nidicala.
Hie monamidee may also be regarded aa the acids in which the OH of
the group (XK>H has been r^ilaoed bj (KHJ :
cn,
I
COOH
AiwUcMia.
CONH.
The primary monamides, containing radicals of the acids of the aeefic
aeries, ore formed : (1.) By the action of heat vpcm an ommoniacal salt :
AmswBlnm Mrtato. V»tar.
AoettinkU.
(2.) "Bj the action of a compound other upon ammonia :
(CA°);|o.H
(cao)'|n
+
'^\o
Eth)-I McUta- JLmiMMil*. Aectuattla. AleuhoL
(3.) Bj the action of the chloride of an acid radical upon dry N^ :
(C.H.O)'
Cl^
+ 2
NH
«,[.mo^|N
Amman 1*.
AnuBMilam
eblorUa.
The eecondanj monamides of the same class are obtained : (L) By the
action of the chlorides of acid radicals upon the primary amides :
<o.h.o^}n+(«AO^} = «'.h.o^|k.h|
AocQrl c'bloiUi,
AUIDO-AOmS OF THIS PATTY &T:RIES.
209
(%) Bj the action of HCl upon the primary moDAmidea at high tern-
peratures :
BnlrDctilario
DIaccUiuklB.
Aiuitioiiliim
ublurUlc.
The tertiartf monamideH of this series of ntdimls have bcon but im-
perfectly Htudii'tl ; saiDQ of them have been obUuiiitd l)y ttie action of
the chlorides of acid rodicak upon metallio derivntiTes of the woondary
•iinides.
The primary Tnon&inideH containing nulicftla of the faitj noide are solid,
cry stall izable, neutral iu reaction, vobtile without decomponiliou, nioeily
soluble iu alcohol and ether, and mostly capable of uniting with acids to
form compounds nimihir in conatitution to the ammoniacal salU. Tbey
are capable of uniting with H,0 to form the omnionical salt of the oor>
responding acid, and with the alkaline )iydrat«H to form the metjillir wilt
of the corresponding acid, and ammonia. The germuhry monamtdca.
containing two radicals of the fatty series, are acid in reaction, and their
remaining atom of extra-radical U may be replaced by an clectro-pofiitiTe
atom.
Aoetamide — ' * ^U >N — 59— is obtmncd by heating, underpress-
ure, a mixture of ethyl acetate and aqua ammoniip, and pnrifying by
diatillation. It is a solid, crystalline eubstauce, ver^' soluble in H,0,
alcohol, and ether ; fusee at 78° (172".4 F.) ; boils at 221'^ (429^8 F.) ; baa
a sweetitUi, cooling taste, and on odor of mice. Boiling potassium hy-
drate aulutiflu decomposes it into potassium acetate and ammonia. Phos-
phoric anhydride deprives it uf H,0, and forms with it aivtonitTUt or
m^hyl cijanuie.
AMIDO-ACIDS OP THE PATTY" SERIES.
Those compounds, also known m* (flycrtnjlti. aro of mixed function, acid
and l>asic, obtained by the Kubstitution of the univalent group (NH^J' for
an atom of radical H of an acid :
CH.
COOH
Aorilo aciiL
CH,(NHJ
COOH
Ainli]o«(Kllo Mill (gljflocalU
Some of them, and many of their deriTati\-eB, exist in animal bodies.
Oorrespniiding to them are many iaomeres belonging to other series.
Ainido-aoetio add — Glymcol — Su^ar of statin — Ql}fco(amic add —
CH,.NH,
Glycine — I —76— was first obtained by the action of H,SO, upon
gelatin. It ih beat prepared by acting upon ghie with caustic potaasa,
NH, being liberated ; H SO, is then mldeil, and the ci78tftlB of potassium
sulphate separated ; the liquid ia evaporated, the residue dissolved in>
alcohol, from which solution the glycocol is allowed to crj-stuUize.
UAKUAL ov cmansT&T.
It may also be nbtainevi ^nthetically by a method which iD(U<at« its
consUtutiou — by the uctiou of ammoaia u{>on chloracedc acid :
COOH
+ H-N =
H/
CH,NH,
COOH
+ S
Chkneatk
MM.
AmrnvnU.
Hjrdfncblorie
mM.
It may l>e obtained from ox-bile, in which it exists as the salt of ft coo-
jufi^ate acid ; Crum uric acid by the action of bjdriodic acid : and hj tbe
union of formic aldehyde, hydrocymnio acid, and water It is iMmoie
with giycolamide.
It has been found to exist free in animal nature only in the muscle of Ui«
scallop, and, when taken inteiTially, its constituents are eliminated asuitt.
In combination it exists in the t^t^lalinoidti, and with cboHc acid as sodium
glycocholate {a. v.) in the bile. It is one of the productsof decompoeitioDof
glycocholic acid, liyoKlycocbolic acid, and hippuric acid by dilute odds aod
by alkalies, and of the deoompobitiou of tissues containing gelatinoid&
It appears as large, colorless, transparent crystals ; ha^ a sweet tast«;
melts at ITU"" (388^ F.); deoomjxisi-s at Li;^her temperatures; spuringl;
soluble in cold U,0 ; much more soluble in worm H.O ; iusoluble in sT
late alcohol and iu ether ; acid in reaction.
It combines wth acids Ui fonn crystalline compounds, which are
composed at the tumpenituro of boiling water ; hot H,SO, carbonizes it;
HNO, converts it into glycolic acid {q. v.) ; with HCl it forms a chlohde ;
heated under pressure with benzoic acid it forms hippuric acid. Its add
function is more marked ; it expels ciirbonic and acetic acids from calcium
carbonate and plumbic acetate. The presence of a sninU quonUtj of
glycocul prevents the precipitation of cupric hydrate from cupric sulpbsts
solution by potassium hydrate ; the solution becomes dark blue, does not
yield cuprous hydrate on boiliug, and precipitates crrstalliue ueedles of
copper glycolamate on the addition of alcohol to the cold solution. M'itli
ferric chlorido it f^^res au intense red solution, whose color is discharged
by adds, and reappears on neutralizstion. With phenol and sodium hypo-
chlorite it gives a blue color, as does ammonia. By oxidation with potas-
sium permun^nate in. alkaline solution it yields carbon dioxide, oxalic,
carbonic, and oxamic acids, and water. It also forma crystalline com-
pounds with many salts and ethers. Methyl amido-acetate ia isomeric
with sarcosine :
CH,NH,
COOH
Qlycoool
(uiudo-MCKla Mcitl).
CH,NH,
COOCH.
Mothyl
Mnllto-MVUU.
CH^TICCH,)
COOH
SMWfDO
-80— ^isomeric
CH.INH(.CH,)]
Methyl-glycQCOl — Sarcomne — 1
COOH
alanine luul with lactamide (q. ti-), does not exist aa such in animal nature,
but has been obtjdned fi-om creatine {r^. v.) by the action of barium hydrote :
CH.KA
4-
Water.
C.H,NO,
SWOOdlM.
-f
CON.H, ;
4
hp^
nrea being formed at the same time, and decomposed by the further
action of iJie barium hydrate into NH, and barium carbonate.
AWTDO-ACIDS OF THB FATTT
211
Ita coDstitTitinn ia indicBte<] by iU ^mthetac formation from chloracetic
rid aud metbjlainiue :
CIi,Cl
OOOH
H— N
H/
VetlijrlMnlai!.
OH,[NH(CH,)J
COO]
CI
a»rwMfa». Hrdmohlorlo
noM.
It crjatalUzea in colorless, trausporent prisma ; vers- soluble in water ;
q)U'ingly solublo in otcofaol and etlior. Ita aqueous solution is not add,
and has a sweetish taste ; it anit«8 with acids to form crystalltue salts, but
does not form metallic salts. It ia capable of combining with (^anamide
to form creatine.
» Beta.ine-^ Trimethylgiycocol-^Oxyneurine^OxychoUne —
CH.— CO
J 1 = C.H„NO,— 117— was aretobtained from the juice of tb«
(CH.).i!r - 6
sugar-beet ; afterward it was oblainea br oxidation of choline ; and is also
produced Bj'ntheticallv, pithsr by anting nj)nn tHmethylamine with mono-
chloracetio acid, as glycerol in obtained by the action of the eamn acid upon
ordinary ammonia ; or by acting upou glycucol it^ielf with methyl iodide.
BetaKne cr>'8tallizes in large, brUUant crystals, contaiuing one molecule
of water of crystallization. At the ordinary temperature tbey ore deli-
quescent, but at 100° (212" F.) effloresce, and lose their Aq. It ia very
soluble in water and in alcohol. It is decomposed by heat, with eTolution
of trime thy lamina It forma crystalliuo saltA Its chloraurato is crystal-
line and very sparingly soluble in cold water.
The method of its syntheaia and the composition of its chloride indi-
'cate it to 1x1 related to tetramethylommonium hydnite, but when He chlo-
ride is decomposed by silver oxide, it is not with substitution of OU for
CI, but with separation of 01 H- H,0.
Betalne is tne type of a number of aimilar compounds derivable from
the amido acida by substitution of variouti hydrocarbon radicaia
. CH.-CH.(NH,)
I Amidopropionic Add — Alanvie — j — 89. — Isomeric
with sarcosine and with lactamide ; does not exist, as far as is known at
present, in nature. It is obtained by the action of aJooholio ammonia upon
bromopropionic acid :
CH.Br
COOH
Brodtoprapl-
ontc Mdd.
. «(h)n) =
AmatonU.
CH,(NH,)
OOOH
AmMapro|iI-
onloacU.
+ BrNH.
bromlda.
Hpt may also be prepared by starting from lactic acid, from which it differs
^^y containing 5rH, in place of OH.
It crj'staUizes in large, oblique, rhombic prisms ; very soluble in H,0 ;
sparingly soluble in alcohol ; insolnble in ether. Ita otjueous solution is
neutral and sweet. Nitrous acid converts it into lactic iicid, N, and H.O.
It dissolves in ncids without neutralizinfr them, but yet, in certain caaes,
with the formation of cr>'^talUno compounds. Its Ba, Pb, Cu, and Ag Ba]ta
are soluble and oiystaliine.
313
MARTTi
Ainldobut3nrlo Aoid— /Tu/n/a/iine— C,H,NO,— and Amldovalerl-
anic acid— CjH,, NO,— are only of theoretic interest at present. Tbe
Utter baa beon found iii the LiBsue of the pancreas and among the prodncts
of tho action of pancreatic juico ui>on albumin. They are among the pro-j
dnota of the decomposition of albumin by caustio baryta.
CH— C,H,— CH,(NH,)
Amldocaproio Add — Leucine— I — C.H .NOJ
COOH
— 131— exists widely distributed in animal nature ; it has been obt
firom Uie normal sjdeon, pancreaa, salivurir, lymphutic, thymua. and th\Toitl
^ands, Itznga, and liver. Pathologically, its quantity in' the Uver is inuch
increased in diseases of that organ, and in typhus and variolA ; in the hil
io fyphufl ; in the blood in lencocyLhoimia, and in yellow atrophy of thl
liver ; in the uriiio in yoUow atrophy of the liver, in typhus, and in variola!
in choleraic discharges from the intestine ; in pus ; in tho tluids of dropsy?
and of atheromatous cysts. Tn these situations it is usually accompanied
by tyrosine {q, v. ). It is much more abundant in the tissues of the lovec
forms of animal life, and has also been found in regetable tissues.
It is formed by the decorapo«iiiou of nitrogenized animal and vcget
Bubstances, by heating with strong alkalies or dilute acids ; by the dec
position of elastic tissues it is formed with a small quantity of tyrosinE ;
by that of gelatinoid materials, ienciuo luid gheinc are obtained ; by that
of albuminoids, leucine and a small, but variable, quantity of tyrosine ara
formed ; antl tliat of epidermic tissues pelds leucine and tyrosine. It U
also one of tho products of the puLreCactiou of animal and v^etable nlbn-
rainoiila, and of tlie action of jmucreatie juice upon fibrin. It has also Iweii
formed synthettcaily by tho action of XH, upon bromoraproio aciti, in tlie
same way that aliuiiue la formed from bromopropionic acid i_aee above).
It may be obtoine*! by a variety of methods, the most advantageous of
which cousista in boiling I pL horn shavings \rith i pta. H,t>0^ and 12 pta.
H,0, for 36 hours, renewing the H^O as it evaporates ; the acid liquid in
saturated with miUt of limo and boiled agaiJi for 24 hours ; it is tha^^
filtereil through linen, a slight excess of H,SO. is added, and the liqui^H
again filtered and evaporated ; tjToaine first crystallizes out and is sepo^^
rated, after which leucine sepiutites in crystals, which are purified by re-
orystoUizatiou from a small quantity of HO, tho ciystuh^ first foruietl
being rejected. Tho leucine so obiainod is further purified by solutioniii
hotH^O ; digestion with lead hydrate ; filtration ; treatment with H,iS ; fil-
tration ; treatment with animal charcoal ; filtration and crystallization.
Leucine crysbdliues from alcohol in soft, po.irly jilatea, lighter than
H,0, and somewhat resembling cbolosterin ; sometimes iu round niaaaea
composed of cloaely grouped needles radiating from a centre. It is spar*
ingly soluble iu cold HO ; readily iu warm H.p ; almost, insoluble in cold
alcohol and etlier ; soluble iu boiUng alcohol, which deposits it on cooling ;
it is odorless and tasteless, and its solutions are UQutral. Ita solubility iu
H,0 ia increased by tlie presence of acetic acid or of potassium acetate.
It sublimes at 170 (338" F.) without decomposition ; if Rnd<lenly heated
above 180* (350^ F.). it is decomposed into amylamine and carbon dioxide.
When heated to 140' <284T.), withliydriodic acid underpressure, it is
decomposed into caproic acid and ammonia. Nitrous acid converts it
into leucic acid, C^H,,0,, H^O and N. It unites M-itli acids to form solu-
ble, cryatallino salt^. It also dissolves I'eadily iu solutions of alkaline hy-
drates, forming crystalline comixmnds with th^motalUc elements.
The formation of leucine iu the body is one of the steps of the traufl
AMIDO-AOIDS OF THE rATTT SERras.
218
formation of at least some jmrt oi the olbummoids Into uireo. Tlmi leucine
is formed at tbo expense of the albutninoicU bj Rome fermentation- like
prooeBB, there can be no doubt. As it is only ilischarged in the urine in
oertain exceptional pstbulogicul condiUous, and an at the same time Uie
elimination of tirea is greatly diminished, it seems highly probable that
under normal conditions the N of leucine finally makes its exit from the
bo«iv aa urea, notwitlistanding the fact that c-liemista have hitherto been
unable to obtain urea trow, leucine artificially. As to the nature of
the changes by which leucine is converted into uroa in the body, we are
as vet in tJie dark. When leucine and tyroHine apiH-ar in the urine, that
fluid is poor in urea and uauidly contauia biliary coloring matters ; the
substitution of leucine for urea may be so extensive that the urine con-
tains no ui-ea, and contains IcuciDe in such quantity that it crystallizes out
spon taneously.
AxALvriCAx. CaAEACTEBS. — ^The presence of leucine and tyrosine in the
urino may ho detected as follows : the freshly collecfceti urine is treated
with basic lend oceiate, filtered, the filtrate treated with H,S, fi^ltered from
ths precipitated lead sulphide, iin<l the filtrate e\'a.poratml over the water-
bath ; leucine and tyruiiine crystallize ; tlit-y may be sejMiruted by extrao-
tiou of the i-eaidue with hot alcohol, which dissolves the leucine and
lesves the tyroBiQe. The lencine left by evaporation of the alroholic soln-
tkm may be recognized by its crystalline form and by the following
characters : (1) a small portion is moistened qu platinum foil with HNO^
which is tiien cautioualy evaporated ; a colorless residue remains, which,
when warmed with caustic soda Bolutjon, turns yellow or brown, and by
further conceutntiou is converted into oily drops, which do not adhere Lo
the platinum (Schercr's test) ; (2) a portion of the residue is heated in a
dry test-tube ; it melts into oily drops, and the odor of amylaniine (odor
of ammonia combined with that of fusel oil) is observed ; (3) if a boiling
mixture of leucine and solution of neutral lea<l acetate be carefully neu-
traiized witb ammonia, brilliant ciystals of a compound of leucine and
lead oxide separate ; {41 leucine carefully heated in a glass tube, open at
both ends, io 170^ (338^ F.), sublimes without fusing, and condeLses in
flocculout ihrods, resembling those of sublimed zinc oxide. If heated be-
yond IKO^ (3aG^ F), the decomposition mentioned in 2d occurs.
Tyrosine — C,H NO, — 1-45 — is a Bubstance which does not belong to
this series, and is proLrdflv an amido-ocid of the aromatic scries ; uevcrthe-
leas, as its constitution is still undetermined, and as it in almost imiverHoIIy
found to accom[HiDy leucine in animid tissues and iu the products of their
decomposition, it may bo considered in this place.
The methods of its formation and preparation are given under leucine.
It crystallizes from its watery and animoniacal solutions in silky needles,
arranged in stellate bundles ; very sparingly soluble in cold K,0 ; almost
insoluble in alcohol ; more soluble in hot H,0. When heated, it turns
brown and yields an oily matter having the odor of phenol ; when heated
in small quantities to 270^ (518" K), it is decomposed into carbon dioxide
and a white solid, huving the composition C^,,NO, which sublimes. It
combines witli both acids and bases.
It has been found in nninud nature in Uio same sitoations as leucine.
When taken into the stomach it is nut altered iu the economy, but is
cUminated in the urine and fii>ces.
A^'ALr^cAL CuASACTEas. — (1) its crystalline form ; (2) when heated it
fives off an odor of phenol ; (3) when moistened with HNO, and careful-
evaporated, a deep yellow residue remains, which turns darker with
2U
MATTDAL OF CHEMISTBr.
NaHO ; (4) with concentrated H,SO^ and sUglitly warmorl. it i)ino1i
Willi a tnnsient red color — the solution, filtered and neutralized with
CaCO,, gives a Tiolet color with Fe.CI, eolution ; (5) when boiled mtit
add nitrate of mercory solution, a pink color, and later, a red predpi*
tate.
Biliary Acids. — The bile of most auimaU contains the sodium salts of
two nniido-acitls of complex cooBtitution. These acids may be decomposed
into a non-nitrogeiiized acid (crholic acid), and either an amido-ncid (gltco-
col), or an amido -sulphurous acid (taurine). The following biliary acids
have been described :
G-lyooohoUo add — 0,^NO^—4G5— (sometimes designatod aaoetde
ch(^ique, choUHure, cholic cund, by French and Gefiaan writers). It exisU
as its sodium salt in the bUe of the herbivora, and in mnoh smaller
proportion in that of the camivora ; it cxifitii in sninll quantity in htiniiin
blood and urine in icteros ; in htuuao bile its quantity Tories with tha
diet
It is best obtaiueil from ox-bile ; this is evaporated to one-fonrth nf
its original volume, the residue is ground up with nniiunl charcoal, an d
dried at 100** {^12' h\); the dry maAS, while still hot, is broken up ai^H
introduced into a tlask, in wbirii it ia digested with absolute alcohol, wit^H
repeated agitation, for some da^-a ; tlie colorless, filtered alcoholic solutioa
is partially eTaporated, but not to the eitent of becoming s^Twpy, then
mixed with an excess of anhydrous ether, which, if the reagenta were free
from H,0, causes the iumiedinte separation of a crjstaUine jottcipitate
of the mixed biliiirj- salta. If the alcohol or ether used contun H,0, ths
precipitate is at first resinous and only becomes cn,stallino after standing,
or does not become crystaUine if the proportion of HO be too great
The ctystolUne deposit is collected upon a filter, washed with ether and
dissolved in a email quantity of 11,0 ; to the a(|ucous solution a small
quantity of ether is added, and then enough dilute H^SO. to render the
mixture permanently cloudy ; the glycocholic acid gradually ciystoUizes
out, aud may be fui-thcr puritiod by solution in alcohol, and precipitation
with a great excess of ether.
Glycocholic acid forma brilliant, colorless, tranKparent needles, which
are sparingly soluble in cold H,0, readily soluble iu warm H.O and in
alcohol, almost insoluble in ether. The watery solution is acid in reac-
tion, and tastes at first sweet, afterword intensely bitter. Its alcoholic solu-
tion exerts a right-handed polarization [a]p = -f 29*; when evaporated
it leaves the acid in a resinous form.
When heated with potash, baryta, or dilute H,SO^ or HCl, it is de-
composed into cholio add oad glycoool :
C„H„NO. -f IT,0 = C.,n„0. 4- C.H,NO..
aSr«oc^llc B^id. Wat«i. OhoUc ttcU. Ot/DOooL
Glyoocholic acid dissolves unchanged in cold concentrated H,80,, and is
precipitated ou dilution of the solution with H,0 ; if the mixture be warmed
the bile acid is decomposed, and tliere sepai-ate oily drops of chiAoriic
acidt C,,H„NO,, differing from glycocholic acid by — H,0. Vlien allowed
to remain lon^ in contact with concentrated H^SO,, glycocholic acid is
converted into a colorless, resinous mass, which slowly forma a saflrou-
yellow solution with the mineral acid, which turns flanie-rc<l when
warmed, and whirh, on dilution, deposits a flocoulent materinl which ia
colorless, greeniah, or brownish, according to the temperature at which il
jUnDO-ACIDS OF TirE PATTT SEBHA.
U formed. Glycocholic add, altered hy contact with concentrated H,SO^,
ibaorba O wben exposed to the air, and tuma red, tbeo blue, and utollj
brown after a fow dajs.
SoDiTM GLYcofHOLATE, C H,^NO,Na, existi in the bile ; it crrstallizeB in
stellate neeiUua, very soluuLe in U,0, leas no iu absolute idcobol, and
insoluble in etber ; its acoholic solution exerts right-handed polarization
[oJ.= 1-25^7.
IjK*d Gltcxk^omte, ((^„H,^X0,), Pb {?), is formed as a white, flocou-
leut precipitate, whcu solution of luml subuctitiite is added to a solution
of a glveoclioLite or of j,'lycocholic acid ; with the veutmi acetate tlie pre-
cipitotion iloi>9 not occur in the presence of an excess of acetic acid. It
is soluble in alcohol, and'in an excess of lead acetate solution.
Tlie glycocholates of the alkaline earths are soluble iu H,0. Gly-
eocbolic acid and the glycocholates react with Pettenkofcr's test (see
below).
Glycocholic acid forms compounds witli the alkaloids, some of which
are crystalline, others nmorpbouH : tUey are for the most part very epar-
ingly soluble in U,0, but readily soluble iu solutions of the biliary ^ts
and in bile.
TaurochoUc aoid— C,,H„NO.S— 615 — {choleic acid of Strecker)—
exista as its sodium salt in the bile of man and of the camix'orui and in
much less abundance in that of the Iterbtvora ; in the bile of the dog it
seems to be unaccompanied by any other biliary acid. It may be obtained
from dog's bile by a modiiicjtLiou of tlie method described under glyoo*
cholic acid ; the watery solution is not treated with H,SO,, aa in the
preparation of that acid, but with solution of basic lead acetate and am-
monia. The precipitate so formed is extracted with boiling alcohol, the
■oluiion filtered hot and treated with H.S ; the clear liquid, filtered from
the precipitated lead siilpliide, is evaporated to a small bidk and treated
with a large excess of ether ; the acid is precipitated in the resinous form,
but, after standing for a Tarying period, assumes the crystalline form.
When carefully prepared it forms silky, crystalline needles, which,
when exposed to the air, deliquesce rapidly, and which, even under abeo-
Inta ether, are gradually conTcrted into a tmnsparont, amorphous, resinnua
mass. It is soluble in H,G and alcohol; insoluble in ether; xia aqueous
solution is very bitter ; in alcoholic solution it deviates the plane of polar-
ization to the right, [al,= 4- 24 '.n ; its solutions are acid in rem^tion.
Taurocholic acid is very readily decomposed by heating with barium
hydrate, with dilute acids, and even by evaporation of its nolution, into
eholic acid and taurine:
I
C,.H..N0.8
+ H,0 =
Wa
0..H..O.
OboHoacM.
+ CJI,NO.f
TUrw*:
'Hie same decomposition occurs in the j>reBence of putrefying material
and in the intestine. Taurocholic acid lm8 not been found to acoompany
glycocholic in the urine of icteric patients.
The taurocholates are neutral in reaction ; those of the alkaline metals
are soluble in alcohol and iu water; and by long contact with etUcr they
assume the cryHtulliuo fonn. They may be separated from the glycocho-
Utes in watery solution, either : (1) by dilute H.,S(.)| in tbo pi-esence of a
small quantity of father, which prectpitAles glycoclmlic arid alor.e ; or (2) by
adding neutral leail acetate to the solution of tho mixed salts (which must
neutral i)i reaction) lead glyeocholute is precipitated and separated by
^e Be
KAWAL or CnBMSTKT.
tiltmtioQ ; to the mother liqnor bnedc lead acetate and ammoiua ore wUed,
when lead taurocliolAU^ is pi-ecipitateiL The acids are obtained Erooi Ibe
Lot akuhulic tiulutions of the ?b Bolts bj decompoattion with H^ filtn-
UoD, coacDutrfttion, aud precipitatioo bv ether.
SolutioDH of the taurocliolates, like tho«e of the glyoocbolatei, have
tlie power of diattolrin^ choleeterin ood of eiuulaifviug the fats ; Uin
lUuo funii with the tsttilA u{ the alkaloidti compoiuids which are ii]H>lnli]«l
in H,0, but soluble iu on excess of the biliary salt. The taurocbokte of
morphine is crprtJillizable, They react with Pettonkofer's test
HyoglycochoUc acid, C.,H ,KO,, and HyotaurochoUo acU,
C,,H„NO^S, (?; ai't fonjutjHte aciJuuf h>/ocftolic acid, C,^H„0,, luid ;;]yoo«)l
and t^iurinc, which exist in the bile of thepij;. Cfaenotaiirocholic aoid,j
a conju}^it« acid of taurine and chenociiotic acid, C„H^,0,, is obtained faoi
Lhe bile of the gooee.
ChoUo aold--C,,H„0,— 408— (cAoW tc acid of Strecker), is a pi
af dooomposition of glyco- and taurocholic acids, obtained na indicat
above. It also occurs, as the result of a similar decomposition, in
inteatinea and ffeces of both herbivora and comivora. It forms large,
clear, deliquescent crystals ; spfiriiiKly »*>i'il>l<i in H,0, readily Kuluble in
alcohol and ether; intensely bitter in ta&te, with a sweetish oftertabtc ;
in alcoholic solution it is iletti^prjTic \a]^ =. +35". Tlie alkaline
cliolates lire crv'stullizable luid rea^Hly soluble lu H,0, the others difficultly
soluble. Cholic acid luid the cholates respond to Pcttcnkofer's test. j^H
By boiling witli acids or by continued heatin);; to tiDO (8!t2'^ K), choH^I
acid loses the elements of H,0, and ia Iransfbrmed into df/nJij/nji, C H^^O,,
a neutral, resinoue material, insoluble in H,0 and alcohol, sparingly solii^
bio in ether.
The FETTiotjLOFEK Bkactiov. — All of the biliary adds, and the cbnl
acid aud dysl,iisiu obtained by their decouijKiuitiun. Lave the pixiperty
funning a yellow solutinn with ccmoentrated U,iSO„ the color of wf
rapidly increases in intensity, and which exhibits a green iluorcscen<
Their water\' solutions altto, wlicii treated witli a small quantity of cone^
sugar luid with touccutrated U,SO^, so addc<l that the mixture acquires a
temiierature of 70'^ (158^ F. ) but does not become heated much beyond
that point, develop a beautifnl cherry-red color, which gradually changes
to dork reddish purple. Although Ibis reaction ia obser^'ed in tbe pres-
ence of very small quantities of the biliary acids, it lof>es its value, unless
iwplied OS directed below, from tiie fact that many otlier substances give
the same reaction, either with H,>SO^ alone, or in tbe presenc* of cane>
' sugar. Among these substances are many whirh exist naturally in animal
fluids, or which may be iutruduccd with the fuod or as medicines ; snch
are cholestorin, tbe albuminoids, lociibin. oleic acid, cerebrin, phenol, tur-
j>entine, tannic acid, salicylic acid, morphine, ccxicine, many oils and fats,
cod-liver oU, etc. It has been suggested that a dislinr'tioii could l>e made
between the color produce<l by tlie Pettenkofer test with the biliary acids
and those pralucecl by the samo test with other substances, by spectro-
scopic,' obseni-ation ; the test with biliarj^ acids in watery solution exhibit-
ing a single doik aud broad absorj}! ion -bond (Fig. 34, No. 2) ; the same
test iu alcoholic solution shows two bauds (No. 1) ; but wliilo this spec-
trum differs from tlioso observed in the purple solutions obtained with
many other substimces, such na albumin (No. 3} ; it does not differ suffi-
ciently from that obtnlued with the morphine salts (No. 4) to render it
aafe method for contrnllitig tliB tflst.
The following method of applying Fcttenkofer's test to liie uxine
AMTDO-ACIDS OP THE FATTT SPRIGS.
217
Other floiila remorea, we believe, every aourco of ei-ror. Tho urino, etc,
ii fint eviii>orated to <lryD6^ Q^ tli@ U-uipemture o£ the wuter-bath, a
mhuU i|uauUlj' of ooorse unimnl charcoal having bocu added ; the ruiudue
is extraot«il with ahsolute alcohol, tlie lUcohohc liquid filtered, portia]]}'
evaponUMl, and Lreiited with ten tiiuos its bulk of alwolute ether ; aftei
Htanding ao hour or two, auj precipitate which mav have formed ia col-
lected up')a a Biuall filter, wo&hed with ether, luid dissolved in a small
quauUty of U,U ; this aciueous Bolution is placed iu a ieut-tube. a drop
or two of a strong aqueoua RolutioD of caue sugar (sugar, 1 ; water, 4), and
then pure couccutrated H,HO, ore addctl ; ilie addition of the arid being
BO reguhited, and, the test-tabo dipped from time to time in cold water,
that tho tcmpcratoro shall bo from GO'-TO" (UO'~lf>T F.). In Iho pres-
ence of biliary acids the mixtnro usually becomes turbid at fxrui, and
then turns cherr^'-red and tinally purple, the intensity of tho color varying
with liie amoimt of biliary acid present
R G H
Pio. Si
PsTBioijoaiCAi. CHzyisntY of the Biuutv Aons.— Thofle BnbitaliQM do
Dot iiormallv pre-exist in tlie blood, and are consequently fon&ed in tiiie
iJTor, and tftey are not reabeorbod from tho intestine unchanged. Solu-
tions of the bili.or}' ualUi, injected into the cirrulation in Bmall quanti^,
cause a diminution in the frequency of tlie pulse and of the respiratory
joovements, a loweriu}^ of the temperature and arterial tension, and dis-
integration of tho blood -corpuedos. In large doses (2-4 grams [30-((0
cnuns] for a dog) they produce the same effects to a more mttrked
degroo ; epileptiform convulsions, bUck and bloody urine, and death
more or less rapidly. ITieae effects do not follow the injection of the
products of decomposition of tho biUury acids, except cholic acid, and
in that rase the symptoms are much less marked. Nor are the biliary
acids discltarged unaltered with the f:i*ces ; they are decQm{>osed iu the
iotesUue. The eitnict, suitably purified, of tho coutents of the upper
part of the aniall intestine, gives a well-marked reaclion with I'cttonkofer's
test ; while similar extracts of the contents of tlie lower })art of the largo
intestine, or of the f«x:es, fail to give the reaction, and consequently nro
free from glyco- or taurocholic, cholic acid, or dyslysin ; tho f;rcos, roore-
L iwar, do not contain either taurine or glycocol During the processes, at
A
218
XAKUAL OF CIIEMISTBT.
present but unpcrfectlj understood, which take place id the intestine, iba
bile-ftcids are undoubtedly dccompOBcd into choUc acid and tamine nr
glyooool, which are BobBequentiy reabsorbed, either as such, or after
haring been subjected to furthfr derompoaition ; and oa a conttequeuw
of Lbeir decompusitiou thejr probably have some iullucuc« upon intestiDal
digestion.
The biliar}* salts are precipitated from their aqueous solatiou. or tram
bile, by fresh gafttric juice ftxim the same animal ; but tbey are not »
precipitated if the gastnc juice contain peptone. Tbe proportion of
biUarv ualts in human bile licems to Toi^ considerably, as shovn by tin
following analyses :
I
Macin
Obolcatoiia
Fate
Taarocholaie of mkUuiii, )
Oljooobokt* of sotliont f * *
Soapi
Woeiml uUta
Water
Total Bolida
XL m. XT,
3.60
O.IC
0.33
S.fi8
0.2G,
o.ua
T.
n.
(0,25
JO.04
7.38 ir.U m79 5.M h^'
0.65 on !.0e O.flS 8.86|
<i6.ODHa.g9 82.3768.81! ..
14.0014.06 17.7810.19 ..
3.48
0.25
0.05
0.75
3.00
o.btf
0,49?
90.88
9.1s
.
TO.
tul
1.99
0.84
0.80
1.93
\.!il
0.44
4,00
1.63
1.4S
140t
1OI.O6
* • * ■
8.9a
....
t!3»
n
Li
■■m
i
I. PreriLihR : nUe from mui, tct. 18. killed b; a fall. II. Frericbii : Mftle. at
die4 of a wound. III. Oorup-B«uu)(n : Male. et. 4D. decapitated IV. Gonip>
aanas: Ftimale, at, 30. decapilatetl. V. Jaoobsea : Sink, biliaiy Sxtula. VI..Va
Trifanowakli ttalfla. VIII. Sooolof: Veaa of &ix aualyHHK of haman bile. fX. Uoppe-
Seller: Mean of five auolyw* of bile froui itubj«cta with healthy lireis. ^^^^M
Pathologically, the biliary ucida may be detected in the blooiJ^S^^
iii'ine in icterus and acute atrophy of tlie liver, alttiovigb by uo means an
frequently as the biliary coloring matters. ^M
Creatine — C,H,N,0,+ Aq — 131 + 18 — i» aaother complex amido-aci^^
which occurs iis a normal constituent of the juices of muscular tissue^
voluntai-y and involuntarj', of bmin, blood, and amniotic fluid. ^m
It ia t>est obtiiiuod from tbe flesh of tlie fowl, which contains 0.32 pd^|
cent, or from becf-hcurt, which contains 0.14 per cent, by hashing
warming with alcohol and expressing strongly ; the alcohol is distilled o$ '
the residual Kquiil precipitated with lend acetate, filtei-cd. treated with H,Si
again filtered, the tiltnite evaporated to a syrup, from which the creatine
on'stallizea. It is soluble in bailing H,0 and in lilcohul, insoluble in
ether ; crystallizes in brilliant, oblique, rhombic prisms ; neutral, tasteless,
loses aq. at 100" {'2VZ° F.) ; fuses and decomposes at higher temperatures.
When long heated with H^O or treated with concentrated acids, it loses
H,0, and ia converted into creatinine. Bar^'ta wtiter decomposes it into
sarcosine aud urea. It is not precipitated by silver nitrate, except when
it is in excess and in presence of a small quantity of potAKstum hydrate ;
the white precipitate so obtained is soluble in excess of potash, from
wliich a jelly separates which turns black, slowly at ordinary- leii)|>eraturea,
rupidly at lOO" ('J12^ F.). A white precipitate, which turns bhick when
heated, is also fonned when a solution of creatine ia similarly treated with
mercuiic chloride aud potash.
COMPOUITDS OF ALCOHOLIC RAmCALS.
Creatinine — C,H,N',0 — 113— a prwluct of tlie dolmlraUon of crea-
tiae, is a uonnol and couetant oou&lituent uf the urine aud amniotic fluid,
aad also exists in the blood and muscular tissue.
It crystallizes in oblique, rhombic prisms, soluble in HO and in hot
aloobol ; insoluble iu ether. It is a strong base, has an alkaline Uiate and
reoctioD ; expels NH, from the ammouiacol salts, and forms well-defined
tUta, among which is the double chloride of zinc and creatinine (_C,H,N,
0),ZdC1|, obtained in very spaiingly BoIul>le, obliqus prisnmtic crystals,
wbeu alcoholic solutions of creatuiino ami zinc chloride ai-§ mised.
The quantity of creatinine pliuiiuuted is slightly greater than that of
uric acid, 6-1. it gram (9/25-20 grnins) in '2i liours ; it is not increased
by musouhu' esercise, but is diminished in progressive muscular atrophy.
It is obtained from the urine by precipitation with zinc chloride.
Xanthine — Xanthic ojride — Crous ond~C^H,N,0, — 152 — occurs in
a rare form of urinary calculus ; in the pancreas, spleen, liver, thymus,
and brain of mammals aud fishes ; aud in human urine after the use of
sulphur baths or inunctions.
It is an amorphous, yellowish-white powder ; rerj slightly soluble in
cold H,0. If dissolved in HNO, and the Holution evaporated, ?:anthine
leaves a yellowish residue, which turns reddish-yellow on the addition of
potash solution, and violet-red when heated.
Xantliine calculi vary in nize from that of a pea to that of a pigeon's
egg. They are rather lianl, browniah-yellow, smooth, nhiniug, and made
up of well-defiuet.!. concentric layers. Their broken surfaces assume a
waxy polish when rubbed.
Hypoxanthine — Sarrine — C,H N^O — 136 — occurs in the spleen,
muacular tisHue, thyrauH, Huprareniu capsules and bruin of mammals ; iu
the liver iu acute yellow atrophy ; aud in the blood and urine in leucocy-
thtcmin. It may be obtained from the mother liquor of the preparation
of creatine {q. v.).
It forma nodular masses ; soluble in 300 parts of cold, and 78 ports of
boiling 11,0. It is produced from uric acid or from xanthine by the
action of sodium amalgam, and when oxidized byHNO, it yields xanthine.
Guanine— C^H^N^O — 151 — occurs in guano, in the excrements of
the lower animals, and In the paucx'tas, luugs, and liver of certain mam-
molions. It is a white or yellowisli. amorphnus. o«lorle-js ami tofitclesa
■olid : almost insoluble in H,0, alcohol and ether ; readily soluble in acids
and alkaliL-H, with which it forms compounds.
Canilne^C,H.N.O. 1 H,0—iy'i + 18— is obtained from Liebig's*
meat extract in choky, microscopic crjRtAls, readily soluble in worm 11,0.
It fortQS compounds with acids and alkalies, similar to those of hypoxan-
thine.
COMPOUNTDS OF THE ALCOHOLIC RADICALS WITH
OTHER ELEMENTS.
The organic substances hitherto considered are composed of seven ele-
ments only ; C, H, O, N, CI, Br and I; but compounds of C containing eveiy
known clement have been observed to exist in nature, or liavc been pro-
duced artificially. Of these quite a number may be considered as con-
taining the radicals of the series C^H,,,,, which exiat in the nionoatomio
alcohols. These bodies are almost exclusively the productd of the laborft'
290
UXSfTJAh OF CIIIEHI&TRT.
tory, and resemble in consUtation eonie of Uie cotnpounds alnndy ooi-
itidered.
Sulphides. — The compoaudii of the alcoholic radicals wiUi S ue Uv
mme in oonstitation as thoae with O* S taking Lhe placo of :
C.H.
BUiyl lifilnM
(laaMpUii).
Eruiix SuLFsmBATG, usually known aa mercaplan, from iU teadencT in
unito with mercury {cvrjMW viercurium captannj, in formed in a vorietv of
reactions. It is beat prepared by treatizig alcohol with U,SOj, ft6 iu the
preparation of aulphovinic acid \q, v. ) ; mixing the crude product with
exoesa of puta^h ; separating from the oryst^ of potaasiuin tnilplute;
aaturattDg with H,S ; and distilling.
It is a mobile, colorless liquid ; sp. gr. 0.832{i ; has ao inteiuelv (IJu-
^reeable odor, combined of those of garlic and H,S ; boils at 30 i!
(97°.2 F.) ; ignites readily and bums witli a blue fLune ; may be reailil;
frozen by the cold produced by its own evaporation ; neutral in reactim:;
8p.arin;?ty soluble in H,0, soluble in all projxirtions in alcohol and ether ;
tlissolves I, 8 and P.
Fotasaium and sodium act wilJi mert!aptaii od with oluohol, repladiis
the extni-radical hydrogen. In its bebuvior toward tho oxides it mow
closely roBcmbles the acids than the alcohols, being capable oven of eotM-
ing into double decomposition to form salts, called ifulphethyialrti or mrr-
caplttU'n. Ita action with merciu'ic oxide is characteristic, forming a white,
crystalline sulphide of ethyl and mercury :
HthjlHlphTilnhi.
+ Hg'O -
(C
"^^JS. + H.0
VmdwIc axUau XCbrl-WMviulo iDtphhla.
wu«.
Ethyl Sulfhiuk, a colorless litpid ; linring a penetrating, disagreeable
odor of garlic ; boiling at IS" (1G3'*.4F.) ; insoluble in U,0, soluble in
alcohol ; inHammable ; obtained by tho action of ethyl chloride upon
jratassium snlphida
PbosphineB, arsines, and stittines are compounds resemhUng Uie
amines in conatituiion, in which the K is replaced by P, As, or Sb. like
the aminos, they may bu piimory, secondary, or tertuuy :
(Pdnuy},
Hi
EtHylphnapIno
As
PliiUiyl-MniliM
(MMXKlArjt).
'^0
There also exist compounds containing P, As, or Sb, which are similar
in constitution to the hydrates and salts of lummonium, and of the com-
pound ammoniums :
NH,I
Aminonlnai
todMc
N(CH,).I
TotlBIDllhl I ■HUDOOlOID
Udlda.
As(CH,)J
TdnoiBtfail WMDlnn
L
iXLTUO SERfKa.
dst
&£ost of these compounds, wlilcli tu-e veiy numoronit, are an yet only
of theoretic interest One of them, however, is deserving of notice hers :
CH 1
DnarrHVL Aftson, CH, >■ As — 106 — which mav be considered as being
Hi
the hydride of the radical [As(CH,),], does not' exist as such; there is
however, a liquid known as the/uiuing tiqunr of Cadet, or aikars'm, which
is obtained by diRHlHng a mixture of potassium acetate and arsenic
trioxide. Tliis liquid contains tlie oxide of the above radical, and a sub-
stance which IguiteH ou contact with air, and which conaistsof the Bome radi-
cal united to itself 2[A8(CH,),]. Tliisnulicid, called tacodyle (Kano^ = evil),
IB capable of entering into a great number of other combination a. Cacodyle
and its compounds are all exceerlingly jx>isonou8, especially the cyanide,
an ethereal liquid, very volatile, the presence of whose vapor in inspired air,
even in minute tnu;es, produces symptoms referable both to oraeuic and
to hydrocyanic acid.
Organo-meballio substances are compounds of tlie alcoholic radi-
cals with metuJs, They ore verj' numerous, usually obtained by the action
of the iodide of the alcohoUc rodicnl upon the metallLC element, in au
ntmoai>here of H. They are substances which, although they have been
put to no uses in the arts or in medicine, have been nf great service in
chemical reseorclL As typical ol this clasa of substances we may men-
tion :
Zwo-crHTi^-S=5' I Zn— 123— obtained by heating at 130° (2G6* F.)
in a sealed tube a mixture of perfectly drr zinc amalgam with ethyl iodide ;
the contents of the tube are then distilled in an atmosphere of coalgoa,
or H, and the distillate collected in a receiver, in which it con ba sealed by
fusion of the glass without contact with air.
It is a ci>]orle88, transparent, Iiighly refracting liquid ; ap. gr. 1.182 ;
Ijoils at 118' (244 -.4 F.). On contact with air it ignites and bums with a
luminous tlome, bordered with green, and gives off dense clouds of 7,ino
oxide, a property wliich itnders it very dangerous to handle. On contact
with H,0 it is iiuiue<liutely decomposed into zinc hydrate and ethyl
hydride. It is cliiotly usefui as an agent by which the radical ethyl can be
introduced into organic molecules.
AIXVTJC SERIES.
The compounds heretofore considered may be derived more or lens
directly from the saturated bydi-ocnrbons ; in the derivatives, as in the
hydrocarl>on». the valences of the O ntnmR are all satiKfied, and that in the
simplest and most complete manner, two neighboring atoms always
exchanging a stinyte valence. There exist, however, other compounds,
contnioing less H in proportion to C than those already considoiod, and
yet resembling thera in being monoatomic. These compounds have
usually been consitlered as }um-Mtntyit''/l, beeanse all the /w«*j'W'* valences
are not satisfied, and the substances are therefor capable of forming pro-
ducts of addition, while the gatnnxted oomiwmida can only form products
of nubntUation.
In this (tense the substances composing this series are non-saturated,
but they are not so in the sense that they contain G or other atuuis whose
%'aleucea arc not satisficl The following formuhe indicate the constitu-
393
HANUAL OF
tion of tbe mibstanoea of ihia scries, and their relation to those of the pn-
Yious one It will be observed that in tho allvl compouiuls two nei^bor-
iug C atoma exchange two valencea :
on, .
CH.
Off,
1
cu^
CH,OH
OOH
COO
or
or
or
or
(«^[ (^.«^}0 e^AOri (C.H.0^1o ,C.H,)'
Tnvji hxilnilB PKipvI hjAnU Fm>U»rl hjrilnta Ptnfrtanrt bjdnU rropjl
CH.
II
CH
or
or
70H
or
h
OOH
or
CH.
II
CH
DUllyl
(hjdncmrboii).
(C.H^|0
(ideohiil).
(O.H,OV)
(CAOVjo (C.H.)
(•elil).
Altyl
(ndlci)).
OH)
DlaUyl — «*g» J —82— formerly Inown as lUhjl, is obtained by the
action of sodium upon hU}'1 iodide, and is not, aa its empirical foraoU
would bcem to indicate, a euperior homologue of acetylene and allTleoe
It is a colorless liqnid, hnrlng a peculiar odor, somewhat resembliog
that of borseradiHh ; boils at 59" (138*.2 F. ;; Bp. cr. 0.684 at 14^ (57^2 F.).
C H )
Allyl hydrate — Albjlic alcohol — ' rf f ^^ — ^^ — ™*y b<^ obtained by
the action of sodium upon dichlorbydrine in ethereal solution ; or by
heatirp four parts of glycerin with one part of crystallized oxalic acid.
Allylic alcohol is a colorless, mobile liquid ; solidifies at —54'' (— 66".2
P.); boils at il" (20G'.6 F.); sp. ^t. 0.8507 at 26= {IV F.); soluble in
H,0 ; baa an odor resembling the combined odors of alcohol and eseextce
of mustard ; bums with a luminous flame.
Allyl alcohol is isomeric with propylic aldehyde and with acetone.
Beiopf an unsaturated compound, it iu capable of forming; products of
addition with CI, Br and I, etc., which are isomeric or identical with pro-
ducts of Bulistitution obtained by Uie action of the same elements npon
glycerin. Oxiiliziug ugeuta convert it first into acrolein, acryUc alde-
hyde, CjH.G, and tinally into acrylic acid. It does not combine reodily
with H, but in the presence of nascent H combination takes place slowly,
with formation of propylic alcohol
ALLTLTO SERraS.
253
CHI
AMyl oxide— Altt/lic ether— Q*^* fO— 98— exists in amftU quftntities
in crude essence of garlic. It is obtained as » colorless liquid, having on
alliflceoua odor ; ioBolublo in H,0 ; boiling at 82° (ITD^.C F.), by a num-
ber of reactions, but bent by ilio action of allj'l iodide upon uodium ally]
oxido.
Allyl sulphide — ernxncc o/ijarlic — «'ij' J 8 — 114— is obtained by the
action of an alcoliolic solution of potasHinm sulphide upon allyl iodide ;
also as a constituent of the volatile oil of garlic, by macerating garlic^ or
other related vegetables, iu water, and diatilling. Crude essence of garlir
is thus obtained aa a heav^', fetid, brown oil ; tliisi is purified by redistilla-
tion below 140" {284'^ F.) ; contact with potassium and subsequent redia-
tillation from calcium chloride.
It is a colorless, traiiaparent oil ; lighter than H,0, sparingly soluble in
H,0, very soluble iu alcohol and etlier ; boils at 140" (iiHO* K) ; lias an in-
tense (Klor of garlic. It do«s not exist naturally in tlie plant, but is formed
during the process of extraction by tho action of H,0, probably iu a man-
ner similar to that iu which essence of mustard Is formed under similar
circamstances. It is to the formation of allyl sulphide, which is highly
volatile, tliat garlio owes the odor wliich it emits.
Allyl sulphooyanate — K&sentiaL i>U of mnslard — Oleuni sinapiit vda-
tUe {C. S,)—^ i S— 99.— If the seeds of white or blick mustard be
strongly expressed, a bland, nentml oil is obtained, which resembles rape-
seed and colza oils in its physical properties, and in being composed of the
glyoerides of stearic, oleic, and erucio acids. The cake remaining after tlie
expression of tliis oil from black mustard, or the black-mustard seeds
themselves, pulverized and moistened with ILO, gives oil a stroma, pun-
gent odor. II tlie H,0 bo now distilled, a volatile oil passes ovei' with it,
which is the crude essential oil nf mustard.
In practice the powdered cake of black-mustard seeds, from which the
fixed oil has beeu expretued, is digested with H,0 for 24 hours, after which
the H/> is distilled as long as any oily matter passes over ; the oil is col-
lected, dried by coutjict with calcium cldori<ic. and rodistillod. Essence
of mustard may also bo obtained sj'utheticaUy by the action of allyl bro-
mide or iodide ujK)n potassium sulpliocyauatc, or by the action of allyl
iodide upon sUver sulphocyanute.
This essence does not exist preformed in the mnstard, but results from
tlie decomposition of a peculiar constituent of the seeds, potassium vii/ro-
naie, determined by cn'ptolytic action set up by another constituent, myro-
tine, in the preseuoe u^ U,0.
Potassium myronaie exists only in appreciable quantity in the black
variety of mustard, from which it may lie obtained in the shape of short
prismatic crystals, transparent, odorless, bitter ; very soluble in U,0,
Bpftringly so in alcohol.
Myroeine is a nitrogenized cryptolite, existing in Uie white as well ns
in the black mustard, and iu othtr liceils, It iniiy bo obtained from white-
mustard seetls, in an impure form, by extraction with cold H,0. filtering
and evapomling the solution at a temperaturo below 40' (104° F.) ; the
syrupy fluid so obtained is precipitated mth aloohoL the precipitate washed
with alcohol, rodissolved in H,0, and the solution evaporated below 40"
(104' F,; to dryness.
At temperatures above 40' (104* F.) myroeine becomes coagulated and
SS4
MAKUAL OF CH£108THr.
inoapable of decompnsin^ poiABsinm myronato. a chango which is also pro-
duced by contact witli acetic acid. Ah the niLefticient and recant so-
tiouB of muutarJ when uioisteiicd with H,0, ore due to the productica o(
aUjl solpbocyonatc, neither vinegar, acetic acid, nor heat greater ihaaW
(104° F.) should tie used in the preparation of mustard catapUsma
Pure allvl Rulpbocyanate is a tranRparentf colorleHS oil : sp. gr. LOIS
at 20° (68° 'F.) ; boUs at 143° (289°. 4 F.) ; has a penetiatiug, ptugect
odor, sparingly soluble in H,0, very soluble in alcohol and ether, miea
exposed tn the light it gradually turns brownish yellow and depoeitfi n «■
mnoid material . ^Vl1en appliedtotheskinitproducesrabe^otion, qui«kh
ioUoved by vesicatiuu.
ACII>S AND AT.T^EHYDES OF THE ACRYUC S£IRIES.
These BubstaiicoR bear tho same relation to tho alcohols of the
Heries that the volatile fatty acids and the corresponding aldehydes besri
the ethyltc series of alcohols. The following terms of the series have been
obtained :
Acids.
CLH„.,CK,
AerjHe kU 0|0,Ht
CktMote C,0,U«
At«*Ue C,U,U,
Fmtmlito CaOJl,o
OWb .....OhOjUm
AUia&vder.
AcroMn ,
CrutuBio Aldat>]rd«....». ...
Acrylic acid— ^•"'^
Tho acids of this series differ from those con tuning the same number
of C atoms in the fonnio series, by containing two atoms of H less ; they
are readily converted into acida of the formic series by the action of potas-
sium hvdratc in fusion.
> O — 72 — ia obtiuueti by oxydation of acrolein
bv silver oxide, and is formeil in a number of other i-eactions. It ia a col-
orless, highly acid liquid ; has a ])euetnitiug odor ; solidifies at 7' (44''.6
F.); bf)il» at 110^ ("iK^^ F.). Nascent H unites with it tn form proptonie
acid. It forms rrj-Htnlline salt* and ethers.
Acrylic aldehyde — AUylic aldeht^e— Acrolein — C,H,0 \ -j.
H( — &».—
When the fnts and fi\ed oils are decomi>osed by heat, a disagreeable, irri-
I tftting odor is produced, which is due to the formation of acrolein by tho
dehydration of the glycerin Contained in the fatty uialeriaL Acroleinmay
be obtained by heating glycerin with strong H,30., or with hydropotaseio
sulphate. Glycerin is the alcohol (hydrate) of a radical haWng the same
composition as allyl, but ro differing from it in constitution as to be trira-
lent in place of univalent
(C.HJ"'(OH), = 2H,0 + {C,H,0)'H
Olyeerin. W«t«r. Aentrin.
Acrolein is a colorleaa, limpid liqaid ; lighter than H,0 ; boiU &t 52°.4
(136°.3 F.) ; sparingly soluble in H.O, more soluble in nlcohol ; very vola-
tile ; its vapor is very pungent and irritating. When freshly prepared it
is neutral in reaction, but on contact with air it rapidly becomes acid by
oxidation. For the some reason it does not keep well, even iu closed vu-
ACIDS AWD AIJ)iaTTl>ES OF THB ACllTLIO SEItlES. 99a
' aals ; on standuig it deposita a flocculent material, which hiis been called
4i»jcryl, while at the Bauie time formic, acetic, auil acrylic acids ore formed.
Oxidizing agents oonvert it into ociytic ncid, or, if they be ener^^etic, into
I % mixiure of (onnic and acetic ocidtL The caiiHtic alkalies produce from
I it reainoid substances similar to those formed from acetic aldehyde. ^S'ith
Kti, it fonus a cryiitalline, odorlcsa compound, which behaves as a base.
Acrolein is formed whenever glycerin, or any subatanco containing it
or its compounds with the fatty acids, is heated to a temperature sufficient
to effect its dccompositioa ; fur this reason, and because of the irritating
action of the acrolein, the heavy petroleum -oils arc preferable to those of
vegetable or animal origin for the lubricatiug of machinery operated in en-
closed plaoe&
f^ IT rt )
CrotOOio add — vc \ O — 86— was first obtained from croton-oil,
ofeum tujlii {U. A'.), oleum crotonig {lir.), in which it exists in combination
vitb glycerin, and accompanied by the glycerin ethers of several other
&tty acids ; it is, however, neither the vesicant nor the purgative prin-
ciple of the oil. It may be obtained by aaponiOcation of croton-oU, or,
better, by the action of i>otaasium hydrate upon nllyl cyanide.
It is an oily liquid ; t>ulidi6es at —5" (23" F.) ; acrid in taste ; gives
off highly irritating vapors at temperatures Blij*htly above 0'' (32" F.).
Wien taken internally it acts as an irritant pniafui.
An acid obtained by oxidation of crotonio aldehyde is probably an iso-
mere, oa it is In. the form oi crystals at ordinary temperatures, and only
I fuses at 73<» (163M F.).
Orotonlo aMehyde^^'^*^ I —70.— If aldehyde. H,0, and HCl, be
mixed together at a low temperature, and the mixture exposed to diffused
daylight for some days, an oily liquid is formeii, whir.h, after purification,
baa tlie comjxisition C,H,0,. This mibstimce, knon'u as alfl<yl, when ex-
posed to heat, is decom}>osed into water and crotonic aldehyde : C.H O
= H.0 + C.H.O.
Crotonic aldehyde is a colorless hqnid ; boils at 105® (221* F.) ; gives
ofT highly irritating vnjtora It bears the some relation to croton chloral
that aldehyde does to chloral.
I| Croton chloral— 7V«?A/orocTOton o/deAyrfe— *^*^«*^*>g I — 173.5— a
substance whicli luis been used aa an aurcsthetic whose action is particu-
larly directed to tlio sensory nerves distributeil to the head and face. It
is prepared by dii'ecting a current of CI through acetic aldehyde, aa ordin-
ary chloral is obtained by the action of CI upon ethyiic alcohol. The ttrst
action is to convert ethylio aldehyde into crotonic aldehyde by condensa-
tion and elimination of H,0 ; in the seooad stago of the reaction the
substitution of three atoms of CI for an equal number of atoms of H in the
croton aldehyde thus formed takes place.
C H O )
Angello aoid— * '« ( ^ — ^'^ — exista in angelica root, in the flow-
ers of chamomile, Anlhemi-i (U. S.), and in croton-oil.
It cryetidlizea in colorless prisms, which fuse at 46'.5 (IIS^.O F.) ;
boils at 185^ (S65=* F.) ; has an aromatic odor and an acid, pungent taat« ;
BjMringly soluble in cold H,0 ; remlily soluble in hot 11,0, alcohol, and
ether. By the action of heat it ia converted into its iaomere, methyicro-
Ionic acid. C.H.(CB.)0 | q
11 ""*
^
1
MANCAI. OF CnEMlSTRT.
Oleio tLoiA—Acidum oleicum {U. S.]
~24G— exists
its glyceric other, olein, in moet, if not in all the fats and in all fixed oik
It ifl obtained in an impure fomi on a large ftcale as a bv-product in tliK.
luannfactiire of candlea. Tliis product is, howtver, very impare
^purify it, it is tinst cooled to 0"^ (32'^ F.), the liquid [tortion coUectedjj
T cooled to —10' (14' F.), expressetl, and the soUd portion collecied ;
'is melted aud treated ^ith Wf ita weight of moasicot ; the load oleat«Bo<
obtained in dissolved out by eUier ; tlie decanted ethereal solntian ii
Bfaakeavith UCl, the ethereal Liyer decant«d and evaporot«d, wltea it
leaves oleic at^id, Cf^iitaminatetl widi n small quantity of oxyoleio Acid,&xici
which it can bo purified only by a tedious process.
Pure oleic acid is a white, pearly, crystalliue solid, which fuses, to s
colorless liquid at 14* (.')7'*.2 F.) ; it is odorless and tasteless ; soluble id
aUwhol, ether, and cold H,SO, ; insoluble in HO ; sp. gr. 0.8U8 at 19'
(66°.2 F.). Neutml in reaction. It can be disLilleil in vacuo without decam-
positiou, but when heated in contact with air, it is decoiutioHed vitli
formation of hytirocorbona, volatile fatty acids, and sebaeic acid, li dia-
solves the fatty acids readily, forming nuxturca whose consistency mm
with the proportioDs of liquid and solid acid which they coulain. The
Bohd acid is but littlo altered by exposure ttt oil-, but when liquid it ahsariw
O rapidly, l>6conie8 yellow, rancid, acid in reaction, and incapable of
solidifying when cooled ; these changes take place the more rapidly tlu
higher the temperature.
CI and lit attack oleic acid with formation of products of BubsUtatioo.
If oleic add be heated with an excess of caustic potassa to 2W (392^ F.),
it is decomposed into palmitic and acetic acids ; C,,H.,0 -f 2EH0 =
C, A.O.K + C,H,O.K + H, ; a reaction which is utilized indoatnalh
to obtain hard soaps, palmitates, from olein, whicii itself only forms soft
•oapa. Cold H^SO, disBolves oleic acid, and deposits it unaltered on tha
I Addition of H,0, but if tho acid solution be heated it tuma brown and
^ves off SO,. Nitric ocid oxidizes it energetically, with formation of k
number of volatile fatty acids and acids of another seriefl — sulieric^ odipie,
etc. The o1eate.s of tiie alkaUne metals are soft, soluble soaps ; thoes of
the earthy motals are insoluble in U,0, but soluble in alcohol and in
ether.
Efaidic acid is an isomere of oleic acid, produced by the action npon
it of nitroua acid in the preparation of Vngufittum hytlranjt/ri nitralu
{r. S. ; lir.). The nitrous fumes formed convert the oleic acid, contained
in tlie oil and lard nsod. into claidio acid, which exists in the ointment in
combination with mercury.
POLYATOMIC COMPOUND.S.
J
The organic compounds biiherto considered may be looked upon as
oompminds of umvaient carbon nuliealfi, these radicals existing in the ah
oohols and acids in combiualioit with an atom each of O and H ; they are
^called munoaiomic because they contain a aiugle atom of H citpable of being
xeplaced by an alcoholic radical There exist other C compounds, in
which tlie radicals, containing a less nxiraber of H atoms as compared
with the number of C atoms, liave a valence greater tlian one ; those radl*
cals form ncids, alcohols, etc. in which the number of atoms of replaceable
H is greater tban one, and which oro doaignated aa polyatomic.
M
U
n\
n
d
to 8 uf m| td| c^ I ^1 B N n
d| d^ d^ us di? d3 d d d
" d? d d
;p
n
d
d
d
ri
5i w| agl tal a^ w
d? 05 ;:i| u| 3| d
< -^ J. ^. a
^& n t^ t^ td
dS d d d d
22S^ UA27CAL OF OHEJilSlHT.
NON SATURATED HYDROCAHBOSa
Bwldes the corapounde of C and H desci-ihed on pp. 172 ei swj., in vlud)
on the Talences of the C atoms ore satiafied, either by the attachment of H
atoms, or by the iDterchauge of a sittgle valence botweeu ncigbbonngC
atoms, there exist many others in which the proportion of U to G ii leiu
These oompounds are non-naturaied, in this, that they are capable of ooil-
ing directly with atoms of other elements, or nith radicals, to fom pro-
ducts of addition, while the composition of tbe saturated bydrocu-DOOi
can only be modified by subg/Uulion : they are Bot, howerer, to bo connl-
ered as containing any unsatisfied valence.
These hjdrocarbous are very uumeruus, and may be arranged in bo-
xaoIogoaB aeries, as shown in Uie table on page 227, each succeedifig
series oontaining a leas amoimt of H in proxwrtion to the C :
6E0OND SEIRIES OP HYDROCARBONS— OI.EFINES.
SmuEs 03,-.
The terms of this serie« contain two H atoms less than the corre^Mfid-
ing termu of the lirat series ; they differ in constitution in this, tlut,
while in the £rst series a Hinglo valence is exchanged between each two
neighboring^ C ntoms, in the second series two valences are exchanged be-
tween two of the C atoms :
C=H, C-H
I II
ProfMD*. FnpfliBfc
They are designated as olejine* ; or, to distinguish them from the tennsof
tlie tirst sent^ by the terminations ylene or ene^ thus the second is called
cthf/ietie or elhene. They behave as bivalent radicals.
Ethene — Ethylene — (Mejiant you — Btayl — Heavy atrtntretted hydro-
CH.
gen — || — 28— ia formed by the dry distillation of fate, reains, wood.
CH,
and coal, and is one of the moat important constituents of illuminating
gaa. It is also obtained by the dohydrutiou of alcohol or ether.
It has been obtained synthotically: (1) by passing a mixture of H,8
and cjirhon monoxide over iron or copper heated to redness; (2) Inr hent-
ing acetylene in the presence of H, f>r by the action of nascent H upon
copper ooetylido ; (3) by the action of H ui>on the chloride C,t'l,, obtained
by the action of CI upon carbon disulphide. It is prepared in the labom-
tory by the dehydration of alcohol : s mixture of 4 pts. H^SO^ and 1 pt
alcohol is placed in a flask coutaiuiug enough sand to form a thin paste,
and gradually heated to about 170~' (338" F.) ; the gas, which is given off
in abundance, is purified by causing it to pass through wash-bottlea con-
taining H,0, on tukoliue solution, and concentrated H,SO..
Pare etbjlene is a nolorloss gaa ; tasteleBs ; boa a faint odor renembliug
tliat of aalt water, or an etliereaJ odor when impure ; irrespimble : apar-
in^lj soluble in li,0, more soluble in alcohol. It bums with a luminous,
vrlute flame, and forms exploflive mixtures with air and oxygen. ^Vhon
)ieat«d for some time at a dull red heat it is converted into acetylene,
ethyl and methyl hydrides, a tarry product, and ciirboa.
Ethvleiie roaiUly enters into combination. It unites with H to form
etbjl hydride, C,H,. With O it unites exploHively on the ftpproach of a
flame, with formation of carbon dioxide and H,0. OxiiUzing ageiita, such
as potassium permanganate in alkaline solution, convert it into oxalic acid
mnd H,0. A mixture of 01 and ethene, in the proportion of two volumes
of the former to one of the latter, unit© with an explosion on contact with
flazue, tlie union being attended with a copious depositioD of C and Uie
foimation of HCL Chlorine and ethene, mixed in equal volumea and ex*
posed to diflfused daylight, unite slowly, with formation of an oUy liquid ;
^ene chloride, C,H,C1 = Z>u/c^ liquid, to whose formation ethene owes
the name olrfiant gas. By suitable means ethene may also bo made to yield
chlorinatCKl products of substitution, the highest of wliich is carbon
dicfUoride, C,C1,. Br and I also form products of addition and of substitu-
tion with ethene. By union with (OH), it forms glycol {(j. v.). It slowly
disBolTas in ordinary H,SO^, with funnution cf sulphovinic acid ; witii
fuming H,SO it combines with elevation of temperature and formation of
ethionic anhydride.
When inhaled, dilut«tl with air, ethene produces effects somewhat
similar to those of nitrous oxide.
Pentene —Amt/lene or vnlerene — C,H,^ — 70— a colorless, mobile liquid,
boiling at 39° {10*2^2 F.) ; obtained by heating alcohol with a concentrated
solution of zinc chloride. Its use as an auiBsthetic has been, suggested.
CH,C1
Ethene chloride — Bichloride of ethylene— DttU^ liquid — | — 99
CJHjCl
— is obtained by passing a current of ethene through a retort tn which
CI ia being generated, and connected with a cooled receiver. The dis-
iiIUt« is washed with a solution of caustic potassa, afterward with H,0,
and is finally rectitied.
It is a colorless, oily liquid, which boils at 82.5^ (180'^.5F.); has a sweet-
ish taste and an etbereul odor. It in isoiueric with the chloride of mo-
CJH.C»
nocbloriuated ethyl. I , which boils at Gi"* (147°.2 F.). It is capable
k
of fixing other atoms of CI by subatilalion for H, and thus forming a
aeries of chlorinated derivativeB, the highest of which is 0,01,.
r
DIATOMIO ALCOHOLS.
Serikb C„H^,,0,-
Tbeao Buhstances are usiuilly designated as glycol*. Tliey aro the
bydrfttes of the hydrocarbons of the series C,H,„ and consist of those
hydrocarbons, playing the part of bivalent radicals, united witli two groups
OU ; their general typical formula is then (C,H,J' I q ^^^ ^^^ ^^^q
(p. 178) that the primary monoatomic alcohols contain the group of
S80
MANTTAL OF CHEMISTBT.
mioma (CH,OH), united with d(C.H^.,); ihe primary gWcoU ue aimi.
larW ooQstructed, ftutl consist of twice the group (CH,OH), united in tbe
l^gfaert«mie to n(CH,). The constitution of the ffljcols and their reU-
tions to the monontomic alcohols are indicated bj the following fonsu^ :
CH^OH CH,OH
CH,<
,OH
As the monoatomic alcohols are such by containing In their moleculu
a group (OH), clonely attached to aii electro-positive group, and capable
of removal and replacement bv an electro- negative group or atom, eo tlie
glycols are (fio/mTiic by the fact that they contain two such group8(0H).
As the uionoatotuic idcohola arc therefor only ca[>ablc of forming a sc^
ether with a monobasic acid, the glycols are capable of forming two suet
ethers:
CH, (C^OJ'
Bthxt MwtmtB
CH. (C^OJ'
CH,OH
Konoaovllo k1 jooL
CH, (C^O.)'
DtMedfl glfenl.
CH.OH
Ethene glycol — Ethylene glycol or Alcohoi or Hydrate — | '-
CH,OH
62. — This, the beat known of the glycols, is i)repared by the action of dr?
silver acetate upon ethylene bromide. Tlie ether bo obtained is p\uified
by redistillation, and decomposed by heating for some time with bariaB
hydrate.
It is a colorless, slightly nscous liquid ; odorless ; faintly sweet ; up.
gr. 1.125 at 0' [m^ F.) ; boils nt 197* VAH&'.Q F.) ; sparingly soluble \a
ether ; very Holuble in water and in alcohol.
It is not oxidiiied by simple exposure to air, but on contact with plati-
num black it is oxidized to glycoUc acid ; more energetic oxidants tranfr*
form it into oxalic acid. Chlorine acts slowly upon glycol in the cold ;
more rapidly under the influence of hcftt, producing ch!orinate<l and other
derivatives. By the action of dry HCI upon cooled glycol, a product is
formed, intermediate between it and ethylene chloride, a neutral com-
CH,OH
pound — e(htm« chlorhydrtUe or ethene chhriiydrin, I , ivhich boils at
CI
130° (2GG-' F.).
Ethene oxide — Ethylene oxide — (0,H,)"0— 44,— This subatanee, iso-
meric with aldehyde, ia obtained by the action of potassium hydrate upon
ctlieuo chlorliydmite-
It is a transparent, Tolatilo liquid ; boils nt IS^'.S (54°. 3 P. ) ; gives off
inflnmraable vfipors ; mixefl with HO in nil proportions. It is capable of
uniting directly withH,0 to form glycol ; and with HCI gas to regenerate
ethene chlorhydrate.
Taurine~SO,C,H,N — 126~iB isomeric with a derivative of glycol,
iae^ionamide. It is obtained from ox*bile by boiling with dilute nCl ;
^H,a
ACIDS DERIVED FROM THE GLYCOLS.
231
I
iOeaDtiiig And ooncentratlng the liquid ; sepciratiiig fi-ora the Bodiam chlo-
Tide which cr)'}ftaUtzeH ; evaporating furtlter, nml precipttaling with alco-
boL The deposit is purified by recrjirtaUization from olcohoL
It cn-Bfidlizes in large, traiiaparciit. obUquo, rhombic prisms, permuient
in air, soluble in H,0, almost insoluble m absolute alcoUol and ether.
Taurine has acid pnjiKrtien and forme salts ; it is not attAcked br
H^SO,, HXO,, or n it ro muriatic acid, but is oxidized by nilrouH acid, witli
formation of HO, N, and isetbiouic acid.
It exists iu the animal eeonomy, in tho bile in tanrocbolic acid (q. it.) ;
ud has also b«en detected in the intestine and frec«s, muscle, blood, liver,
kidneys, and lungs. The pneiimic acid, described aa existing in the lunf^,
ii taurine. When taken iDt«rualiy, it ia eliminated by the luiue, not in ita
own form, but ns taurocarbamic or ieethionuric acui, C,H^,SO,.
ACmS DERIVED FROM THE GLYCOLS.
As the acids of the acetic series are obtained from the primary mono-
atomic alcohols by the substitution of O for H, in the characterizing
group CH.OH :
CH.
CH,.OH
Btlijl alouhol.
■ SO the diatomic alcohols may, by oxidation,
formed by the same substitution of O for U,.
the monoatomic nlcohols iu containing two groupfl CH,()H, and they con-
sequently }'ield two acids, aa the subsLitution occurs in one or both of
the alcoholic groups :
r
CO,OH
be made to yield acids.
But tho pflycols differ from
CH„OH
CH„OH
niMMiljrcoL
CH„OH
CO.OH
CO,OH
I
CG.OH
OnlteMld.
A study of these two acids shows them to be [xisseKsed of ])ecu1iar
differences of fiinctifm. Koch of tbeni contains two groups (OHf, whose
hydrogen ia caixible of replacement by im acid or alcoholic railical :
CH,.OC.H,
COOH
CH„OH
CO.OC^H,
CH.OC H, CO.OH
Kll>jl|1r«<))ic»cU. Ettiyt sljtx'^''
CO.OC,H.
CO.OC^,
BtbjrlanUk- aHC.
CO.OC.H,
CO.OC.H,
They are. therefor, both said to be diatomic. Tlie ability, however, of the
two acids to fomi salLs is not tho eamo, for while oxalic acid is capable of
forming two salts of univalent meUls, and a salt of a bivalent metal with
a single molecule of the acid ; glycolic acid only forms a single salt of (ui
uui<riili-ut meted, and two of ita molecules are required to form a salt of a
bivalent metal ; in other words, glycolic acid is monobasic while oxalic acid
is dibasic. It is only that H atom which is contained in the electro-nega-
tive group COOU, which is replaceable aa acid hydrogen, while that of
I
XAinTAL OP CRXIfTBTRT.
tbe deetro-poeitive p-otip CH,OH ia only replaceable, as la the MmpnA-
ing hydrogen of an alcohol.
