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DICTIONARY OF CHEMISTRY 



VOL. I. 



lOHSOH 

VBIVTSD BT SrOTTXSVOODX AVJ> CO. 

KXW-GTSKBT 8QVABS 




A DICTIONARY 



OP 



CH EMISTKY 



AlTD THB 



ALLIED BRANCHES OF OTHER SCIENCES. 



Founded on that of ike late Dr. Ure, 



BY 



HENRY WATTS, B.A., F.C.S. 

XDEIOB OF 
*TBS JOtTBVAL OV THB CHBOGAL BOGBIT.' 



ASSISTED BY EMINENT GONTBIBUTOBS. 



IN FOUR VOLUMES. 



VOL. I. 

ABICHITE— CONGLOMERATE. 



^ LONDON: 
LONGMAN, GREEN, LONGMAN, ROBERTS, & GREEN. 

1863. 



ChcT)i ?'65 



! V ^ 3 • -^'«- / 1 ( ' ?' 



^ 



<^-^y 



*>^fe'^**-r 4 



PREFACE 



rpniS WORK was originally intended sb a New Edition of Ure's 
J- Dictionary of Chemistry and Mineralogy ; bnt the great changes made 
m chemical science since the publication of the last edition of that Dictionary 
(1831) — changes, not merely consisting in the addition of new discoveries, 
but inTolTing a complete revolution in the mode of viewing and 
expressing chemical reactions— have rendered it almost impossible to adapt 
any matter written so long ago to the existing requirements of the science. 
The present must therefore be regarded as essentially a new work, in 
which <»ily a few articles of Ube's Dictionary are retained, chiefly of a 
descriptive character. In compiling it, the Editor has freely availed 
himself of the stores of information in Gmelik's " Handbook,^* Gerhardt's 
" Chimie Organique,'' Rose's " Traits d' Analyse Chimique," Dana's 
^ Mineralogy ,*' Rammelsbero's '^ Mineralchemie," the '* Handworterbuch 
der Chemie," &c. ; and has endeavoured, by careful consultation of original 
memoirs, to bring the treatment of each subject down to the present time. 
He has also been fortunate in obtaining the co-operation of several 
chemists of admowledged ability and eminence, who have kindly con- 
tributed articles on subjects to which they have paid special attention : — 
a List of their names is given on the next leaf. 

The work is essentially a Dictionary of Scientific Chemistry, and ia 
intended as a Gompamon to the New Edition of Ure's Dictionary of Arts, 
Manufactures^ and MtTies^ to which therefore reference is, for the most 
part, made finr the details of manufacturing operations; but those branches 
of chemical manufacture which have come into existence, or have received 
important developements, since the publication of that work, are described 
in this Dictionary as fully as its limits will allow, and in all cases ex- 
planations are given of the principles on which manufacturing processes 
are conducted, and the chemical changes which they involve. Particular 

A S 



vi PREFACE. 

attention has also been given to the description of processes of Analysis, 
both qualitative and quantitative. 

In order that the work may, as far as possible, truly represent the 
present state of scientific chemistiy, it has been found absolutely necessary 
tq make the modem or " unitaiy " scale of atomic weights the basis of the 
system of notation and mode of exposition adopted. Especial care has, 
however, been taken that the treatment of all Articles which are likely to 
be consulted, for the sake of practical information, by manufacturers, or 
others not exclusively occupied in chemical pursuits, shall be such as to 
make them readily intelligpible to all who possess a general knowledge 
of chemistry, though they may not have followed closely the recent 
developements of the theoretical parts of the science. Hence, in all such 
Articles (as Acetic Acid, Aktimont, Copper, &c.) the formulae are given 
according to the old notation (printed for distinction^ in Italics), as well as 
according to that adopted in the rest of the work. 

Temperatures are given on the antigrade acale^ excepting wheil the 
contnuty is expressly stated* 



HENKT WATTS. 



7 Pbovost Hoad, LoKDoir, N.W. 
Jidy 1863. 




LIST OF CONTRIBUTORS, 



>^ 



EDlfUNI) ATKINSON. Ph.D. P.C.8. 

of Chemistry at the Royal Military Colle^, Sandhant. 



FRANCIS T. CONINOTON, M.A. F.C.S. 

rdlow of CorpM Chriati Collefce, Oxford, and late BxamiQer in Natural Science at that 
Univenity ; Author of a * HandbcK>k of Chemical Analysia.' 

WILLIAM DITTlf AB, Bsq. 

Aaaiatant in the Chemical Laboratory of the Unif eraity of Bdinbuif h« 



GEOBGB G. FOSTEB, BJL F.C.S. 

on Natural Philosophy at the Andersonian Univenity, Olaagow. 



EDWABD FBANKLAND, FIuD. F.B.S. 

FoRign Secretary of the Chemical Society, and Profetaor of Chemistry at the Royal Institution 
of Great Britain. 

FBEBBBICE GUTHBIB, Fh.D. F.C.S. 

Profeaaor of Chemiatry at the Royal CoUe^, Manritius. 

A. W. HOFMANN, LL.D. F.B.8. V.P.O.S. 

Fkoteaor of Chemistry at the Government School of Mines. 

WILLIAM 8. JEVONS, M.A. 
* Oatdy) Gold Aasayer in the Sydney Royal Mint. 

Cff ABLES B. LONG, Bsq. F.CJS. (the late) 
Analytical Chemist. 

WILLIAM ODLING, MB. F.B S. 

Secretary to the Chemical Society, and Professor of Chemistry at St. Bartholomew's Hospital ; 
Aathm' of a * Manual of Chemistry.' 

BENJAMIN H. PAUL, PIlD. F.C.S. 
Consnltio|( Chemist 

HENBY E. BOSOOB, Ph.D. F.C.S. 

Professor of Chemistry at Owens CoUejpe, Manchester. 

WILLIAM J. BUSSELL, Ph.D. F.C.S. 
or Unirersity Collie, London. 

ALEXANBBB W. WILLIAMSON, Ph.D. F.B.S. Pros. C.S. 

Professor of Chemistry at University Colk^e, London, and Bxaminer in Chemistry at the 
University of London. (A. W. W.) 

ABTHUB WINCKLEB WILLS, Esq. 

Analytical and Mannfactnrini^ Chemist, Wolverhampton. (W. W.) • 



%* Aritoles oommunioated by the several oontributors are signed with their 
initials ; articles taken from Ubb'b JHelionary of CAfmisiry (fourth edition, 1831) arc 
Btgnod with the letter U ; those which have no signature arc by the Editor. 



ERRATA. 

T%e asterisk in the second column indicates thai the line is to be counted 

from the bottom. 



PAUB ' 


LUCE 


9 


35 


— 


16« 


3 


10 


— . 


35 




«• 


4 


3 


6 


88 


6 


1 


— 


9 


.—~ 


19 


** 1 


»• 


IS 


30 


" 


29,33 


in 1 


13« 


18 ' 


88 


30 


84* 


21 


5 




38*, 94* 


» 


»• 


» 


97 


-i/k 


16» 


— 


8« 


31 


fO 


— 


85 


— 


ST 


33 


13 


33 


9 


34 


10» 


— 


8» 


M 


83 


— ^ 


86 


U 


9 


— 


37 


36 


4« 


CO 


IB 


«s 


3 


64 


34 


68 


18 


74 


%• 


76 


31 


— 


25 


81 


85 


84 


23*. 4th ool. 


85 


33*,4thcoL 


— 


23*, 6th ool. 


90 


4» 


9ft 


33 


100 


9 


__ 


14 


103 


1» 



104 




37 


— 


»•. 


11»,18« 


— 




10« 


107 




39 


litO 




1 


110 




37 


— 




10 • 


— 




3» 


113 




17 


110 




25 



£RKOR COBRSCnOV 

Arftooid Acaroid 

C»H»NO« C»H»NO 

CH"0" CrH"0» 

proportioii prepomtion 

p. 19 p. 5 

NaBr 2NaBr 

C»H»0 CH»0 

(CPH'NO)* (CH'NO)' 

PCCH*)^) PCCTI')^)* 

CH'NO* C*H»NO 

00"Ba CJOTBa" 

C» C» 

3Pao +3Fao 

C"H^)T»b C'H'O'Pb 

principal, axiii principal axii» 

CTB-(frQ C»H»0 \ o 

c*H^r" C»H«or" 

Benaoil Benzoyl 

oonTertB into converts it into 

C%31*0" CKn*0 

mrthyl methylic oxide 

(propylic) propylic 

^^>"}o..... <<^Hr|o. 

C*HT?aSO" CH'NaSO* 

CHTIaSO* CHTNaSO* 

for which which 

C«ff«0 C'H"t) 

C"H'"1TO" C*H"N*S* 

C»H«IO.HJJ C*H»IO.ir.N 

CHI-O.IP.N C*HI-O.H*.N 

(CW)'"|p. (C-HW-Jo. 

treated heated 

(7H» C^' 

C^-H"irO* CH^N-O' 

phon>hoTOQ8 phosphorus 

oonsuting of containing 

and « ttie 

diflBolTQB dissolve 

in water ; less in idoohol in water, leas in alcohol ; 

of birds of of birds 

C^*0* C*H*0» 

100* 160*» 

160° 140° 

when ^ with 

1-0000 ~ 

9141 — 

25 — 

A to the mark < « to the mark « 

C0« 00' 

phosphoric aoid, and amyl- phosphoric add and amyl- 

aloohol alcohol 

bromoid^ bromides 

The aldehydes may be re- The aldehydes are isomeric 

gaitled as the ethers of the with the uthen of the 

diatomic alcohols. diatomic alcohols (see 

Btrkbs, and Ethtlsxk, 
Oxide of) 

C"H"W C"H"^) 

Mannite Mannitan 

C"H"0» C«H»"0» 

C'*H^ C"H»»S' 

c*H»cio« c*irno« 

are the ethen are isomeric with the eilicr* 

C"H"— «0 i>\\*«-*0 

C"li3n _o» C"H*»-'0 

condennatlon couomtration 

to NUt of tartar and «• to wit of tartar, and tu 

ciirhoiiatr of xtotaMslum CHrbonate of potassium 

obtained obtained 



■MACID8, Ke p. M KB Acms, p. W 

uuntl^] ..cBDuithjt 

PbBnn.[8] 1. Phuin. CMm. 

BDlpbocTulde mlphooTUUte 

CH-Bf JCH'Bi* 

"^lAg HAjC 

•^UCH^)) '^1{(7H'0)' 

. O^'Br.Bi* O^'Bi-.ftr' 

nl^MCTiaiide n^diMaraiuta 

cm iCHI 

<CHT'.(C?H').0' (C"HT'-(C*H')'0* 

nlpluHTUlde ..,^...^.....,,.,,,nilphoo«uiAte 
Alblene ii not knowD tn It bH dji» boon [» 

hyphoiulphlte'.... hTpoAnlphlte 

100 pB. □( axfgen 100 pU. of bIddiIiis 

dyed-Toodi ..,.., ,...,..,......dje-WDOdfl 

butbawi ........................ frtffbon" 

PtCl.'0"H"N" PtCl'.C'H'TJ" 

Ths pJiifAHnn«itt. li Tlwji/atinirBi-iBll In 

K^di .,.,,..,....,.,....... 4., .addfl 

MH* NH' 

S<H^)f »(H^))f 

H" jo* H- <)■ 

«H^)i MH^»r 

CH-Br"! (TH'Bf I 

(CH')-? f (CH-j-Pf 

0^.0 1 ■ (TH'.O I 

ffiS* i??S{ 

«?TI')T ■ (CH*)*?! 

iiH*0| >>B*0) 

«HS)t nH^; 

v(<J^')i\v////^\y^"','."'.'.'.'.v(l7B•'yI 

^aOJaic' ll\y.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'. '. .' J jroO.MBO" 

it>diit«..l'.!!''. '.'.'!'.'.!!'.'. !!!!'*"iodki» 

mnat becdded to npmenta tha isfadtr of 

to ba ■Uid to rapmniclDg tlia tmfmAtj of 

H+ft+/. iT+ll-/ 

■topooi^'' itinxockB 

polBt a pouil ■ 

trWAffO' 0'H"Ag^>' 

C'H-O' - (TH'WtO'H')' 0"H*H)- = C'ff'O'tO'H')* 

CBWIq. (O-H-WMq. 

hrhnohloilc brdnKblDrlo' 

CoBbQ* CnSbO' 

tilnumjl MbtriraMliyl 

iCJtHiiditjliiiiii lUlKit^lliim 

C"H■^>• .o»ir"o" 

CK'W CH-W 

An-mra* Aira"s^* 

tFSKy.'UV tFe^.ATV 

<">£(<>• '"fflo- 

IBaH'AaO'.Airo' + }H\) !D«H>A«-.Ai^>' + SHM 

Cn'A*'„ Oa'AaW 

AKCTnTCH-) A>{0'H")({J'H^* 

A*^0^')"(CB-> Aj-d^HWCH')' 



ERRATA. 