Id general terms, therefor, the atomicUy of &n organic acdd mux be
greater tliao its bwicity, the former repreaendng the number of B AtoiDi
coutoiuecl iu ita molecule, which are capable of being dispLkced hj alco-
holic rodiciUs. while the latter represeiiU the number of H atomi n-
placpabte by electro-positive elements or radicals, with fonnatUm of altl
or of ethers.
There may, therefor, be obtained from the glycols, by more or ka
complete oxidation, two series of acids; those of the first are diftlotoic
and monobasic ; those of the aeoond diatomic and dibasic.
DIATOMIC AND MONOBASIC ACIDS.
Ssans C,3,.0^
The acids of this series at present known are :
(Osrtxinte acU) COiH. I BntylMXk arid C.O^a | t«Mis«U 0«0^,,
OlrcoUoMi.] 0,0,11, OZ7valBri« MM 0«iMIm (T) OkMMUo add. 0,iO|Hm
X(bfUa»-l«caoBeld C^»U, | I
The HrHt-named of these acids, although not capable, so far as yet
luiown, of extHting in the fi'ce state, is widely represented in nature in
the shape of its salts, the oar1>onates. Its position in tliis series is an
anomaly, and at first sight a contradiction, as it in certainly not a mono-
basic, but a diatinetly dibasic acid, or, more projKTly speakiUK, would be
such were it obtained iu a utate of purity. It is, however, iu tJiia poeitiOD,
aa the inferior liomologue of glycolic acid, that carbonic acid is most
naturally placed, and the dibasic nature of the latter acid does not pre-
sent any valid objection to such a position, for if we consider one term ol
a isries ns derivable from its superior homoloprue by the subtraction of
CH„ and if we bear in mind that the basic nature of the hydrogen atom
in a group OH depends upon its rfose union with the group CO (or with
some other electnj-negative group), it will become evident that the in-
ferior hoinologue of glycolic arid must contain two groups OH united to
<me OO, and must, therefor, be dibasic :
C0,(
CH.OH OH ,«„
- CH, - I or CO/"g
,0H CO,OH ^"**
Olfcollc aeld. CartiMJe add.
The other acids of the serioe ore formed : (1.) By the partial oxidation
of Uie corresponding glycol :
H\q
H/"
Water.
CH.OH
CH.OH
J 4- 0.
CU,OH
"" CO.OH
o^rxiL
OItvoIIc acU.
OXTDES OF CATOBOir.
288
(2.) By the combined action of water and ailTer oxiilo upon the mono-
dhlor-Acid of the acetic aeries, or by beating the alkaline wilt ol Budi ui
acid with water or potassium hydrate :
CH,a
L
OK **/
Benoehlorawtat*.
VTUer.
CH,OH
I +
CO.OH
OljrooHe add.
Ka
PdUadim
chlorkU,
(8.) By reducing the correspondiug acid of the oxahc seriea by nascent
liTdrogen :
COOH
OCX)
H
+ 2H, =
QsftUaKld.
CH,OH ^^
COOH "/
Oljpvollc Mrtd. vrumr.
Carbonic acid— CO ^q^— 62.— Although this acid has not been
isolated, it probably exiata in aqueous solntiona of CO,, which have an acid
reaction, while dry CO; is neatraL Its aalts, the carbonates, are well ohius
acterized.
Oxides of Carbon.
Carbon monoxide — Carbouom oxiHe — Carbonic oxide — CO— 28.
FoBM\TioN.^(l.) By burning C with a limited supply of air.
(2. ) Bv pasaing diy carbon dioxide over red-hot charcoal.
(3.) By heating oxalic acid with H,SO, : C,0,H, = H/) + CO -f CO, ;
and passing tbe gas through sodic hydrate to separate CO,.
(4.) By heating potassium forrocyanide wiUiH^BO^.
PnDPEKTtKs, — A colorless, tasteless gaa ; sp. gr. O.Dt»78A ; Tery sparingly
■oluble in HO and in alcohol
It bums in air with a bhie flame and formation of carbon dioxide ; it
forms explosive mixtures with air and oxygen ; it is oxidized to carbon
dioxide by cold cliromic lu-id. It iti a valuublu reduciug agent, and is ubbH
for the reduction of metallic oxides at u red heat. Aiumonincal aoluiions of
the cuprous salts absorb it readily. Being n on -saturated, it unites readily
with O to form CO,, and with CI to form COCl,, the latter a colorless, sui*
foeating gas, known as pho»gene, or mrbonyl chloride,
ToxiooLoor. — Carbon monoxide is an exceedingly poiaonons gas, and
Is tbe chief toxic constituent of Uie gases given ofT from blast-furnoces,
from defective flues, and open coal or charcoal tires, and of illumiuatiug
cos. An atmosphere containing but a small proportion of this gas pro-
duces asphyxia and death, even if the quantity of oxygen present l>e equal
to or even fO'eatcr tluiu that normally existing in the atmoaphcro ; O.o per
cent, of CO in air is Kuflicicut to kiU a small bird in a few momouis, and
one jier cent, proves fnbd to small manimals.
Poisoning by CO may occur in B*;vcnil ways. By inhalation of the gaofifi
discharged from blast-furnaces and from copper-furnaces, the former con-
taining 25 to .'(2 per cent., and the latter la to 19 per cent, of CO. By
the fumes given off from charcoal burned in a con6ne<l Fpace, which con-
sist of a mixture of the two oxides of carbon, the dioxide predominating
2S4
MATTTTAL OP CHEMISTRT.
largely. CBpeeiallT when the combustion is moat active. Tlie folloiinng jg
the composition of an atmoepbere produced by buruixig charcoal io & con-
£ued space, oud which proved rapidly fatal to a dc^ : oxygen, 19.19 ; uitTo-
gen, 7G.C2 ; carbon dioxide, 4.(il ; carbon monoxide, U.G4; mazslyfia,
.04. Obvioooly the deleterious effects of charcoal- fumes are more npAlj
fatal in proportion as the combustion is imperfect and the room amaS uid
ill-veutihit«d.
I A fruitful Bource of CO poisoning, eometimea fatal, but more freqneoll;
producing languor, headache, and debiUty, is to be found in the stoiM,
furnaces, etc., used in heating our dwellings and other buildings, cspedBDy
when the fuel is autliracile coaL This fuel ptWuccs in its comlnatioD,
when the air-supply is not abundant, considerable quantities of 00, to
which a furtlier a<idition may l>e made by a reduction of tlie dioiida, alio
formed, in passing over red-hot iron ; this poisonous gas may find its na;
into the rooms either through crocks or other defects in the stove*, flue?,
or pipes ; by occasional downward currents of air passing over fires in
open fireplaces, or, much more frequently, by direct passage through the
heated metal. Kxperiment has shown that metals, notably castr-iroD, urs
quite pervious to gases when heated lo redness ; when, therefor, a stove or
the fire-box of a hfit-nir furnace be«x>mes red-hot, a portion of the gases.
formed by the combustion of the fuel, passes through the pores of tba
metal to coutaminate the air without, and gives rise to CO poisoning to a
degree depending upon the degiee of imperfection of the ventilation, Ui©
nature of the fuel, and tlie amount of air supplied to it. The precautiona
required to avoid this form of what may be colled chronica CO poisoning,
and which is by no means uncommon, are: (1) To liave the stoves or
furnaces linctl with fire-clay, which tends to prevent their overheating and
to diminish their perviousness to gases ; (2) to avoid heating to redness ;
(3) to furnish an abundant supply of air to the fuel ; (4) to secure proper
Tentilatiou ; and (5), in the case of bot-air furnaces, to obtain, by an abun-
dant supply of external flir to the air-chamber,a large supply of moderately
heated air rather than a small qiumtity of very hot air.
Of late years cases of fatal poisoniug by coal-gas are of very frequent
occurrence, caused either by acoidcutid inhalation, by inexperienced per-
sona blowing out the goa, or by Baicidea. The most actively poisonoQS in-
gredient of coal-gas is CO, which exista in the ordinor}* illuminating gas in
Uie proportion of 4 to 7.5 per cent, and in water-gas, made by decompoH-
ing superheated steam by pasRago ovpr red-hot coke, and subsequent
charging with vapor of hydrocarbons, in the large proportion of 30-35
per cent.
The method in which CO produces ita fatal effects is by forming witii
the blood-coloring matter a compoimd which is more stable thou oxyluemo-
globin, and thus causing asphyxia by destroying the power of the blood-
corpuscles of carrying O from the air to the tiwues. This compound of
CO and hoomoglobin is quite etable, and hence the symptoms of this form
of poisoning are very persistent, lasting until the place of the coloring-mat
ter thus rendered useless \h mtppUed by new-formation. The prognosis is
very unfavorable when the (unount of the gas inhaled has been at all con-
sifierablo ; the trcatuient usually followed, i>., artificial respiration, and
inhalation of O, failing to restore the altered coloring- ma tier. There
woiUd seem to be no form of poisoning in which transfusion of blood is
more directly indicated than in that by CO.
IMfction afii:r rfwi/A.— The blood of those nsphyxiated by CO is per-
sistently briglit red m color. When suitably diluted, and examined with
OXTDTO 07 CAHBOIT.
S3S
the Bpectroacope, it presents an abaorption Bpertnim (Tig. 35) of two bands
aiiuiUr to that of oxvhffimogloblu (Fig. 14, No. 11) but iu wbicb tbe t^o
bands are more equal and Bomowhat nearer the violet end of the spectrum.
Owing to tbe greater stability of the CO compound, its epsctnim may bo
readily distin^ruiuhed fruin that of the O i^ouipound by the addition of a
reducing agent (an ammoniacal solution of ferrous tartrate), which changes
the spectrum of oxyfaeemoglobin to the singlo-bnnd spectrum of Lu^mo-
globin {Fig. 14, No. 12), while tliat of tlie CO compound remains unaltered,
or only fades partially.
If a Bolutiou of caustic soda of sp. gr. 1.3 be added to normal blocMl,
a black, slimT mnss is formed, which, when sproad upon a white plate,
liaa a greeniiin-brown color ; tbe same reagent a<l<ie<l to blood altered by
CO forms a llrmly clotted mass, wLicli in thiu layers upon, a white surface
is bright red in color.
A.a'Be D F.t
mn
k
Via. SL
For tbe method of detecting and determining CO in gaseous mbcinrea,
KB p. 243.
Carbon dioxide — Carbonic anhydride — Carbonic add gas — CO, — 44.
pRKPARATiON. — (1.) By burning C in air or O.
(2.) By deoomitoaing a carbonate {marble = CaCOJ by a mineral acid
[HCI diluted with an equal volume of H,0).
I^noFiSTiBs. — At oniinaiy temperatures and prcsBores it is a colorless,
mffocAting gaa ; has an acidulous taste ; sp. gr. 1.529A ; soluble in an equal
Tolume of U^O at the ordinary pressure ; much more soluble aa tbe
preasure increases. Soda xvater is a solution of carbonic acid in li,0 under
increased pressure. When compressed to the eittent of 38 atmoRplierea
at 0* (32^^ F.) ; 50 atm. at 15" (50* F.) ; or 73 atm. at 30° (86° F.) it forma
ft transparent, mobile liquid, by whose evaporation, when the preasure is
relieved, sufficient cold is produced to solidify a portion into a snow-like
mass, which by spontaneous ovaporatioh in air, produces a temperature of
-90" (-ISO' F.).
Carbon dioxide neither bums nor does it support combustion. When
heated to 1,300° (2,370" F.), it ia decomposed into 00 and O. A simihir de-
composition is brought alwut bv the paa.sage through it of electric sparks.
Wlien heated with H it yields CO and H,0. When K. Na or Mg ia heated
in an atmosphere of CO , the gas is decomposed with formation of a car-
bonate and Bcparation of carbon. Wbcti caused to pass through solutions
of the hydrates of Na, K, Ca, or Ba, it is alisorbed, with formation of the
carbonatea of those elements, whirh. in the cajte of the last two, are de-
posited as white precijiitates. Solution of potash is frequently used in
analysis to absorb CO,, and lime and barjta water as tests for its presence.
Tbe hydrates mentioned »lso absorb CO, from moist air.
A-ntoentERia Carbom DioxmK. —Carbon dioxide is a constant constituent
of atmospheric air in small and vart-ing quantities ; the mean amount in free
country air being about 4 in 10,000. Tbe variations in amount under
different conditions is shown in the following table:
k
^K dM OP OHBMTSTKT. ^^^^^^|
^^^^V AMomtT or Cavbox Dioxidb nc Air. ^H
^^M OoOMtod It
puts bi ni.QOO.
^H V..4.
8.190
8.980
8.8
4.2
0.43
8.34S
4.88
4.79 to 0.18
8,57 to4.B6
8.8S to 4. S3
4.-57
4.87
4.S9
4.68 to 6.41
8.49
14.04
4.n
9.89
16.01
81.0
S8.8
79.3
1.0
S8.0
43.0
80.0
800.0
7,380.0
BoojBitigmnlt tDd htwj.
Botuaiagaolt uil Umj.
BooHtniaalt.
Bnamiiig:aalt
Lewj.
Lewy.
Buumn.
BMuann.
SuuBura.
Btttuvon.
BaoMnxct.
SwUBtLTO.
Saoimre.
Uou.
CbaaBMH*.
ChsOHIOBt. ^^J
Chaamont. ^^M
Gbaunumt. ^^M
ChaomoDt. ^^H
Ch&amant. ^^H
RoflOM. ^^H
W«ar«r. ^^H
P«ttenkof«t. ^^1
F. Lsblaaa ^|
F. Leblue. ^H
F. Leblanc. ^^H
^^^■.
^^^^V Kaftdow — tfaree-foortha mil* from 0«o«v« i
^H It will be obaerred that on land the amount is greater hy night than
^H hj day, while the reverae is the case at sea ; oq Innd the green parts o(
^H ]^uit8 nbflorb CO, during the hours of sunlight, but not during those of
^H darimaBB. The increaae in the amount in air oyer large bodies of water
^B during the daytime is due to the leas solubility of CO, in the surface-
^H water when beatod by the eun's rays. The nbi»ence of vegetation accounts
^H for the targe quantity of CO, in the air of the polar rogiona, and the same
^H cause, aided by an incroased production, for its excess tn the air of citiM j
^^k over that of the country. ^^H
^^M The sources of utmospberic CO, are : ^^M
^H (1.) The T^spimiion of animaJ*. — The air ©Tpired from the lungs rf
^H animals coniiina a quantity of CO,, varying with tlie age, nex, food, and
^H muscular development and activity, while, at the same time, a much '
^H Bumller quantitv is discharged by the skin and in solution in the urine.
^H In females the incresBO of elimination follows the same rule as with
^H males until puberty, when it O'eoses, and the amount exhaled remainn about
^H the same until the menopause, when the elimination of CO, suddenly in-
^H creases to nearly the sntne as that occurring in males of the same age, and
^^ subsequently grftdunlly declines with advancing age. I>uring pregnant^
^H the elimination of CO, ia temporarily increased. In both sexes and at aU
^H ages the exhalation of CO, is greater during muscular activity tban when
^H the individual is at rest, and greater in those whose muscular development
^H is more perfect An adult man discharges ^0.77 litres == tbree-fourtha
^H cubic foot^ of CO, per hour, or 49S.88 litres = 18 cubic feel, per diem. J
L ^
t
OXIDES OF CABBOir.
S87
The foUowixig table, from the experiiuenta of Andral and Gavortci, iudi-
oabM the quantity of CX), eUniiuatea by umUss of various ages :
ElDOKATION of CABlM»f DlOXIDB.
ft
IB>Mn
Hymn
«lolO
Hfu
VMfllt
la
UkM.
InRM.
»»
4»,9T
«141
IW.M
».SB 117. TO
00. W IM.tt
WW H7.«
ST 13 14S.M
68.8S;i»,H
tnKud. In kI« pllinUi»-
BO
8.T
10.3
11.4
ia.3
10,1
D.S
Mcbwl, In
Inl tuH
bou. hoank
iM.e
»6tl
950.1
ST8.«
S9a.8
U14
au.fl
ts.a
si.i
89.0
41 8
44 T
no
».7
iDl
kMB.
laM
bMva
Chrboa dioz- Oxjim ab
Id* «llmln»- MTlxd, III
l«l,teltbM. Utow.
411.0 u.ei3«T4.n
I 7aS.6<T.IMm.Wi
iocni.saG.st»t»4.»
,I0n.8!«.0M;9l4.»
(l88.8n.MT,7M.W
eaB.6«.7rr,«eB.4s
I I I I
Inl
boar.
InS4
baan.
Ul
boor.
Jn*i
bout.
t.20 936.11 6.RS WI U
1«.«1 Mi H 16,01 >463.t«
20.19 4Sa-I7 S3. 48 SOS. 40
VI.SS &l».(i| S4.7b t,\n.n
M.TX & 15 1-1 aft.Bi ffM.«T
18. m 4A1 Mt 91 va IiW
lT.l!lj4irsa »).Oirl47B.MB
Tbo expired air under ordinary conditions contains about 4.5 por cent,
by Tolume nf CO,, tlio prnportion being greater the slower the reHpiration.
(2.) Combustion. — rb« greater part of the atmospheric CO, is a pro-
duct of Uic oxidation of C in Home form aa a source of light and heaL
In the following tnbte ore given the amounts of CO, produced, and of air
consumed, by different kinds of fuel and illuminating malerials ; by com-
unring them with the quimtities of tho same g&Kes produeed and consumed
by on ulult man it will be seen that, in equal times, an onlinury gas-burner
produces nearly six times as much CO,, and consumes nearly ten times as
much air as a man. Tlie amount of airnonsnmed by fuel is, for practical pur-
poeea, neater than that given in the table, as the oxidation is never com-
plete, the air in the chimney frequently containing ten per cent, of oxygen
by Tolome (see below).
CoMBUsnox OP Fuel.
238
ICATTTAL or CHBMISTRT.
(3.) Feme niat inn. — Motft fermraitations, inclnding pntrefactive changes,
are Attended br the liberaticm of CO, ; thus, alcoholic fermentation iakm
place acconling to the equaticn :
C^.,0.
180
and consequently dtsebargos into the air 44 parts bj weight of CX), lor^
eretj 9t2 portn of alcohol formed, or 191.6 litzM of gas for evexy Utn ol
abeolate alcohol ohtoiued.
(4.) Trllurul wurct*. — Volcanoes in activity disohar^ enormous qnun
titiea of CO,, and, in volcanic countriea, tbe same gas is thrown oat idion-
dantly through fissures in the earth. All waten*. sweet and mineral, boU
tluB gas in solution, and thosti vhich have bi^come charged with it vndv
preaeure in the earth'u crust, upon being relieved of the pressure when itej
reach tbe surfoco. discbarge tbe excess into the air.
(5.) Manufiifiuring processea. — ^lArge quantities of CO, are added iothe
sir in the ricmity of lime- and brick-l^nB, cement-worka, etc.
(C.) In mines, after explooioua of "fire-damp." Those explosiona ate
e&UAod by the euddon imion of the C and U of CH, with tlie O of the air,
and are consequently attended by the formation of large volumes of CO^
known to miners as a/liT-damp.
Constancy of the amount of almospheric carbon rfiwrfrftr.— It has
roughly estimated by Poggendorff that 2,500.000,000,000 cubic metres o!"
CO, ore aunujilly discharged into our atmosphere, and tiiut this quantity
represents one eighty-sixth of the total amount at present existing therein.
This being the cafM>, with the prpsent production, &e percentage of atmoa-
uheric CO, would be doubled in eighty-six years; no such increase baB^
however, been observed, and the average percentage found by Angus
Smith, in 1872, is about the same as that- observed by BoxiSMngault in
1840, te,, four parts in ten thousand. The CO, discharged into the air is,
therefor, removed from it about aa bst as it ia produced. This removal is
effected in two ways: (1) by the formation of deposits of earthy carbonates
by animal organisms, corals, mollusks, etc; f2) princii'ially by the process
of nutrition of vegetabfea, which absorb CO both by their roots and
leaves, and in the tatter, under the influence of the sun's niys, decompose
it, retaining the C, which passes into more complex molecides ; and dla^l
charging a volume of O alxmt equal to that of the CO, absorbed. ^|
Air vontamiriatfd vilh txccKti iff carbon (iio.ru/<*, an J its cjfi'ctg upon the
organism. — \Vlien. from any of the above sources, the air of a given
locatify has receivoil sufTicieut CO, to nuse the pro)K>rtiou above 7 in
10,000 by volume, it is to bo considered as contamiuatcd ; the seriousacss
of the coutuminatiou depending not only upon the amount of the increase,
but also upon the source of the CO,. If Uie gas be deiiveJ from fermen-
tation, or from tellurnl or manuiftcturing sources, it is simply added to
the othem-ise unaltered sir, and the absolute amount of oxygen present
remains the same ; when, however, it is produced in a confined space by
tbe ppooeases of combustion and respiration, the composition of the air
is much more seriously modifiedj as not oidy is there addition of a de-
leterious gas, but a siimiltaneous reniovnl of an equal volume of O ; hence
the importance of prottding, by suitable ventilation, for tlie supply of new
air from without to habitations and other pbtces where human beings orO
collerted within doors, especially whore the illumination is ortifieinl.
Although an adult man dt'oxidizes a little over 100 litres of air in on
hour, a calculation of tbe quantity which he would rcquii-a in a given tim^
OXIDES OF CARBON.
239
Duiuot bo based oxclasivclj upon that qimutity, ns the dcoxidatioa cauDot
be carried to rompletenetiH ; iiit)*^e<], wlif^n the pro^Hirtion of CO, in air ex-
ceeds five per ceuL. it becomes iucapable of sup|>ortiog life, while a mucb
■mailer <]uautity, one per cent., is provocative of eevere discomfort, to Bay
the least.
In calculating the quantity of air which should be supplied to a given
enclosed space, most authors have agreed to adopt as a basis that the per-
centage of CO, should not bejiUowed to eiooed O.G volume per 1.000 ; of
which 0.4 ia nomiallr present in air, and 0.2 the product of respiration or
combustion. Taking the amount of CO, eliminated by an adult at 19
Utree {=0.7 cubic foot) per hour, n man wUl have brought the air of an
air-tight space of 100 cubic metres ( = 3,C00 cubic feet) up to the permia-
nble maxiintim of impurity in an hour, The following tihle in given bv
fin^es to iDdicate the contamination of air by the respiration of an adult
in an liour, and the supply of external air required to I'eatoro the proper
equilibrium :
' AinoiiQt of ftir diwm-
AmmnxotmhicMimc^^^^'^'^^'^^J T^a^Z* ?n"" > Amount DDCMMry to
in oubio
hm.
tho end ot ooo hoar,
if Lhere bave been uo
ohsugB of air.
eluding initial CU,.
of an per t.OUO vnl-
ttntea dnrijig the fiist
hour.
2,900
2,800
2,700
2.600
2.500
2,400
2,3(}0
2,200
2.100
2,000
dilute t« tbo giTcQ
■tandard vrviy nour
after Um) &nt.
3,000
8.000
3,000
8,000
3,000
3,000
8,000
3,000
3,000
3,000
Prnctically. owing to the imperfect closing of doors and windows, and
to ventilation by chimneys, inhabited spaces are never hermetically closed,
and a leas quantity of air-supply than that indicated in the table may
usually be considered as efficient
A sleeping-room occupied by a single person should have a cubic space
of 30 to 50 cubic metres ( = 1,050 to 1.800 cubic feet), conditions which.
are fulfilled in rooms measuring 10 x 13 x 8 feet, and 13 x 15. 6 x 9 feet.
In ailculatmg the space of dormitories to be occupied by several
healthy people, the smallest air-spat^e tliat should, under any circuin-
stances, bo allowed, is 12 cubic metres ( = 420 cubic foet) for each person.
To determiDo the number of iudividiials that may sleep in a room, multi-
ply ita length, width, and height together, and divide the product by 420
it the mea^iurement be in feet, or by 12 if it be in metres. Thus, a dor-
mitory 40 feet long. 20 feet wide, and 10 feet high, is fitted for the ac-
commodation of 19 persona at most ; for 40 x 20 x 10 = 8,000 and ^M^
= 19.05.
As a rule, in places where many persons nre congregated, it is neoes-
to resort to some scheme of ventilation by which a sufficient supply
340
JCANUAL OF OHX1CIBTSY.
of fresh air shall be intxoduced and the ritiated air removod, the qmntity
to be supplicU ToiTiug accordijif; to ctrcimiBtoiicea. £xperimeitt bw
shown tha^ in order to ke«p the nir pure to the senses, the qoADtiljr of lir
which must be supplied per head and per hour in temperate cHmatman
as ahuwu in the table :
tUaaaaa.
ODbkBMrw.
OnMelMC,
1
OiAlelK.
9hvmA> AqtAm)
WodMbopi ItBOduakal)
»
flfi
1,I9S
i.aa
no
110
IM
no
MM
MM
Hoirittl wany , ,
The amounts given are the smallest jwrmissible, and should he ex*
ceeded wherever practicable;.
Light's. — The unuunt of air to be supplied to each individnal, given io
the la»t acctioa, arc, with the exception of those furnished in mines, bnsed
upon tlie Huppoeition that coal-gas is not used as a means of artidcial il-
Inmination, or that the burners are so airanged with reference to the
veutilating-tlues tliat the products uf combustion ]nihh out immediatelj.
Each cubic foot of ilium iuntiug- gas consumeu in its combustion a quae-
titv of O equal to that contained in 7.14 cuhio feet of air, and produces
0.8 cubic feet of CO) , besides a large quantity of waterr vapor, and lees
amouuts of H^SO,, BO,, and sometimes CO ; and on ordinary gas-buraer
consumes about three feet per hour. It is obvious, therefor, that a much
hu^cr quantity of pure air must be furnished to maintain the atmusphera
of an ujiartnient at the standiu-d cf 0.6 j>er 1,000 of CO,, when the vitia-
tion is produced by the combustiuu of gas, than when it is the result oi
the renpiratinu of a human being, and that to such an extent that a singlfl
three-foot burner requires a supply of air which would be sufficient for
six human Ijeinga Ati a basis fur coiuputution, it may be considered that,
for each cubic foot of gaa consumed, l,tiOO cubic feet of air should he
furnished by ventiktion.
The contamination of air by gas-lights becomes a question of seriouB
importance iu our dweUiugs upon occasions of socijil gatherings, and in
theatres and other places of public resort which are used during the hours
of darkness. The average size of a parlor in a city dwelling is 15 x 25 x 16
feet ; it therefor contains 4.875 cubic feet, and its atmosphere would, if it
were hennL'tically closed, be brought to the standnnl of mnximDro allow-
able contftuiiufttiou by the respirution of four adults in an hour, allowing
1.200 cubic feet per head, per hour. If such an apartment be illuminated,
upon the occasion of an evening party at which fifty a«^Iults are preeeni
for four hours, by ten three-feet gas-burners, the amounts of air i^ch
should be supplied by ventilation are as follows in cubic feet :
If Uia pnahtcta uf wimtii*-
Islo Elic roont.
If Ita« prO<lllcU of OOfDtlB^
tlnn nt tiM CD* b* caniad
Per boor.
Fof ItSttr bouria
rwtioar.
Por toor bgvn.
ra.<ioo
64.U0D
ncouo
«0.K»
S«,OQO
iiijaDO
4H,«U
•OkOOO
' »ajm
h« first instance, in wliich the proclncta of the combustion of f^as
rJinj'getl into tUo aportmeut, ou ailei|iiAte Teniilaiion can only be
Becured bv a completu chnn^o of the air evuiy 2.6 tuinuUis, wbic-h cnn
only be attoiued bv tbo ii»e or mechanical ooutrivtuices, mid willi the
prodnetion of dranghts ; in the wcoud instance, in which it is presumed
that tlie gas-bumora oi'e so situated, with rcforence to a ventilatiug-sliaft
or shafts, that the products of combunlion are imniedialely carried off,
not only is the period in which a complete clianRo of air is required ex-
tended to 4.8 minutes, but the heat of the burners, causing an uptake
current in the ventilator, favors the exit of the vitiated air, and the con-
■equent entrance of external air (o tjikc its place.
In theatrrs the cotitaniiiialioii of the air by the burning of gas should
be entirely chmiuated by placing the burners either under the dome ven-
tilator, or in boxes which open to the air of the house only below the
level of the burner, and which are in commtuiioation with a ventilating-
ehaft Bven under these conditions it in necessary, to enmire perfect
ventilation, to resort to some mechanical contrivance to remote the air
vitiated by respiration aud to supply its jilaco by fresh air from without,
which may bo previously wftnne<l or cooled according to the season, and
which, in cities, should ho littered.
When artiticiid illumination is obtained from lamjw or candles, or from
gas in small quantity and for a short time, the contamination of the air
is suflBciently compensateii by the ventilation thr«.)uph imperfect closing
of the windows. A room without a window should never be used for
human habitatinn.
One important advantage of tho electric light, if it over become prao>
ttcable, will be that it eonsunips no O and produces no CO,.
Althougli, by tho combustion of fuel, O is consumed and CO^ pro-
duced, heating lurangementa only become a source of vitiation of air under
the circuni stances deUtiled above (see p, 234) ; indee«l, in the majority
of cases, if properly an*anged, tiiey are the means of ventihition, either by
aspirating the vitiated uir oi tlie apartuieut, or by the introduction of air
from without.
Activn vn the economy. — An animal introduced into an atmoKphere of
fmre 00, dies almost instiintly, and without entrance of tho gas into the
lings, death itimdting from spasm of the glottis, aud couMxiuent apna-a.
When diluted with air, the action of CO, varies according to its pro-
portion, and according to tho proportion of O present.
FtntL — When the pn)portiou of O is not diminished, the poisonous
action of GO, is not as manifeKt, in equal quantities, as when the air is poorer
in oxygen. An animal will die rapidly in an atmosphere composed of 21
per cent. O, 59 per cent N, and 20 per cent CO, by volume ; but wiU live
for several hours in an atmosphere whose composition is 40 percent, O, 37
per cent N, 23 per cent. CO,. If CO, be added to normal air, of oourse
the relative quantity of O is slightly diminished, while its absolute quantity
remains the same ; this is tho couditiuu of affiiirs existing in nature when
the gas is discharged into the air ; under these circumfttanccB an addition
of 10-16 pflr cent, of CO, renders an air rapidly puisononB. and one of
&-8 por cent, will cause the death of sniull .iiiinmls more slowly. Even a
loes proportion than this may 1>ecame fatal toau inrltvtdual not habituated.
In the higher states of dilution, CO, produces immediate loss of mus
oular power, and dcjith without a stniggle ; when morb dilute, a sense ol
irritation of the larynx, tlrowsiness, pain in the head, giddiueas, gradual
loss of muscular power, and death in comx
12
243
MATTITAI. OF CTTEITTSTIIT.
JSt*cionrf. — If tlie CO, presertt in air be produced by respiration or mid*
bustion, the proportiuu uf O is at the same time diminishod, and much
smaller absolute and roUtivo amounts of tiie poisonous gas will produce
the effects mentioned above ; thus, an atmosphere containing in Tolamcs
19.75 per cent O, 74.25 per cent X, tJ per cent CO^, in muL>h more
ntpidlr fatal than one composed of 21 per cent O, 59 ]icr cent N, 20 per
cent C'O,. With a oorreaponding reduction of O, 5 per cent of CO, ren-
ders an air FuffirienUy poiHonous to destroy life; 2 per cent prooooes
severe suffering; 1 per cent, caxisea great *Uacomfort, while 0.1 per oent,
or eTcn less, iu recogutzed by a eeuso of closeueas.
The treatment in all cases of poisoning by CO, consists in the inhal&UoQ
of pare air (to which a small excess of O may be added), aided, if neoM-
sary, by art iliciul respiration, the cold douche, galvanism, and frietion.
When it chances that an individual entering an aUnosphere containing
an excess of CO,, or other noxiouA gas. is seen to fall insensible, it is
simply multiplying the number of Tictima, for others to follow, unpro-
tectetl, with u vievr to efTecting a reacoe. Probably the moHt readily ob-
tainnble protection is a towel saturated with lime-water, and so held over
the month and nostrils that the inspired air paflAos through it, and also
through two or three layers of dry towelling iuteqHJued between tbe inoisU
ouod part and the skin.
JhHt'rtion of itirbon dioxide atui analysis of confined air, — Carbon diodde,
or air containing it causes a white precipitate when caiisfld to buhble
through Ume or barj-ta water ; normal air contains enough of the gaa to
form a scum upon the surface of these solutions when exposed to it
It was nt one time suppose^! that air in which a candle continncd to burn
was also capable of maintaining respiration. Tliia is, however, by no meins
neocaaarily true ; n caudle introduced into an atmosphere in which the
normal proportion of O is contained, bums readily in tlid presence of 6
jter cent of CO, ; is perceptibly dulled by 10 per cent; is nsually extin-
guished vith 13 |>er cent; always extiuguislied with 16 per cunt Its ex-
tinction is caused by a less propoi-tion of CO., 4 per cent., if the quantity
of O be at the same time diminished. Aloicover, n contaminated atmos-
phere may not contain enough CO^ to extinguish, or perceptibly ilim the
flame of a caudle, and ut the s[imo time contain enough of the monoxide
to render it fatally poisonous if inhaled.
The presence of CO, in a gaseous mixture ia determined by its absorp-
tion by a solution of pctasli ; it« quantity either by measuring the diminu-
tion in l)ulk of the gas or by noting the iucrenso in weight of an aUuUino
solution. To deicrmino the proportions of the vtu-ioas gases proeeut in
air the apparatus shown in I'^g. 36 is used. A ia an aspirator of known
capacity, HUed with water at the beginning of the operation. It connects
by a flexible tube from its upper part with an absorbing apparatus con-
sisting of a, n U-shaped tube containing fragments of pumice stone, mmst-
ened witli H,SO,; by the increase in weight of this tube the weight of
watery- vapor in the volume of air drnwu through by tlio aspirator is de-
termined ; A, a Liebig's bulb tilled with a solution of potash ; e. a U tube
filled with fragments of pumice moistened with H,SO,^ ; 6 and o are weighed
together and their increase in weight is t}ie weight of CO, in the volume
of air operated on. Every gram of increase iu weight represents 0.50607
litre, or 31.60356 cubic inches ; d is a lube of difficultly fusible glass, filled
with black oxide «f copper and heated to redness ; p is a tl-tube tilled
with pumice moistened with H SO, ; its increase in weight represents H,0
obtained £rom decomposition of CU^. Every gram of increase in weight of
OXIDES Ot CABBOW.
^3
rraprescnld 0.444 gnm. or 0.G21 litre, or 38.761 cubic inches of marsh
gas ; / UDil g oro similar to b and c, nnd their increase in weight represents
CO, formed by oxidation of CO and CH, in d. From this the amount of
CO ia thus calculated : FirBt, 2.76 gramB are deducted from tbo increase of
weight of / and g for each gram of CH, formed by f ; of the remainder,
etery pram represents 0.G364 gram, or 0.508o litre, or 31.756 cubic
incites of CO. The air is drawn through the oppanitus by opening tho
stopcock of A to such an extent that about 30 bubbles a miuute paaB
through 6.
^^
^
^
\i^
Fia. an.
Carl>on disulphlde — Tiisiulphi/ie of carbon — CofbonH tnnutphidum (V'
S.} — OS, — 7t> — 18 formed by pM.'wiiig T:ipor of S over heated to rednetia,
and is partly purified by rectification.
It is ft colorles-s lii^uid ; when pure it has a peculiar, but not dia^rree-
able odor, the nauseating odor of the commercial product being due to the
preseuco of auothcr sulphurated body ; boils at 47^ {IIG^.G F.) ; sp. gr.
L293; verj' volatile; its i-npid e%'nponition in vacuo produces a cold of
—GO* { — m'' v.); it does not mis with HO ; it rpfracta hght strongly.
It ia highly intlamnudde, ami bunm witli a bluiMh flame, giving olT CO,
and SO, ; its vapor forms highly explosive mixtures with air, which deto-
nate on contact with a glo-ss rod heated to 250" (482" F.). Its vapor forms
a mixture with nitrogen dioxide, which^ when ignited* bums with a bril-
liant tlame, rich in actinic rays.
There also exists a substanco intermediate in composition between CO,
and CS,, known as <tirbun or>j«iiJjihul{'. CSO, which is an inflammable, ool*
orlesfi mis, obtained by decomposing potassiam sulphoc\'anata with dilute
H,SO..
Toxionuioy. — Cases of acuto poisoning by CS, have hitherto only been
observed in animals ; its action is very similar to that of chloroform.
Workmen en^ged in th^ nmiiufacture of CH, and in tlie vulcanization
nf rublwr. aa weU as others cxpose«l to the vapor of the disulphide, are sub-
ject to a form of chronic poisoning which may bo divided into two stages.
The first, or stage of excitntion, is marked by headaclic, vertigo, a dia-
a g r ee able taste, cramps in the legs ; the patient talks, laughs, sings, and
weeps immoderately, and somotimes becomes violently delirious. In the
244
UAXVAl* OF €HE3U8TST.
■wond vbge thepaftinit TMoomes and and sleepy, MosAnUty <liiiuiui^
aMDefeiiDM to (be extent of complete BnsEathesiii, mptamUy of tlio k;«g-
«Jill«iiiiiiM^ the beodacbe becomes more intenae. the niipetite is gie«tl;
imiMind, and there ia general wwiHuw of tlie limbe, whidi tcnuiiutKa m
panljnB.
ITie oolj remedy which haa been aoggested is tfaonmgh ventihtion of
the workshops, and abandonment of the trade at the fint vppa a a B M of
the ajmploms.
CH,OH
Glycollio add— I —76— is fonned bj the oxidation of glycol, by
the action of nitrous acid on glvcocol, and hj the action of poto^ on mooo-
chloracetic acid.
It forms deliqnescent, acicnUr crrBtals ; veij solnble in water ; boIuU*
in alcohol and ether ; has a stronglv add taste and reaction ; fneee at ItC
(172°.4 F.) ; is deoompused at loO^ (302^ F.) ; at an intermediate ten-
perottire it loses HO. foj*aiing glycotlUte, or glycUUc atUiydride, CM 0,.
liEOtic acids— C,H,0,— 90. — There ore probably three, certainly tm
adds hnvinfj this conipoeition. Two of these would seem, frf'io their pro-
ducts of dt;<x>niiH)Hitiim, tu be of similar oonstituUuu, while the tanleciilir
composition of the third is distinct ; the two of similar oonsLitution m
BoinotJtnes desif^nated as eihtttidene la/iu: actds, liecause of their coutaintag
the group of atoms CU^ while the third is designated as ftht^em^^tili
acid, as it contains the group Cll, ; the constitution ia expreased by '
formnliE :
1
CH.OH
I
OOOH
SEhylldeulKtteMld.
CH.OH
^
COOH
BtliTleao-lMtlc idd.
Obrionsly it is the ethylene acid which is the superior homologue of gly*
ooUkaoid.
BrsTLEifo-LAmn Aero. — MusciiUr tisHue contains a mixture of this and
optically active cthylidene lactic acid, which has been known as mrvoioiik
add.
Ethylene' hictic ncid may be obtained from muscular tissue or from
liebig's extract of meat. It is optically inactivo, as are also solutions of
its salts ; its ziuc salt contains 2 Aq, and is very soluble in water sad
quite soluble in alcohol. When oxidued by chromic acid it yields malomc
acid.
Of the two »rrmn.n>ENE uumn aridb, tliat which is optically active is
the one accompiuiyiTig ethylene lactic acid, and predominating over it in
amount, in dead uiuscle ; it iu to this acid that the name paralactic acid ia
most pi-operly aiiplied. It may 1« obtained from Licbig's meat extract
Paralactic ncid dtfTc^rfl from its two isomeres in that its solutions are
dextrogyroua, and the goluticius of its salts ore lievogyrous. Tlie specific
rotaty power of the acid is [«!,.= +3'*.6; that of the zinc salt [a] ^=
—7.6*; and of the ralcium salt [«]„= — 3*.8. Its products of decomposi-
tion are the same ns those of ordinary lactic acid.
OamKAKY Lactic Acid — Lactic acid of /ennentation — OfyticaUi/ inartii'e
tihtilidene lactic acid — Arittum l^Ufum (V. S.) — exists in nature, widely
distributed in the vegetable kingdom, and as the product of a fermcnta-
OXIDBS OF CABBOir.
1M5
tion which is dcsif^aotcd as the lactic, in milk, Rour-krouk, fermented beet-
juice, ami rice, and in the Hquid refuse of swrch factories and tanneries.
Lactic n<;id ia obtained as a product of the fermentation of certain
sugars, milk-sugar and grape-sugar ; as a result of the processes of nutri-
tion of ft minute vegeUhle, the Lactic feimeut, in which the sugar ia con-
vertr^d into its polymern : C,H,0, — 2C,H,0,. It is usually produced
by allowing & mixture of oane-sugm*, tartaric acid, water, rotten cheese,
akim njllk and chnlk to fomient for 10 days fit 35^' (95"* F.). The calcium
lictato prtxluced ia separatod, pxtri&ed and docom|K>8ed witli an equivalent
(luantity of H.SO,.
It has alao been obtained synthetically by oxidation of the propylglycol
of W'urt2, which is a Hecoudary glycol, a synthesis which indicates its con-
stitution :
CH,
I
CH.OH
HOH + O, =
Ozjgtn.
CHOH
OOOH
+ H,0
Water.
It is a colorless, Bynipf liquid ; sp, gr. 1.215 at 20" (68" F.) ; doo« not
solidify at —24'' { — 11 '.2 F.) ; aolublo in water, alcohol, and ether ; is not
capable of distilhition without decompouition ; when heated to 130"
(SCO"" F.) it loses water and is converted into ditactio acid, Cfi O^, aud,
when heated to 250'' (482 " F.), into lacHde, C,H,0^ It is a good solvent of
tricalcic phosphate.
Oxidizing agents convert this acid into formic and acetio acids, without
the foi-mation of anyxoalonic aoid.
PmrstouMtoAr^ — ^The three lactic acids occur in animal nature, either
free or in combinHtion. Free lactic acid of fermentation occurs in the
contents of the small intestine, and. when vegetable food has been
token, in the stomach ; it is not, however, the acid to which the normal,
unmixfd gastric juice owes its aciility. Its salts have been found to
exist in the oonteule of the stomach and those of tlie intestines, chyle, bile,
parenchymatous fluid of spleen, liver, thymus, thyroid, pancrtms, lungs,
and br:uu ; urine. PiitholoKJi'^Uy in the blood in leucocytlia-mio, pyae-
mia, puorijeral fever, and after excessive muscular effort ; in the duide of
ovarian cysts and transudations. In tlie urine it is abundant in phos-
phonis-poisoning, in acute atrophy of the liver, and in rachitis and oateo
tuolochia.
Muscular tissne, after death or continued contraetions, contains the
mixture of acids known to the older authors as sarcolactic acid. Normal,
quiescent muscle is ncutnd in reaction ; but, when rigor mortis apjiears,
or if the muscle be tetauized, its reaction becomes acid from the liberation
of sarcolactic acid, \Vliethcr these acids are foi-med di' now during the
contraction of the muscle, or whether they are produced by the decora*
position of lactates existing in the quiescent muscle, is still undetermined:
certain it is, however, that a given quantity of muscle has, when scparat«d
from the cii'ctdation, a tixe<l niaximum of acid-producing capacity, whu&
is greater in a muscle that has been tetauized during the interval between
its removal and the estabUahmeat of rigor, than in one which has beea
- at rest.
■ There exist no grounds upon which to base the supposition that, in
I rheamatic fever, lactic acid is present in the blood.
I
I
V A37UAL OP CJTESnSTRT.
DIATOMIC AND DIBASIC ACIDS.
otaUcKU 0(0 «n,
IUnile«M t:,0,H,
JhrntelRMU C,0,H.
kDMontahwIaheM CtO.II,
Shrm C^,_,0,.
Adipic mM 0404B|«
J*tiiMtk; Kkl OtOJlia
ButMrte acM €.0,0,4
*wMn ■!« .<V).&„
BtbMfoKdd C,/>;i,
JteeodUcMld C,^,8„
They are derived from the primarj gljcola hj complete oxiditioD ;
they are diutoiiiic and dibauCr aud couhitu two groups, CO, OH. The;
form two Borics of salts with the univalent metals, and two aeries of
ethers, one of which contains neutral, and the other acid ethera. Tkey
tn^ he obtained &t}m the corresponding glycols, or from acids of the pn-
oeung eeries, by oxidation.
COOH
Oxalic acid —
— 90— C,0,H,,aAq— 126 — does not occur free
COOH
in natiiTO, but in the 03(alatea of E, Na, Ca. Mg> and Fe ta the juioee <A
many plants, sorrel, rhubarb, cinchona, oak, etc^ as a native fsmxiB osi-
late ; and in small quantity in human urine. It is pre|>ured artifidaDT br
oxidizing sugar or starch by HNO^ or by the action of an alkaline byonte
in. fusion upon sawdnst. The soluble alkaline oxalate obtained by tl:«
latter mothod is converted into the insoluble Ca or Pb salt, which is vaelied
and defomjK>sed by im equivalent quantity of H,SO, or H,S ; ami llit
liberated acid purified by recnstalliyjition.
Oxalic acid is also formed by the oxidation of many organic substanres
—alcohol, glycol, sugar, etc; by the action of potasaa in fusion upon tke
alkaline formiates ; and by the action of K or ha upon CO,,
It crystallizes in transparent prisms, containing 2Aq, which efflor^an
on expfwnre to air, and lose their Aq slowly but completely at 100° {2\T
F.). or in a diy vacuum. It fuses at 98" (208".4 F.) in its Aq ; at liO'-
132" (230^-2G9''.G F.) it sublimes in the anhydrous form, while a portion
is decompose*! ; above 1G0° (320'* F.)the decomposition is more extensiTe ;
H,0, CO., CO, and formic acid are prodiice<l, while a portion of the acid
is sublimed uncbanKcd. It dissolves in 15.5 parts of water at 10*" (50" F.);
the presence of HNO, increases its solubility. It is quite soluble in alcobtJ.
It has a sharp taste and an acid reaction in solution.
Oxalic! acid in reiuiily oxidized ; in watery solution it is converted ijito
CO, and H^O, slowly by simple exposure to air, more rapidly in the pres-
ence of platimun black or of the salts of platinimi ajid ^old ; under the
influence of sunlight ; or when healed with HNO,, manpanese dioxide,
chromic add, Br, CI, or IjypocblorouB acid. Its oxidation, when it is
triturated dry with pure oxide of load, is sufficiently active to heat tlie
Tnass to redness. H.^SO , H,PO,, and other delivdrating agenta decom-
pose it into H,0, CO, and CO,.
Amalytical Ckajuctehs. — {1.) In neufnd or alkaline solution a white ppt.
with a Bohition of a Ca salt
(2.) SilvGf nitrate, a white ppt-, soluble in HNO, and in NH^HO. The
ppt. does not darken when the nuid is boiled, but, when dried and heated
uu pluliuum foil, it oxploilc&
(3.) Lead acetate, in sohxtions not too dilute, a white ppt, soluble in
HNO^ insoluble in acetic acid.
DIATOVTO AND DTBASTC ACTOS.
247
ToiiooLrtOT, — Althoiigli certain oxalates aro fionBtanl constitnepfe of
Tcgetable food tuid u£ tho biminu bod^-, the ucid itoeli, as well aa b.rdro-
potassic oudate, is a Tiolent poison irben token intomaUy, acting both
locally OB R oorrusiTe upon the tissues with which it oomes in contact,
and as a true poii«ou, tbe predumiuanco of either action depending npon
the concoDtrutiou v( tbo solution. Dilute eolutions may produce death
without pain or vomiting, and after irrmptoms reacnibliug those of narcotic
poisoning. Deatli ban followed a dose of 3 j. of the soUd acid, and re-
corery a dose of 5 j- ba solution. AVhen death occurs, it may be almost
inHtautoueouBly, usually within half an hour ; sometimes after weeka or
months, from secondarj* caiiseB.
The treatment, which must be aa expeditioiui an possible, consists in
the administration. ^p«^ of lime or ma^ut;sia, or a salt of Ca or liIgBUB-
pondod or dissolved in a sttuiH quantity of H^O or mucilaginous fluid ;
afterward, if Tomitiug have not occurred sjmntaneously, and if the
symptoms of corrosion hare not been severe^ an emetic may be given.
In tue treatment oC this form of poisoning Bovoral points of negative cau-
tion are to be obsened. As in all coses iu which a corrosive has been
taken iutemally. the iwe of the stomach-pump is to be avoided. The al-
kaUne carbonates are of no value in cases of oxalic acid poisoning, as the
oxalates which they form ore soluble, and almost as poi.S(}uouH as the acid
itsell The ingestion of water, or the aii ministration of warm water as an
emetic, is oontraindicated when the poison has been taken in the eolid
form (or where doubt exists as to wluit form it wan token in), as they dia*
soh*e, and thua fuvor the abHorjUion of the poison.
AtuU'juii. — In faLil cases of poisoning by oxalic acid the contents of
the stomach are sometimes strongly acid in reaction ; more usually, owing
to the administration of antidotes, neutral, or even alkaline. In a S}'s-
tematic analysis tha poison is to bo sought for iu the residue of tho por-
tion examined for pruasic acid and phosphorus ; or, if the examination
for those sub.st'uices be omitted, iu the residue or final alkaline fluid of
the process for alkaloids (seep. 332 I'f Sipq.). If oxalic acid alone is to
be sought for, the contents of the stomach, or other substances if add,
are extracted with water, the liquid filtered, the filtrate evaporated, tho
re.sidue extmcted »vith ah»hol, tho alcoholic fluid evaporated, tho residue
rodisaolvcd in water (solution No. 1), Tho jjortion undissolved by al-
cohol is extracted with alcohol acidulated with hydrochloric acid, the
solution evaporated after llltrutiou, tho residue dissolved in water (so*
lution No. 2). Solution No. 1 contains any oxalic acid which may have
existed free in the substances examined ; No. 2 that which existed in the
form of soluble oxalates. If lime or magnesia have been administered aa
an antidote, the substances must be boiled for an hour or two with potas-
sium carbonate (not the hydrate), filtered, and the filtrate treated as above.
In the solutions so obtniueil, oxalic acid is cliaracterized by the teata given
above. TJje uriuo is also to be examined microscopically for crystals of cal-
cium oxalate. The stomach may contain small quantities of oxaUtes as
normal constituents of certain foods.
CH,— COOH
Malonio aoid — I — 104 — is
COOH
a proiluci of oxidation of
cthyleno-lactic acid, and is identical with the nicoUc acid of tobacco. It
forma prismatic crystals, very soluble \\\ H,<!), alcohol, and ether ; vhiob
at 110^ (284^ F.)> '^^ i^ decomposed at ISO" (802° F.).
848
MANUAL or OHEMIBTBT.
CH,— COOH
Succinic acid — | — 118 — exists in amber, ooaI,fo^ wood,
CH— COOH
and in amsll quantity in animal and regetable tisBoes. Its jirmmaat Iob
been detected iu ttie uortnal urine afUrtbe use of fruits andofaspangiB,iii
the parenchjinatoua fluids of the spleen, thyroid, &nd thymus, and in the
flmds of hydrocele and of hydatid cysts. It is also formed in small qnm-
tity. during alcoholic ferojeutation : as a product of oxidation of many fati
and (ntty licids ; and by f^thosis from ethylene cyanide.
It may be obtained by dij distillation of amber, or, preferably, by the
fennentation of malic acid.
It cijstallizeB in large primus or hexs^md platefl, \rbjch are coloriesa,
odorleiB, permanent in air, acid in taste, ftoluble in water, sparingly m in
cthev and in cold sloohol. It fuses at 180' (366~ F.), and distils with par-
tial deconipositiou at 235" (455'^ F. ). It withstandfi the action of oxidiz-
ing agents ; reducing agents convert it into the correBpouding acid of the
£atty uries, butyric acid; with Br it forms pixhlucts of substitution;
U,SO« is witliout action upon it ; phosphoric anbydhdJe remoTcs 11,0 and
conTerts it into tuccinic anhydridet C^H,0,.
COMPOUND BTHERS OF THE ACIDS OP THE SEBIES
C^^O.AKnCja^O..
4
s
I
The members of both of these series contain two atoms of H replnre-
nble by alcoholic nulicals. In those of the series C„H,„0, (with the
exception of oarbonic acid), being monobasic, althoiif^h diatomatic. it is
not immnterial which H ie so replaced. If it be that of the group CH^OH,
the resulting compound is a monobasic acid, in which the H uf the group
COOH may be replaced by another alcoliolic radical to fonn a neutr^
ether of the new acid ; if, ou the other hand, the H of the group COOH
be first replaced, a neutral compound ether is formed. In the members
of the series C„n.„,,0,, which are dibasic, the substitution of on alco-
holic radir.ll for the H of either group COOH produces a monobasic
acid, in which the H of the other COOH may be replaced by onothei
radical to fonn a neutral ether. The following formuhn inchoate
differences in the nature of these compounds :
CH,OH
i<
300H
oiraaUc acdd.
CH,OC,H,
k
:ooH
CH,OH
cooc^.
CH,OCA
COOO^,
ZXbyX ot&Tlclyoaliti.
COOH
I
COOH
Outic mU.
COOC,H.
COOH
BlfeftoBdlaMM.
OOOO^
COOCA
EthjrlozKlAla.
AUSRS OF TinC ULTCOLS.
S49
AUDEHTDES AND ANHYDRIDES OF THE SERIES
In treating of the moooatonuo compounds, it was atatod that sub-
itances existed correspond in g to the fatty neids, known as aldt-h^ydes and
uhydrides, the former ditTenng from the acids in that thej contained the
group COH instead of COOH ; tho latter 1}eing the oxides of the acdd
xadic^. Similar compounds exist corresponding to the acids of theee
two aeries.
The aldehydes corresponding to the series CJS^^O^ contain the group
COH iu place of the group COOH, and ns they also contain the group
CI{,OH, they are possessed of the double function of primary alcohol and
aldehyde. Those of tlie series CnH,«_ ,0, form two series ; in one of which
only one of the groups COOH is deoxidized to COH ; in the other, both.
Those of the ilriit scries, still coutoiniug a group COOH, ore mouoboaic
adda as well aa aldehydee :
CE[,OH CH,OH
COOH COH
COOH COOH
COOH COH
OskUc uM. atronUr acid.
COH
COH
QVmaL
"While the anhydrides of the fatty aeries may bo considered as derived
from the acids by tho subtraction of H,0 from two molecules of the acid ;
thoae of both the series of acids under consideration ore derived from a
fliagle molecule of the acid by the subtraction of U,0 :
OOOH
AMttCMtd.
CH,OH
i
OOH
Otr«riio»aU.
OH,— COOH
I
CH— COOH
BnodnkAcld.
CH— CO-
CH.— CO/
AoKiaaabrdTUa.
CH.
io/
N)
OlyMllauhrdridA
CH,-CO
CH,-C0/
SacdNle aobgrdiiile.
AllIINES OP THE GLYCOLS.
EraTLEnC COMPOUKD AmtOKIAS.
These anhstancefl are derived from a double molecule of NH,, or of
ammonium hydrate, by the subHtitution of Uie diatomic radicals of the
glycols (hyth-ocarbona of the serieH C„H,,) for an equivalent number of H
atoms. They are diHtinguished from the correaponding compounds of the
radicals of the monoatomio alcohols, the monamirie«, by the designation
of diamiruis.
When it is considered that in the formation of these subetanoes doablQ
250
MANUAL OF CUEtflSTBY.
H atoma can be replaced bj diatomic iiadicala to form primary, aecondan,
and tertiary aminos :
mokcate.
/'rtman/-
TnMhjlHM HBlDT.
(C.H,)'
{C
(C
that others exist in whicli two univaleni radicals replace a bivalent rad-
ical ; otliers. ofifaiii. iu which H atoms have been replaced by ^roupfl OH;
and tinaUy, that similar compoonds of V, As ami 8b exist, it is not astos-
iitliing that the kIuiIv of the vast number of sulmtances, the pocBibility d
whose existence is thus indicated, is still iu its infaucy.
Some recently discovered allaUoids, produce*! durinjj putrefaction («e»
Ptomaines, p. 343). are diumiiies ; and there is sti-oiig pixibability that fur-
ther investigation will show some of the vef^etable alkaloids, whose cocisti-
tuUon is as yet unkuowu, to belong in this class.
ABUDES OF THE ACIDS OF THE SERIES
1
Tbia dasa of substances, formed by the substitution of radicals of line
acids for H atoms in NU, molecules, contains some substuuces ol Uie
greatest medical interest The radicals of tlie acids of tlie stria
C,H,.0,, except carbonic acid, being univalent, form amidea similar in i'oc-
Btitution to those of the acids of the series CJI^O, (p. 208).
Iu the cose of the dibasic acids no less than tliree aeries of amides iw
known to exist ; thus we have, corresponding to oxalic acid :
OalraldMi
OaeMdofv "KMNtmMtf*
CO
^N.
oq/
Oiunldv.
COOH
C0\
H— N
H/
Oiftmlo h4i1.
COOH
COOH
OuHomU-
In the first of these, two H atoms of a single NH, molecule are re-
placed by the bivalent radical uf the acid : these ore distinguished m \
imides. Those of the second series are normcdly formed rfiamv/trs. In the I
third series, the uniralent remainder, left by tlie removal of OH from the '
add, replaces an atom of H in one molecule of NH,, and the resulting '
compoimd, still coutainiug a group COOH, has the functions of a mono-
basic aoid.
Amides of Carbonic Acid.
(CO)"\
Carblmide— N — 13. — Although cyanic acid (q.v.) has ireqi
^^
been regarded as the imide of carbonic add, there are many reasonR,
J
i
I
W-
JUUP£S OF CAUBOI«IO ACID. 251
methods of formation and propertiee of ojanic acid,
CN
which lead us to assign to it the constitutiou I , rather than that given
OH
iboTe, and to consider it as an isomere of the hitherto cmdiacoTered oarb-
imid«.
(CO)" )
Caibamlde— Urea— H, ;N,— 60.
H, )
OooiTBRBfci. — ^Urea does not occur in the vegetable world. It exists
principally in the urine of the mammalia ; alao in smaller quantity in the
fcxcn^iiieLtfi of birds, fishes, and some reptiles ; in the mammalian blood,
chyle, lymph, liver, spleen, lungs, brain, vitreous and aqueous humors, stt-
livo, perspiration, bile, milk, amniotic and allantoic fluids, muscular tiseoe.
and in serous fluids (see below).
FouuTioN. — (1.) As a product of the decompoeition of uric acid, uauallj
hy oxidation :
C,H.N.O, + H,0 + O - CON.H, + C,H,N,0,
UrtottckL Valar. Oxysm. Vtm. Allona.
(2.) By the oxidation of oxamida
(3.) By the action of caustic potossa upon creatin :
O^N.O. + H.0 = CON^. + C^,NO,
OraiudB. W«ur, Vn^ Svoodn*.
(4.) By the limited oxidation of albumincnd sabstonoes, by potassium
armanganate, and during the processes of nutrition.
(5.) By the action of carbon oxychloride on dr^' ammonia.
(6.) Br the action of ammonium h3*drate on ethvl carbonate at ISO"
(866° P.).
(7.) By heating ammonium carbonate in swiled tubes to 130° (266° F.).
(8.) By the slow cvaponitiou of un atiueouu solution of hydrocyanic
id.
(9.) By the molecular transformation of its isomeride, ammonium
eyanato.
CN (CO))
O (NH.) H, \
Anmuniuin cjrMiata. Ci
^H FsBPAiuTios. — (1.) From the urine. — Fresh nrine is evaporated to the
^BKoiBiBtency of a syrup over the water-bath ; the residue is cooled and mixed
"Trith BQ equal volume of colorless HNO, of sp. gr. 1.42 ; the crystals are
washed with a small quantity of oold HO, and disaolveil in hot H,0 ; tlie
solution is decolorized, so fior as possible, without boiling, with animal
charcoal, filt«red, and neutralized with potassium carbonate ; the liquid is
then coiirentrated over the wator-bath, and decanted from the aystals of
potastsium nitrat-e which Bepnrate ; then evaporated to drynesa over the
water-bath, and the residue extracted with strong, hot alcohol; the alco-
hoUc solution, on evaporation, leaves the urea more or loss colored by uri*
naiy pigment
(2.) 3iy npUhesi*. — Urea ia more readilr obtained in a stal« of purity
from potau&ium cjanate. This is dissolved in cold H,0, aud drr uutnio-
aium sulphate is added to the solution. Potumom sulphate cjTstallua
out and is separated by decanting Uie liquid, which is then evsponited
over the wat«r-batij, Ii'esh quantities of potassium sulphate crrstallizing
Bud being separated during the first part uf the cvapomiion ; the dr^- resi-
due is extracted with strong, hot alcohol ; this, on ernporaiion, leaves tlie
urea, which, bj a second c:rk*stalli2atian frcmi alcohol, \» obtained pure.
Properties. — Physivt^. — Urea L-r^Btulhze8 from its aqueous solution in
long, flattened prisms, and by spontaneous evaporation of iia aloobolic
solution in quadratic prisma witii octahedral eud& It is colorless and
odorless ; bos a cooling, bitteriBh taste, retembUug t}int of 8alt|)etre ; is
neutral in reaction ; soluble in one part of H,0 at 15' (59° T.), the solu-
tion being aitendad with diminution of tempcrnture ; soluble in five ports
of cold ^cohol (sp. gr. 0.81G) and in ouc part of boiling alcohol ; very
sparingly soluble in ether. WTien its powder is mixed with tliat of cer-
tain sftltn, such as so^^Uum sulphate, the Aq of the salt separates, and tbt
mass becomes soft or even liquid, ^\'hen pure it is not deliqiieticen^ but
is slightJv hvgronietric, and when it is to bt: weighed it should be dried at
100' (212^ ¥.) and cooled in a desKicator. Fuses at 130" (iGd" F.).
C/i<*nn(vjA — Hftftted a few degress above 130'' (2CG'' F. ) urea boila, giving
off ammonia and ammonium carbonate, and leaves h residue of ammelidf.
C.H.N.O,. Wlien heated to 150^-170" (302* 338" F.), it is decompowd.
leaving a mixture of ammelide, c}'auuric acid, and biuret :
8C0N.H, = 2C0, + C^N.O,
Cn». CBrt>OB dioxide. AnuMlido.
3C0N,H, = C,O.N,II,
+ 7NH.
+ 3NH.
H.O
W>Mr.
2CON,H.
= C,H.N.O. + XH,
Dlnm.
If nrea ia maintained at ISO'-ITO" (302''-338* F.) for some time, a dry,
gra>*ish mass remains, which consists principally of cyauuric acid. In tliia
reaction, the volatile products coutam urea, not that that substance is
ToUtile, but because a portion of the cyanuric acid and ammonia unite to
regenemtc urea )>y the reverse action to that given abore.
Dilute aqueous snlotions of area are not decomp')sed by boiling ; hut
if the solution be concentrated, or the boiling prolgnged for a long time,
the urea is parliiOly decomposed into CO, and NH,. The same decompo-
sition takes place more rapidly and completely when a solution of urea is
heated under presmire to 110 (284^ F.). A pure aqueous solution of urea
ia not altered by exposure to filtenwl air. If urine he allovred to stand,
putrefactive chiuigea tjike pbice under the influence of a peculiar, organized
ferment, or of a diastase-Uko body which is a constituent of nomiid urine.
Chlorine decomposes urea with production of CO,, N, and HCl. Sola-
tdons of the alkaline hypochlorites and hypobromites effect a similar de-
composition in the presence of on excess of alkali, according to the equation :
CON.H.
+
3NaC10 •-
= CO,
Vrm.
Sodlam
hTpoehtoriM.
Ovbon
dtOTl^Ie.
+ 2H.O
Wcter.
+ N, 4-
SNaCT
AJODEa OF OAHBONIO AOIZX.
253
Upon thia dccompofliUon are based the quontitatiTc processes of Enop,
iilner, Yvon, Dnvy, Leconte, etc.
Nitrous acid, or HSO^ charged with nitroua ispors, deoomposes urea
according to the equation :
kp
CON,U,
Vtm.
4- N.O. =
(1)
or the equation :
2CX)N,H,
+ N.O. = 00.(NH,).
Aumvantam
carUia*ta.
+ N. +
KUR«n.
CO. (2)
Uuboa
klf the mixture be made in the cold, of one molecule of nitrogen tri-
ide to two molecules of urea, the decomposition is that indicated by
Equation 2. If, ou the other hand, the triuxide be fin^tulual]^* added to the
previously warmed urea solution in the same proportion, half the urea is
\ decomposed while the remainder remains unaJtereti, and, ujwn the addi-
tion of a further and uufficienL qiumtitj uf the trioxide, all tiie urea in de-
compoaed according to Equation 1. Upon thia reaction are buited the
processes of Gr^hant, Boymond, Draper, etc.
When heatetl with mineral arids or alkalie.t, nrea is decomposed with
I formation of CO, and XH. ; if the decompoHiug agent be an acid, CO, is
I giTOi oS, and an ammoniacal salt remains ; if an alkali, a carbonate ot the
I alkaline metal remains, oiid Nil, ia given off. Upon this decomposition ore
baaed the proceHses of Fleintz and liagsky. Bunaen, etc.
Urea forma dolinite compoumhi, not only with acidii, but also with trer-
tain oxides and s-dts. Of the compounds which it forma with acUis, the
most important are those witli nitric and oxalic acids.
Vrea ni/ro/tf— CON,H,,HNO, — is formed as a white, crystalline mass
wheu a concentratod solution of urea iH treated, in the coUf. with IINU,.
It is mucli less soluble in H,0 thou is urea, espeoially in the preaenoe of
an excess or liXO,. It derompoeea the carbonates wiU] libemtion of urea.
If a solution of urea uitmte be evaporated over the wat«r-batb, it is de-
compoacd, bubbles of gas being given off beyond a certain degree of
concentration, and large crystals of urea, covered with smaller o&e« of
KA nitrate, separate.
Vrea oxalate — 2C0X.H .H^C,0, — sepiUTites as a fine, crystjilline powder
m mixed aqueous solutions of urea and oxalic acid of sufficient con-
oentratioD. It is acid in toate and reaction, less soluble in cold H,0 than
the nitrate, and less soluble in the preseuco of on excess of oxalic acid than
io pure H,0. Its solution may be evaporated at the temperature of the
water-bath without Kuff^ring dooom[>oHttiou.
Of the compounds of urea with oxides, the most interesting are those
u with mercnric oxiilo. three in number :
" a. (.'0N,H,.2H^'0 is forraetl by gradually oilding mercuric oxide to a
solution of urea, heated to uecir its boiiiug-poiiit ; the filtered licpiid. on
stAniiing twenty-four hours, deposits crj-stalUno crusts of the above com-
position.
fi. C0N,H.,3HgO ia formed as a gelatinous precipitate when merciurio
chloride solution is added to a solution of urea containing potassium
hydrate.
254
MANUAL OK CHKMI3TUY.
y. CON^,,4HgO is formed fts a white, amorpbous precipitate vhca
a diJuto soIutioD of mercuriL* nitrate is gradually added to a dilute alkft*
line solution of urea, and the esoeas of acid neutralized from time to
tirao. A yellow tinge iu the precipitate indicates the formation of
mercuric subnitrate after the urea has been all precipitated (JUebig's
procGsa).
Of the compounds of urea with KUfo, ihat with aodiom chloride is
only one of importance :
C0NjH,,NaCl,H,O.— It ia obtained in prismatic d^stals when
tiuua of equal molecules of urea and sodium chloride arc evnporated to-
gether. It is deliquescent and very soluble in water. Its solution, when
mixed vaith solution of oxalic acid, only forms urea oxalate aft«-r long
standing, or on evaporation.
PnvmoLouY. — Urea ia a constant constituent of normal mammalian
blood and urine, and ia the chief product of the oxidation of albonunotd
substances which occur in the body ; the bulk of tlie N assimilated bom
the food ultimately making its exit from the body in the form of urea
in the urine.
The determinations of the amount of urea in the blood and fluids
other than tlie urine are, owing to imperfections in the proceBaes of analy-
sis, not as accurate as could bo desired, the error being generally a miniui
one. Some of tho more prominent are given iu the following table :
QDAirarrr of Vbea ra Pabts per 1,000 m AimtAi. Furnw other Taur
Ueu-'s.
KocmU bkMd-ilat DW-O BS
DotiBitl bload-biiiMa O.S -11,4
VMVMlUanl— haiDui 0.11
HoraMl Uood— haiiHa 0.14-0 IS
KonwIMnod— tinBwn ptemUd i*.ttM).«t
Moniul Mood— bniiu>n toUl , S7
Bk»d at do* twfora D«pluo(MaT O.SlM>.8S
BIoxl urdoii, ihmu boun kfUr nwphratam J D jli-0 B3
Bknl of iliift, twrttt^-fleren bumaftar iwpbnitniuy X. 0(^.1.7(1
Hntnui hkhiii In choiBni S.4
Jluown blood In t:lw)M» 9.0
Unnuii biwdtu angttl'V »0
Lyinjita— iloB U 1«
iJtmph—aaw , O.ltt
CvrW— oow 0.19
Mdk H
Ballra 3A
BUf O.W
PloLdarMvltH O.IB
PMvpJndon 39
rwwttUlm O.HI
Himk.
0«Btt«V.
Plotid. .
OrMMBt.
Ur^lHutt.
VuU.
CbolvaU
Bn«bt * a»blfl«tgA.
Wurti.
WurlB.
WnrtL
PhMTd.
PtcuiL
FtowA.
Pontn.
PUmid.
The quantity of urea contained in human urine under various circum-
stances of health and <lise&8e has been the subject of a groflt number of
investigations, and a determination of the amount roided in a give-n case
ia frequently of great importance to the physician, as indicating the
amount of disas-similatton of nitrogenous material occurring in the body
at the time. Under normal conditions, the quantity of urea Toided in
tweuty-fuui- linurs is subject to coaaiderable variatious, as ia shown iu the
subjoined table :
ATnryss op CARsomo ACn>.
23;
Axovyrt of UasA is Hl'uan Urdie — Nubhai.
Onun* la tnt&l
nrliM of
H
boon.
MUIoa.
UiUoD.
Boymood.
SlilloD.
HiUoa.
BojmoDd.
Miiloo.
BcneUoa.
28.053
Lecaao,
sa-89
Neubaoer.
32-43
Kenier.
»9
VoffeL
51-02
Fimaqao.
SB-tH
Fraoquc
24-28
Franqua
10
Frauque.
an
Lecnno.
19. lift
LecaiHi.
Sft-3S
Qiiinquftod*
20-23
Qninquasd.
0.0;f-0.(>4 Qainqaond.
0.13-0.15 Qnuiquuid.
0.3 -02AQuiii<|u«od.
0.S -0.04 Qaiaqund.
4.505
LeooDU.
13.471
Lecanu.
8-13
Muley.
0-0
iUrlej.
pMWpor
LuDu.
Uriaewf »p k' 10** 2 »^
UtiMof ap. gr. lOll.G ll.au
Urmeof «p. pr. 1010.0 18.58
Utlaeof «p. gr. 1026.0 3S.B0
FrioBof tp. gr. Iim.7 9ft.70
VtiatQtgp. RT. I02H.0 27.08
Uria«of 8p. gr. 1030.0 31.77
Urina of adnlt mata (arerage) tI0.0
Urine of adult male (averaga)
UtiB« of adull male <aT«ng«>. 2$-^
Urioe of odatt male (averag*)
rrine of adult ma]« (av«rag«). 3S.8
CriDt? of ndult mole-, auirual food ..>• .*•■
Ulioe of adult male, mix«d food
Uhue of sdult male, TOgetalilo food
Urine of adult mal«. nou-uitrog«niz«d food
Urine of old men. b4-W ]r«an
Crina of Adult female (aTSnga)
Urine of prt-^aut female.
Urino of fem;i]e, 24 honin af t«r d«IiTer;f
Untie of iuf&nt, drat day
Uiine of infant, Rfth di^
Uruie of iufaiit, eighth day ....
Urine of infitnt. flftoeoth day
Urint! of child four jearR old
Uriite of child eitfbt years old
Urine of lioj (-ightt^en mrjnth.4 old ...,,.,
Uxine of girl eighteen montha old
The variationa ore produced by :
(1.) Age. — In new-bom oliildren the eliminfttion of urea is insig-
nificant By growing children the amount voided is absolutely less than
tlut dischurgiMl by lulults, but, relatively to their wei>{ht, cousiderably
greater ; thus, Hfu-ley gives the foUofting amounts of urea io grams for
each pound of body-weicht in twenty-four hours : bny, eighteen months,
0.4 ; girl, eighteen montos, 0.85 ; uau. tweuty>seveu years, 0.25 ; woman,
twenty-seven years, 0.20. During adult life the wean elimination of urea
roniains stationary, unless modified by other causes than age. In old age
the amount sinks to below the absolute quantity discharged by growing
children
(2.) Sf-x. — At all periods of life females eliminate lees urea than males.