XI 



TAGS 



4Q0 


10» 


407 


11 


409 


%&• 


411 


13 


4» 


17 


4S4 


8 


427 


18 


433 


foot-note 


44S 


18* 


•^ 


17« 


444 


33 (of table) 


— 


» (of table) 


-^ 


84» 


445 


3 


446 


1 


— 


13 


— 


S3 


■>^ 


5» 


— . 


4* 


447 


17* 


449 


39* 


450 


94* 


4U 


13* 


— . 


10* 


-» 


9» 


458 


18* 


461 


6» 


— 


6« 


465 


16* 


469 


34 


009 


«• 


531 


io», n« 


584 


23» 


937 


38* 


714 


13 


—. 


10» 


799 


8» 


1038 


88 


1041 


11 


1043 


89 


1041^ 


19 


1049 


21« 


— 


«• 


1047 


80* 


—. 


!«• 


—. 


lartline 


1048 


6 




8 


1049 


last line 


1050 


14 


— 


89 


— 


18* 


106S 


14 


— 


19* 


1094 


19 


1058 


94 


— 


!!• 


1059 


9 


1090 


81* 


1066 


10* 


— 


9* 


1097 


1«* 


1099 


15 


1101 


98» 


1103 


1 


1104 


84 



ERKOR CORBKCriON 

Aj((?H«)Pt A«(CJ^")»Pt 

Afl"(CH*)1 Afi(CH»)»I 

4N0»Cu 2N0»Cii 

AflMeE* AsMeB* 

O'H'CuNO* C*H'CuN*(>' 

C^HTfO^-SO-H" C*H'NO*.SO*H« 

chalk, or, limestone with chalk, or limestone, with 

i»*=l n"-l 

C?"H*0» CTE[*0 

C!^'*0" C*H»«0 

CJ*BTO* OH^O* 

C*H»«0* C-H»«0» 

(rH*0" C«H*"0" 

(?T3}*0 Off«0 

CTa*o cp'H*©" 

(CIP)-;" (CHrl^ 

3*36 23*6 

C*H*"SO* (Tff'SO* 

CS- , C»« 

Tolnmes whence volnmes : whence 

C»H*NO* (3TI-N0 

KNifio* KNiSO*. 

•©• ©•© 

•® mo 

®#® o«o 

sojphide snlphate 

Odoride of of Hypochlorite of 

Hypodilorite Chlorite 

87*6 187-6 

Csb)« (SO*)" 

WBctlou reaction 

an ontwaxd presenile a pressnie from withont 

[2] 59 [23 269 

wort wool 

Kisselzinkerz Eieeelzinken 

Od Ca 

18'51 1851 

P<80 p. 1086 

p. 40 p. 1046 

p. 86 p. 1043 

p. 53 p. 1058 

P.«7 p. 1048 

P-89 p. 1045 

P*84 p. 1040 

P-46 p. 1063 

P. 88 p. 1044 

p. 88,84 p. 1039,1040 

P*88,88 p. 1044,1045 

P.fiO p. 1066 

p. 87, 88 p. 1048,1044 

p. «1 p. 1057 

p. 88 p. 1044 

p. 48 p. 1064 

P>48 p. 1064 

P*45 p.1051 

P-44 p. 1050 

p. 87 p. 1043 

p. 40 p. 1046 

p. 58 p. 1069 

p. 61 p. 1067 

p. 59 p. 1065 

p. 63 p. 1068 

p. 88 p. 1094 

p. 89 p. 1095 

p. 88 p. 1094 

p. 94 p. 1100 



DIOTIONAET OF OHEMISTET. 



(Aphaneiiie, Sirahlerg, Strahlenhipfer*) A natiye arsenate of 
eopper, found cliieflj aasodated with other oopper ores and reins in Cornwall, and 
in the Harts. The cejBtalB belong to the monoclinic or ohUque prismatic system, 
bat thej seldom exhibit any definite shape, being aggregated in radiating groups, 
or disposed, as extremely minute individiials, in cavities of quartz. Sp. ^. 4*2 
to 4*4. Hardness, 2*5 to 3. Translucent or opaque, with Titreous lustre. Colour, 
blaAish green inclining to blue. Streak, bluish-green. Dana (Mineralogy, iL p. 428) 
gives for this mineral the formula SCuO^AsO^ + ^CuO.HO\ or AsCu>0« + Cu'HO*, 
deduced from the analyses of Rammelsberg andBamour. L. Gmelin (Handb. y. 471) 
gives the formula 60uO.AsO^ + 5H0, deddeed from the analysis of Chenevix, who 
Ibnnd 64 per cenL of protoxide of copper, 30 per cent, of anhydrous arsenic acid, and 
16 per eent of water. 



EC ACXB. C'H'K)^ When Strasburg or Canadian turpentine (ob- 
tained respectively from Abies picea and Alnes haUamea^) is distilled with water; the 
residue exhausted with absolute alcohol ; the solution evaporated to dryness ; the re- 
sidual resin boiled with twice its wei^^ht of solution of carbonate of potassium ; the 
alkaline liquid poured off; and the residue, which is a mixture of abietin and abietate 
of potassium, treated with 30 times its weight of water, — abietin separates in 
the oystalline form, while abietate of potassium remains in solution. This solution 
may be decomposed bv sulphuric or hydrochloric acid, and the precipitated abietie 
add purified by digestion in hot aqueous ammonia. As thus obtained, it is a resinous 
mass which dissolves easily in alcohol, ethtiir and volatile oils, forming acid solutions, 
from which it separates in the oystalline state« At 66^ it becomes soft and trans- 
lucent. Its barium-salt is said to contain 191 parts of the add to 76*6 parts ^1 at) 
of baiyta. The add is perhaps identical with sylvie or pymaric add. (Caillot» 
J. Fhum. xvi 436; Gerh. iii. 666.) 



Prepared as above. It is a tasteless inodorous resin, insoluble in 
water, soluble in alcohol, espedaHy at the boiling heat, also ia ether,^ rock-oil, and 
strong aoetie add, and separates in the crystalline form from these solutions by evapo- 
ration. It melts when heated, and solidifies in a crystalline mass on cooling. It is 
not acted upon by caustic potash. (C aillo t.) 



( Gismondin,) A mineral of the zeolite frmily, containing, according 
to Uarignac*8 analyds: 

8(CaKO.SiO«) + 4Al<0*.SiO« + 18H«0 ; [Si - 28 ; « 16]. 

or 2(CaO.KO)Ac^ + 2(AP(^,8iO^ + 9HO; [-«-21; 0«8]. 

It is found on Yesutius, at Ad-Castello in Sidly, and at Capo di Bove, near Borne. 
It ocean united with Phillipsite in quadratic octahedrons, generally aggregated in 

• The stenic weffhts adopted In thli work «ra those of the imlunr iritem (U •• 1 ) O » 16 ; S = 8S t 
C a |«). Fr«qiMotlj, bowerer, the formute of compound! wiU likewise be given aecordlne to the 
doalistic system {Om 8, 5 a 16, C« 6) ; and for distinction, these Utter formulse will be printed ia 



Vol. I. B 



4 



2 ABSINTHIN—ACEDIAMINE. 

maflses. Transparent or translacent, with greyish-white colour. Hardness » 4*5. 
Sp. gr. s 2-265. Giyes off one-third of its water at 100^. Easily dissolves in acids 
and gelatinises. It was formerly supposed to be a Tsriety of Phillipsite or lime- 
harmotome ; but it diifeonr from harmotome in composition as well as in crystalline form, 
the latter mineral crfstallisi^g in the dimetric system. (Dana, ii. 322.) 

JLBSZMTBIVk CE'H)*. The bitter principle of wormwood (Artemisia ahnn- 
thium). It is prepared in the pure state, according to Luck, by exhausting the leaves 
of wormwood with alcohol, evaporating the extract to the consistence of a svrup, 
and agitating with ether. This ethereal solution is evaporated to dryness, and the 
residue treated with water containing a little ammonia, which dissolves the resin, and 
leaves the absinthin nearly pure. To complete the purification, it is digested with 
weak hydrochloric acid, waaned with wat^, dissolved in alcohol, and troated with 
acetate of lead, as long as a precipitate is formed. After the removal of this precipi- 
tate by filtration, the excess of lead is precipitated by sulphuretted hydrogen, and the 
solution is evaporated. The absinthin then remains as a hard, confdsedly crystalline 
mass, possessing an extremely bitter taste. It is but slightly soluble in water, very 
.soluble in 'alcohol, and less so in ether. It possesses distinctly acid characters, and 
is dissolved by potash and ammonia. (Kein, Ann. Ch. Pharm. viii 61 ; Luck, ibid. 
Ixxviii. 87; Gerh. iv. 258.) 

AB80&FTZ0W OF OABB8. See Gases. 

ACACZV, or ACACXA-OUSK. Known in commerce as^um-aro^. See Ababin 
and Guic. 

AOABXO&ZTB. A variety of chabasite firom New Caledonia, distinguished by 
its laige amount of alkalL (H ay e s. Sill. Am. J. [2] I. 122.) 

ACAJOV. The stem of the Acj\jou or Oashew-nut tree, Anaoardium ocoideniaUj 
yields a yellow gummy substance, sparingly soluble in water, which is a mixture of 
ordinary gum and bassorin. The pericarp of the nuts of the same tree contains a 
large quantity of a red-brown resinous substance, which produces inflammation and 
blistenng of the skin. It may be extracted by ether, and the ethereal solution when 
slowly evaporated, leaves a residue consisting of a network of small crystals of ana- 
cardic acid, soaked in an oily liouid called cardol, to which the resin owes its acrid pro- 
perties (Stadeler, Ann. Ch. Pharm. Ixiii. 137). The name acijou is also applied 
to a gum and resin obtained fkom the stem of the mahogany-tree. The g^om re- 
sembles that of the cherry-tree. 

AJKACOXB SBSZV. The resin of Xanthorrhea hasHliSf a liliaceous tree grow- 
ing in New Holland ; also called resin of Botany Bay. It has a yellow colour, an agree- 
able odour, and is soluble in alcohol, ether, and caustic potash. Its potash-solution 
treated with hydrochloric acid deposits benzoic and dnnamic acids. Nitric acid con- 
verts it into picric acid, and so readily, that this resin appears to be the best raw material 
for obtaining picric acid. By distillation, the resin yidds alight neutral oil, which ap- 
pears to be a mixture of benzol and cinnamol, and a heavy acid oil, consisting of hydrate 
of ph^ivl, mixed with small quantities of benzoic and cinnamic adds. (Stenhouse, 
Aim. Ch. Pharm. IviL 84.) 

AOBCnnbOBXBB OP F&ATZVmMC. See Acbtomb, Deoompotiiioru (p. 29). 

ACBBZA Ml Jl Mm G*H*N'. When hydrochlorateofacetamide is heated in a sealed 
tube to 180^ — 200^, and the product afterwards distilled, or when acetamide is dis- 
tilled in a stream of dry hydrochloric add gas, several volatile |nx)ducts pass over, and 
a residue is left consisting of hydrochlorate of acediamine^ mixed with sal-ammoniac. 
(See Agbtamide) : 

2C»H»N0« + Ha - C«H«N«. HCl + C»H*0«. 



"Y" 



Acetunldei 11]rdrochlorRte Acetic add. 

ofacediamlne. 

Alcohol extracts the hydrochlorate of acediamine from this residue, and deposits it 
by spontaneous evaporation in prismatic crystals, which may be completely fireed from 
adhering sal-ammoniac by solution in a mixture of alcohol and ether, and evaporation 
in vacuo. The hydrochlorate decomposed by sulphate of silver, yields the avfphate of 
acediamine (CHW)'. SO*H', which aystallises in colourless nacreous laminse, easily 
soluble in water. The aqueous solution of the hydrochlorate mixed with dichloride of 
platinum yidds the chloriplatinate of aoediamne^ CH*N». HCi PtCl*, in rather large, 
hard, yellowish red prisms. 

Acediamine is very unstable, and cannot be obtained in the free state. When the 
sulphate or hydrochlorate is heated with potash or baiytOi ammonia is given off, and 
an acetate of tiie alkali is produced : 

C«H«N« + 2H«0 = C«H*0« + 2NH«. 



ACETAL. 8 

Aeediaaiiiie nuiir be veguded as ammonU in which 1 at. H is replaced Inr the moxia* 
tanie ladieal C*H*N (acethyl), its rational fonmda being then K.H'. CH^N or as a 
^tooble molecule of ammoma» N'H^haTing 3 at. H replaced by the triatomic radical 
C*IP, making its formula N*.H*. (C^*)'" It bears the same relation to aoetamide aa 
ethykmine to aloohol: 

C*H«0 + NH* « (^BTS + HK): and C»H«NO + NH« « C»H«N« + H«0. 

(Streeker, Ann. Pharm. diL 328.) 

HI' HPMQgCIMlO ACD and ACB9KIIS8XC AOSD* Componnds produced 
by Ihe action of phoq>hoxuB on acetone (see page 28). 

A.GSVA&. C^"0>.— [Gm. ix. 38 ; Gerh. iL 268.] A product of the oxidation 
of alcohol, first observed by Bobereiner, more fully examined by Liebig (Ann. Gh. 
Pharm. t. 25; xiy. 166), still further by Stas (Ann. Oh. Phys. [3] xix. 146^ who 
first correctly determined its empirical formula, and finally by Wurtz (Compt. rend. 
xlriiL 478 ; Ann. Ch. PhysJ^S] xlviii. 370 ; Ann. Ch. Pharm. cviiL 84). It is also 
obtained from aldehyde. (Wurtz. u. Frapolli, Ann. Ch. Pharm. cvii. 228.) 

Pr^uraiion. I. From Alcohol. 1. Sy the imperfect oxidation of alcohol, under 
the inflnenoe of platinum-black. Pieces of pumice-stone previouslv washed and 
ignited are moistened with nearly absolute alcohol, and placed at the bottom of a 
large wide-necked fladc, which is then filled up with eapsules containing platinum- 
black, oorered with a glass plate, and exposed to a temperature of 20°, tifi the whole 
of the alcohol is acidified. Alcohol of 60 per cent, is then poured into the flask, in 
qnantity not quite sufficient to coyer the pumice-stones, and the flask left to itself for 
tvo or three weeks in a room at a temperature of 20°, the glass plate being removed 
from time to time to admit f^h air. The thickish liquid is then drawn oS, and the 
same process repeated with fresh alcohol, till several quarts of thickish acid liquid are 
obtained. This liquid is neutralised with carbonate of potassitun, saturated with 
chloride of calcium and distilled, and the first fourth of the distillate is saturated with 
fused chloride of calcium, whidi separates from it a mixture of alcohol, acetic-ether, 
aldehyde^ and acetaL The aldehyde is removed by distillation over the water-bath ; 
the residiie treated with strong potash to decompose the acetic ether; the alcohol 
rmoTed hj waahing with water; and the remaining liquid, the acetal, dried over 
chloride or oalcinm and rectified. (Stas.^ 

2, By difftilling alcohol with dilute sulphuric acid and peroxide of manjD;anese. A 
mixture of 2 parts alcohol, 3 parts peroxide of manganese, 3 parts sulphuric add, and 

2 parts water (the proportions given by Liebig^ for the proportion of aldehyde), 
is subjected to distillation as soon as the frothing which first ensues has ceased ; 

3 parts of liquid are distilled ofiT; the distillate is rectified ; and the portion which 
goes over at 80° is collected apart from that which distils between 80° apd 95°. 
The first portion is mixed wim chloride of calcium and rectified, the distillate 
obtained below 60° chiefiy consisting of aldehyde, while above 60° a product is 
obtained, which, when treated with a strong solution of chloride of calcium, yields 
an ethereal liquid. The portion of the former liquid which came over between 80° 
and 96°, is also rectified, and the first portion of the resulting distillate treated with 
stnmg aofaition of chloiide of calcium, inierenpon it likewise yields an ethereal liquid. 
Tiieae ethenal liquids, containing aldehyde, acetic ether, £e. and acetal are united, 
and shaken with caustic potash to resinise the aldehyde and decompose the acetic 
ether. The brown liquid which fioats upon the potash-solution is separated and 
distilled; the distillate again mixed with chloride of calcium; the liquid thus separated 
is heated to 100° for twenty-four hours with twice its volume of caustic potash in a 
sealed tube ; the lower stratum is rectified ; the distillate again shaken with chloride of 
calehim ; and the separated liquid is digested with pulverised chloride of calcium, and 
submitted to simple xectaflcation. Pure acetal then distils over from 100° to 105°. 
(Wurta.) 

3. By the actk>n of chlorine upon alcohol, acetal being indeed the {vincipal pro- 
duct of that reaction, so long as no substitution-products are formed: 

30«H*0 + 2a - C«H»H)« + 2Ha + H«0. 

Chlorine is passed through 80 per cent aloohol cooled to between 10° and 15°, till 
a pofrtion becomes turbid on the addition of water, indicating the formation of substi- 
tation-prodncts. One fourth of the strongly add liquid is then distilled off; the dis- 
tillate nenbralised with chalk ; one fourth acain distilled off; and the distillate, con- 
sisting of alcohol, acetic ether, aldehyde and acetal, treated as above to separate the 
acetal. (Staa) 

According to Li eb en (Ann. Ch. Phys. [3] Hi. 313), the chief products of the action 
of cfalraine on alcohol of 80 per cent, are monochloracetal and dichloracetal. (p. 19.) 

n. Vrcfm Aldehyde, 1. By treating aldehyde with pentabromide of phosphorus, 

b2 



4 ACETAL. 

whereljy it is converted into hronUde ofethylideiM C«H*Bi* (a compmmd iflomeric inth 
bromide of ethylene), and acting on this componnd with ethylate of sodiom. 

C*H*Br* + 2C«H*NaO « NaBr + 2C«H"0«. 

This mode of preparation is, however, veiy troublesome, on account of the difficulty 
of obtaining the bromide of ethylidene. Chloride of ethylidene C*H*C1«, (produced by 
the action of pentachloride of phosphorus on aldehyde) does not appear to yield acetal 
when treated with ethylate of sodium. 

2. By passing hydrochloric acid gas into a mixture of 1 vol. aldehyde and 2 vols, 
absolute alcohol immersed in a freezing mixture, whereby the compound C*HH)10 is 
obtained in the form of an ethereal liquid floating on aqueous hydrochloric acid, — 
and treating this compound with ethylate of sodium: 

C*H*0 + C"H«0 + Ha - C*H"aO + H«0 
and C«HK310 + C«H»NaO = NaCl + C^»*0« 

(Wurtz imd FrapoUi, Compt. rend. xlviL 418 ; Ann. Ch. Pharm. cviii- 223.) 

Properties, — ^Pure acetal is a colourless liquid, less mobile than ether, having a pecu- 
liar agreeable odour and a refireshing taste, with an after-taste like that of hazel nuts. 
Sp. gr. 0-821 at 22-4. Boils at about 106° C, with the barometer at 0768 met 
Vapour density == 4*141. 

It dissolves in eighteen times its volume of water at ordinary temperatures, the 
solubility increasing as the temperature rises. From the aqueous solution it is sepa- 
rated by chloride of calcium and other soluble salts. Ether and alcohol dissolve it in 
all proportions. 

Decompositions, — 1. Acetal is not altered by mere exposure to the air, but in contact 
with platinum-black it is quickly converted, first into aldehyde, and then into acetic 
acid * 

C«H"0» + 20 = 8C«H*0 + B?0. 
> — r— ' "*— t— -^ 

Acetal. Aldehyde. 

It is likewise oxidised by nitric and by chromic add. 2. Caustic alkalies do not decom- 
pose it, if the air is excluded. 3. Chlorine abstracts hydrogen from it and forms sub- 
stitution-products. 4. Strong sulphuric acid dissolves and. then decomposes it, the 
mixturo turning black. 6. Hydrochloric add likewise dissolves and blackens it, form- 
ing choride of ethyl. 6. Pentachloride of phosphorus acts strongly upon it, formine a 
la^ quantity of chloride of ethvl, together with other products. 7. Heated in a sealed 
tu^ with several times its weignt of glacial acetic add, it yields acetic ether, more than 
1 atom of that compound being formed from 1 atom of acetal. 

These reactions tend to show that acetal is an ethyl-compound. Stas regarded it 
as a compound of 1 at. aldehyde with 1 at. ether: 

C*H*0 + C*H»»0 = C^»0« ; 

and YTurtz, in his earlier researches on glycol (Compt. rend, zliii. 478), regarded it as 

glycol m [ 0*, in which 2 at hydrogen are replaced by ethyL^jg^^v, [ 0*. This view 

of its constitution was corroborated by the result of distilling a mixture of alcohol and 
wood-spirit with sulphuric add and peroxide of manganese, wheroby a distillate was 

obtained consisting of dimethylate of ethylene /rvat^At 0*, and methylethylate of ethy- 

CH* ) 
lene nH'CH*[^* Subsequent researches have however shown that acetal is not 

identical, but only isomeric with diethyl-glycol, or diethylateof ethylene CH*. (CH*)*. 0'. 
For, when glycol CH^.H'.O' is treated with sodium, 1 at hydrogen is eliminatecl, and 




specific gravity of 0*7993 at 0^ C, and boils at 123*5 C, whereas acetal has a sp. gr. 
of 0*821 at 22<^*4, and boils at 105°, that is to say, 18^*5 lower. Becent experiments 
byBeilstein (Ann. Ch. Pharm. cxii. 240) seem to indicate that the ration^ formula 
of acetal is CH»O.CH».0. 

Chloraoetals (A.Lieben,Ann.Ch.Phys.[3]lvi. 313). Three of these compounds 
have been obtained ; viz. mono-^ di-, and tri-cluoracetal. The two former are produced 
by the action of chlorine on alcohol of ordinary strength (80 per cent) When the 
chlorine has been passed through for some time, and the heavy oil which separates on 
addition of water is washed several times with aqueous chloride of caldum, and sub- 
mitted to fractional distillation, it begins to boil at 80°, and the boiling point gradually 



ACETAMIDE. 5 

rises to 200^, not^ howerer, zemaimng stationazj at any intermediate point. The por- 
tiott vliieh distOa below 120^ oonsiBts of aldehyde and compound ethers ; that which 
diatila abore 120° (which is the larger portion) contains monochloraoetal and diehlor- 
leeUL On again aabmitting it to fractional distillation, the greater part goes oyer 
between 170^ and 185° ; tiiis portion consists chiefly of dichloracetal, whi(£ may be 
obteined pore by sabseqnent rectification. To separate the monochloracetal, the por- 
tion of the seeond distillate boUing below 170°, and the portion of the first distifiate 
which passed aver aboTe 120°, are heated for several days with aqueous potash, 
whereby a watearr liquid ia obtained, containing chloride and formate of potassium, 
sad an otQy liqida consisting chiefly of monochloracetal mixed with dichloracetal ; these 
compounds are finally separated by fractional distillation. 

Aeootding to lieben, the product of the action of chlorine on alcohol of ordinary 
stRDgth does not contain acetaL This is contrary to the statement of Stas, who, in 
fiieth prepared acetal by this reiy process. Probably the relative quantities of acetal, 
moooddoraeetal, and dichloracetal obtained depend on the duration of the action of the 
dilorine (eompare page 3). 

MfmoeUcraettal, O^*H)10', is a colourless liquid, having an ethereal aromatic odour, 
and boiling at about 155°. Vapour-density, by experiment 6*38 ; by calculation (2 vols.) 
5*29. It IS perfectly neutral, insoluble in water, soluble in alcohol It is not attacked 
bj aqoeoQS potash, and does not precipitate nitrate of silver. 

Diehloraeeial, G^H^'Cl^O', is a colourless neutral aromatic liquid of sp. gr. 1*1383 at 
14°. Boils at about 180°. Yapour-density, by experiment 6*45 ; by calculation 
(2 voh.) 6-435. (Lieben.) 