The proportion given by Beigel differs slightly from tliat of Harley, viz. :
one kilo of male, 0.35 grains urea in twenty-four boiira ; one kilo of female,
0.26 grams. During pregnancy females discharge more urea than moles ;
Tery shortly after delivery the amount sinks to the normal, below which it
piMses during lactation.
(3.) /borf. — The fjuantity of urea eliminated is in direct proportion to
the amount of N contained in the food. The ingestion of large cjn.intities
of watery drinks increases the amount, and a contrary etTecrt is produced
by tea, coffee, and alcuhoL With iusufHcient food the excretion of urea ie
diminished, although not arrested, even in eitremo starvation.
<4.) Exercue. — The qucKtiou whether the elimination of urea is in-
creased during violeut muscular exercise is one which has been the subject
of xoany observatioos and of much disoussion. An examination of thftj
25G
VAXTTAl. OP CITEMISTBT.
various results shows that, while the «icretion of area is slightly gntto
•luring' vloleut exercise thrm duriDg pericMlB of rest, that increnee in so in*
signilicant in pomparison to tbo work done, and, in some iDStnncca. to Uie
loKs of Ixidy weight, an to render the (WHiimption thut musrular forct ii
the result of the oxidation of the nitrogenized conHtituents of niuade in*
probable. (See Ganigee : " Fhjaiologic^ ChemiBiiy/' L, pp. 386-4U1, (orb
full review of the subject.)
The percentage of urea in the urine of tlie same indiTidual is not the
same at different timea of the tla^. The niinimum hourly elimination it
iu tlie morning hours ; an increase begins iounediately after the priucipil
meal, and readies ita height In about aix hours, when a diminution sets in
and progresses to the time of the next meal. Gorup-Beaanez gives h
curve representing the hourly variations in the elimination of urea, which,
reduced to figures, giveti the following :
UtM
Vrtm
Vtm
■mt.
In
aoiir.
In
Boar.
m
gnoM.
cnnc
moi.
1.0
3.8
13-1 A.M
1.1
l.(V
8.1
1-2 A-K
1.9
1.4
3.8
l.«
11A.M.-ISU
1.3
7-8P.K
3.0
1.8
12 M-lP.M.
1.8
8.S
4-5 A.M
1.9
I.B
3.0
0-8 4.M
1.6
2.1
10-11 P.M
2.0
0-7 A.M
1.8
S.8
3,3
7-8 A. «
UI
The total of which, however, represents a quantity above the nontud
The absolute amount of urfa eliminated in twentv-four hours is in-
creased by the exhibition of diiiretic!!i, alkalies, colcliicum, tiu-pentine,
rhubarb, alkaline silicates, and compounds of antimony, arsenic, wid phoa-
phoruH. It is diminished by digitalis, calTein, potassium iodide, and lead
acetate ; not sensibly afiected by quinine.
raOxoloijicallij the quantity of urea voided may be either iocrenaetl or
diminished : an increase above the normal indicating an increased oxicla>
tion of nitrogenous material, or the retention of the urea formed within
Uie l>ody ; and a diminution a deficient oxidation of the same class of sub-
stances, or, as is frequently the case, a diminution in the supply of nitro-
gen to the body from loss of appetite or power of assimilation.
In acute febrile diseases both the relative and absolute amounts of
urea eliminated augments, with some oscillations, until tlie fever is at its
height ; tliere is, however, no constant relation between the amount of
urea eliminated and the body tempeiBture. During the ]>eriad of defer-
Tesceuce, the amount of urea eliminated in twenty-four hours is diminished
below the normal ; during convalescence it again slowly inci-eases. If the
malady tenninate in death the diminution of urea is continuous to the
end. In iutermitteut fever the amount of urea discharged is increased on
the day of the fever snd diminished during the interval. In cliolera. dur-
ing the algid stage, the elimination of urea by the kidneys is almost com-
pletely arrested, while the quantity in the blood is greatly increased.
When the secretion of urine is again established, the excretion of urea
is greatly increased {60-80 grams :^!)26-123ft grains a day), and tlie
abundant perspiration is also rich in urea. In cardiac diseases, attended
J
AMIDES or OAKBOinO ACID.
957
wiUi respirator; difficulty, but witboui albumiimria, the eliminatioii of
urea is tliminisbed aaii that of uric acid increased. In nephiili^ atteuUed
with albuminuria, the elimination of urea at first remains normal ; later
it diminiuhes, and the luva, accumulaling in the blood, gives rise to
urarmic poisoning. The quantity of uroa in tbo uriuo ia also diiuinishod
in all diseases attended with dropsical effiisiona ; but is in<Tease<l w))en the
dropsical fluid is reabsorbed. In true diabetes the amount of urea in tin
urine o/ twenty-four hours in greater tliau normal In chronic diseases the
elimination of urea is bc-Iow the normal, owing to imperfect oxidation.
AiciLmcAi. CuAEACTUES. — To detect the presence of urea in a fluid, it
ia mixed with three to four volumes of alcohol, and filtered after having;
stood aeveral hours in tiie cold ; tlie filtrate ir evaporated on the water-
batli, and. the rcuiduo extracted witli strong alcohol ; the filtered alcoholic
fluid is evaporated, and the i-eaiduo tested as follows:
(1.) A small portion is heated in a diy test-tube to about IfiO"
(320° F.), until the odor of ammonia in no longer observed ; the residue ia
treated with a few drups of caustic potassa so-
lution and one drop of cupric sulphate solution.
If urea be present-, the biuret resulting from
ita decomposition by heat causes the solution of
the cupric oxide with a reddish- violet color.
(2.) A portion of the residue is dissolved
in a drop or two of 11,0, and an equal quantity
of mloHfug concentrated HNO, added ; if urea
be present in sulTicient quantity there api>ear
white, shining, hexagonal or rhombic, crystal-
line plates nr six-sided prisma of urea nitrate.
(3.) A portion dissolved in water, aa in (2),
is treated with a solution of oxalic acid ; rhom-
bic plates of urea oxtUate ciystjdlize.
Detkrmtnatios op Qu.^xTrrT of Ubea nr
TTkine. — It must not be forgotten that^ in all
auantitative determinations of constituents of
\e urine, the question to be solved is not bow
much of thnt constituent is contained in a giv-
en quantity of urine, but how much of that sub-
stance the patient is discharging in a given
time, usually tweuty-four houi-a. Quantitative
determinations are, therefor, in most cases,
iKirren of useful results, unless the quantity of
urine passed by the patient in twentv-four
hoars ia known ; and, in view of diamal van-
ations in elimination, unless tlie ui-ine ex-
amined be a sample taken fi-om the mired
uritw of twenty four hours.
Th^ ^TX)OBm gMng IV riimI mn^nte n«u1U !■ Itikf. of Ttnaapn,
In whkh the nr«i U d^compo-ml inio rn. ^nA NH> th* lotmtrr i-t
whkh U valiibaA Mteriuia OKrlKiDiiU'. Uli(ijitiiiMU-ly. thU proor**
nqalrw ma oxpandJInra nf tlnrn «n4 » dorrw u( skill lii nianlinil*-
tlon, wMcrt) render Iti KppHc«ttton povlble •vtlj In a w«ll«pptitnled
UbonU(i«T.
A proooi* whtoh !■ daHtrilMd In iKwt trat-bonk* apoo Drln»r* MiAljtrtii, uid wtiloh 1* mnnh ium) t9 phj-
■IciMM. tolhat of Lleblf. ABlfalii mMhod tiuap. hmrvvn-, whldk oonfaUna mum MMRVa ft pm>r Ihanuif
OtlMT, AMd mt It ran np\j h iniuir I.1 fUild KpprDiirnKir); airrMvt roMilU bf ft verj CBrrfiil eliBiinmUiim, M
far M pMttlhl*, «< tbnM ilof^-K it U tiotonc v>hlcb i* utiiptn.! to ttewwaf Ui« rli;iU)tMn.
rrotaUy u» noaC wUintiKlatj prov«M IB lb* toadi of IIm ptMtMoiMr t* tbu ol HttrMr. bM*4 ipon
th* riMCcion, to wMcb ftUmtlon wHllntoaiM b j Knop, ot Ui» klkaUn* bn)«)>nMnltM nprmnn^fp. IW);
Birinc. h^wamr, DMrieh'a ■|Ipllr■tlB^ or Um m>on rinpla wodlflostlafi Hgiwtal \kj Rnmpt, la piMM of
Uut af Harner. The umuBtiM (Fig. 87} ooMlli of » bnraUe at KMH co. otpMrttr, InunarMd hi ft tall
18
Fio. ST.
S5S
M AH UAL OF CUBMISTRT.
Table or tbz 'Wkmbt of Ose
700
793
7M
795
1.14H
788
730
738
TM
T36
T3B
7i0
74S
i
144
no*
1
i.isn'i.tsm
1.1409
l,t40R
M4»
I.Kw'l.lBRl
i.iws'i.ie»
1 in- • •'"
•I
Il-
1 I»«t l.l-OI) l.l%9 t.llM LHlD 1 1447
l.HI'J 1,1011
l.lJMa t.l&T4
1 ;■ rv
a
ls-
i.txffii.imi i.ia.>i i.iusii.iaM,! 13W
1.14W 1*14W
l.HVI \ 1U3
1 :.■ . . -.'J.
D
!»•
I itRT'i.iaiu 1.13&1 i-iwali.tm MSU
l.lST7il.]4VS
1 144U i.uta
1 1I>).. 1 ^^'» 1 iM
"m
14-
I n3K turn 1 I'jDu i.i«iti;M«a 1 im
MSM t iae7
i.i»t>a 1.14W
1 14U11.I4CBI1.1M1'
B
1(1-
1.106R 1,1117 I.ll*»iMIM l.ISn M»«,M»74iI,ia06
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B«ran«tfle pnatvrv lii nllllitittn*.
ItUMrrtlniVrrfltMwItbwatar.mdKiiwofU'llnMieb ■ ««r u toailtnll at being nlwd or loawnd •tdtMVR.
TIM upper «n>l ut a>« burriM MwnBHiMCMM wtUt lb* •votaOan bont* a, wbicb bw « UfMcltj oT 7B cc. tf
mnui* of k rubber uib«L
T1i« m««nt rfnoiM-l !• inM]«> ■> folKxra: 97 co. of apolotlon of eaiuUo Mdft, mnd« by tltMrfr lf WC
ynOM NaUO tn nu l-.l-. H^O, are bfuu«)it Into k icImBkBtvppvral boUla^ S.5 ft.c. bnttnJfHr an adiM, U(
nJimiVB ifaalwa, and dUulnl with int«T la ISO c.i.'. Thp chihIIc ■■!» wtallaii may >« Jir^i*. ta • ltlM»'
atoppcrwl bout*, »bca«aUip|vr U wril paraRlnM, liat the tnlTtnre tnnat bonkde np m* rKiB)i«J.
T» coAduct « ilnRiDlaailoti, attont Vi cx.ot lUf b\po»n)a)li*«olutlon arvplaoiol Ui tbrbotUvoi Icb
«f Itw orin* to bo uaaliMd U* filan^ la the ahcrt UaMUba, wlllch U tbcn iiilruauonl Uito iIm poAM
dMMni In tba fiitura, cantatevnul tliac uo arin« iw.-a|MC Tlwcarfc wlib It* tltUnipi U Llim Intmlumd, 0«
piBOb mok A Dpoinl, Mul aliMed again wlim Ibr levirt of IklllU la Uie IninlUt U Ibo (MfM aaihaiUi ili
sjrllDdCT. l%a itMOBipMlng TtMKl g ia tbeii IncUncil to that Uh urine and hnxilitxMnlM •otntian ati;
Uw dMocapoatUoB btcbu at oner, aod the crolved K pa w aa Into th* t>nTMt«, which U rslatNl hvn tiwm <•
ttsw, ao M lo kMp th« at«nial and latmul l«vH* of wat*r ftboot aqTisl ; tba CO, fnnnral la malM4 bp
tba aoda atilaUoB, In almul an hour (tli« deoontpa4ltti4t la nawUlj «omp1oU la llttcvn inbuitn, b«t II la
wdl to wait an bour^tbu hi-lk:)tt Umj adjiialaa tlini tJia liiDtr aiid oabr tovaUof wairr an fxmt*ijrtm,
■Bd dw grviliwClim la rend, while tbaManillng of Ibc iNumirter and Ibmnonctrr am noud n UtitMK
tUM.
In cftlcalatlng tba [>an«Bt«iro i>r uma rruoi tbv toIimm of N oMalnoit. It la e«P«nllAl ihU m eamttien
ahoiM be inailB fur iliffnrncui of teniiiriutur0 aiMl iiiwwira, Wltbiiut «bSi-b Um tnalt Tttita mtt ordinan
noiple of nrlnr aajr ta« rldaud branMTOr of tenparaenl. If, howrvn. tlie IrnipmJim and banuwlrk
pmanra have boMi BoWd, tbi cMTOCtiao U tvPdtij nad« bj tba nar of th« pm«1lnx lablr, aampau« tj
IlWtrlth,
In tbo K|Dan of Uia babte ta wMab Um hariaairtal lino vt th« obMr<<«i1 tanporatnre o r w wa tba tMtkal
tin* ft thr nbaarrad banxnetrio prmeiv trUt ba Ivand tb« w«-lf ht. In titOHgnuna, at a r.a. ol S ; tbim malt^
plird bf tn« obwrvo rt Tolum* «f K. glVM tba waiabt CrI N pro>1uc«irl by tho deooHipcaiUeti ol the iin« om-
taliMl m b CO. urine. Bal m ■} pauta nrui j-lctd as to^^ ^' 1^' ivrlKtit "f N. Ri»ltiptM by t-lA. (Ctw Ibf
wHffht uT ornt In itiilltirmina In 5 ce. nrinc Ttiii <|i]anilty, raitttlpllni l>v twii-e the aniatuit of nrina (■ M
lM»n,anitdlvlil<«Ilk; lO.OttO, iilvM tbs amanm ol nrMHlniliiaica In S4 hour* In graou. If tlw nndtbt
dcafrvd In ftndnathr amount In Brain* iiniuldp1l4vl bj 1V494.
Arvmftte.— S c.e. orino dMvmpofMt : batvMirtrr = TtS mm : ttttrwtvmHet b 1i:« : bnmUi r«*dtiir ba>
foradaeompoaUlons! Itua: Mm* after dPoainpiMmnn = ttl6: cp. N wll««d = ."».«. rrom tiM laWo
1 e.C 5. M 10- «Bd TSB nun. BP. wriithal.lMn, Thr piUlcnt paiMv ISiXIc.v. WllW lb t4 kOUa:
81,fl ■ l.lUe = »IK88It= nilllgr. H In A co. nrtna,
88.100 N 914 = TS.SDflS = mntiffr err* In S r.o. uria^
T&nn - OKW
»I,UUU
fS.SIO = gnun* area In 24 himn.
t9.51» > 15.484 = 803.99= gnltianrM la a4lM)Wi>.
In twins ttilii pmxm it U wctl to have tha iir«K wJaHaa aa near the ttnii^tb nf on* p«r otet. aa i
tfatnrfur, ir the mine baroni-rntmiiil, n •farnildbadltidad. Bvan wbL-n rarvfully c^aMlnctodi, tbvpfoma I*
Boi itnctly an-iiracr ; i;r«nticili; and cHc *e\A ar« aho ducompqaaii iHtl) tlbrraiioti of N. thn* cwnalng a •llitbl
plaaaror: on tlu) nth«r hand, a TnlniivcrrM-iacaBacd Irr tb« fael, thai In thr daeompoidilMi of nr«* by the
fc y potromllo, tho Ibcvrrtkal rr»uR It nvtt oljtained within aly>at tight per Mnt. In arln». Tboae erroi*
Bay banoWMtoaHT'-atFitnit bTinaUiHyinu Ihe rmilt b)i ].0t4.
A prtieMa which dam n^C jlriil at ai<cniate ntiitOi aa Uir pntwdlnfr. ImC which U ni«tv oaay ot apF"*
oaUon, ia that nt Powlet, Ixutxl npi'n thp Im* iif ■)>. (,t, of thm iiriiiii afVr Uin (Ifxnaippaitlon of ita utrmbj
hTpnchlorIt*'. To apfnly thl» ni«tlii<d Ihr "p. irr. i>f Ihr iirinr I* rsrnriilly ilrti-rminml, a* wpll *■ ibat ttt tba
llq. ndjB chloriutai 4S<ialbb>J. Use *olnine of tbcnrlnu t* ihvn mixed with exactly aovco votunMof Um
COaJPOtTXD VRXA8.
Ctbto Cextimktre of KrmooEM.
Ytf
MTU 1
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1 1619 I
I UW 1
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im
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^V Bannnetrle ^ t mmm In inUHnwcrH.
Uq. tni. chVir,, ftni). Ktrcr the tnt tIoIoicb el the n»»<,l»jii (■■• anbrfdad, th* nlztin* la ahklrMi from ttaw lo
Una faring *n huur, wiMn th« daoomptwltloa ia co w p tote : (b* «p. «r. a( th* niintm i» ib«a iMMrntiMd.
JU Uw r— ««lni) bcfflna iiMxntaMoaBly wbra th* mliM ■i>d rM|t«Ti( arc ralx«t. the »p. iir. of tbc mfitnre
•■M bv ^dnUlcd bf BiMliis logvtiMr ooo* Ute ap. kt- o( Ul" aliac mrl arvxii Unim Ui« •(!- Kr. of Uif Irq.
■flfl. Alar., and dividing tlit-uiul (17 vlRht. From tboquMienl hu I'blkiiu-J tlir >|>- RT- »' thf* miilun.- BfUr
i1«»miij«m1iIim Ib MtblnKUd : •very doicim of kas In ■!>. |[r. IndlrMea O.TfUl |ir*>ni of una In 100 cc, nf urlit*.
Tfe« ap. cr. dfMfinlWtlDns ma« all bn mmila at the mme traipermtnrT ; ani] tbal (A tli« nUairo onir trbm
the «roluttoB of «u liu OMaad *ndntr.
Finally, when it is only desired to clctcnmno whether the urea is
greatly in excess or much below the normal, adrantAge may be taken of
the formation of crystals of urea citrate. Two samples of the urine are
talceu, one of 5 c.e. and one of 10 c.c. ; the latter ia evaporated, at a low
temperatore, to the bulk of the former, aud cooled ; to both one-third
volume of rolorlesa HNO, is added. If crystals do not form within a few
moments in the coucentratetl sample, the quantity of urea is below the
normal ; if they do in the uncouceutrateil uatnple, it is in excess. In using
this veiy rough method, refnwtl must be had to the quantity of urine
passed in 24 houra ; the above applies to the normal amount of 1200 c.c. ;
if the qnantity be greater or less, the urine must be concentrated or
dilated in proportion. This method cannot be used if the urine is
JUUUDOUS.
Compound Ureas.
These compounds, which are exceedingly numerous, may be considered
m fonned by the substitution of one or more alcoholic or acid ratlicals for
OD6 or more of the rcmniuiiig U atoms of urea.
Those containing alcoholic radicals may be obtained, as urea is ob-
tained from ammonium cyanatft, from the cyannte of the corresponding
compound ammonium ; or by the action of NH,, or of the componnd
ammonias, upon the ci'anic etlier*.
Those contjiininj; acid radicals have received the distinctive name of
ureids ; some of them are derivatives of uric acid^ which is itself probablj
260
MAirtTAL OF CKKKISTRY.
an nreid. We will limit oar consideration of them bodies to mie add laA
the ureids obtained from anil relateil to it
Uric acid— i^iWiicocK/— C,HN,0,H,— 168.— OocuBKCfCR.— So br u
yet known, iiric acid in eicluaivcly an animal product It exists in Um
urine of man &nd of the CAmirora, and in that of the herbiron «b»u,
during early life or storrBtion, tliey are for the lime being caruivora ; as a
constituent of uriuiuy calculi ; and yery abuudantlv in the excrcmeDt a(
serpents, tortoises, birds, molluecB, and insects, also in guano. It is prce-
ent in very small quantity in the blood of man, more abundantly in tint
of gouty patients and in that of birds. The so called "rbalk-etonai''de-
poeited iu the joints of gouty patients ore composed of sodium urate. It
also occurs in tho spleen, lunps, liver, pnncreji.% brain, and muscular fluid.
pKEpiRtTLox. — Although uric acid may t>e obtained from calculi, tuine,
and guano, the source from which it is most readily obtained in a state of
purit}' is tbe solid urine of larce serpents, which is composed almost
entirely of uric acid and tlie acid urates of uxlium. potassium, and un-
monium. This is dried, powdered, and dissolved in a solution of potasmnm
hydrate, eontaiiiitig one jhu-I of [M>tash to 20 of water ; the eolutioD n
boiled until all oilor of Nli, has disappeowxl. Through the filtered solu-
tion CO, is passed, through a wide tube, until the precipitate, which ni
at first gelatinous, has become granular and sinks to the bottom ; the add
potassium urato so formed is collected on a filter, and washed with cold
H,0 until the wash-wat«r becomes turbid when added to the first filtrate;
the deposit is now dlasolved in hot dilute caustic potassa solution, and the
solution filtered hot into HCl, diluted with an equal volume of H,0. The
precipitated uric acid is washed and dried.
Pboperttes — Phijsicai.—Vric acid, when pure, crrstalliees in smalL
white, rhombic-, rectangular or hexagonal plates, or in rectangular phsnii;
or in dendritic crv-stals of a hydrate, C.H.N.O.,2H,0. Aa crystaUiaed
from nriuR it is more or less colorcil with uriimn.- pigmenta, and fi
rectangular or rhombic plates, usunily with the angles rounded so
form lozenges, which are arraiige<l in bundles, daggers, crosses, or den-
dritic groups, sometimes of considerable size. It is almost insoluble in
H,0, requiring for its solution 1900 parts of boiling H^O and IS.IKK) psrta
of cold H,0 ; insoluble in alcohol and ether ; its aqueous Folntion is odd
to test-paper ; cold HCl dissolves it more readily than H,0. and on evapo-
ration deposits it in rectangular plntea It is ta.steless and odorlesa
Chemicat — When heated, it is decomposed without fusion or sublimi-
Hon. Its constitution is unknown. Heated in CI it yields eynnuric add
and HCl. >i\*hen CI is passed for some time through H,0 holding uric
acid in suspension, alloxan, parabanic and oxalic acids, and ammonium
eyanate are formetl. Similar decomposition is produced by Br and L U
is simply diaaolr&l by HCL It is disaolved by 1I,S0, ; from a hot soltt-
tiou in whi^'b a duli<iucsront, crystallino compound, C^li.N.O,, 4H,S0 is
deposited ; it is partly decomposed by H,S<\ at 140" (284 F.>. It iii»-
solves in cold HNO, with efierveecence and formation of alloxan, alloxan*
tine, and urea ; with hot HMO, parabanio acid is produced. iJolutioBS of
the alkalies dissolve urio acid with formation of neutral orstea. Uric acid
is dibasic
Ammmtium uratei'. — The neutral salt. C^H.N.O^fNH.) ,'is nnloMnnt.
The acid salt, C,H,N.O,(NH,), exists as a constituent of the urine of the
lower animals, and occurs, accompaui.ing other urates and free uric add,
in unnarr sediments and calculi. Sediments of this salt are rust-yellow or
pink in color, amorphous, or composed of globular masaes. set with pro-
COMPOUND VREA8. 86'1
ieoting points, or elongated dumb-bells, and are formed in alkaline urine.
It is very Bpariugly tioluble in H,0 ; soluble in warm UCl, from which
■olutioD rry$t»lliue plates of uhc acid are deposited.
J'o{a*ifium urales. — The neutral salt, C\HjN^O,K,, ia obtained when a
•olntion of potassium hydrate, free from carbonate, is Baturate<l witli uric
add ; the aolutiuu on c<mceutratiuu depomt^ the salt in Eue needlea. It
ia eoluble in 44 parts of cold 11,0 and in 3o porta of boiliut; U,0. It is
alkatioe in taste, and abeorbs CO fr^m the air.
The acid salt, C,H N,0,K, is formed as a gnmujar (at first gelatinous)
precipitate when a solution of the neutral siut is treated with CO,. It
dissolves in 800 parts of cold H,0 and in 80 parts of boiUng U,0. The
occurrence of potassinm urates in urinary sediments and calcuh is very
exceptional.
ivdium uratet. — The neutral salt, C^H^N^O^a^ is formed tmder simi-
lar conditions as the corresponding potassium salt It forms nodular masses,
soluble in 77 parts of cold H,0 and in 75 of boiling H,0 ; it absorbs CO,
from the air.
The acid salt, C^H,N,0,Na, is formed when the neutral tuUt is treated
with CO^ It is soluble in 1200 partn of cold H,0 and in I2o parts of
boiUng H^. It occurs in urinary stwlinients and calculi, very rarely crys-
taQsied. The arthritic calculi of guuLy putientu are almost exclusively
composed of thia mdt, frequently beautiftilly crystallized.
Valcium uraim. — The neutral salt, C^H,N,0,Ca, is obtaineil br drop-
ping a solution of neuti-al potassium urate into a boiling solution of cjU<
cium chloride until the precipitate is no longer redissolvcd, and then IkuI-
ing for an hour. A granular powder, soluble in loUO parts of cold 11,0
and in 1440 parts of boiling HX).
The acid salt, {C,H,N,0,),Ca, is obtained by decomposing a boiling
solution of acid potamium urate with calcium chloride solution. It crys-
tallizes in needles, soluble in tiOS parts of cold H,0 and in 27(> parts of
boiling H,0. It occurs occasionally in urinary sediments and calculi, and
in "ch&lk-^onea."
Lithium uratet. — The acid salt, C,H.N,0,lji, is formed by dissolving
urio acid in a warm solution of litbiiim carbonate. It crystallizes in
needles, which dissolve in 60 parts of H,0 at 50'' (122" F.) and do not
separate when the solution is cooled. It is with a view to the foiumtion of
this, Uie most soluble of the acid urates, that the oompounda of Uthium
are given to patients suffering with the uric acid diathesia
pHYsioixKiv. — Uric acid exists in the economy chiefly in combination as
ita sodium salts ; it ia oooaaionally found free, and from the probable
method of il« formation it is difficult to understand how all the uric acid
in the economy should not have exist^nl there fi'cc, at least at tlie instant
of its formation. It can scarcely bo doubted tliat uric acid is one of the
products of the oxidation of the albumiuoid substances — an oxi<latioQ in-
tennediat« in the production of urea : luid that consequently diseasee in
which there is an excessive formation of uric acid, such as gout, have their
origin in defective oxidation.
In human urine the quantity of uric acid varies with the nature of
the food in the some manner as does urea^ and in about tho same pro-
pcniion:
Anlwlftwd ; T1.5 l.« Vt%
KIsodfcod "I" o.:» »^
TiOtebte fund K.U 06U nid
MoibnUnvHU^l foal ».« 0.34 «7.0
36a
MAXUAX/ OF CIJEMI8TRT.
The mean elimination of una ftcid in the urine is from one -thirty-fifth
to one-«ixtieth of that of urea, or about 0.5 to 1.0 g^ram (7.7-1&.4 gniiu)
in 24 hours. With a atrictly ve^^etable diet the elimination of 24 boon
maj fall to 0.3 gram (4.G grains), and nith a surfeit of animal food it mikT
rise to 1.5 gram (23 grains), 'fhe hourly oliminaliou is increased aflct
meals, and diminished by fasting and by muscular and mental activity.
Deposits of free uric acid occur in acid, .concentrated urines. In gout
the proportion of uric acid in the urine is diminislicd. although, oving to
the smiUI quantity of urine parsed, it may be relatively great ; daring tba
paroxysms the quantity of uric acid is increased, both relatiTely odJ
absolutely. The pn^>ortion of uric acid in the blood is invariably ia-
oreaaed in gout.
Akalytical Chakactebs. — Uric acid may be recognized bj its CTjst«lli]]«
form and by the marexid ttist. To apply tluB test the substanoe is
moistened with HNO,, vhich i.s evaporated neaily to dryness at a low
tenqierature ; the cooled residue is then moistened with ammonium hydrate.
If uric nci<l be present, a yellow residue— sometimes jiink or rt*d when the
uric acid was abuudont — remains after the evaporatiou of tlie HXO„ and
this, on the addition of the alkoU, assumes a rich purplish-red color.
To detect uric ncid in the blood, about two drachms of the senun are
placed in a flat glass dish and faintly ucidulateH.! with acetic acid ; a Teiy
Eue fibril of Uuen thread is placed in the liquid, which is set aside sad
allowed to evaporate to the consistency of a lelly ; the fibril is then removed
and examined microscopically. If the blooii contain uric acid in abnonusl
proportion, the thread will have attached to it crystals of uric acid.
QuASTrrATivE Determwation. — The best method for the determinotioD
of the quantity of uric acid in urine is the following : 260 c.o, of tbe iil-
tered urine are acidulated with 10 c.c. of HCl, and tlie mixture set aside
for 21 hours in a cool place. A small filter ia washed, first with dilute
HCl and then with H.O. dried at loO^ (212* F.), and weighfvd. At the
end of 24 hours this filler is moistened in u funnel, and the crystals of uric
acid collected upon it (those which adhere to the walls of the precipitating
vessel are beat separated bv a small section of rubber tubing jfassed over
the end of a glass rod, and used as a brush). No HO is to l>e used in
this part of the process, the filtered urine being {Hissed tlirough a aBtxmd
time, if this be required, to bring oU the crj-st^Us u]k)u the filter. The
deposit on the filter is now washed with 35 cc. of pure H,0, added in emoD
portions at a time ; tlie filter and its contents are then dried and weighed.
The ilifferenoe between this weight and that of the dry filter alone is Uie
weight of uric acid in 250 cc. of uriue. If from any cause more than 36
C.C of wash-water have been used, 0"*'.043 must be added to this weight
for every cc of extra wash-water.
If the urine contain albtimen, this must firat 1)e separated by adding
two or three drops uf acetic acid, boating to near 100"* (212" F.), until the
coaculum becomes flocculout, and filtering.
Ureids derived from Uric Aold.— These eubatances are quite numer-
ous, and are divisible into ureida, diureids, triureids, and unrmic acids, ac-
cording as tboy ore formed by substitution in one, two, or Uiree molecules
of urea, and according as the acid radical substituted docs or does not re-
tain a group COOH. Some of these substances require a brief mention :
^CO)" j
Oxalylurea — /^raianic acirf— (C,0,) ' J- N,— lll-ia urea in which
two atoms of H have beeu replaced b^ ik« bivalent radical (C,0,)", of
SUBSTAyCES OF tmSKOWN CONSTlTmOy.
K
oxalic acid. It is obtaiiied by oxidizing uric acid or eUoxan hy hot
AUantoin — C H^N.O, — 130 — occurs iu the allAntoic fluid of the cow;
in the urine of sucking coIvps, in that of dogs and cats when fed on meat,
in that of children duriug the first eight daja of hfe, iu that of adults
after the ingestion of tannin, and in that of pregnant vromen. It is pro- ^
duced artificially by oxidizing uric acid, su^ended in boiling H,0, with
lead dioxide.
It crvBtullizeH in small, tasteless, neutral, colorless prisms; spuriuglj
solablc in cold H,0, readily Boluble in warm H,0. Hented with alkalies
it yields oxalic acid and NH ; aud with dilute ocidR, allatttuno acid,
C,H.N,0,.
Alloutoln has been obtained synthetically by heating togotuer gly-
D^lic acid and urea.
Mesoxalylurea — Alloxan — C«H^,0, — 142— is a product of the lim-
ited oxidation of uric acid. It has been found iu the intestinal mucus in
a case of diarrha;a. It forms colorless crystals, readily soluble in il,0.
It gradually tnnia rod in air, and stnins the skin red.
Oxalurio acid — C^H.N'jO, — 132 — occurs in its ammonium salt, as a
nonual oonstituent, in smoU quantity, in humau urine. It may be obtained
by heating oxidylurea with c^dciuni catbounte.
It is a white, sparingly soluble powder, which is convertetl into nrea
and oxalic acid when boiltid with water or alkalies. Its ammonium salt
crystallizes in white, glistening, sparingly soluble needles. Its ready con-
versioD into urea and oxalic acid and its formation from oxalylurea, itself
a pi"oduct of oxidation of uric acid, render it probable that oxalurio acid
is one of the many intermediate products of the oxidation of the ultroge-
D0U3 constituents of the bo<Iy.
Dialurio add — Oxybarbituric add — C^H^M^O, — a dibasic acid, pro-
uced by reduction uf ullcxau. ^
Alloxan tin e—C,H,N,0,~is a substance crystallizing in small, brill-
t, very sparingly soluble prisms, produced by the action of reducing
agents upon alloxan, whose action is less powerful than that required to
convert alloxan into dioluric acid.
Mxxrexlde — Ammoinum p>irf>urcUe — 0,H.(NH,)N,0, — is produced
by oxidation of nrio acid, of alloxan, and of a number of other deriTstivci)
of uric acid with Hubtie<iu&ul cuutact of ammunium hydrate. It iu sup-
posed to be the ammonium salt of a h^iiotbetical and non-isoluted acid.
The ammonium salt is uf a brilliant^ but evouosceut purple color. (See
Murexid test for uric acid, p, 2G2.)
Hydurilio aoid— C,H,N,0, — is produoed as a yellowish, crystalline,
sparingly soluble powder by beating together glycerin and dialuric acid.
It is a strong dibnsic acid.
Vloliirio acid — C,H,N,0,- — is produced, along with alloxan, by the
action of nitric acid upon hydurilic acid. It forms small, readily soluble,
octahedrnl crystals. It is a strong mouobasio acid, whoso suits are brill-
iantly colored. %
^64 MAXUAL OF CltEMISTRV.
TRIATOMIC AIiCOHOIiS.
Series CUI,*t,0,.
Thare is as jet only one alcobol known containing b trivalent ndioiL
Thin is gii/ctirvi, wfaoso relAtion to the monoatomto and diatomic aloobolt
IB shown by tbe following fonuulfe :
CH,OH
HOH
i
CH,OH CH,OH CH,OH
Pntpaam. Propyl »lPoboL Prap^l glfcoU Olyecrio.
Glyceiia—Oh/cerinum {U. &)— C,H.(OH),— 92— was Erst obtained
u ft aecondary product in the mauufacture of lead plaster ; it is now pto-
daoed as a Ity-jiroduct in the manufaoture of soaps and of stoarin candlce.
It exists free in pjilm-oil and in other vegetable oils ; it is produced in
scnaU quantity durinj^ alcoholic fcrmeutatiou, and ia consequently present
in wine and beer. It is much more widely disseminated in its ethers, tko
neutral fats, in the animal and vegetable langdoma.
It has been obtjiined by partial syuthesin, by heating for some time a
mixture of ollyl tribromide, silver acetate and acetic scid. and saponifying
the triaoetin so obtained.
The glycerin obtained by the process now generally followed — the d^
compusitiua of the neutml fats and the distiUution of the product in a cur
rent of superheated stenm^is free from the impurities which coutnruinnt«d
the proiluct of the older processes. Tlie only impurity hbely to lio pres-
ent is wBter, which may be recognized by the low sp. gr.
Glycerin is a colorless, odorless, e^i-upy liquid, has a sweetish taste ;
Bp. gr. 1.26 at 15" (59" F.). AlUiough it cannot xisually be caused to
cri'stallize by the application of the most iutenso coU), it does so some*
times under imperfectly imderstood conditions, forming small, vrhite
needles of sp. pr. 1.2G«. and fusible between 7" and 8'*<44°.6-46".4P.). %!
It is soluble in all proportions in water and alcohol, insoluble in eUier and
in chloroform. The sp. p*. of mixtures of glycerin and water increase
xfiih. the proportion of glycerin. It is a good solvent for a number of min-
eral and organic substances [ghjcenteg and giijccrolai). It is not r<ilatile nt
ordinary ternperaturea "When heatetl,aportiondiatils unaltered at 275'^ -280"
(527''-53C^ F.), but the greater part is decomposed into acrolein, acetic acid,
carbon dioxide, nnd combustilile gases. It may be diKtillMl unchaoged
in a current of Bupcrheated steimi between 285'' and 315" (545°-699° F.).
Coucoutrated glycerin, when heated to IGO** (302'' F.) ignites and bums
without odor and witlinut leaving a residue, and with a pale-blue flame.
It may also be burnt from a short wick.
Glycerin is rAdily oxidized, yielding different products witli different
degrees of oxidation. Platinum black oxidizes it, with formation, finally, of
H,0 and CO, ; oxidi7.e<l by manganese dioxide and H,SO„ it yields CO, and
formic acid. If a layer of plyocrin, diluted with im equal volume of HO
be (lottted on the surface of HNO, of sp. pr. 1.5, a mixture of several acids,
is formed : oxalic, 2C.O,H, ; glyceric, C.H.O^ ; formic, CH,0, ; glycolUc,
C H,0, ; glyoxylic. C,H,0, ; and tartaric, C,H,(),. When glycerin is heated ^
mth potjisiiilun hydrate, u mixture of (lotasstum acetate and formiatfi is
J
XTUEBS OF gltcebht.
irodueed. "When glycerin, diluted wiUi 20 Tolntnes of H,0, ia heated with
Br ; CO,, brouiafom], glyceric acid, and HBr are produced. PhospUorio
uibydride removes Ihe olenienta of H,0 from glycerin, with formation of
icroleiD (see p. 224). A flimtUr action is effected by heating with H,SO,,
or with potassium hydroaulpUate. Heated with oxalic acid, glycerin ^^-ields
C30, and formic acid.
The prcscnco of glycerin iu a liquid Toay be detected tis follows ; Add
NaHO to feebly alkaline reaction, and dip into it a loop of Pt wire hold-
ing a borax bead ; then heat the bead iu tlio blow-pipo tlame, which Is col-
oi«d green if the Liquid contain -j^ ^ of glyccrixi.
The glycerin lued for medicinal purpoBeo aliould renpoud to the fol-
lowing testa : (1) ita ap. gr. should not ^-arj' much from that giveu above ;
(2) it should not rotate polarized light ; (3) it should not turn brown
when heated with sodium hydrate ; (4) it should not be colored by H,9 ;
(5) when dissolveil in its own weight of alcohol, containing one per cent.
of H^SO^ the Holutiou should be clear ; (6) when mixed with au equal
volume H,SO,, of ap. gr. 1.S3, it should form a limpid, brownish ouiture,
hot should not give off gas.
ACIDS DERIVABIiE FROM THE GliYCERINS.
Two series of acids ore derivable from the glycorins by substitution of
tor H, in the group CH,OH :
CH,OH
CHOH
CH,OH
Oljmrla.
CH,OH
OOOH
HOH
COOH
OlTovteadd.
HOH
300H
Tuwonlo mU.
The terms of both seriea are triatomic ; thoae of the glyceric series are
monobasic, and thone of the tartrooic series arc dibasic (see p. 231).
MaUo acid--C^H,0, — 134— ia the second term of the tartronic series,
and is therefor dibasic. It exists in the vegetable kingdom ; either free
or combined with K, N», Ca, Mg. or organic bues ; principally in fmits,
such as apples, cherries, etc. ; accompanied by citrates and tartrates.
It cnstallizes iu brilHaut, prismatic needles ; odorless ; acid in taste ;
fusible (it 100'^ (212- P.) ; loses H O at 140^ (284-' F.) ; deliquescent ; \-erv
soluble in H,0 and in alcohol Heated to 175'-180'' (;U7^-35B' P.), it is
decomposed into H.O and maleic octJ, C,H,0^. The malates are oxidized
to carbonates in tho body.
ETHERS OF GLYCERIN.
Gltcebiiibs.
glycerin is a triatomin alcohol, it contains three oihydryl groups
which may be removed, combining with H from au aciil to (urm U,0. and
learing a univalent, bivaleut, or trivalent xem&iuder, ■^hifth. taa.^ r«<(WiQ
S of monobaaic acids to form three sexi&ft ol ft^iieift. Ka, VniOsiKt^'Oofc
MANUAL OF CQKMISTBT.
OH i^roupe diRer from each other ui that two of iliem are contained in Uut
primary group CH^OH, tlie other in the aecoodary group CHOU, Uiers
exist two i&oiuereii vi uiu:h tuouo- aud di-gljcorido.
CH.OH
I
CHOH
CILOH C
CH,— O— C^O
^HOH
?H,OH
JH,OH
HhumcUo.
CH,-0— CJH,0
CH-
[— O-C,H,0
CH»— O-C^O
CH-
IH,OH
DtaiMtia.
CH,
:— o— c^,o
,-o-c^o
TriMHlM.
Of the many substaQces of this class, only a few. principally those en-
toring into the composition of the neutra] fats, require consideiratioa hen.
Tributyrin— C,H, (0,C,H,0),— 302— esiste in butter. It mw ate
be obtained by beating glycerin with butyric acid and H.SO^. It is i
pungent liquid, very prone to decomposition, with liberation of butyric
acid.
Trlvalerin— C,H, (0,C,H,0), — S44 — exists in the oil of some mari-
time iimi]iiii»lia, and iu idcuticid with the j>hocenvitr of Clievreul.
Trlcaproln -- C,H, (O.C.H,,Oj, — 3«C — Trioaprylln C.H (0,C.
H„0),— 470— and Trioaprin— C,H, (O.C„H„0).— 554^-exi8t in small
quantitiBs in milk, butter, and cocoa^bulter.
Tripalmitin— C,H, (0,C,,H„0),— 80G — exists in most animal aod
Tsgetable fats, notably in palm-oil ; it may also be obtained by heating
glycerin with 8 to 10 times its weight of palmitic acid for 8 hours at !250
(482'' F.). It forms crystalline plates, vei-y siioiingly soluble in alcohol,
even when boiling ; Teiy soluble in ether. It fuses at 5^ (122'' F.) and
Bolidifiea again at 4«' (114°.8 F.).
Trimargarin— C,H^ (O.C.,H„0).— 848— ban probably been obtained
artificially as a crj-stalliiio solid, fusible at GO'' (14U"'>M, soliditiable at 52'
(125*.6 F.). The substance formerly described under this name as a con-
stituent of animal fats is a mixture of tripalmitin and tristearin.
Tristearin— C,H, (0,C,.H„0),— 8!>0— is the most abundant constit-
uent of tlie Roliit fatty substanccH. It is pre|^red in large quantities os on
induHtrifil produot in the manufarture of Btearin candles, etc., but is ob-
tained in a btate of purity only with great difficulty.
In as pure ii fona as rcadilr obtainable, it forms a hard, brittle, crystal-
line mass ; fusible at 68^ (154\4 F.). solidifiable at 61'' (14r.8 F.) ; soluble
in boibng alcohol, almost insoluble iu cold alcohol, readily soluble in
ether.
Triolein— C,H^ (0,C„H„0),— 884— exists in varjing quantity in all
fats, and is tlte predominant constituent of those wliich are liquid at ordi-
nary temperatures; it may he obtained from animal fnts by boiling with
alcohol, filtering the solutiuu, decimting after twenty four hours' sttuiding ;
freezing at 0^ (^2"' F.), and expressing.
It is a colorlesfi, odorless, tasteleas oil ; soluble in alcohol and other,
insoluble in w.'iter ; Bp. gr. 0.92.
Trinitro-glycerin— A7(ro-^/(/«n'n — C,H, (ONO,),— 227— used oa
an explosive, Iwth pure and mixed with other substances, in dynamite
giant powder, etc., is obtained by the combined action of H,oO, and
HNO, upon glycerin. Fuming HNO, is mixed with twice its weight of
H,SO, in a cooled earthen vessel ; 33 parts by weight of the mixed acids
ore placed in a porcelaiu vessel, and 5 parts of glycerin, of 31° Beaumi6,
are gradually added with constant stirring, while tlie vessel is kept well
cooled ; after Jive miaatos the ■VfYioVe \& Viiio^«u \ii\.o V^ noVoxosa o{ cold
J
NEFTBAL OILS AND FATS.
2BT
wat«r ; tbe nitro-glycenn eepAraics as a hoavy oil vrhich is woBhed witli
cold water.
I Nitro-glyoerin is an odorless, jellowisli oil ; has a sweetish taste ; sp.
gr. 1.6 ; Luuolublc lii water, soluble iu alcohol luid ether ; not volatile ;
crystallizes in prismatic neeiUes when kept for some time at 0^ {-H" F.) ;
fuses again at ti ' (46 '.4 F.).
{ When pure uitro-glycerin is exposed to the air at 80° (SG*^ F.) (or some
time, it dfcomposes, without explosion and with production of j^lyceric
and oxalic iicids. When heatetl to IWJ' (21'2° F.) it volatilizes without de-
compoaitiou ; at 185^ (365'^ F.) it boils, ^^ing off nitrous fumes ; at 217'
(422^.6 F.) it explodes violently ; if quickly heated to 257' (494".6 F.) it
anomes the spheroidal form, and Tolatilizes without explosion. Upon the
approach of tlame at low temperatures it ignites and bums with slight
decrepitAtiona. "VSIftm subjected to shock, it is suddenly decomposc<l into
CO ; N ; vapor of U,0, and O, the deoompositiou being atteuued with a
violent explosion.
In order to render this explosive less dangerous to handle, it is now
usually mixed with some inert substance, usually dmtomaceous earth, in
which form it is known as dynamite, etc.
When taken internally, nitro-glycerin is an active poison, producing
eflfecta somewhat similar to those of stri'chnine ; in drop-doses, diluted, it
I causes violent liuadHche, fever, intestinal piuu, and nervous symptoms. It
has been latterly used as a therapeutic agent, and has been used by the
^^tfmcBopatbs under tlie name of ^onoin.
f Tll€
NEUTRAL OILS AND FATS.
'Hieae are mixtures in varying proportions of tripolmitiii, iristearin,
and triolein, witli small quantities of other glycerides, colorutg and odor-
ous principles, which are obtained from animal and vegetable bmlies,
The uils arc tluid at ordinary tein{>eratur68, the solid glyoerides being in
solution in an cicess of the liquid triolein. The fats, owing to a less pro-
portion of tlie hquid glycei'ide, are solid or semi-solid at the oiilinary tem-
perature of the air. Members of buth chisses are fluid at sufhciently high
tempcraturea, and solidify when exposed to a sufScicntly low temperature.
They are, when pure, nearly tuBteless and odorlesis, unctuous to the Unich,
insoluble in and not miscib'io with H,0, upon which they float ; oombua-
tible, burning with a luminous flame ; when rubbed upon jmper they ren-
der it translucent. Wlien heated with tlie caustic alkalies or in a current
of superheated steam, they are mpomjled, i.e., decomposed into glycerin
and a fatty acid. If the saponilicatiou bo produced by an alkali, the
fatty acid combines n-ith the nLkaliue metal to form &noap {q. v.).
Most of the fata and many of the oils, when exposed to the air, absorb
O, are decomposed with liberation of volatile fatty acids, and acquire an
acid taste and odor, and an acid reaction. A fnt which has undergone
these chan;jea is aaid to have become rauind- Many of the vegetable oils
are, however, not prone to this decomposition. Some of them, by oxida-
tion on contact witli the air, become thick, hard and dry, forming a kind
of varnish over surfaces upon which they ore spread ; these are designated
OB drying or eiccatiw oils. Others, although they become more dense ov
exposure to air, become neither dry uor gummy ; these ui'u known as non-
drying, tj}-m»y, or lubrwating oils.
Under ordinar)' conditions, oils and melted fots do not mix with
■
water, and, if shaken with that fluid, ionn a temporary milky mixtore,
which, on fltjuidiiig for a short time, separates into two distinct lajeTS, the
oil douting ou the wuter. In the presence, howerer, of small qaauUUoa of
certain substances, such as albumen, poncreatin {q. v.), ptjaiin, etc, tl]«
milky mixture obtained by ^laking together oil and water does not sepa-
rate into distinct layers on standing ; such a mixture, in which the lut
is held in a [A'rmanent state ot suspension in small globules in u watci^
fluid, is called au emulsion. Perfect emulsions m&j bo easily obtiuned l^
BgiUting nn oil containing a trace of free oleic acid with a very dilai«
solution of soilium carbonate and borax.
Fixed olls.—These substances are designated as "fixed," to distisguiili
them from other vegetable products having an oily appeamnce, but which
differ from the tme oils in tlieir chemical composition and in their physical
properties, especially in that they are volatile without decum]jOBition, anJ
are obtained by distillation, while the fixed oils are obtained by expivasioii.
with or without the aid of a gentle heat
Paim oil ift a reddish-yellow solid at ordinary temperatures, has a bland
taste and an aromatie odor. It aaponifies readily, and in Ubually acid and
contains free glycerin from spontaneous decomposition.
liape need and colza oil«, produced from various species of Brasnca^ are
yellow, limpid oils liavjng a strong odor and disagreeable taute.
Crvfon-oU — Otrum iifjlii {U. S?) — Ohum crotoriis {Jir.) — varies much in
color and activity, according to its eoiurce ; that which is obtained from
the East is yellawisli, liquid, transparentt and much less active than that
prepared in Europe from tlie imported seeds, which is darker, leas fluid,
caustic in taste, and wholly soluble iu absolute alcohol CrotOD-oil eoa-
tains, besiile tlie glyeerides of oleic, crotonio and ^tty acids, about four
per oent of a pecoUur principle called crotonol. to which the oil owes its
vesicating properties ; it also contains an alkuloid-like substance, also ex-
isting in castor-oil, csJled nci/unt*. None of these bodies, bowever, are
posaeesed of the di-nstic i>oweni of the oil itself.
Peanut-oil — Gronnd-uut oil — an almost colorless oil. very much re-
sembling oUvo-oil, ill place of which it is frequently iised for culinary
purpos4?s, intentionally or otherwise. It is readily saponifiable, yielding
two per.iiliar acids, arachaic and h»ipoga^c (see Ohve-oil).
Cotion-vevd oil — Oleum gogntfjfn tfoninit {C. S.)^a pale yellow, blond
oil, also resembling oUvc-oil, for which it is frequently substituted.
Almond-oil— Ot'Tum amygdaio! expreaeum {C. S.)—Olettm amt/gdatce
{Br.) — a light yellow oil, reiy soluble in ether, soluble in nlcohol ; nearly
inodorous ; has a bland, sweetish taste. The pure oil has no odor of hitter
almonds.
Olitie-otl — (Meum ditxe {U. S., Br.). — A well-known oil of a yellow or
greenish-yellow color, idmost odorless, and of a blnnd and sweetish taate.
The finest gnides have a yellow tinge and a fiuiit tttste of the fruit ; they
are prepared by cold pressure ; they are less subject to rancidity than the
lower grades. Olive-oil in very frerjuently otluUerated, chietly with poppy-
oil, sesame oil, rotton-seed oil and ])eAnut-oil ; the presence of the first is
detected by Poiitefs reagent (made by dissolving G parts Hg in 7.5 parts
of HNO, of 36^ in the cold), which converts pure olive-oil into a aoUd
mass, while an oil aitnlterated with a drying oil remains semi-solid. A
contamination with oil of sesame is indicated by the production of a green
color, with a mixture of HNO, and H,SO,. Poanut^oil. an exceedingly
cx)mnion adulterant in tliis country, is rwognized by the following methml:
ten grama of the oil arc saponified ; the soup is decomposed with HCl ; the
HKtfTRAt, OTt.fl Aim TATa,
269
Hborated ffltty actJs diasolvetl in GO c.c. of strong^ alcohol ; the solntlon
prccipitntod with lead acetate ; the precipiUtti washed with ether ; tho
residue decomposed with hot dilute HCl ; tho oily lajer separated and ex-
tractnd with strong alcohol ; the alcoholic fluid, ou evaporation, yields
cryatala uf aracha.c add, if the oil contains pcanut-oiL
Coroa-batter — Oit^um tkeobromo! [C. S., Br.) — is, At ordinary tempera-
tures, a whitish or yellowish solid of the consistency of tuliow. and having
an odor of chocolate and a pleasant taste ; it does not easily become ran-
cid. The moat reliable test of ita i>urity is its fusing-point, which ghould
Dot bo much below 33^ (9^.4 F.).
Liriived oil^Flaxseeti oil — Oleum lini ( U. R, Br.) — ig a. dark, yellowish-
brown oil of disagreeable odor and taste. In it oleic ncid is, at. least par-
tially, replaced by Unoleic acid, whose presence causes the oil, uu exposure
to air, to absorb oxygen and Ixichiiiio thick and finally RoUd. This diyiiig
power is increased by boiling the oil with litharge (boiled oil).
Caaior-oU —Oleum ridni {U. S., Br.) — is usually obtained by expression
of the seeds, although in some countries it is prepared by decoction or
by extraction with alcohol It is a thick, viscid, yeltofvisb oil, bos a faint
odor and a nauseous taste. It is more soluble in alcohol than any other
fixed vegetable oil, and ia also very aolable in ether. It snponifies very
readily. Ammonia sepumt«!s from it a crystalline solid, fusible ut G6^
(158° ,8 F.) ricinolamide. Hot HXO, attacks it energetically, and finally
~ )nvert« it into nuln^rin acid.
WJiale-oil — Train-oil — obtained by tryinfj out the fat or blubber of the
'right whale " and of other species of batceme. It is of sp. giv 0.924 at 15"
\^' F.) ; brownish in color ; becomes solid at about 0" ; has a very nanse-
(ijnate and odor. It ia colored yellow by H,80, ; and is blackened by CL
HetU't-fool oil — is obtained by tie action of boiling H,0 upon the feet
of neat (»ttle, horses, and shocp, deprived of the llesh and hoofa It is
Btraw-yellow or reddish-yellow, odorless, not diaigrceable in taste, not
prone to rancidity, does not solidify at quite low temi^mtures ; sp. gr. at
15^ (59' F.) = yi6. It is bleached, not colored, by chlorine.
Lard-oH— Oleum adipiJt {V. S) — obtained in large quantitioa in the
United StAies as a by-product in the manufacture of caudles, etc., from
ligH fat. A tight yellow oil, used prxQcipally as a lubricant ; is ni-H colored
HjSO., but is colored brown by a mixture of H SO, anil UNO,.
_ Tallow-'iil — uhtaineil by expression with a gentle heat from the fat of
the ox and sheep. Sp. gr. 0.5*003 ; light yellow in color. Colored brown
by H,SO,. Formerly Ihiy oil, under the trade name of "oleic noid," was
simply a hy-product in the manufacturo of stearin candles ; of late years,
Jiowever, it is specifllly prepared for the mannfncture of oleo-margarine.
Cod-titrer oil — Oleum morrhtitp. { V. S., Br.) — is obtnmed from the livers
cod-fish, either by extraction with water heated to ab«)ut 80' (176' F. ),
or by hanging the livers in the sun and collecting the oil which drips from
im. There are throe commercial varieties of this oil : a. Brown. — Dark
}wn, with greenish reflections : has a disagreeable, irritating taste ;
lintly acid ; does not solidify at - 13' (8^.6 F. ). ft. Palf. ftroirji.— Of the
color of Malaga wine ; has a peculiai- odor and a fishy, irritating taato ;
strongly acid . c. Pale. — Golden yellow; deposits a white fat at —13*
{8\6 F.); has a fresh odor, slightly fishy, and a not unpleasant taste, without
after-taste.
Pure cod-liver oil, with a drop of H,SO,, gives a bluish-violet aureole,
which pratlually changes to crimKon, ond later to brown. A tlrop of fum-
ing UNO, dropped into the oil is surroonded by a pink aureolo if the oil
ro
VATYlfAL or CirEMlSTRT.
be pure ; if Urgely odultenLtcd witH other fish-oils, the pink color is no!
observed aud the oil booomcs BligliUy cloudy. Freeh cod-liver oil ia om
colored hj roeaniline. If a third of the oil be distilled, the distillate be-
comes solid ; while if it be contaminated with vegetable oils, the difltillate
becomes liiiuid.
Cod liver oil contaios, besides the glyccrides of oleic, palmitic mil
etearic acids, tho«e of butyric and acetic acids ; certain biliary prineipki
(to whose presence the sulphuric acid reaction given above is probably dact,
a phosphurizcd Uti of uudetermitied compusitiuu ; amall quautities ul Ivo-
mino and iodine, probably in the form of organic compounds ; a peculiar
fotty acid called gadinu- at-id, which solidifies at €0*^ (140^ F.) ; and a brovti
Bubatance called tjatluin, or gadinine.
Tu which, if to any, of thtise substoncca cod-liver oil owes its value u
a Uicmpcutic agent is still nnknon-n, although many theories have been
advancer!. (Certain it is, however, that one of the chief values of this oil
is as a food in a reatlily assimilable form.
Solid Animal Fats. — The glycerides of stearic, pahnitie, and oleic
acids exist, in health, in nearly all parts of the body ; in the fluids in solu-
tion or in suspension, in the form of minute oil-globules ; incorporated in
the soUd or semi-soUd tissues, or deposited in collections in certain loo^
tiona, as under the skin, enclosed in l-«11s of connective tissue, iu which the
xnixtiure of the three glycerides is in such proportion that the contents of
the cells are fluid at the temperature of the body.
The tot^il amount of fat in Uie bmly of a healthy adult is 6-om 2.S to
6 per cent of the body-weight, although it may vary considerably from
that proportion in conditions nol^ stnctly speaking, pathological. He
appn)ximate quantities of fat in 100 parts of Uie various tissues and fluids,
in health* ore the following :
Vrine *
pBPflpiration 001
Vitreous hamor 0.003
Bali»a 02
Lymph 0.05
SirDovial fluid 0.06
Amniotic flaid 0.3
Chyle 3
Uboiu 0.4
Blood 0.41
CartilBge 1.8 I
Uoae l.4i
Bila 1.4
CrreUlUne lens 2.0
Liver 2.4
Hnwlo 8.S
lUlr 4.2
HUk 4.8
Cortex of bndn.
Brain g;K
Hen'iegg 11.6
Vi'hiUiDiRtlerof brain. M.O
NerTe-tiune. 23.1
Spinal cord 8$.6
Fafc-tiMoo BB 7
Harrow
The amount of ffit, under normal conditions, is usually greater in women
and children tliaQ tu men ; genei-ally greater in middle than in old age,
altljough in KOine individuals tlie reverse is tlie case ; greater in the inhab-
itants of cold climates than in those of hot countries.
Id wasting from disease aud from starvation the fats are rapidly ab*
Borbed, and are again as rapidly deposited when the normal oondition of
aflairs is restored.
Besides, as a result of the tendency to corpulence, which in some indi-
Tiduols amounts to a pathological couditiou. fats may accumulate iu cer*
tain tissues as arenult of morbid changes. This accumulation nmy be due
either to degeneration or to infiltration. In the former case, as when mus-
cular tissue degenerates iu consequence of long disuse, the natural tissue
disappenrs and is replnced by fat ; in tlie latter case, as iu futty infiltration
of the heart, oil-globules ai-e depositerl between the natitral morphological
ekmonts, whoso change, however, may subsequently take place by true
fatty (legeu oration, duo to ijressuro. Fatty degenenition of the liver anj
of other organs occurs also in phthisis, chionic heart, asd limg affecti<
KBUTRAL OILS AITO FATS.
ia a result or ovcrfocrling, from the abuse of alcobolic Btimulonts, and
from the action of certain iwisona, eBpecialli^- of pJioBphorus. Tumors com-
posed of adipose tissue occur and are known as *' lipomata."
The greater part of tbe fat of the hod^- enters it as such with the food.
Not unimporUnt quantities aie, however, formed in the body, and that
from the albuminoid aa well as from the starchr and saccharine constitu-
ents of the food. By what steps this transformation takes place is still
onodrtaiu, although Uioro is abundant evidence that it docs occur.
Those fat-3 taken in with the food are unaltered by the digestive fluids,
except in that they are freed from their enclosing membranes in the
stomach, until they reach tbe duodenum ; here, under the inHuence of the
pftncreatic jutce, the major part is converted into a fine emulsion, in which
form it is absorbed by the laoteals. A smaller portion is saponified, and
the products of the saponification, free fatty acitis, soaps, and glycerin,
lubsequcutly absorbed by lacteals and blood-vesBels.
The service of the fats in the economy is undoubtedly aa a producer of
heat and force by its oxidation ; and by its low power of conducting heat,
and the position in which it is deposited under the skin, as a retainer of
heat produced in the body. Tbe fats are not discharged from tbe system
in health, except the excess contained io the food over that which the
absorbents are capable of taking up, which passes out with the fceces ; a
Hmall quantity distributed over the surface in the perspiration and seba-
ceous secretion (which con hardly be said to be ehminated) ; and a mere
trace in the urine.
Butter, — Tbe fat of milk, separated and made to agRlomerat* by agi-
tation, and more or le&s salted tu iusiu-e its keeping. It consists of the
glyccrides of stearic, paljnitic, oleic, Imtyric, capric, cnpryhc, and caproic
acids, Tvith a small amount of coloring matter, more or less water and salt,
and caseine. Good, natural butter contains 80-00 per cent of fat, Ct-IQ
per cent, of water, 2-5 per cent, of curd, and 2-6 per cent of BiUt ; fuses at
from 32^8 to 34^9 (•JZ=-M^8 F.).
Butter is adulterated with excess of WAt«r and salt, starch, animal fata
other than those of butter, and artificial coloring matters.
Bxcess of salt and water are usually worked in together, tho former
up to 14 |>er cent, and the latter tfl 15 per cent To determine the pres-
ence of an excess of water, about 4 grams {CO grains) of the butter,
taken from the middle of the lump, are weighed in a fwrcchuQ capsule, in
which it is heated over tho T\-ater-bath, as long as it loses weight ; it is
then weighed again ; the loss of weight is that of the quantity of water
in the original weight of butter, lees that of tbe capsule. The proportion
of salt is deteruiined by incinerating a weighed quantity of butter and
determining the chlorine in the ash by tlio nitrate of silver method (see
Sodium chloride). Roughly, the weight of the ash may be taken as salt.
Starch is detected by spreading out a tWn layer of butter, adding solution
of ioilitie, and examining under the microscope for pur^ile sjiots.
The detection of foretgu fats id bntler, formerly a most uusalisfactoi-y
problem to tbe analyst, has now become one which may be answered with
great certainty. All of the chemical processes used ore based upon a pe-
cuhar dificrcucc in the composition of butter-fat from otiier animal and
vegetable fats and oils. When butter-fnt is saponified, it yields from i> to
8 per cent, of butyric acid and its near homologucs, which are wduble in
H,0, and may be tliatilled without suflering decum position, and from 85.5
to 87.5 of stearic, palruiiic, and oleic acids, which arc neither soluble
in water nor capable of being distilled. The other fats and oils, when
273
MAHUAb Of OHBMIHTKy.
itaponificd. yteUl mere tmccs of the volatile or soluble fattr ftttcia, nml
much Iw^or quantities {i)5.'^ to 95.7 per cent.) of iusoluble acidai Tlien
variationn are utilizeJ directly id some processes, sucli as those of Hfiltner
and Beicbert, iu which the percentage of fixed and volatile acids an di-
rectly determined. In other processes, such as that of Koetlatortn',
advantage is taken of the different neutralizing power of the two gTQu|»
of adds. Thus, aa butyric acid, C,H O,, and stearic acid, C H„Oy m
each capable of ueutraliziiij> KUO, molecule for molecule, it foUavratbut
their ueutraliziiif; power is in proportion to their molecular weights, and
that 50 partM KHO will reauire for neuiraliKilion 88 parts of bubnic sckt,
or 284 parts of stearic ocia For descriptions of processes the atodect ii
referred to Alien: "Coinmercifil Orfjanic Analysia,'' 2d ed., IL
Methods for detecting a<lmixtnre of foreign fats by phyaieal means m
unreliable. One of the bei<t, which may be of service for preliminairta^
ing, is tlutt uf Ajagell and Hehoer. A peur-tjlia^^d bidb of thin g£ua ii
made of such size as to displace 1 cc. water, is weighted with niemii;
until it weighs 3.4 grams (52,5 grains), and the pointed end cloee<l by fnaoo.
The butter to be tested ia fused in a beaker over the water-bath, and whan
qnite fluid is poured out into a test-tube, about j inch diameter and 6
inches long, which ia kept rooderately warm and upright until the fat Im
ge|>arftted in n clear layer aliove the water, and then immersed in watsr
at 15° (59'' F.) until the fnt lina solidified. Tlie test-tube is then orranfied
as shown in Fig. 38, the btUb being laid \i\k>u the surface of the fuL The
water in the beaker is now heated until tlie globular part of the bulb has
just sunk below the surface of the fat. at which time the height of the
thermometer is noted ; this is the "siuking-|wiiit"
The sinking-jwint of pure butter is 34.3 to 3G*.3 (93°.7-07°.S F.).
, that of oleomargarine in lower, that of butter adultw*
ated with other fata is higher.
"Oleomargarine" is a product made ia imitation of
butter, which it resembles Tery closely in color, taste,
odor, and general appearance. Under the original po-
tent, it is made from beef-fat, which is hiunhed, steamed,
and subjected to pressure at a carefully regulated tomiier-
ature. Under this treatment it is sepanited into two
fatly products, one a white solid "stenrine," the other a
faintly yellow oil, " oleo-oiL" This oil ia then mixed
with milk, the mixture colored and churned. The sub-
sequent treatment of the product is the same as that of
butter. " Butterine," " suine," etc, are products made,
by a modification of the above proress, from beef or
mutton tallow, lard, and cotton-seed oiL
Butter is frequently, and oleomargarine ia always,
colored witli some foreign pigment, " butter color,"
which is usually a preparation of annoto.
Soaps— are the metallic salts of stearic, palmitic, and oleic acids:
those of K, Na, and NH, are soluble, those of the other metals iusoluble-
Those of Na are hard, those of K soft
Soap is made from ohnost any oil or fat, the best from oliTe-oil. or pea*
nut, or palm-oil. and lard. The first step in the process of manufacture
is the napotiijicatiun of the fat, which consists iu the decomposition of the
glyceric ethera into glycerin and the fatty acids, and the combination of
the latter with an alkaline metid. It ia usually effected by gradually
adding fluid fat to a weak boiling solution of caustic soda, or potassa, to
Fro. w.
LKcmirNS.
273
aatoration. From this woftk solution the soap U separaUd by " RolUng,"
wfaioh cousisU iu A«liling, duiiug consUnt nf;ttation, a sbUitiou of caustic
alkali, heavily ch&rge<I with coiniuou salt, until the soap Bepnrates in gru-
luous masBeH, which float upon the surface and are separated. Finally the
aoap is pressed to ffepiimtc adhering water, fused, and cast into moulda
H%iU coxtile mnj> — Sapo {U. S.) Sof>o ditrti^ (Jir.) — is a Na soap made
from oliTe-oil ; atroiiirly alkaUne. hanl, not fn"ea6y, very soluble ; contains
21 i»er cent. H^O, Sn/io vwllii (Br.) is a K soap made from olive-oil, and
contains nu excess of olkiili and glycerin. Vellow voap is made from
tallow or other animal fat, and contains about ^ its weight of rosin,
EmjAasirum plumbi {U. S. ; Br.) ia a load soap, prepared by saponifying
olive oil M'ith litharge.
The Bonps are decomposed by weak acids, with liberation of the flatty
ncid ; by compounds of the alkaline earths, with formation of an insolu-
ble eoaji ; and in the same way by most of the metallic salts.
LEiCmnNS — NERVE TISSUR
^V IjecitMn — is a substance first obtained from the yolk of hen's ef;g8,
^Bd fiubsequontly found to exist in brain-tissue, particularly the gray
^^pstjince, nerve titwue. semen. blood-corj)uscles, bliHKl-Herum, milk, bile,
'^rad other animal tissiiea and fluids.
As obtained from brain-tissne lecithin ia a colorless or faintly yellowish,
imperfectly crystiUliue HoUd, or sometimes of a waxy consistency. It is
veiT hyfjroacopic. It does not dissolve in H,0, in which, however, it
Bwells "p and forms a mass like starch-jiastrf*. It dissolves in alcohol or
ftlier, very sparingly in the cold, but readily under the influence of heat.
It dissolves in chloroform ami in benzol Lecilhiu iu veiy prone to
decomposition, particularly at sUgUtly elevated temperatures. Its chlo-
ride combines with PtCl, to fonn an insoluble yellowish chloroplatinat«.
When an alcoholic solution of lecithin ia brought into contact with hot
solution uf barium hydrato it yields barium glf/ccro/jhotfihaie, barium str'arate,
nnd choline (see p. 207). This decomposition indicates the constitution
of lecithin and its relations to tlio fats. Glyrerophosphoric acid ia ortlio-
pbosphoric acid in which an atom of bydnigon has been replaced by the
univalent remainder 011,011— CH OH— CH, — left by the remo\-al of OH
frora glycerin.
|_ /OH
^L o^r— OH
^p \o— CH,— choh-ch:.oh.
Wr Tn lecithin the remaintni; oxhydryl groups of the glycerin remainder
are remove/1 by union with the basic hydrogen of two molcculee of eteario
Bcid, nnd one of the two remaining basic hydrogen atoms of the phos-
phoric acid is displayed by choline. It is obvious that the number of leci-
thins is not hmited to one, but that many may exists and probably do,
into whoee composition any one, or any combinatioQ of two, of the acida
of Uie same series as stearic acid may enter.
/(CHT
/0_N CH,— CH,-OH
0=P— O— H
\0-CH.-CH(0.^..0.)-CH.(C..H„OJ.
UUUMol-lKdlbtD.
IfANUAI.
CireMlSTRT.
Nenre-Ussue, trbicb is exceedingly complex in its cbemical rniDpoti-
iion. Rnd whose' chemistry is still in ft mewl nulinK^ntArT cotulitioti, HetM
to contiun similar constituenta in its diRerent parts, which differ, lunreni;
materiallr iu their tjunntitativc compoaitiotL
TJio following substances liavo lAien obtained from cerebral tissas:
Mineral Subatances.
Water.
FboBphatea of Na, K, Ca, Mg.
Ferric oxide.
Silicic oxide.
Tracee of solphatea, chlorides, and
fluorides.
Albuminoids.
Products of DeoompotB ^ oiL
GlTC«ropho^horic acid.
OleoplidKphori*! acid.
Volatile falty amda.
IJaotAtes.
UTpoxAUthine.
Xnn thine.
Creatine.
Subfltaiice related to myosin.
Soluble albuminoid, cougulablc
75° (167-' F.).
Casein (?).
at
Organic Subetancea.
XHasttn. Lacitbia.
Neurokeratin- Fata (?).
Mcucletn. Inoeite.
Oerebrin. Choleaterin,
The coinpo^tioii of white and gray matter difTers quantitativelT, h
Bhown below :
Albuminoids 66.87 S4.7S
Lecithin ITU 9.90
Choleaterin and fata 18.88 51.91
Cerebrin 0.53 9.55
I^iractivo matters, insoluble in ether 6.71 3.34
Salts 1.46 0.67
Cerebrin is a substance deposited in liio CTTstalline form from hot
©thoro-ftlcoholio extracts of brain-tissue. It is white, verr light, odorlM»,
and tasteleas ; initoluble in miter ur in cold alculiol or ether. Its aululicms
are neutral. It does not coulniu phosphorus.
The Bubstanco known ns protagou, described by Liobrcich as baring
been obtained from bmin-tissue, wouLl Bocin to exist there notal>ly in the
white substance of Schwann. It apjwara to be a comivound formed bv
the union of lecithin with cerebrin.
Neurokeratia is a aubatauce, occurring priacipally in the gray mat-
ter, which is insoluble in all solvents, and ia not acted ujmu by digestiTe
liquids.
TOIRD SEOQES OF UTDROCAItnOXS.
275
THIRD SEBISS OF H7DROCABBONS.
Series CaH,n-«*
The lenns of this eeriea at present koowu are :
Aoofylaae CH, I CroUtnjrleo* ....
I Allylene « C*H, 1 ValerylQoe
CtK* I Bonyleno.
C..B,.
^
Acetylene — ^^fteii*;— C,H,^-26— exists in coal gas and ia formed iu
the decomposition, by hent or otherwise, of many orpauic subslftnccs. It is
best prepared by paRsing a slow current of otwU gas tlirongh a iuutow tube.
traversed by induction Hporks ; directiu;; the gas tlirough a solution of
cnproua chloride ; and collecting and deconiiKJsing (he precipitate by HCl.
It may be obtained by direct Hyntliesis from H and C, by producing the
electric arc between carbon points in a ghuis globe filled with hydrogen.
It is a colorlesa gas, rather Boluble in H.O ; has a peculiar, diwigree-
eble odor ; such as ia observed when a llunecn burner burns within the
tube. It forms explosive mixtures with O. It unites with N, under the
inriuecce of the electric discharge, to form hydrocyanic acid. Mixed with
CI, it detonates riulently iu diffuse daylight, without the aid of heat. It
may be made to unite with itself to form its polymorcs benzene, C,H^
Btyrolene. C^H, and naphthydrt-ne, C H .