TrieUoraeetal^ C^"C1*0', is produced, together with dichloracetal, by the action of 
ehlorine on highly concentzated but not absolute alcohoL (Dumas, Lieben.) 

ACmrjkMBmm, Cm'NO » N.H'.G*H"0. Produced : 

1. By heating acetate of ethyl with strong aqueous ammonia to about 120° : 

C>HK).C*H».0 + NH» - NH«.C*H»0 + C?H».H.O 

Acetate of ethyl. Aceumlde. Alcohol. 

2. By tlie action of ammonia on acetic anhydride : 

(C«H»0)H) + NH» « NH«.C«H«0 + C«H«O.H.O 

Acetic Acetamide. Acetic acid, 

anbjdride. 

3. By distilling acetate of ammonium (C«H<0«.NH« « C«H»NO + H«0). A large 
quantity of ammonia is given off at first, then at 160° an acid distillate, consisting 
diiefly of acid acetate of ammonium ; above 1 60°, a distillate containing acetamide 
which crystallises in the condensing tube ; and above 190° nearly pure acetamide. 
By saturating glacial acetic acid with dry ammoniacal ^, and then distilling, | of the 
acetic acid may be converted into acetamide. (Kundig, Ann. Ch. Pharm. cv. 277.) 

Acetamide is a white crystalline solid, which melts at 78° and boilB at 221° or 222°. 
It deliquesces wheA exposed to the air, and dissolves readily in water. Heated either 
with adds or witJi alkalis, it takes up water, and is converted into acetic acid and 
amiiMwiin. — ^Distilled with phosphoric anhydride, it gives up water and is converted 
into aeetonitrile or cyanide of methyl CH*^. — Heated in a stream of drv hydrochloric 
add gas, it yields a liquid and a crystalline distillate, and a brownish non-volatile 
residue; The liquid portion of the <£8tillate consists of strong acetic add, together 
with small quantities of diloride of acetyl, and perhaps acetonitrile. The crystalline 
distillate ia a mixture of hydrochlorate of acetamide, and a compound of acetamide 
and diacetamide CH*N0.OH'N0* ; the latter compound may be extracted by ether, 
in which the hydrochlorate of acetamide is insoluble. The non- volatile residue con- 
sists of hydrochlorate of acediamine mixed with sal-ammoniac The decomposition is 
r^oesented by the following equations : 

2C*H»N0 + Ha = C*H'NO« + Nffa 

' 1— ^ 

DiaceCamide. 

2C«H»N0 + HCl = C*H«N«.Ha + C«H<0« 



Hydrochlorate Acetic 

or acediamine. add. 

O«H»N0 + 2Ha « C*HK)CI + IfKHJl; C*H^O - H«0 = C«H*N. 

f I 

Chloride of Acetonitrile. 

acetyl. 

Acetamide acta both as a base and as an add, combining with hydrochloric and with 

nitrie add, and likewise forming salts in which 1 atom of its hydrogen is replaced by 

amet^ 

b3 



5 ACETAMIDE. 

1 By mixing acetamide fused at a gentle heat with oxychlonde of phosphorua, 
diflflolTuie the resnlting crystalline mass in absolute alcohol, and learing the solution 
to cooLop better, mixing it with ether; hydrochlorate of acetamide is then obtained 
in colourless crystaUine needles. The crvstaUine mass first produced, appears to be 
a compound of acetamide and oxychlonde of phosphorus, and this, on addition of 
alcohoV yields phosphate of ethyl and hydrochloric acid, which unites with the 
acetamide : 

2OTt*N0 + POa« + 3(C*H*.H.O) « (C*H»NO)«.Ha + P(C«H»)«0 + 2HCL 

2. By directing a stream of dry hydrochloric acid gas on a solution of acetamide in 
alcohol and ether cooled from without, washing the resulting crystalline mass with 
anhydrous ether, and dissolving it in warm alcohol The solution on cooling, or more 
quiily on addition of ether, deposits the hydrochlorate in crystals. This mode of 
preparation is preferable to the former. The compound forms lone spear-sha^ crystals, 
having an add taste and reaction, easily soluble in wat«r and alcohol, but insoluble in 
ether. Heated in a sealed tube to between ISQO and 200°, it decomposes, yielding 
the same compounds that are obtained by heating acetamide in dry hydrochloric acid 

^^itrate of Acetamide, C"H»NO«.NO«H, is obtained by dissolving acetamide in cold 
strong nitric acid. It forms colourless acid crystals, which melt at a moderate heat, 

and detonate at a higher temperature, leaving scarcely any residue. 

CBLORACsetAMny^ — Monochloracetamide, C*H*CLNO = N.H«.0*H«C10. is 

obtained : 

1. By the action of ammonia on monochloraoetate of ethyl: 

C«BW:!10.0«H».0 4- NH» - N.H».C*H«C10 + C^W. 

2. By bringing perfectly dry ammoniacal gafl in contact with chloride of mono- 

chloracetyl : QtstdOQi + 2NH» - N.H".0»H"C10 + NHKJL 

The product is a white amorphous mass, from which absolute alcohol extracts the 
amide, and deposits it in large shining laminae. The amide dissolves in 10 parts of 
water and 10| parts of alcohol at 24° but is very sparingly soluble in ether. It is 
decomposed by potash, yielding chloride and acetate of potassium. (E. Willm. Ann. 

Ch. Phys. [3] xlix. 99.) 

Trichloracetamide. C*H*Ca«NO « N.H».C«C1"0. This compound is produced 

by the action of gaseous or aqueous ammonia: 

1. On chloride of trichloracetyl : 

(?a«o.a + 2NH» - N.H».(?a»o + wssx 

2. On trichloraoetate of ethyl : 

C?C1K).C«H».0 + NH« - N.H«.0«C1"0 + C«H«0. 

3. On ohloraldehyde, G*C1^ 0, or the polymeric compound, perehloracetie ether, 

c*a«o*: 

C*aH) + 2NH» - C«H*a«NO + lTH*a 

Also by the action of ammonia on the perchlorinated ethylic ethers of formic, carbonic, 
oxalic, and succinic acids, dSi these compounds yielding chloraldehyde when heated. 
The best product is obtained from perehloracetie ether. The mass is treated 
with cold water to dissolve the sal-ammoniac, and the residual trichloracetamide is 
crystallised from ether. It then forms snow-white crystalline laminse. It dissolves 
also in boiling water and in alcohol, and crystallises from the aqueous solution in ta- 
bular crystals belonging to the rhombic system. It has a sweetish taste ; melts at 
136°, begins to turn brown at 200°, and boils at about 240°. It gives off ammonia when 
heated with potash. Ammonia dissolves it after a while, and the solution yields, by 
evaporation, beautiful prisms of trichloracetate of ammonium. Anhydrous phos- 
phoric add converts it into chloracetonitrile or cyanide of trichloromethyl : C'H'Cl'NO 
-H«0«C»C1"N. (Cloez, Ann. Ch. Phys. [3] xvii. 806; Malaguti, ibid. xvi. 6; 
Cahours, ibid, xix. 362; Oerhardt, Compt. chim. 1848, 277; Trait^ i. 760; 
Gm. ix. 270.) 

Tetraohloracetamide, C*HC1^0-«N.H.CLCK?1^; sometimes called chlora- 
cetamic add, is formed by exposing trichloracetamide, slightly moistened with water, to 
the action of chorine in sunshine. It then sublimes in needles, which may be purified by 
crystallisation from ether. It is permanent in the air, melts when heated, and partly 
sublimes undecomposed. It is nearly inodorous, but has a harsh disagreeable taste. 
Insoluble in water, but dissolves pretty readily in alcohol and wood-spirit, and very 
easily in other. It dissolves without decomposition in cold aqueous alkalis, forming 




ACETIC ACID. 7 

aysUOisable salts. When boiled with potash, it gires off ammonia^ and leaves chlo- 
nde and carbonate of potassium : 

C«Ha*NO + 8HK) = NH» + iKCi + 2 C0«. 

(Cloes, Ann. Ch. Phys. [3] xvii. 305.) 

Bromaeetamides and lidaeetamidea are likewise known. 

IhACKTAMiDB, C^H'NO* » NH(CHK>)*. The ethereal solution of the oomponnd of 
aoetamide and diacetamide obtained b^ the action of hydrochloric add gas on ace- 
tamide, deposits, when hydrochloric acid ^as is passed through it, spicnlar crystals of 
hydiochloiHte of acetamide^ and the liquid filtered therefrom yields by cTaporation 
OTcr sulphuric add, crystals of diacetamide, easily soluble in water, alcohol, and ether. 
The eiystals when boiled with adds are resolved into acetic acid and ammonia, but 
not so readily as acetamide. The alcoholic solution boiled with dichloride of platinum 
deposits chloroplatinate of ammonium. (Strecker.) 

Ethtlacbtaiiidb. See Ethtlamikb. 

Mebcubaobtamidb, CH^HgNO. An aqueous solution of acetamide saturated 
with mercuric oxide deposits by evaporation in vacuo, colourless ciystalline crusts 
sparingly soluble in aloohoL mlver-acetaimde^ CH^AgNO, is obtained in a similar 
manner in oystalline scales. 

PHBirrLACBTAlfXDB, OT ACETAllILIDa, SCO PHHNn.AiaiIB. 

Synonyme of ErKVUsini and QLBiiAin Ga s. 

Esmgaavre, Adde AcHique. C«HH)» = ^^^^ \ 0, or 0»H»0«.H. 

The hydrate or hvdrated oxide of acetyl; it may be regarded as a molecule of water 
(HH)), in which ha]f the hydrogen is replaced by acetyl CHK). (It was formerly 
supposed to be derived from a nulide, C*M\ also called acetyl, which, in combination 
with 3 atoms of oxygen, formed anhvdious acetic add C*JI*0^i and this in com- 
bination with an atom of water Hu, formed hydrated acetic add, C*H*O^MO=^ 
C*B*0^ SeeAcBTTi« 

SemrecB, — ^AeeCic add exists, in nature, in the oxsanic kingdom only, being found 
in the juiees of many plants, espedally of trees, and existing probably also in several 
of the animal secretions ; but more commonly it results from the decomposition and 
oxidation of organic bodies. 

ForwuUion, — 1. By the destructive distillation of organic substances, especially of 
wood. — 2. Sy the action of oxidising asents, viz. atmospheric oxygen, chromic add 
nitric add, hypochlorons add, &&, on alcohol and other organic b<>dies. — 3. By. the 
action of hydrttke of potassium or hydrate of sodium at a high temperature on various, 
oiganic bodies, e.a. suodnic add, oldc add, malic add, sugar, alcohol, &c. — 4. By 
heating cyanide of methyl, with aqueous caustic alkalis: CH'.CN + 2HK> w, C<H*0* 
+ NH*. — 5. By the action of carbonic anhydride on sodium-methyl ; CO* -i- CH'Na » 
C^'KaO* (acetate of sodium).— > 6. By the reducing action of sine or sodium-amalgam 
on ehloiaoetic add. 

Prep€tration. — 1. From alcohol. Alcohol is converted into acetic add by various 
processes of oxidation; e.^. by the action of spongy platinum. If a tray of finely- 
diTided ^ongy platinum be placed on a triangle over a porcelain dish containing a litUe 
alcohol gently warmed, and the whole covert with a bell-glass standing on a wedge, 
and open at the top so as to allow a gentle current of atmospheric air to pass through 
the apparatus, the oxidation of the alcohol proceeds rapidly, acetic add condensing in 
abundance on the indde of the bell-jar. 

By this process, however, much of the alcohol is converted into aldehyde, and lost 
by volatilisation. It would appear, in fact, that, in the formation of acetic add by 
dirwt oxidation, aldehyde is always developed as an intermediate product^ espedally 
if the ooddismg influence be not sufficiently rapid — 

(?H«0 + O - C«H*0 + H»0; and C»H«0 + - C«H*0«. 



m' 



Alcohol. Aide- Aide- Acetio 

hyde. bjde. add. 

The oxidation of alcohol by atmospheric oxygen is greatly promoted by the presence 
of ferments ; and, in £ict, in the ordiuury processes for making vinegar, an alcoholic 
solution is exposed to the joint influence of air and a ferment. In Prance and Ger- 
many wine is usually employed, and in England malt 

Won VnraoAB ( Wdnetng, VinaigTe\'-T\M following is the pUn of making vinegar 
piaetised in Paris. The wine destined for vinegar is mixed in a large tun with a 
quantity of wine-lees, and the whole being transfenred into doth-sacks, placed within 
a large iron-bound vat, the li<ffid matter is squeesed through the sacks by superin- 
cumbent pressure. "What passes through is put into large casks set upright and 

b4 



8 ACETIC ACID. 

haTing B small aperture at the top. In these it is exposed to the heat of the san in 
summer, or to that of a store in winter. Fermentation supervenes in a few days. If 
the heat should then rise too high, it is lowered hy cool air and the addition of fresh 
wine. In the skilful regulation of the fermentative temperature consists the art of 
makinff good wine-vinegar. In summer, the process is generally completed in a 
fortn^t ; in winter, double the time is requisite. The most favourable temperature 
is between 25^ and 30^ (77^ and 86^ FX The vinegar is then run off into barrels 
containing several chips of birch wood. In about a fortnight it is found to be 
clarified, and is then fit for the market. It must be kept in close casks. 

At the same time that the alcohol is thus acidified, the nitrogenous organic matters 
which have served as ferments have likewise assumed new forms, and settled at the 
bottom of the vessel in the form of a white gelatinous mass, known as '* mother of 
vinegar." This substance, which has been described bj Mulder as a AingoSd plants, 
under the name of Mycoderma Vini, is a nitrogenised body, which has the power of 
exciting tSie acetiftcation of pure alcohol in the presence of atmospheric air, probably 
in consequence of its own tendency to change. By treating it with potash, the whole 
of the nitrogen is removed, pure cellulose alone remaining. 

A slight motion is found to favour the formation of vinegar, and to endanger its 
decomposition after it ia made. Chaptal ascribes to agitation me operation of thunder, 
though it is well known, that when the atmosphere is highly electrified, beer is apt to 
become suddenly sour, without the concussion of a thunder-storm. Vinegar does not 
keep well in ceUars exposed to the vibrations occasioned by the rattling of carriages. 
The lees, which had been deposited by means of isinglass during repose, are thus 
jumbled into tiie liquor, and promote the fermentation. 

Almost all the vinegar of the north of France being prepared at Orleans, the manu- 
facture of that place has acquired such celebrity as to render the process worthy of a 
separate consideration. 

The Orleans casks contain nearly 400 pints of wine. Those which have been 
already used are preferred. They are placed in three rows, one over another, the upper 
ones having an aperture of two inches diameter, k(n>t always open. The wine for aoe- 
tification is kept in acyoining casks containing beech shavings, to which the lees 
adhere. The wine thus clarified is drawn off to make vinegar. One hundred pints of 
good vinegar, boiling hot, are first poured into each cask, and left there for eight days; 
ten pints of wine are mixed in, every eight days, till the vessels are Aill ; and the 
vinegar is allowed to remain in this state fifteen days, before it is exposed for sale. 
The manufacturers at Orleans prefer wine of a year old for making vinegar ; but if 
the wine has lost its extractive matter by age, it does not readily undergo the acetous 
fermentation. 

The used casks, called motherSt are never emptied more than hali^ but are succes- 
sively filled again, to acetify new portions of wme. In order to judge if the mother 
works, the vinegar makers plunge a spatula into the liquid; and according to the 
quantity of froth which the spatula shows, they add more or less wine. In summer, 
the atmospheric heat is sufficient. In winter, stoves heated to about 76^ Fahr. main- 
tain the requisite temperature in the manufactory. 

Qtdck mfithod of Vinegar-making {SchndUsaigbereitung), Since the efficient con- 
version of the alcohol into acetic acid essentially depends upon the completeness of the 
oxidation, the German chemists have proposed to promote this result by enlarging 
the surfiicc of the liquid exposed to the air. This is effected l^ allowing the alcoholic 
liquor to trickle down in a fine shower from a colander through a large oaken tube 
(called the vinegar generator, or graduator), filled with beech chips, up which a cur- 
rent of air ascends mrough apertures in the sides. By the oxidation which goes on, 
the temperature of the liquid rises to 37® or 40® C. (100 or 104° Fahr.). The liquid 
requires to be passed three or four times through the cask before the acetification is 
complete, which takes place in twenty-four or thuly-six hours. Care should be taken 
to allow a sufficient supply of air. 

In England the same result is often attained by causing the alcoholic liquor to be 
distributed by means of a Barker's mill or other contrivance, over the beech shavings 
in a tun, whilst a current of air is forced up through it by two boating gasometers 
which are made to rise and fall alternately by steam power. 

Wine vinegar is of two kinds, white or red, according as it is prepared firom white or 
red wine. It contains, besides acetic acid and water, sugar, colouring matter, gum, and 
salts, especially bitartrate of potassium. Its specific gravity varies from 1-014 to 1*022. 

M\LT VnfBOAB. — This is prepared from malt or a mixture of malt and raw barley, 
which is mashed with water as in the ordinary operation of brewing ; the wort is then 
submitted to the vinous fermentation and tne liquor thus obtained is converted by 
oxidation into vinegar. This effected in two ways ; either by the process of fielding 
or stoving. 

When fielding, that is, exposure to the open air, is resorted to, tlie wort must be 



ACETIC ACID. 9 

made in the ipring months, and then left to finish during sereral months of the 
vum season. In eonseqnence, therefore, of the length of time required, the latter, 
or giomnff prooess, is more generallj used. The wash is introduced into barrels 
wtinding endvaya, tied oTer with a coarse doth, and placed dose together in darkened 
chambers. aztificiaUy heated hy a store. The liquor remains in these barrels nntQ the 
aoetification is eomplete. This nsnallj occapies several weeks or months. The product 
is next xntrodnoea into large tons with false bottoms, on which rape (the residuary 
frnit from the making of British wines) is placed, and allowed slowly to filter througn 
them. Bdow the fidse bottom and above the true one is placed a tap which allows 
the vinegar to flow into a back or cistern. From this cistern a pump raises the liquid 
to the top of the vesselt and thence it flows through the rape to be again retomed. Or 
sometimes the npe tuns are worked by pairs^ one of them beiuff quite filled with 
risegar from the barrels, the other only thi^ parts, so that tiie acetification is 
exdted more readily in the latter than the former, and every day a portion of the 
rinegar is oanveyed firom one to the other, till the whole is finished and fit for sale. 

Ibdt vinegar has a yellowish red colour, an a^eable add taste, which is due to 
acetic add ; but the aromatic odour which distingmshes both it, and also wine vinegar, 
from p^rroligneons add (to be afterwards described) is imparted to it by the presence 
of acetie and other ethers. 

Vinegar of four dififerent strengths is sold by the makers, distinguished as Kos. 18, 
20, 22, and 24. The last, which is the strongest, and is called proof vinegar, contains 
6 par eent. of real acetie add ; its specific gravity is 1*019. (Per eir a.) 

vinegar is liable to undergo a putrefactive decomposition, which was believed by 
the makers to be prevented by the addition of sulphuric add, and they are allowed 
hj law to add one-uiousandth part by weight of sulphuric add. It is now known that 
thia is unnecessary; nevertheless the practice is stUl continued. 

XhsmxED YiMSOAB. — ^By submitting wine or malt vinegar to distillation it is deprived 
of its eolouring and other non-volatUe matters, a colourless limpid liquid being obtained 
which is known in commerce as distilled vinegar. The product is, however, always 
weaker than the vinegar from which it has been derived, because the boiling point of 
strong acetic add is above that of water ; it is also liable to be contaminated with a 
BBttQ quantitv of alcohol and empyreumatie bodies. 

2. From Wood. Wood YuraaAB, or PTBOiJOiniOus Acm.— The ^naier part of the 
aeetie add now employed in the arts is obtained by the destructive distillation of wood. 
The wood is heated in large iron cylinders like gas retorts, connected with a series of 
condensing vessels, the uncondensable ^ases which are evolved in large quantity being 
eonvayed by pipes into the fire and aiding to maintain the heat. The liquid which 
eondeDses in the receivers consists of water, tar, wood-spirit or methyUc alcohol, 
acetate of methvl, and acetic add. The watery liquid, after bein^ separated from the 
tar, is redistillecl, the wood'Spirit passing over among the first portions of the distillate, 
and the acetic or pyroligneous aad afterwards. The add thus obtained is coloured, 
and has a strong tarry flavour, which cannot be removed by redistillation. To purify 
this crude add, it is converted into acetate of sodium, either by direct saturation with 
carbonate of sodium, or more economically by saturating it with carbonate of caldum, 
and decomposing the caldum-salt with sulphate of sodium ; and the acetate of sodium is 
purified firom tany matter, flrst by gentle torrefaction, and afterwards by recrystallisar 
turn. It is then decomposed by strong sulphuric add diluted with hdf its weight of 
water, whereupon the sulphate of sodium, being insoluble in acetic add, separates in 
the crystalline form, and may be separated hy simple decantation ; and the acetic acid 
thus separated is purified from the last traces of sulphate of sodium by distillation. 

The process just described yidds a very pure acid, but it is too ezpendve, prind- 
pally in consequence of the large quantity of fud which it requires. A more economical 
process has been proposed l^ Y olckel (Ann. Ch. Phaim. IxxxiL 49 ; Chem. Soc. Qu. J. 
V. 274). In this process the crude wood-rinegar is immediatdy saturated with lime, 
without previous rectification. Part of the tarry matter then separates in combination 
with the lime, while tiie rest remains in solution with the acetate of caldum. The liquid, 
after being diarified by repose, or by filtration, is evaporated down to half its bulk in 
an iron pot, and nuxed with a quantity of hydrochloric add, sufficient to give it a slight 
add reaction. The greater part of the tarry matter then separates, and may be skimmed 
off from the surfikce. The hydrochloric add also decomposes certain compounds of the 
lime with creosote and other volatile substances, which are then expelled by heat ; 33 
, gallons of crude wood- vinegar require for purification from 4 to 6 lbs. of hydrochloric 
' add. The acetate of calcium thus purified is completely dried and distilled with hydro- 
chloric add, 100 parts of the dry salt requiring from 90 to 95 parts of hydrochloric add 
of sp. gr. 1*15 (or 20^ Bm.). The sp. gr. of ttie acetic acid thus obtained is about 1*06 
{89 Bm.). If it contains hydrochloric acid, it may be purified by redistillation, with 
addition of a small quantity of carbonate of sodium, or better, 2 or 3 per cent of 



10 ACETIC ACID. 

bichromate of potaasiiim, which; at the same time, destroya certain oigaaie impnritiea 
tiiat impart a peculiar odour to the acid. 

The presence of hydrochloric or aulphuric add in yinegar is easily detected by boil- 
ing the liquid for about twenty minutes with a small quantily of potato-starch, then 
leaving it to cool and adding; a few drops of iodide of potassium. If the vinegar is 
pure, Uie bhie colour of iodide of starch immediately makes its appearance, but not if 
sulphuric or hydrochloric acid is present^ because these acids boiled with starch con- 
vert it into dextrin, which is not coloured blue by iodine (Payen). Sulphuric acid 
may also be detected by chloride of barium, and h^rdrochloric acid by nitrate of silver. 

[For further details of the manufacture of acetic acid, see the new edition of Ur^s 
JHctionary of JrtSy Manufactures and JIftnef, toL l pp. 6 to 20.] 

Cr tstaixisablb or Gijlcial Acetic Aoid. — This term is applied to the pure acid 
C'H*0^[or C*IP(F\ of sp. gr. 1*0635, because it is at ordinary temperatures a ciTstalline 
solid. The acid obtained by either of the processes above described consists of this com- 
pound more or less mixed with water. On difltilling this dilute acid, a weaker acid 
passes over, and a stronger add remains behind, because the boiling point of aqueous 
acetic add increases with its concentration ; and by repeated fractional distillation, an 
acid is at length obtained which crystallises at a low temperature. Ciystallisable acetic 
add is, however, more conveniently obtained by distilling certain acetates in the diy 
state with an equivalent quantity oi concentrated sulphuric add or disulphate of potas- 
sium; tbus with acetate of potassium: 

20«H«K0« + SO*H« - 20»H*0« + SO*K«. 
and: C«H>KO« + SO^HK «. C*H*0« + SO*K«. 