Its presence may be detected by the formation in an ammoniacal solu-
tion of cuprous chloride of a blood red precipitate, which is explosive
when diy. It is probable that explosions which sometimes occur in brass
or copper pipes, thfough whicli illuminating gas is conducted, are due to
the formation of thin compound.
lUumiaatlag gas — is now manufactured by a nuriety of processes,
almost every company using some nioditication of the metliod, or of the
nature and proportion of the materials ; tlius we have gaa made from
wood, from coal, from fats, from petroleum, and by the decom}x>sition of
H.,0 and subsequent charging of the gas with the vapor of naphtha.
The typical process ia that in which the gas is produced by heating
bituminous coal to bright redness iu retorts. As it issues from the re-
torts the gas is charged with substances volatile only at high tempera-
tures; these are deposited in the condensers or coolers, and form conl-
nr gns-tnr. From the condensers the gas passes through what are known
ae •' scrubbers " and " lime purifiers," iu which it is deprived of ammoni-
cal compounds and other impurities. As it comes from the condenaers,
coal-gas containa :
I Hydrogen milphlde.
r CarboD distilpbUle.
t tiulpbnretted bj-
d roonrboni.
t Nitrogen,
f Aijucoua vapor.
* Aootylaoe.
* Etbjrlene.
* Mmnb-gM.
* Botyleoe.
Stf roleno.
MapbtbiUeno.
AooDspbCbaleno.
Flaoreoo.
Propvl bfdrldo.
Butyl bjrilrulc.
Carbon monoxiile.
Carbon dioidde.
Amicouin
Cjanogea.
SuLpbucyaaogen ,
In paaaing through the puriiiera the gas is ^ed of the impuntiee to
a greater or loss extent, and, as usually delivered to consumers, contains :
Mofih-gna.
Acet7l«iie.
t Hydrogen. | j Acjaeoos vapor.
* Vaponi of Uydrocorboiu.
It
Carbon monoxide.
Carbon dioxide.
lUaminatuiK ooiutitDeDta.
t Inipuxitiea
t DUoenL
276
MANCAL OF CHEMISTET.
TBTRATOMIC AIXOHOLa
Sbbizs C^, + ,0^
Very few of these compounds have yet been obtnined. They nity 1*^
. reg&rded aa tbe Lydrates of the hydrocorboua C,H^_, ; aa the glycda m
"le hydtates of the ethylene Bories.
CH.OH
CHOH
Brythrite—Phycite— | :^C,H.(OK),— 122— is a prodncio(d«-
CHOH
CH,OH
composition oferythrine, C,,H„0,„ which exista in the hehensof the cennB
fwW/a. It crystallizes in large, brilliant prisms ; very wihihle in H,0 and
iu hot alcohol, almost ins{)luble tn ether ; sweetish in taste ; its solutionfi
neither affect polarized light, nor reduce Fehhng's solution, nor are capable
of fermentation. Its watery solution, like that of sugar> is capable of di&-
living a considerable quantity of lime, and from this solution alcohol
"precipitates a definite compound of erytlirite and calcium. By oxida*
tion with platinum black it yields erythrogtucic add, C.H.O^. With
fuming HNO, it forma a tetranitro compound, whiol\ explodes under the
hammer.
ACIDS DERIVABLE FROM ERYTHRITE.
Theoretically erj*thnto should, by simple oxidation,
erj'tuni
one of the series C.U^O^, and another of the series CJi,
botli of these acids are known, only the first, erythrogtucic
obtained by oxidation of erythrite :
yield
4
two acids;
Although
acid, has bc«it
-^O..
CH.OH
CHOH
CHOH
CH,OH
COOH
CHOH
CHOH
CH,OH
Krythrattnolo mcM.
COOH
CHOH
1
CHOH
k
;ooH
TartuloMid.
Tartaric adds— Jci'dum taHaricuin (U. 8., Br.) — C,H,0,— ISOtJ
iThero exist four ncida having the composition C,H,0„ which differ from
each other only in their physicjU properties, and are very readily converted
into one another ; they are designated aa : lat, Rifjht ; 2d, l^t ; Sd, Inac-
tive tartaric acid: 4th, Ila&^iic acid. Bighi or Dexirolartaric twid crysia\'
lizos in lai^e, obHqne, rhombic prisms, having hemihedral focettes. Solu-
tions of the acid and its salts are dextrog^Tous.
Lrevotartaric add crystaUizea iu the same form as dextrotartaric acid,
only the hemihodral facettes are on the opposite sides, so that cijBtala of
DSBITABLE FHOH EBTTIiraTE.
277
the Iwo acids, when held facing each other, apjwar lite the reflections one
of the other. lU solution and thoM of its salts are hi?vo^'rous to the
fiaine degree that corresponding solutions of dextrotartaric acid are dox-
trogrrous. liacf^iic add is a compound of the two preceding ; it forms
crystals having no hemihedral faccttes, audits solutions are without action
on polarized Ught It is readily se^mrated into its components. Itutiiio*'
Utriaric acid, although resembling ror^mic acid in its cr^'stalline form and
ioactiritj with respect to polarized light, difTers essentially from that acid
in that it cannot bo deoompoaed into right and left acids, aud in the
method of its production.
The tartaric acid wliich exists in nature is the dextrotartaric ; it
occurs, both free and in combination, in the sap of the vine and in many
other vegetable juices and fruits. Although tliis is probably the only tar-
taric acid Rxiflting in nature, all four vari&LicH mar and do occur in the
commercial acid, being formed during the process of manufacture.
Tartaric acid ta oblaiued iu the arts ^m hydrojutassic tartrate, or
creun of tartar {q. v.). This salt is dissolved in U,0 and the solution
boiled with chalk until its reaction is neutral ; calcic and potossic tartrates
are formed. The iuaoluble calcic salt is separated and tlie potassic salt
decomposed by treatiug the solution with ci dcic chloride. The united de-
posits of calcium -tartrate ore su&peuded in 11,0, decomposed with the pro-
per quanti^ of H,SO,, the solution separated from the deposit of calcium
sulphate, and evaporated to cr^'stallization.
The ordinary toitoric acid eryatallizes in large prisms ; very soluble in
H,0 aod alcohol ; acid in taste and reaction. It fuses at 170 (338° F.) ;
at ISO'' (356° F.) it loses H,0, and is gradually converted into an anhy-
dride; at 200^-2 W (392*^10'' F.) it is decomposed with furmution of
pyruvic add, C,H,0,, and pyroiariaric add, C.H.O, ; at higher tempera-
tures CO,, CO, HjO, hydrocarbons and clinrcool ore produced. If kept id
fusion fiome time, two molecules unite, with loss uf H,0, to form tarCralic
or diiartaricadd, C,H,,0,,.
Tartaric acid is attacked by oxidizing agents with formation of CO,, H^O,
and, in some iustanccB, formic and oxalic ocida Certain reducing agents
convert it into malic and succinic acids. With fuming HNO, tt forms a
dinitro-compound, which is very unst^^ble, and wbich, when decomposed
below 30^ (06'. 8 F.). yields tnrtmic acid. It forma a precipitate with
hme-water, soluble in on excess uf H,0 ; in not too dilute solution it
forma a precipitate with potassium sulphate solution; it does not precip-
itate with the salts of Ca. When Ueuttid with a sululion of auric cfdoriue
it precipitates the gold in the motaUio form. As its fonnula indicates
liseQ above), tartaric acid is tetratomic and dilmsic. It has a great teu-
Hlfc CT to tlie formation of double salts, such as tartar emetic (a. v.).
P" when token into the economy, as it constantly is iu the lorm of tar-
trates, the greater part is oxidized to carbonic acid (carbonates) ; but, if
taken in sufficient quantity, a portion is excret«tl unchanged in the urine
aud perspiration. The free acid is poisonous iu large doses.
Citric aoid—Andum dtricum (T. 5.. J?r.)— O.H.O, + Aq- 102 +
18 — is best considered in this place, although its constitution is different
from that of tartaric acid. It exists in the juices of many fruits — lemoD,
strawberry, etc.
It is obtained from lemon-juice, which is filtered, boiled, and saturated
with cbalk. The insolnblo calcium ritrat* is separated and decomposed
with H,SO,, the solution filtered, and eviipomted to err stall i^ali on.
U ciystoUizes iu large, right rhombic priraas, vhich lose their aq. at
drs
VXyrVXt OP CTTEMIftTRT.
100'* (212*' F.) : rerr solnble in iratoT. less KnInWc in nloohot spariiigWl
Boluhle in etiier ; heated to 100^ 1212" F.) it fuses ; at 175' (^47^ F.| il a
decomposed, with lose of H,0 aiid formation of aconittc acid^ 9^i^*' "^
a liigber temperature CX), is given ofl^ and itaconio add^ ^fio^ lad
citraconic arid, C',H,0,, aro formed.
Concentrated H,^, decompones H vith evolution of CO ; oxidianc
B(;entH couvcrt it into formic acid and CO,, or into acetone and CO^ or
into oxalic nud acetic acids and CO,. It is tetratomic and tribaaic. In the
body its salts are oxidized to carbooatos.
FOURTH SEmiES OF HYDROCARBONS.
HBiinti CnU^^^
Bot one of the lover terms of this aeries is Inown ; this is vaiylfM,
C,H,, obtained by the action of an alcoholic eolution of potaafa on Tsleij-
leue dibromide. It is a liquid, boilinfv at 45" (113* F.).
Ainon(7 tlie hif^her tenus of the series are many sabstanoes of indostriil
and medical importance.
Terebentbene — C,,H„ — 136— is the type of a ^rreat number of iso-
meric substances existiu^ in the voialilc oU« or^stsenccs. It is the chief coa-
stituentof oil of turpentine.
To obtain it in a state of ptmty, oil of tnrpentine is mixed with nn
nlkaliue carbonate, and distilled in vncao over a water-bath, or lij frsc-
tioual distillalion of the cniile oil, those portions being collected which
pass orer at about 156^ {312 .8 F.).
Pure terebentbene ia a colorless, mobile liquid ; has the peculiar odor
of turpentine; boils at sbout 156" (312''. 8 1',) ; bums with a smokv,
Inminons flame. Obtained from the turpentine of jjinux maritima, it is
IiHTogjTous, purified by distillation in vacuo, [aU = —42*^.36, by fme*
tional distillation^ [a]j, = — 40^32 ; that obtained from jnmig atur/ra/uataJ
ilextrofo'rous, [ujc = + 18».9 ; specific gravity at 0"' (32° F.) = 0.8767.^H
It absorbs oxygen rapidly fi*om the air, whether pure or in the coi^^l
mercinl essence, becoming thick and finally ^lumy. Oxidizing agents,
such as ItNO^ attack it energetically, cautung it to ignite and bum end*
denly, T\"ith separatinn of a large volunift of carbcm. Ht'l unites with it to
form a number of compounds, aa do also HI and HBr — all the compounds
baring the odor of camphor. Wlipn mixed witli HNO,, diluted with alco-
hol, (uid exposed, to the air, it forms a crj-stnlline pseudo-glycol, Irrpine.
CI, Br and I form compounds of substitution or of addition.
Tfitt'EsmfF — Thrbrnthina {V. S.) — is the name fpren to the concrcfts
juioe of various species of trees of the genera Pitnt», Abiex, and Lahx,
which coDBtst of terol tenth eue. its isomcres, and resinous and other sub-
stances. The product differs in composition and propertiee sccordnig to
the kind of tree from which it is pnKluced.
White turpi'nline — Common American turjif^iine — obtained from Ptnvt
jtoluxtrig and P. tivfla : is yellowish-white, semi-fluid at sammer tempera-
ture, hard and »>lid when cooled ; on exposure to air it becomes diy, bard.
and brittle. It ia usually subjected to diatilI;ition near the place of its col-
lection, by which process it is separated into the volatile oH, or cuaenre o/*
turpcnUne {q. i\), and rosin, or f^doiihony {q. v.). Eiw^tpean UtrpciUirte-—
Ihirdeaux turprntine — obtained {rttm P. gylivittriin and /'. maritima. Canada
(Mrjwnein* — Canada balmm — BaUam of fir — ItTeten/Aino cwnadenxis {V. S^
FOTTRTIT SEBras OF nTPBOCARBONS.
279
— U from abie9 balaamea. It ia a tenaciotu wmi-soliil, of the conuBtency
of honey wheu fresh, colorless or yeliowiah, sticky, bitter in taste, and
havini^ a baUamic odor ; wheu long exjiosod to tho air, or when heated
orer the water-bath, ita volatile coustituenta am lost, and it ia converted
into a hard brittle masa. Veriice turpentine — produced from larix EuTopcEt^^
is a thick, riscid liquid, yellowish or greouish iu color ; Holuble iu alcohol ;
does not concrete as reat^Uly as other turpentines. Chian tui-jieiUiue, the
product of pwtadUa Utr^uUhus, ia a tluck. greenish-yeUow Hquid.
BsBEsrE or TuBPXirnsB — OU of turjtentiiie — Spi7-ilg of turjientwe — Oleum
tertbiiUkuKe ( U. S., Br.) — is the volatile product of the distillation of tur-
pentine. It 18 not identical with tcrcbcnthcDO, although that substance is
ita main coiiBtituent ; it contains also hydrocarbons isomeric with tui'pen-
tine and substancea containing oxygen, whicli either pre-exist in the turpen-
tine, or, more usually, result from the mt-thud of prepariug the oih When
recently distilled, it is a colorless, limpid, neutral liquid ; sp. gr. O.UG ;
usually UeTogyrous, sometiinee dextrog^TOUs. WTien expoBe<l to the air it
ra^iidly becomes yellow and Wscid. The action of reagents u|K>a it is
practically tlie same as upon terebeutheue.
Tho number of isoiucndes existing in oil of turpentine is very great ;
some nro optioally active, othei-s ijinrtive ; they also vai-y in their sp. gr.,
fusing- or boilinj;-i>oint4, ami ciipacity for abw>rbiiig oxvgeu.
iMmeres of Terebenthene. — There exist a great number of botlies,
Ua pradaeta tA distillation of vegetable subetanoes, which ore known aa
eMSHcas, esaentiat oUg, volatile oiU or dintUkd oiU. They resemble each
other in being odorous, oily, sparingly soluble in water, more or less solublo
in oloohol and ether ; colorless or yeUowish, inflammable, and prouc to be-
come reainoua on exposure to air. They are not simple chemical oom-
pounds, but mixtures, and iu many of them the prindpal ingredient ia a
hydrocarbon, isomeric with t<;rebentheue, and cousc<iuently having the
composition h^',.U,.- Home contiuu hydrocarbons, others aldehydes, acet-
(mes, phenols, and ethers.
Of the numerous other hydrowirlwus closely related to tcrebcuthene,
but two require further consideration as being tho principal constituents
of caout'^hou'-^ and Qtitia-percha.
Caoutchouc — India-rubber — ia a peculiar subsiaDoe existing in sus-
pension in tho milky juice of quite a number of trees growing in warm
climates. It is, when pure, a mixture of two hydrocarbons— coou^-^ne,
C„H,^ and isoprene, C H,.
liie commercial article is yellowisb-brown : ap. gr. 0.910 to 0.942 ; soft»
flexible ; almost impermeablo, but still capable of acting aa a dialyzinfr
membrane when used iu sufficieuUy thin layers. It is msoluble in H.O and
aloohol, both of which, however, it absorbs by long immersion, tlie former
to the extent of 25 per cent., and the latter of 20 f>er cent., of its own
weight ; it is soluble in ether, jietrolemu, tatty and essential oils ; its beet
solvent is carbon disulphide, either aloue, or, bettor, mixed with 5 ports of
absolute alooboh
It is not acted upon by 'Hlute mineral acids, but is attacked by concon-
tratod HNO, and H,SO„ and especially by a mixture of tho two. Alkalies
tend to render it tougher, although a solution of soda of 10^ B. renders it
soft after an iminenuon of a few hours. 01 attacks it after a time, do-
priring it of its elaslicitT, and rendering it hard and brittle. \Mieu heated
it becomes viscous at 145" (293 F.), and fuses at 170*-1S0- (347'-35a' F.)
to a thiok liquid, which, on cooling, remains sticky and only regains its
primitiTe character after a long time. On contact with llamo it iguitea»
MANTAL OTP CITEIfXSTnT.
k
Irtiniing with a reddish, smoky flame, which is extisgntfihed with dif-
The most valuable property of india-rubber, apart from it* eUstia^,
is that which it possesses of entering into combination «'itli 8 to form vbit
iA known as vuUxmiied rubber, which is produced by heating together tie
uonual oaoiilchmic and S to ISO^-IGO" (26tl°-302'' F.)'. Ordiuary Tulctniwl
rabber differs materially from the natural gum in its properties; itsehe-
lioily and tiexibility are much in<Teafted; it does not harden when ex-
' posed to cold ; it oiily fuaes at 200' (3*J2'' F.) ; finally, it resists the actioD
of reagcuta, of solvents, and of the atuiosphero much better than does Ibt
natural gum.
Frequently rubber tubing is too heavily charged witli aiilphur for cer-
tain chemical uses, in which case it may be desulphurized by boiling -vith
dilute caustic soda sulutiom
Hard rubber, vub-anUe, or ebomite, is a hard, tough Tariety of Tulcauized
rubber. Rusceplible of a good twlisli, and a non-<^nductor of elttctricify. It
contains 20 to 35 per cent of B (the ordinary Tulcanized rubber contains
7 to 10 [wr cent).
Gutta-percha — is the concrete juice of wonanrfro yuUa. It is a toogb,
inelastir, brownish substance, having an ndor similar to that of oaoot-
pchouc ; at ordinnry temperatures it is rather hanl, but when warmed it
becomes soft and may be mouldttl, or even cast, so as to assume any fens,
which it retains on cooling ; it may be welded at ftlightly elevated temper-
atureM, is a goni insulating and waterproofing material, and is tough and
pliable. It is inuoluble in ivat«r, alkaline soluliona, dilute acids, inclml-
ing hydi-oHuonc, and iu fatt^' oils ; it is soluble in benzene, oil of turpentine,
essential oils, chloroform, nnd especially in carbon disulphide. A solution in
chloroform is known as ^roMma^irfne or Liq. ffiitta percbis { L'. S.), and is nsed
I to obtain, by its evaporation, a thin film of gutta-percha over parts wliidi
it is desired to protect from the air. It is attacked by HNO, and H,SO..
When exposed to air and light, it is gradually changed from the sur-
face inward, assuming a sharp, acid odor, becoming hard and cracktxl,
and even a conductor of electricity.
Outta-perchn is a more complex substance than caoutchouc, and eeema
to be made up of three substances : (iutia, C^^H , 75-l!t2 per cent, a whita,
tough Bubatauco, fusing at 150" (302'' F. ), solublo in the ordinary solvents
of guttA-percha, but insoluble in alcohol anil ether. Allfine, C,.H„0,, 14-
19 per cent., a white, crystalline resin, heavier than water, fnaible at 160^
(^0' F.) ; soluble in benzene, essence of tiirjwntine, carbon diaidphide,
etner, chloroform, and hot absolute aleohol ; not attacked by HC^ Flu-
viale. 4-C per cent., C,,H O, a vellowish resin, slightlv heavier than water,
hard and brittle at 0' (32° F.j'soft at 50* (122^^ F.),'Uquid at 100' (212°
T.); soluble in the solvente of gutta-peroha.
Camphors and Reslca— ^fost of the essential oils yield on distiUa-
tion two products of different boiling-points ; one of tliesc is a hytlrocarbon,
in most instances of the terebentheno series, liquid at onlinary tempera-
tures, and sometimes knoirn as an tU'opUvie. The other, of higher boihng-
point and solid at ordiuan* temperatures, designateil a uteamplene, is an
oxidized product, and either exists as such in the vegotftblc exudation, or
is pn>diiced under subsequent treatment The ramjAom are probably
aldehydes or lUcohols corresponding to hydrocarbons related to tereben*
thenc. although their constitution is still uncertAin.
Common campbor — Japan ca7njihor — Laurel camphor- — Campbolic
oldehi/de — Campiiora. ( V. S., Br.) — C^JS^fi — 152. — Thi-ee modifications are
FOUBTIt SERIES OF ITTDnoO ATI BOWS,
281
known, which acem to differ from each other only in their aelion upon
polurizefl light: (1.) lifj-tro camphor =■ camphore officinarum ; obtained
from iaurua mmphnra — [aj^ = -f 47^4. (2.) Lacoo caiupkor ; obtiuuiMl from
matricaria jjO!*ttanuim—[a]^ = —iVM (3.) IniuHitu' camphor, obtained
from the essential oils of roeomar)', sage, lavender, and origanum.
Tlie first t!) the ordiuary camphor of tlie shops. It is a white, tranalu-
cetnt, crvHtnllino solid ; sp. gr. K.lWfl-O.y'JG. hot and hitter iu tiiate ; aro-
matic ; sparingly soluble iu HO ; quite sohibJe in ether, acetic acid,
methylic and ethj'lio alcohols and the oUa ; fuswd at 175* (347" F.) ; boils
at 2U4' (3i)a'.2 F.); subliineH at all (cmpcnitures.
It ignites reailily nnd bums with a luminiiua flame. Cold HNO, dis-
solves it, and from the solution H,0 precipitates it unchanged. Boiling
HNOj, or potassium periuanganate, oxiilizes it to dextro camphoric acidj
C„H,jO,. C<inrfrntrated H,SO, forma with it a black solution, from which
HjO precipitates an oily material called camphene. Distilled wit-h 1*,0,, it
yields ciimenc, C,^,,. AlkaUne solutions, by long heating under prvssure,
convert it into camphio acid, C„H,^0,, and borneol. CI attack» it with
difficulty. Br unites with it to form an unstable compound, which forma
rabv-red crrstnlB having the coroposition C,^H OBr,. These ci-j-stals,
whe'n heateti to 80^-00' {176='-:94" F.), fuse and give off HBr, tliere re-
maining an amber-colored Ui:|uid, which solidities on cuohog iiud yields,
by recryfitftllization from l>oiltng alpohol, long, hard, rectangular crvHtals
of mnnotjvomo camphor — campho}yi monobromata { L'. S.) — C^^H ()Ur. \\1ien
vftpir of camphor is passed over a mixture of fused {Mtash luid iiitie, heated
tfl a()0--400'' ^572^-752^ ^k'^ unites directly with the potash to form the
K salt of camphotic acid, 0„H,^0,.
Bomeol — Bm'iieo camphor — Camphol — Camphyl ulcoiwl — C,^H„0—
154— is usually obtained from dryobalanops camphora, although it may be
obtained from other plants, and even artificially by the hydrogenation of
laorel camphor. The product irom theue different sources is the same
chemically, so fjir as we can determine, but varies, like the modifications
of camphor, iu its action on polarized light
It forma small, white, transparent, friable crystals ; has an odor whach
recalls at the siime time those «>f liturel camphor and of pepper : has a hob
taste ; is insoluble iu water, readily soluble in alcohol, ether, and acetic
odd ; fuses at 1!J8" (3HK'.4 F.). boils at 212= (413".G F.). _
It 18 a true alcohol, and enters into double decumjKiHition with acids to
form ethers. Wlieu heiited with P,0^, it yields a hydrocarbon, borneaie,
C„H,,. 0.\idizod by HNO., it is converted into laurel cjimphor. ^
Menthol— JffH(/ii/? a/oVio/— 0„H,.O — 15G — exists iu essential oil of
peppermint It crj'staUizes in colorless prisms ; fusible at 3(>° (IHJ\8 F.) ;
sparingly soluble in water ; rea^lily soluble in alcohol, ether, carbon disul-
phide, and in acids. Correspouding to it are a series of mcnlhyl ctlier&
eoraetimos spontaiieoualy deposited from oil of turpentine containing
wi^er; it may bo obtained by frenuently agiti^ting for a mcmth or more u
mixture of oil of turjjentine, alcohol, and ordinai-y nitric acid. It forms
fine, large, rhombic prisms; bp, gr. l.ODW ; sparingly soluble in cold
watar; soluble in hot water, alcohol, and etlier; fusible at 103" (217".4 P.).
Terpinol — (C,,H,,),H.O — 290 — is formed when terpine in solution in
water is treated with a very small quantity of H,UO^ or UCl, and
KAKCAL OF CITEMISTHT.
diatiUed. It is a colorless liquid ; bu an odor of hytuinUi ; sp. gr. 0.&52 ;
boils at IHH" (:}:m''.-( K.). at which temperature it suffers partial decoiui»*
aition. It appears to paasesii the function of aa ether.
Resins — are ^eoeraUy the products of oxidation of tbo h^rocarfaoas
allied to tarebeDUiene ; are amorphous (rarelj cryBtallixie) ; iDsolublo in
water ; soluble in alcohol, ether, and eaaenoes. Many of them oootida
ricidH.
They may bo divided into BcvenU groups, according to tho natur* ol
their constituents: (I.) UaljtamH, which are usuallj soft or Uquid, and
ore distiu^iisbed by containing; free cutnamic or benioic add (a. v.). Ibe
principal uiembcrs of tiiia gruup are beiuoin^ liquidambart leru 6ii2aun,
«<</raj-, and bal«am toiu. (2.) iUeo-rmins GonsLst of a true resin mixed
with an oil, and usnally with an oxidized product other than cinnainio or
benzoic acid. The principal momberB of this group are Burgunniy auil
Canada pitch, Mecca fiu/^tom, and the reaixu of oop«u.-um, cupaiva, cu^k:Ai;
eUmiy taLhnam, and luptUin. (3.) Oum-reww are mixtures of tnw nesiitf
and guDis. Atany of tliem are poesefised of medicinal qnalitiee ; (dots,
ammonwi\ anaffHida, bdMlium, FitjihorhiHiiXy galhajmui, gamboge, gumac,
mytTh, oiibanitm, (ip'^jfjuox, and acnmmony. {i.) True tvsinsare hard aub-
atancea obtainable firom the members of tho three previous classes, and
cootaining neither essences, pims, nor aromatic acids. 8ucb are cole
ox rofin, C'»i>ai, tlamniar, dragon's hlood. Jalap, lac, mattiCf tutd.
(5. ) ioMtf resine, such as aitiber, oiipkalt, aiul ozocerite.
CARBOHYDRATES.
These substanoes are composed of C, H and O ; they all contain
or some multiple thereof; and the H and O which they contain is alwmx'S
in the pro])ortion of H^ to O. Their constitution is still uuknon-u ; pn^i^H
ably some are aldehydes, ntliers alcoliols and others etbera Moist <j^H
them are constitUE^nts of nnimol or vegetable organisms, and hare not been
obtained by complete eyntheiua.
Tliey ore diviuiblo into three groups, the members of each of which
ore isomeric with each other :
L Glucoses.
n. SAairuBOscs.
UL Amvlosss.
.(C.H..O..)
.(C.^„0.,.)
.(0.H..0,)
+OlaooM.
+ Rar<cJiiuroM.
-t-Stiwch.
(Dexiroie.)
-f Liictosi!.
-t-Gljc^gcn.
— IiffiviiloKe.
-^UolbMA.
+ Dvstrm.
Mamitose.
4~Melito«e.
— InaliD.
+OaU(itoM.
+ Melu[ftOB8.
Ttuiioin.
Jnoidte.
-H Tr«haIoee.
CcUuloM.
— Borbin.
+Myco«o.
Guua.
— EnoaUn.
4. PacuMLccbaroM.
1
Glucoses, C,H„0,— 180.
Glnoose — Omjip.-itngar — Dextmm — Lit^:r'sugar — Diabelic sugar. — The
subalimce from which this group tokcu iU name exists in all sweet and
acidulous fruiU ; in many vegetable juices ; in honey ; in the animal economy
in the conteota of the intestines, in the liver, bUe, thymus, heart, h
OLTTC08ES.
SS3
blood, and in Bmall qoantit; in the urine. Pntbologicnlly it ib found io
the saiiTo, perBpirattoo, frocee, anj largely- increawd in tbe blood and urine
in diabetes mellitua (see bolow). It may also be obtained by decomposi-
tiou of oertoiu vegetable substances called (jluamiies (a. v.).
It is prepared artiticially by heatiii^; starch or ccUuloae for 24 to 36
hours wiUi a dilute mineral acid (H^SOJ. Olucotte oblninnd by tliis
metUod is liable to contominatiou with tntces of arseuic, which it receiraa
from the H^SO . Starch is also oonrerted into glucose by the ioflueuoe of
dkut^ut, formed during the germination of grain.
Glucose crystallizes with difficulty from itti aqueous solution, in whit
c^jaque, ST^eroidal maeses eontaiuiug 1 a<i.; from alcohol in lino,
parent, anhydrous prisms; at about Wl" (1411" F.) in dry air the hyc
Tflrioty lojMJs H,0. It ia soluble in all proportions in hot H,0 ; verv solo*'
hie in cold HA) ; st^iluhle in alcohol. It is leas sweet and less soluble tliau
cime sugar. Ib^'solutions are dextrogyrous : M ■■ — + 52^85.
At 170^ (333" F.) it loaea H,0 and is conrerted into glurcjmn, C^„0 .
Hot dilute mineral adds convert it into a brown substance, lUmw arid,
and. in the presence of air, formic acid. It disaolves in ouuceuirated
HSO,, without coloration, forming sulphogiitcie aoiiL CoUl concentrated.
Hj^O, converts it iuto nitro-gliicose ; not dilute H2^0, uudizea it to
mixture of oxalic and oxysacchoric acids. With organic acids it formiJ
ethers. Its solutions diasolve ^totasli, soda, lime, baryta, and the oxide*'
of Pb and Cu, with which it forms compounds. When its aolutiona are
heated with an ulludi they assume a yellow or brown color, and give off a
moUaaefrUke odor, from the furmalion of tflut-ic and meiassic acids. Glu-
cose in alkaline solntioti exerts a strong reducing ai-tion, which is favored
by beat ; A^, Bi, and Ug are precipitated from their salts ; and cupric are <
reduced to cuprous compuunda with separation of cuprous oxide. In
the presence of yeaet, at suitable temiieratures, glucose undergoes alco-
holic fermentation.
PursioLooicvL. — The greater part of the glucose in the economy in
health is introduced with the food, either in its own form or as other car-
bohydrates, which by digestion are converted into glucose ; a certain
quantity is also produced in the hver at tlte expense of glycogen, a for-
mation which continues for some time aft^r death. In »jmo forms of
diabetes the production of glucose in the liver ia undoubtedly greatl/
increased. Tho quantity of sugar normally existing in the blood varies' |
from 0.81 to 1.231 partjier thousand ; in diabetes it riaos as high as 5.8
parts per thoinumd.
Under normal conditions, and with food not too rich in starch and
Ba?charine materials, the qiutntity of sugar eliminate*! as such ia exceed-
ingly small — so small indee<l tlinl some observers have contested tho foot
of any being eliminated in health. It is oxiilizcd in the l)ody, and tfaft
ultimate products of such oxidation eliminated as CO, and H,0. Whether
or no intermediate products are formed, is fitill uncertain ; the prolubility,
however, is that tliere ore. The oxidation of sugar is impeded in diabataarj
Where this oxidation, or any of its steps, occurs, is at present a matter of '
COnjectore merely ; if, as is usmdly bfliovod, ghirose dtsapiicars to a
ui<irkf<il extent in the passage of the blnoil through the lungK, the fact ia ft.
strong supi>ort of the view that its tiiiUHformation into CO, and H,0 doeff'
not occur as a simple oxit^lntiou, ns the notion that migar or niiy othor suV
ataoco is " burned " in the lung, beyond tho small amount retpiired by the
nutrition of tho organ itself, is scarcely tenable nt the present day.
tio long as the quantity of glucose in the blood remains at or below
XAKUAL or CnEMTSTRT.
the normal percentage, it ia not eliminated iu the urine in qnanti
appreciable by tlie tests usiially employed ; when, bowover, ibe unoont
of glucose in the blood BurpaBsee this limit from any cause, the unss
becomes saccharine, and that to an extent pro{x>rtional to the increase of
gluoofle in the circulatiug duids. The causes which may brins about nicb
an incrcaRO ore numerous and varied ; many of them are entirely ronaskat
with hen.Uh, and the mere presence of increased quantities of ^ugar in th«
urine is no proof, taken by itself, of the existence of diabetes.
Sugar ii) detectable by the ordinary teets in the urine under the fol-
lowing cirtiiunstauces :
rUysiologicaHy.~{\.) In the urine of pregnant women and during lu>
tiition. It appears in the Utter stages of gest&tion and does not diaapptir
entirely untU tlie suppreiision of the lacteal secretion.
(2.) Id small quantities in sucking children from eight days totwosnd
one half months.
f3.) In the urine of old persona (seventy to eighty years).
(4) In those whose fotxl contains a large amount of starchy or
ttwJ^
charine muteriaL To tJiis cause is duo the apparent prevalence
diabetes in certain localities^ as in districts where the different varietii
of Bugar arc produced.
PathfA'jfficatly. — (1.) In abnormally stout persons, especially in old !>«•
sons and in women at the period of the menopause. The quantity lioM
not exceed 8 to 12 grams per 1,000 ca {:).5-6.6 grains per ounce), and
disappears when starchy and saccharine food is withheld. This form of
glycosuria is liable to develop into trae diabetes when it appears in yaoog
persons.
(2.) In disctujeu attended with interference of the respirator}' processes
— Imig diseases, etc.
(3.) In diseosf^R whore there ia intoi-ference with the hepatic ciroulatiou
— hepatic congestion, comprcttsioii of the [jortal vein by biliarj cslcoh,
cirrhosis, atrophy, fatty degeneration, etc.
(4.) In many cerebral and cerebro-fipinal i1istuv^>ancefl — general paresis
dementia, epilep^ ; by puncture of the fourth ventricle.
(5.) In intermittent and typhus fevers.
(6.) By the action of many poifions— carbon monoxide, arsenic, chloro-
form, cTirari ; liy injection into an artery of ether, ammonia, phoepboric
ncid, soflium chloride, lunyl nitrite, glycogen.
(7.) In true diubt-tes the elimiiiation of sugar in the urine is constant,
unless arrested by suitiible regulation of diet, and not temporary', as in the
conditions previoxtsly mentioned. ITie quantity of urine is increased, some-
times enormously, and it is of high sp. gr. The elimination of urea is id*
creased absolutely, idthough the quantity iu 1,000 c.c. may be less than that
Bormally existing iu that bulk of urine. The quantity of sugar iu diabetio
urine is sometimes enormous ; an elimination of 200 grama (6.4 ounces)
in twenty-four hours is by no means uncommon ; instances in which (be
amount has reached 400 to €00 grams (12.9-19.3 oimces) are I'ccorded, and
one case in which no loss than 1,37G grams [A^ ounces) were discharged
in one day. The elimination ia not tlie same at all hours of the day;
during the niii^ht less sugar is voided than during the day ; the hourly
eliiiiiuiitiou increases after meals, reaching its maximum in 4 hours, after
wliich it diminishes to reach the minimum in 6 to 7 hours, when it may
disappear entirely ; this variation is more pronounced the more copious
the meal. It is obrioos from the above, that, in order that quantitative
determinations of sugar in urine shall be of r^lipi^'^l value, it is necessary
OLtrCOSKS.
285
that the (leUrmination be made iu a sample taken from the iiiixecl urine of
twenty-four honrs.
Tlie relation existing between the quantity of iiugar in the blooc! and
its elimination by the nriue in diabetes Is well shown by the following re-
sults of Pavy, which also uho^' the boucficiol oficcLa of resti-ictlui,' the diet :
Cue I. Mixed diet
CMe II. Mixed diet
Oa«e II. Ke^tricted diet
CaM III. Mixed diet
Cue 11 L Hf^Htnot^rd diet
CkM IV. P&ttly rRfltricted diet. .
Cbm IV. Partly restricted diet, i
9i monUts later. . . . f
tfauB.
Mloou.
QoanlHrlu
BpfdUo
Biwar extnted
III S4lionn,
BnsaitH
l,0lM|«i1a.
109.01
04.08
01. »4
03,90
46.40
48.11
31.70
eflt)8 O.C.
MIA o c.
3407 O.C.
587S ao.
2470 C.C
1704 c c
fm CO
1040
1041
103!
loac
I0;}8
1036
1084
751 .(t praroB.
03;). grams.
345.3 grams.
507.7 grams.
Its. 8 grami.
31.81 grsms.
14.40 gtams.
6.788
6.640
2.033
4.070 '
2.7W
1.848
1.M8
AxALTTicAi. Cbak,\ctebs. — A Bac^chariDe urine is usually abundant in
quantity, pale in color, of high sp. gr., covered with a persialeut froth
on beintj hhaken, and exhales a peculiar odor ; when evaporated it leavoa
a sticky residue. The presence of gluoose in urine is indicated by the
following tetitH :
If the vrine f/e albiiminmia, it is indxKjiensahlc that Uie aibumfinbc fejjorated
btfort- any of the testtt/or ssu/jar are applied ; tliis is done by adding one or
two drops of acetic acid, or, if the urine be alkaline, just enough acetic
acid to turn the reaction to acid, and no morv, heating over the water-batk
until the albumen has separated in Hocks, and filtering.
(L.) When examined by the polarimeter (see p. 36) it deviates the
plane of polarization to the right
(2.) When mixed with on equal volume of liquor potas*e and heated,
it turns yellow, and. if sugar be abundant, brown. A molaaaes-like odor
is obHervable on adding HNO, (Moore's test).
(3.) The urine, reudercd fuintly blue with indigo solution and faintly
alkaline with sodium carbonate, and heated to lx>iling without agitation,
tarns violet and tlicu yellow if sugar be present ; on agitation the blue
color is restored (Mulder-Neubauer test).
(4.) About 1 C.C. of the urine, diluted with twice its bulk of water, is
treated with two or three drops of cnpric sulpliate solution and about
1 c c of caustic potassa solution ; if sugar be present the bluish precipi-
tate is dinwilved on ngitatton, forming a blue solution ; the clear blue tlaid,
when heated to near boihng, deposits a yellow, orange, or red precipitate
of cuprous oxide if sugar be present (Trommer's tci^t). Iu the applica-
tion of this teat an excess of oupric sulphate is to be avoided, leat tho
color l>e masked by the formation of the black cnpric oxide. Sometimes
no precipiUto is forraod, but the liquitl changes in color from blue to
C" fw ; this occurs in the presence of suiidl quantities of cnpric salt and
e quantities of sugar, the cuprous oxi'k being held iu solution by the
excess of glncose : in this case tlio test is to be repeated, using a sample
of uriuo more diluted with water. In some instances, also, the reaction
IS interfered with by excess of normal constituents of the urine, uric acid,
creatinine, coloring matter, etc, and instead of a bright precipitate, a
muddy deposit is formed ; when this occurs tho urino ia heatod with oui*
MANUAL OF CUBHISTUr.
rail diarcoAl rui<1 filtered ; the filtrate evaporated to drfnus ; the resicliK
extracted with alcohol ; Uie alcoholic extract CTaporoted ; tlie resLdne n-
disBolved in water, aud tented as described above
(o.) Four or fire c.c of KoUiug's solution <aee p. 287) are heated in «
tesUtube to boiling ; it should remain unaltered. The urine is Urn
Added gottatim ; if it contain Hugar, the mixture turns i^^een. and a yellow
or red precipitate of cuprous oxiilc ia fonueil, usually darker in color Ibjui
that obUiiueil by Ti-ouimer'a test The nbscnoe of fj^lueose is not to be iu-
ferred until a bulk of urine equal to that of the Fehling's eolnticw csed
has been wUled, and the mixture boiled from time to time withool tb»
furmatiou of a precipitate. Thia lest in the most convenient and tbonoal
reliable for clinical purposes.
{G. ) A few CO. of the urine are mixed in a test-tube with an Mjiial
Tolumo of Bolutitm of Bodium carbonate { 1 pt crystal cjirbouat^ oud 3 pta,
water), a few gmuuleti uf bisuiutii subnitrute are added, and the loixtun
boUcd for Bomo time (until it be^ns to " bump," if necessary). Ilfiugu
be present, tlio bismuth ptiwiler turns brown or block by re«]uctiott to
olemeulury bismuth (Boettger'a test). No other normal coustilueut of tie
urine reacts with thi» lest ; a follncy is, however, posaiblo from the pm-
«Doe of some oomponnd, wfaicii, by giving up salpliur, may cause tk
formation of tho black bismuth sulphide ; to guard against this, when an
affirmative result has been obtained, anotlier sample uf urine is rendered
alkaline and boiled with pulverized Uthargo ; the powder shooUl not
turn black.
(7.) A solution of sugar, mixed with good yeast ond kept at 26*^ {IT
F.) is decomposed into CO, and alcohol. To apply the fermeutatioD-teit
to urine, take three test-tubes, A, B, and C, place in each some vrasberl (or
compreawd) yeast, fill A completely with the urine to l>o tested, and place
it iu an inverted jXJtution, the mouth below the surface of some ol the
aame urine in another veseel (the entrance of air being prevented, during'
the inversion, by dosing Uie opening of the tulje with the t'mger, or a corfc
ou the end of a vnre, until it has been brought below the surface of the
uriuc). Fill B completely witli some urine to which glucovu baa been
added, and C with distilled water, and invert them in. the aame way as A;
B in saccharine urine, and C in distilled water. I.eaTO all three tubes io a
place where the tem{)eratiire is about 25° (77° F.) for twelve hours, and
then examine them. If gas hare collected in B over the surface of the
liquid, and none in A, the uriuo is free from sugar ; if gas have collected in
both A and D, and not in C, the urine contains sugar : if no gas have col-
lected ill B, the yeast is wortlilene, and if any gas be found in C. the yeut
itself has given off CO,. In the last two cases the process must be repeated
with a now sample of yeast
QiAXTTTATivK I)BTnucniATtn>t OF GLtrcosE.^(l.) Btf the poiarimrtrr,—
The filtcreil urine is observed by the polariscope (see p. 38) and the mean
of half a dozen readings taken as the angle ol deviation ; from thia the
peifoentage ol sugar is detemiinod by the formula p = cn ne — n in wtudi
p = the weight, in grams, of glucose in 1 c.c. of urine ; a = the sd^ of
deviation ; I = the lengtli of tlie tube in decimeters. The name locmilk
may be umd for other uubstuncca by substituting for o'2.BH tlie value of [a]„
for that subetancOL If the urine contain albumen, it must be removed «-
fortiiftrrmining the tvltieofa.
(3.) ^y ijxri^r qravit^t ; Hobert't m^hod. — The sp. gr. of the urine is
cun/uUr determined at 25° (TT*^ F.^i ;r«>x^ i)^ Uunx add^ and the aixtan
J
oxrcosKS.
kqil ftt 25* (77" F.) unlil f«rmentatiou is complete ; the ap. gr- is again
ob«ervecI, and will be found to be lower tluin before. Each degree of dim-
inntion repreaenta 0.21U6 gnun of sugar In 100 o.c. (1 grain per ounce)
oi urina
(3.) By Fehiing's solution. — Of the many formula- for Fehling's boIu-
tioBA, the one to which wo give the preference is that of I>r. Pifiard. Two
■t^tionfl are required :
X Cnpric sulphate (pore, crrBtals) 61.98 grams.
Water 600.0 c.c.
IL Rorhello aalt (pure, cryatalB) 259.0 grams.
Sodic hydrate tiolutiou, ep. gr. 1.12 1000.0 c.c.
When required for use. one volume of No. I. is mixed with two toI-
umes of No. IL ITie copper contained in 20 c.c. of this mixture is pre-
cipitated as cuprous oxido by O.I gram glucose.
To use the solution, 20 c.u. of the mixed Boluiions are placed in a ftuk
of 250-300 c.c. cajiocity, 40 c.c. of distilled wnter are atfdod, the whole
thoroughly mixed and heated to boihng. On the other hand, the urine
to be tested is dilute<l with four times its Volnmc of water if poor in su-
gar, and with nine times ita volume if highly Hacchariue (the degree of di-
lution required iu, with n little practice, detormiucd l^- the api>earance of
the deposit obtained in the qunUtatire testing) ; the water and mine are
thoroughly mixed and a burette tilled with the mixture. A few drops of
aqua ammouiiu are tulded to the Fehiing's solution and the diluted urine
added, in small portions toward the end, until the blue color is entirely
diacharged — the contents of the flask being niaile to boil briskly between
each addition from the burette. When tlie liquid in the fhwk shows no
blue color, when looked through with a white bnckground, the reading of
the burette is taken ; this reading, divided by five U the urine was diluted
with four volumes of water, or by ten if with nine vohimes, gives the num*
ber of ac. of urine containing 0.1 gram of glucose ; and consequently the
elimination of glucose in twenty-four hoiu^, in decigrams, is obtained by
dividing the number of cc of urine in twenty-four houTB by the result ob-
tained above.
Example. — 20 c e. Fehiing's solution used, and mine diluted with four
volumes of water.
Beading of burette : 36.5 0.0. — ^= '^'^ *^-^ urine contain 0.1 gram
glucose. Patient is passing 2,486 cc. urino in twouty-four hours.
— ^ ^ — = 3;J3.G decigr. = 33.30 grams glucose in twenty-four hours.
The accurticy of the determination may be controllcil by filtering off
some of the fluid fi-om the ll<hsk at the eud of the reaction ; a portion of
the filtrate is ucidul'itml witli aeetio acid and treated with potissium fer-
rooyonide solution ; if it turn reddish brown the reduction has not been
complete, and the result is affected with a plus error. To another portion
of tno filtrate a few dropa of cupric sulphate solution are added and the
mixture boiled ; if any precipitation of cuprouH oxide 1>e olHu-rved, an ex-
cess of urino has been added, and the result obtained is less than the true
one.
This method, when carefully condncted with accurately prepared and
MANVAL OF CHEMISTRY.
unJoterioraied solutions, is the best adapted to clinical uses. The coffer
solution should he kept in the dark, in a weU-clD»ed buttle, and tlic Rtopper
and neck of the No. ll. bottle should be well coated with paraffin.
(4.) GratvwWric method. — When more accurate results than are ob-
t.iinuble by Fehling's Tolumetrio process are desired, recourse must be bad
to a deter tnination of the Meij^hl of cuprous oxide obtained by reduction.
A small quantity of frcalily prcpai'cd I^'ohling's solution is heated to boil-
ing in a small flask ; to it is gradually added, with the precautions ob-
served in the Tolumetric method, a known rolume of urine, such that at
the end of the reduction there shall remain an excess of unreduced copper
salt The flask is now completely filled with boiling H,0, corked, and al-
lowed to cooL The alkaline fluid is separated as rapidly as possible from
tho precipitated oxi<le, by decantation and tiltratiou through a small double
filter, an<l the precipitate and flask repeatedly washed with hot H,0 until
the waaUingf) are no longer alkaline ; a small portion of the precipitate re-
mains adhering to the walls nf the flask. The Alter and its contents are
dried and burned in a weighed porcelain crucible ; when this has cooled,
the flask isriuHed out with a Hiuall quantity of HNO,; this tH added to the
coutenta of tho crucible, evaporated over the water-bath, Uie crucible
slowly heated to rednesa, cooled, and weighed ; the diflir-rence between
this last weight and that of the crucible -f that of the filter ash, is the
weight of cuprio oxide, of which 220 parta = 100 ports of glucoBe.
Lcevulose — VncryMaUizable sugar — forms the uncn'stallizable po^
tion of the sugar of fruits and of honey, in whicb it is associated with
glucose ; it is also produced artificially by the prolonged action of boiling
water upon iriulin; and as one of the constituents of inverted sugar.
IdT^'ulose is not capable of cr^-stalliTalion. but may be obtained as a
thick syrup ; very soluble iu water, insoluble in absolute alcohol ; it hi
sweeter but leas readily fermeutablo than glucose, which it equals in the
readiness with which it reduces cupro-poUissic solutions. Its promineut
physical property, and that to which it owes its name, is ita strong left-
handed iwlurizuUou, [aj. =-^106" ai 15^ (59' F.). At 170" (338° F.J it
is converted into the solid, amorphous la'vuloaan, C^„0,.
Mannitose — is obtained by the oxidation of mnnnite. It is a yellow,
uncrystallizable sugar. Laving many of the oharactera of glucose, but opti-
cally inactive.
Galactose — sometimes improperly called lactose— is formed by the
action of dilute acids upon lactose (milk sugar) as glucose is fonned from I
saccharose. It differs from glucose in crystallizing more readily, in being '
very eparingty soluble in cold alcohol, in its action ujwn ]>olarized light, '
[flj„ = +83°.33, and in being oxidized to mucic acid by HXO.- j
Ino8ite—J/««c/e-«iif7nr— exists in the liquid of muscular tissue, in the \
lungs, kidneys, liver, spleen, brain, and bloo<l ; pathologically in tho
urine in Bright's, diabetes, and after the use of drastics in unemia, and
in the contents of hyilatid cysts ; also in the seeds and leaves of certain '
plants. What the source and function of iuofidte in the animal economy
may be is still a matter of conjecture.
It forma long, colorless, monoclinic crystalH, confauning 2 Aq., usually
arranged in groups having a cnuUflower-like appearance. It eflloresces in
drj- air ; has a distinctly sweet taate ; is easily soluble in water. difliculUj I
in alcohol ; insoluble in absolute alcohol and in ether ; it is without action i
upon polarized light
The position of inosite in this series is based entirely upon itB ohem- I
ical compositioD, as it does not possess the other chimtcteri&tica of the
^ J
SACCUAKOSn.
S89
group. It does not enter directly into alcoholic fcrmentatiou, oltLougb
upoD oontact with piitrefving animal matters it produces lactic nnd butyric
■cida ; when bulled nitli barium ur putassiuin Lyilnite, it is not even col-
ored ; iu tlio presence of inosit*^, potu«h precipitates with cupric sulplmto
eolation, tlie precipitate being redisRolved in an excess of potosb ; but no
reditotion tjikea jUaea upon boiling the blue Holution.
The presence of inoait« ia indicated bythe following rSactiona: Scherer'g.
—Treated with HNO^ Uio sututiou evaporated to near drynesjs, and the
residao moistened with ammonluiu hydrate and calcium chloride, and ngnra
eTapomted ; a rose-pink color is produced. Succeeds only with nearly
pore inoaite. Oalloi^'. — Mercuric nitrate produces, in solutions of iuoflito,
a yellow precipitate, which, ou cautious hc-niing, turns red ; tbo color dis-
appears on cooling, and reappears on beating.
Saocdiazosea, C,^,0„— 842.
Saccharose — Cane'Sagar — Btvl-sugar — Sacchartim (U. 5.)— The most
imiwrtaut meml>er of the group, exists in many rootfl, fniitu, aud graaeea^
and is produced fi-om the bugar-<auie, mccharum officinarum, sorghum»
sorghum tnccitanttum, beet, beta tfiUgaris, and sugar-maple, acer mccba-
rinum.
For the extraction of sugar the exi>re8aed iuice i« heated in large pan'J
to about "iW {2VI' F.) ; milk of lime ia added, which causes the preoipi>
tation of albumen, wax, cidcic phosphate, etc; the clear lit}uid is dmwn
ofli and " doUmeil " by pnsfiing a current of CO^ through it ; tho clear
liquid is again tlrawn oft' and evai>orated, during agitation, to the ci^-stal-
lizing-point ; the product is drained, leaviug what is termed raio or mus-
cfi\yuio KiKfir, while the Ut|nor which drnins off is ntfJits^n. The sugai- so
obtained is purified by the proi-css of " retining," which consists essenliidly
in adding to Uie mw (iujr«-r, in solution, albumen in some form, whicJi in
then coAgiil^tted. Illteriug firtib through cnnx'iis, afterwanl tlirough animal
charcoal ; the dear liquid ia oraiwrnted in " vacuum -pans," at a temper-
ature not exceeding 72' (lGl".(j F.), to the crystallizing-point The pro-
duct ia allowed to crystallize in earthen moulds ; a saturated sohitinn of
pare sugar is puiired upon tho crystalliuo mass in order to displace the
uncrystalHzable sugar which still remains ; and Uio loaf is (in.'dly dried in
an oven, llie liquid displaood aa above ia what is knowa as sugar-house
tijruv.
I'ure sugar should be entirely soluble in water ; the solution should not
turn brown wht-n wormed with dilute potassium hydrat« solution ; should
not reduce FchUng's solution, and eliould give no precipitate with ammo-
nium oxah\te.
B^-*»gar is the same as cane-sugar, except that, as usually met with
in commerce, it is lighter, bulk for bulk. A'u^r-eantiy. "r rovK'-iiiiidy, is
cane-sugar allowed to crrstnllizo slo»iy from a concentrated solution with-
ont Agitation. Maple.-«n'jar is a pdurtially refined^ but not decolorized va-
riety of cana angar.
Saccharose cri|-stallizes in small, white, monodinio prisms ; or, as sugar-
candy, m large, yellowish, transparent crystals ; sp. gr. 1.G0C. It is very
soluble in water, dissolving in about one-third its weight of cold water,
and more abundantly in hut water. It is insoluble in absolute alcohol or
ether, and its solubility in water is progressively fiiminished by the addi>
:
tion of aloobol. Aqueous solutions of cane-sugar aro dcxtrogyrons, [a]^ =
When saccharose is heated to 160° (320^ F.) it fuses, and Uio Liquid,
on cooling, nolidifies to a yellow, transparent, amorphous mawt, Imovn as
barlfy-eufjar ; at a aligbtly liigber temperature, it in decomposed into ghi-
oose and Luvulosiiu ; at a stiU higher temperature, H,0 is gircu oS, and tlia
glucose alrea^iy formed is converted into glucosan ; at 21U^ (410"^ F.) the
evolution of H,0 is more abundant, and were i-emoina a brown matehsl
known ns carumelt or burrU smjar ; a tasteless substance, inauloble ia
strong alcohot but soluble in }{,0 or aqueous alcohol, and usch] to com-
municate color to spirits ; finoUj', at higher temperntnree, methjl hydride
and the two oxides of carbon are given off; n brown oil, acetone, acetic
acid, and oldelijde distil over ; and a carbonaceous residue remains.
If saccharose be boiled for some time witli H,0, it is converted into
ineerted nufjar, which is a mixture of glucose and la-\iiloRe: C, H,,0 +
H,0 = C^„0, 4- C^„0,. With a solution of saccharose the poWizaUau
is dextrogyrous, but, after inveiliou, it becomes lu:Tog}-rouH, because th?
lefthauded ootion of the molecule of k'Tulose produced, \fi}„~ —106,* is
only partly neutralized by the rightdianded action of the glucose, [a], —
+ 5*2 .85. This iuveniiuu of cuuc-sugnr is utilized in the testing of samples
of ftugar. On the other hiuid, it is to avoi<l iU occurrence, nud the conse-
qaent lose of sugar, that the vacuum -|>au isuse^l in refining — itsobject be-
ing to ivmove the H,0 at a low teni|>eniture.
IliOBe acids which ore not oxidizing ogcutg act upon saooharoBe io
three ways, according to circumstances : (1) if tartaric and other organic
acids be heated for some time witli saccharose to lOu" — 120° (t213°-24Ji'
F.), oompoimds known as aa/xharides, and having the constitution of
ethers, are formed ; (2) heated ^-ith niinenil acids, even dilute, and less
rapidly with some organic acids, saccharose ia quickly converted into io-
vcricd sugar ; (8) concentrated acids decompose cane-sugar entirely, more
rapidly when heated thou in the cold ; with HCl, formic acid and a brown,
flocculent miiteriftl (uhuic flcid?) are formed; with H,S>0,, SO, and H,0
are formed, and a voluminous mass of charcoal remains. Oxalio aoid.
aided by heat, produces CO^ fbnuio ooid, and a brown substACtoa
(humine ?).
Oxidizing agents act energetically upon cane-sugar, which is a gooil
reducing agent. Wiih potassium chlorate, sugar forms a mixtui-e which
detonates when subjected to shock, and which deflagrates when inoisteued
with HjbO^. Dilute HNO„ when heated with saccharose, oxidizes it lo
sacchanc and oxalic acids. Concentrated HNO,, alone or mixed with
HfiJO,, converts it into the explosive nitrv-siuxiiartMe. Potassium per-
manganate, in acid solution, oxidizes it completely to CO, and H,0.
Cane-sugar reduces the compounds of Ag, Hg and An, when heated
with their bolutions ; it does not reduce the cupro-potasaic solutions in tlio
cold, but effects their reduction when heated with them to an extent pro-
portional to the amount of excess of alkali present
When moderately heated with liquor potasBw, e^ne-sugar does not turn
brown, us dtwa glucose ; but by long- ebullition it is decomposed by the
alkalies much less readily than glucose, with fomiatiou of acids of the
^tty series and oxalic acid.
With the bases, saccharose forms definite compounds called Kucro/ca
(improperly sacchamtcii, a name belonging to the tudts of saccharic acid).
With Oa it forma tive corapouudR. Hydrate of calcium dissolves readily
in solutions of sugar, with formation of a Ca compound, eohtble in H,0,
A
AMTL08E9.
291
tionfaining an excees of sugar. A golulion oontaining 100 parta of sugnr
iu GOO ports of H,0 dissolves 32 ports of calcic oxide. These Kulutiona
h&ve an alkaline taatc ; are decomposed, with formation of a gelatiuoua
precipitAte, when htuitefl, and, with depoflition of calciiuu carbouato and
regeneraLiou of saccharose, when ii-eat«d with CO,. Quantities of cal-
ctum sucratea are fi'cqueutly iutruduced into augare to increaae tlietr
weight — an adulteration the leaf) readily detected, as the aucrata diaaolfea
ii-ith the BQgar. Calcium aucrates exist in the Uq. coicis itaccharataa (Jtr.).
Yeaat cauaea fermentation of soltiUons of oane-imgar, but only aft«r its
conversion Into fj;lucose. Fermentation ia alao caused by exposing a aolu-
tion of sngar containing ammonium phosphate to the nir.
During the process of digestion, probably in the small intestine, cane-
sugar is conrerted into gincoae.
Lactose — MUk-ttu'jar — Laotine — Saccfutrum laciig ( U. S., Br. ) — has
hitherto been found only in the milk of the mammalia. It may be ob-
toined from skim<milk by coagulating the casein with a small quantity of
H,SO^, filtering, evajxirating, redisaolviug, decolorizing with animal char-
coal, and reci-ystallizing.
It forms prismatic crystals; »p, gr. 1.53; hard, transparent, fiuntly
sweet, soluble in 6 parts of cold and in 2.5 part« of boiUng H/) ; soluble
in acetic acid ; insoluble iu alcohol and iu ether ; Ha solutions are dextro-
gyrooa, [0]^=+ 59^3. ITie crystals, dried at 100^ (212' 1'.), contain 1
Aq., which they lose at 150° (302'' F.).
lACtose ia not altered by contact with air. Heated with dilute nuneral
or with strong organic acids, it ia converted into galactose. HNO, oxidizes
it to mucio aud oxalic acids. A mixture of HNO, and H,SO, couvurts it
into an expIoaiTO nitro-compound. With organic acids it forma ethers.
With soda, potash, ami lime it forms compounds similar to those of sao-
charoae, from which lactose may be recovered by neutralization, unless
they have been heated to 100^ (212^ F.), at whidi temperature they ore
decom|wseJ. It reduces Fehling'a solution, and reacts with Trommer'a
test • •
In the presence of yeast, lacioM ia capable of alcoholic fermentation,
which takes place slowly, aud. as it appears, without previous tranaformo-
UoD of tlio lactose into eitlier glucose or galactose. On contact wiOi
putrc-fying albiimiuuidH it entt^ni into lactic fermentation.
The average proportion of lactose in different milks is as foUowa : Cow,
5.6 per cent ; more, 6.5 ; ass, 6.8 ; human* 5.3 ; sheep, 4.2 ; goat, 4.0.
When taken inlemally, it ia converted into galactose by the panoreatio
secretion ; when injected into the blood, it does not appear in the urine,
which, however, contains glucoae.
Maltose — A sugar closely resembling glucose in many of its proper-
ties, is formed along witli dextrine daring the conversion of starch into
Bi^ar by the action of diastase and of the cT^-T>tolytea of the saliva and
pancreatic juice. It cryatollizea as does glucose, but diflera from that sugar
in being less soluble in alcohol and in exerting a dextrogyratory power
three times as great.
Amyloaea, ,(C.H„0,)— nlGl
Staroh — Amyium (U. 5.)^the most important member of the group,
exists in the roots, stems, and seeds of all plants. U ia pre(iared from
ruse, wheal, potatoes, ni'aniot, beans, sago, arrow-root, etc. The com-
minuted Tegutablo tissue is steeiK^l for a considerable time in H,0 ren-
15
293
MANUAL or CBEMISTRV.
dered CiUDtl^ alkAline with eodft ; tLe Boftciied mnaa is tfaco rubbed oo a
nere under a corrent of water, which waehea out ttie el«rch gfracnles ; the
waaihinga are allowed to deposit the starch, which, aiter waahing br dr-
oftoUtiaii, is dried at a low temperaturo.
Starch is a white powder, liuving a pocuUar uUppery feel, or it appears
in short eolumoar masses. Tlie granules of at&roh dilTer in size lod
appearance aoconling to the kind of plant from which tlicv have been ob»
taijied. They are rounded or egg-shaped massen. having at the centre or
toward one end a spot, called the hilum, around which are a series ofcoo-
eentrio lines more or less well marked. Piffcrcnoss in size, shape, and
markings of starch granules are shown in Fig. 39,
F1«.8Sl
St&rdi is not altered bv exposure to air, except that it absorbs
moisture. Commercial stardi contains 18 per cent, of H.O, of which it
losea 8 per cent, in vacuo, luid the remaining 10 per cent, at 145" (2*J8*'
F.). It is inaolnble in nicoiiol, tther and cold water. If 15 to 20 jjarts
nf KO bo grndunlly heated with 1 part of stareb, the granules swell at
about 55" (i:n^ F.). and ul 80^ (176° F.) they have rea-'hed 30 times
their original dimensions ; their structure is no longer distinguishnblo,
and they form a translucent, gelatinous mass, commoiUy known as starch
AMTL0SE9.
past«. In this etato tbe starch is AaUI to be lijdrated, and, if boiled witli
much U,0, uud tbe liquid filtered, a solution of starch pussea through,
which ia opaleacent from tlie auBpenaion in it of undissolved particlea.
Cold dilute snlutious o( the nlkalies produce the same eflcots uu starch oa
does hot wat«r. Hydmtcd stai-ch ia deitrogyrous, [u], = + 216". Dry
boat causes the granules of Btarch ia swell and burst : at 200"" (392'' F.) it
ia conTertod into dextrin ; at 2M[)'^ (Wfi^ F.) it forms a brownirth-yellow,
fused maas, composed principally of pyrodextrin. Hydratcd starch is
oooTeried into deztriu by hentiuf; with HO at IGO" (320' F.). <uid, if the
action he prolonged, the new product is changed to glucose.
The amount of starch contained in food vegetablea varies from abont
5 per cent in turulps to B9 per cent lu rice, aa will be observed in the
fc^owing table :
GoMPoarnon or YtosnBtx Footw.
Kltrovm- | .IMrtritt.'Octlii'
toad nuttar. Starch. aW. I
WlMK, himl
VbcMt, hMrd
Vimi, lurd... , ..
WHMt, aamt-bald ,
WlMtf.HA
«r-
Bsrli^....
Tkiar .... .
UrmA -..
CUyitiemi ....
QvlAiM Soar . . .
VhlMbMR...
FaM.drti>d...,
LanUta........
PMkhi
PoUlo
K mH. pfMotD- .
I'untiip
Twui|i
tLTi
ULM
».u
UlS
Ifttt
11.00
taw
H-W
It-M
TW
8 10
n.m
H,»
11.0
MM
SB as
■uo
n.m
aw
aiD
i.eo
i.*o
1.10
HlflS
».«
Sim
To.ca
76.S1
M.I1B
«.4i
mm
61M
Vim
w.ao
Bft»
W-IU
66.70
Ban
W.tt
i&ai
1&0B
a«
«.ffi
ciu
too
&SD
a 10
7.08 B.BO
aoo
8.U
B.HU
MO o.ao
t.lB
1.0
i.m
t.m
ao
.... fi.U
.... 8.0
ao ,i.«o
I.OB ^.0
aOB tfl.80
«.M t.lO
tM tl.U
. . |0.»
0.4B iQ au
... 10 9U
.... oeo
carte iVacf«iHa
<a«
10.60
M.<0
•ato
KJ.9
10.0
u.o
ie.0
UM
aw
aiM
aao
11.00
74.0
n.o
■T.IO
810
sau
n.o
au
AuUioHtjr.
l%k}WI.
Paytn.
p»r«i.
r*fan.
r»r«i.
Utbaby.
Utiiabj.
LMbNtl).
Pann,
I*ajMi.
Pajm.
Papn.
PayMi,
PatMU.
(.Klicby.
MO IVmi.
t.afh*tar.
r*'
If starch be pround up with dilute H,SO,, after about half an hour the
mixture gives only n riolet color with 1 (ace l>elow) ; if now the acid ho
neutralized with cliallc and the ^tcred liquid evaporated, it yields a white,
granular product, which differs from starch in bein;;r soluble in H,0,
eapecially at CO" (122^ F.), and in having a lower rotary power, [a], =
4- 21 P. If the action be prolonged, the value of [aj.cnutinuestofnnlc until
it reachea +73.7^, when the product consLsts of a nuxtiire of dextrin and
glucose. Concentrated HNO, dissolves starch in the cold, forming a
aitro-product called arylodin or pfjro.ram, which is insoluble iu JLO, sol-
uble in a mixture of alcohol and ether ; explosive. HCl and onalic acid
convert starch into glucose. When starch is heated under preaaure to 120^
(248" F.) with ateai'ic or acetic a<ud. compounJa are formed which seera to
be ethers, ami to indicate tliat starch is the hydrate of a trivnleut, oxygen-
ated radical, (C\H,Oj'". Potash and soda in dilute solution convert
■torch into the soluble modificatiou meutiooed above.
KANtrAL OF OHTOngTBT.
A dilute eolation of I produoea a more or less intense blue-Tiolet cokor
viih atorcb, either (by, faydrat«d. or in eolution, the color disappeuisg
on the flpplicntion of heat, and returning on rooling. If to a solution of
storeli, biumi by I, a Bolution of a neutral salt bo added, there eeparates t
blue, flocculcnt deposit of the so-called iodide of atarch. Iodine reuden
starch soluble in water, and a Bolubie iodized starch, Antylum iodatum
{ V. S.f, is obtained by triturating together lU pta. Htardi, 2 pta. water, anj
1 pt. iodine, and drjiiig below -iO" (104" F-).
Starch has not been found in the animal economy outside of the ali-
mentary canal, in which, as a prerequisite to its absorption, it must be
converted into dextrin and glucoae. Thia change ia partially effectCfl by
the action of the saliva ; more rapidly with hydrat«d than wiOi dry starch,
and more rapidly witli the saliva of some auima^ than that of othera ; tbou
of man and of the rabbit acting much more quietly than those of the horse
and dog. A great part of the starch taken with the food passes into the
small intestine unchanged ; here, under the influence of a pancreatic cnp*
tolvte, a further transformation into glucose, and of a portion into lactic
and butyric acids, takes place.
During the germination of grain, as in the process of malting, a pe>
ouliar, nitrogenized substance is produced, which is known as diasioie.
Under the influence of this body the starch is more or leas comptetelj
oODTerted into glucose, iu very much tho same way as the converaiou occurs
in the body.
This " diastatio " action, whether produced by regetable or animal
prooeasee, does not take place by a simple conrersiou of starch into glucose,
by some auch single reaction as that expressed by C,li,,0, + H,0=C^,.0„
but by successive stages in which "soluble starch " is first produced, tnea
aereral bodies called dextrinesj then maUose, and finally glucose. (Sea
Dextrin, p. 295.)
Glyoogen occurs in the liver, the placenta, white blood-corpuscles,
pus-cdlts, young cartilage-cells, in many embryonic tissues, and in rouHcular
tissue. During the activity of muscles the amount of glycogen which they
contikiu is diminished, and that of augar increased.
Pure glycogen is a snow-white, jlloury powder ; amorphous, tasteless,
and odorless ; sohible in U,0, insoluble in alcohol and ether. In H,0 it
swells up at tirst, and forms an opalescent solution, which becomes dear
ou the additiuu of potash. Ita solutions are dextrogyrous to about three
times the extent of tlioae of glucose.
Dilute acids, ptyolin, poncrcatin, extract of liver-tissue, blood, diastase,
and albuminoids convert glycogen into a sugar having all the properties of
glucose. Cold HNO, converts it into xylaidin ; on boiling, into oxalic
acid. Its sulutioiis dissolve cuprio hydrate, which is, however, not reduced
on boiling. Iodine colors glycogen wine-red.
Concerning the method of formation of glycogen in the economy, but
little is known with certainty ; there is little i-oom for doubting, however,
that while the bulk of the glycogen found in the liver results from mod-
ification of the carbohydrates, it may be and is j>roduce<l from the al-
buminoids as well. The ultimate fate of glycogen is undoubtedly its
trnusformation into Hu<^nr under the iuflueuce of the many substances ex-
isting in the body capable of provoking that change. This transformation
is continuous in the liver during life, and is accomplished through the
same series of intermedlitry changes into dextrins and maltose as iu the
case of the conversion of starch into sugar, except that possibly the struct-
ure of the dextrins umy be different.
AMTLOS^.
L
Dextrin — British gum — a substance tesembling prum arable in appear-
anco aud in aiauj properties, is obtainecl byouo of tbrce methods : (1) by
Rubjecting starch to a ilry heat of US'* (347° F.) ; {^) br heating starch
with dilute H,80, to SK)' (194° F.) until a drop of the liquid gives only a
tvine-rcd color ; iieutnilizing with chalk, iUt<:i-iug, concentrating, precipi-
tating with alcohol ; (3) by tho action of diastase (infusion of malt) upon
bjdrated starch. As soon as the starch is dttwolved the Uquid must be
rapidly hented to boiling to prevent saccliohtication.
CoiumcTciul dextrin is a colorless, or viUowish, amorphous powder,
soluble in H,0 in all proportions, forming niueilnginous liquids. When
obtaine<l by evaporation of its solution, it forms masses resembling gum
arabic in appearance. Its solutions are dextrugyrous, and reduce cupro-
potaasic solutions under the influence of heat, to amounts vnrying with
the method of formation of the sample. It is colored wine-red by iodine.
It is extenmTcIy used in the manufacture of mucilage.
Becent investigations have ahown that by the action of diastase upon
starch, four dextrins are produced : 1st, Erythrodextriti, which is colored
red by iodine, and wiiich io eaiily attached by diaatase ; 2i1, AvhroOdexirv/i
a, not colored by iodine ; partially converted into sugar by diflBtaRe ;
rotary power [«]p= + 210" ; reducing power (glucose — 100)= 12 ; 3d,
Achroi^iextrin fi, not colored by iodine, nor decomposable in 24 hoiurs
by diastase ; rotar)' power + 190* ; inducing power — 12; 4th, AcbroOdex-
trin y, not colored by iodine, nor decomposed by diastase ; slowly con-
verted into glucose by dilute H,SO^ ; rotary power = -f 150* ; i-educiug
power = 28.
An explanation of this seriea of transformations has been snggested in
the supposition that the molecule of starch consists of 50(C,^,O,J ; that
this is first converted into soluble starch 10(C,.H,,O,,), and that this is then
oottTerted into the different forms of dextrin by a seties of hydrations
attended by simultaneous formation of maltose, of which the £iud result
might be represented by the equation :
10(O.^«OJ + 8(H,0) = 2(C.^0J + 8(C.,H„0„)
Solnbln aturoh. VaXar. AohraOdrntrin.
Cellulose — Cdbdin — Li^in — fonns the baais of all vegetable tissues ;
it exista almost pure, in the pith of elder and of other plants, in the purer,
unsized papein, in cotton, and in the silky apjiendages of certain seetla.
Cotton, freed from extraneous matter by boiling with potash, and after-
wartl with dilute HCI. yields pure cellulose.
It is a white material, having the shape of the vegetable structure
from which it was obtained ; insoluble in the usual neutral solvents, but
soluble in the deep-blue lii^uid obtained by dissolving copper in ammonia
in contact wiUi air.
Vegetable parchment^ or parchment paper, is a tough material, poases^
ing all tha valuable properties of parchment, made by immersing imsized
paper for an instant in moderately strong H^SO^ washing thoroughly, unci
drying,
NilroceUuhsfi. By the action of HNO, upon cellulose (cotton) three
dillerent products of substitution may be obtained : mononilro-ceUuioM!,
soluble in acetic acid, insoluble in a mixture of ether and alcohol ; dinitr<h
e^vlvae, iuaolublo in acetic acid, soluble in a mixture of ether and alcohol ;
trinitr<hcdtuto9e^ soluble in both the above solvents. Qun-c(Mon or pyroay-
296
IT.
hn is fiompo«ed of varying proportions of tbesd three' <lRnTaUT«fl. '\^tm
guD-cotton is required as au oxploeivo agent, tho proccsB is bo mauaj^
ihat ilie product hIjaU contain the greatest possible proportion of trinitro-
celluloae, the most readily inflanuuable of the tUree. When required for
the preparation of culloilion, for uee iu medicine or in pliotograpby, dinitro-
cellulose is the most vnlunhle. To obtain this, a mixture is made of equsl
weights of HNO, and H^SO^ (of each about 6 times the weight of the cot-
ton to be treated) ; in tliis the cotton is immersed and w^ stiiTed (or
about three minutes, after which it is well utirred in a large TSBsri of water,
washed with fresh portioDR of water until the wosUlnga are no longer pre>-
oiniLoled by barium cliloriiU-, and dried. CoHodinn is a solution of diuibtv
cellulose in a mixture of three rolumes of ether and one volume of aleoboL
Vdlnlotii is gun-cotton and camphor compacted under pressure;.