The proportionfl required are 98 pts. of dry acetate of potassium, or 82 acetate of 
sodium, or 79 acetate of caldnm, or 163 acetate of lead, to 49 parts of monohydrated 
sulphuric add, SO^H*, or 186 parts of disulphate of potassium, SO^HK. Gladal acetic 
acid may also be conveniently obtained from diacetate of potassium, C^*KO'.G*H^O* 
by simple distillation. Wben neutral acetate of potasdum is mixed with aqueous 
acetic add, not too dilute, and distilled, part of the acetic acid unites wim the 
neutral acetate, and a weaker add passes over. But as the distillation goes on, the 
acid potassium-salt decomposes, the distillate becomes continually richer in acetic 
add, and at length the pure crystaUisable add distils over. The temperature must 
not be allowed to exceed 300^; otherwise the acid suffers partial decomposition, and 
becomes coloured (Melsens, Gompt. rend. xix. 611). — Crystallised acetate of copper 
also yields gladal acetic acid, when dried at a temperature between 160° and 180° 
and afterwards distilled at a higher temperature. Towards the end of the distillation 
the add becomes mixed with acetone : that which passes over towards the middle 
must be redistilled to free it from copper mechanically carried over, probably in the 
form of cuprous acetate. The add obtained by this process was formerly called 
Spiritua Aeruginis or Spiriius Veneris. 

Properties. — ^Pure acetic add solidifies at or below 16^ C. in prismatic or tabular 
crystals. In dosed vessels it remains liquid at 12°, and does not solidify till tiie 
Tessel is opened and shaken. Its i^>edfic gravity in the solid state is 1*100 at 8*5 
(Persoz). It melts at 16° (Lowitz), at or above 22°'5 (Mollerat), forming a 
thin colourless liquid of sp. gr. 1*063 (Mollerat) ; 1*065 at 13° (Persoz) ; 1*0635 at 
15° (Mohr); 1*0622 (Sibille- Auger); 1*08005 reduced to 0° (Kopp, Pogg. Ann. 
Ixxii. 1). It boils at 119° (SAbille-Auger); at 117°*3 (Kopp). The density of its 
vapour is different at different temperatiures, compared with an equal bulk of air at 
the same temperature. At temperatures considerably above the boiling point, it follows 
the ordinaipr law of condensation to 2 volumes ; thus at 300° and upwards the sp. gr. of 
the vapour is found b^ Cahours to be 2*00, wluch agrees almost exactly with the calcu- 
lated density, supposing the molecule to occupy 2 volumes. For the atomic weight of 
acetic add, compared with hydrogen as unity is 60 (^ 20 + 4H + 20 ■» 24 + 4 + 32); 
and if this be tne weight of 2 volumes of the vapour, it follows that the weight of 
1 volume of vapour, or m other words, the specific gravity as compared with hydrogen, 
will be 30 ; and multiplying this number by 0*0693, the sp. gr. of hydrogen referred 
to air as unity, we obtain for the sp. gr. of acetic add vapour referred to air as unity, 
the number 2*079. 

But at temperatures near the boiling point, the density of the vapour is much 

greater, exhibiting a condensation to |-volume, or even less. The following table ex- 
ibits t^e density of the vapour at various temperatures as determined byOahours 
(Compt rend. xix. 771 ; xx. 51): 



Temperature. 125° 130° 140° 150° 160° 170° 190° 200° 230° 250° 800° 
Density. 3*20 312 2*90 2*75 2*48 2*42 2*30 2*22 2*17 2*09 2*08 

The tension of the vapour is 7 mm. at 15° ; 14*5 mm. at 22°, and 32 mm. at 32°. 
(Bineau, Ann. Ch. Phys. [3] xviil 226.) 



ACETIC ACID. 



11 



The add iuB a pungent sour taste and odour, blisters tHe eikm, and acta as an acrid 
poiBon. It does not redden litmus paper per se, but very strongly when mixed with 
vHter. 

DeeomptmHens, — 1. The Tapour of aeetio acid is inflammable, and bums with a 
blue flame, pfodudng water and carbonic acid. When it is passed through a red-hot 
tabe, the greater part remains unaltered, but a portion is cwcomposed, yielding free 
caiboii and combustible gases, together with acetone, napthalin, hydrate of phenyl and 
benaoL (Berthelot, Ann. Ch. Phys. [3] zxxiiL 296.) 

8. A mixture of gladal acetic and strong aulphurie acid blackens when heated, 
giving off carbonic and sulphurous anhydrides. Fvming sulphuric acid mixes with 
gladu aeetie acid without evolution of gas ; but the mixture becomes hot, and if it be 
raised to a higher temperature, carbonic anhydride is given ofi', mixed with onlv a small 
quantity of siuphuious anhydride. Sulphuric anhydride disqplves in acetic add without 
evolution of gas, and on heating the mixture, sulphacetic add is produced. 

3. Acetic add is not sensibly attacked by nitric acid. 

4. Beriodie add converts it into carbonic or formic add, with formation of iodic 
add and separation of iodine. 

5. Chlorine in sunshine converts acetic acid into monochloracetic and trichloracetic 
adds^ the quantity of the one or the other being greater, according as the acetic add 
or the chlorine is in excess. See CHLOBiLCBTic Acid. 

6. Glacial acetic add heated with bromine in a sealed tube forms bromacetic and 
dibRMoaoetLe adds. Iodine has no action on acetic add even in sunshine. 

7. WUh peniaehloride of phosphorus, gladal acetic add forms hydrochloric add, 
'^^^iT''^* of acetyl and oxyehloride of phosphorus : * 

CWBP0.H.0 -¥ PCl«.a« - C«H«0.C1 + HCl + P0.C1«. 

8l With pentasulphide of phosphorus^ it forma thiacetic add and phosphoric 
gnfavdride: 

6(0»H«O.H.O) + P*S» « V^O* + 5(OTP0.H.S). 

The difierence between the mode of action of the pentachloride and pentasulphide 
of -diosphorus, the former giving rise to two distinct chlorine-compounds, CH'O.Cl and 
HQ, whereas Ute latter forms only one sulphur-compound, is very remarkable, and 
shows dearly tilie propriety of regarding chlorine as a monatomic, and sulphur as a 
diatomie radidc 

Aqubous Acsno Acm. — Acetic add mixes with water in all proportions, impart- 
tqg to it its taste and smell. The dendty of the aqueous add varies with its 
strength in a remarkable manner. When water is gradually added to glacial acetic 
add, the density increases till a hydrate is formed containing 79 pts. of crystallised 
add to 21 water, and having the composition CH*0'. HK). This hydrated add has 
a density of 1*073 and boils at 104°. All farther additions of water diminish the 
density of the add. 

The following table constructed by Mohr (Ann. Ch. Pharm. xxxi. 277) gives 
the quantity of crystaUisable acetic add in 100 pts. of the aqueous add of different 
denattiea. 



F^cffc 


Sp^ Gr. 


Perc. 


Sp. Gr. 


Perc. 


Sp. Gr. 


Perc. 


Sp. Gr. 


Perc 


Sp.Gr. 


100 


10636 


80 


1-0736 


60 


1-067 


40 


1-061 


20 


1-027 


99 


10666 


79 


10736 


69 


1066 


39 


1-060 


19 


1026 


98 


10670 


78 


1-0732 


68 


1-066 


38 


1-049 


18 


1026 


97 


1-0680 


77 


1-0732 


67 


1066 


37 


1-048 


17 


1-024 


96 


1-0690 


76 


1-0780 


66 


1064 


36 


1-047 


16 


1023 


96 


1-0700 
1-0706 


76 


1-0720 


66 


1064 


36 


1-046 


16 


1-022 


94 


74 


1-0720 


64 


1-063 


34 


1046 


14 


1-020 


93 


1-0708 


73 


10720 ; 


63 


1-063 


33 


1-044 


13 


1-018 


92 


1-0716 


72 


10710 


62 


1062 


32 


1-042 


12 


1-017 


91 


1-0721 


71 


10710 


61 


1-061 


31 


1-041 


11 


1-016 


90 


10730 


70 


1-0700 


60 


1060 


30 


1-040 


10 


1016 


89 


1-0780 


69 


10700 


49 


1-069 


29 


1039 


9 


1-013 


88 


10730 


68 


10700 


48 


1-068 


28 


1-038 


8 


1-012 


87 


10730 


67 


10690 


47 


1-066 


27 


1036 


7 


1-010 


86 


1-0730 


66 


1-0690 


46 


1-065 


26 


1-036 


6 


1-008 


S6 


10730 


66 


1-0680 


46 


1065 


26 


1-034 


6 


1-007 


84 


10730 


64 


1-0680 


44 


1054 


24 


1-033 


4 


1-006 


88 


1-0730 


63 


1-0680 


43 


1-063 


23 


1-032 


3 


1004 


82 


10780 


62 


1-0670 


42 


1062 


22 


1-031 


2 


1002 


81 


1-0732 


61 


10670 


41 


1-061 


21 


1029 


1 


1001 



12 ACETIC ACID. 

Mollerat, Ann. GliinL Ixviii. 88, and Ad. van Toorn (J.pr. Chem. vi 171) bare 
also given tables of the specific gravities of acetic acid of different degrees of concen- 
tration. 

It will be seen from the preceding table that the specific gravity of acetic acid varies 
bat slowly, a difference of 1 per cent, corresponding to a difference of only *001 in the 
density, and sometimes even less. For this reason, the determination of the strength 
of commercial acetic add by the hydrometer or acetometer^ as it is called when gra- 
duated for this purpose, is not much to be depended on. The presence of colouring 
matter, saline substanees and other impurities, which frequently occur in vinegar, are of 
course an additional source of inaccunu^ in this method of estimation. It is better, 
therefore, to determine the strength ox the add by ascertaining the quantity of a 
standard solution of caustic soda or ammonia, required to neutralise a given volume. 
(See AcfmDCBTBT and Analysis, Yoluiietbio.) This method, when applied to acetic acid, 
is affected with a slight source of inaccuracy, arising from the fact that the normal or 
neutral acetates of the alkalis exhibit a slight alkaline reaction. The error thence 
arising is, however, of small amount, not exceeding -^ per cent for an add containing 
10 per cent of crystallisable acetic add, as shown by Otto (Ann. Ch. Pharm. cii. 69). 
Moreover, it may be completely obviated by using a solution of caustic soda^ g^uduated 
for the purpose by means of a solution of pure acetic add of known strength (Ajtaltsis, 
VoLUMBTBic). Greville Williams (Pharm. J. Trans, xiii. 694) recommends for the 
volumetric estimation of acetic add a graduated solution of lime in sugar-water. 

Acetic add mixes in all proportions with alcohoL It dissolves resins, gum-zesins, 
camphor, and essential oils. Its use for culinary purposes is well known. Its odour 
is employed in medicine to relieve nervous head-ache, fainting fits, or sickness occa- 
sioned by crowded rooms. Pungent smelling salts consist of sulphate of potassium 
moistened with gladal acetic acid. P^ligneous add is largely used in calico-printing ; 
the tar and empyreumatic substances present in it appear to \^ rather advantageous 
than otherwise for that purpose. Large quantities of acetic add are also used for the 

Separation of the acetates of lead, copper, aluminium, &c. (See Dictionary of Arts, 
'ant{faeture8, and Mines,) 

Acetates. — ^Acetic acid is monobasic, the general formula of its normal salts being 
C«H»0*.M [or C^H^O'M - C^IPO'.MOX the symbol M denoting a metal It also 
forms basic salts, whidi may be regarded as compounds of the normal acetates with 
oxides^ The normal acetates all dissolve in water, and most of them readily. The 
least soluble are the silver and mercuiy salts, so that solutions of other acetates added 
to mercurous nitrate or nitrate of silver, throw down white shining scales of mercurous 
acetate or silver-acetate ; but generally speaking, acetates are not formed by precipita- 
tion : they are produced by the action of acetic add on metallic oxides or carbonates ; 
many carbonates, however, the barium and calcium salts, for example, are not decom- 
posed by acetic add in its most concentrated state, but only after addition of water. 

All acetates are decomposed by heat ToiotA of them yielding carbonic anhydride, ace- 
tone and an empyreumatic oil. Those which are easily decomposed, and likewise contain 
bases forming stable carbonates, are almost wholly resolv^ into acetone and a car- 
bonate of the base ; this is especially the case with acetate of barium : 

2C"H«0«Ba « CTa[«0 + CO^a. 