Qums—aie Bubetancea of unknown constitution, existing io planli;
amorphous ; ttohible in water, insoluble in alcohol ; converted into gluooM
by boiling with dilute H,SO,.
Lichenin is obtained from vanons lichens by extracUon with boiling
water, fonuing a jelly on cooling; it is oxidized to oxidic acid by HKO, ;
ifl colored yellow by iodine ; and is precipitated from its solutioua by
aloohoL
Arabin is the iMiuble portaon of gum arable and gum senega] — Atada
(U. S.). To separate it, giuu arabic is dissolved in water acidulated with
HC'l, and precipitated by alcohoL It is a white, amorphous^ tasteless sub-
Atjiiice, which is not colored by ioiliue ; ifl oxidized by nNO^ to muoic and
saccbnric acids ; is converted by H,SO^ into a non-fermeutable sugaj', ara-
6»io8e ,■ and Iins tho composition, t'.,H„0„ -f 1 Aq.
liaxmrin constitutea tho greater part of gum tragacantb ; it is insoluble
iu water, but swells np to a jvUy in that lluid.
Cevtuin is on insoluble gum exuded by cherry- and plum-troca ; water
acta upon it as upon bassorin.
AROMATIC SUBSTANCES,
The name of aroin(Uic gubntancea was 6rst given to a class of bodiefl
relftted to ben7^io acid, and including a number of products possessed of
aromalio odors. At present the meaning of the term has been extended
to include a groat number of bodies belonging to, or derivable fn)m, the
hydrocju-bons of the tifth and higher series, all of which may, in fact, be
oonaidereii as prmbicta of addition or of substitution, or both, derivable
from Iwnzene, C,H,.
A few of these Bubstancefi, such as benRoicr acid, have long been known,
and occur in nature in quantities sufficient to readily supply idl preaent
demands. Others, such as salicylic acid, althongh existing iu nature, are
found in small amoimt, and artt now manufactured artificially by processes
which could only have been devised after a knowledge of "their oonstitti-
tiOD was obtaineil. By fj»r the greater numlwr of aromatic compounds at
present knnwn have no existence in nature, and are obtained as products
of tlie laboratory or of maniifncturing industries. Anioiig thtse are many
substances for which Taltiiible uses have already been found in the arts
and ill medicine— *'.(/., the aniline, anthracene, and naphUialene dyes,
carbolic and cresylic acida^whilo harillv a day pusses without a sugges-
tion of the practical utility of some substance formeriy known only aa a
" chemioal cnzioaity."
4
FIFTU 6SBIB8 OF UYUKOOARBONS.
m
FIFTH SERIX» OP HYDROCARBONS.
Sehies C.H,i^,.
Tbe hydrocftrbons of this serieB ai-e tlie nbirting-points from -wliich the
major part of that numerous and iinjxirtant class of substancea usaallj
elaased »s aromatic are obtainable or derivable. Tboec of the series at
preeent knovm are :
...CJU ....hort.»t W.^dTB-. 7P.) J Cbiw™ C^H,, ....Iwlta k tB1*.4{»l". Br )
IMmd* OtU» ....lKiluUlll>'.1(S.V>. BP.l OynwM CmH,4... .b>'lb>u tTC-.tl(](«>. U r.l
XylMH C.U,t....bottNUl-tt>.0i«T-.aF.) lLaamw C„U||.. ..bofiB at llStr.Oino*. 4 V.)
Benzene — Benzol — phenyl hydridf! — C,H, — 78 — (not to be confounded
vith tbe commercial benzine, a uiiiture of by<lrocarbuns of the serin
C.H^^ , obtained from pcti-oleum) does not exist in nature, but is yro-
duced in a number of reactions. It is obtained by one or two melliods,
according as it ia required chemically pure or mixed with other eub-
stouoca.
To obtain it pure, recourse must be bad to tlie decomposition of one
of ita derivarives, benzoic ncid ; this aiibstance ia intimatj>lT mixed with
Spt& slacked lime, and the mixture heated to dull reduesH lu an earthen*
ware retort, connecteil witli a well-cooled receiver ; the upper layer of dia-
I tilled liquid is separated, shaken, vdth. potaasium hydrate aolution, again
■ ti^Bparated, dried by contact with fused calcium chloride, and redistilled
r over the water-bath.
For use in the arts, and for most chemical purpoaefl, benzene is ob<
tained from conl- or ga.s-(tir, an exceedingly complex mixture, contaioing
some forty or lifty substances, among which are :
1^
HTDnOCARIKIKa.
ACIDtL
Bj
kBIlL
S«oc«o«.
AoetiaplithaleDe.
Cu-bolio.
Pyridine.
IridoliDe.
Votoene.
FlooreDQ.
OMylia.
Aniline.
CiTptidin*.
X/ltne.
AnUiracvoo.
Pblurvlio.
Piooliuo.
Acridioe.
Cnmeac.
Eeteoe.
Itofolio.
Lntddine.
Coridine.
CftiM^oe.
Cbryanoe.
Osypheoio,
ColluliDe.
Butiidiafi,
yaphthaleae.
Pyreoe.
Leuoollne.
VtridiiM.
By a primary diatillation of rool-inr the most volatile constituonts. in-
cluding benzene, are separated as light (til ; this is washed, tirat with,
H,SO.,iuid then with caustic soda, and afterward redistilled : that portion
being collected which lusaea between HO* and 85' (17C'-186' F). Tliis
is the 'commercial benzene, a product still contaminated witb the higher
homologues of the same scries, from which it is olinoHt imjwssible to
fleperate it, but whose presence is rather advantageous than otherwise to
the principal use to which benxol is put. — the manufacture of aniline dyes.
Bouzcub is a colorless, mobile liquid, having, wheu pure, an agreeable
odor; sp. gr. 0.86 at 15^ (59' F.) ; crystallizing at + 4^ 5 (40°. 1 F. ) ;
Irailing ut 80". o 076^.9 F.) ; xery sparingly soluble in water, soluble in
alcohol, ether, and acetone. It diaaolves I, h, P, reeina, caoutchouc, gutia-
percha, and almost all the alkaloids. It is iuflommable, and bums with a
luminous, smoky flame.
Benzene unites with CI or Br to form products of addition, or of sub-
stitution ; tbe corresponding iixline compounds can only be obtained by
indirect methods. Hulphuric acdd combines with benzene to form a neu-
MAJTTTAL Oy CITRMISTRT.
^ira] sahBttmce, xulphn-itnuide, ivlien th(> anhjrlrotia odd isnaed, Uidp^n^-
ttdphuruue acid with Uie ordiniiry H,80 .
If fuming UNO, of sp. ijr. 1.52 be uovIt ftddod to benzene^ a nAAtA
li(]aid ia formed ; from wliich, on the addition of H,0 a reddisli-rellow
oil separates, aud is purifit^d bj washing wiUi JLO and with sudiam ou-
bonato solution, driving aud rectifying. Tbia oily material is mononitnh
\Umxene (aoo p. 313). If bt-iizol bo boiled with fuming HNO,, or if ii be
droppeil into a mixture of HNO, and H,SO^, so long aa the fluids mix,!
^crystalline product, dinUro-beiizene, ia formal.
The conttUulion of benzeoe, the nucleus of the Aromatic compouDiIti,
differs in character from tbtt of the hTdrocnrbons of the Bonee Litli«rl«
lOonsidered, and ia of importance in connection with the fnrmationof ill
Sumcrous derivalivee. ^Vriting the mulecular foi-muUe uf the mxth of odi
of the first three series (the constitutioD of those of the tercbeoUieiie
series is still doubtful) we have:
CHH.
C = H.
ThMBMlM.
CHH.
i = H.
i.,^
A = H.
t.
=-■
C = H.
A = H.
i-H
i>
i^H.
L^
III
C-H
c^..
0^..
C.H.
It will bo observed that in each of these tho chain of C atoms is an
open one, and that tho series diRer in this, tliat in the first each of the
C stoniB exnhangeB with its neighbor a single valence ; in the second two
neighboring C atoms exchauge two Mdences between them ; and that in
the third there is an exchauge of three valenees l>etweeu two neighboring
C atoms. And, further, that in tenns above the second in tlie first two aeries,
and the third in tha third serieR, superior homologiie-i may be considered
as forme«l by interpolation of CH, iu the chain of the one next below.
In the case of l>enzene the C atoms are arranged, not in an open, but a
closed chtiiu, and exchauge with each other alternately one and two tip
lences, and consequently the molecular formula of boiizol ia :
H
A,.
c/
^rr\/^
,/
Tlie superior homologues of l>en7ene are derived from it bv the mib-
etitutiou of CH, for H^ and all the derivatives of benzol are formed
FIKTH SKRlEa OK UYDBOCARBOIfS.
299
Bucli subfltitutioo of a group or groups for an atom or atoms of H, in such
a way Uiat they all coutain one or mure groups uf aix atoms of C arranged
as aboire :
H
H
' A
A
H-C C-C=H,
H-C C-O— H
1 11
H-C a-H
H— C C— H
f \c/
\c/
- ^
k
Mmm.
Pli«Ml(Mrbi>lloMMX.
H
}{
' A
A
H-C C— (NO.)'
H— C C— <NH,)'
H-C C— H
1 II
H— C— H
' \c/
\c/
! ^
1
H
The superior homolopues of benzene include many iscmeres. As they
are derirable from benzene by BubHtitution of a hydrocarbon radical or
radiculu CnH,H + ^ for one or more atoms of hydrogen, the following iso-
maj exist :
C,H (CHX = I>imethylben7.en6 1 /^ tt
C^,{C^J ^ EthylbcuzcDc \ ^-"»«
C^H.jCH.i, = Trirnethylbenzene )
C^,{C,H.) = Propylbciizeno \ = C,H„
C,H,(CIi,)(C,H ) ^ Methviethvlbenzene J
C.HJCH.), r= Tetraiuethylbenzene "1
C^.(C,H,), = Diethylbenzene
C.HjC.HJ = Butylbenzone } = 0,^,
C.1I,(€H.),(C H ) - Wmetbvlethylbenzene
C,H,(CH,)(0^) =: Hethylpropylbenzene J
The number of isomeroa of the higher terms of tlie Beries Is further
increased by tlie ooctuTenco of increaeing numbers of iaomereB in the rad-
icals tbemaelves in C,H, and all higher terms. (See graphic formula,
p. 172.)
In these hydrocarbons and in other dcriTatires of benzene the six atoms
of oorbon belonging to benzene constitute what is known on the benzene
nudetts, benzene ring, or the principal chain; while the substituted groupa
are designated as the lateral chains.
K
800
^AmTAL OF OREMIffrBY.
Toluene— Toluol— Mahyl-}>emene—C,H^,CB,—Q^— exifiU in the pro-
dticis of diBtUlation of woud, coal, etc, aud aa uue of tiie constituents oi
commercial benzooe. It bos been fonnod syntbetioally by acting upon &
mixture of monobromo-ben7*iie and methvl iodide ■witli sodium.
It is a coIorleaB liquid, having a iMJcuHar odor, differing somewhat from
that of benzene ; boils at U0°.3 (230".5 F.) ; doea not solidify at -20'
( -4"' F.) ; sp. gr. 0.872 at 16* {59* F.) ; almost insoluble in water, solu-
ble in alcohol, ether, cArbon dimilphide. It bum» with a bright, but verr
smoky flame. It jielda a number of derivativea similar to those of ben-
zene, among which may be mentioned nitr'>-tuiitrne and toiuidiiuf, the ho-
niologues of nitro-benzene and aniline, which accompany those subetances
in the commercial products ; creeylol, tlie superior bomologue of carbolic
acid, and tenzylic alcohol.
Xyiene~Xylol—Dimetht/l-brnzene— C.H,(CH,), — 106 — aocompaniM
ita inferior homologues in coal-tar. When pure it is a liquid of an aro-
roatic odor; ap. gr. 0.865 at 20^ (68** P.) ; boila at 142" (287*.G F.);
iuaoluble in water, soluble in ether, benzene, etc., sparingly soluble in
alcohol.
There are three isomeric substances having this composition, and
differing in the position in which the substituted CH, groups are pbred.
XCach of these corresjwuds to a serieu of derivativca parallel to thoao of
benzene.
Cumene-Ciinu-tl—Propifl-hrnzenf' — 0,Hj(0,H,) — 120— ia obtained br
distilling a mixture of cimiinic acid and lime, aa benzene is preiNU-ed
ftvm l>enzoia acid. It is a limpid liquid, having a strong aromatic Oilor ;
boils at 151'.4 (304''.5 F.) ; insoluble in 11,0, very soluble in alcohol anJ
other.
There are several isomeres of this eubstanco, among which are
cumene, or Irimethijl-ht'mene, C,H, (CH,),, and nu'sHi/hrne, or mi-lhi/l-rih
jmzme, C,H, (Cn,)(C,H.} ; each oorrespondiiig to a aeries of derivati
Cymeno — CyTntA/. —There are uuiuy isomeres, of which one exists r
formed iu eaacuce of cumin, and In hemlock- It is a colorless, oilv liquid^;'
has an o^lor of lemon ; sp. gr. 0.S.17 at ItJ'^ (fitr.8 F.) ; boila at 175' (347'
F.) ; insoluble in water, but readily soluble in alcohol, ether, and essential
oils.
HALOID DEmVATIVES.
4
By the aubslitulion of atoms of 01, Br, or I for the hydrogen of the
principal and latn-al chains of the hydrocarbons, products are obtained
which include numerous and peculiar cases of isomery.
In the case of benzene itself there exist products of substitution con-
taiuing 1, 2, 3, 4, 5, and G atoms of CI, Br or I, or combinations of two or
three of those elements. In the case of the unisubstitutod derivatives. C,
H.Ct. CjH^Br, and C,H,I, but one of each exists. Of the biaubstitutcl.
trisubstitutod, and qmidrisubstituted derivatives three of each are known.
From the existence of but one uuiitubstituteil derivative it is obriouei
that it is immntcrinl in which of tlie CH groups this sultstitulion occurs, and
hence these six groups are equal tn each other in vahie. The existence of
isomeres of the higtier products of substitution depends upon differences
iu the relaiiLV posifions of the substituted atoms to each otber, their orien-
tation as it is sometimes called, and not to their absolute positions.
If we represent the molecule of benzene by a hexagon, leaving out the
UALOID DERIVATIVES.
301
C and H s^'mbols for the soke of brevity, vi& maj start at any angle and
aainber Ifae auglee corresponding to each and H from one to six :
\4/
In Encfa B hexngon we may represent the fonnubo of the three biaab-
Btituted Br derivateH ihua :
Bt & Br
6 3— Br
i i
^4/
\
\4/
-Br
t 2. 8.
In No. 1 the poettlons of the substituted atoms are connecutive, and
fta the abaoliUe positions in the molecule have no influence, it follows that
2 — 3 ; 3 — 4 ; 4— fi ; 5 — 6 ; fi — 1, a]] nro the sanoo aa 1 — 2. In number
S the positiouB are unsi/mntfiricui, or HepiirattHl from each other by a sin-
gle H atom; and 2— 4; 3—5; 4 — G. rtud 5 — 1 are equnl to 1 — 3. In
number 3 Uie positions are fftjmvtetrical, or separated from each other by
two H atoms ; and 2 — 5 ; 8 — 6 ; 5 — 2, and B — 3, are the same ns 1—4.
From this it appears that but three bisubstiluttHl Br products of benzene
can exist
The three Beries of hi- and tri -substituted derivatives of benzene, whether
the BobBtitution be of a halogen or of any univalent element or radical, are
designated by the prefixes ortho, mda, and jfora. Thus, iu the figiuro above :
Na 1 = 1^2 — Or thohibi-ouio- benzene.
No. 2 = 1 — 3 = Metjibibro mo- benzene.
No. 3 = 1 — 4 = Parabibromo-bonzene.
The distinction between the three groups is heat made by the relations
between the hi- and tri-Bubslituted derivatives. The consecutive or vrthu
bisubslituted derivatives can produce by further substitution two tri-de-
rivativ<!8 ; the unsymmetrical, or meta, can produce three trisubslituted
derivatives ; and the symmetrical, or para^ can produce but one trisubati-
tuted derivative.
In expressing thecoustitutiou of substituted derivatives it is customary
either to use the prefixes ortho, para, andmeta, as explained above, ortodes-
ignate the sulMtance by the numerical iM>sitions of the substituted atoms or
radicals, as in the following notices of the chlorine derivatives of benzene :
.VonocWoro-6ementf—Cj,CI— liquid ; boils at 132° (269°.G F.) ; sp. gr.
1.12« at 0* ; obtained by the action of CI upon C,H, in the cold, \n the
presence of a little I
Orthudichloro-lKiizene — 1—2 — liquid ; boils at 179* (354*". 2) ; up. gp.
1.328 at 0° ; obtained by the action of CI on C^,.
Mffiulichloro.henz«n€—\—\i~'\if\md\ boils at 172* (341°.6 F.) ; sp. gr.
1.307 at 0" ; obtainable indirwtly.
302
HANDAL OF CHBMIfiTRT.
Pandichloro-bmieM— 1—4— cryniAiMnc; fuaes at 56^4 (l33^5 F.);
boils at 173** (343" .4 F.) ; » tbe principal product of the action of CI oa
C^, in preBence of L
IHcWort^^iCTia.'na— 1— 2— 4— cryataJs ; fuses at 17° (GS^.G F.) ; boils at
213^ (415^4 F.).
Trichloro-bemene— I— S— 6— cryMUA^; fuses at 63o.4 (146MF.): boilu
at 208* (406\4 F.).
Tetrachloro^mene— 1—^—3—$— erjBtala; fuses at 50*" (122' F.|;
boU8at246''(474'.8F.).
Tefr(U'hioro-bemen^—l—2-^ — 5— cn-atala ; fuses at 187" (278°.6 F.) ;
boila between 243°-246^ (469M-474'.8 ^.)-
PHENOIf.
The brdrocarbona of tho benzene eerica, nnlike those previously cod-
Bidered. form two distinct kinds of hydrates, differing froin each other
materially in their prox>erties. Tbe terms of one of those series exhibit
all the functions of the alcohols, nml are knovn ns aromatic tUcohoU. The
terms of the other series differ in function from any snbstance thus fir
cousidered, and are known anpfienolg. The diflereiice between them and
tbe aromatic aleobob is due to tbe fact that in the phcnola tbe OH i^
directly attached to a C atom, while in the alcohols it forms part of tbd
group of atoma CH,OH, characteristic of tbe alcohols :
H-C
A
0— CH,OH
H
BeaijUa riMaaL
H-O O-H
The phenols differ from the tUcohols in not furoisbing by oxidation
COrrespoudiuF^ aldehydeu and acids ; in not dividing into water and hydro
oarboa under the influence of dehydrating agents ; in not reacting with
adds to form ethers ; in combining to form directly products of substitu-
tiou with CI and Ur ; and in forming with metallic elements compounds
more' stable than similar compounds of tlie true alcohols. In abort, the
phenols ap^iear to have, besides an alcoholic function, more or less of the
xuuotiou uf ucida
Phenol — Phfn^yl hi/drate—P/ienio add — CarboOc acid — Aciduni corboli-
cum {U. S., Br.) — C,H,OH — 94 — exists in considerable quantity in coal-
aud wood-tar, and in small quantity in costoreum, and poHsibly in urine.
It is formed : (1) by fusing s<iilium phcnylsulphidc with an excess of
alkali ; (2) by heating phenyl iodide with potnasium hydrate to 320" (608*
F.); (3) by heating togcUicr salicyUc aciil and quicklime; (4) bj total
synthesis from acetylene ; (.')) by dry distillation of benzoin.
The source from which it is ol>tained is that portion of the product of
diatillatiou of coal-tai- which passes over between 150* oud 200° (802"-
392" v.). This is treated with a saturated solution of potasb, containing
undissolved alkali ; a solid phenato is formed, which is diBsolved in hot
U^O; the Jiquid is allowed to Be\)aiatQ iuUi tvio la^aw. tbe luwer vl which
L
is draivn off and neutmlized with HCl ; the phenol rises to the surftice, is
separated, washed with water, dried over calcium chloride, redistilled,
crystallized at —10* (14' F.), and the crystals draiuwl.
Pure phenol rr^-fltallizea iu long, oolorleRA, prismatio, noodles, fusible at
86* (95" F.), boiliiig at 187" (JWS-.B F.). It haa a peculiar, well-known
odor, and an acrid, burning taste ; very spariugly soluble iu water, rea<lily
soluble in alcohol aud in ether ; sp. gr. 1.065 at 18'' (W.-l F.) ; neutral in
reaction. On rontact with the akin or witli niurous surfaces, it produces
a white ataiu ; it eou^latea albuminoids, and is a powerhil autinepfio.
It may be disiill&d without dceoui position. It absorbs H^O from damp
air to form a hydrate, which crrstallizea in six-sided prisms, fusible at Itr
(60^.8 F.). Its >-apor is reduced to benzene when heated with Zn. It
combines with H,SO, to form phcnt/Isuiph'trio adds. It forma trinilro-
phenic arid (?. v.) with HNO, of 3C^ B. When heated witli H,SO. and
oxalic acid it forms rogolic twid or corallin, which is a mixture from which
the pigments aurin, peonin, anilin, and phcniciti ore obtained.
Akalytical Chmui^teos. — (1.) Its peculiar odor.
(2.) Mix with one-quarter volumo of NH,HO ; add two drops sodium
hypochlorite solutiou, aud warm ; a blue or green color. Add HCl to acid
reaction ; turns red. »
(3.) Add two drops of liquid to a little HCl, add one drop KNO, ; a
purple red color.
(4.) Boil with HXO OS long OS red fumes ai*o given oS. Noutlralize
with KHO ; a yellow, crystalline precipitate.
(5.) With FeSO, solution ; a lilac color.
6.) Float the liquid uu H,SO,, add powdered KNO, ; violet colon
7.) With excess of Br water ; a ycUowitih-whitc precipitate.
ToxiooLoOY. — When token iutenially, phenol is an nt^tive poison, and
one whose una by suicides has became quite common. When it has been
taken the mouth in whiteued by its cautitic action, and there is a moi-kcd
odor of curbohc acid iu the breath. It is eliminated by the urine, i>artly
unchanged, and partly in the fonn of colored deriratiTea, which color the
urine greonish, brownish, or even black. Tlie treatment oousists iu the
admiuLstration of albumen (white of egg) and of emetics.
To detect phenol iu the uriue, that liquor must not bo diatilled with
H,SO,, as stimotiraes recommended, as it contains normally substances
which by such treatment yield carbolic acid. The beat method consists iu
adding an excens of bromine water to about 500 cc. (1 pint) of the urine ;
on standing some hours, a yellowish precipitate collects nt the bottom of
the vessel ; this is removed, washed, and treated with BOflium amalgam,
when the chnract eristic o<Ior of phenol is developed. From other parts of
the body, phenol raay bo recovered by acidulating with tartaric acid ; dis-
tilling; extracting the dLslillato by sbakiug with ether; ovtijiorating the
ethereal solution ; extracting the residue with a amatl quantity of water,
and applying to thin solutton the tAsts described above.
Cresylol — Cre»al — Cresylw acid—Bcnzylio phenoi — Crest/tic pJmwl —
C.H (CH,)OH — 108 — accompanies phenol in coal- and wood-tars, from
wLich it mar bo obtained by fractional distillation ; it is more readily
obtained pure from toluene.
When pure it is a crystalline solid, fusible at W".E (94M F.); as
usually met with, however, it is a liquid, whicli does not solidify nt —18^
(-0'.4 F.), and boils at 203=* (3!)7^4 F.) ; it has an odor of creaaote. Its
propertiea, decompositions, and products resemble those of phenoL
CasftflOTi — OnaMOtnm (U. H.) — in a complex mixture, containing phenol,
oresylol, cnaacl, C.H„0,, and other subatonces, obtained from wood-tar.
KAN0AL
CHBMISTRT,
jmlnv. !
ud fonaerij exdennvelj tued nsan tmtineptir. It is an oily liquid, color-
Ins yrbea freat^j praptred, but buxmunfr brownish on expoenre to Ufrfal ;
it hu a burning tute And a sbtniK, peeaUar odor ; il boik at 203' {^HT.i
F.), and does not golidify at — 27^f-lG-.6 F.).
Crude phenol is often Babstituted for creaaota ; the two aubalaiiew
may be diatingitiBhed by the following cbaractats :
OasAaoTH.
%
Imetoble hi coni uier efal pljoeritL
DoM BOl precipitate oollailion.
QiTeM R ^Tv«a color with fecrio dilorida
Bod aloobol.
QWfn A jrri'pn rolor. pawog- to bnwni. with
fvrrio chloride on^ aminoiiium liTdnte.
FUEKOL.
BolublA in eomnnToikl fftjoerin
PT«cipitAt«flnitro-c«Uulaeefr-tin ooUodion.
GlTftJi ft bro«-n oului will) ferric dilonde
U)d ajcohol
Oivitt A violet color «rltb ferric chloride *Dd
anmoDitim bjdr»t«
Xenola— A'v/'^oi*— CH(CH,),OH— 122.— Theorotically Oiere ax^ six
poaaible xonols derivable m>m corrcsi>ouiliii^ xvleucs ; of Ihcso, four have
be«u thus far obtainc<l by the general methods of obtaining tbe pbem^
None is of practical interest
Thymol— Cyj"!/'"^ phfrnol — C^H(CH,)pH— 150— exists, accompany-
ing cymene and thymene, C,,H,^. in essence of tbymc. from wbicb it is ob-
tAiued. Tbe essence t-ontoius about onu-holf it« weifTht of tb^iuul, which
is acparated by agitation with a concentrntod solntion of cauatie aoda ;
aeparatinu of the alkaline liquid, which lb diluted and ncntraKzed with
HCl; thymol aeparatea and is purified by rectification at 230° (446° F.).
It crysbdlizes in lar^o, trunsporent^ rLombohedral tables ; baa a
pery taste and an agreeable, aromatic odor ; it fuses at 44'' (111''.2
and boila at 280° (446'' F.) ; is sparingly soluble in water, veiy soluble
alcohol and ether; with tlie alkalies it fonns detinite compounda. which aju
very soluble in water. It« reactions ore very similar to those of phenol
Tliymol ia nn excellent difiinfpeting and antiseptic agent, and one of
the begt of embalming materials^ poBseming the advantnge over phenol
of ha>'ing itself a ploofiaut odor.
BUBSTITUTin? PHENOI^.
W* fane aaen abofe {p. 301) how three bi- and tri-substituted deriva-
tirei are derivable from benzene. Vhenol ia a uuisu1>6tituted denvatire of
the eame snbst&nce nnd hence atiU contains five U atoms which may bo
replaced by other elements or radicals. So long an but one utlier univalent
atom or nulica]iHintro<luce<), the number of possible derivatives remnimithe
aaroe as if but one kind of atom or rndicul were iutnxluced, aa the reversal
of the order CI Br or Br CI cannot iullueuce the nature of the compound.
But when the number of substituted atoms, differing in kind, ia increased
beyond two, or tbe valence of one or more of them exceeds one, the cnm-
bar of possible isomerea is progresaively iucroaeed. Thus, wliile there are
bat Ihree tribromo-bcnzenes :
ie in^
Br
4 a— Br
3— Br
5
^4/
Br
/k
6 2
I I
5 a— Br
^4/
t .
"Be
Br
Bi
A
-5 3— Br
\4/
aCBSTITUTED PliKNOLS,
Uiere are eix chlorobromO'beiuenes :
305
-CI
Br
6 2— ca
8.
CI— 5 3— Br
^4/
5 a-01
\4/
of which 1 and 2 niw (^eriTable from orthobihromobonzene (sm p, 801);
3, 4, Mid Ii from mf>tAbibroraob«n»>no, and l> from parabibromobeitzeiiA.
If, in pbice of two elements or rwUralB, we have three, the number of tri'
Hiibstitutcd derivatives is increased to ten.
In the place of CI and Br in the above exflmplp« any wnivoleut atou) or
Fftdicol maj be substituted, thus giving rise to a groat number of deriva-
tive. Certain of such substituted nulicals determine tbe (unction of the
origioal nnisubstituted derivative of beuzono and of all of it« poly substituted
derivatives. Thus the group (OH) is character! stio of the phenols ; (CH,)
or (C,H,, + 1) of the suiterior homologuea of benzene ; (CH,OH) of tbe
alcohols ; (COOH) of tbe acida ; (XO,) of the Ditro-derivatiTos ; (NH,) of the
•minefi, etc.
Tbe naming of such polyaubsiitutcd derivatives preaenta many diffi-
onltiea. Adherence to the principle tliat the name of a compound shall
indicato its constitution, involves the conafTiictioii of names which are fi-o-
quently of unwieldy length. It is usual tu consider the characterizing
group as occupying the position 1 in the hexagon, and to prefix the term
ortho to the name of that radical or atom oocup'i'ing one of the ortho-poei-
lions 2 and 6 with relation to the characterizing group; metti to that
occupying one of the meta-{)UBttion8 3 and 5 ; and para to that occupying
the para-position 4.
Thus the substance baring the constitution indicated by the forraala 1
(see next page) is designatetl by the name orthonitroparahromo-ptuntof. Bui
even this is not always sufficiently defimte, for to each uf the substances
2 and 3 (see next page), although differing in charactors, the name or-
thonitrometabromophrwtl applies. It haa been suggested, to avoid thia
difficulty, that the prefix altoriho be used to designate the second or-
The name of Na 3 would thus becomo meiabromoaOorthonUiWihennl.
When formalDc arc used, all confuaioD may bo readily avoiden, eren in
the meet complex substances, by the nse of the mimeral correspoudiug i<i
the position in the benzene chain, enclosed in brackets Thus, tbc fat-
uiulaj of 2 aud 3 above luav be wnttcu :
C.H.(0H)fer(>6,)(^
Nitro-phenols— -VowmtiVm^fc<moto — 0,H.(NO,)OH— (I— 2), (1—3),
and (1 — 4) are formed bj the acUon of HNO, on C,H,OH. The ortlio com-
pound (I — 2) crvstiillizeH iu large yellow needles, Hparingly Bohible. and
capable of ilistiltatiou with etoam. The ueta and pani eoiuponnds are
both coloriees. Tion-volatile, crystalline bodies. Two dinitro-pfumols, C,H,
OH(NO,)(,-,) and C.H,OH(Nb,),(,_,: are obtained bythoaHion of stroLg
nitnc acid on pbeuol, or on ortbu- or pftra-monunitro-phenol. TUej jum
both solid, cryatoUine Bubstonces, convcrtM by further nitration into pic-
ric acid.
JVini/ro-pAenob— C,H,(N0j).0a Two are known. (1.) J'icric acid—
Carhaxotic uctd — TriiiUro-phemc acid — (XO,) in 2- — i — 6. It is formed by
nitrification of phenol, or of 1 — 2—4 or 1^2 — G dinitro-pbenols, and also
by the action of HNO, on indigo, silk, wool, resins, etc. It crystallizes in
railliant, yellow, rectangular plates, or in six-sided prisms ; it is odorless,
and baa an intensely bitter taste, whence its name (from -ntxpits ~ bitter) : it is
acid in reaction ; epuringly soluble iu water, vary soluble in alcohol, ether,
and benzene ; it fuses at Vi2'.5 (2.'>2''..'JF.), and may, if heated with cau-
•Kon, be HubUmed unclianged ; but, if heMed suddenly or in quautity, it
explodes \ntb %io]ence. It behaves as a monobasic acid, forming Baits.
which are for Uie niOHt part soluble, yellow, crystalline, and docojupowd
with explosion when heated.
Picric acid is valuable as a dye-stuff, coloring silk and wool yellow ; at
a staining medium in histological inTestigations ; and as a reagent for
the alkaloids, with many of which it forma crystalline precipitates. Itii
also sometimes fraudulently added to beer and to other food articles, to
communioate to them either a bitter taste or a yellow color.
AsALvncju, CuAKACTEHs. — (1.) Its intensely bitter taate.
(2.) Its alcoholic solution, whou shakeu with a potassium salt, gives a
yellow crystalline ppt.
DIATOMIC PSEKOIS.
aof
(S.) An ammoniocAl solution of cupric sulpliato gives a groen, crystal-
line ppU
(4.) Glucose, lieatAcI with a dilnte alkaline solution of picric acid, com-
muDicates to it a blood-reil color.
(5.) Wanued with uu alkaline aolulion of potassium cyanide, an in-
t«nBO red color is produced (tbo same effect ia produced by ammouium
Bulphydrnte),
(6.) Unbleached wool, immersed in boiling solution of picric acid, is
dyed yellow.
Koa. i. 3, 5, and 6 arc quite delicate.
AVlien taken internally in overdose, it acta as a poison ; it may be
separated from animal fluids or from beer by evaporation to a syrup, ex-
Imctiug with 95 per cent alcohol, acidulated with H,SO, ; Altering ;
evaporating ; and applying the tests to a solution of the residue.
DIATOMIC PHENOLS.
IHatomifi phenols are derived from the bensene series of hydrocarbons
by the tnibtjtitution of two (OH) groups fur two utoma of hydrogen. In
obedience to the laws of substitution already discussed, three such com-
pounds exist, corres|K]nding to each hydrocarbon. Thus, in the case ot
benzene :
OH OH OH
6 3— OH
1 i
V
fi 3— OH
V
I i
V
9
Onha.
1—*
PrnxKUKlUn.
Hala.
1-9
1— <
BjOroqolBoiM,
Pypooateohin — Oryphenic acid — Orihodioxtj^bemene — CJ3,(0H),—
'2 — is obtained from oatechin or from morintannic add by dr^' distiila*
tion ; also by the action ol KHO on ortJiochlor- ororthoiodo-phenol, or by
decomposing its methyl ether, guaiamt, by HI at 200" (392*" F.), It crystal-
lizes in shoit, square prisms ; fusesat 104" (219^2 F.), and boils at 24d''.5
(473°.9 F.). Iteadily soluble in water, alcohol, and ether. Its aqueous
solution gives a dark-green color with Fe^Cl, solution, changing to riolet
on addition of NH,H0, NaHCO,, or turfjiric acid.
ReBoroin — Mftadinxy-benzene — C,H.(OHl,— 1 — 3— ia obtained by the
action of fiwed KHO on paracljlnr- or iodo-phenoL It ia usually prepared
by dry distillation of extract of Brayil wood.
It forma short, thick, colorless and odorless, rhombic prisma. Fuses
nt 104* (219<'.2 ¥.). and boiJs at 271" (5I9*.8 F.). It ia very soluble in
water, alcohol, and etlier. Its a(|ueou8 solution is neutral in reaction, and
intensely sweet With Fe,Cl, its aoluttona assume a dark-violet color,
which is discharged by NH.HO. Its ammoniocal solution, by exposure to
air, assumes a pink color, changing to brown and, on evaporation, green
308
MAXUAt OF CIIKMISTRT.
I
and dark blue. Healed with phthaUo anhTdrido at 196" (388" F.) il
yields fluorescein (see page 300). It dissolves in fuming II,SO^. forming
an orange-red Bohition, whirli hecomea darker and then changea to green-
ish-hlack and then pure blue, and to purple on being warmed.
Eesorcin han been recentW used in medical pmctiee.
Hydroquinone— Parflrfiojrf/fjffni^n/' — C,H,(OH), — 1 — 1 — is formed by
fusing paraiodo-phenol with KHO at ISO^ (:^56'' F.), by dry distillation
of ox}'8aUcylic acid or of quinic acid, and by the action of reducing agents
on qninone. It forma colorless, rliombic piisms, which fuse at 169'
(33f>^2 F.). Readily soluble in water, alcohol, or ether. Its aqoeons
solution ia tamed red-brown by KH,HO. Oxidizing agents conrert it iato
qui none.
Quinone — C,H (00)" — is the roprosentatiro of a number of rimikr
com[)onnds, derivable from the aromatic hydrocarbona It is prodnced by
the oxidizing action of llnOj f H,SO,, or of dilute chromic acid, upon
quite a number of pftro-benzcno derivatives ; but best by the limited oxida-
tion of quinio acid.
It cj^atollizea in yellow priams ; fuaea at llfi* (240". 8 F.) ; sublimes at
ordinary teni|>er!itnreB ; is Hjmringly soluble in cold, but readily soluble in
hot water and in alcohol or ether. It gives off a peculiar pungent (kIot
and stimulates tlie lachrymal 8e<?retion. Redncing agents convert it into
hydroquinone.
Tboro la no similar substance known corresponding either to pyro-
oatechin or to reeorcin,
Or«in— i>»metedwxy-/o/i(CT«— 0^,(CH,)i,)(OH)(,)(OH)(^, — exUta in
nature in those lichens which are nsed as sources of archil and litmua
(Jioceila tvwtaria, etc). It cr}'8tallize8 in six-sided prisms ; ia sweet ; read-
ily Bohiblfi in water, alcohol, or ether ; fuses at 5S''(136*'.4 F.). Iteaqneous
solution is colored violet-blue by Fo^Cl^ It unites with NH to form n
compound which absorba O from the nil- and is convertetl into orcein,
C,H,NO, ; a dark red or purple bo^lv, which is the chief constituent of tlie
dye-stuff known aa archil, cudbear, French purple, and litmus.
TRIATOMIC PHBNOLS.
The only compounds of this class at present known with certainty are
two isomeric triatomic phenols, which owe the differences in propertiwi
oxisliug between thom to a different placing of the OH grppps. They are
phloroghirin and pyrogftHnl.
Phloroglucln— C,H,(OH), — 126— ia obtained by the aetion of potaah
upon phlorcHii, qaorcitriii, madurin (see Glucosides), cntechin, kino, etc
It crystnllir^s in rhombic prisms, containing 2 Aq ; is very sweet ; very
soluble in water, alcohol, and ether.
Pyrogallol — Pj/ro'jaHic acid — C,H/OH), — 126— is formed when gil-
lie acid (7. V.) ia heated to 200° f3'.J2- F.). It crystallizes in whit« nee-
dles ; neutral in reaction ; verr soluble in water ; very bitter ; fuses at 115"
(239° F.) ; boila at 210° (410" F.) ; poisonona Its moat valuable property
H that of absorbing oxygen, for which purpose it is used in the laboratory
in the form of a solution of potasaium pyrogalUte.
ABOMATIC ALOOaOLS.
PHENOL DYSS.
Aurin — 0„H,,0, and Rosolio aoid — C„H O, — aro Bubstoucee ei-
isting in the dye obtainen:] by tlio actiou of oxalic acid upon pheuol iu
preaeiico of H,^0^ known ns coralline or pieonme, wliicb oomuiuuicates to
silk or wool a tine yeliow-red color.
Aurin crvstallizeti in fine, rRil Tir^edlen from its BolnHon in liCl. It is
insoluble in H^O, but Holuble in HCl, alcohol, and glacial acetic acid. It
forms a colorless coropound with potassium biBulphitc.
Phttaalelnav— Thcso substances are produced by boating tbo phcnola
with pbthalic anhydride, C.H.O^, water l>eing at the same time eliminated.
Their constitution is that of a benzene nucleus, two of whose H atoms
bavo been replaced by two sceioue groups (CO), whose remaining valences
attaches them to two pheuol groups by exchjuige with an atom of hy-
drogen.
Thus Phenol-phthalein, the simplestof tlie group, Las the constitution
/CO— C^.(OH).
C^. Phenol-phtlialein is a yellow, cuTstalliiie powder,
\CO— C,H,(OH).
insoluble in water, but soluble iu alcohol. lU alcoholic solution, perfectly
colorless if neutral, aRsiinieR a brilliani nmpfenta-red in the presence of an
alkali. This property renders phenol-phthaleiu very Tuluable as an tn-
dic(Uor of reaction.
Resoroln-phthalein— /'/worcwrrn — C„H,,0^ — bears the same rela-
tion to resorcin that phenol-phthalein does to phenol, and is obtained
from resorcin by s corresponding method. It is a dark-brown crystalline
powder, which dissolve-it in ammonia to form a red solution, exlubttiug the
most brilliant green fluoresoenoe. A tetrabromo^erivative of fluorescein is
Qsed as a dye under the name eastn.
AROIdATIC ALCOHOLS.
The nlcoliolfl corresponding to this series of hydrocarbons have the some
composition ns the corresponding; phenols, from which they differ in con-
etitntion and in having the functions of true alcohols. They yield on
oxidation, tirst an aldehyde and then on acid, and they coutiuu the c.hnr>
aoteriKing group of the primary alcohols, ClI,OH ; once if the alcohol be
moQoatomic, twice if diatomic, etc Thus :
C,H ,CH.OH = Benzylic alcohol
C.H„COH = Benzoic aldehyde.
C.H^COOH = Benzoic acid.
As they contain the benzene nacleus they are capable of yielding
iiiomeric products of further substitution, ortbo, para, or meta, according
to the position of the Hubstitutcd atom or radical
Benzylio aloohoI^Vteizoic alcohol — Hmzyl hijfinUe- — C,HJCH,0H)
— lOH— does not exirtt in nature, and is of interest chiefly aa correspond-
ing to two important compounds, benzoic acid and benzoic aldehyde (oil
of bitter almonds). It is obtained by the action of potassium hydrate
upon oil of bitter almonds, or by slowly adding sodium amalgam to a
boiling solution of benzoic acid.
I
I
310 MANUAL OF CFIKMISTRT.
It ia a colorleaa liquid ; boils at 206*.S (403®.7 F.) ; has an aromatic
odor ; is insoluble in water, soluble iu all proportions in alcohol, ether,
and carbon disulplude. By oxidation it yields, first, benzoic aldehyde,
C^,(COH); and aftorwanl, benzoic acid, C.lI,(COOH). By the saino
luoftiia it may be made to yi(>ld products similar to those obtained from
the alcohols of the saturated hydrocarbona
ALPHENOLS.
These Bubfitancea are intermediate in function betw^n the alcohob
and the phenols, and contnin both substituted groups (OH) and CH-OH.
/CH,OH
Saligenin, C^H, — 121 — is obtained from salicin (7. v.) in
\0H
large, tabular crystals ; quite soluble in alcohol, water, and ether. Oxi-
dizing agents convert it into salicylic aldehyde, which by further oxidatioD
yields salicyUc acid. It iu also furmed by the action of uuacent hydrogen
on sahcylic aldehyde.
AIJ)EH7D£S.
4
I
Benzoic aldehyde — Bemoyl hydride — C,H, (COH) — 106— is the
maiu constituent of oil of bitter almonds, although it dnes not exist in the
almouds (see ^ 329) ; it is formed, along with hydrocyimic acid and gin-
cose, by tlie octiou of water upon amygdtilin. It is also formed by a Dum-
ber of general methods of producing aldehydes : by the dehydration of
buuzylic alcohol ; by the dry distillation of a mixture in molecular pro-
portions of calcium benzoute and formiate ; by the action of nascent
hydrogen upon benzoyl cyanide, etc
It is obtaineil from bitter almonds. The crude oil eonUins, besides
benzoic aldehyde, hydrocyanic and benzoic acids and cyanobenzoyl ; to
purify it, it is treated with three to four times its volume of a concea-
trated solation of sodium bisulphite ; the crystalline mass is expreaaed,
dissolTed in a small quantity of water, and decomposed with a ooaoen-
trated solutlou of uuclium carbonate — the treatment being repeated, if
necessary.
It is ft colorless oil, having an acrid taste and the odor of bitter
almonds ; sp. gr. 1.043 ; boils at 179*^.4 (354^9 F.) ; soluble in 30 ports
of water, and in all proportions in alcohol and ether. Oxidizing agents
convert it into bt-niMic acid, a cliauge which ownira by mere exposure to
air. Nascent hydrogen converts it into benzylic alcohol. With CI and Br
it forms benzoyl chloride or bromide. H^SO, dissolves it when heated,
forming a purple-red color, which turns black if more strongly heated.
When perfccthj pure, benzoic aldehyde exerts no deleterious action
vheu taken uiterually ; owing, however, to the dilliculty of completely
removing the hydrocyanic acid, the substances usually sold as oil u/' bUiet
almondit, ratafia, and almond Jlavor, are almost always (wisonous, if taken
in sufficient quantity. Xhoy may contain as much as lO-lo per cent, of
hydrocyanic uuid, although said to bo "purified." The presence of the
poisonous substances mny be detected by the tests given on page 327.
SalicyUc aldehydfr—.Sa/iri// hi/dride — Haticylol—Saliq/loug acid —
0,H^(OH)GOH — 122— exists in the dowers of fpircea tdmaria, and ia the
I
ABOMATIO A
priocipal ingrecliont of the eaaential oil of that plant. It is host obtainod
by oxidizing aalicin (o. v.).
It is a colorleas oil ; turns red on e^posiire to air ; has an a<rreeable, an>-
matifiodor, and a sharp, burninff taate ; ap. gr. 1.173 at IS^.C (G6°.3F.) ;
boils at IBB^.S (SeS".? F.) ; soluble in water, more bo in alcohol and ether.
It is, aa wo ahoulil saspect from itd ori^n, a substance of mixod func-
tion, poasesaiuf? the characteriBtic properties of aldehjde and phenol. It
produces a great number of derivatives, eome of which have the charac-
terfl of ealts and ethers.
Methyl-protocateehulo aldehyde— TanWin — C,H,(OH)(OCH,)
COH— is the otlorifeionrt principle of vanilla. It is produced artifidoUy
by oiidation of m/ii/>nn, C,.H„0., a glucosido ooeurring iii coniferous
plants. It crystallizes in uetdlea, fuses at 80° (176"" F.) ; is sparingly sol-
uble in water^ reatlily Bohible in alcohol or ether. It has a pungent tAste,
and a fatut odor of vanilla, the latter more marked when the substance is
heated. On exposure to air it becomes partially oxidized to vaniUio acid,
C.H.O.-
AOmS CORRESPONDING TO THE AROMATIC HYDRATES.
Tlie acids, possibly derivable from benzene by the substitution of
(COOH), or of (COOH) and (OH), for ati^ms of hydrogen, would form, were
they all known, a great number of aeries ; there are, however, oompar-
atively few of them which have been as yet obtained, although the num-
ber of acid series known is greater than that of corresponding alcohols.
Each series of mono- and diatomic alcohols fumiahos a corresponding
series of acids ; thus :
C.H,^CH,OH
C.H.-COOU
f,„/CH,OH
^*"'\CH,OH
«„/00OH
^•"*\OOOH
c.H/gg:«»^
Sdt(«ala.
^ jj /COOH
saieriioMid.
There ore still a number of other series of acids possibly derivable
directly from benzene, without sjieaking of substituted acids of more com-
plex nature ; of these, however, the majority are wiiutiog.
By the progressive substitution of groups (COOHJ for atoms of hyd^>-
geu in benzene, we may ubtaiu six series of acids, five of which have been
isolated:
C,H.(C00H) -C,H,,_ ,0, Benzoic seriea.
C.H,(COOH),-G^,_.,0, PhthaUc seriea.
C^(OOOH). -C.H,^..0, TrimeUitic series
C.H,(COOH),-C,n^,.0. Prehnitio seriea
C^(COOH), -CJI^_„0, Wanting.
C^{C00H), -C4I^.,0„ MeUiUo aeries.
' The alphenolft, containing a single group (OH), are at present repre*
seated by u tiiugle series :
C,H,(OH)(COOH)— C.H,»^0,— SalioyUo seriea.
Iu_
312
OF CHEMlSTRr.
OoTTB^Kniding to Uic unknown alphenola, containing a greater nnmber
of (OH) grouiw, Uioro are at present but two series uf tcids known :
and
CA{OH).(COOH>— Oja^.O,— Veratric series,
C^(OH).(OOOH)—CLH,^0,— Gallic aeries.
In each of those eerifM the basidfy is, ns usual, equal to the number d
groups (COOH).
Benzoic &cdd—Acidum benxoicum {V. .*?.) — C,H,(COOH)— 122-
ezista retuiy fonocd in bonzoin, tolu balsam, cnstoreum, iinJ beveral resins,
It does not exist in Euumal nMaire) ho fnr as is at present known ; in tlioiiB
BitiUitioDS in which it has beeu found, it has renulted from decoropoaitioii
of liippuric acid {q. v.), or has boeu iuLroduced from without Viben
taken in moderate doses, it does not pass out in it« own form, but in con-
verted into hippnric acid ; in cxcessiTe doses a portion is cUniiuat^d uq-
cboD^ed in the urine. It ia obtJiined from Ijenzoin. or from the urine o(
berbivorous animals ; and is formed in a variety of reactiona.
It cryBtaitizes in white, tranaparc-nt pintee ; odorless ; acid ; fuses it
122^ (2ol=.fi R); aubUmes at 145° (293" F); boils at 2W (404° F.); spar-
inr];ly soluble iu cold water ; soluble iu hot water, alcohol, and eUier.
Pilute UNO, does not attack it It dissolves in ordinary U,SO,. and is
predpitatcd unchanged by H,0. Its salta are all soluble.
Hippuric acid — Jienzyl-i^ycocol — Henzxjl-<im\do-acetic acid- — C,H,NO
— 17a — is a constant constituent of the urine of the berbivora, and m
human urine tn the extent of 0.2J>-2.H4 grama (4.5— 13.8 grains) in 24
houTH. It is mure abuntlant with a purely T^etable diet, after the ad-
ministration of benzoic acid, and in diabetes meUilus and chorea.
It crystallizes In (i-aiisparent, colorless, odorless, bitter prisma; spar-
ingly soluble in water; fiiRcs at 130^ (2C(i^ F.). It dissolves unchanged
in HCl ; but on builin;;; the solution it is decomposed into benzoic arid
and glycocol The samo decomposition is eflettwl by dilute H,SO.. HNO^
and oxalic acid, and by a ferment developed iu putrefying urine. Oxidizing
agents convert it into benzoic acid, benzamide, and CO,.
The characters of hippuric acid are : (1) when heated in a dry tube it
f OBOs and gives ofT a sublimate of benzoic acid and on odor of hydrocyanic
acid ; (2) it gives a brown ppt. with ferric chloride ; (3) when boated with
lime it gives off ht^nzine and ammonia.
Salicylic Acid — Oxt^hcnznic acid — Jcidian txiiicijlicum (U. &)— O^,
(OH) OOOH — 138 — was first obtained from essence of spircBa, which con-
aiste largely of salicylic aldehyde, and subsequently from oil of winter-
green (gaultha-ia), wlbich contains methyl salicylate ; and also from mUicin,
a glucoside yielding salicylic aldehyde. It is now obtained fi-om phenol.
This is fused, and, while a current of dry CO, is paasetl through it. small
portions of Na are added ; the sodium salicylute thus formed is dissolved
u H,0 and decomjMaed with UCl, when the liberated stUicylic acid is
precipitated
It crystallizes in fine white needles ; very sparingly soluble in cold
water, quite soluble in hot water, alcohol, and ether ; it fuses at 158*
(816''.4 F.), and may be distilled with but alight decomposition, if it be
pure. CI and Br form with it pnxlucts of substitution. Fuming HNO,
forms with it a nitro-dcrivative and, if the action be prolonged, converts
it into picric acid. With ferric chloiide, its aqueous solution assumes a
fine violet color.
Aam>0-T>F.UTVATITES.
313
Salicylic acid and ita salts (it is monobasic, although diatomic) are
extoosivelj used in medicine, both externally as anti»eptica and internally
in the treatment of rheumatism, etc It is not without caustic projjertieB,
and hence, when token internally, it fdiould be largely diluted.
GaUlc acid— ^cirfuin gaUicum {V. &)— C.H,(OH),COOH— 170—
existe in n:ittu-e in certain leaTett, see^la, and fruits. It is bcHt obtained
from gall-nutii, ivhich contain ita glucoaide, gallotAnnic aoid {q. v.). It
can be obtained from Holicylio acid.
It cryBtaUi7.e8 iu long silky needles with I Aq ; odorless ; acidulous iu
taste ; sparingly solnble in cohl water, very soluble in hot water and iu
aloohol ; ita solutions are acid. WiiBU heate<l to 210--215=' (4l0''-419'
F.) it yields CO, aud pyroguUol (7. i;.). Its Hulution doea not precipitate
gelatin, nor the salts of the alkaloids, an doos tannin. It forms four
seriea of saltii.
NITRO-DERIVATIVES OF BENS^INE.
By substitution of the univalent radical (NO,) for the hydrogen of ben-
sene a series of substitution proiluots are obtivinable, corresptMiding to the
Hries of haloid derivatives, phenols, etc (see pp. 301, 304. 305).
Nitro-beDZOl — Sitro-benzene — Mono-nitrv-lettzene — En-sence of Mir^
txine — C^H^(NO,) — 123 — is obtained by the moderated action of fuming
HNO,. or of a mixture of HNO, ami H,SO.. on benzene.
It is a yellow, sweet liquid, with an odor of bitter almonds ; ap. gr.
1.209 at 15" (59^ F.) ; boila at 213' {ilS^A F.) ; almost insoluble in water ;
very soluble in alcohol and elhcr. Concentrated H,80, dissolves, aud,
vheu boiling, deconiposea it. lioiled wifh funiiog HNO,, it ia converted
into binHrft-ttemoL It is converted into aniline by reducing agenta.
It has boon used in perfumery oh artificial etaence of bUter almonds ; but
08 inhalation of its vapor, eveu largely dihitcd with air, causes hea<laehe,
drowsiness, difticnlty of respiration, cardiac irregularity, Idas of muscnlar
Kwer. convulsions, and coma, its use for that purpose ia to be condemned,
ken internally it in an active poison.
Nitro-beiiBol may be distinguished from oil of bitter almonds (benxt^ie
aldehyde) by H^Sl),, which does not color the former ; and hy the sulion
of acetic acid and irtm filings, which convert nitro-benzul into aniline, whose
presence is detected by the reactions for that substance (7. t<.).
AMtDO-DERTVATIVES OF BENZENE.
Theee snhstancea are derivable from benzene and ita homalogues by
the aubstitiitinn of one or more univalent groups (NHJ (amidogen) for
atoms of hydrogen. They may also be considered as j^ht'/ii/lantintv, pro-
duced by the snbHtitntion of the univalent radical phentjl (C,H^), or ita
bomologues, derivabhi from the benzene nucleus, for the hydrogen of
ammonia. They all are strongly iMutic in character.
Aniline — AmiUo-bemcne — Amido-itt-iizol — ['hrmjlamine — Kyanol—
C H )
CrutaUinc— '™* > N— 93— exists in Bmall quantity iu coal-tar and is one
of the products of the destructive distillation of indigo. It isprepared hy
the reduction of nltro-bonzeito by hydrogen : C,H,(NO,) + 3H, = C^,
(NHJ + 2H.0 ; tlie bydi-ogen being liberated in the nascent atatein con-
tact vrith nitro-benzol by the action of iron filings on aoetio acid.
u
F.) ; ci7atalli7^&t — 8" (17°.6F.): fwilubla inSl pta. of cold water, Bolablfl
iu all proportions in alcohol, ether, carbon disulpbido, etc.; when exposed
to air, it turns brown, tbe color of tbe commercial "oil," and, finiUly, resini-
fiea; it is neutral in reaction. Oxidizing agcnU convert it into blue, riolel.
red, green, or black derivatives. CI, Br, and I act upon it Wolentlv to
produce products of substitution. Concentrated H,SOj converts it accord-
ing to tlte conditiona, into auIphanUic or iOxulphanilii: acid. With acifitt it
unitea, after tbe manner of the ammooio, without liberation of H.^0 or H to
forin salts, most of which are cryatallizable, soluble iu water, and colorlett,
although by exposure to air, especiallj if moist, they turn red,
Akalytkul Chaiucters. — ^1.) With a nitrate and H SO,, a red color.
(2.) Cold H.SO, does uot color it oloue ; on addition of potassium di'
cbromatc, a tine blue color is produced, which, on dUution with toater, paasea
to violet, and, if not diluted, to black.
^3.) With cAlcium hypochlorite, a violet color.
li.) Heated witli cupric chlorate, a black color.
(5.) Heated with mercuric chloride, a deep crimson color.
ToxiooLoov. — Aniline itiuOf, when taken in the liquid form or by inholor
lion, is an active poisou, producing symptomti similar to those caused by
uitro-benzol [q. v.). Its aalts, if pure, aeem to have but alight deleterioiu
action.
DERIVATrVES OF AinUNE.
By the substitution of other radicals or elements for the remaining by*
drogen atoms of the benzene nucleus, or for the hydrogen atoms of tha
amidogen group, NH,, a great number of derivatives, including many ieo-
meren, are produced.
In all of tliese derivatives the group (NHJ is considered as occupying
the position I.
Chloraniliues. — Three mwiochloranUint^s are known, of which two.
ortho- (1 — 2) and meta- (1 — 3), are liquid. The other, para-(l — 4), is solid
and crystalline.
Four dichlnranUiiusn, 1—2—4, 1— 2— C. 1—3—5, and 1—3—4, are
known, all solid and crystalline.
Two trtchhraniliiK9, 1—2 — t— 6 and 1—2—4 — 5 are known, both solid
and cr^'stalliue.
The correspondingfrromantfinw are also known ; also & tetrabromanUine,
1 — 2 — 3 — i — (>, and a pentabromaniliue, C,tNH,)I5r .
Of the possible iodauiiims, but four have l>een described: Metamono-
tof/aniiirie (1 — 3); jjaramomodaniline {\ — 4); the dtiodaniline (1 — 2 — 4); and
the triiodauiline (1 — "2 — 4 — 6).
Nitranilines. — The three iaomeres, ortho-, meta-, and para- Jfononi-
tranilines, C,H,(NH,)(NO,) ai« formed by imperfect reduction of the di-
nitro-benzenes.
Two dinitranilinefi, C,H,(NH,)(NO,), (1—2—4) and (1—2—6). are known
A single trtvUramliuc. C^,(NH,)(NO,). (1— 2— 4— 6), haa been ob-
tallied by tbe action of nlcobolic ammonia upon the ethylic or metbylic
ether of "picric and. It is sl«o culled picramiJe.
Anilldes. — These are compounds in which one of the H atoms of the
amidogen group has been replaced by an acid radical Or they maj also
J
AJIILINE DTE3.
be oonmdered as nmideft, whoae remaining hjdrogon has been more or lesa
replaced hy phenji, C,H,.
^Cf(ant/u.>~C,H^{NH.C,H,0) = J'henyl-acetamide—is obtained either
hj heating together aniline nnd glncial acetic acid for several hoiin), or,
b«tter, hy the action of acetyl chloride on aniline. It forms colorless,
ahining, crj'ataUinc ocalea ; fuses at 112°.5 (2^''.5 F.), and volatiH/^s nn-
ehangod at 295^ (563" F.). It is Bparingly Boluble in cold water, soluble
in hot water nnd in alcohol.
It has been recently introduced into medical practice aa an antiperiodxa^
under the name anU/etnine.
ANIUNE DYES.
It was observed at an early period that when crude aniline was acted upon
by oxidizing agents a brilliant red color was produced. Efforts to isolate
this color, beginning in 1856, have led, not only to sucoeBS in the end de-
Bired, but also to the discovery of a great number of subHtances, many of
which are valimble as dye-atufla communicating not ouly brilliant colors, but
the greatest vaiiety of ohades and colors. Among the substances oom-
merci^ly clnsBified as aniline dyes are many pigments which do not prop-
erly belong here, being derivatives of phenol, naphthalene, anthracene, etc.
Of the true auiliue dyea the most imiKirtaut, and that from which most
of the others aro industiinlly derived, is/ucheine, also called magenta, (2»t-
line Tt^d, roseiup., azaleint^, etc
Although fuchsiue ia obtainable by a great variety of metlKxIs, those
industrially used arc limited to modificatiuDs of two : the oxidatiou of
commercial aniline by arsenic acid, or by a mixture of nitro-beoxene, hy-
drochloric acid, and iron, filings ; and the puriiication of the product after
combination with an acid, by repeated recr>'stallizations.
The commercial fuchsiue, which varies muoh in quahty, is a hard, more
or less crystalline substance of a brilliant gi-een color, sparingly soluble in
cold vater, readily soluble in hot water and iu alcohol, the aolutionu having
a brilliant red color.
The TOmmeroial fuclmiues are salts, usually the chloride or acetate, of a
base which is itself culorlose, eallfd roftamline, whose constitution has been
but recently determined, having the empiricoJ formula C,^.,N^,H,0.
RoganUinr is one of a serien of homologous substanceo the tirst term of
which is jMraroMini/irie, C„H„N,0 — whose molecule: '
H
H
•Iv
r. A
NH,— 4 6— H H-2 4— NH.
H-3 1 OH ^ ^^
-H
\o/
i
H-6 2-H
818
UANUAt OP CBEMISTKT.
couaiflU of three beuxeae cucloi, united bj a group (COH). the para H
atom of each of the beuzene nuclei being rpplaccd by a group (XHj,
Ttie remaining H atoms of the benzene nuclei may be reptuc«d. cilhtr hj
CH, to produue the higher homolugucB, or by other stoma or radicals.
Neither pm-o aniliuc nor pure toluidiue will produce a red color hr
the action of oxidizing agents, the fonnatioa oi a rosanilino requiring a
combination of the two.
The robouiliueti are powerful iriacid buBea, forming solU which an &11
colored, aud from which the colorless baaea maj be separated by decom-
posing concentrated eolations of their salts with conccutxatcd KHO aolu-
tion.
Socman's violet is tricthyl'i-omnUine ctUoride, prodaoed by heating to-
gether ethyl iodide and rosauiline.
LytifiA Uut'. — tripSienyl-Tosanilitw. chloride, obtoincil by heating rosaniliiii^
with nu excess of ouiliuc ; (/as rfreim, obtained by heating rosauiline chlo-
lidc with uldehytle aud sulpbui'ic acid ; rarin violei, obtained by theoxida-
tiou of methyl auiliue.
Jfauvein is a base whose sulphate, obtained by mixing cold dilate boIu-
tiona of potaiwium dichrumate and aniline Hulphiite, is a tine, purple dye.
A blue dye is also obtained by heating luauvcin with aniline.
Aniiiiie black ia obtaiucd by acting on aniline with a mixture of cupn«
Bolphide or a vanadium salt and potassium chlorate.
Sajfronin is a base derived from commercial oils, rich in the miperior
homoluguL'S of oniliuu (toluidiues). ltd hydrochlurate is used iu place uf
Boffluwur.
AZO AND DIAZO DERIVATIVES.
The azo corapounds arf* derivable from the aromatic hydrocarbons by
loss of twu H otunifi from two molecules of the hydrocarbon, and union it
the remaiudera through the intermiMliary of a group ( — N — N — )". The;
are formed by the action of certain reducing agents upon the uitro-derir-
ativee, and may be considered as intermedial^ products in the reduction
of the nitro-derivatives to amines. Thus iu the case of benzene ;
.[C.H.(KO.)], + H.
HikobeiMBBO.
= 3H,0 4-
= HO +
AnujtbeojniA,
C,H-N\
C.H.-N\
C.H,— N/^
Aii>b«iisini«.
+ H. =
C.H,NH/
lljdnuobcDlrtiti
C.H.NH\
C,H.NH/
+ H, =
2[CA (NHJJ
Antllao.
The diazo compounds consist of an univalent remainder of an aromatlo
hydrocarbon, united by tlic group ( — N — N^ — ) with a haloid atom, or an
acid residue : C^, — N = K — Br = Diazobenzeuo bromideu
PTKIDWE BA3KS.
817
HYDRAZINXIS.
The Jiydrftzinfis are theoretically deriTflble from the group H,N — NH,',
dUaiitlogeD, bj tlie Bubstitution of acid, alcoholic, or phenylic tadicola for
one or more of the hvdrugen ntoms.
Phenyl hydrazine— C,H,—HN — NH, — is obtained by the action of
zinc-dtiHt anil acetic acid on diazo-atnidobenzene. It is a yellow oil, spar-
ingly soluble in water, soluble in alcohol and in ether ; posacseed of strong
reduciug power, and acting as a uiouacid base to form cryatallizod aalts.
PYRIDIN£ BASES.
These interesting^ subetances. closely related to the vofyetAble albaloids
08 well as to some of the alkaloida produced durinfj putrefactivn dor,ompo-
mtion of animal matters, were first discovered in 1851, as constituents of
oil of Ih'ppel — olcxim animde — oleum comv cervi — bone-oU, an oil pro-
duct during the dry distillation of bones, horns, etc., and as a hy-prod-
not in the raanufarture of aromoniaenl compounds from those sources.
They nliw occur in coal-tar, naphtha, and iu commercial amuiouia, me-
tliylic spirit, and fusel oiL
The pjTidine bases at present known are :
Pyridine CI.H.N
Picoline C.H,N
LuUdino ^,H,N
CoUidine C.H„N
Parvoline <^.H,,N
Coridine C..H,»N
Rubidiue C.,H„N
Viridine 0,;H.,N
Dedlti^inliil.
ap.Or. all
115**
0.324
IW
0.933
154-
0.y45
170*
0.053
188'
0.966
211*
0.974
230^
1.017
25V
1.024
It will be observed that tlieee compounds are mptameric with thp ani-
lines, from which they differ in constitution, as shown by the structural
formulco ol picoline and aniline :
CAN
31S
XAKITAL OF OUEKISTBT.
Thej are all liqaid nt the ordinary (empomtiirc, bcbavo as tertifiir
moiiamiDoa. react with Deveral of the general reagents of the alkaloids, and
form chloroplatinates which ore decompoaed by boiling water.
Pyridine — C/ ch^^H^'*^ — ^ obtained from oil of Dippel, ind i»
fdso obtainable Bjntbeticallj from piperifhne, ^^m\cK—Ch1/^~^
which 18 itself a derivative of piperine, C,^0^, a constituent of black
and white pepper.
It is a colorless, mobile Uqaid. having a peculiar, very penetrating
odor. It boils at US'" (239'* F.). It mixes with water in nil proportioni
It ia atroDgly alkaline, and combinea with acids as does NH,. Like all tlie
bases of this series, it is veir stable, and withstands the action of such ox-
idizing agents as fuming HNO, and cliromio acid. It forma crystaUioe
salta
i^n»/ine, C^„N ; CoUidine, C;Bt„N ; and ffydroixtllidine, 0^„N— hsTt
been noted oa products of putrefactive decomposition of albuminoids.
Pyrrol — HN/ qwj ~ «« / — ^ * weak base accompanying the py-
ridine bases in oil of Dipj)el, and also obtmnable from other soureea. It
is a colorless, oily liqiiid, whose odor reaombirs that of chloroform.
By acting upon pyrrol with an ethereal solution of iodine, a quadriitub-
Btituted derivative, tetriodopyrrol, C.HI^N, is obtained as a brown jKjwder,
which has been used uuder ibe name ludol as a substitute for iodoform in.
surgical practice.
CHINOLINE BASES.
The bases of this group at present known are :
I
Chinoline C,H,N I Pentahiroline C„H,>'
Lei)idiiie C„H,N Iwoline C 'h"N
Cryptidine C..H.,N Ettidine C, H„N
Tetrahiroline C.^,.N | Validine C,.H„N
whose constitution and relations to the pyridine bases are shown by the
fonuuke :
OH
CH CH
CH CH
\/
N
OH OH
.^Y^
CH
CH C CH
They are obtained by the destructive distillation of the cinchonine,
quinine, and other natural alkaloids, to which thev are c1os?lv related.
Chinoline— C.H,N— is a mobUe liquid ; boil^ at 238' (4fi0'.4 F.) ; be-
comes rapidly colored on coutjict with air. It has an intensely bitter and
acrid taste, and an otlor somewhat like that of bitter almonds. It u
sparingly soluble in water, readily soluble in alcohol and ether.
nroioo oBorp.
819
CbmoUne is the nucleus of a vast uuruber of products of subatitution,
flmnng which are four Bubetonces which hato recently assumed medical
importanre :
Thalllae = JHrahydroparachwaniaol — C,.H,,NO— is a deriTatiTe of the
paramctbvl ether of chinohDe. It is uici with in the fonu of sulphate and
tartrate in the shape of crystalline powders. The odor of the sulphate is
similar to that of anisol (methyl phenol); that of the tartrate to that of
coumorin. The histe of both is bitter, acrid, and salty. Both salta tire
readily soluble in H,0, the siilphato the more readily. Solutions of thai-
line wila ossunie, even when Terf dilute, a laa^iiQcent emerold-grcen
color witli Fe,Cl, solution.
Etbylthallioe — C H,^0 — ia a dcrivativo of thalline, whoso chloride
is hygixnicopic ; readily lurmuit; Bolutious which are acid iu reaction, bitter
in taste, and assume a red-brown color with ^*eX)l|:
Antipyrine ■= JMmethyloxychmizine — C H„N^O — is obtained by
heating methyloxychiuizine with methyl iodide and methyl alcohol in
sealed vcsselti at 100" (212'^ F.); the first-naiued Rubstouco having beeu
previously obtaiue^l by the aotiou of acetylacctio ether upon phenyl hydi-a-
zine.
It couatitutes n volumiuous, reddish, crystalline powder ; readily soluble
iu water, ether, alcohol, and chloroform.
Its solution with Fe CI, ia colored deep red-brown, the color being
diBchorged by H,SO,. . NitrouH acid colors dilute solutions of antipyrine a
biight green, which persists for several days at the ordinary temperature.
If the mixture bo hent-ed, and a drop of fuming HNO. a<)de<l, the color
changes to light re<l, then blood red, and the hquid deposits a purple oil
on continued heating. Addition of a drop of fuming ID«0, to a cold con-
oeotrated solutioa of antip^Tine produces precipitation of small greea
cryatolB.
Kalrine — MethyloxtjchinoUne hydride — C„H,,NO — ia more nearly de-
rived from chinoliuo than the substances previously mentioned. Ita chlo-
ride is a oryHtalUue, nearly white, eceily soluble powder, whose taste is
at onco bitter, aromntir., and salty.
Thulline, ethylthnlliue, antipyrine, and kurine are posBeaaed of onti-
poriodic and antipyretic properties.
Lp
INDIGO GROUP.
In this pronp are included a number of substances, derivable from
indigo-blue, which are evidently closely related to the benzene group, as
ia shown by the number of benzene derivatives which are obtained by
their decomposition, yet whoso constitutioa is not yet definitely esUb>
liahed.
Indlgotin — Indigo-blm — C,^,,N,0, — constitutea the greater part of
the commercial mdiijo. It does not eiifit preformed in the plants from
which it is obtained, whoso juico is naturally colorless, but is produced
bv decomposition of a glucoaide contained in thom (see Indicoc, p.
320).
Indigotin may bo obtained by the aotiou of phosphorus triclUoride on
iinUin ; or, in a nearly pure form, by cautiously subhiiiiug commercial in-
digo. It forms purple-red, somewhat metallic, orthorhombio prisms or
plates, odorless, tasteless, neutral, insoluble in water, ether, or dilute
acids or alkalies. By dry distilblioii it yields aniUue and other producta
S30
MAITTTAL OP CH'BMISTBT.
By moderate beating with dilute HNO, it gives off ^ns and is conrert'
into iaatia
tedlgo Sulphonlc Acids. — When indigo is heated for some time with
fuminj; ^I'^i i^ dissolves. If the solution bo diluted with B,0, a biufi
povder, soluble in H,0, but insoluble in dilute acids, is precipitat«<L
This ia Jndigo-monosulphojnc or phwnicin-sulphonic acid— C,^H N,0,SO,H.
Tb© filtrate from the loat-iooutioucd precipitate coutuizis indigo-diMui-
pho»ir, sttiphindijUc, or auiphintligoiic acid — C,,H,N,O,(y0,H), — wbou K
and Na anlta conHtitute soluble pastes known in the arts as goltibte indi^,
or indigucarmine.
Isatin—C.H^NO —obtained by oxidation of indigo-blue, forms shin-
ing:, transparent, red-brawn prisms. It is odorless, sparingly soluble in
water, readily soluble in aloohoL
Dioxindol — Uydrindic acid — C.H,NO, — is formed by the action of N»
on isatin suspended in U,0. It forma yellow prisms, soluble ia H,0, auJ
combines witti both bases and adds.
Oxindol — C^H,NO — is obtained from dioxindol by reduction -with Na
amaltfam in acid solution. It crystallistea in easily soluble, culorlow
needles, and onmbinos with aci^ls and bases.