Those which, like the potassium and sodium salts, require a higher temperature to de- 
compose them, yield more complex products, but always a certain quantity of acetone. 
Amo ng the products are found certain homologues of acetone, viz. methyl^wttons 
C?H»(CH")0 and ethylacetone 0«H»(C«H")0, together with dumasin C^»»0. (Fittig, 
Ann. Ch. Pharm. ex. 17). Acetates containing weaker bases, give off part of the 
acetic acid undecomposed, the remaining portion being resolved into acetone and 
carbonic anhydride, or if the heat be strong, vielding empyreumatic oil and charcoal : the 
residue consists sometimes of oxide, sometimes, as in the case of copper and silver, of 
reduced metal ; in this case part of the acetic add is burnt by the oxygen abstracted 
from the metal. Acetates heated with a large excess of fixed caustic alkaU, are resolved 
at a temperature below redness into marsh gas and alkaline carbonate, e, g, : 

C«H*KO* + KHO « CH* + CO"K«. 

Acetates distilled with sulphuric add, give off the odour of acetic add, and yield a 
distillate which dissolves oxide of lead, and acquires thereby an alkaline reaction. Dis- 
tilled with sulphuric and alcohol, thej 3rield acetate of ethyl, recognisable by its odour. 
The neutral acetates impart to solutions of ferric salts a reddish yellow or red-brown 
colour, according to the degree of dilution. Acetates heated to redness with ar- 
senious add give off the odour of cacodyl. The acetates of the alkali-metals, and 
probably others also, treated with oxychloride of phosphorus, yield chloride of acetyl, 
together with a tribasic phosphate: 

3(C*H«O.Na.O) + PO.a> « 3C*H»0C1 + PO<Na«. 



ACETIC ACID. 13 

AcsiATBS OF Aldoniuii. — o. TnooetaU, As alnminiiun is flesquiatomic (Al* being 

eqinTalent to B^ or Al^ to H) the normal salt should be a triacetate C'HK)*jSi^ or 

(C^K)^^*, [or APO^.ZC*H*(^t regarding it as a compound of alumina with an- 
hjdrons acetic add]. This salt, howeyer, exists only in solution, and is decomposed 
hj er^oration. The solution is obtained by digesting recently precipitated trihydrate 
of almtiininm in strong acetic acid, or by precipitating a solution of the trisulphate 
vith acetate of lead: 

(S0*)»A1* + 6C*H«0*Pb « 3S0*Pb« + 2(C«HH>*)»A1«. 

Tlds salt 18 largely used as a mordant in dyeing and calico-printing, and is generally 
prepared for this purpose by precipitating alum with acetate of lead. The solution 
thus formed contaJTis sulphate of potassium as well as acetate of aluminium. 

iSL Diaeetaie. When the solution of the triacetate obtained by decomposing trisul- 
pbite of ahiininium with acetate of lead is evaporated at a low temperature, with 
sufficient r^ndity, as by spreading the concentrated liquid yery thinly on plates of 
gjaas or poroelain, exposing it to a temperature not exceeding 100° F. (37^*7 C.), and, 
as it runs together in drops, rubbing it constantly with a spatn^ diacetate of aluminium 

nmaina in the Harm of a dry powder containing ^ a1« [ ^^ "^ 6H*0 [or, using the 

snaller atomic weights of carbon and oxygen, 2C*JS*0^,AjP(^ + BHO], The diacetate 
thus obtained dissolves easily and completely in water, and the solution when heated 
deposits dihjdrate of aluminium soluble in water. (See AxnoMiuic.) But when the 
aotution, instead of being quickly evaporated, is left to itself in the cold for some days, 
it deposits a white saline crust, which is an allotropic diacetate of aluminium imoluble in 
water. Heat effects the same change more rapidly, and the insoluble diacetate then 
separates in the &rm of a granular powder. At the boiling temperature, the liquid is 
thus depnved in half an hour of the whole of its alumina, which goes down with } of 
the acetic add, leaving 1 in the liquid. The insoluble diacetate digested in a lar^ 
quaatily of water is gndually changed into the soluble modification, part of which is, 
however, decomposed during the process into acetic add and the soluble dihydiate. 
(Walter Crum, Chem. Soc Qu. J. vi 217.) 

AcBTATBS OF AjocoKixjic. — a. Normal acetate, 0*H^0* NH^ A white odourless salt, 
obtained by saturating glacial acetic acid with dry ammonia. It is very difficult to 
obtain it in the cxystcQline form : for its aqueous solution loses ammonia on evapora- 
tion, and is converted into the add salt {fi). It is readily soluble in water and alcohoL 
Its aqueous solution, known in the Pharmacopda as Spiritue Mindereri, is prepared by 
saturating aqueous acetic add with ammonia or carbonate of ammonium. This solution 
is tzan^wrent and colourless, with a peculiar odour and cooling pungent taste. 
When kept it is decomposed, and becomes alkaline, owing to the formation of carbonate 
of ammonium ; by heat it is converted into a solution of the acid salt ($). 

$. Acid Acetate, C«H»0".NH*.C«H*0» [or CIPO^.NH'O + CH*0*,HO]. Obtained 
as a white crrstalline sublimate when dry powdered chloride of ammonium is heated 
with an equal weight of acetate of potassium or caldum, ammonia being given off 
nmultaneGiisly. A warm saturated solution of this salt, kept in a dosed bottle de- 
posits long needle-shaped crystals. This salt is also obtained in a radiated crystalline 
mass, by evaporating the aqueous solution of the normal salt (a). The crystals redden 
h'tmus and deliquesce rapidly in the air. They mdt at 76°C. and sublime undecomposed 
at 121^. The compodtion <^ this salt is probably that expressed by the above formula. 

AcETATB OF Babixtic, CH'O'Ba. — ^Prepared by decomposing carbonate or sulphide 
of barium with acetic acid. The solution evaporated at a genue heat yields flattened 
prisms containing 2OH'0^Ba + HK), but when cooled to 0° C. it yidds rhomboidal 
prisma, iaomorphous with acetate of lead, and containing 2C^*0'Ba + SH'O. The 
oystals dried at OP yield the anhydrous salt in the form of a white powder, which, 
when strongly heated, is resolved into acetone and carbonate of barium. 

AcBTATB OF BisMUTK Separates in micaceous laminae from a warm mixture of 
sitnte of bismuth and acetate of potassium. Acetic add mixed with a solution of 
nitrate of bismuth prevents the predpitation of a basic salt of that metal .by water. 

AcBTATB OF Cadmiuic. — Small prismatic crystals very soluble in water (S t r o m ey er). 
According to Meissner and John, it is not crystallisable, but forms a gelatinous mass. 

AcKTATB OF Caiciuu, 0*fl"0'Ca, crystallises in prismatic needles, which effloresce 
in the air, and dissolve in water and in alcohol. The salt is decomposed by heat 
into acetone and carbonate of caldum. A solution of acetate and chloride of cal- 
dum in equivalent proportions yields by slow evaporation, large crystals containing 
C?H»0«Ca.ClCa + fiH*0. 

AcBTATB OF Csuux. — Small needles sparingly soluble in alcohol. 



14 ACETIC ACID. 

AGRA.T18 or Crboxivic. — Thechrcmoua salt, 2CH*0*Cr + HK) is, prodnoed hj 
poTiring protochloride of chromium into a solution of acetate of potassium or sodium. It 
rorms red transparent crystals, wbich when moist absorb oxygen yeiy rapidly from the 
air, undeigoinff a tarue combustion. The chromie salt is obtained as a ^reen cijstalline 
crust, yezy soluble in water, by dissolying chromic hydrate in aoetic acid : the so- 
lution scarcely reddens litmus. 

AcBTATBS ov CoBALT. — ^Tho red liquid formed by dissolying carbonate of cobalt in 
acetic acid, yields by evaporation a red residue which turns blue when heated. It 
may be used as a sympathetic inlc. The oxides Co^O' and CoK)* also dissolve in 
acetic acid without sejMntbn of oxygen, forming brown solutions. The solution of 
the sesquiozide sustains a boiling heaJt without decomposition. 

AcsTATBS or OoFFEB. — o. CupToiu AottoU, C^'O'Ccu. [Ccu«>Cu*»63*2]. This 
salt sublimes toii^ffds the end or the distillation of normal cupric acetate. According 
to Berzelius, it is contained in common green verdigris, and sublimes when that sub- 
stance is distilled. It forms soft, loose, white flakes, which redden litmus and have a 
caustic astringent taste. Water decomposes it into normal cupric acetate and yellow 
cuprous hydrate. 

b. Ouprie JaetaUa, — (Berzelius, Pogg. Ann. iL 233; Trait^ iy. 173; Gm. viiL 
323 ; Gerh. i 728.) Four of these salts are known, viz. : — 

Normal Capric Acetate C«H'0«Chi - C*H*(^ . CuO, 

Sesquibasic. . . (0«H«0'Cu)< . Cu«0 - (C^H'O^. {CuOf. 

Dibasic . . . (0*HK)«Cu)« . CuK) - C*^»0» . {CuO)\ 

Tribaaic . . . C»H»0«Cu . Cu«0 - C*H*C^ . \CuOy. 

1. The normal salt CH*0<Cu, called also Crystallised Verdigris, Verdet, Criataux 
ds Venus, is produced l^ dissolving cupric oxide or common verdLigris in acetic acid, or 
by precipitating a solution of nonusil acetate of lead with sulphate of copper : in either 
case, the liquid must be highly concentrated and then left in a cool place. It 
forms dark bluish-green prisms belonging to the monoclinic system, and containing 
2CH»0*Cu + EPO. The ordinary combination is oo P . OP . + P . 2P oo . Twin- 
crystals also occur. Batio of the axes : a : 6 : o — 0*6473 1 : 0'6276. Inclination 
of the axes a 63^. Inclination of the feuies, oo P : oo P in the plane of the ortho- 
diagonal and the principal axis « 108^ ; oo P : OP » 106^ 30' ; OP : 2P oo - 
119^ 4'. Cleavage parallel to OP and oo P. The salt is efflorescent, soluble in water, 
sparingly soluUe in alcohol, and poisonous like all soluble copper-salts. The ciystals 
after drying in vacuo at ordinary temperature^ suffer no fiirther diminution in weight 
at 100°, but give off 9'6 per cent, of water between 110° and 140°, then nothing more 
below 240° ; between 240° and 260° strong acetic acid, which when rectified yidds 32 
per cent of the ccystallisable acid ; at 270° white fumes which condense into white flakes 
of cuprous acetate ; and lastly a mixture of carbonic anhydride and a combustible gas. 
At 330° the deoompoeition ia complete, and a reddish substance remains consisting 
chiefly of metiJlic copper. The solution boiled with sugar yields a red precipitate of 
cuprous oxide. Acetate of copper crystallised at a temperature near 8°, yields ciystals 
containing 20«H"0'Cu + 6H*0. 

2. The basic cupric acetates are contsdned in eammon verdiaris {yert-^te^ffris, 
Grunspan), a substance obtained by exposing plates of copper to tne air in contact 
with acetic acid, and much used as a pigment and as a mordant in dyeing wool black. 
There are two varieties of this substance, the blue and the green, the former oonsiRt' 
ing almost wholly of dibasic cupric acetate, the latter of the Besquibasic salt mixed 
with smaller quantities of the dibasic and tribasic acetates. The aibasio salt or blite 
verdigris is prepared at Montpellier and in other parts of the south of France, by ex- 
posing copper to the air in contact with fermenting wine-lees. The wine-lees are 
loosely packed in casks together with straw, till they pass into Uie state of acetous fer- 
mentation ; and when that is ended, they are arranged in pots covered with straw, in 
alternate layers with rectangular plates of copper, which when used for the flrst time, are 
previously moistened with a doth dipped in a solution of normal acetate of copper, and 
then dried. At the end of three weeks, the plates are taken out ; placed in an upright 
position to dry ; dipped six or eight times in water in the course of as many weeks ; and 
again left to diy, during which operations the verdigris continually swells up. It is 
then scraped o^ the plates again arranged alternately with sour wine-lees, and the 
same processes are repeated till the plates are quite corroded. The same compound is 
obtained by exposing copper plates to damp air in contact with normal acetate of copper 
made into a paste with water. It forms delicate, silky, blue, ciystalline needles and scales, 
which yield a beautiful blue powder. Thejr contain 6 at. water, which they give off at 
60°, and are then converted into a green mixture of the monobasic and tribasic salt : — 

(C?H»OKhi)«.CuK) - C^WOu + (?H»0«Cu . CuH). 