Indol — C,H,N — is produced by distilling oxindol overzino-dast, orl^
heating orthunitrocinuumic acid with KHO and Fe lilingv.
It crystallizes iu large, shining, colorless plates, having tbe odor
naphtliylaminf>. It is a weak base, forming salts with acitls, which are,
however, decomposed by boiling water. Its aqueous solution, acidulated
with UCl. is colored rose- red by KNO^ li is converted into aailioe by
fa8e<l KHO.
It ia one of the products of putrofactinn of albuminoid substances, and
is formed durin;; the af-lion of the jiancreatic secretion upon albuminoi'
It is partly eliminated vfith the Ixcea aud partly reabsorbed.
In the intestine and fiecea indol ia invariably accompanied by Steal
C.H,N, its superior homologue, which may also he obtained by the octioD
of Sii and HCI on indigo. It crystallizes in brilliant plates, and ts leas
soluble than indigo. The pi-oduct obtained from indigo bos a penetrat-
ing hut not disagreeable odor, while that obtaine<l from putrid albumin
and from fjeciil or intestinal matter baa a disgusting odor, probably due to
the presence of foreign substauces.
Ihdioan— 0„Hj,N",, — is a gluooside existing in the different varietiea of
indigo-prod uclug plants, and also in the urine and blood of man and the
berbivonu
It is a yellow or Hght-brown syrnp, which rnnnot bo dried without
decomposition, bitter and disagreeable to the taste, acid in reaction, and
soluble in water, alcohol, and ether.
It is very prone to decomposition. Even slight heating decomposes it
into leucin, mdicanin, C,,H NO , and indigluirin, 0,H,,0,. A churoct^ria-
tic decomposition is that when heated in acid solution, or tmder the in-
fluence of oertain ferments (?) it is decomposed into indigo-blue and indi-
glucin, the latter a glucose :
2C,.H..N0„ + 4H,0 - C.,H,.N,0, + CC^,.0.
InaLawt. Watar. IndlgoUn. ladlKtnoto.
re. '
sd
by
fUltl
>ida^_
SIXTH SERIES OF HYDnoCARDON'S.
SIXTH SERIES OF HTDROCARBONR
Serie3 C,ll^|_^
This scries bos at preseut but two rei)resenUllTOs, derivable &om ben-
seuo bv tbc substitution of ono lateral chain for an atom of b^fdrogen.
Cinnamene — Styrvtene — Cint\am<d — Styrol — Liquid etitence of sUjtox
— C,H, — 104 — exists read^ formuJ iu eastjutiol oil of styrax ; it is also
fonned by decomposition of uinnamic acid (y. v.), or, ayntbctically, bv the
action of a red heat upon pure acetylei)e, n luixtiire of acetylene and ben-
zene, or a mixture of benzene ami ethyleuo. It iii a colorless liquid, boa a
penetrating odor, reiraliiug tbose of benzene and uapbtb/iloue, and a poi>-
jwrv taste ; ha'xU nt 143"^ (289'.4: Y.) \ soluble in all proxiurtious in alcohol
anJ WAt«r; neutral in reaction.
^^^B ALCOHOLS.
^ SUUES C3^.0.
I There ore but two alcohols of ibis seriea known :
I Cinnjl alcohol C,H„0 | Cboleeteriu C„H„0
I Cho
nlthoud
Cholesterio alcohol— (7M<rs(ertTi—C,.H„OH— 372— ia an alcohol,
although usually chuwed l>y ]>hrm<ilogista nmong the £ita, because it is
greasy to the touch and soluble in ether.
It occurs in the itnimal economy, nominlly in ttie bile, blood (especially
that coming from the brain), non-o-tiaaue, brain, spleen, sebum, contentaof
the iulcatiues, meconium, and Cteces ; pathulogieally in biliiu^' calculi, iu
the luine in diabetes and ict«ruft, in the fluids of nficites, hydrocele, etc., in
tubercular and cancerous deposits, in CAtarocta, in atheromatous degenera*
tions, and ftometimes. in mnsses of considemblfl size, in certain cerebral
tumors. It also exiBts in the rcgptable world in penR. beans, olive-oit
wheat, etc. It has not lieen obtained by synthesis. It is best obtained
from biliary cjilruli, the lij^ht^r- colored varieties of which consist almoHt
entirely of thia sulmtance. The calcuU are pulverized, extracted n-ith
boiling ether, the solution filtered hot, the ether distilled off, the residue
dissolved in boiUn^ alcohol, and the solution allowed to cool ; tlie crys-
tals which seiMxrate aie heated for some time with alcohol containing a
little potash ; on cooling, crystals form, which are finally wnshed with al-
cohol so long ns the washings are colored or alkaline, and recrjbtoliKed
from ether.
Choleaterin crj-stallizes with or without Aq. ; from benzol, petroleum,
rldoroform or anhydrous ether, it separates in delicate, colorless, silky
needles, liaving the composition C,,H,,0 ; from hot alcohol, or a mixture
of alcohol, and ether, it crystallizes iu rhombic plates, usually with one
obtuse angle wanting, having the composition C,,lI..O -f 1 Aq.; those crys-
tals, transparent at tirst, become opaque on exixisiuv to air, from loss of
>.q. It is insoluble in water, in alludies and diluto acids, difficultly soluble
822
HANUAL OF CnZMISTST.
in cold alcohol, readily soluble in hot alcohol, ether, lienzol. ac«tic add,
Klvceriii, au(l aolutiona of the biliurv aciJa It is odorless and tOHt^esB.
When anhydrous it fuMts at 145^ (293^ F.) and solidifies at 137^ (278\6
i''.); sp. gi'. l.imi. It 19 liDvojirTous, [o]^ — 31". (J in any solvent.
It combineH rendily with tJio volatile fully ncidtt. From its solutioii
in glftcinl acetic acid a cnm^KJUud having the compositiou C,,ll„O,C,Ii,0,
serparateB in fine curved crj'stnls, ivhic4i arc decomposed on contact with
Vfftter or alcohol : when heated with ncids nnder pressure, it forma tme
ethers. Hot HNO, oxidizes it to choleMerie acul, C.H^^O^, wliich is also
prwiuced by the oxidation of biliary acids ; a fact which indicates the prob-
able existence of some relation between the methods of formation ot cho-
lesterin and of the biliary* acids in the economy.
ANALYTICAL Charwh-ers. — (1.) Moistcned with HNO„ and evaporated to
dryness, a yellow residue remains, which turns brick-red on addition of
NH.HO. "
(2.) It is coloretl violet when a mixture of 2 vols. H,SO, (or HCl) :inl
1 voL ferric ohloiide solution is evaporated upou it.
(3.) When ground up with H,SO, and chloroform added, a blue-red or
violet color is produced, which changes to green on exposure to air.
SEVENTH SERIES OF HTDROCAKBONS.
Skbub C«H,i^,o.
The only representative of this series at present known ia
Naphtiiydrene — Naphlhylene. hydride — C„H,, — 130 — obtained by
heatiag naplith:deno with potassium, and decomposing tlie product with
water. It also occurs in heavj- petroleum. It is a colorless liquid ; boils
at 205*^ (IQl*^ F.), and has a strong, disagreeoble odoi^
EIGHTH SERIES OF HYDROCARBONS.
SeBIES GnH^M— ir
The only term of this series is
Naphthalene — C „H.— 128 — occurring in coal-tar. It has been formed
by a synthesis which indicates its constitution ; benzene and ethylene,
when heated together, unite to form, first, cinnameue and afterward
naphdmlcne. It is constituted by the fusion of two benzol groups by
two C atoms, thus :
H
A
H~C C C-H
H-C C-H
\c/N)^
H
H
NAPIITnOLS.
83S
It cryfttAllizoe in large, brilliant plates ; has a burning laste and a faint
aromatic odor; fuaee at 80" (176° F.) and boila at 217^ (422^6 F.), sub-
liming, liowever, at lower teiiipemiures ; burns with a bright, BOioky
flame ; iosolublo in water, soluble in alcohol, ether, and essences. It forms
II g ubstitution compounda with CI, Br, I, HNO„ and H^SO^.
I B7 the replacement of the hvclrogen alomR of naphthalene br other
I atomn or by radicals, substituiion products are obtained Booiewbnt in the
^ same manner as iu tli© case of benzene (see pp. 301, 304, 305). In the
case of naphthalene, however, the number of isoineiPH is much greattr lh:in
with beozese. Iu the Bti-uctm-ul formula uf uaphlhalene Ihti puaitiouH
SUBSTITUTION DERIVATTVES OF NAPHTHALENE.
H
H
1—70
k k
1. 4, 6, 8, although equal to each other, are of difTorent vtduo from the po-
ationa 2, 3, 6, 7, also equal to ejich other, as they are differently disposed
with regarti to the carbon atoms x and y* There exiut, therefor, twr>
possible amsubstitated derivatives of naphthalene for a single such denv-
alive of benzene, etc. If the substitutt-d group occupy the approximate
positions 1, 4, 5, or 8, it is called im a-derivative ; if it occupy tho remota
poiutions 2, 3, 6, or 7, it ia a j3-derivatiro.
Of the numerous derivatives of nuphtbalene, the only cmes of present
medical interest are those corresponding to tbo monopbenob :
Naphthols — O H„OH — of which there are two :
n-Naphthoi baa been obtained by beating phenyl-isocrotonic aoid ;
also by boiling an aqueous solution of diazonapbtbalene nitrate witli
nitrous acid, or by fusing a-naphtbaleoe'Sulpbonic (icid with KHO.
It crystallizes in colorless prisms; fuses at94'' (201^2 F.) ; boils at 280"
(•SBA" F.) ; ia nearly inaoluble in water, but soluble in alcohol and in ether,
and gives a transient violet color with Fo.Cl, and a hypochlorite.
fi-Xaphlhol — Iiki»ai>lithol — is prepared industrially by fusion of ;9-naph-
tfanlene sulphonate of sodium with NaHO, for tho manufncture of a yellow
dye-stuflF: Campobt'Uo t/fUow. The commercial procbict is in reddisli-gray,
friable^ light masses. The pure substance forms colorlesa, silky, cr^'staUine
plates, having a faint, phenol-like odor, and an evaneeceut, sharp, burning
taste. It fuses at 123 (263^4 F.), boils at 2H6* (514*.8 F.), and is spar-
ingly Bolable in water, but readily soluble in alcohol and etlier. Its aque-
ous solutions are not colored violet by Fe,Ct^ Tbe pure substance is a
valuable antiseptic
&S4
MANUAL OP CHKMWTllY.
NINTH SERIES OF HYDROCARBONS.
Saaxa aH^_„.
Is represented bya single hydrocarbon : Acenaphthalene — C,.H,„—
154 — produced B}-nthelicjiIly by continuing the beating of naphtholciis
^'ith ethylene, tbe reuctiuu oocorring in three steps. It also exists in
coal-tar.
TENTH SERIES OF HYDROCARBONS,
Sebies CJi,^,,.
Is represented by two terms : Flxiorene, a solid, crystalUne body, boil-
ing at 305^ (581^ F.), obtjiined from rool-tar ; and StUbene, obtained bv
the action of ammoniiuu uulphyJrate upon an alcohohc solution of benzoir
aldehyde.
ELEVENTH SERIES OF HTDROCARBONS.
Seiubi C.H^_it.
Anthracene — C,,H,. — 178 — enstB as a constituent of coal-tar, and U
obtnined by expression from the substaope remniuing in the still aft^r the
distillation of naphthalene, etc The oommercial product thna obtaineii
is a yellowish mauH coutaiuiug 50-SO per cent, uf authnicene, the pun-
ficaUou of which is a matter of coDKlJemblo di^culty. It 1i:ls also been
obtained syuthotically, by the action of the heat on benzyl-toluene, and in .
other ways.
VTben pure, anthracene crystallizes in rtiombic tables bavisg a bluiiih
fluoicaccnco ; fusible at 210=* (-HO" F.) and boiling above 360* (GSO' F.) ;
its best solvents are benzene and carbon disulphide, in which, Lowever, it
is only sparingly soluble.
The constitution of anthracene is that of two benzene nuclei united
throu<?b two of their C atoms :
niGUKK SERI£9 OF HTDBOCARBON9.
8S5
hydrocarbon boiling above 360^ (648" F.). Br and CI attack it violenUy,
1 more slowly, forming products of addition.
An isomere, rhvnunihrcw, C,,H„, which boils between 320° and 350*
(608°-€62'* F.)t accompanies anthracene in the crude product.
Dioxyanthraquinone — Allmrin — C.H
DERIVATIVES OF ANTHRACENE.
Ae may be inferred from the complex molecule of anthracene, the
xiiunber of possible derivatives of substitution and of additiou, including
many iaomei-es, is very greaU
Our knowledge of these derivatives is an yet fragmentary', and hut
few of those known are of present medical iuterast.
/CO
Anthraqninone — OJH,/ >0^.— is formed by oxidaiioQ of au-
thraceno. It forms yellow needles, whicli fuse at 273°* (523^4 F.). It is
not easily u:tidiztid, but is couveilcd iuto authiiicene by mifUcienlly active
reducing agentsi
.CO. .OH
m_CH/ 7C,h/ —is the
O/ -OH
[^d pigment of tlie madder root {Uabia lindorm). Artificial alizarin has
now almost completely displaced the natuiul product in dyeing. Il is ob-
tained by the ocliou of fused KHO on mtmy anthracene derivatives, the
one gencrdly uw^I being atithntquinunt'-diHidphonic arul, C,,H,0 (SO,H),.
Methylanthracene-^/j4H,,CH, — is obtainable by syutueuis, and
also by bunting clirytiuphiinic acid, emodiu, or clutu with zinc-dust.
Chrysophanic Acid— rarietic Acid — Rheic Acui—Hht'^tn, 0,jH„0, —
is a derivative of motbyl autbracene. which exists in the lichens Parmelt'a
parielina and Squamaria degatu, iu senua, and iu rhubai-b, and obtainable
to the extent of 80 jier cent fi-um Goa yowtier = Chrjftarubin, C„H„0,.
Chrysophanic acid crystallizes in golde&> orange-yellow, interlaced
Deedlea It is almost tiatcless and mlorlesa ; fuses at 162^ (291°.6F.);
almost iuBoluble in cohl M'ater, sparingly Holuble in hot xrater, alcohoL and
ethei*. readily aolublo iii benzene. It foi*ms a tud eolutiuu nitli U,.SO^
from wliich it is deponited, uuebangetl by water. It ftl^o forms red bolu-
tions mth alkalies. Reducing agents convert it into melbyliuilliraceue.
Trioxymethylanthraquinone — Kmodin — C^Ji.^iiM^{OB).0^—
oocars in the bark of Jiliainnitx framjula, and ac»ompauiua chrysu-
phanio acid iu rhubarb. It crystuUizes iu long, orango-red prisms which
fuse at 350^ {-Ui'I^ I*'.), and yield metbyhmthraceno when heated with zino-
dusL
HIGHER SERIES OF HYDROCARBONS.
Tlio iweUth seriea is not at proscut represented. Of the thirteenth
ficriea, one hydrocarbon, pvTfm% C ,H,., is kuown ; and one of the four-
teenth series, chri/gene, C,,H,^ — both obtained from coal-tar.
J'tjrene crystallizes in plates ; fuses at 142^* (287''.6 F.). It fomia a
comiiouud nith picric acid, which crystallizes in red needlesi
CVirywHc en'Mtallizee iu bright-yollow, glistening scales ; is sparingly
soluble in alcohol, and forma a com|>ouud witb picric acid which crystal-
lises iu brown needles.
The aubfliaoces which we hare so far cotiHidereil are all derivable, more
or less directly, from tLo \-ai'ious hvdrocarbuos, iind may be ctniHidered,
upon tbe theory of types, as produced by the substitution of radicals com-
posed of C and H, C and O, or C, H and O, for atoma of H of the three
typical aubaUnces H,, H,0 and H,K.
The subatancos of this class are t^-pically considered as containing^ the
radical (CN)', which is known as cyanogf*», and has the sajne p?wer of
paaain;? anrhaiit^cd from counx)iind Ut ciiniiKiund, an do methyl and ethvL
Dlcyajiogen— (CN)^ — 52 — is prepared by heating mercurio cynnida
It iii ft colorltjsa gas ; has a pronounced odor of bitter almuuds ;*Bp. gr.
1.80fi4 A,; bums in air with a purple flame, piving off N and CO,. It is
quite wjluble in H,0, the Holution tumiuff brown in air.
With H,0 alone, or with H,0 and KH,, dicyanogcn enters into com-
binatioua which indicate Uie relations existing between tbe cyanogec
compounds and those previously considered :
(CX),
+ 4H,0
Waur.
= C.O,(NH,),
(CN) +
DlcrmnocMi.
H,0 =
Wotci.
CNOH -h CNH
Cjanic add. Rjrdraejruilc >cid
CNOH +
H,0 =
VVUar.
NH, + CO.
JIniTiwnta. Cartno iUozmIl
CNOH
CT»nk: Kid.
+ NH,
Dr«t.
It has a very deloterions action upon both animal and Tegetable life,
even when largely diluted with air.
Hydrogen cyanide — Cyanogen h^iride — Hydrocyanic add — Prumc
acid — n [ — 27 — exista ready formed in the juice of oossawi, and is
formed by the action of H,0 upon bitter almonds, cherry-laurel leaves,
etc. It is also formed in a great number of reactions : by the passage of
the electric discharge through a mixture of acetylene and N ; by the action
of chloroform on NTH, ; by the distillation of. or the action of UNO, upon,
many organic siibstancea ; by the deconijuisition of cyanides.
It is alwayB pre|iared by the decom^ioHitiun of a cyanide. Its prepara-
tion in the pure form is an operation attended with the most serious
danger, and should only bo attempted by those well trninpd in chemical
manipulation. For medical uses a very dilute acid is required ; the at-id.
hydntcyanicum dil. (V. S., Br.) contains, if freshly and properly prepared,
two per cent- of anhydroua acid ; that of the French Codex is much stronger
— ten per rent.
The pure acid is a colorleas, mobile liquid, has a penetrating and
characteristic 6dor; sp. gr. 0.7058 at 7^ (44 .6 F.) ; ciystallizes at -15'
(5° F.J; boils at 26^5 (79".? F.); is rapidly decomposed by exi>ogure to
light The dilute acid of the U. 8. P. is a colorless liquid, having the
odor of the acid ; faintly acid, tlie reddened litmus returning to blue on
exposure to air ; sp. gr. 0.997 ; 10 grams of the acid should be accurately
neutralized by 1.27 gram of silver nitrate. The dilute acid deterioriatea
CYWOQ'KS COMPOUNDS. 327
on erposnre to ligbl, althouf;;!! more slowly than the concentrated ;a trace
of phosphoric acid added to the solution retards the deconipoHtttoo.
Most Btroap acids decompose HCK. The alkaliea enter into double de-
composition with it to form cyanidrti. It in decomposed b^'Cl and Br, with
formation of cyanogen chloride or bromide. Nascent H converts it into
roethylamine.
AsALi'TioAL Chabactebs. — (1.) "With silver nitrate a dense, white ppt. ;
which is not dissolved on addition of HNO, to the liquid, but dissolves
when separated and heated vrith concentrate<l HNO, ; soluble in solu-
lions of alkaline cyanides or hypoBulphitea.
(2.) Treated with NH,HS."e>iiporated to dryuees, and ferric chloride
added to the residue ; a blood red color.
(3.) With potash and then a mixture of ferrous and ferric Bulpbatee :
a greenish ppt., which is partly dissolre<l with a deep blue color by HCL
(4) Heated with a dilute eolation of picric acid and then cooled : a
deep red color.
(5.) Moisten a piece of filter paper with a freshly prepared alcoholic
solution of piainc ; dip the paper into a very dilute solution of CuSO,, and,
after drying, into the liquid to be tested. In the presence uf HCN it aa>
sumes a doop blue color.
Toncou»oT.— Hydrocyanic acid is a violent poison, whether it bo in-
haled as vapor or swallowed, either in the form of dilute acid, of soluble
cyanide, or of the pliarmaccutical preparations containing it, such an oil
of bitt«r almonds anil cherr^'-laurel water ; its action being more rapid
when taken by inhalation or in aqueous solution than in other forms.
When the medicinal acid is takeu in poisonous dose, its lethal effect may
seem to be produced instantaneously ; uovertheless, several respiratory
efforts usually are made after the victim seems to be dead, and instances
are not wanting in which there was time for considerable voluntary motion
between the time of the ingestion of the poiwm and unconsciousness. In
the great majority of cases the patient is cither dead or fully under the in*
flueuce of the poison on the an-ival of the pliysician, who should, however,
not neglect to apply the proper remedies if the faintest spark of life remain.
CUemicid antidotes ore, owing to the rapidity of action of the poison, of
no avail, although possibly chlorine, recommended as on antidote by
many, may have a chemical action on that portion of the acid already
absorbed. The treatment indicated is directed to the maintenance of
reapirotion; cold douche, mdvaniam.«rtjiicial respiration, until eliuiinutiun
has removed the poison. If the patient survive on hour after taking the
]X)isuu, tlie prognosis becomes very favorable ; in the first stages it is ex*
ceedingly unfavorable, unless the quantity taken has been very small.
In cases of death from hydrocyanic acid a marked odor of the poison
is almost always observed in the apartment and upon opening the body.
even several days after death. In cases of suicide or accident, the vessel
from which the poison has Iwen taken will iisnally be found in close
proximity to the body, although the absence of such vessel is not proof
that the case is one of homicide.
Notwithstanding the volatility and instability of the poison, ite pre-
sence has been detected two mouths after death, althou'th the chances of
Bepnratiug it are certainly the better the sooner after death tlie analyaia is
mnde. The search for hydrocyanic acid is combined with that for phos-
phorus ; the part of the distillate containing the more volatile products
is examined by the teats given above ; it is best, when tlie presence of
free hydrocyanic acid is suspected, to distil at first without acidulating.
1
J
UASVJiL OF CBEHT6TBT.
in tiwh nuenthe Miomach uhouJtl never be opened until tmnuWio/efy bi^orc Oie
Cyanic acid — Cyanogen hydrate — g/O — (13 — does not exist in
nature ; it is obtaiued b^ c«lcining the crauules in prpseuce of no oxi<]ia-
tuff ftp^nt ; or bir the action of ificvanorton upou solutions of the alkalies
or alknline oarljonaten ; or by the <li«tilUtion of cj-anuric acid.
It ia a LHtlorless licjuid ; haa a siroug odor, reaombling tbnt of formic
noifl ; its vni>or is irntntini^ to the eyc-B, and it pnxtuco^ vesication when
r'leil to the skin ; it is »^lublo in water. When free it is roadilj
ge^l by expOBore to air into cjsmelide.
Sulphooyanio aoid — Cyanogen tulphydrate— g /S — B9 — bean the
SADiP relation to cyanio acid that C3, does to CO.. It is obtained l»y the
deooropoeition of ita aalta, which are obtained by boiling a eolutiou uf
the cyauiJc with 8 : by the acliuu uf dicyauogen upou the metallic ral-
phide ; and in aovcral other ways.
The frffi arid is a colorleBS liqnid ; cr^'atalllzea at — 12\5 (9^fi F.);
boils at 1U2^.6 {'llQ.h F.) ; acid in reiictiuu. Tlie {iroininent rvacUon of
the acid oud of its salts ia the production of a deep red color with the
ferric Balta ; the color being disohArged by eolution of niercnrio chloride,
but not by HCl.
Hulphocyauic acid exiRta in human saliva in combination, probably,
vnih so;iiuui. The free acid is at-tiwly poisonous and ita Bidia were fur-
iiiorjv mipposetl to be so niao ; it is probable, however, that mui-h of the
deleterious action of the potUHsium hhIl — that usually expei-iuieuted with
—is due OS much to the uietal us tu the acid.
MetaUooyanides.^Tho radical cyanogen, besides combining ^'ith
metallic elements to form true cyauiJea, in whicii the radical (CN) enters
aa a univideut atom, is enimble of combiniug H-ith certain nietuls {notably
those of the iron and platinum groups) to form complex nulicols. These
conibiniiig with H, form acids, and wiUi basic elements form salts in
which tiie aiialyticid reaotiuus of the metallic element entei'ing into the
radical ai'o cnuiplctely masked. Of these fntV(i//(M-i/artuf«« the best known
are those in which iron enters into the radical. As iron is c^uble of
fonning two series of coTnpounda, in one of which the single atom Fe"
enters in its bivalent cnpicity, and in the other of which the hexavalent
double atom (FcJ*' is contained ; so, luiiting vitb cyanogen, iron forms
two feiTocyanogeu nididds: [(,CNV,Fe '|". fen\ic}ftn*ufn, and ((CN) ,,
(Fe,)"|"_/trrTicwno5fen ; ouch of which tmites with hydrogen to form an
acid, oorTBHponding to which are numen>us saltx : (C.\N,Fe)H^, hydrofttr-
riK-f/atiic acul, Ictraboutc ; and (C,,N,.Fej)H^ hydroj'erricyanic acid, hex-
abasic (see potassium and iron 8ult«).
coatPorxDs of unkxown cokstitutiox.
GLUCM3SIDES.
I
Under this head ore classed a number of substances, some of them im-
portant metlicinol agents, which are the products of vegetable or animal
nature. Their ehnrjictfiristic proiwrty is tiiat, under the intluenoe of a
dihite niinend arid, they yitld glucose, phloi-oglucin or mamiito, together
with some other substouco. Under the suppoeitiou that glucoeo and its
ooDgenera are alcohols, it ia quite probable that tho glucosiues ore their
corresiJOudiufT ctbcni.
AmygdaJin, C,,H,.NO,, — 157— exisU in cherry.-Iaurel and in hitler
almonds, but not in sweet almonds. Its characteristic i-vactiou ia that,
in the prcflence of emiJjiin, \rltich existH in sweet as wcU as in bitter
almonds, and of water, it is dccoiupow>d into prlurose. lienzoic aldehvde,
And hvdroc.vnnic acid. The saiile reaction is bi-oiight about by boUinfif
n-ith <iih]te 'U,SO, or HCl. Bitter almonds contain about 2 per ceut. of
omy^lalin.
XHgitaUn. — The pharmoceutipal products sold under the above name,
and obtained from iH'/itolix, lux- iiiixturcH in varvinjj iirojiortioiis of several
pliicostdf^s. />i'f7i/onin, C.H^.O,,. nn ainorpliouB, yc-IIowish fiubstanee, ven."
soluble in a<|Ucoua alcohol, fh^fitaliu, C.H.O^, the priuciiml conRtituent of
the French digitaliu, is a colorless, ver}- bitter, crystalline solid, insoluble
in water, soluble in alcohol. 0igi(nfe:u, a white, iutenscly bitter, amorphous
solid, rery soluble in ivater. soluble in alcohol. JH'iitoain, C,,H.,0., n
colorless crk-stalline solid, insoluble in water, sparingly soluble in alcohol.
It is not a ^lucDside, and ia converted into tu.cirfgin by dilute acids.
The (iftKtraetum di^aiis (U. S.) luxtbably contains all the abo>-c, tho ex-
traction of tho first being more oomplete witli weak alcohol, that of the
oUieni with Htnjuj,' ulcohoL
Glyoyrrhizin. — A non-orystaUizable, yellowish, ptdverulent principle,
obtnine^l from liquorico ; soluble with ditHoulty in cold water, soluble in
hot water, alcohol, and ether ; bitl«r-H\veet in t;ute. By lonj; boiling with
dilute acids it is decomposed into glucose and f^f'/cyiThetin, C,,H.,0,.
Jalapin — C^.H^^O,, — 7*Ji» — is the active princii)le of ecamuony, and
exists also to a hmited extent in jalap (see lielow). It is an iusipid, coloi'-
leaa, amorphous substance, which is decomposed by dilute acids into glucose
Uidjaiapiuol, Tho active ingredient of jnlap ia not, ns tho name would
im]>iy, jalapin. but a resinous Bubstajice called com^frtilln, whicii ia in-
soluble in ether, odorless, and insipid. It is not attacko<l by dilute
KSO,, althouji^h the concentr.iled acid di.sKolve» it with a canuiue-red
color, slowly turning to brown ; in alcohoUc solution it ia doooinpused by
gaseouB Ht'l into glucose and f^mvolvutinic afi't
Quinovin — Quinomlic arul. — A bitter principle, posses8e<1 of aind fuuo
lions, obtained fi'om tho faliio h:irk, known as cinvhoua nova : it in a ght-
ooRtde, Wing ilecomposed by dilute acids into a sugar rostombling maii-
nitou -ind •^uinoniir acid.
Saiivin—Silicinuni {C S.) — 0„H,.0, — 286— occurs in the liark of the
willow (naiix). It ia a white, crjstallino substance ; insoluble in ether,
soluble in water oiul in alw>h«.'l ; very bitter, ita solutions oio iIcxtiog_vrou8,
\a]u~ 4-55.8. Ihlute acida decompose it into glncisse anri mfifi«mn (9. u.).
OraoeotratoLl H.SO, colors it red, the color being discharged on the addi-
tion of water. When tidien into Uie economy it is converted into salicylic
aldehvde and acid, which ai-e eliminated in tho urine.
Santonin- .%ij;oMi> atwi— C,,H„0,— .Sim/onmum (V. S., .Wr.)— 24^—
A glucoside liaving distinct acid proi>ortiea ; obtained from various siwciea
of Artcmiiiui. It cr^-stollizes in colorless, rectauguljir prisms, whi<'h turn
yellow on exposuro to liglit ; odorless auil tasteless; insoluble in cold
water, sparingly soluble in hot wa1«r, alcohol, and etlier ; its solutions ore
faintly acid in reaction. Hantouin, in solution, gives u chnmuis-coloreti
precipit.'itu with tho ferric salts, and a white precipitJito with silver, zinc,
and iner<!urr>iiH nnUjn ; no precipitate with mercuric salts.
Palieuts taking santonin pass urine liaving the appearance of that
coutoiuiug bile, which, when treated with putaiUi, turns cberr}*-rod or
■
u
crimson, the color being discharged by an acid, and regieneratod on nen-
h'ftUzatiou.
Solanin. — A glacofiide, haring basic properties, existing in different
ftlant^ of the ^enus Sofannm. It ervatallixes in fine, white, fdUcy needles;
laving an acrirl, blttor taste ; insoluble in water, and but eporinglj aolaUe
io ether and in alcohol. By tlie action of hoi dilute acids it is deoonir
jMsed into (glucose find a basic substance, solanidiii. When not beate^l
solanin coiuliinefl with ai'ida to form uncrvBtnllizjihle salta. CJold conoea-
trated H^SO colors it orange-yellow, an^ finally forma with it a brown
solution ; U^O, dissolves it> the solution being at first colorless, afterward
rose-pink.
Tannins — Tannic avid — C,,H,,0,— 322.— Quite u number of difforenii
substances of vegetable origin, principally derived from barkR, leaves, and
seeds. They are amorphous, sohible in water, astringent, capable of pre-
cipitatiug albumen, and of forming imputrescible couipuuuds with the
gelaiinoids. They ore, with one possible exception, glacoeides.
Gai.i/>-tansic Acm — Acidum tannicum {C S., Hr.) — is the best known of
the tannina, and is obtained from nut-gaUs, gaila {C. S., Br.), wluclx are
excrescences pnxluced upon oak-trees by the puncture of minute iusecis.
It ajipears as a yellowish, amori»liniis, odorless, friable muss ; has an astrin-
gent taste ; verj* soluble in water, leas so in alcohul, uluiust iuHoluble in
ctlier ; its solutions are acid In reaction, and on contact with ouimal tivtiueti
give up the dissolve*! tannin, which becomes fixed by the tissue to iorm a
bough, iiiAoUible, and non-putrescible material (leather).
A freshly prepared solution of pure gal3o-tannic acid gives a dark blue
precipitate with ferric salts, but not with ferrous aalis. If, however, the
solution have bepn exposed to the air, it is altered by oxidation, and gives,
with fcrruu» salts, a black color (in whotie production gallic acid pn^bably
plays an important part), which is the coloring material of ordinary writ-
ing-ink.
CAJ>rGTA!(:«ic Acid — exists in naline combination in coffee and in Pua-
guny tea. It colors the ferric salts green, and does not affect the ferroua ;
salts, except in the presence of ammouia : it precipitates tlie salts of quinina^
and of cinchoniue, but does not precipitate tartar emetic or gelatin. It is
a gluooside, being decomposed by suitable means into cojfeic acid and
mannitan.
Cachoctakstc Aero — obtained from catechu, is soluble in water, oloobol,
and ether. Its soluticua precipitate gelatin, but not tartar emetic ; they
color tlie ferric salts grayish green.
MoKi>TASMC Acid — Maviurin — a yellow, crystalline substance, obtained
from fustic ; more soluble in alcohol than in water. Its solutions precipi-
tate green witli ferroso-ferric solutions ; yellow with lead acetate ; brown
with tartar emetic ; yellowish-brown with cupric sulphate. It is deoom-
posable into phon.»gluciu and ■protoi'atechuic acid.
QirEBCTT.MtNic ACID ifi the actlve tanning priiiciple of oak-bark ; it differs
from gallo-tannic acid in not being cupable of conversion into gallic acid,
and in not fumishlug pyrogallul on dr}' distillation. It forms a violet-
black precipitate with ferric salts. The tannin existing in black tea seomij
to be quercitannic aciil,
QnxoTASKic Acm, n fannin existing in cinchona barks, probably in era
binatiou with the alkidoitls. It is a light yellow substance ; soluble iu water,
alcohol, and ether ; its taste is astringent, but not bitter. Dihite H.SO,
decomposes it, at a boiling temperature, into glucose and a red substance
— jHinoLd rvd.
ALKALOIDS.
381
AUCAIiOIDS.
The atkaJoida are organic, nitrogenized stibfitanr&t, alkaline in reaction, and
capable of combining with acids to fortn nfiUtif in the same way as does am-
monia, Tbey are also knon-n &s vegetable or organic bases or aUcaUeii, aud
ore probiiblj amines of complox constitution. Tlie RimUftrity between the
rclutiuu of the free alkiUoul» tu their suite luid that of amiuouia to the am-
mouiacal salts is shown in tho foUon'iiig equations :
2NH, + H,80. = (NHJ.SO.
JLmnwiilM. Bulpburio mU AmmmlUBi tulitlMte.
2C.,H..N0.
+ H,SO. =
SaJphDflc Mid.
(C.A>0.).SO.
Uorphoafum Kiptwt*.
CL&BSiFtCATiox.' — The natural alkaloids are temporarily arranged in two
groups :
(1.) Those whioli are liquid and volatile, and consist of C. H aud N.
Tiie aynthesia of one of their nnmbftr shows that thoy are true amines.
(2.) Tho»e which are solid, crystalline, vohitile with difHculty, if at all,
an J consist of C, H, N and O. No representative of this class haa yet been
obtained by syntliesis.
Gkxeral Pk^-hical CaARACTEBS. — As a rule they are infwihible. or nearly
so, in wat^er ; more soluble in alcohol, chloroform, pelnileunt-etber, and
benzol. Their salts arc, for the moat parC> soluble in water and insoluble
or bparingly soluble in petrol Rum-ether, benzol, ether, chloroform, and
amyl alcofaoL All uxert a rotary iictiou on pohtrized light :
Qaininfl
Qaiuidjoe ,
CioQboniD« . . .
CiachoDidiuo .
Mon>>>in«
KuooUne . . . .
= -126'. 7
= +850*. TO
= + 190-.4
= -144 .01
= - 89'.4
=-103 .a
Codelns . .
Nsroeliw .
Hnioinn . ,
:-ll8'.8
:- cr.w
!- 98'.5
Generally, combination with an acid diminishes their rotary power ;
with quinine the reverse is tho case. Free nareotine is Isevogyrous ; its
salts ore dextrogyrous. They are all bitter in tost^.
Gesioui, CmcMicAi. HKAfTiosft. — Potash, soda, ammonia, lime, baryta, and
magtu-ifi/i precipitate the alkaloids from solutioim of their salta.
Puospu-iMoLYuiJic Acu> foriiia a. precipitate which is bright yellow, with
aniline, uioi-phiue, veratrine, aconitine, emetine, atropine, hyo)M*yamiue,
theiue, theobromine, coniYne, and nicotine ; bi-ownish-yellow with nareo-
tine, oo<ieiue, aud piperioe ; yellowish-white with quinine, dnclioniiie and
atryabuine ; yolk-yellow wiUl brucine.
TiM P Mtcwtt* pnpAra'l M foUotn: AmewHUam mnti-hdBtw U dlMol*«d In Vi/X th« vlatlim flltovil, mill
k^auitlt; of hr'^ro'tluyttc i4iMi>l)ata '/» In w*tg*t of thu iDoljrtMtaw nMd U oJ-lfa Mid lb«n NU.tt le
Mruar miM mctlun. Tb« nlxUm U wtf&Md ; Mt nildi> fur • itej : tba r«Uow p|it. t-oUntnl on n niln ;
WM'iH with R.,Oaclrtia«Md wlthNO«H; nnd white Btill moiK tnusfarrvil to n inrailMin (BtMutn. Wvbbub
Ih.' .1 hr evhaiMthHribamnnlndaroB UwlUbo- with NHtHO li a.klnl. Tbn niiM l> VMrmnl
». . < otnl with tmlvertoed wtdlnm outKnuito aniltknolrKlfw inliiitmi 1> nbtatnnl. ThU ■• mnji-
orn< -' : H •iMll (inuiti^ <4 loMnta nttrM« U added. lunX tho whnli- imrfn»llT hnticd lo qiiM
faooit nn<\ unW all Ml^ b pximIIoL Tb« rail<ln« t« dlawlvod tn wartn lljU (1 to liJ). aoidotitad with IfO^Il,
■mldennUi.
Ta aw ttea rM«ctit, a dnp vt Um aiuoacted IkioU (• pland oa a Rlaa platv nltb ■ Uadc bnehynoad,
and WW It n drop of tlM mgaat ; and tlw two dnipa u« idmI* to mU alowlj by a polnlad gla« tod.
UAirrAl OF CBXKISTltT.
PotaJmnm iodhijdrargijratt' gives a yellowish pivcipitato witU olkaloidal
aoIutioDs which aro ocic^ neutral, or uintly ulkahue ia I'eoctioa.
riM iwtBiBt !• oMutwd Uf dlatDlTlag liMI cnai at nwctute sUsdl* Ukl -ttLS cmiM of MMirtsa
ktdbla 16 • llln tg mntn.
Tb*— hm— miy Wiii—JlBraiwBMfaawa ij l MiiaiiMiniw . Tlw rvtipnt !• MUbtf IRhs « ImtXM to
pdotlan >rf kllHUuld niitll k ilioih B/ural rnm tb* lalaUaci witkli U Iwiar (a««il, kn4 pimmt \,p>m • Itatit
«rtlM<«^ fm* no t>r«dptiMB -wRh ■ drap <it Ih* nvcMit, Bu4i c.c of r«aiimt wad )i><H«^m tlw ;«^^hv b
Ifea v«laiM of liquM iMtad olilw loliewliic vuMUlM wl •UotkOt, tA gnuM ;
Alrairiii* O.Oia I V«»ntiM U-OMH , OalnlM OJiM
SiMWiMM HmH I MorpklM ft,<«nO DbMAMiM .•««
■BTcmau ...« €.0167 1 OuDllM OMUt QuinhUM Q^UU
Of ooona, tbv prar— «aa b* uMd odlj bi * ■otakM wMwIm n riacb alimlnM.
Separation of Alkaloow froh Oboanic Mn-nraES axd pieum Each Otkeb.—
One of the most difficult of the tuxicologist's tasks ia tUo soj»aratioii fittm a
mixture of orp;amc niaterinl (cont^-ut^ of atniiiarJi, riacern) of &ii alkaloid
such a state of purity lu* to reudcr i\s itleutiticatioD perfect. The diiScu}
is the greater if the iimouut preaout be siuiUl, an in uxually the case ; and ff
tbo search be not contiuod to a single alkaloid, »!> frcquititty occurs. Sotue
of UiP^^ anhRtjinc^s, as strrohuiue:, are detectable with much greater facility
oud certainty tlum others.
Of the proceiucB hitherto suj^ffostod, the best is that of Drajitudorfl^
devised for the det^otion of any alkaloid or poiannoue orpniiic jjriticiple
presfut in the nubstances examiued. It is very exlianstivf*. and mcU
adapted to cases £reijucul]^' arisiug iu cbemico-Iegal practice ; hnt^ on
the other hand, is too intricate to be serviceable to the general pnicti-
tioner.
Au abridgment of this process may be of u»e tu detect the pmoDCO
of the more comniouly used alkaloids in a mixture of organic umteriaL
27i(* jihijsininn shnuffi, /loiA'ivr, ftear in mind that, in aui's HafJe to yiv
riae to legal jtroa^'htuji*, Ihet^ maif heryjnic serioufhj rnmitiirateti by the
atialytiii of any parts v/ Uit Ifdij, Jyfda, or iiii»j>evicd articlcn of food,
efc., by any process open to aUack by the moiA emrching crost-examiiiation.
TbmmOmbMem ta bo mxaatimt* «• ndvead Ui * fln^ tun of rabdtTW'-D. anil *n itlmMtm] ttm an hour
or morB in wMier Kldiitefisl with 80,(1}. «i ■ iBoiuvraUuv «i( 40* to Oii- ;I'>t*'lVif" !'.>, ihU U tr>
(■■led tJirwllRiM. Ihnll(tiilit bclivr Olteml «D't UirntlU mtilvnal riiiraw'.. I .>< «i.|«-:l r >ir...'i< ..txruKf
<-r«l«iil u Um tMn(JM«t)it« at ibv wanv-lMth to n tMi« ajmip; Uite h ml- : >.>• .i
>'ooti(4, llw mlstiin> kept M HiiiMt tC (W* F.) I'lr %t hmn, eocded «' • < ,,
w«ali«dwltltivv*nl«|>rr •«Kl. aieolMl. TIm «lodti«l k dtatflUd Iron tJ<< ' ' ., iv^iJ^il-
diJMlad trlUi II,<J anil taurml.
T1>«llltntt«K>i'Mnln.-1oiititlMUiaei)ptiateaortlM>llnMdKMidfr(i(n It llM ilkaMd* tbnumtrfwmv
•BIwrUcilbr Uielotluuitif Mtiiai:
A, TIM uld WkCtt; h'lfii'l Li ahalwn wUli rnNblv nctiOca v<trol«n vtbtf Oklcb Bbould IxA fet Uuil
n*>n* (IdB'-l&r V-l. nrntrhoiilil Ir luMl with anitkn, MlHaVMy tnttmaatHiH ; kflar anwal aKiaMlMBa
tlHi«k«r laTerlaMlliHrioi >■> ■.■amK htwI U fMno*«l ; thk ivMOtBrot i» ret«Klrd ■• hMttf m tb« aUiv dl*
■ilna aiiTthliW' T)mi << ■ ■■ cr^x^ntU'tt of th» rihwr—KtMtiltM l.—iM moMf etnapimi nl
MlWtog aMtUt^ oic. k I im]i>v<
B. Tbo MUKi tiMliU' r L _ ,L,1U' rvpwlod wll*» liMiMlM. wblok «n nvttpontnm j\M»^
rtiTMlI-. whleh la, It ptjti^iiia-. ui Ui ummI lor cMidiondtn, Mnumta, Mid dljritall)! (v. r.i: If wwarvluMi),
Ikr iAMbHii muI iidaMctH.
r rtii' .1. I.I ».i<.>->iia it"M 1> thm tn«l«d In Die mtim wht wtUi chtnrolinnii In i>1)t«tii AnWim TTI.,
W- ' <-)eti<iBliMKdW^tMln, Mid iihvaiMda bf HM fraparlMBK
»ft<>r uiMi uiurv ■baJduc with imtralmnt «ther »Dd raaMval <^ tbn vUiOMit layH^ li
m. I iLnmunluin ti^lraleMid duLto Wtlta prtjolcum aURr » -ID* {ltM° P i. tti< d'lm-al
JatfT Ih4i.k nmir-ml iw. iinlcfcl; lu puwililr while ntlU w'inn ; tlih h n^-alril liTu ur (br*« tJni
Willi 'v>M |>'lTi'lrtiiii rlliirr, <rhli*ii l« rmuirMl nhrr n Ilaic. The wbpiii vtiimail lafiis ](WM /■
ttio cnid r>i>af R«>Mi*« IV. 6. Tb« tornHr k t«<«d for •ijyehnlixi, i(ulnliva,famr1nf^ rMstrlsr . ^
ounltn* Mkd nl«aUM».
R. Th* allMUnA. wNlarr Anld to tlikkMl w1U« bonMB*^ wM^. on nrapcmdoQ, yMilt Autd«# V.. wlikb
nmy «ai>t»lii Mr7«bnln<^ bninUw, ifnoOiM, oloolwnlii& ■tmpliifc hjOK^ainliw, phjMrtlitMiiM, MomlUnc, no-
iIbIim, UMtattnn. niul nanvlnn.
F. A dni\lnr traklmfnt <rilh rhinmfmn jlrMi ilMf^aw %'!„ wbloh mhj fltnlaln « tnc* of morphliw^
O. TIw'kIm > .' I. rhn, .bAken vlih BiMjl Aloohol, wblob to HpanttO uul «««r<«il«d: AmWw
Vll. !■ r- ' fill', lt>»i tmllH'!.
U. Fii ' I i* lt»r|t (^N(viratai1 vtth {vfliB'li'il cUm, Ui« r«4itiM oxtiMUd WUIl tMes>
tDnn,BDij ;.-.^ . 1 ..<-, w.i uj ite ■rapunUuu ol ifea (Aksotufn, tMtad toe ounriiM.
VOLATILE ALKALOIDS. SSJT
Volatile Alkaloids.
Conllne — C«j>mW/w — Cictitine—0,H^JN — 125— is obtftined from Con-
turn macniatfun, in which it iit accompanied by two oilu-r nikiUoids, methtjl-
coniine^ C,H,,N(CH,l, and vonhtjJrtnf, C,H,,NO — tke former a volatllQ
liquid, the second a crvstallino solid.
Coniiiic is a colorless, oilv liquid ; has an acid tosio and a disagree*
able peneti'ftting' odor; sp. gi-. U.878; can be dintilled when protected
from air : boils at 212^ (413°.6 F.) ; exixiacd to air it resinifiea; it is very
spai-iii^'ly soluble in water, but is more soluble in cold thau in hot water ;
soluble iu all proportions in alcohol, soluble in six Tolunies of ether, Tei7
soluble in fixed and volatile oils.
The vapor which it gives ofT at ordinary temperatures forma a white
eloud when it comes in contact xnik a gltihsi rod moistened with HCl, as
does NH,. It forms salts which crystolliio with tlilEcuUy, CI and Br
combine with it to form crystfllliMible compotindB ; I in alcoholic Bolntion
forms a bronii precipitate in alcoholic solutions of conime, wliich is solu-
ble without color in an excess. Oxidiung agents attack it with production
of biitrric acid (see below). The iodides of ethyl and methyl combine with
it to form iodides of cthvl and metliTl-conium. It has been obtained
rmthetiralty by firat allowing butvric aldehyde and an alcoholic Bolntton
of ammonia to remain some xuonlhs in contact at SO'' (86^ F,), when
dibntjraldiue ia formed
2(C.H,0) 4- Nir, = C,H.,NO + H,0
Batf rlo aUebjcle. AminnnlB. IMhutTTftldlna, WMtr.
The dibutyraldine thus obtained is then hoat«d under pi-easure to 150^-
180° (302^-35ti° F.), when it loses wat«r :
C,H„NO = C.H..N + H,0
[Hbatynlillae. OadttBc Water.
A synthesis which, in connection with the decompositions of coniTnei
(C,H,)')
shows its rational formula to be {C,H,)' >-N.
^ L
AK.u.TTrcAL CiuB.\oTCQs. — (1.) With diy LICI gaa it tarns reddish pur*
pie, and then dark blue.
(2.) Aqueous UCl of sp. gr. 1.12 evaporated from cooilnfi leares a
green-blue, crystalline mass.
{3.) With iodic acid a white ppt. fW>ra alcoholic solutions.
(4.) With H^SO, and evajwiatiou of the acid : a red color, chftjiging
to green, and an odor of butyric acid.
Nicotine— C„H,,N^—1G2 — exists in tobacco in the proportion of
2S per cent.
It is a colorless, oily liquid, which turns brown on exposure to light
and air; has n burning, caustic taste and a disagreeable, penetrating odor;
it distils at 250* (aiJ2" F.) ; it bnms with a Inniinons flame ; sp. gr. 1,027
at 15^ (50 ' F.) ; it is very soluble in water, alcoltol, the fatty oils, and
ether ; tbo last-named fluid removes it firom its atpicous solution when the
two arc shaken together; it absorbs water rapidly from moist air. Its
salts are deUquesceot and crystallize with difficulty.
I
334
MAKUAL OF CItEMISTBT.
Akaltticai. Charactsrs. — (L) Ita etbereol Bolution, added to an ethereal
Bolution of iodine, sepaiatas a reddish-brown, roainoid oil, wbidi gradu-
elly becomes cn'stalUue.
(2.) With HO. a violet color.
(3.) Willi HNO^ an orange color.
Bfttii nicotine and conilne are actively poieonoos, producing
by asphyxia, somotimeB aa rapidly as pnuaio acid.
Fixed Alkaloids.
These arc much more numerons than those wliich. are volatile, and form
the active prinripleH of a great number of poisonous plants. As we
yet in the dark as to the constitution of these bodies, the classifieaiic
Tvhicb we adopt is the temporary one, based upon the botanic charactf
of the plants from which they are derived.
Opium Alkaloids.
Opium is the inspissated juice of the capsules of the poppy. It is of
exoeediugly complex comjiosiUou, and contains, besides a ueulral Itody
called vieamin (probabiy a polj-atouiic alcohol, C,.H„0 ), a peculiar acid,
meoonic acid (g. v.), lactic arid, gum, albumen, wax, and a volatile matter
— no lesa than eighteen dilVereut alkaloids, one or two of which, how-
ever, are probably formed during the process of extraction, and do not
pre-exist in opium.
The following is a list of the constituenta of opium, those marked *
being of medical interest :
Nunc.
Fonnul^
•Meconio iLcid.. CiH.Oi
Lactic ftcid CiUtO*
MeooiiiuQ- I-'iiHmO,
'Morphine 0,,H.,NO.
Pwudomorpbine CiiHi>NOi
Hydrocotamine. CuIIitNOi
*CDdeiiie C;,H,iNO,
*Th*)Miite ,O..U,>NO,
Protoptne l0i*H,.NO.
lUuwdiM |Ci.H,,NO,
Codamtne {Oi*Ut»NOt
4.70
1.S3
0.06
lO.SO
o.as
OilS
4.38
0.80
4.50
1.63
NWBM.
LaudwDlne.
Opianioe C„H„NO,
Hecooidiae.... C..H,.NO«
Crjptopine. . . . C»,H|,IfOi
Laodaaorin^. . . . CtiHuNO.
•Noroolina iOtilli^NOi
LuiUioplne. .... iCtH^^SO,
'NarcBioe- 'C„H„NO,
rorphjroxiDe...|
1.30
0.7*1
3.47
'd'4S
m
ISorpbine—Morpkina{U. ^.)— C,.H,,NO. + Aq— 285 + 18— crystal-
lizes in colorless priflms ; otlorless, bnt very bitter ; it fuses at 120'' (248'"
F.), losing its Aq. More strongly heated, it swells up, becomes carbon-
ized, and finally bums. It is soluble in 1.000 pte. of cold wat^r, in 100
pts. of boiling water ; in 20 pts. of alcohol of 0.82, and in 13 pts. of boil-
ing alcohol of the s.imc sIrengUi ; in 300 pts of cold amyl alcohol, much
more soluble in the same liquid warm ; almost insoluble in aqueous ether ;
OPllTM AZKALOmS,
rather more solublo in fJcobolic ether ; almost ineoluble in benzene ; solu-
ble in GO pts. of chloroform. All the Bolvontit diBsolve roorphino more
readtW ana more coptaunlj when it is fretthly precipitated from eolutions
of its aalta than wheu it haa usaumed the crystaUlne form.
Morphine combiuea with ncida to form crv&tallizablo Baits, of which
the chloride, sulphate, and ooetAte are used in medicine. If mori)hino
be heated for eonie hours witli excess of HCl, under pressure, to 150*
(802'^ F.), it loses water, and is converted into a new base — apoviorphine.
By the action of H,SO, on morphine at 100 , two amorphous, ba-
sic proilucts of coudensatioD, trimorj}hine and teiramorjjhinef are pro-
duced.
By heating together acetic anhydride and luorpliino, three mod)6ca-
ttions, (L, p, y oi aceiyl-morphine, C,,H„(C,H,0)NO,, are formed. Simi-
larly substituted bfityryl-, tenzoyl-, succini/l-, camphorj/l-, meihyi-, and d/tyl-
morphine ore also known.
Although the eynthcsis of morphine has not yet been accomplished,
enough is known of its constitution to indicate tliat it contains the
phenolic group (OH), and thai it ia a derivative of phenanthreae (see p.
The salts of morphine are crj-BtnlHne. The acetate; — Moriihiiue Acefa/t^
U. 8. — MorphuB A\xtas, Br. — is a white, crystalline powder, soluble in 12
parts of water, whick decomposes ou ex}>UMure to air, with loss uf
Bcetio acid. The chloride — Morphinvs U;tdrochlora», V. S, — is less soluble,
but more pennnnort than the acetate. The nulptiatfi — AtiyrnhnKn »SW/>/i(W,
V. S. — .Uitrj)huv Sittphoji, Hr. — ia the form in which morphine is the most
frequently used iu medicine. It is a very light, cryhtalliue, feathorj* pow-
der ; odorless, bitter, and neutral in reaction. It dissolves in 24 parts of
vater. Its solutions deposit morphine lis a white precipitate on lulditjon
of an alkali. The cryatola caotain 5 Aq., which tUey low at 180°
(266» F.).
AxALTTioAL CnjkBACTeBS. — (1.) It is colored red, changing to yeHow, by
HNO,.
(2.) Cold concontratod H,SO, dissolves it^ forming a colorless solu-
on, which after 21 hours turns ]iink on addition of a trace of H
NO, ; and the fluid when warmml, cooled, and dilnted with H/), turns
deep mahogany-brown ou the addition of a splinter of potassium dichro-
nuite.
(8.) A mixture of morpbine and cane-sugar (1 to 4) added to concen-
ted H,SO, gives a dark red color, which is intensified by a drop of
romine- water.
(4.) If iodic acid solution and a drop of chloroform be added to mor-
plune, free io<line is Uberatod, which colors the chloroform violet. If
now dilute NH,HO bo flnuted on the surface of the liquid, » dark broxvn-
iob zone is formed.
(5.) A neutral solution of n morphine soli gives a blue color with neu-
tral solution of ferric chloride.
(6.) A Bohition of molybdic acid in H,SO, (Frfthde's reagent) gives
with morjihine a violet color, changing to blue, dirty green, and faint
pink. M'ater discharges the color.
(7.) Solution of morphine acetate produces a groy ppt. when wormed
with aminoniacul silver nitrate solution ; and the filtrate turns red or pink
with HNO,.
(8.) Auric chloride gives a yellow ppt, luraing violet-blue, wiUi boIu-
tions of moi-pbine aaltt).
(D.) A'1'1 BnliiJion of F<^^C1, (2-10) to Rolntion of pofcamn-iim ferri-frn-
iii.lo (Uie mixture tnuat not aaamue a blue color), udd xaui-phiao suloUoo
— n deep blue L'olor.
(10.) Hoat morphine wiHi coneentratetl H,SO. to 200" (3a2'' P.) untO
^rcuu-blnck ; odd n drop of the liquid cautiously to water ; the Bolutioa
tnma blue. Shake a {v^rtion with ether ; the ether turns purjJe. •Shako
another portion with chloroform ; the chloroform turns blue.
(11.) Warm the Holid ftlkaloi<l with concfrntratM H^SO, ; add cao*
tiously a few dmps of olroholic solution of IvHt> (30 ^} ; a yellow color
is produced, cbaiirriucr to dirty red, tben stvel blue, luid aky blue, and, with
a further qiirintitv of KH(> fmUition, cherry red.
Codeine— CW^»r.n( r..S)—C,.H„NO,+ Aq—2i)9 + Ifi — rrystolKres
in large rhombic prisms, or from ether, mthont Aq,, in octobeilra ; bit-
ter ; aoluble in 80 ptH. cold wrtt#r ; 17 ptfl. boiling water; very soluble
in alcohol, ether, chloroform, benzene ; ahnoHt insolablo in jietroleain
ether. •
AvALTTiCAL OB&KjumsM. — (1.) Cold conceQtnted H,SO, forms with it
a colorless solution, wliich turns blue after some days, or wheu winned.
(2.) Friihde'a reagent disaolToa it with a dirty (*rv«n color, which after
a time turnH blue.
(3. ) Ctilorino watfr formA with it a colorleas solution which tarns yel-
lowish red with NH,H(>.
Narceine — C, H.,NO,-f 2Aq— 4e:i+3ti— erystallizes in bitter, pris-
mstie neeillcM ; spnriu^dy soluble iu wuler. alcohol, and lunyl (dcohol : lii-
eoluble in other. {>euzol, and petrotcuro ether.
AsAi.vncvL Ca-iR^PTEML — (1.) Concentrate<l H,SO^ disaolTes it with a
gray browa color, which cliangea to red, slowly at ordinary tempeniturea,
rapiilly when heated.
(2.) Frlihde'fi reagent colors it dark olive preen, passing to red after a
time, or when beateil.
(3.) Iodine solutiuu colors it blue violet, like starch.
Narootine — C„H„NO — 4i;t — crystallizea in trftnnparent prismB,
altnost iiiHoluble in water imd iu petroleum ether ; soluble in alcohol, ether,
benzol, and chloroform. Its units are moetly uucn-stolliziible, unstable,
and rf-oilily soluble in water and alcohol.
An.vlitical CiUBAnrEnH. — (1.) (oncentnited n,SO, forms with it a
solution, at first colorless, in n few monieut^ yellow, and after a day or twa,
red.
(2.> Its ixjlution in dilute H,80,, if pfradually evaporated until the acid
volatilizes, turns oranjje rwl. bluish i-iolet, and reddish violet.
(3.) Fhihde's reagent dissolvcB it with a greenish color, passing to
cherry red.
Thebaine — i^mwnorpAtne — O H„NO, — 311— crrstalli/^s in white
plates ; tastelesa when pure ; ineolnble in water ; soluble in alcohol, ether,
and benzol.
AsALTTiCAL CeARACTKBa— (1.) With concentrated H,SO^ an immediate
bright ret! color, turning to yelloT^ieh red.
^2.J Its solution in cldoriue water tuma reddifih-brown with NH,HO.
(■'J.) With Fnihde's ri'B^i'ut aame as 1.
Meconio acid— C^H,0, + 3Aq — 200 + 54 — is a tribnmo acid, peculiar
to opium, in which it exists in combination with a poi't, at least, of the
alkaloids. It crystallizes in small prismatic needles ; acid and astringent
in taste ; loses its Aij at 1'20" (2iS° F.) ; quite soluble in water ; soluble in
akwhol ; sparingly soluble in ether.
AxALiTtCAL CiL\BAcnEa8. — ^Yitli fettic chLonde, a. liloodted color, whidi
U not diacharjToJ by dilute acidB or by merrnric chloride ; but ia dischorgod
h\ etoniiouN cliluride ntid by tbe alkaline lirpQchloHUEL
Aporaorptii"e"C,,H„NO, — is used fiypodermically aa an emetic in
the sliape of the chloriJe, (^niorfi/iuuv kydrochloras, C S. It in obtained
by sealing luorphiue with an excess of atrong HCl in a thick glass lube,
and heating tlie whole to UO" (252* F.) lor two to three bourn. It is ob-
tained also by the same process from codeine. The free alkaloid ia a
white, amorpbouH solid, difficultly solnlile in water. The chloride fonna
colorless, shininK crj-ataia, which have a tendency to assnmo a green color
on enpoaure to light and air. It in odorless, bitter, and neutral ; soluble
in 6.8 parts of cold water.
ToxioouMT or Opitm \sd its D^n'ATi%'£s. — Opium, its preparations and
the atknioiils obtained from it are ail active poisons. They produce drow-
siness, stupor, slow and stertoroua res]iiration, contraction of the pupil ;
small and irregular pulse, coma, and death. The symptoms set in fmm 10
minutes to 3 hours, sometimes immediately, sometimes only after 18 hours.
Death has occurred in fi-om 45 minutes to 3 days, Tisnally in 5-18 hours.
A/ter 24 hoars the prognosis is favorable. DeaUi has been caused in an
adult by one-half grain of acetate of morphia, while 30 grains a day have
been iuken by those accustomed to its use without ill eficcta.
The olkaloicls of opium have not the same action. In eciporific action,
beginning with the moat powerful, they rank thus : Narceiue, morpliine,
codeine ; in tetuuizing action : thebnint;. jmimveriiie, niuvotine. codeine, mor-
phine ; in toxic action : thobaino, codeine, papaverine, norceine, morphine,
nanrotine.
The treatment should oonsiat in the remoral of nnabsorbed poison from
the stomach by omesis ami the utomaeli-pump. and washing out of the
stomach after injection into it of powdered charcoal in suspension, or tea
or colTee infusion. Cold affusions should be used and the patient kept
awake.
After death the reactions for meconlc acid and narcotine ]>ermtt of dis*
tingutshing whether the poisoning was by opium or its preparations, or
by morpUine.
Cinchona Alkaloids.
Although by no means so complex od opium, cinchona bark contains
a great number of substances : quiniue, dnchoninf, /ftiinidine, cmchonuiine,
aricine : quinic. iininotannw, and ouinovic aciiif: ; cinchona red, etc. Of
Mwee the most important are quinine and cinclionina
Quinine— Vutmna [U. &)— C„H,,N,0, + 7i Aq.— 824-l-nl8— eiiate in
the l>ark of a variety uf trees of the genera Cinchutia and China, indigenous
in the mountainous regions of the north of South Americji, which vary
considerably in tlieir richness in this alkaloid, and consequently in value ;
the beat samples of coUsaya bark contain from 30 to 32 parts per I.UOO
of the sulphate ; the poorer grades 4 to 20 parts per 1.000 ; inferior
grades of bark contain from mere traces to 6 parts per 1,0U0.
It is known in three different states of hydration, with 1, 2, and 3 Aq.
and anhydrous. The anliydrous form ia an amorphous, resinous sub-
stance, obtained by evaporation of solutions in anhyilrous alcohol or ether.
The first hydrate is obtained in crystals by exposing to air recently pre-
cipitated and well-washed quinine. The second by precipitating by am-
monia a solution of quinine sulphate, in which H has been pravi o ua ly
liberated by the action of Zn upon H^SO, ; it is a greenish, reaiDOOt
I
body, which loses H,0 at IBO^ (302<> F ). The third, that to which iie
foUowiuf^ romarlis npply, is formed hj precipitatiiig solation of quinine
saltd with aiiitiiuuiu.
It crvstiillizea in hexagonal prisms ; very bitter; fuses nt 67° (134^6F.■|;
losea Ail- at UK)" (212^ F.) and Uie remainder at 125* (257' F.) ; becomes
colored, swells up, and, tinally, bums with a amokr fl-iuie. It does nor
Bublime. It tiiaeolves in 2.200 pts. of cold H,0. in 7G0 of hot H,0 ; vei)-
soluble in alcohol and chloroform ; soluble in amjl alcohol, benzone. fattjr
and esftential oils, and ether. lis alcoholic solution is powerfully' la^rogy-
TOus. [a], = -270''.7 at 18' (64". -4 F.), which ia diminished by increase of
tempemture, but increased by the presence of ocida.
AXALTTicAi. CHAaunras. — (1.) Dilute H^SO, disaolTes quinine in eolor-
leaa but riunrescent solution (see below).
(2.) Sobitiuuu of quinine salt« turn green when treated with CI and
then withNH..
(3.) CI passed through H^O holding quinine in Buspension forms a red
solution.
(4. ) Solution of quinine treated n-ith CI water and then with fragments
of potassium fen-ocyanide becomes pink, passing to red.
Hn.vn\TK—Digutphate — QuinijuE mtijthas { L'.S.) — (^fitinitg intlphax(ffr. ) —
80^(C^^ff }r,0,\ + 7J*?— 740 + 126— orystallizca in prismatic needles;
very liffht; intensely bitter; phosphorescent at 100^ (212* F.); fuses
retilily : loses its Aq. at 120^ (248^ F.), turns reil, and finally carbonizes;
effloresces in air, loaiu'; 6 Aq.; soluble in 740 pts. H^O at 13° (55\4 F.|,
in 30 pts. boiling H,0, and GO pt& alcohoL Its solution with alcoholic
sohitiou of I deposits brilliant green cr^-stals of iod'yjuinine giilphole.
— i22 -i- 120 — is fonnetl when the sulphnte is disHolved lu excess of dilute
H.SO,. It crystallizes in long, silky neeclles, or in short, rcclan^rulnr
prisms; soluble in 10 pts. H,0 at l/)" (iS'J^F.). Its snlutions exliiMt a
marked fluorescence, being colorless, but showing a fine pale blue color
when iUuniiuated by a bright light againKt a dark background.
iMpi-wrriBS. — Ijuinino sulphate should respond to the following tests :
(1.) When 1 gram (1S.4 grains) is shaken in a test tulM? with 15 c.a
(4 fl - ) of ether, and 2 &c. (32 m.) of NH,HO ; the liquids should sep-
arate into two clear layers, without any milky zone between them (cin-
chonine).
(2.) Dissolved in hot H,0, the solution precipitated with an alkaline
osalate. the filtmte shoidd not ppt with NH.HO (quinidine).
(3.) It should dissolve completely in dilute U,SO, (fata, resina). «
(4.) It shoidd dissolve completely in boiling, dUute alcohol (gum, starch,
Baits).
(6.) It should not bbicken with H,SO, (cane-sugnr).
(6.) It should not turn red or yellow with H.SO, (saliciu and phloriKic).
(7.) It should leave no reeidue when burnt on platinum foil (minenil
Bubstannes).
By the action of nlkaline hydrates upon quinine, formic acid, chinoUne
(see p. 31B), and pvridiue bases (see p. 317) are produced.
Concentrated HCl at 140"-160'* (284''-302' F.) docompoee« quininp.
with separation of methyl chloride and formation of ajtoquminHf C„H,,N.
O,, an amoi-phous base.
Oxidizing agents produce from quinino oxalic acid and acids related to
pyridine, notably pi/ridindxcarbonic or cinchomcronic acid, C,H,N(COUH),,
which are also formed by oxidation of cinchonine.
BTRTCirXOS ALKALOIDS.
339
AIt)ionr;h cinchonino (soo lx;low) <liffera from quinine in composition
by -f O, and although the derom positions of the two bases show them
both lo be related to the chinoUue and pyridine banes, attempts to convert
cinchoninc into quinine have resulted only iu the formation of other prod-
ucts, among which isi an isomere of quinine, oj-t/cinchfjnim:.
Alfthylquiurne, C H N,0,CH , ia a base wliicli has a ourarenlike action.
Cinohonlne — C'lnr/tomna {U. 6'.)— C,.H N,0— 294— occurs in Peru-
Tian bark in from 2 to 30 pta. per 1.000. It crystallizes without Aq. in
colorless priiiuju ; fuses at 150" (302^ F.) ; soluble iu 3,810 pta. H,0 at
10** (50" F. ), in 2,500 pta. boiling H,0 ; iu UO pts. alcohol and iu 40 pta.
chloroform. The KaltH ot cinchonine resemble those of quinine in coroposi-
tion ; are quite soluble iu H,0 and alcohol ; are not fluorescent ; perma-
nent in air ; phoBphorescont ut 100' <212' F.).
Quinldlne and Qtiinlclne — arc bafles isomeric with quinine ; Uie
former occurring in cinchona bark, and distinguishable from quinine byits
strong dextrorotary power ; the second a product of the action of bent on
quinine, not existing in cinchona.
Cinchonidiae — a base, isomeric with ciuclionine, occurring in certain
varieties of bark ; Isevogyrous. At 130" (266" F.) H,SO, converle it into
anotber isomere, rinrhonmne.
CaSbine—Tfi*-ine-—Ouaranine~Cqfntia {C. S.)— C.H„N.O, -f Aq—
194 4 18 — exists in coffee, tea, Paraguay tea, and other plants. It crje-
tallizes in long, silky needles ; faintly bitter ; soluble in 75 pts. H/> at 16"
(69° F.) ; lesa soluble in alcohol and ether. Hot fuming HNO, con-
verts it into a yellow Equid, wbieli after evaporation, turns purple with
NH.HO.
Alkaloids of the Logaxilaoee.
Stryohnine— N^ri/rAain/i (U. .9.)— C,,H„N,0,— 834 — exista in the
seeds and burk of differt-iit Varietiea of iUrj/chmtK.
It orystaDizcB on slow evaporation of ita sohitions in orthorhombio
prisms, by rapid eTaporatinn as a cryatalline powder ; very spitringly sohi-
ule in H,0 and in strong alrohol ; soluble in 5 pts. cUlorofurm. Its
aqueous solutiou ia intcuat'ly bitter, tlie taute being perceptible in a solu-
lioD oontaining 1 pt in GOO.OOO.
It is a powerful base ; neutralizes and dissolves in concentrated H SO,
vi-ithout coloration ; nnd precipitates many meUdlic oxides from solutions
of tlieir salts. Its salts are mostly crystaUizable, soluble in H,0 and alco-
hol, aud intensely bittt-r. The acetate is tbe most soluble. The veutnl
fniJphat'P aystallizeB, with 7 Aq., in rectangular prisms. The iodides of
metliyl and ethyl react with strj'chnine to produce the iodides of vifJJtyl
or ethiiblr'/ckmum, whit*" crystalline basic substances, producing on ac-
tion on the economy similar to that of curare. When acted on by U^SO^
and potassium chlorate, with proper precautions, str}fchn\c or igaaurv; and
is formed.
AnALTTicAi. CHARAnxBs. — (I.) DiflsolTeB in concentrated H SO, without
color. The solution depoaita atrychuine when diluted with H,0, or when
neutralized with magnesia or an alkali.
(2.) If a friLgmentof potaesinra dichromate for other substance capable
of .lielding naa^wnt O) ia drawTi through a solution of strjchnine in H^SO,,
it is followed by a streak of color ; at Erst blue (very transitory and fre-
quently not olMerved), then a brilliant violet, which slowly poases to roee-
pink and finally to jellow. Iteaota with rv&oo grain of strychnine.
S40
MANUAL OP 0ITEMT9TRT.
(3.) A dilute eolation of potAssium diohromai* forms a yellow, eTystal-
line ppt. in stryefaDine solutions ; which, when washed and heated with
concentrBted H^SO, pirea the play of colors indicated in 2.
(i.) If a Bolulion of fitrrchtuue be e\'Hporated on a bit uf platinum fnil,
the residue moistened with concentrated H,.SO., the foil connected wjtli
the + pole of a single Grove cell, and a plattnutn wire from the — polo
brought in contact with the aor&ce of the acid, a riolet color appears upon
the surface of the foil
(6.) Strychnine and its salts are intensely bitter.
(6. ) A solution of sttrchnine introduced under the akin of the back of
a frog causes difficulty of ro8j)ir&tion and tetanic spasms, which are aggra-
vated by the sHghtest irritation, and tM-itchiog of the cioaelefl during the
intervals between the conmlsions ^Vith a small frog, whose surface has
bepn dried before injection of the solution, TTii-gi;^ grain of ncetnte of
strychuine will producv tetanic spasms in 10 minutes and death in 2 hours.
(7.) Solid strychnine, moisteuotl with a solution of iodic acid in H,SO,,
proiiuces a yellow color, changing to brick-reil and then to riolet-red.
(8.) Moderately concentrated HNO, colors strrrhnine yellow in the
cold. A pink or red color indicates the presence of brucine.
ToucoLoor. — Strychnine is one of the mont active and most freqnently
used of poisons. It produces a sense of sulToration, thirst, Manic trfta»»i»,
usually opisthotonos, sometimes emprosthotonos, oocaaionally vomiting,
couli-action of the pupils during the epaama, and death, either by aaph^^-xia
during a paroxysm or by exhauelion during a remisaion. The srymptams
appear in from a few minutes to an hour after taking the poison, nsnally
in about 20 minutes ; aud death in frum 6 nitimteH to ti houni. usually
within 2 hours. Death has been caused by \ grain, and recovery haa ful-
lowed the taking of 20 grains.
The treatment should consist of the removal of the nnabsorbed poison
by the stotnat-h-pump, injecting charcoal, aud [nimping it out after Bl>out
5 minutes ; underthe influence of chloroform if neoesaat7. Chloral hydrate
should be given.
Strycbnine is one of the most stable of the alkaloidB, and may remain
for a long time in contact with putrefying organic matter without suScring
docompn«ition.
Brucine — C„H„N O. + 4 Aq— 894 + 73— accompaniee stryclmine.
It forms obUquo rhomboidal prisms, which lose their Aq. in dry air.
Sparingly soluble in H^O ; readily soluble in alcohol, chloroform, and
amyl alcohol ; intensely bitter. It is a powerful baso and most of its salts
are soluble and crystalline. Its action on the economy is similar to that
of strychnine but much less energetic.
AsALvrrcAL Charactebs. — (1.) Concentrated HNO, colors it bright red,
soon passing to yellow ; stannona chloride, or colorless NH,HS, change
the reil color to violet.
(2.) Chlorine water, or CI, color brucine bright red, changed to yellow-
ish brovra by MH.UO.
AlkaloidB of the Solanaceee.
Solcinlne — C,,H,,NO,, — 857 — obtained from many species of ^)/anr/m;
crj'stallizes in small, white, bitter, sparingly soluble prisma Concen-
trated H.SO, colors it orange red, passing to violet and then to brown.
It ia colored yellow by concentrated HCL It dissolves in concentrated
ALKALOIDS.
341
HNO^ tho eolation being at firat colorless, but after a time becomes pur-
ple.
Atropine — Daiurine — Alropina, V. S.—AtTopia^ Br.— Cj^-jNOg—
289 — occurs in fUropa beiiudunna and iu datura atmntaniam. It fonua
oolorless, silkj needles, which oi-e spariTigly soluble in cold water, mure
readilT soluble in hot water. Terj eoluble in chloroform. It is odor-
Imb, bnt has a disagreeable, pdraistciit bitter taste. It is distinctly
alkaline, and neutralizes acids with fonnatiuu o( salts. One ot these, the
aulpUnie^Atropince Sulphas, V. 8. — is a white, crystallino powder, readily
soluble in ti'ater, which is the form in wliich atropine \a usually adminis-
tered.
TonooLooy. — It is actively poisonous, producing drowsiness, diyseaa
of the mouth and throat, dilatation of the pupils, loee of speecli, diplopia^
dixsinesa, delirium, coma.
The treatment should consiut in the admimstratioii of emetios and the
use of tho stomach-pump.
Akalttigal Cb^uuctera. — (1.) If a fragment of potassium dicliromatc be
diiiBolTed in a few drops of U,SO,, the mixture warmed, a fra^jment of
atropiue aud a 4ln>p or two uf H,0 added, and the mixture stirred, an
odor of ora]](*e-blussom8 is develn{teil.
(^) A Roluttnn of atropine dropped upon the eje of a cat produces di-
latation of the pupiL
{R.) The drj' alkaloid (or salt) is moistened M-ith fuming HICO, and tho
mixture dried on tlie water-bath. ^Vhen cold it is raoiatctied witli an al-
coholic solution of KHO — a riolot color which chnngeB to red.
When atropine Is Leuted with concentrated HCl to I'iO^-lSO" (248**-
266* F.) for several hours, or when it is warmed with, barjta-watcr to 58*
(I36*.4 F.) it is doeomi»osed into a base rotated to the pyridines : Troplne
— C^„— OH. NCHg— and, at tirst, tropio acid— CgH^(,0,— but later
atropio acid — CH, — C(C^g)COOH. Tropino is also prmluced by a
aiuiilor decomposition of hyoscvunuuc.
HyoBCyamine — Cj^H^^O^ — occurs, along with another base, hyoe-
ciitf, i»K>niHric with atropine, in kyojfci/amus mtfer. It cr}'Ktjdlizefl, when
pure, in odorless, whit«, silky needles, whoso taste is very sharp and dia-
agr<^eable, a.\i<i which are very sparingly soluble in water. As most com-
monly met with, it forms a yellowish, soft, hygroscopic mnaa which gives
offa peculiar. tubacco-Uke o^lur. It neutralizes acida. Its sulpliut^.- — liyoa-
cyantina; Sulphas, U. X — forms yellowiah crystals^ very soluble in water,
hygroscopic, aud neutral iu reaction.
Alkaloids firom other Soturoea.
XiTgotine— OncH^gN^Og — and Boboline — are two brown, amorphous.
faintlv bitter, and idkuliuu aJkaloids obtained from crput. They are reatl-
ily soluble in water and form amorphous salla. The medicinal prepara-
tions known as ergotire are not the pure alkaloid
Colchicine — JCj,H,,NOj — occurs iu all portions of coichicum autum-
nale and otht;r members of the same gcnue. It is a rellowish-white,
gummy, amorphous substance. h'Kving a faintly aromatic odor and a per-
aislentiy bitter taste. It is wlowly but completely soluble iu water,, form-
ing faintly acid Bulution& It forms salts which are, however, very unsta-
ble.
Goncontrated HNO^ or, preferably, a mixhire of H,SO, and NaNO,
eoton colokicine bluo-violet If the solution be tUcn tlilutcd with H,0, it
becomos jellow, and on addition of NaHO solution, brick-red,
Veratrine — VercUrina, l\ A'.— C„HN,0— occurs in veralrum n£fid-
nali» ~ aaagncQ ojhcinalis^ accnm^-Miifni by Sabadilline — C,,H, Jf O^ —
Jervine— C„H^^,0, — and otlier nlkaloida. Tbo substance lo whi<aj the
name Vertj^rina, L'. S. , applies is not the pure alkaloid, but ft mixture of
thorn occurring in the plant.
Conceatrateil H,>^, ditisolves veralrine, forming li yellow solution turn-
ing orange in a few momenta, and then, in about half an hour, bright car-
mine red. Concentrated HCl fonna a colorless solution with veratrine,
which turns dark red when cautiously heated.
Piperine — 0,,H,,NO,— occurs in bkok and white pepper. It crystal-
lizes in colorless, tnuisparent prisms ; almost tasteless when pure ; rory
sparingly Htiluble in water. It is a veiy weak base.
If piperine be heated with alcoholic KHO, it is decomposed iuto uiper-
idinff — C,H,,N — and jjijieric aciil — 0,,H,,O,. If piperidiue bo treated with
silver oxide, pyridine (see p. 317) is formed.
Berberine — ■XanihopirnJe — C„H NO, — occurs in berberist vulgaris.
coccylug paimaiiis, and many other plants. It crystallizes iu line yellow
needles or piisms ; bitter in toato and neutral iu reaction. It is diffi-
cultly soluble in cfild water, rea^iily soluble in alcohol and in boilisg water.
It forma well-<lo6ned, crystalline, yellow salts.
Aoonitine— C„H,^NO,(0HXb(C0,C,H,)— is au olkiUoid obtained
from acorii^um napt'llus and other spocicsof aconiium. It iaa colorleea and
Oiiorlf-HS iK>wder, possessed of an intensely bitter tast**, and sharp, burning
after-taste. It is strongly alkaline ; almost insoluble iu water, i^adily solu-
ble iu alcohol, ether, chloroform, or benzene. It neutralizes acids com-
pletely, with foiination of well-ilefined, crystalline salta
Aconite contains, besides aconitino, three other alkidoida, if not a greater
number: NaptUtine, acohjctine, and hjcoclonine. These tliree alkaloids, no-
tably the first named, along with small quantities of aconitiue, coustitote
the English or Morson's " aconitine," which is probably made from acuni-^^^
tum/erax. Probably, also, all commercial samples of aconitine are mix-^^^f
turea of aconitine and nepolliue with leaaer ({uoutiiics of the other alkft-^'
ioids and acvnine and parrtdaconin^
If aconitine be heated in sealed tubes with H,0 to IW-ISO" (284'-
302° F. ) for several hours, it is decomposed into benzoic acid and aconine,
C..H..NO,(OH),. . , . .
A Japiinese variety of oooniU) contains a peculiar alkaloid : Japaconiiine,
AsALYTioAL CHAOACTass. — (1.) Concentrated H SO dissolves aconitine.
forming a hght, yellow-bruwn sulution, which sluwly turns darker, and
ohangesto light yellow on addition of HNO,. (2.) If aconitine bo dissolved
iu aqueous phosphoric acid, and the solution Tery gradually evaporated, a
violet color is produced.
ToxiooLoov. — Aconite and nconiUne have been the agents used in quite
a number of homicidal poisonings.
The symptoms usually manifest themselves within a few minutes ; some-
times are delayed for au hour. There is numbness and tingling, first of
the mouth and fnuces, later liccoming general. There is a sense of diyuess
and of constriction iu the throat IVr«iHt**nt vomiting usually occurs, but
is absent iu some cases. There is diminished sensibility. M'ith uumbnees,
great muscular faebloneaa, f;^ddine«a, Ions of Hpeeeh, irregularity and fail-
ure of the heart's action. Death may result from shock lif a lurge dose of
the alkaloid be taken, but more usually it is by eyncope.
The treatment should be directed to the removal of unabaorbed
poison by the stomuch-pump, and waaliing out of the fliomach with in-
fusion of t«a boldiug powdered charcoal iu suspeusiou. tjtiiuulauts should
be freely administered.
Pilocarpine — C„H,^,0, — is the principal alkaloid of ^'o^^aftf/i. It
forms a colorless, amorphous mass, readily soluble iu water, alcohol, ether,
and chloroform. It readily forma salts. Its chloride — PUocarpime hy-
drocliloran, V. S. — occure in white, deliquescent, odorless crystals.
Cocaine — C H^,0, — is an alkaloid obtained from the leaves of ery-
tkronjhn coca. It crystallizes in large, six-sided prisms. Its taste is at
first bitt«r, producing parnlyHis of the sense uf t.-isto subsequently. It is
strongly alkaline. Itj* chloride, extensively U8e<i for the production of
local acKSthesiu, cr^'stallizcs iu well-formed prismatic needles, readily sol-
uble iu water.
When heated with ooucentraicd HCl, it is decomposed into benzoic
acid, nifihyl nJcolioI, and a new base, eajonin, C,H,^NO,.
Phyaastigzuine — Eat-rine — C„H^,N,0, — is an alkaloid existing iu the
Calabar bean, })hn»osiofjma vetiKNogutit. It ia a colorless, amorphous
solid, odorless and tasteless, alkaline and difficultly soluble in water.
It neotralizfta acids completely, with formation of tasteless salts. Its sali-
cylate — FhyitoHtiijmiua.' Salirtjlaa, U. S,—iorDiB short, colorless, prismatio
crystals, spuringly soluble in water.
Concentrated H,bO, forms a yellow solution with pliyaostiginino or
it« salts, which soon turns olive-green. Concentrated HNO, funns with
it a yellow solution. If a solution uf tlie alkaloid iu H,SO, bo neutralized
with NU,liO, and the mistuie warmed, it is gradually colored red, red-
dish yellow, green, and blue.
Curarine — C,.H,,N (?) — is an alkaloid obtainable Irom the South
Amertcau arrow-poison, curare, or wooi'ara. If crystallizes iu four-sided,
colorless prisms, which are hygroscopic, faintly alkaline, and intensely bit-
ter.
Curarine dissolves in H,SO,, forming a pule violet solution, which
slowly changes to red. If a crystal of potassium diehromate be drawn
tlirough the H,SO, solution, it is followed by a violent coloration, which
diflfors from the similar color obtained nith strychnine under similar cir-
cumstances, in being more permanent, and in the absence of the following
pink and yellow tints.
Bnaetine~C,,H.,N,0, — an alkaloid exisUug in ivAOicuanha, which
crystallizes in colorless neettles or tabular orystola, slightly bitter and
acrid ; oclorless, and H|>aringly soluble in water.
It dissolves in concentrated H SO,, forming a green solution, which
gi-atlually changes to yellow. With Fruhdo's reagent it gives a red color,
wluch 8O0D changes to yellowiah-groen and then to green.
Ptomaines.
f This name, derived from mV^ = that wliich is fallen — Le., a corpse —
was first suggested by Selmi to apply to a classof substances, first distinctly
lecoguizod by him, which are produced from albiuuiuoid substonocs under
844
UASVAL OF OBEHtSTItr.
tJie iii6a«nce of pntrefantire decomposition, antl nhioh are diatmctly alk»>
loitlftl in chomctcr.
TLo ptoma'incs are pomeeeed of all of tbe diatin^iahin^ rlutTBolere of
tbe Tegetable Alkaloids. Tbcy are alkaline in rcocUon, and couibiuo viUi
Bcida to form aalta. Some are liijuid, others are BoUd and crrsialline.
Some are actively puisonous, otberaare practically inert. They behave
ward the (foncral rcaguuts for alkaloida iu much the aauio wiijr aa do the
Tegetftble alkaloids.
Although tbo namoa ptomabieg and txidoveric aUaUaidti am applied to al-
kaloids of animal origin, it ia certain that such alkoloida may be and are
produced during life in tbe animal economy.
It waa feared thai, aa alkaloidal substances iu many renMotg reeembUng
those of vegetable origin are produced iu the animal body, not only after
death, but during life, grave doubts vould be ca«t upon the results of an-
olysee made to detect tlte presence of poiMonoua vegetable alkaloids in th»
cadaver iu caaea of suspected poisoning. Such feooa were by no meaosi
groundless, aa there in abunduiil tivideuce that ptumatnes have been
taken for vegetable alkzdoids in ehouico-legul analyses. Tbe ptomaine^
howevor. as welt as the vegetoldn alkaloids, may be ptimtively identified by
a careful nnalysia based upon the ukb, not of a single reaction, but of all
known mtctioM for the alkaloid iu quLutiou. Therefor, it in poamble to
positively predicate the existence or non-existence of a given vegetable al-
kaloid in a ondnver, but it can only be done nftera thorough and conscien-
tious examination by all physiological and chemical reactions.
Tbo ptomaJ'ues have of recent years anumed great importance to the
phynician by reason of their bearinff upon the etiology of disease, and suf-
ficient experimental evidence has nirently been obtained to warrant tiio be-
lief that the method of action of many uf the known pathogenic bacteria
is bv their proilnciion of alkaloidal poisons {see below).
One of the first of the putrid iilkaloids to ho formed in cadaveric matter
is chrttme (see pp. 207, 27:^), which undoubtedly liua its origin in the de-
ooinpositiou of the lecithin^.
Neuridine — C,H,^N, (?) — is a diamine, related to tuturitie (soe p. 208),
which is formed during the early stages of cadaveric putrefaction. It is
gelatinouM, readily soluble in water, insoluble in alcohol and ether, and
very prone to decomi>oeition, yielding dimethylamine aud trimetbylamine.
It forms a chloride which crystallizes iu long, transparent needlea, veiy sol-
uble in water. It is non-poisunous.
Cadaverine — C,H,,N, — identical witbpentamethylendianiine, NH,—
(CH,), — XU,, is formed at a somewhat hitcr stage of cadaveriu putrefae-
ttou, aluug uith putresciuo and saprine (see below).
Ita chloride is crystalline, bygroacopic, very solnUe in water, ineolu-
ble in strong alcohol and elher. Like most of the ptomalnee and sev-
eral of the vegetable alkaloids, it gives a liiatinct blue color with ferric
chloride and pot;isHiiiiii ferricynni'Je. It is n on -poisonous.
Putresciuo — C,H .^N, — oud Saprine — CjH.^N^ — are two non-poiaon-
oua diamines produced idonjr wilU caduverine. They are both liquid, and
each forms a crystalline chloride.
Mydalelne is a putrid idkaloid, of nndpfermined composition, forming
a difficultly cryatalUzable, hygioscopic chloride, which is actively }ioi8on-
ous. Five milligrammce admiuiijtcred hypodermically to a catcauaett death
after profuse diarrhoea and secretion of tialiva. violent convulsions, and
para]%-8i8 beginning with the extremities and extending to the muscle* of
respiration.
I
ALBUKINOIDS ANH OELATINOIDS.
H5
Neurine feee p. 208) is prtxlnced diirinp tho Inter slopes of piitrefao-
tiou. It 18 actiTely [wisanoiiA, ftnil proHiicfH i^TmptoniD nirailni' to those
caused b,v uiuauuiue. Alrupiuc itt a powerful antidote to its action.
Mydine^ — C.H^^NO — is a base prcnluced after continued putrefaction
at cftmiiamtively low tenip^ratuif-s. It is a powerful base, and a etroug re-
ducing a;;eiit, aud ImR an amraoniacal odor. It is nnn -poison ous.
Mydatoxlne — C^,,NO^ — is a stronglv ulkaJine B}Tup, which pro-
daces, when adniiuistcrod to animals, violent eluuio spuams, followed by
pftnUyua and death.
Other ptomaioes produced during putrefaction of meat, fiah, etc,, are
methylguanidine, C,H,N, — poisonous ; muscaiine, O.H,^NO, — poi-
Bonoiis ; and gadinine, C,H„NO,,~rion-poisnnous.
An alkaloid, many of whose chemical reactiona have l)eeTi determined,
although ita oouiposiliou iu uuliuown, hus becu obtained from the inter-
nal organs, and dejecta of cholera victiniH. as well ns from cultures of (he
oomma badllus. Tliiin alkaloid, when administei-ed to animals, causes
FjmptomH of poisoning and death.
From the cultuieH of the Koch-Eberih typhus bacillus an alkaloid haa
been isolated — Typhotoxine — C,H,,NO, — which, when administered
to animala, causes paralvMfi, copious diiirrhn-a, and death.
Tetanine — C,,H,,r3r,0, — ia nu alkaloid obtained fi-om cnltnrm of a ba-
cillus originating from a wound which had been the canse of death by te-
tanus. It forms n dehcpiescent chloride, and a very soluble chloroplali*
nate. The free baae or its chloride, when injected into mice or pnnea-
piga, causes clonic or tonio convulsions of the greatest intensity, which
terminate in death.
Mytilitoxlno — O^.^NO, — is on alkaloid obtaine«1 from poisonous
mnaaela, vhich. when adraini^«red to nnimals in small amount, causMi
tbe aama symptuma as are produced by the muusels.
AliBUMINOZDS AND GELATINOIDa
Pkotkim Bonnas.
Th« subafanoee of this class are never abeeni in living vef^etable or ani-
mal cells, to whose '■ life " they are indispensable. They are as yet the
prodncta exdunvely of the organized worhL
PavHicju- CiiAiatTEft.*. — They aro almost all nncrystallizable and incap<
able of dialysis Some are soluble in water, others only in water contain-
ing traces of other Bubatau<rea, others are insoluble. Thuir solutiuas are
all Irevogyroua. Some are separated as solids from their solutions, in a
permanently modified form, by heat and by certain reagents ; a change
called ciri^/uiation. When once coagulated they cannot be rediaaolTod.
The temperature at wliieh coagulation by heat occurs varies with dif-
ferent albuminoids, and ia of value in distinguishing them from one ao-
other.
CoMFoarno!!. — They oonaiat of C, N, H, O, and nsually a small qoanti^
of 8, and form highly complex moluculea whose cxiict cumputiitiou is un-
certain. Of their CQni/tUution nothing is dehuitcly kuowu, although there
is probability that they are highly complex amiiles, related to the ureids,
and formed by the combination of glyoollamine, leucine, tyrosine, etc., wiUi
XBdicoLs of tho acetic and benzoic seriea.
846
XAKVAL OF CHBMISTRY.
OnmnAi. RKAcnotra. — They all respontl to the follnwing terta ;
(1.) A purple red color when warmed to 70" (158'' F.) with MUlnn'a »-
n^ent. The reagent is matle by disAolving, by tho aid of hcnt, 1 pt Hg in
2 pis. HNO, of sp. gr. 1.42 ; diluting with 2 Yols. H,0, and decwiting after
2-4 hours.
(2.) A yellow color with HNO, ; dumging to oraago with NH.HO
(Xanthoproteic reaction).
(3.) A purple color with Pettenkofer'a teet {q. v.).
(4.) With a drop or two of cvpric sulphate solution and liquor potusa
a violet color.
(5.) A Holutiou of an albuminoid in oxoeaaof glacial acetic acid isoolorod
Tiolet and rendere*! faintly fluorescent by concentrated H,SO .
{6.) With XKJtaBHium ferrocyauide, ia solutiona strongly acid withaoetie
acid, a whit« ppt.
DBooHPosmoxn. — Dilute acids decompoae them into two subatanoes :
one insoluble, amorphous, yellowish, called hemivrolein ; the other soluble
in water, insoluble in alcohol, faintly aciil, called fiKmialhumin. A pro*
longed boiliufic v^'ith moderately concentrated H,SO^ decompoeee them,
forming well-defined subst.aniiefl— plyoocol, leucine, tyrosine ; aspartie and
glutamic onids. Alkalies <Ub!*o1vb them more or less readily ; on boilmg
the solution, part of the sulphur is converted into sulphide and hyposul-
phite. Thcii' alkaline solutions, when neutraUzed by acids, deposit Unl-
der'u proleitu^. Cancentrated alkalies decompose them into amirlo-arids.
By fiuion with alkalies, alkaline cyanides are also produced. When they
are heated with caustic baryta and water at 100' (212^ F.) carbonate, sul*
phate, oxalate, and phosphate of bariutu are deposited, and CO, and NH,
ore given off in the same proportions as when urea is similarly treated;
wheu the temperature is raised, under pressure, finally to 200° (392^ F.),
a crystalline moss is formed which contains oxalic and acetic acids, a num-
ber of amido-acids, nsp'^rtic and glutamic acids, and a substance re«emb-
ling dextrin. Heated with H,0, under pressure, they are partly disaolred
and p'trLly de(!oni[><>sed. A mixture of U,SO, and manganese dioxide, or
pot)t!^ium dichromato, produces fi'om the albuminoids, aldehydes, and
acids of the fatly and benzoic series, hydnwyanii^ acid, and cyanides.
When heated under pressure with Br .and H,() they yield CO., oxalic and
aaparlio acids, amido ocida, and bromine dcnviitives of the fatty and ben*
Eoio aeries. Potassium permanganate produces from them urea, CO,, NH,
and H,0.
PirraEFACTicx — ia a decomposition cf dead aibuminoid and gtiaiinous mat-
ter, ailended by the gfS}luiion ^ fetid gas, and by the appearatKe of low /ormx
^organized beitujg {bacteria).
That it may occur there must have been contact with air, and there
must be presence of moisture and a temperature between 6°-90° (41''-1U4'^
F.). It ia atteuded by the bi-eakiug down and liquefaction of the material
if it be soUd ; or its clouding and the formation of a scum upon the sur-
face if it l>e hquid. The pnxliictM of putretuction vary with tlie conditions
under whicb it occurs, tho most prominent me : N, H, hydrix-arbona,
H S, NK„ CO,, ceriniu iLl-deliued photfphurizcd and sulphurated bodies
acids of the acetic and lactic scrica. amido acids, and alkaloidal subetances.
Under certain imperfectly defined conditions, buried animal matter is
OfJUvertt'd into a substance resembling tallow, and called ndtjtocpre, wliich
consists chictiy of palmitute, steorate, and oleale of aaunonium, phosphate
and carbonate of CAlcinm, and an undetermined nitrogenous substance.
Putrefaction may be prevented by : (1) exclusion of air ; (2) removal
ALBUMINOIDS AND OBLATIKOIDS.
s4r
of water ; (8) maintaining the tenipcraturo below 6" (41 'F.); (4) the acUoD
of autisepUca.
Anlt^^i/^9 are attbslttncev xohkh prwetU or re»tTain putrefaction.
Ihodfyrixer/t, or air p urifier*^ are tiUmUsnon tohich destroy the odorou* pro-
duct* of putrefaction.
DisinfectanUi are tfudsto'icea which retrain infectious diaeaaet by degtrotfing
their ^ft&rific pOMong.
Certum subsUuicea ore antiseptic, deodorant, and disinfectant ; such
ore : chlonno, bromine, iodine, the bjpoclilorites, and sulphur dioiide ;
others lack one of the powers, as the mineral acids and the uon-volatile
" diaiufectanta," which are antiaeptic and diaiiifectant, but not deodorant.
3tJU others exert but one of the powers, as wat4*r and air, which may be
mechanical deodorants, but neither disinfectanta nor antiseptics.
There occurs a decomposition of vegetable tissues under the icfluenoe
of warmth and moiature, which is known a» ei-evuicaugui, differing from
putrefaction iu that the subntuuces decom{X)iied are the carbohydrate in*
stea>l of the azotized constituents, and in the products of the decomposi-
tion, there beinjj no fetid gases evolved (except there be simultaneous
putrefaction), and the final product ia a browniah material (humns or ulmin).
Cl.issu-ication.— In the jiresent uiwatisfactory state of our kuowledj-e of
the chemical constitution of those substances, we can only adopt a tempo-
rary claaaification, baaed upon their phyaioal and physiological characters.
A. Albvuinuids:
I Mohibie in pure water ; coagiUated bt/ had. — The true albumina of
white of egg, serum, and vegetable albumin.
n. Insvluble in pure water; aoliMe in waler without alteration in prexneg'
of nealrat salts, alkaiiea and acida; and capable of preciintation unc/umged
front these solutions.
1. Globidins. — Vitellin, myosin, poraglobulin, libhnogen.
2. Animal caseins. — Milk casein, aenuu casein.
3. Vf^gett^e twA^iVw.— Gluten casein, legumin, conglutiu.
4. F^st termg of dtv-ompitsitinn of itie albtiminoidtt by acids, altalies, and'
eryptolytet. — Albuminates (so culled), acid albumin, syntonin, hemiprotein,
peptone.
nL Insoluble in water and only soluble after decomjtosition. Cannot be
wparated withoul tdleration frtjm. tiieir solutions in acids and alhaHea. — Gluteo
fibrin, gliadiu. muuedln.
IV. Coagulated. — Coagulated albumin and fibrin.
V. Amyloid matter, — lArdacoin.
R Gei-atinoids :
L Collagcnes. — Collagen, olastin, ossein and its derivatiTea, choudrigea ?
chondrin ? gelatin, keratin.
IL Mucilagitwus bodies. — ^Mucio, paxalbumin, coUoidin.
Albcmihoiss.
I. — Egg albumin exists in solution, impnsoned in a network of deli-
cate membriiucs, iu the white of egg. It is obtained in an impure condi-
tion by cutting the whites of eggs with scisaora, csprosalug thi-ough linen,
diluting wiUi an equal vulumo of water, fdteriug and concentrating the
filtntle at a temiwrature below 40° {104" F.); mineral salts, which wlhero
to it tenaciously, are separated by dialysia It seema to bo a mixture of
two different BuiwtAnces, one of which coagulates at 03^ (145^4 F.). and has
the rotarj- power [a]^ = -43^; the other ooaguktoe at 74"* (1(J6^2 F.J,
)
and haB the Tolne of [a], ——26°.
lU solutions are nob precipitated by a Bmall quAntilv of HCl. but u'
excess o( tbat add pruducea a deposit which is dilficultly soluble iu HCL
H,0, and salt solation. Its obaracteristie roaotton ia that it is coagulated
by agitation with Htber.
Serum-albutzun exists in Uood-acrum. chvle, lymph, poriamlbil
flaid, tht' flui'ls of evsts au<l of IrauhmbitionM, iu uiilk and, patboloj^ioilly, iu
tbe urine. It id best obtiiined from bLcKxl-8(>nim, after remoral of par^
globulin {(J. v.), by a te<Uous proce8s, and only then in a state of doubtful
purity, it is Icsii abund&ut in tbe blood of some "n'nu^W Lboa poni^lobo-
lic, but more nbtuidant in tbat of mnu.
Solutions nf Renini-albnmin are berogypous [a], ~ — 66* ; they are not
procipitiited by'CX),, by acetic or ortbophoaphoric acid, by other or by
mi^nieaium sulphate. Tboy are precipttate<l by mineml acids, tsanieociiL
metaphosphoric acid, and most metallic anlt^. When heated they become
opalescent at BO"* (14U^ F.), and coagulate in the Hocculcnt form at 72 -
76^ {161^ft-l67* F.).
I>BTB(7nost ASD Dbtiirminatiox OF AuuiuN IU Usuff. — If the oriue be not
pnrfeetly clear it ia tillered, if tbts do not render it perfecUy tcanaparent,
it ia treats vrith a few drops of mar^esia
mixture (p. 65 note), and u-pun liltereiL
The filtrate, if olkaUne, is rendered juM
acid by adding acrtic aoid giittntitn (nitric
acid sliould not be used, and tbe acidur
lation of ullcaUuo urine is imitenttivo). Tbe
urine is now heated to near Itoiling, and
if a cloudineu) or precipitate be formed.
HNO, is added slowly to the extent of
about 10 dropB. If heat produce a cloudi-
ness, ^'hich clears up completely on addi-
tion of HNO,, it is due to an excen of
earthy pho9|)bates. If a cloudinees pro-
duced by beat do not clear up (it may in-
crenitc} on addition of Hl^O^ it is due to
albumin.
Small qonntitics of albumin may some-
tinies be better detected by Heller's test : A layer of HNO, is placed in a
te8t-tuV>e^ which i^t then held at an angle and the mine allowed to fluw
simply upon its surface (Fig. 40) so as to form a distinct layer, with tbe
miidmum of mixing of the two liquids ; the test-tube is then brought to
the Tertical slowly, oiul tbe point of junction of the two liquids examined
against a dark background. If ulbuuiiu be present a white, opaque band,
M'liose upi>er and lower borders areiihtirpli/ dfjitifd, will be seen at the line
of junction of the two liquids. When urates are present iu excess, a
white band will be observed, but its position will be rather above the line
of junction, and its upper bonier will not bo sbariily defined, but gratlunJly
diminish iu density from below upward. In non-albuminous urines tbei'e
is usually a darkening, but never an o]>acity at the line of junction.
Qwuittlih — Tlw only vtthoil r>( daUrmlalog tlia qTiantllr of Hlbntnln In urln?, with iti BMawMth tn
Mnata^r, U KnvlmMrlo : Jllf-fiU c.c (CLlr-K.b 11 } ) of Ibo SlWnd diIim {kcrurdttin iu tb« qaalim-K'- I. •tinit
rtiMn albuBtln w to inwent In iRtn vr mmU (|iuuitttrj «« •ia«ly EiMthl avvr the wKtrr^n ' >..•
M1Ib( unpofamre U •ppimohMl, H-4 dfop* at mMIc Mild tu« adikd. ktW Iba iirins bw ' - •<
meaimau. It la Uirown npMi » fllinr. Ths ooaBuIntn la wubod wkli balitag 11,0, Uian irUli t . < • a
wHk HO^ Umd wilt) >|i.i>hi>t nnd AiMlly with Pthirr. B; lhi-«« wuhli>ita InipnrlllM urc KiubVol, uMul Uta
ftUnualn w caotnl lx> vuau'vcl flrtuly , *o itM- ft e*n be «Milr <)i.-ucti«d aimI trkiuitnTMl to » mwl^md mtoh-
gfciwi: B|MiUilaU ladtlt-lal ilf ft'W I'. ) nnci tho wholo ««lichM]. TlMdllVnvficebaMreai ttoU«w«||tal
mad thai ot Ua vaU^-iliw, ia Um walgtit at Oxj *Miiimlii ia Uw valnOMOt ortne nwd,
Pio. iV.
ALBTTjnWOIDS AXD OEI-ATITl'OIDS.
349
Vegeta'blo albumin — exista in solution in all vegetable juices, and
forms the most valuable constituent of thoso vegetables which are hs^hI aa
food. It is coajrulated from ita aolutioiia at 61'-63° (Ur.8-U6 .4 F.).
and b^ nearly all acida.
n — Vitelln. e\i9ts in the yolk of Of^ and in the cryatalline lens. It
i« soluble in dilute Rohition of nodium chloride, from which it is precipi-
tated by ftxcesa of H.O ; by heotiiig to 75°-80" (1G7^-176^ F.); and by
alcohol It is not precipitated by solid sodium chluride. It dissolves iu
weak alkaline solutious without altei'ation and in very dilute UCl (1-IOUOj,
by which it is quickly converted into svutoinn.
Myosin — is one of the principal couHtituentH of the muscular fibre in
rigor mortis. It ia a fuiutly yellow, opalesccut, distinctly alkaline lit{uid,
which, when dropped into distilled H,0, deposits the myosin in globular
maeisea, while the H,0 assnmea an acid reaction. It ia insoluble in H^O,
eaailr soluble in dilute salt solution, from which it is precipitated by the
addition of solid sodium chloride, or by a heat of 55*-(!0'^ (131^-140" F.).
fery dilute IICI disfti^lves and converts it into B}-ntonin.
ParaglobuUn. — This aubstance has been described by various authors
'under the nanius: plafmine (Denia), «tTum casnri (Paaum], acrum glob-
uliite, Jibrinof:hiMic matter (Schmidt), term (DentsV It exiats in blood-
sernm, in pericaniial ftuiii, hydrocele fluid, lymph and chyle, from which
it is obtained by diluting with 10-15 volumes of ice-cold H,0, trentment
of the solution with strong current of CO,, and washing the collected
dejMsit with H,0 as long as a portion of the tjltrate precipitates with
neetie ncid and potassium ferrocyanide, or with silver nitrate. It ta n
granular sulmtance, which gradually becomes more compact ; insc4uble in
HfO, sparingly soluble in U,0 containiug CO, ; soluble in dilute alkalies,
in lime>water, in solutions of nentral alkaline salts, in dilute acids. Its
solution in very dilute alkaline fluids is perfectly nentral and is not
cotuTulatod by heat, ext^pt after faint aci<luiation with acetic or minerul
acids ; it is precipitated by a largo volume of alcohol ; its solutions are
also precipitated incompletely by dissolving sodium chloride in them to
saturation, and completely by similar solution of magnesium sulphate;
this last method of precipitation is used for the separation of paraglobuliu
from serum-albumin (sec Fibrin).
Fibrinogen — after the separation of parnglobulin from blnod-plasma,
as described above, if the litjuid be still further diluted wid again treuie<l
with CO,, a substance is obtained which, although closely resembling
paraglobulin in many characters, is distinct from it, and, unlike paraglob-
uliu, it cannot be obtained from the scrum separated from coagulated
blood.
Para^lobulin and fibrinogen are both soluble in a solution of sodium
chloride containing 5-8 per cent, of the salt ; when the degree of concen-
tration of the Bolt solution is raised to 13-lG per cent., the fibrinogen ia
precipitated, while the parj^lohulin rciuains in solution and is only pre-
ctpitiitetl, and then incompletely, when the percentage of salt surpasses
twenty {sec Fibrin).
Milk casein — the most abundant of the albuminoids of the milk of
mammalia, closely resembles alk:ili albuminates, witli which it is probably
identical, as the main point of distinction baa been fotud to be without
significance. Unlike pure alkali albuminatos, casein is coagtdated from its
solution by rennet (the product of the fourth stomach of the calf) at 40^
(104'' F.) ; but it has been found that alkali albuminate is also so coii^-
Tbfl compontioa of eows' milk nries ootmdenU; aeeordiBg to the
agai, oonflilion, breed and food d th« oov ; to the time and fic qu euey of
milldng ; wul to whethar the aample eiaminad i> trofa the finrt, middW, or
liet jMvt of each millun((.
dowa' milk in rurj frequently adulterated, both by tbe remoTa] of the
ereaio aod the addition of water. For ordinanr parpoaes, the pmitr of
tbe milk may be determined by obaerring tbe sj). px. and tbe psraentage
of rream by tbe Ucto meter and creamometer, m^ither of wkick, vaedtlame,
ij^vrdn indioatioiig tthu-h can be relied upon. Tbe sp. gr. fllioald be ob-
mnrtd at the temperature for which the instrument is made, as in a ocod
plex lluiil mti'h lu milk no valid oorreotion for temperatnre ia practica] ;
it nitiiroN in pure milk frum 1027 to 1034, tt bein^ ^iienlly the lower in
milk which haa been watered, and in such as ia very rich in cream, and
Uie hif^hor tlio less cream is preaenL The areroge sp. gr. is 1030 ; the
aTera;;(o porrfintn^e of cream 13.
Ttie percentngti of cream ia determined by the creamometer : a glasa
tobe aboat a foot long and half an inch in diameter, the upper fifth (ex-
cluding about an incli from the top; being graduated into bundre«^ltL8 nf the
whole, tbo being at the top. To uae it, it ia aimply filled to tbe
with the milk to be tested, set aside for twenty hours and the point of sep-
aration btilwoou milk and cream read oflC It should be above eight per
cent
This method of determining the purity of milk, although anfileient for
ordinary TiurposeH, should not be cuusidcred as affording eridGuce upon
which to biiao legal proceedings ; in such cases nothing short of a chemical
detenu injiiioii of the percentage of fats, and of solids not fat, should be
aooepted (m evidenco of tbe impurity of milk.
Serum-oaseia is a substaiice ubtained from blood-serum diluted with
10 voliunoH of H,0, freed from paraglobuHn by CO,, and from albumin by
Aootio acid and heat. It is inffoluble in salt solutioDS, slowly soluble in a
one per cent, solution of sodium hydrate. Such a solution ia partially pre-
cipitatcd bj CO,, almost completely by aeotic nciil, outl completely by faeatr
iijjf witli excess of powdered sodium chloride ; incompletely soluble in di-
late UCl
Gluten-casein. — ^Tbat portion of crude gluten (a soft, elastic, grayish,
material best obtained £rom flour) which is insoluble in alcohol, hot or cold ;
Ijeguinin — a sparingly soluble albuminoid obtained from pens, beans, etc ;
and Conglutin — a substance closely related to legumin and to gliadiRt but
differing from them in some characters, obtained from almonds, are Uirec
Tegetabio albuminoids resembling casein.
They ore inHolublo in pure water, readily Roluble in dilute alluUine so-
luliouB, from which they are precipitated by acids and by rennet
Alkali albuminates— /jrci(t-i;t-t of Hoppe Seylor — are formed when an
albuminoid i-i dissolrefl in concentratetl solutions of potassium and sodium
hydrates ; it is very probable that they are identical with scrum and milk-
cose in.
Aold albumins — are substances obtained by precipitnting solutions
of ailmmiiioids by the simultaneous addition of on acid and a large quan*
tity of a neutral salt ; they vary esceedingly in compoiiition and proper-
ties.
Syntonln — Parapeptone — is ertraoted from contractile tissuea Tlie
some substance is formed by the action of dilute acids upon the albumi-
noids, and as the £rst product of tbo action of the gastric juice, or of niis-
tures of pepsin and dilute arid upon nlbuminoida It resembles serum
oaaain closely, the only divergence in their properties being that ayntonin is
much more readily soluble in a 0.1 per cent solution of HCl, and in faintly
alkaline liquids.
peptone — Alhuminnnf—iH the product of tlie action of the gaatrio
and p:mcreatic jtiices upon albuminoids during the proce.s8 of digestion.
It is soluble in H.O, insoluble in alcohol and in ether. Its watery solution
is neutral, not precipiiablo by acids or alkalies, or by heat when faintly
acid. Alwihol precipitates it in white, casein-like flocks, which, if alowly
heated to 90^ (104° i . ) while still moist form a transparent, yellon-ish hquid,
and, on cooling, an opaque, yellowish, glassy mass. It has a greater power
than other idbuminoids of combining with acids and bases.
The most important character of peptone, in which it differs from other
albuminoids, is that it is readily dialysable. Its presence in the blood has
not been demonstrated, and it is probable that immediately upon its en-
trance iiil/) the circulation it is converted into albuminoids resembling, yet
differing from, those from which it was derived.
Peptone is pro<luced by the action of many chemical reagents upon
albuminoids ; and also as one of the first product^) uf putrefaction.
Wheu produced by putrefaction, or by artificial digestion, it is accom-
panied by pfjtiutoxini!:, a crj'stallizable and actively poisonous alkaloidal
substance.
It has been claimed that the gastric digestion of different albuminoids
produces, not a single substance, but a distinct peptone for each albumin-
oid. If such bo the cose, and the present state of our knowledge does not
permit of a detiaite answer to the question, these bodies ore very closely
related.
Peptone responds to the general reactions for the albuminoids (see p.
346), from which it may be distinguished by the biuret rcwHion. If a
mere trace of CuSO, solution bo added to a solution of peptone and then
KUO or NoHO solutiou, a pur|)]e or reddish violet color is produced. A
similar apx^eurance is produced with acid albumins.
S5S
MANUAL OV CEntMlfiTP-T.
tV. — Coagulated albumins — are ohtained, as dmoribeil above, frvrm
the soluble varietiea bj the action of acids heat, alcohol etc. Thev an
insoluble in water, alcohol, solutiona of neutral Baits ; difficultly soluble ia
dduto alkaline Holntioitg. In acetic acid ther swell up and dissolve slowlj;
from thiA solution they are precipitated by concentrated salt solution.
Concentrated HCl dissolves them with formation of syntonin. By the ac-
tion of gastric juico, natural or artificial, they ore converted first into irjni.
tonin, then into peptone.
Fibrin — is obtiiinefl iv'tien blooil is allowed to cottffalate or is whipped
with a bundle of twigs. When pure it is at first a gelatinDas mass, which
ooutracU t<j a white, strinp)', tenacious material, mode up of numerous
minute fibrils ; when dried it is lianl, brittle, and hygroscopic. It is iit-
Boluble in water, alcohol, etlier ; in dilute arid it swells up and dissolves
slowly and incompletely. When heated with water to 72 (1G1°.6F.). or
by contiict with alcohol, it is contracted, and is no lonf^er soluble in dilute
acids, hnt soluble in dilute alkalies. In solutions of man;* neutral salts
of 6-10 per cenL, it swclla np and is partially dissolved ; from tliis sola-
tioQ it Rppiirates on the addition of water, or ujwn the application of
heat to 73^ (l(j3^4 F. ), or by ocetic aeitl or nlcohoL Moist fibrin has
the properly of decomposing oxygenated water with copious evolulinn of
oxygen.
Fibrin does not exist as such in the blood, and the method of its form-
ation and of the clotiing of blon<l ho-s been the subject of much experiment
and argument ; nor can the question be «aid to bo definitely set at rest In
the light of the researches of Denis, Schmidt, and especially of H:immar-
aten, it mny be considered as almost proven that fibrin is formed from
fibrinogen nnder favorable circumstances, and by a transformation which
ia not yet understo«L Whether paniglobulin plays any port directly in
the formation of fibrin or not. is still on open question.
V. — Amyloid - is a pathological product, occurriug in fine grains, re-
sembling staxTh-gnvnules in appearance, in the memlimneR of the bmiti
and cord, in wnxy and lanlaceouH liver, and in the walls of the bIuod-\'e8-
sela, Its composition is that of the idbuuiinoids, from which it difiera
in being colored red liv iodine ; violet or blue by iodine and H,SO^
Soluble in HCl with formation of syntonin ; and in alkalies. It is not at-
tacked by the gastric juice, oud ia not as prone to putrefaction as the other
albuminoids.
GKLATIKOmS.
L — Collagen. — Bony tissue is made np mainly of tricalcic phosphate,
oombined with an organic material called o«w'n, which is a mixture of
ooUagen, dnstin, and an albuminoid existing in the Iwne-celU. Collagen
also exists in all substances which, when ii-eated with H,0, under the ia-
fluence of heat and pres.«rare, yield gelatin. It is insoluble in cold H,0,
but by prolonged boiling is converted into gelatin, which diseolves. It is
dissolved by alkiUics.
Gelatin — nlitained aa above, from ossein, exists in the commercial pro-
duct of that name, and in a less pure form in glue. When pure it is an
amorphous, trnuHluc'eut, yellowish, tostcle.ss substance, which swells up in
cold H,0, without dissolving, and forms, with boiling H,0, n thick, sticky
solution, which on rooHng becomes, according to its concentration, a hard
glasBv mass or a soft jelly — the latter even when the solution is very dilqte.
It is insoluble in alcohol and ether, but soluble, on warming, in glyceric ;
AiriMAL CRTPTOLTTES.
S53
the aoIutioB in Ihe lasi-iiiuueil liquid forms, od cooling, a jelly which lias
recendy been applied to varioaa contiirances for copying writinp;. A fibn
of gelatin it)ipregniit«d witli potassium diclironiate beoomee hard and iuaol-
uUe on exposure to sunhght.
Owndriti is the uiiuie given to a substance obtained from cartilaginous
tissne and Rupposed to bo distinct from geiaUn. It is probably a nuxttu?e
of gelatin and imicin.
Elastin — in obtained from clastic tissueH by succeBflive treatmeiit with
boiling alcohol, ether, water, couccntraioxl acetic acid, dilute potash solu-
tion and water. It is fibrous, yellowiRh ; swells up in water and becomes
elastic: soluble with a brown color in ronrentrHt«<l potash solution. H
contains no S, and on boiling with H.,SO, yields glycol
KeratJQ — is the organic basis of horny tisHues, bair, nails, feathenii,
whalebone, epitheHum, tortoiso-shell. etc. It is probably not a distinct
ctiemical compound, but a mixture of several closely related bodies.
H — Mucin — is a substance containing no 8 and existing in the differ-
ent varieties of mucus, in certain pailiological fluids, in the bodies of mol-
luscs, in the italiva, bile-, conuectivo tissues, etc. Its solutions, like the
fluids in wliich it occurs, are viscid. It is precipitated by acetic acid and
by HNU,, but is dissolvfid by an excess of the latter; it disfiolves readily
in alkaline xolution.s, and swells up in H,0, with which it forma a false
solution. It is not coagulated by beat
ANIMAL CRYPTOLYTES.
Soluble Axihal FKitME?jT8.
Under this head are classed substances somewhat resembling the al<
buminoids, of unknown composition, occurring in animal fluids, and having
the power of efTectiug chaugeH in other organic substaucoa, the method of
whotie action is undetermined. (See p, 182.)
Ptyalin — is a substance occurring in saliva, and having the power of
converting starch into dextrin anil a sugar reHembUiig glucose (ptyalose),
in liquids having an alkaline, neutral, or faintly acid reaction.
Pepsin — is tlie cryptolyte of tlie gastric jiiiee. Attempts to separata
it without admixture of other substancoB have hitherto proved fruitless ;
nevertheless, mixtures containing it an<l exhibiting its cbaracteri»tic prop-
erties more or less actively liave been obtained bv various methods. The
most simple cousiats in macerating Uie finely divided mucous raembione of
the stomach in alcohol for 48 hours, and afterward extracting it with gly-
cerin ; this forms a solution of pepsin, which is quite active and resists
putrefaction well, and from wliich a substance containing the pepsin ia
precipitated by a mixture of alcohol and ether.
If pepsin be required in the solid form, it is best obtained by Briicke'fl
method. The mucous membrane of the stomach of the pig is cleaned and
detached from the muscular coat by scraping ; the pulp so obtained is di-
gested with dilute phosphoric aciil at 38" (100". 4 F.), until the greater
part, of it is dissolved ; the filtered solution is neutralized with lime-water ;
the precipitate is collected, waflhe<l with H^O, and dissolved in dilute
HCl ; to this HoIutioH a saturated solution of cholesterin, in a mixture of
4 pts. alcohol and I pt ether, is gradually added ; the deposit so formed
is repeatedly shaken with the liquid, collected on a filter, washed with H,0
and then with dilute acetic acid, until all HCt is removed ; it is then
Infttod with ether and H,0 : the former diiiwilres cbolesterin und U
poarod off^ the Intler the pepsin ; oiler several sbukiugs with etber th«
aqtieouH liqtiur U evaporated nt H8^ (10(P.4 F.;, wheu it leaves tbe ptpsiL
as na amorphotiB, gmyish-wbitc anbetance ; almost insoluble in pure £lo.
readil^r soluble in nciitulated H,0 ; probably formiDg^ a compound with
the ai-id, which powessea the property oi coDTartiug albumiuoids inU>
jK-pUme.
'ITio wi-cAlled MmiKt ytorci la either the calcium precipitate obtained
na deacrilwHl in tlio nntt ]iurt of the above inetbo<l : or, more eommouly,
tlio mucous membniuo of the i^tomAcb of the pig, scraped oS, dried, and
luixnl with ri»*o-Btar<'h or milk Bupur.
Panoroatin. — Cndtr thii; name, Rubatanoea obtained from the panrre-
atic sQcrotiou, and from extracts of the organ itself, have been deschbcil,
nml to Bomo extent used therapeutically. They do not, Lowuver, contain
all the cryptolytee of the pancreatic juice, and in many instances are inert
olbuminoiaa. The actions of the pancreatic juice are : (1) it rapidly coq-
»rt> starch, raw or bydi-aied. into eugax ; (2) in alkaline solution—its
Sl&tural reaction — it oouverte albuminoids into peptone ; (3) it emulsi&eK
neutral fats : (4) it decompoMS fate, with absorption of H,0 and libera-
tion of };lycerin and fatty acids.
^^K The pancreatic aecretiou probably CDutotiia a number of crypttjlyteH —
^^P certainly two. The one of these to which it owes its peptonc-furmiu^
^^^ power lioa Vwon o)>tained in a condition of comparative purity by Kubue,
^^^ and called by him tnjpgifx ; in aqueous solution it digests fibrin almost
^^ft iminiHlialvly, but it exerts uo action upon starch.
^^P The ditwtatic (sugar- forming) cryptolyte of the pancreatic juice has not
w been separated, although a glycerin extract of the tinely divided panore-
^^_ atio tissue contains it, ^oug with tiypain.
ANIMAJb COLORING MATTERS.
Bnmoglobiii and its Derivatives — ff,rmato-crifslaiiin. — The color-
ing matter of the blooil is a highly complex subetamie, reMmbliug the
atbumiuoida in many of its properties, but diAbriug from them in being
coTBtelHsable and in containing iron.
Hiemof^lobin exists in the red-blood corpuscles in two oonditiDns-<rf
oxidation : in the form in which it exists in arterial blood it is looeely com-
hined with a certain quantity of oxygen, and is known as ojyluemt^obiu,
Tbe mean of many nearly conoonliug analysee shows its oompoeition to be
0,„H,^N,,,Fe8,0,.,. >\lien obtained frt>m the blood of man and from
that of imkuy oi tho lower animals, it cr.-stallixies in beautiful red |mams
or rhombio pUtee ; that from tho blood of tbe squirrel in hexagonal
plates : and tlmt from the gmuoa*pig in tetrahedro. Tbe oiystals are
always doublv refracting. It mav be dried in vacuo at 0' (^ F.); if
thoroughly <lried below 0' (32" F.). it may be heated to 100^ (213' F.)
-without deeompontion, but the presence of a trace of mcnsture cooees its
dseonpoaititm at a mof^ lower tamperatore;. Its sohibihtT in water varies
vitt the species oi animal fmm whose blood it was obtalncnl ; thus, that
from the gnine«-pig is but t^iriugly soluble, while that from the pig is very
soluble. It is aJso disaolre^i unchanged by very weak oQcalino cotatiocia,
but is dscompoaed by acids or aslts having aa aad wactton.
Um mt fhi t ut, at ndmeai kamogtokm, is f onnad from o^hcmo^ofaca in
i
m
xsmiXL coLoniKO vattkrs. 335
the cconomj during tho passage of artoriAl ioto Tenous blood ; and bv the
action of retlucing agents, or by boiling ite eolutiou at 40* (104° F.) in tlio
um of tho mercury pump.
Oxyhoeiuoglobiu is of a much brighter color than the reduced, and hog
a diflcrcnt atworption spectrum. Tlio spectrum of oxyhtenioglobin varies
with the concentration. In concentrated solutions the hght in entirely
abflorbed, in more dilute solutions the spectrum 10, Fig. 14, is observed,
ind iu still further dilutions U, Fig. 14 ; iu which the baud at D is nar-
rower, darker, and more shoiijly dofiued than tho other. In highly diluted
solution the band at D is alone Tisible. The Rpectrum of ha'nioglobin
consists of a single Imid much brooder and fmntcr than either of tho oxy-
hfuiQoglobin Uiuds (12, Fig. 14).
H:i'nioglobin, iu contact vrith O or air, is irame<liate]y converted into
oxyhiwuoglobiii. With CO it forms a compound resembling oxyhii-moglo-
bin in the color of ita soluliou, but in which the CO conuut be replaced by
O ; for which reason luemoglobin, once combined with CO, becomes i>er-
manently unfit to fulfil its function in respiration (see p. 234).
When a solution of oxyhaanoglobin is boiled, it becomes turbid, and
a dirty, browniah-red coaguhim in deixisited ; the hitiuoK^jbin has been
decomposed into on albuminoid (or mixture of nlbuminoidn), called by
Prf-yfT ^Ifitiin, and iumtalin. The latter, at one time supposed to be the
blood -coloring matter, is a blue-block sulistance, having a metallic lutili'e
and incapable of crvHtidlizrition ; it is insoluble in water, alcohol, ether, and
dilute acids; suliible iu alkidine solutions. It has the composition C,.H
K,Fe,0„. Its alkaline solutions exhibit the spectrum 13, Fig. 14. Althougn
itself uncr}-stal1izuble, luematiu combiueti with HCl to form a comt>ouud
which cr^'stollizes in rhombic prisms, and which is identical wiUi (he
eai'Iiest known crystalline blood jugment, htrmin, or Teichmann's erystala.
When reduced hiemoglobin is decomposed as above, in the absence of
oxygen, ha^matin is not produced, but a sulistance identical with that
colled reduced hasmaiin, and colled by Hoppe-Seyler hainocromoffen ; whose
^wetrom is shown in 14, Fig. 14.
If a solution of h.i>moglobiu be exposed for some time to air it changes
in color from red to brownish, and assumes an acid reaction ; it then ex-
hibits the Bpectmra 15, Fig. 14, due to the production of uietha'mofihhin^
probably u stage in the conversion of hiemoglobin into ha-matiu and globin.
Biliary pigments. — Thei-e aie certainly four, and probably more,
ligraentory bodies obtainable fi"oni the bile and fi*om bihary calculi, some
of which consist in great part of them.
Bn.iRiT»N — C H„N,0, — is, when amorj>hous, on ornnge-yellow powder,
and when crystaJUine, in red rhombic prisms. It is sparingly soluble in
U,0, aloohoh and ether ; readily soluble in hot cldoroforro, carbon disnl-
phide, benzene, nnd in alkaline solutions. "When treated with HNO, con-
taining nitrous acid, or with a mixture of concentrated HNO, and H SO,,
it tarns first green, then blue, then violet, then red, and finally yellow.
This reaction, kno«-n as Omelin's, is verj- delicate, and is nsetl for the de
lection of bile-pi^^ments iu icteric urine and in other fluids
B1UVEIU.1N— C„H,,N,0,— is a green powder, insoluble in H,0, ether,
and chloroform ; soluble in alcohol and in alkaline solutions. It exintfl iu
green biles, but its presence iu yellow biles or biliary ciUculi is doubtful
It responds to Cornelia's test. lii alkaline solution it is changed after a
time into l>iliprnsiu.
BiUTOScni— C,,H,,N,0, — obtained in small quantity fmm human goU-
BtoncB, is an almost blark substance, speriugly soluble in H,0, ether, and
356 UAiniAL OF CHEMISTBT.
chloroform ; readily Bolnble in alcohol and in dilute alkaline solutiona.
Its existence in the bile is doubtful
BnjpRAarw — C,,Hj,N,0,(?) — exists in human gall-stones, in ox-gall, and
in icteric urine. It is a bla(^ shining substance, insoluble in H,0, ether,
and chloroform ; soluble in alcohol and in alkaline solutions.
VsoBius ~- Sydrobiliruinn — C,^„N,0,. — Under the name urobilin,
Jaffg described a substance which he obtained from dark, febriie urine,
and which he regarded as the normal coloring matter of that fluid ; subse-
quently he obtained it from dog's bile and from human bile, from gall-
stones and from foces.' Stercobilint from the faeces, is identical with
urobilin.
Urinary pigments. — Our knowledge of the nature of the substances
to which the normal urinary secretion owes its color is exceedingly unsatis-
factory. Jaffe in his discovery of urobilin shed but a transient light upon
the question, as that substance exists in but a small percentage of normal
urines, although they certainly contain a substance readily convertible into
it. Besides the substance convertible into urobilin, and sometimes urobilin
itself, human and mammalian urines contain at least one other pigmentary
body, uroxanthin, or indigogen. This substance was formerly considered
as identical with indican, a glucoside existing in plants of the genus Iiiati»,
which, when decomposed, yields, among other substances, indigo-blue.
Uroxanthin, however, differs from indican iu that the former is not de-
composed by boiling with alkahes, and does not yield any glueose-like
substance on decomposition ; the latter is almost immediately decom-
posed by boiling alkaline solutions, and, under the influence of acids and
of certain ferments, yields, besides indigo-blue, tn^t^Iucin, a sweet, non-
fermentable substance, which reduces Fehling's solution.
Uroxanthin is a normal constituent of human urine, but is much in-
creased in the first stage of cholera, in cases of cancer of the liver, Addi-
son's disease, and intestinal obstruction. It has also been detected in the
perspiration.
In examining the color of urine it should be rendered strongly acid with
HNO, or HCl, and allowed to stand six hours to liberate combined pig-
ment, and then examined by ti'ansmitted light in a beaker three inches iu
diameter.
Iilelanin is the black pigment of the choroid, melanotic tumors, and
skin of the negro ; and o<;c^jr» pathologically in the urine and deposited in
the air-passages.
PART III.
LABORATORY TECHNICS.
CHEinRTRT is e8Rentia]ly a science of experiment ; ami not only .'s »
knowledge of )t« truths much more mpidlj and easily af^qiiired by the stu-
dcut tbrougb the actual perforinouoe of experiment, tbuii by au^- amount
of reaJiug or attendance u^>ou illustrated lectures ; but it is even <loubtful
whether a thorough knowledge of tlie facta and theories of the science can
be obtained in any other way than by personal obRerralion.
A description uf the various manipulations of Uie general chemical la-
boratory would fill volumes. A short account of tho more prominent of
Ihoae required in a study of rudimentary chemistry, awl in. those pro-
kOesses of au:Uyuis which are likely to be of service to Uie phy&iciou will, we
[believe, not be out of plaoe in a work of this nature.
GENERAL RULES.
" Cleanliness," said John Wesley, " is next to godliness. " The chemist,
whatever his supply of godliness, must bo tlioroughly imbued with the
spirit of cleanliness ; not so much as regards liinmeU, for he who fears to
soil his fingers is not of the material whereof chemists are made, but as
regards the vcsselu and rcagcuta which are his tools. Any substance for-
eign to the matt«r under examination and the reagcute used, whatever be
its nature, is dirt to the ehctmiat
Olaw vessels kIiouU always be cleane<l as soon as possible after using,
■8 foreign Kuhittances ore much more readily removed theu than after
they have dried upon the glass. Usually rinsing with clear wat«r, and
{notion with a probang or bottle brush is sufficiont ; greasy and resinous
■abstances may be removed with KHO solution ; and other adherent de-
posits usually with HCl or HNO, ; tlio alkaU or acid being removed by
clear water. After washing, the vesH«-ls arc drained upon a clean surfooe,
and arc not to bo put away uuIcrs per/ccUy bright.
Order and system are iraperaLive, espedsLlly if sevorol operations are
conducted at the same time. If there be "a place for cverytbing. and
ovorytliing in its place," much time will bo spared. If a process be of
such a nature that it requires a number of vefi«(>lB, each vessel ahonl<l bo
numbered with a small gum hiliel, and the notes of the operation should
indicate tlie stage of tJic process in each vessel.
The habit of taking full and ^stematic notes of experiments and
aoalysea in a book kept es])ecially for the purpose, is one which the stu-
dent cannot contract too early. Ue wUi bo surprised, in looking over and
I
358
MANUAL OF CHEMISTRY.
comparing his notes, st tho Amount of iDfomuition lio will have collected in
a Ebort tune ; much of whicli, bad the momorj been trusted to, would
have been lost
B&^£NTa
Tlie stock of rcft|a:euts required vftries, of course, with the nature of the
work to be done ; from the sninll number required in urinary analjaiss to
the array on the Bhelvea of a fully fti>pointed analytical laboratory.
The hquid rea^euta aud soluliuua should always l>e kept in glass stop-'
pered bottles (the 4i I bottles, with labels blown in the gljwB. serve very
well). The solid i-eagents may be kept in cork-stoppered or, preferably,
glB8»«toppered battles. The onlinary (•laas atop|>erH should never be laid
upon the table, lest they tiike up partiL-les of foreign matter and contamWI
Date the contents of the bottle ; but should be held between the thii-d and
litUe tingers of the left hand.
The reagents required for ordinary urinary analysis are :
NiWcunld,
SiUjiliiirlo M!ii],
AMPCKld,
Those required for onliuary qualitatire snalyaiB are :
Ilydrocttlofl« meU,
Mitnc u;l>l.
Suliihnrtu acid,
UrAravra nJpUda^
ABUDMilaa MtpbkM,
Anunonhiia lijdnU^
PotM«ltua bjilnlA,
Ammonhim obloctdM)
AnaiMdiuB (KrtMaaiU,
HrdnHllKtdlo phovhalBV
I'otftMlwn tnrlcTUikl*,
IMi^iiwi nUiThntrmrtt.
IViiaMliun aautanabs
PnUHlnBi iliimilii.
ODptlBMiIpbUih
T«a|«pan,
Cklctiltu «ult>lMt«,
Ciitrh-' tulphata,
lIumMc MKOM.
PUtuUs oMonilft.
The chemicals must bo C. P. (= cbemicidly pure); and the solutiona
musi be made with distilled 11,0. It is well to put eoiTPsponding num-
bers on each bottle and stopper to prevent their becoming mixed iu^
cleaning.
QhASS TUBING.
The tubing used in making all usual couuectiona and apparatus is the
soft (iermrin or AmoricAn tubing. When the tube is to be strongly
hcateil, Bohemian tubing must be used. The fashioning of tubing of ^a
diameter generally used for gas connections is a simple matter.
CuUin{i into desired lengths is ao*
complished by ranking a scratch with a
triangular file at the desired point ;
hulding the tube as shown in Fig. 41 ;
and partly drawing, and partly bending
it
Larger glass surfaces may be cut
in any required direction, by first making a deep scratch with the file ;
starting the break by l>ringing in contort %\'ith scratched spot a piece of
red-hot glass tubing : and leading the "break in the deaired ilirection by
applj'ing a heated piece of J-inch iron wire, as shown in I'^ig. 42.
ends nf tiabing should always be rendered smooth by heating them t
d^ient fusion.
I-'IQ. -U.
LABOBATOKY TKCIINICS.
859
Pending ia done by heatinc Ibe lubo ai the desired point in an ordinai7
gas flame (not a blow-pii»e name), without rotating it. until softf^ned ; re*
moving from the flame and bending toward that surface wLicb waa near-
est the orifice of the gas jeL
Closirtfj. — For this and other oparationa with <!lasa tubing, the glass-
blower's flame, obtAine<l with a burner (Fig. 43) wliich pennit« of the in-
jection of air into the giui flame, is required. To make a teat-tube a piece
of tubing of the length of two test-tubes ia drawn out at the middle (sec
below). The small end of each piece is thcu heated and
the superfluona glass remov(?«d by a warm glasa rod,
which IS brought into contact for an instant and then
drawn away. The closed end is then hcak>d during
rotation until soft, and rendered hemisphprical by
gently blowing into the mwn end. The own end ia
tUt!U 'h(!iited and while hot furrued Into a Up by a circu-
lar motion with a hot ii-on wire.
Dmwimj out consists in beating the tube at tha
point desired, <luring robitiun, and drawing it apart
after removal from the flame.
Joining, — Two pieces of tubing of difteront diame-
ters may be joined end for end if they be of the same
kind of glasa The ends of each are closed, heated,
and blown out iiito thin bulbs. The bull) ia tlicn
broken oK ihe ends heated, pressed flrmly together,
and re-heated daring alternate pressure and drawing
apart, and gentle blowing into one end while the other
ia closed, until an cTeu joint is obtained,
Stirrinrj rwh are made by cutting gloss rods to the "^ ^ -
required length and rounding the enda by fusion. tia. u.
COLL£CrnON OF OASES.
Oaaea ore collected OTer the pneutnoHc trough, by dwpltxcement of air :
or orer the vteri^urial trough.
In the pneumatic trough (Fig. 44) gases are collected over water in
liell jars filled with that liquid. This method of collection can only Ix*
uaed for insoluble or spariujily soluble gases ; and if heat have been used
in the genemtion of the goa the disengagement tulte must bo romoved from
the water bi/ore the heat is discontinued, to nroid an explosion.
360
KAVUAL OF CIIEUIdTBT.
Soluble leasee are collected over wercary or by upward or downw&nl
diR{i1ar<>tnp.rit of air, according w they are without action on Hq, or heavier
or lighter thwn air.
T
PlO. 4L
SOLUTION.
Ab tlie particlefl of liquids can be brought into closer contact than those
of solids, reactions arc ubiuiUy facihtatcd bv bringing the reagents into eolo*
lion or into fiirtion.
At a giren temperature solution of a solid
is wore rapid the greater the surface exposed
to Uie solvent, i.e., the gi-eater the degree of
sabdivision.
Onlimiry salts are ground to powder in
Wedgwood or glass mortars. Very harti sub-
fttnjices are lirsi coarsely powdered in steel mor-
tars and then finely ground in a{»ate mortaitt.
Soft substances are best 8ub<li\idwl either by
hashing, as in the case of niuacular tissue, or
by forcing through the meshes of a fine sieve,
S8 in the case of white of egg, brnin tissue, etc
Wlien only certain constituents of the sub-
etance are to be dissolved, jjercviatiun may be
reaort«d to. The substance to be extracted is
parl[e<l in a pen^nlator in such a manner that
the extracting liquid filters through it slowly.
WiGu the solvent is a volatile liquid — ether,
chloroform, carbon dianlphide— extraction is
beet aocomplinlied in an apjiarntuH such as tliat
^'**- ^ shown in tig. 45, in which the liquid in boilwl
in A ; Uie vapor passing through a, h. is liquefied in the condenser and
flows batik over the subbLance in B. The extract collects in A.
LABOR ATOBY TEOHNICe.
361
PKECrPITATION—DECANTATION-FILTRATION— WASHING.
Wbon the oonTersion of an in{:rrcdient of a solution into on insolublfl
compound, and iUt at^naration from tlte liquid arR deeire<], both the liquid
uid the recent sbonlu be in dear solution, and the latter should lie added
to tlie iormer, which has been warmed. The Toseel ia then set in a warm
PMkO.
fm.41;
place until the precipitate has Rubaided, a few dropB of the precipitAnt are
added to the clear liquid, and if no cIoudincHH be pnnluced the piTcipita-
Uon is complete. Precipitiilioii should be effected in Erlenmcyer fliisbe
(Fig. 40) or in precipitatin)^ jars (Fip. 47) tliat the precipitate may not
collect on the aiden, and may be readily detat^hed by the wash-bottle.
Precipitates are separuted from the liquid in which they have been
formed by dcvantaitou or jUtraiwii,
Kiu. 4tt.
DRCAVTATtOTi ronRiats in allowinf; tlie predpUatc to subside and pouriuR
ofl* the Hupernatont liquid ; it should always be employed ae a probininnry
to tiltmtiou, and is sometimes used excluRively. when the precipitjite in
washed by repeatedly pouring ou clear water and decautiug it outil it no
longer oontaina any aulid matter.
362
HANTTAL OF CHEillSTEY.
In ponringf liquid from one TeRsel to another it shnald be guided hj t
gUuB rod. aa abowa in Fig. 48 ; the uuLer siirfftce of the lip of the pouriug
Toasel bftviug been sUghtlj greased.
Fu/nuTKQC is resorted to more frequent!/ tlun decaniatioiL Filters an
made from muslin, paper, asbestos, or glass wcwL
Huslin SlterB ore only used for ooaiBO filtration.
Paper tUtei-a are the most frequentlr used. For conrse work the <
gray or German white paper is used ; but for anal^-tic work a paper whu
IfiftTes but a small amount of ash is required ; the best now in the markel
is ScLlcicLer & Schiill's Noh. 597 and 589. The tilter should be taken of
Buch size that when folded it will be smaller thiui the funnel in which it ia
to nisL It is folded acmm one diameter, and again over the radium at
right angles to the firat diameter ; one of the four layers of paper, tLtn
seen at the circular poiiiou of the filter, is separoted fi-om the other three,
in such a way as to form a cone. The filler so formed is brought into the
no. 49.
rto. M.
funnel, nnd, wliilo held in position by a finger-nail over one of the iolds. is
wetted witli water from the wash-bottle. .Wter the pfti>er baa been brought
in ooutuct with the funnel by a gloMt rod, the hquid to lie tiltered ia intro-
duced, care being had not to overflow the filter, audio allow any superna-
tant liquid in the precipitating jar to pass through, before brin^nng tlie
preeipilatc itself ujioii the filter. Funnels used for filtering should have
an angle of GO", and a lung stem, the point of which is ground off at an
octite angle.
Asbestos and glass wool pings loosely introduced into the stem of a fun-
nel, are used in filtering such liquids as would destroy paper.
For filtratious whirh take pliice slowly the JiHer-jjuvip is now est
aively ufwtd It ih siniply an appliance for exhausting the air in the stem'
of the fumiel, and thus taking lulvantage of atmospheric pressure. A sim-
ple and cftWtive form of pump is that shown in Fig. 4i), in which the
water (und^^r 10 feet or more of pressure) entere at a and ospImteH the air
hova b through c. Wlieu the pump is used a small cone of platinum
lahohatort TEcmnoa
863
foil must' be placet^ at the apex of the fiinnol to BUpport the point of the
filter, which would otherwise be nij>tui-ed.
'Wbeu the prccipitnto haa been collected npon the filter, it must bo
vxished until free from extraneous niatUr. Tliis la Hftertml bv bltm-in^ into
the tube a of tlie waah-bottle, Fig. 50, while the end of the tutw b is held bo
as to deliver a genile stream into the filter ; core being had tliat tlie precipi-
tate is not lost by spurting, overflowing, or creeping up the sides of the
funnel. The conipletenetta of the washing is not to be ffiu'sgivi at but in to
be judged by adding reagents, suiUble to the case, to portions of the £!•
trate until they foil to cauHC a cloudiness.
EVAPORATION— DRyiNG-IGNrnON.
EvAPonATioss are usually condnctfKl on the sand- or water-bflth. Thd
Kantl-l>ath is simply a flat, iron vesRel, filleil with wind and heated. By ita
use the heat iu more evenly distributed Uiao ^vith the naked flutne.
The water-bath, usually of the form tihown at a Fig. 51, is used where Uie
temperature is to be kept below IfKl* ('212" F.). It should alumj^ be naed
in evaporating liquids containing organic matter, and care should be had
that it doeB nut become dry.
)
FiihOL
In cases where it is deeired to boil an oqucons ]iqiii<I in a ghisa or porre-
lain vessel ; this is supported on a pieoe of wire gauze and a Uunsen
burner or spirit lamp brought imder it (Fig. 52). A pie<!e of sbeet-iron
may bo siilistiiut«d for tlie wire gauze, with flat-bottoued veffiela. The
oaiaide of the heate<l vessel must be dr>j.
In beating Uquids in tcst-tulies, the mouth of tkf- tiihe mugt be Md atmy
from the permn. It is best held by a piece of thick paper l>ent around the
upper end of the tube (Fig. 53). The tube should be heated uear, not at
ite bottom.
In no case should flame, or the aand of the Bond-bath, come id contact
with a glass vessel almve the level of the lic|uid within.
Dbyiko is always necossat^- as a prehrainary to weighing, whether the
364
KAMUAL or COEUiarUT.
8iib«Unco is bvfTroMopic or not It is usaaDj effected in water orem
(Fig. r>4), if a teinpemtiire of 100' (212° F.) be sufficient ; or in uir orena,
•mnewhAt similarly conatructed, if a. hifirher temperature be deeired. As &
BobataDce can never be accurately weifj;hed while it is warm, it is removHl
from the oren and placed in the desiccator (I'ig. 55), over H,SU, or CaQy
until it has cooled.
-'^ft
tw. ii.
Fra (Ui
In cases where tlie anhatance wonld be injured by elevation of t^m-
peruture, it ia dried by allowing it to ivuxoin in the deaiccator until it ceaaea
to loee weight
loxmoN has for its object the remoTnl of ot^^anio matt«r by buroing,
and is conducted iu platiuum or porcelain rruciblee. If a filter and pre-
cipitate are to be ignited, tbcy are first well dried "oa much as possible uf
the prc-cipitate is detached and brought into the crucible, placed upon a
Fio- M.
Fl«.66.
nheet of white jMijwr ; the filter, with nrlKerent preripitate, ia then rolled
into H tUiu cone, ax\)und which a piece of platinum wire ia wound ; by
moans of the platinuiu wire the filter is held in the flame and burnt : the
remaina of thfi fiUor are then added to the contents of the crucible, which
ia sup^rted iu the position shon-n in Fig. oG, in which it is heated, at first
LABORATORY TIEOI
365
moderately, and the heat p-ndually increased to bright redness, at which
it is mAintained until no carbon remainB. iiefoi-e weighing, the crucible is
to be cooled in the desiccator.
In igniting it mnst not be forgotten tliat uiiuerol substanceB may be
modificci or lost. Carlwu at bifih l^mperaturo dcoxidizt.'S easily reducible
subHtances ; alkaline chlorides are partly volAtiti?»Nl ; mineral bases com-
bined with organic acida are converted into carlxjnatcs. In every instance
only that aniuuut of heat which is required is to be appIietL In some
oaaee it is well to accelerate the oxidation by the addition of ammonium
nitrate.
WEIGHING.
The balance. Fig. 57, should always he kept in a glass case, containing
a vessel with CaCl,, and in a situation pi-otected from the fumes of the lab-
oratory. The weightii shoulil be kept iu a box by or in the balance case,
which is to be closed when not in use.
\
rz
^-<%^
^
Fio- B7.
In weighing obserre the followinjj mlfia:
(1.) See that the balance is in adjoBlinent before using, especially if
more than one person tise it^ (2.) ,\Jway3 put the substance to be weighed
in the same pan. usually the left hand one, and the weights in the other.
{3.) Never bring any chemical in contact with Urn pans, but have a pair of
large M-ntch- glasses of etgujd wci^'ht^ one in either pan. Pieces of paper will
not serve the purpose. (4.) Never add to or remove from cither pen a
weight of more tlian 0.5 gram without putting the Iwlance out of action.
(5.) Never weigh any thing warm. (G.) In weighing a substance whicli has
been dried do not consider the weight correct until two snccesaive weigh-
ings, with an interrening drying of a half hour, give identical results. (7.)
see
MANPAL OF CUEMISTBr.
In adding' the weigbts, do so in regular order from above downward. (8.)
In counting the weights, reckon the amount first hy the empty holes in the
box, and then tolly u repLadng the weights (9.) Substances liable to ak-
6orb uoiature {rom the air are to be weighed in closed ves&ela. Thug,
h'to. M.
when a filter and its adherents preoipitnte are to be weighed toother, they
must \ie placed tjetween the two watch- glasses (Fig. 5H) rw soon as tojcen
from the drying<oven ; one of the watch-glaasee being oaed to support the
filter in the oren.
ItEASUIUNG— VOLL^METRIC ANALYSIS.
The principle upon which volumetric anal}-st3 is based ia that by deter-
mining the Toiume of a solution nf known strength, required tn accuratelv
neutralize another solution of luikuonn strength, the amount of active sub-
stance in the hitter may ho calculated.
If, for esaraple, we have a solution of silver nitrate wliich contains 170
gramti to the litre, and we find thnt 12 c.c. of this solution preripitate all
the chlorine from 10 c c. of a ttolution of XaCl, it follows thnt the NaCl so:
lution contains 70.2U grams of that substance per Utre, because :
NO^g
170
NaCl
fiSJt
= NO.Na
Aga
and therefor each c.c. of tlic NO,Ag solution will accurately precipitate
0.058r> fprm. NaCl ; but as it has requlretl 12 c.o. of the NO,Ag solutitm to
neutralize 10 c.c. of the NaCl solution, the latter contains 0.0585 x 12 =
0.702 grm. NaCl or 1,000 coiiUiin 0.702 x 100 =: 70.20 Krum. NnCl
It is obvious, therefor, that the value of voluioetrio methods depends,
among other things, greatly upon the accurary of the etandard sotutioits,
as the solutions of knon-n strength are called, and
upon tlie RtT-uracv of the measurements of volume.
A standard solution containing in a Utrc of liquid
a number of grams of the active substance, equal
to its molecular weight, is a normal solution ; one
containiug -^ ihnt EUrount is a deciuomml sUiUinn.
An irttlicatur is a substance which, by some char-
acteristic reaction {end reaction), which will occur
only when the substance to be determined has been
completely removed, indicates the point when a
proper volume of the standard solution has been
added.
The apparatus required for volumetric aualysie
consists of:
(1.) A Wre-Ha^k (Fig. 69) ; a flask of mch size
that, when filler! to the mark on the neck, at the temperature for which
it has been graduated, it ooutaius exactly 1,000 cc. of water.
I
no. eu
)BT TBCHM03,
307
(2.) A burette, wUicU is a glass tube gniduated into cubic centimetres,
and baviug a Blopcofk or piucljctn^k at its lowor extremity.
(3.) A senea of pipetie* (Fig. 6U), which are glosa tubes, having bulba
FiaOO,
blown upon them of such size that when they are fiUecl to a mark on tho
lube above th6 bnlb, thej contain a given number of cubic centimetres.
(4.) SiuiJl beakers ; etirring roda ; bottlea for standard solutions.
In making a attuidanl Bolution Uic object to be attained is to have a
solution, ouc litre of which shall contain n known quantity
of the active materinl If then in tho formula for the uor-
mol solution of olver nitrate :
Silver nitrate 170 graros.
Difliilled water 1,000 c.c.
we weigh out the NO,Ag on the one hand, and meaaiu^
the H,0 on the other, and mix the two, we will have, not
what is desired, a Holutiou ouuiainitig 170 grmu. NO,Ag in
1,000 C.C. H,0, but a solution of 170 grms. NO.Ag in 1,000
+ r C.C. H,0, in which x — the volume occupied by the
NO.Ag. Therefor, in making standard aolutiona, weigh
out the active subatouces; introduce them into the htre-
flask; and then HU that to the mark with U^O. Too much
caution cannot be used in having pure chcmicAls and mak-
ing accurate weighings in preparing volumetric solutiona ;
iudet^l the great disadvauti^^e of tho use of these methods
by physicians is that the solutions which they use are care-
lessly prepared and. consequently, tlie time which they spend
in obtaiuiug inaccurate, but seemingly accurate rcHultit is
worse than thrown away.
To use a vnluraetric solution it ia poured into the bu-
rette, whose stopcock has been closed, until above the o
mark ; the stopcock is then slightly opened so as to exjwl
all air from tho delivery tube. The float (Fig. 01) ia now
introduced from above, and touched with a glasa rod to
free it from adhering air-bubbles; and the solution allowed to flow out
from below until the mark on the float is opposite the o of the burette.
AH ia uow rciuly for use ; a given quantity of the solution to be analyzed
is measured into a pipette and placed in a bcokcr, a few drops of the indi-
cator fwlution are adJefl, and the standard solution allowed to flow in until
the end reaction is reached Tho reading of the burette is then taken and
tho calculation made.
Fio. U.
368 XANTTAL OF 0HKMI8TBT.
SCHEME FOR BETEBMENINO THE COMPOSITION OF CALCXJLL
1. Heat a portion on platmum foil :
a. It is entirely volatile 2
b, A residue remains 6
2. Moisten a portion with HNO, ; evaporate to dryness at low heat;
add NH.HO :
a. A red color ia produced ." 8
6. No red color is produced 4
3. Treat a portion with KHO, without heating :
a. An ammoniacal odor ia observed Ammonium urate.
b. No ammoniacal odor Uric acid.
i. a. The HNO, solution becomes yellow when evaporated ; the
yellow residue becomes redilish-yellow on addition of
KHO, and, on heating with KHO, violet red. .Xanthin.
b. The HNO, solution becomes dark brown on evapora-
tion Cyetin.
5. Moisten a portion with HNO ; evaporate to dnmess at low heat ;
add NH.HO :
a. A red color is produced 6
b. No red color is produced 9
G. Heat before the blow-pipe on platinum foil :
a. Fuses 7
b. Does not fuse 8
7. Bring into blue flame on platinum wire :
a. Colors flame yellow Sodium, urate.
b. Colors flame violet Potassium urcUe.
3. The residue from 6 :
a. Dissolves in dil. HCl with effervescence ; the solution forms -
a white ppt. with ammonium oxalate .... Calcium urate.
h. Dissolves with shght effervescence in dil. H^SO, ; the solu-
tion, neutralized with NH,HO, gives a white ppt with
HNa,PO^ Magnesium urate.
9. Heat before the blow-pipe on platinum foil :
a. It fuses Ammoniomagneeian phoapkater.
b. It does not fuse 10
10. The residue from 9, when moistened with H,0, is :
a. Alkaline 11
6. Not alkaline Tricaldc phosphate.
11. The original substance dissolves in HCl ;
a. With effervescence Calcium carbonate.
b. "Without effervescence Calcium oxalate.
Note. — A fresh portion of the powdered calculus is to be taken for each
operation except where otherwise stated.
ANAXTTICAL 8CHEMK.
M9
SCHEME FOR DKTERMINmG THE COMPOSITION OF AK IN-
ORGANIC COMPOUND. SOLUBLE IN WATEiC Oil ES ACIDa
Dbteugkatioit or BABBa.
1. Acidulate witli HCl :
a. No ppt is formed , ,,.. 5
b. A white ppt ia formed ,, 2
2. Add HCl drop by drop to complete precipitation, ooUect on filter,
wash: *
a nitrate 6
b. Precipitate 8
a Trent ppt on filter with boiling H,0. test filtrate witb H,S :
a. BJy produces a black or brown color Lead.
b. H,S does not cause darkening 4
4. Treat ppt on filter with NH.HO :
a. Ppt turnii graj or black Mercurt/ioua).
b. Filtrate gives white ppt. witb HNO, Siiver,
&. Faa» H,S Uirough dear, aoi J liquid :
«. No ppt is formed i 18
b. A ppt is formed 6
6. Treat with H,S, with occasional warming, to complete lurecipit&tion ;
collect ppt on filter ; wash with H,0 ooutaining trace of H^:
a. Filtrate IB
6. I*recipitftte 7
7. Treat a portion of ppt with NH.HS, warmed in test-tobe :
a. Ppt is diifuolred 8
b. A reeiduc remains ondissolved 13
8. Dry the remainder of ppt from C, mix it with eqnnl partn of Na^CO,
and NaNO,, and throw mixture iu small iKirttons into red-hot porcelain
crucible ; when cold dissolve residue iu H,0 ; filter:
a. Filtrate 9
b. lleeidao 10
9. Add to the filtrate NH.HO.MgSO. and NH.Cl. and rub inside of
(iBfc-tnbe with glsAs rod :
0. A white, crystalline ppt forma immedialely or lifter a
time Afmnie.
b. No ppt fomu AbamceofAa.
10. The residue ia :
a. White 11
b. Brown or black 12
11. Heat a portion of the residae in a pUtinum capsule with HCl,
place a small piece of Zn in liquid :
a. The plntimuu surface turns black Antim<my.
b. The UCl liquid, removed by decautation, gives a white ppt
with exceaa of HgOl, sol Tin,
$10
UANtJAl. OF CHEMrSTBT.
12. Tlie original Bolution :
a. Givea a brown ppt Trith FeSO, sol Gofff.
b. Does not give a browu ppt- ^>itU FeSO, sol, but gives a
yellow ppl, with KCl 6ol Platinum.
13. Vfaah nndiaaolred residue imd boil with diL HKO, in poroelain
capsnle, 6Iter:
a. Filtrate... li
& lioaiduo (if any) 17
14. Add diL H^BO, to a portion of filtrate, warm, and let stand eome
kazne:
a. A [ipt. forma Mix whole of filtrate witli H,SO, diL, CTflp.
over water-bath, extract residue with U,0, filter, and
treat tiltraie au»niing to 16 ....Lead,
b. No ppt. (onoB 16
15. Add NH,HO to remainder of filtrate (or to filtrate from U a) :
a. A ppt is formed. Filter and teat filtrate acconling to
16 Bunnufh.
b. No ppt is formed 16
16. Add 80, and CNSK to the liquid, evaporate, diasolve leaidoe in
H,0, add H,S to sohition :
0. The Holution 15 b. waa bine Copper.
b. The treatmout 16 produced a yellow ppt Cadmium.
17. Is blacl, disaolves iu aqua regia, and the solution gives a gray
ppt with SuCl f Jtfercrury(Kr).
18. Boil portion of liquid to cxjwl H,S. add a few drops HNO,, boil,
odd NH.HO ]u8t to alkaline rea^ition, add NH.HS :
a. Neither NH,HO nor NH HS caused ppt 31
6. NH.HS caused ppt, NH^O did not 20
c NH.HO caueed ppt 19
19. The original liquid is :
0. Neutral , 20
b. Alkaline or acid 28
20. Add to remainder of liquid 5 a. or 6 a. NH.Cl, NH.HO jual to alkiu
lino reaction, and excess NH,HS, warm, filter, wash :
a. i'^iltrato 31
b. Deposit 21
2L The deposit is :
a. lATiite 22
b. Colored 25
22. Dissolve deposit in small quantity HCl^ boil, concentrate to small
bulk, add NaHO, boil some time :
0. A ppt fonns, which afterward dissolves 23
b. A ppt forms, which does uut redisaolve 24
23. Tlio solution 22- o. is divided into two parts :
a. Treated with & »tnaU quantity of H^S n'lvea a white ppt.^inc
b. Treated with HCl to acid reaction, and then with slight
cxcesa NH,HO, gives, when heated., a white ppt insol-
uble iu NH,C1 Aluminium.
24. Dilute, filter ; test filtrate for Zn and Al as in 23. Dissolve ppt
HOI, evaporate to small bulk, dilute, neutralize nearly with Na.CO^ at
BaCO^ mter, after staiuliug :
ANALTTICAL SCHKSTE.
371
& Filtrate, treated with H,SO, anj again filtered, gives boIu-
tiou which, when made alkaliue with NaHO, gives white
ppt with H,8 Zinc
b. Residue (if any), heated with Na.CO, in outer blow-pipe
fiaine, gives bead which is green when hot and bluish-
green and opaque when cold JUanganete.
25. The deposit ia :
a. Coraj)lot<;lv dissolved in dil HCl. 26
6^ Not dissolved in diL HCl 27
«a Boil
bcol, filter. Conoentnte, add exceea
cpel H,S, add HNO
NaHO sol., boil, filter from residue b.:
I a. Filtrate. Test for Zu and Al aa in 2a
I b. Divide residue into 3 ports :
I aa. Dissolved in HCl dil. gives red color with CXSK , . Tron,
I 66. Fused with CO,Na, and EClO, forms yellow masa,
I which foruia yellow sol, iu H^O Chromium.
I re. Treated as in 24 b. gives same results Mant/anese.
n
^Bn.
27, Filter, wash, examine filtrate according to 26. Heat portion of re-
ndue with borax on platinum wire in blow-pipe flame :
a. A transparent blue bead is obtaiued CobalL
b. A bead ia obtoinod, which ia yellow when hot, nearly color-
leas when cold NicM.
29. Treat filtrate as in 30. Examine remduo for Ni and Co aa in 27.
30. Boil to exjpel KS, divide into 2 parU ;
a. Add dit H^SO,. If a j>pt form, filter, wash, fuse ppt
2a Add to remainder of liquid 5 a. or 6 u., XH,C1, NH.HO just to alka
le reaction, and NH.U8, warm, filter:
a A residue remains , , . , 29
^K b. No residue remains 30
[ 30
b&.
.. -- »ri
with Na,0O,, wash, dissolve iu HCl, and test soL for
Ca, Bii, and Sr, according to 32.
Heat with HNO„ test small portion for Fe with CNSK,
add Fe^Cl^ evapornta, add H O.Na^CO, to near neu-
tralization, and BaCO, ; btir, let stand uutil liquid is
colorlesa Separate ppt. aa. from filtrate Mi. ;
00. Boil ppt with NoHO sol , filter ; test filtrate for Al \>3
23 h. and residue for Cr bv 26 bb.
Mix filtrate with few drops HCl. boil, odd NH.HO and
NH,HS. If a ppt. form, test for Mn and Zu, as iu
24. If DO ppt form, mix sol. with excess H,SO^, boil,
filter, odd excess NH.HO and (NHJ.C.O,, filter, add
HNa,PO, to filtrate, a white ppt Maynesiitnu
31. Add to a amoU portion of the Uquid NH.Cl, (NHJ,CO, and NH,
HO, warm :
0. A ppt forms 82
b. No ppt forma , 3C
32. Treat the whole of liquid vritli NH.Cl, (NHJ.CO, and NH.HO as
in 81, ait«r :
a. Filtrate 36
6. I'recipitate 38
372
UAjnjAh or ciizinsTRT.
Sa Wuh, dioM^vB in Hmall quantify diL HCl, empoiato orer mter-
b&Lh. duisolTe in a Uttk H,0, &dd CaSO^ to a small portion of liquid :
a. A ppt. foruut «U
b. No ppt forms , 88
34. Add H.SiF. to anolLiftr porticMi of solution S3 :
a. A ppt is fonned. A portion of the ori^nnal solid colors
tJae llnnncn flnme green ftanum,
b. No ppt farmed. A portion of tbs original solid colnzs
tbe Buuscn flamfi red Shwitium*
36. M» soother portio& of Hqud SSvith (NHJ,C,0^ a wfaitfl
ppt Cs/ctunu
36. Add UNft.PO, BoL to a small portion of liquid, mb inner rarfsco
of teat-tulw with gbuut roil :
a. A white, c^mtalline ppt Magnesivm,
b. No ppt 37
37. Evaporate, ignite, diaaolTs in small quantity H^O, divide solution
into two partw :
a. Forma )reUo«, crystalline ppt with PKH. ; colon flame vio-
let (observe through bine glass) PoUumniri.
b. Produces crrHtjdline ppt viUi poiaanom pyroantimonate ;
colors flame yellow Sodium.
38. Triturat* original Bubetanee with CaH,0, and H,0 ; it develops"
an odor of amtuouia. AmiHimium.
DKBafsuT»» or MnriKir. Aom.
After determination of bases, bear in mind what acids can poesiblj
form soluble Baits with the luisea fonnd (aee Table L, p. 3541, and limit the
search to those. Examine aepnrate portions of the original solution ac-
ooidiug to 1, 3, 4, a, 10> 12, and 13.
1. Add Ha :
a, Efferreacea 2
6. A gelatinous ppt. is formed SUicate.
2. Tbe gns given off in 1 a. has :
a. No odor, and forms a white ppt when passed throirgh
Ume-water Carbonate.
A. An odor of rotten eggs, and blaokfus paper moistened
with Pb(C,H,0,), Sulphide.
3. In testing for bases As was found ; add soL AgNO, and NH.HO :
a, A yellow ppt Arsenite.
h, A briok^red ppt Anenate.
4. Add Ba(NO,),, and, if aoid, add NH.HO to faint alkaline reaction:
a. No ppt. formed 8
b. A ppt. is formed 6
6. Add HNO, to aoid reaotion to a portion of 4 6. .■
a. The ppt does not rediaaolve completely ; .61ter ; examine
filtrate by 6. Sulphate.
h. The ppt redissolves 6
ANALYTIOjLL SCIIXII&
378
6. Treat imotbcr portion of 4 6. or 5 a. with acetic aoid :
a It dissoWos completely Phonphaie,
b. It doea not disHolve completely T
7. Filter:
a. Filtrate (in absence of Ah) givee white ppt with NH.HO,
NH.a, uud MgSO Pfioyjjlmte,
h. Fpt. diaBolToa in diL HCl ; boI. gives ppL with ChCI, ia
neutral solution Oxalate.
8. Aciduliited with HNO, ; add eol AgKO. :
a. A ppt ia formed 9
6. No ppt ia formed 10
9. FiltCT ; trent ppt with HNO, :
0. It dissolves completely 10
b. It doea nut dissolve comi>l6tely 13
10. Tlie solid substftnce :
a Produces a yellow color with H,SO, Chlorate,
b. Doea not produce a yellow color with H,SO^ 11
11. Divide liquid 9 a. into 4 porta :
a. Gives white ppt with NH.HO, NH,C1, and M^r
SO, Photphate.
b. Acidnlated slightiy with HCI, turns turmeric paper
red Borate,
c Acidulate with HCl, c\'aporate to dryness, odd HCI, an
insoluble residue remains Silicate,
d, A portion of original substAnce, moisteaed with H^iiiiO,,
givea off gas which oorrodea glasa .Ftuoride.
VL The original liquid gives :
a. A blue color with a drop of chlorine water and starch
paste ffxltde,
h. A Wue ppt with soL FeSO, + re,(SO,), Cyanide,
c. Is oolorea yellow or brown by chlorine water, but doea
not react as in 12 a Bromide.
d. Ppt 8 0. ia readily soluble iu NH.HO Cbioride.
13. Heat the drv salt with Cu and H^O, and conduct the gas through
soL Fo,(SO J^ whicli it turns brown i^ifrote.
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^^^^^^H INDEX. ^^^^^H
ACKMAPnTnALKm, 3S4
Avid, clilorto, 10 ^^^^^H
AMtamlde, 309
chlorous, 58 ^^^^^|
Acetaiiiliilu, 315
oliolalio, 3 IS ^^^^H
cboleld, 215 ^^^H
Aoelona, £04
AoetODM. M3
efaulMtorio, 831 ^^^^M
Amtjrl, SOI
hT<lrat«. 193
obolic. 214, SliS ^^^H
^^^^^1
hVdriiie, Ml
chromic, 100 ^^^^^|
m^lbj-lidv, 301
ehrjsopluuiio, 835 ^^^^^|
Aoetj'lemj, 275
olnnunlo, 3H2 ^^^^M
AchroiJdaxtriD, 395
dtraoonic. 378 ^^^^^|
Aold. M>«ltc, 192
dttio, 377 ^^^H
I uoiiitio. 37S
coovolTuUuio, 839 ^^^^^|
1 Mrvlic, 224
or«srUa, SOS ^^^H
f wll'pio. 34*J
oroluiiic, 33S ^^^^^1
«]luttiir)c 2QR
cjknic, 328 ^^^^H
k wnldwuvtlc. 209
cvatiurlo, 2J)3 ^^^^^|
^K unidobutyrio, 213
d»o;Uo, 190 ^^^H
^H ualdooBproli', 212
dilpbiiiio. 105 ^^^H
^H ualdoproplouio, 211
dftoxjglQUnle, 34fl ^^^^H
^m amtdovalvHaiile, ai3
dextrotarUrtc, 870 ^^^H
^■^ ugtUo, 885
dlAlnrk. 30S ^^^H
< wK^aio, atta
dioliloneelio. 103 ^^H
^^ annhifi, 197
diohromio. 100 ^
^H araunlo, 88
dilactio, 34S
^H BrMnloaa, 88
dUaipbanilio. 814
^H stropic, 941 ^
dtsulpbario, 59
^H atule. 105
diurtkrio, 377
^H Bwlalc, 24a
ditbionia, 06 ^^^^m
^H b«n)o. 191
elkidio. 236 ^^^^1
^H b«DEoi«, fll2
errtltraKlucic, 276 ^^^^^^^^|
^H binnlitliic, vm
^H bbracic, 101
eth^- 1(1 i noetic, 304 ^^^^^^H
^M Iwriv, 101
ethylenolaotic, 344 ^^^^^|
^^1 bromio, 00
etbJLidQUvlocDo. 344 ^^^^H
^H bntjlAotio. 233
ethvlBnlfihurlo, 198 ^^^^H
^H butylfonnio, lOS
^^^H
^^B Imtrrio, 194
^^^^M
^^m oaohoutanntc, 830
gkdiDic, 270 ^^^^^|
^H aaffeio. XVt
gtlUc, 813 ^^^H
^H «ff«tannict 8M
galloUnnle, S80 ^^M
^H eunphlA. 281
glocio, 388 ^^^H
^^M oamphQlic, 291
glyceric, 3A4 ^^^^^|
^H oapric, 196
glyoerophoflphorio, 278 ^^^^^|
^^1 caproic, 190
glyooeholir, 214 ^^^^^|
^M Rftprj-tio. 19A
gljrcolamic. 300 ^H
^1 wrbMotic. SOa
glyoolio. 344 ^^
heptylio, 190 |
^1 Mrbolio. :)02
^H CM-bonio. 233, 335
hoxylic. 106 ^^^J
^H oerotlo, SOO
hlppnrfo, S13 ^^^^M
^^F obeoDchulio, 31')
^^^^H
P ohenotaarocholio, 810
1
hydrlDdio, 820 ^^^H
878
INBXZ.
Acid, hrdriodio, Ol
hjdrobromio, SO
hjdroohlorio, 07
hjdroojuilo, 836
hjdroferriojulio, 828
hjdroferroojsnio, 838
hfdroflaorio, 54
hjdroflaodllolo, 108
hjdrwalphnrio, 64
bydroBalphoroiu, 67
hjdurilio, 368
hjooholio, 216
bjoglyoooholio, 316
hjoUarooholio, 216
hypobromooa, 60
hypochloroai, S8
hypogftic, 368
hjponltrlo, 74
hjrpODftroos, 75
hjrpophosphoroiu, 88
hjrposalphoroiu, 67
indigosalphonic, S20
lodio, 63
iaethioDio, 281
IfletfaioDorio, 281
tsobutjlfonnia, 105
isobutjrrio, 195
iBopropyUiotitio, 105
isovftlerio. 100
iUoonio. 278
lactic, 244
hevotartario, 270
Unrio, 196
laurosteario, 106
leudo, 213. 383
liDoleic, 269
UtUic, 260
maleic, 265
malic, 265
malonic, 247
margario, 197
meconic, 830
tnelassic, 283
iDfllissio, 101
mellitio, 311
metaburic, 101
metantimonic. 08
mutantimonoua, 98
metaphosphoric, 83
motaraenic, 88
metaataiiiiic, 126
metatungstio, 104
methylcrotonio, 225
monochloraoetic, 193
morintannic, 330
muriatic, 57
myristio, 196
nicotic, 247
nitric, 76
nitrobydrochlorio, 57
uitromuriatio, 57
niirosonitric, 76
nitrous, 75
nonylio, 196
Nordhausen, 60
octylic, 106
Aoid, <BnuitbjUo, 196
olelo, 326
orthoantimonie, 08
orthoanenio, 88
orthoborio, 101
orthopboniboria, 88
onnio, 104
oxalic, 246
ozalurio, 268
oxybubitnrio, 268
ozjbenzoio, 813
oxyphenio, 207, 807
oxyvalerio, 333
palmitic. 106
parabuio, 263
paralactio, 244
parieUo, 825
pelargontc. 196
pentathionio, 67
perbromic, 60
perofatorio. 50
periodic, 63
pbenic, 803
phenylBalpbDroua, 398
phlorylic, 297
phocenic, 105
pfaoepbomolybdio, 104, 381
phOBpborio. 88
phoBphoront, 88 ■
phoBpbotun^ic, 104
pbthalic, 811
picric, 306
pimulic, 246
piperic, 843
pivalio, 106
plumbic, 119
pnenmio, 231
prebnitic, 311
propionic, 104
propylacetic, 195
protocatechuio, 880
pmssic, 326
pyroaiitimonio, 08
pyroarsenio, 88
pyrobismuthic, 128
pyroborio, 101
pyrogaUic, 808
pyroligneoua, 102
pyrophoBphoric, 83
pyrosulpliuric, 60
pyrotarUrio, 277
pyroterebio. 234
pyruTic, 277
quercitannio, 8S0
quinio, 837
qainotannic, 330
quinoratic, 329
quinovic, 829
racemiu, 276
rheic, 325
rocellic. 246
rosolic, 303. 300
salicrlons, 810
salicylic. 313
santonio. 829
sarcolaotio, 344
Aoid, wlwoio, 340
silieutunKStlc, IM
8tvuic« 107
Batwrlo, 24fl. S69
iDcoiolc, £48
Kulpliauilio, A14
8al)>hocTsoio, 828
iiulphiiidiKOtiu, ft20
■ulphiu<ljri)c, H'JO
Biilphixtluoio, 3Utl
iulphoviiiio. 108
■alpburio, 67
BulphuroQi, M
aulplivdrio, M
Ixiinic. %{0
Urlarii}. 27B
tirtralio. 277
Uurooarliamlo, 231
liarocboUo, SI A
U'replilhalin, Dll
totrathionlc. 67
lr[olilt>racoUc, 193
Itichrotaic, lUB
trim»Uilio, 811
irimetlirlROvtia. 106
tritiitropWnic, 3ttJ, 300
ththioiilo, U7
trouto, 341
nlnfc. 888
nricMO
uroos, Sl9
Tftlerianio, 1B5
raniUia. 311
TcratrfD, 311
viol uric. 203
AotJH. IM
Aintdo, 300
jm>mati<), 311
liilinry, 214
dlUooiic k.aH dihMfe, 246
ditUumIc mad mouobiuio. 2S2
tMy, 191
mtuvntl. 57 •
mouoboAlfi, 191
Tklerlknlo, IftS
Acolyotuie. 34S
A<H>nine, 342
Acoiiiiina. 343
Aeridfoe, 997
Acrulwia, 224
Afitlon oD the «oonoair
of WMttO ftotd, IM
of aoooUlu«, 843
or nlouhol, 18.1
of ommoQlB. 146
of kiilimoiij, 100
of ar«eulc, 69
of Atropine, 341
of bBriam. 153
of IliMDtllh, 124
of carbolic acid, 303
o' cmrbuii dioxiilx, 241
of carbon dltuivbidv, 848
of trsrlKm inaiionidt, 238
of olilonl. SOe
Aotlon of ehlorofona, ITS
of ohromlam oompoundi, 107
of ooppAT, 161
of other, 191
of hvdroojuiia icld, 327
of )ij-<lrag«n aalphide, OH
of iodine, 60
of lead, 121
of mflpcurr, 167
of ininorol icidg, S8
of nitrogen monoxide, 78
of nitrogen t«troxid9, 7&
of opium, etc., 837
of ozAlio acid. 247
of plienol. 31)3
of phoiphoric acida, 84
of phoBphonu, 79
of potaaaium, 143
of liWer, 144
of flodtum, 143
of Btryt'liuine, 340
ot aulphuric acid, 60
of lino, 1&6
Addition. 172, £31, 228
Adi|NK>i'ri9, 346
Aft«r-diunp, 173
Air, 71
ammonia In, 71
raiban dioxide in, 71, 886
confined, 238
■oltds in, ?i
water in, 71
Alanine, 311
Albane. 280
Albumiu. acid, 3S1
allcali. 301
coiu; iilaled, 353
egg. 347
in urine. 848
wnim, 348
Vf«titable, 340
Albnm{nat«», 301
Albamfnoids, 340. 847
AlbomlnoM. 301
Alcoliol, 178. 181
abaoLuto, 188
sllvlio, 223
am'vlic. 187
beniolo. son, 300
btiutvlio, 300, 300
butyi, 187
camph/l. 281
cprvllo, 188
cet.vllc. 188
choli.'«l'-rlo, 321
cinoamlo, 821
elbytune, 230
ellijllo. 181
menlhrlio, 281
ni«thyilo, 180
proprlio. 187
vlnic. 181
Alooliulio IwvcragMi 184
radicalii. 179
Alooliols I78
amrllc, 180
380
INDXX.
Alooholfl, vonuiio, SOS, $»
bntjiio, 187
diMomio, 178, 220
monoatomlo, 177
primar;, 178
•eoondary, 170
tertiary, 179
tetnitomio. 270
trUtomio, 264
Aldehyde, 201
AceUo, 201
aorylio, 224
ftUylio, 224
beotoio, 810
bntyrio, 200
campholio, 180
ctproic, 200
caprylic. 200
arotonic, 226
iMbutyrio, 200
aBQaatLylia, 200
palmitic, '^00
propionic, 200
Ralioylic, 310
valeriauic, 200
Aldehydes, 200, 810
Aldol. 22S
Ale, 185
Algaroth. powder of, 99
Alixarin, 825
Alkaline metala, 129
Alkaloids, 205, 381
cadaT»ric, 344
cinchona, 337
detection of, 333
fixed, 334
opium, 334
■trvcIinoB, 389
Toiatile, 883
Alkarsin, 221
AlUntoin, 263
AUotropy, 31
Alloxan, 203
AUuxantine, 263
AUyl. 222
hydrate, 222
oxide, 223
snlphide, 223
salpbocyanate, 328
Aliylene, 275
Allylic series, 221
Alphenols, 310
Alnmina, 115
Alnminates, 115
Alaminium, 114
chloride. 115
hydrate. 115
oxide, 115
Baits, 115
Bilicates, 116
sulphate, 115
Alums, 116
Amanitine, 207
Amides, 208. 260
Amido aoids, 209
benzol, 818
Amines, 306, 249
Ammelide, 252
Ammonia, 72
Ammonias, compoand, 206
Ammoninm, 144
acetate, 146
bromide, 145
carbonates, 146
chloride, 146
oompoands, 144
hydrate, 144
Iodide, 146
nitrate, 146
pnrpnrate, 268
MltB of, 145
salphates, 145
snlphides, 145
salpbydrate, 145
tluK>ry, 144
nrat*4, 260
Amorphinp, 27
Amphoteric elements, 105
Amygdalin, 829
Amyl nitrate, 190
nitrite, 199
Amylene, 220
Amyloid, 853
Amyloses, 283, 291
Amylum, 291
Analysts, 8, 44, 860
Analytical oharacterH of alkahrida, 881
of acetates, 193
of aconitine, 342
of albumin, 348
of albuminoids, 346
of alcohol, 183
of aluminium, 116
of ammonium, 146
of aniline, 314
of antimony, 101
of arsenic, S2
of atropine, 841
of barium, 162
of bismuth, 124
of bromides, 63
of brucine, 840
of cadmium, 157
of calcium, 151
of carbolic acid. 8C3
of chlorides, 62
of chloroform, 175
of cholesterin, 331
of chromium, 107
of cobalt, 158
of codeine, 336
of coniine, 333
of copper, 160
of cyanides, 327
of glucose, 385
of gold, 104
of hydrocyanic acid, 887
of hydrogen, 40
of hydrogen dioxide, 62
of iodides, 62
of iron, 118
of lead, 121
^^^^^ INDEX.
881
^1 Anal^^ical char:xt«n of Ifloeln, BU
Anthracite. 103
^
■ of lithinm, 121)
Anthra()uinone, 895
^^^^^M
^H of ina^niiiiD, 154
Antlfebriuo, 316
^^^^^1
^H of manguieM, 106
Antlmooy, 97
^^^^H
^V of taeeonlc iicfd, 889
aRllmnnit«, 08
^^^^^H
^H of Diomury, lOrt
h\a>.')i, 89
^^^^^1
^^^^B of raorpliine. 330
• buttwr of, 98
I^^^^H
^^^^H of uarcuiiirt, I)^
viiinabnr, 99
^^^^^H
^^^V of narcotinv, 330
ofociu of, 97
^^^^^1
^F of nickel, IR7
erodo, 87
^^^^^1
^H nf nicotine, 334
■Ian of, 99
iiitnnumltato oxide, 96
^^^^^1
^1 of nitrmtM, 77
^^^^H
^H of nitrous fntnei, 70
liver of. 99
^^^^^H
^H of ouliiUift, 24tf
penlachloridv, 99
^^^^H
^H of oxvgva. 43
pentasiilphidv, 90
^^^^H
^H of ozotio, 41)
pratoxide, 98
^^^^^H
^1 of phenol. 8(t:)
protoohlorido, OS
^^^^H
^H of phosplialtfn, 83
triohlorid«, 96
^^^^^1
^H of phosphorus, HO
trioxide, 87
^^^^^H
^H of picric ftcid, 306
trisalphide, 09
^^^^1
^H of potusium^ 142
Antlmonyl, 97
^^^^^H
^^ of quinine, H38
AQtfpjrrine, 810
^^^^^H
^^^ ofsitrer. 143
Anliwptics, 847
^^^^H
^^^^H of Mcliiim, VXi
Apomnrphine, 887
^^^^^1
^^^^■^ of etrrcbnin^, II39
Apoqnlnine. 888
^^^^H
^^T of et)lplial«a, C9
Aqua ammonitD, 144
^^^^^H
^H of sulpbideH, Qli
chlori, 56
^^^^^1
^M of sulphites, 66
fortis, 76
^^^^H
^1 oriheb:iine, 830
peffla, 07, 70
^^^^^H
^M at tin. 124
Arabln. 296
^^^^H
^m of tjroaina, 213
Argol, 189
^^^^H
^V of uric su-.id, 303
Aroniatio fierioo, 296
^^^^^M
^1 of zinc. 15Ct
Anunaniintf, 6S
^^^^^H
^M Analytical schema
Arspuia, 85
^^^^^M
^1 for acids. 37S
AnvDio. 84.80
^^^^^M
H for bases 860
aoids,88
^^^^^1
for csloiili. 368
disulpblde, 88
^^^^^1
Anliydrtdu, antinidnic, 9S
flour of, M
^^^^H
^^ antimonoiii, V7
oxides, 86
^^^^H
^1 arattnic, 87
penlaaulphide, 90
^^^^^1
^H antviiious, 80
ppntoxiiW, 87
^^^^^H
H borto, 101
sulphide*, 88
^^^^^1
H carbonic. 2SS
tribromide, 80
^^^^^H
^1 cbloroua, W
triohlorldtt. 60
^^^^^1
^H chroinio. 100
trii1iiiiri<l«, 80
^^^^^1
^H hjimchlnnms. SB
tHIodldu. 89
^^^^H
^M molybdio, 1U4
trloxide. 86
^^^^^H
^M nitric. 79
trisiilphide. 89
^^^^H
^H sitrons 74
white, 86
^^^^^H
^H pb(<<ip)iorio. 83
Araeniosl ereena, 00
Anttneii, 2iQ
^^^^^M
^H pho*^<horoiM, m
^^^^H
^H plnmljtu. 110
AKiods, 15
^^^^^H
H Btlldc. lOS
Atom. 13
^^^^^1
^V aulphtiritr, 67
AtutDic heat, 13
^^^^^1
^V nnlphnrous, M
tbeorv, 9
^^^^H
^P tiitiKstic, 1(14
VHiKht, 11,19
^^^^^H
^ Aiibvdridea, 4.'), 200
AtOTnlcily. 15
^^^^H
Anilirles, 314
Alrupinr-, 341
^^^^^H
^ Aniline. 313
Auric ctklorlclo, 105
^^^^^1
^B Itrnm-. 314
AoHn. 309
^^^^^^1
■ chlor-, 814
AnriplRmantain, 69
Aao-deriTBtlTos, 810
^^^^^1
B <);'«>• 31'''
^^^^^H
H iod-, 314
Axoto, 70
^^^^H
■ nltr-, 314
Axuliu. 303, 306
^^^^H
■ r«d. 315
^^^^^M
^1 AnthraMoa, 334
BAKiHo-rowDEns, 130
\
^
383
TSTDZX,
BalMms. 282
Bmriam. 151
carbonate, 153
chlorido. 162
componndfl. 152
hydrate. 1S2
nitrate, 162
oxides, 152
■alts, 162
sulphate, 162
Baryta, 162
Bases. 18
Basicity, 18, 283
BaSBoHn, 2L6
Beer, 185
Benyleiie, 275
Beniene, 297
amldo derivatives, 818
metadioxy, 807
nucleus, 209
nitro-derivatives, 818
orthodioxy, 807
pu^ioxy, 807
ring, 299
Benzine, 178
Bensol, 297
Benzoline, 173
Bensyl hydrate. 809
hydride, 810
Berberine, 842
Berylium. 114
Betalne, 211
Beverages, alcoholic, 184
BUe acids, 314
pigments, 355
Bilifuscin, 855
Biliprasln, 356
Bilirubin, 355
Biliverdin, 355
Binary compounds, 21
Bismuth, 132
hydrates. 133
nitrate, 123
oxides, 133
8alt«, 123
Bismuth, tricliloride, 122
Bismuthyl, 123
carbonate, 124
nitrate, 133
Biuret. 252
Bleachliig-powder, 147
Boiling-point, 7
Bone. 149
aab, 148
black, 103
phosphate, 148
Borax, 133
Borneene, 281
Bomeol, 281
Boron. 100
oxide. 101
Brandy, 186
Bromal, 183, 208
Brominw, 59
Bromoform. 176
Brucine, 340
Bntalanine, 313
Batter, 271
Bntterine, 272
Cacodtt^, 221
Cadaverine, 844
Cadmium, 157
Cnsiam, 142
Caffeine, 839
Calcium, 147
carbonate, 150
chloride, 147
hydrate, 147
monoxide, 147
oxalate, 160
phosphates, 148
salta. 148
sulphate, 148
uratMfl. 261
Caloali, 149, 160, 262, 268, 868
Calomel, 168
Camphene, 281
Campbol, 281
Camphor, 280
Borneo, 281
Japan, 280
laurel, 280
monobromo, 281
Camphors, 280
Caoucbene, 279
Caoutchonc. 279
Carbamide, 251
Carbimide, 250
Carbinol, 180
Carbohydrates, 283
Carbon, 101
compounds of, 168
dichloride, 176, 229
dioxide. 235
disiilphide. 243
monoxide. 233
ozysulphide, 243
tetrabromide, 176
tetrachloride. 176
trichloride, 176
Carbonyl chloride, 283
Carnine, 219
Casein, gluten, 851
milk. 849
sernm. 349, 360
Cellulin, 295
Celluloid, 296
Celluloae, 295
Cerasin. 396
Cerebrin, 374
Ceruse, 120
Ceryl hydrate, 188
cerotate. 200
Cetaceum, 199
Cetene. 199
Cetine. 199
Cetyl hydrate, 188
palmitute, 199
Chalk. 150
Charcoal, 102
animal, 103
r
Chemtiiti'/, 1
Chliift w», 300
adiuilino. 818
CttlomL, 183, 301
aleuhoUts. 303
b;dnl«. 303
Cbloraniliutfft, 314
Chlortof, SS
ntonoxida. OB
p«Toxide, &6
iMlrtixida, 59
Irioxldc, W
ChlorocArbon, 170
Cliloroform, 174
CholB«b.Tlii. 321
Cbvllni-. 307, 373. 344
OhMiiilriii, aV?
Cbromlam. 1(>0
otiloridf*. 100
oxl(lv«. 106
iulpli»l««. lOO
ChrTMOi, 835
CiouUne. 883
Cid«r, IM
CinDboiiidine. 889
CinoboQln*. 33U
Cinnsbar, 11)3
Clnnsmen*, 1)31
Ciaiiain>l. 331
ClusiflGittOQ. 34
CUr, IKI
(^DJtgaUt«d albnmttut 853
Couolatiun, 845
ComT, 103
CobalL, 1A7
Cocaine. 843 •
Codeine. 336
Coh«, 103
Cutcbioine, 841
CoUueD. 8S3
Oallidliie, 317. 918
Collodion. 390
ColloidB, 33
Colophony, 3^
Combustion, 41
Cotnpmition. 1.38
Cotnponnda, 8
Conglntin. 851
Coubvilrirx-, »33
Cotiii'iiie, 3>'I3
Ccmiferln. 811
OonfltM*. 338
GoniitlliiUon. 38, |70
ConrolYiiHn, 8Sfl
Copper. 158
ooetatvi, 160
«r9i>nite, 11K>
o«rt>un»tea, 160
eblorides, iriO
bvdrfttes, inO
nilntte, ISO
oxide^ IS8
Mlto.l(»
Knlphme. in
Fiilplii'los. 100
OoraUin, W&, 90»
Coridliw, 817
CoiTodrvs, 66
CorrostT« nibllmfttei 164
ConuoUoe, 174
CroMol, 309
CreaMW, 808
Cmatiue, 318
OrcBtlnin*. 319
Cmol. 308
Creaylol, 300, 308
CriKUllio, 313
CWth. 87
<VotoD eblonU, 329
(>olo[i?l«nii. 370
Crjptidine. 8IB
Cryptol/ris, 188, 858
Cryptolytos, IBS. 808
CrysUllliftUoo, 37
CryMalloids. 32
Oitm*n«. 800
Cutnul. 800
CaprJc chloride, ISO
oiide. 154
Ditnte, 159
»u!pba(e, 159
•alpbidff. 159
Cuprous cbluride, 150
oxide. IM
tiilpbide, 150
Curtrlne. IM^J
Cjttno^nn, :i20
bydnU, 338
brdride, 890
Crmene, 381, 800
C/mol, 800
Datthtke, 841
DecftoUtioa. 361
T>eIiqiicMToiicc, 4S
DeoUorii«r», 347
Dt^oxidatiou, 39
DextrlD. 178, 908, 804, MQ
Dextrojiyroiu, 80
l>0Xtr<w«. 388
PiiUlvl. 333
Dlftljsis, 8S
DlMofdai^ 860
DIaiiilnMi, 349
Uiainotid, lUl
Dluuue. 181,283, 3«)4
Diiuto-deriveMres. 310
Dlbromometbyl bromlda, 176
Di<.'1itur4)iD?th«n«, 174
Dichlorm^tby) ubloHde, 174
DicYBno(|!en, 320
nifhiRion. 33. 39
Digitalutn. 330
DIgtUlin. 339
Digttoriin, 339
Diffitoxin, 320
Piiu<loin(!tbyl iodide, 178
DiinetbyUmlne, 206
Dimethyl ursine, 331
Diini-tfarl benz<^ne, 300
niiiK^ihvIiH. 2Uil
trimorpbisiQ, 33
884
THDBZ.
Dioxindol, 830
DieinfectantB, 347
Disocrrl, 226
DtTisibilitT. 7
Drying, 868
Hutch liquid, 229
Dynamite, 267
DjBljBio, 216
Ebonitb, 280
Ecboline, 841
Effloreaoenoe, 45
Elastin, SOU
Elayl, 228
Eleoptene, 280
Electrolysis, 16
Electro-negative, 17
Electro- poHitire, 17
Elements. 8, 12
acidulouB, 54
amphoteric, 105
basyloiis, 129
typical, 37
Elatriation, ISO
Emetine. 343
Emodin, 825
Emulsin. 329
EmulsioD, 368
Eosin, 809
Etiu&tionB, 15
Equivalence, 16
Equivalents, 9
Ergotine, 341
Ervthrine, 276
Ervthrite, 276
Erythrodextrin, 295
Eserine. 'M'S
EssoiicH of bitter almonds, 310
of (tarlic, 223
of mirbane, 313
of mustard, 223
EsRoiices, 279
Ethal, 188, 200
Etlieiie, 228. 275
chlorhvdrate, 230
clilorliydrin, 230
chloride, 229
glycol, 230
oxide, 230
Ether, 189
acetic. 199
allvlic, 223
ethvlic, 189
hydrobromio, 177
hydrochloric, 177
hvdriodic, 177
m'etliylic, 189
murifttic, 177
nitric, 198
nitrous. 198
petroleum, 173
pvroacetic, 204
sulphuric, 189, 198
Etherilication, 189
Etherine, 199
Etherol, 199
Ethen. 188
oompoimd, 107
haloid, 174
mixed, 180
simple, 188
Ethyl aceUte, 199
bromide, 177
oarbiQol, 187
chloride, 177
hydrate, 181
iodide, 177
Ditfate, 198
nitrite, 198
oxide, 189
sulphates, 198, 199
sulphide, 230
salphydrate, 220
Ethylene, 228
alcohol 230
bichloride, 330
glycol. 230
hydrate, 280
oxide. 230
Etidine, 818
Eucalyptene, 281
Eacalyptol, 281
Evaporation, 368
Patb, 267. 270
phoBphorized, 278
Fermentation, 182
Ferments, animal, 858
Ferric acetates, 112
bromide, 111
chloride. 111
citrate, 113
ferrocranide, 118
hydratea, 110
iodide. 111
nitrates, 111
oxide. 110
phosphate, 112
pyropliDsphate, 113
Bulphates, 111
sulphides. 110
tartrate, 113
Ferrous acetate. 112
bromide, 111
carbonate, 112
chloride. 110
ferricvanide, 113
hvdrate, 110
i<^ide, HI
lactate, 113
nitrate, 110
oxalate, 113
oxide, 109
phosphate, 113
sulphate, 111
sulphide, 110
tartrate, 113
Fibrin, 353
Fibrinogen. 349
Fibrinoplastic matter, 8^
Filtration, 50. 361
Fire-damp, 173
^^f ^ INDKV.
^^^^J
1
Fluids. R
0am, British. 303
^H
cuinpressiblo, fl
Gum iT«ins, 3K3
^^H
iooomprMslble. •!
Gums, 3lK)
^^^M
FIUOTODA, iCM
Ouu-«»ttAn, 295
^^^H
Fluor«M«ae«, 807, 800
Outia, 3H0
^^^H
Fluorine. M
GutU pf rcha, 380
^^H
Fluri«l«, S80
G.rpsuu, IM
^^^1
Foudt, vogeubls, 293
^^H
FormulK 10. iSS
^^^H
«iD[Jrioal, 23
Hamattw, fl-VS
^^^1
^H geosral. 169
Uiemaloci-jiiUlliii. 8M
^^H
^^B gmpliio, 23
H-vmiii. Via
^^^1
^T of constitution, SA
HvuiOchroraogvB, 850
^^^^
l/iifral. S-l
Tlarmiiilohin, ^54
^^^M
Fonov] broiaUle. 171]
HKli-id salts. 19
^^^M
chloride, 17-1
llatn^oiM, M
^^H
Iodide. 17*3
llesU. atomic, 14
^^^M
Puclidine, J15
lattmt, 7
^^^H
Kunetimis. 171
siwctflc, 33
^^^1
Fiuk-l <.il. 187
Heinialbnmin, 'iiti
^^^H
Foiiiiff-point, 7
lluiiiiliedral, :)0
Hiitiii)>rnU>in, M(\
^H
^H Oadimm, 370
Upaologoaaseiiea, 169
^^H
^^V Oftdinine, 345
H^druids, 18
^^^1
^^ Okdnin. 370
Jlydratts, 18. 4.'S
^^^1
Gftla<-t»9e, 2da
Hvdnuiii(«, :il7
^^^M
tiftleiio, lllK
Jlvdrolilimliinf 85(i
^^H
Oftllium, 117
Hydronrlionf, 172, 227
^^^1
Gasolinfl, ITS
finit Beri««, 1?3
^^^1
Gelatin, 353
second ti(-rii4, 32S
^^H
mgw of, 309
Ifaird e<^i««, 275
^^^1
OflUtinoids. S^fi, 853
fourlh sfiiett. 278
^^H
Gin. 187
Cftli series. 207 -
^^^H
GlnuWr'fl wit, 133
tixMi M-rifS. ;t2l
^^^^^H
Gtladiu. »^I
wvi^ulL Kri^. 323
^^^^^H
Giobiii, sr^r,
(•i^Uth seriiM, :t23
^^^^H
Globulin. 947
ninth series, ^4
^^^1
evrum. 1110
tenth Bc>rie«. 1)24
^^^H
GUnoYii. 2fl7
eleventh neriet, 834
^^H
Oluciuium. 114
libber s«ri«s, SSH
^^^1
GluGOMUi, 3K8
Mrivs of. 227
^^^H
GIneoM, itfi, 304
DOn-«atMr%t*«I, 238
^^^1
GliMWMi 383
Mtiinitcd, i;2
^^^1
GlneoridM. 383, 898
Hydrocollidioti, 818
^^H
DiTcwrides. 2«9
Hjr^toi^^n, 37
^^^1
Olvifrin. 364
ftntlnonld«, 77
^^^H
etben of, 390
arsenides, 85
^^^1
OlvHn, 3(W
lirumiJv, T)9
^^^1
GiVoocol, 000
chlorldtt. 57
^^^1
GlyooovlK, SOO
oviutidv, 32ft
^^H
GlTcoj{«n. 304
dloxid«, S3
^^^1
OIjopI. 230
fluorid>^>, 54
^^^1
LfiiEvI, ill3
hearjr carbnrcl ted, 228
^^^1
GWcolli>U<.2-14
iodide), r>i
^^^H
GlvcoU. 3*38
light carbunttod, 173
^^H
Glvrjrrrlu'tin, 329
nitridtf. 73
^^^H
Gl'vrvrrhitln, 33U
oxide, 48
^^^1
Gold', lift
jH^roxtdo. nS
^^H
tiichloridti, 100
pliospbldt^ 83
^^^H
Grope- DUgftT, 383
filiddn. 108
^^H
Graphite, 109
sulphide, 64
^^^1
GMvitjr, 3
Hydrometer, 4
^^H
speciflo. 9
Hrdrtiqainone, 806
^^^M
Ooalocol, 807
HroMini!, 341
^^^H
Guanine. 319
Hj-osovamine, 341
^^^H
Gnariintiie, 889
HjrpounthiQe, 319
J
386
TSDia.
iGsnnoK, 9S4
BlamiiiAting gas, 275
Iinid<f«.290
Indestrnetibilitj of nuOtar, 2
Indican, 330. 356
IndiglDcio, 820, 356
Indigo, 319
blae. 319
curnine, 320
talphoDic kcidi, 820
Indtgogen, '4M
Indfgotin, 319
iDdiam, 117
Indol, »20
Inosite, 288
inalin, 288
Iodine, 60
Iodoform, 179
lodol, 818
Iridiam, 128
Iridoline, 297
Iron, Ifle
«cetat««, 113
bromide*, 111
carbonate, 112
cbl(W)dei^ 110
citrates, 118
conpoundi of, t09
ferricyanide. 118
ferTOcfanide, llA
bjdrates 110
iodides. 111
lactate, 113 ,
nitrates, HI
oxideH. I(f9
phosphates, 112
pjrrojjhonphaW, 118
salts, 111
Bulplintes, 111
sulphides, 110
tartratHrt, 113
Isethionamidt^, 280
Isetin, aw, :{2U
Isoliii*^, :^18
IsoinuriHiD, 170
Isomorphisn), 31, 170
Isopreiif. 271)
iTor^ black, 102
■ jALAPrN, 320
Jalapinol. ;!29
Japaconitiiie, i!42
Javellu water, 137
Jervine. 342
Jet, 102
KAIItlNE, 319
Kanliii. 110
Kelp, 00
Kerntin. 3ri3
Kermt'H iiiiinirnl, 09
Keriiitt'iio, I7)t
Ketoiii's. 203
dimethyl, 204
King 8 yellow, 89
Kyauol, S1&
Lacttde, 245
Lsctioe, 291
LactOM, 291
LsTo^rons. SH
LsTnlosan, 288
LsTalose, 288
Lamp-black, 108
Latent heat, 7
Laoghing-gas. 73
Laoreoe, 297
Law of Ampere, 11 ,
of Avogadro, 11
of definite proportions, 8
of DnIoDg and Petit. 13
of mnltiple proportions, 9
of reciprocal proportions, 9
periodic, 117
Lavs of Gay Liusac, 10
Lead, 118
acetates, 120
black, 103
carbonate, 130
chloride, 130
cliromate, 130
compounds of, 110
dioxide, 119
glycocholate, 216
iodide, 120
monoxide, 119
nitrates, 120
oxides, 119
peroxide, 119
protoxide, 119
puce oxide, 119
red, 119
salts. 120
sulphate, 120
Eulphide. 119
Lecithins, 207, 273
Legumin, 351
Lepidine, 818
Lethal, 200
Leucin, 212
Leucoline, 297
Lichenin, 296
Lignin, 295
Lime, 147
chloride of, 147
Blacked, 147
water, 147
Liqneura, 187
Litharge, 119
Lithium. 129
bromide, 129
carbonate. 129
chloride, 129
hydrate, 129
oxide, 129
urates, 261
Lubricating oils, 173
Lutidine, 817
Lycoctonine, 342
Maclurin, 330
Magenta, 315
Magnesia, 153
^^f ^^^^^^^^^f ^^^^M
387 J
L Magnesia iilba IM
Methyl Iodide, 176
^H
^^K^MigUtfsium, I'y'-i
nilniU, 198
^^^H
^^^F cvtionuteA, 154
nitnle. 108
^^H
^H cblnride, 153
oxida, 189
^^^H
^^H oompotinds. 153
MfthrluBliw, a05
^^H
^ hylrKtv. ir,3
M«th;lene bieUoridr, 174
^^^H
oxl<l«, 15:1
MstbyliA, 205
^^H
pliDsphatcs, 153
Milk, AfA)
^^H
MlU. 15»
J41uliiio. MO
^^^H
sulpliAU-, 153
Misturi^ 9
^^H
Ukltose, SUl, 294
Molooiile, 7, 11
^^^1
Muijpkuvw, 107
Mol^Mfniim. 104
^^H
ohIorl<li>i, im
Mnuitiuia««, 2«$
^^^H
oxides. 107
MonuniiKM, 205
^^^H
SftlU. lUH
Mouocblormetb/I chloride, 174
^^H
UnniilkMe. 2flH
MoDoohlurobemene, 801
^^^1
lIiknli-i;M. 178
MonoDitrolMaiol, 298, 8i:j
^^H
^^ViMicut. 119
MorphiiiH, 834
^^^1
^^Ubavvin, 816
Maciii, iHM
^^^1
^■Vecoiiinv, 8S4
Murexid. 2<t2, 263
^^^1
^■lS«luln, 356
Moac&ritM*. 207. 845
^^^1
^■Uetiwin, im
Miutard, oil of. 223
^^^1
^■K«liu7l imlinlut«. 200
MvdkleliM, 844
^^H
^^PVanthal, 281
Mj-diitoxine, 346
^^^1
P Mercaptun, '-'20
Mvdiae, 345
^^H
L M^Tcaptiites, 220
M^uBin, 840
^^^H
^^H UerourntDtnonlam flhlorid«, 164
^^H Vercurio lihloride, 164
Mjricrl bydrate, 188
Mjroeiii, 823
^1
^* cjaiiid«, HJ5
Mjtilitoxlae, 345
^^H
icNlide, 165
^^^H
oxide, 1S8
KAniTiiA, 173
^^^1
sulphide, im
wood. 181
^^^1
Jd^rcuruiu chloride, lt)3
Niphtbaluufl. 323
^^^1
iodide, lOQ
Nft]iLlbQl«, 323
^^H
oxide, laa
^>ptltllvdrt^De. 32-J
^^^1
Merourjr, 163
KipvII'^H, 342
^^H
chloridea, 1(12
Kwoeinv. 336
^^^H
iodides, 165
NnrootiDa, 336
^^H
I oxidoa, 162
Nsseoul sUto. 80
^^^H
1 iiitrit«B, IflS
K«rT« ttMiM, 274
^^^H
1 salU. 165
HouridiM. 344
^^H
L eiilpli«J«e, 166
ItonrliM. 208, 845
^^^H
^^K snlpLidvi^, 163
Nciirulcfi-atiii, 374
^^H
^^BltMltTlciio, ;iuo
Kick-I. iS7
^^^H
^^Blwoxnlrliirfii. 263
Nii-oliiwj. 3:i3
^^^1
^■Plteelilor&l, 2412
Mohhim. 1(M
^^^1
^KibtadkhlorobtiDunp, 303
NitM, 187
^^^1
MctttllucTHiiidtn, 828
UeUlIoidis Sa
Mitro-UnwtiM), 813
^^H
beuiol, 313
^^^^H
Meulft,8a
OHlluloae. 295
^i^^^H
Meumerfmi. 170
glyet rift, 206
^^^^^H
Metli«iiiot[luV>ln, 855
phvnoU, 306
^^^H
Metlul, aOU
Kltrogvu, 70
^^^H
Mrthnne, 17»
bromido, 77
^^^H
H«th«nj'l bromids, 176
eUloride, 77
^^H
o]iIi>rlde, 174
dioxide. 74
^^^H
^K iodld«, 176
iodide. 77
^^^1
^^f Hetliyl iMtuttttie. 800
monoxide, 73
^^^1
bromldfl, 178
p«ntoxido. 75
^^H
oM-liiiiol. IHI
peroxide, 74
^^H
oliloride, 174
protoxidfl. 73
^^H
OOllh'lkV. X).1
tolrDxidu, 74
^^^H
gl.vcocol, 210
trloxide, 74
^^H
giiMiildlue, IMS
Nitrous fumiTS, 74
^^^H
hv(|r(«t«, 180
oxide, T<]
^^^1
li>aride, 17D
NoBifeucUturo, 30
■i
388
INIffil.
OrcLUBios, 39
Oili, 2«7
distiUed, 278
essential, 278
fixed. 268
ToUtUe, 278
Olefluit gM, 228
Olefines, 228
OUin. 226
OLeonrinft, 2^
Opiom, SS4
OpticaLl; Ktire bodies^ SG
Orgnnie suWtau«v«. 168
Oraio, 308
Orthodichlorobenzeiw, 802
Osmium, 104
Obseiu, 352
Oxacida, 18
OxalrlarM, 262
Oxides, 41
Oxindol. 820
0\.Viii:id3, 18
Oxjcholiiie, 211
Oxjj.clnchoiiSuie', 389
Oxygen, 40
OK^ytuFmoglabia, 854
•_»\vin:uriaiB, 311
Oxysalts, 19
Ozocerite, 174
Ozoue, 42
PALLADrUM. 127
I'tiix^iY-iitiUi ;Vj4
Pjiriiffiii, 17'!
rsrtifB,nva, 172
Pafflldeliydc. 21)1
P:iraiiiorphintt, 'iti&
Pur 13 greeut WO
Purvolim. 'il7, 318
iViirUsK, l.ia
I'untene, 229
Peonin, 303, 30ft
Pepsin. 353
Peptone. 351
i'cptotoxine, 351
PtTissads, 15
P.troleura, 173
ether, 173
P-lrolatum, 174
Piiunaiithreiie. 335
riii-iiicin, 303
PIk.ioI. :W3
)^i.'iizylic. 303
iTi^wylic, 303
rvmylic. 304
■iVes, 309
rin,iiol3, 302
diatomic, 307
J litre, 306
:,abstituted, 804
Plienols. triatomio, 808
trinitro, 800
Phenyl. 313
hjdrate, 302
Vdrid*. 29T
FhenjE amine, 313
PhlorotjluoiiB, 30iJ
Plioa^eiie, 233
PJi'T-jptmniii'?, 83
Pliosphioes, 220
Pbosphonia, 83
Phosphorus, 78
bromides, 84
chlorides, 84
fluorides. 84
iodides, 84
oxides, 82
oxychloride, 84
peDtachloride, c4
pentoxide, 82
trichloride, 84
trioxide, 82
Phthaleine, 809
phenol. 309
resorcin, 809
Phthalei'nes, 309
Phycite, 276
Phjsosljgroine, 843
Picii*>iiiel*r, 4
PicoUue. 317
Pilooirpiiiif, 343
Piperidiuc, 318, 342
Piperine, 31ft. 343
Plafimine, 349
Pl*ster-of -Paris, 148
Plfltinic chloride, 127
riatiiiiiTTi, 127
Plumbago, 102
Plumhates, llO
Poisons, 58
mineral, 96
Polarimetry, 36
Polymerism, 170
Porcelain, 116
Porter, 185
Potash, 136, 138
Potassa, 136
Potassium, 135
acetate, 138
fkli,Mbiir;il>i'. 115
arsenite, 90
bromide, 136
carloiiatt'B. i:^
chlorate, 137
chloride, 136
cyanide, 141
dichromate, 137
ferrieyanide. 141
ferrocvanide, 141
hydrate, 130
hypochlorite, 187
iodide, 136
myronnte, 223
nitrate, 137
oxalates, 138
oxides, 136
^^^^ ^^^y
889 .]
^^1 PoUMlum, iMTiniLnfiiuute, 138
Bsl smmonioc, 14S
^^H
rulntito. 146
^^^^^^H
SslsirMuB, 138
^^^^^H
^H BulphRte*, 187
Kxliciii. 310, 320
^^^^^^1
^M aulpbldM. ISO
Saliojif.l, 310
^^^^^1
^H >ulphit«. 187
Ktiligvniii, 810. 82tf
^^^^^^H
^H UrU-ntes, I3B
Salt, Eittoni, 153
^^^^^^1
^V urates, idl
common. 180
^^^^^^H
f PoUkto spirit, 187
Olftuber's, 133
^^^^^^1
L PreuipiUtioii. HO, 361
or K'moD, 188
^^^^^H
^H Proof spirit. IHS
ofiiu-lor, laa
^^^^^^H
^^M PrupTl-benwne, 800
^H hjdrste. 187
Hochelle. 140
^^^^^^1
rook, ISO
^^^^^H
^H PropjUmint}. 209
BeidliU, 138
^^^^^H
^H Protatroii. ^4
sorrel. 138
,^^^^^H
^^M Pn)t«iti bodies, 345
Ssltpetro, 187
^^^^^H
^f Protein. 846
Chill, 133
^^^^^^H
f Prussian blue, 113
»elUi. 18, 10
^^^^^H
Ptomsines, 348
basic, 23
^^^^^^H
Ptj&lin, 353
doable, 33
^^^^^H
Pntrefnolion, ^3, 340
Laloid. Id
^^^^^H
PatrvBcinu, 344
oxr, 23 J
SDb, 38 1
^^^^^^^^H
Pyrene, ai*!
^^^^^^^H
PjHdiae, 817, 318
Bsnlonia. 330 1
^^^^^^^^^1
^K Pjrrocstechiu, 307
SspQiiiiicAtion, 307
^^^^^^^1
^H Pj^rodextrin. 3U3
Saprlue, 844
^^^^^^^^1
^H Pjrogftllol, 3U8
Ssrolne, 310
^^^^^^^1
^H P/rozun, 31>3
8am»ia«, 310
^^^^^H
^H Pyroxjrlin, 205
SoandJum, 117
^^^^^^H
^P P/rrol, 818
Soheele's green. 00, IflO
8aliw«>[nfurth gre«», 90^ 100
^^H
QnCRLIMB, 147
Sw salt, 130
^^^^^^1
Qulniolna, 3S9
Saealin. 206
^^^^^H
Qiiinidiue, 839
8e!en)am. 60
^^^^^H
QuiiilDe, 337
Serin, 349
^^^^^H
Quiuoiitf. 8Ue
Serum
^^^^^H
Quitiova nd. 8dO
^H Quiuuviii, 3«&
albumin. 343
^^^^^^H
cuh'iii. 349
^^^^^H
■
globuUn, 349
^^^^^^1
^H RAmcALJS 17, 23, 16a
Sllflx, 103
^^^^^^1
^M R«sgeDts, 338
Silicates, 103
^^^^^H
^1 lUslgM-. 80
fiillolo oxide, 103
^^^^^^1
Reduction. 39
Silioihromoromt, 103
^^^^^^H
R«Ktuiuet*, 17,23
Hlllcii^liltiruforu), 100
^^^^^H
RsBlnfl, 280, 282
SUJoon, Wi
^^^^^^H
Utfti^ruiu, 807
chloridt!, 108
^^^^^^1
Rvloiiu. 297
Silvor. 142
^^^^^H
Rh«lii. 825
bromide, 143
^^^^^H
RliiicuWno, 173
cbloride, 143
^^^^^H
RUodium. 127
cjaiiidtf, 143
^^^^^H
Riuiiiino, 209
iodide im
^^^^^H
^H Rock crystal, 103
nitrate, 143
^^^^^1
^B otl, ir3
uxldus, 143
^^^^^^H
^m RosuiUlne. 815
Rkatot, 330
^^^^^H
^1 Rosin. 963
Soaps. 372
^^^^^H
^r Bubldlm». 817
Soda, 184
^^^^^H
: RiiUditim. 14a
Sodium, 130
^^^^^H
Rutn, 187
acetate. 134
^^^^^H
Riilh^fnium. 138
atuminate, 115
^^^^^H
Rutjtene, :f75
anvnite, 90
borAU«. 133
^^H
1 SAnAPILLINB, 343
bromide. 181
^^^^^H
1 RMcbsrIdus, 290
oarbonfttes. 134
^^^^^H
1 Ssoohu-oee, S80
Ohloridtf. 130
^^^^^H
Sacohsrose*. 389, fltt
oonipiniiids, 130
^^^^^1
SeHronin, 810
gljrcociioUte, 316
m
390
IND£X.
Sodium, hydrate. 180
hypochlorite, 184
hypoaalphite, 183
iodide. 182
nungftiiite, 184
nitrate, 183
oxides, 130
pemunganate, 184
phosphates, 188
salts, 182
sUioates, 133
solphates, 133
sulphito, 132
snlphorinate, 198
tongstate, 104
oratea, 261
Solanidine, 830
Solauine, 880, 840
BoIdUoh. 81. 44. 800, 874
chemical. 81, 44
physical, 81. 44
saturated, 44
simple. 81, 44
snpersatiumted, 44
Spectroscopj, 88
Spermaceti. 190
Spirits, 186
methylated, 181
of wtne, 181
pyroxylio, 180
wood, ISO
Stannic componndB. 125
Stannous compounds, 125
SUrch, 291
States of matter, 6
Stearopteues, 280
Steel, 108
Stercobilin; 356
Stethal, 200
Stibamine. 97
Stiliines, 230
Stilbene, 324
Strontium, 151
Strycbuiae, 839
Styrol, 321
Styrolene, 321
Sublimation, 7
Sugar, beet, 289
candy. 289
cane, 289
diabetic, 282
of gelatin, 209
grape, 282
inverted, 290
of lead. 120
liver. 283
maple, 289
milk. 291
muscle. 388
teats for, 285
Suiue. 273
Sulphethylates. 220
Sulphobaaes, 18
Sulpliobenzide. 298
Salpbur. 03
dioxide, 66
Snlphor triozide, 67
Superphosphate, 148
Sapersatoration, 44
Symbols. IS
Synthesis, 8, 44
Syntoniu, 861
Tannln, 330
Tantalum. 104
Tar, 297
Tartar, 140
emetic, 143
Taurine, 215, 280
Technics, 857
Teeth, 149
Tellurium, 70
Terebentbene, 378
Terpine. 278, 281
Terpinol. 281
Terra alba, 148
Test, biuret, 357, 851
Boettger's. 286
FehUng's, 286, 387
fermentation, 286
Freseniua' and von Babe's, 96
Gallois', 289
Omelin's, 365
Heller's, 848
Marsh's. 93
Moore's. 285
Malder-Nenbauer's, 285
murexid, 263
Pettenkofer's, 216
Reinsch's, 93
Scherer's, 289
Trommer's, 285
Tetanine, 345
Tetraclilorobenzene, 302
Tetrametliyl ammonium hydrate, 206
Thalline, 319
ethyl, 319
Thallium, 146
Thebaine, 336
Tbeine, 339
Thialdine, 301
Thymol, 804
Tin, 135
chlorides, 136
compounds, 125
hydrates. 126
oxides, 135
Tincftl. 133
Titnnium, 125
Toluene, 300
Toluidine, 300
Toluol, 300
ToxireBin. 329
Traumaticine, 380
Trehalose, 283
Tributyrin, 366
Tncaprin. 266
Tricaproin, 366
Tricaprylin, 366
Trichloraldehyde, 201
Trichlorobenzene, 302
Triethylamiue, 305
^M XBDEX.
391 ]
TrimaT^uin, 266
Tolum^trio analjiis, 800
Trin]t>t1iyUinIn«, 206
Vulcaaiie, 2tW
TriiDtftliyl glyctwol, 211
Trimeilij-lix^ 2(»6
WASHUia, 801
Triiuorjiliism, 31
Watw. 43
TrinltroclvceiiQ, 266
cliloridM In, 47
Tritiiiro phenol, 300
glan. 133
Triolein. J»6a
bardn«fls of, 47
Trlpnluiilhi, 360
iinpiiHliuH of, 44
Triple p)i<wpliat«,153
Trietwiu, ^(t
iiieiah In, 48
miiiwral, 60
TriTftUrio, 2156
natural. 40
TropiM, 841
of oonstUutton, 4S
TiTiwln, 8M
of crystallitalion, 45
TungftWa, 104
organic matUT in, 47
TarubuU'ii bln«, 113
oxrg«Dat«(l, 6d
TuriwnUn^. 278
purification of, 4S
Tutljr. 155
solids in, 46
T/iiltoloxiiie, S45
Wax, 200
Tjrpical tfWmvnU, 87
Weighing, 865
Wefgbt. a
Tjrnwiiiv. 213. 213
abaolote, fl
Ubaxitu, 113
Urei. 251
dutermiuAtlon of, 257
nitrniv. 2^S
atomic, 11
molecular, 14
rftlatWe, 2
speciHc, 2
of gaa«8, 5
of liquldn, 4
of solida, 4
of vapon^ 5
Weifchta, 875
WhlBk^y. ISO
Will tH lead, 120
pr0oipitat«, 103
WIn«, 185
ozalkte, 26a
tests for, 267
TJrHB, conpoaDd, 359
Unlda, 260, d02
Urinary pli^mante, 836
ItrtnuiiicUT, 4
Urobilin, 8Q0
Uroxanlhlu, 360
oil of, 190
VAl.KNrE, 14
ktiiriu of, 181
Vftlereii9, 22Q
Wolfrnin. 104
Valarjiene, 275
Vallidine. 916
Xanthjnk, 310
Valytene. 278
Xcnoli, 8M
VanKdiam, 104
XyUnv, 800
Vaimdvl, KM
Xylttnolfl, 804
Vauilliu, »ll
Xvlnidiii, 388
Vajiorit, a
Xylol, MIO
Varech, 60
Vsitelm, 174
Teast. 181
Veratrine, 343
Verdiffris, 1(10
Zntc, 155
Vermilion, 102
butter of, ISO
Vlnogar. 1U3
carli4inat«ni, 154
vood« 180
chloride, 135
Viridine, S17
eompouuda, 160
ethyl. 231
liydratcr, 155
ViUtlln, M9
Vitriol . Mtie, 159
green. Ill
oxide. l&S
oil of, 07
ftulplintw, IGO
vklt«, ISO
Zlrcoaiuu, 125