ACETIC ACID. 15 

Bf xepeated exhaxud<m with water, it is resolTed into the inoolnble tribane ealt, 
and a aoliitioii of the normal and sesqnibasic salts : 

5(CBW.2Ca«0) - 2(C*H»0».3Cu«0) + 2C*HW.3Cu«0 + C*H«0».Cu«0. 

The idlowing table exhibits the oompoeition of several kinds of bfaie Terdigris as 

delennxiied by BerselxiiB and by Fhiltips : 

PhUUfW. 
French. EnglUh. 

Calealatkm. B«nelias. CryiuUiaed. Comprested. 

2Cii>0 . . 160 . 43*24 . 4334 . 43*5 . 43*25 . 44*25 

C?«H«0« . . 102 . 27*57 . 2745 . 29*3 . 28*30 . 29-62 

6HH) . . 108 . 2919 . 29*21 . 25*2 . 28*45 . 25-51 

Impmities ... • . . • .. .20. . . . 0*62 

370 • 100*00 . 10000 . 100*0 . 100-00 . 10000 

The setquibagio aesiaie is obtained in a state of puritj by adding ammonia in small 
portions to a boiling concentrated solution of the normal salt, till the precipitate is just 
redisMslyed, and leaving the solution to cool; or by treating common green Ter- 
digris ivi& cold or tepid water, and leaving the filtrate to evaporate. It is then 
deposited in bluish scales containing (CrS*OK)u}^ CuH) + 6HK). It gives off half 
its water at 60^, and becomes greenish. 

Grtai VertUgrtB^ according to Bexzelius, is a mixtare of this salt with small quan- 
titiesof the dibasic and tribasic salts, sometimes also containing cuprous acetate and other 
impozitles. It is manufactured at Chrenoble bj frequently sprinkling copper-plates 
with vinegar in a warm room ; and in Sweden by disposing copper-plates in alternate 
layers wiSi flannel cloths soaked in vinegar, tul the green salt begins to form, then 
e^osing them to the air and frequency moistening with water. The greenest 
kind contains aeoording to Berzeliua, 49*9 per cent, of cupric oxide, and 13-5 per cent, 
of water and impurities ; the pure seequibasic salt oontams 43*5 per cent. Ou^O. 

The tribaaie acetate, CHH)*6ilCu*0 + HK), is the most stable of all the acetates of 
copper. It is obtained by exhausting blue verdi^;ris with water; also by boiling the 
aqneoos solution of the normal salt, or byheating it with alcohol, or again by digesting 
the aame solution with cupric hydrate. The last method yields the salt in the form of a 
green powder; as obtained by the other methods, it forms a bluish powder composed of 
fine needles or scales. It gives off its water at 160^, and decomposes at a higher tem- 
peratme, yielding acetic add. Boiling water decomposes and turns it brown. The 
brown substance thus formed was regarded by Berzehus as a peculiar basic acetate, 
containing C^HK)*. 48Cu'0 ; but it is more probably a mixture of the tribasic salt 
with excess of oxide. 

AiseiaU of Copper and Calcium. CHWCa . <?HK)«Ctt+4H«0. — Obtained by 
heating a mixture 1 atom of normal cupric acetate and 1 atom hydrate of calcium 
with 8 times its weight of water and sufficient acetic add to dissolve the predpitated 
oxide of copper, and evaporating the green filtrate at a temperature between 25^ 
uid 27®. It forms large, blue, transparent^ square prisms, often converted into 
octagonal prisms by truncation of the lateral edges. They effloresce slightly in the 
air; fall to powder at 75°, giving off acetic add ; and dissolve readily in water. An- 
other ciqzrioo-caldc acetate, C^H)K)<Ca+(G*HH>^Cu). OuK) + 2HK), often exists in 
aystaUised Terdigris : its optical properties differ- from those of the normal cupric 
acetate. 

Aceio-araeniU of Copper, C«HK)«Cu.3AsO«Cu, or OH^CCuO+SiAsO^CuO).— 
Sekweinfurt areen, Imperial green, Mitis green, and when mixed with gypsum or heavy 
spar, Nettwwier green. Mountain ^een. Used as a piement^ and prepared on the large 
seale by mixing arsenious add with cupric acetate and water. 5 parts of verdigris are 
made iq> to a thin paste, and added to a boiling solution of 4 puts or rather more of 
arsenious add in 50 parts of water. The boiling must be well kept up, otherwise the pre- 
dpitate assumes a yellow-green colour, from formation of arsenite of copper ; in that case, 
acetic add must be added, and the boiling continued a few minutes longer. The predpi- 
tate then becomes crystalline, and acquires the fine green colour peculiar to the aceto- 
arKuite. The salt is insoluble in water, and when boiled with water for a considerable 
time, becomes brownish and gives up acetic add. Acids abstract the whole of the 
oopper, and aqueous alkalis first separate blue cupric hydrate, which when boiled with 
the liquid, is converted into black cupric oxide, and afterwards into red cuprous oxide, 
an *nr*HnA arsenate being formed at the same time. 

AcBTATBS OF Ibok. — o. Ferrous Acetate. When metallic iron or the protosulphide 
is dissolved in strong acetic add, and the solution concentrated, small colourless silky 
needles are obtained, which dieeolve easily in water, and rapidly absorb oxygen from 
the air. 



16 ACETIC ACID. 

^. Ferric Acetate, — Obtained by diasolTixig ferric hydrate in acetic acid, or by deoom- 
posing a solution of ferric snlpbate with acetate of lead. It ia unciyatalliaable and 
yery soluble in water, forming a red-brown solution ; soluble also in aloohoL The 
aqueous solution, when kept in a state of ebullition for about 12 hours, undeigoes a 
jremarkable modification, acquiring a brick-red colour, and remaining dear idien 
viewed by transmitted lights but appearinff opaque and opalescent by reflected light. 
At the same time, it loses entirely the mettulic taste of iron salts, and acquires that of 
▼inegar ; it forms a brown instead of a blue precipitate with feiTocyanide of potassium, 
and no longer exhibits the characteristic red colour with sulphocyanides. Traces of 
sulphuric or phosphoric acid, or of alkaline salts, precipitate the whole of the iron in 
the form of a red-brown precipitate, which, at ordinary temperatures, is perfectiy in- 
soluble in acids, even the most concentrated; hydrochloric and nitric acids throw 
down a red granular precipitate, which, when p^ectly freed from the acid mother- 
liquor, dissolTes easily and completely in water. (P^an de St. Gilles, Ann. Ch. 
Phys. p] xlvi 47.) 

A mixture of tiie two acetates of iron, called pyrolignite of iron {liqueur deferratUe^ 
bouillon 9u>tr), is prepared on the large scale oy treating iron with wood-yinegar, in 
contact with the air. It is used as a mordant for black dyes ; also for preserving 
wood. 

AcETATEa OF Lbad. — The normal acetate C'H?0*Pb, or PbO. C^SPC^ (Sugar of lead, 
saceharum Batumi, sel de Satume, Bleizucker) is prepared by dissomng oxide or 
carbonate of lead in acetic acid, wood-yinegar being used on the laige scale, or by 
immersing plates^f lead in yinegar in yessds exposed to the air. It crystallises in 
prisms containing 2CH'0'Pb + HH), and belonging to the monodinic system. 
Ordinary combination : qo P . OP . oo P oo , sometimes with the face OP predominating, 
so as to give the crystals a tabular form. The length of the orthodiagonal is to that of 
the dino-diagonal, as 0*4197 to 1. Inclination of the axes » 70^ 28'. Inclination 
of the faces: oo P : oo P « 128°; oo P : oo Poo » 116°; oo P : OP - 98° 80' ; 
OP: 00 Poo » 109° 82. Cleayage parallel to OP and ooPgo. «The crystals ai« 
efflorescent, soluble in 0-59 parts of water at 15°*6 ^60° F.), and in 8 parts of alcohol. 
The salt has a sweet, astringent taste, and is yery poisonous. It melts at 75°-5 ; begins 
to eiye off water with a portion of its acid a little above 100° ; and is completely de- 
hycbrated at 280°. Above that temperature it decomposes, giving off acetic acid, 
carbonic anhydride, and acetone, and leaving metallic lead very finely divided and highly 
combustible. The aqueous solution is partially decompose by the carbonic acid of 
the air, carbonate of lead being precipitated, and a portion of acetic add set free, 
which prevents further decomposition. The solution is not precipitated by ammonia 
in the cold, but yields crystals of oxide of lead when heated with a large excess of 
ammonia. Normal acetate of lead forms crystalline compounds with chloride of lead 
and with peroxide of lead. 

(Berzelius, Ann. Ghim. xdv. 292 ; Schindler, Brande*s Archiv, xli. 129; Pay en, 
Ann. Ch. Phys. [2] Ixv. 238, and Irvi 37; Wittstein, Buchner's Bepert Ixxxiv. 
170; Gm. vui. 310; Gerh. i. 736.) 

Pour baeic acetatee of lead have been described, vis. : 

The sesquibasic acetate . (C«H»0«Fb)*. Pb»0 or (C*lPO^y. (PbOY. 

The dibasic „ . (C«H»0«Fb)». Pb»0 or C*H*0^ .(PbOy. 

The tribasic „ . C«H«0«Pb . Pb*0 or C^H^O* . (P60)«. 

Thesexbasic „ . (C*H»0'Pb)«.(Pb«0)» or C*H*0^ .{PbOy. 

All of these however, except the tribasic salt, are of rather doubtM composition. 

The seequibane salt is obtained by heating the normal salt till it mdts, and subse- 
quently solidifies in a white porous mass. By dissolving the residue inwater and eva- 
porating, the salt is then obtained in nacreous laminae containing 2 [(G^'0^)^FbK>] 
-¥ BH), It is more soluble in water and alcohol than the normal acetate, and forms 
alkaline solutions. (Payen, Schindler.) 

The dibasic acetate is deposited in the crystalline form when oxide of lead ^massicot) 
is dissolved in the proper proportion in the normal acetate. The ciTstals contain 
2 atoms water, half of which is given off at 70°, and the rest at 100° (Schindler.) 

The tribasic acetate is obtained in the crystalline form, when a solution of the normal 
salt saturated in the cold and mixed with J of its volume of ammonia, is left to 
evaporate ; also by digesting 7 parts of massicot in a solution of 6 parts of the crys- 
tallised normal acetate. It forms long silky needles, verjr soluble in water, but in- 
soluble in alcohol. The aqueous solution becomes turbid on exposure to the air. 
According to Payen, the crystab contain 2(C«H«0«Pb . Pb*0) + H'O, but according 
to Berzehus, they are anhydrous. 

The sexbasic salt is obtained by digesting the solution of either of the preceding 
■alts with excess of oxide of lead. A crystalline precipitate is then formed, which 



ACETIC ACID. 17 

d a wlrgB mrinelj in boDing water, and Beparates in silky needles containing 
S[(OT»(m)«.(PW0)3 + 8H?0. (Berzelins.) 

TIm liquid called GcuUard^B lotion^ lead^viniaar, aoetwn Saiwmi, is a mixtnre of 
the upiKsaB sckhitions of these baaic acetates of lead, chiefly the tribasic salt. It is 
w^ared bj digesting oxide of lead in acetic acid, or in a solution of the normal acetate. 
It is an alkaliTM* liquid which is decomposed by the carbonic add in the air. It pre- 
cqutates a laige number of Tegetable snbstances, such as gom-resins, colouring matters, 
&& and fiam its power of eoagolating mocus^ is mnch nsed as a lotion for wounds 
sndsares. 

AcRATB OF LcTHiuii. O^HK)^+ 2 HK). — Bi^ht rhomboldal prisms, deliquescent 
in moist air, aohible in lees than a third of their weight of water at 16^, and in 4*6 pts. 
of akohol of sp. gr. 0*81 at 14^. 

AcsTATB 09 HiiTQAiixeBL — Pals zoso-colonred splinters or small prisms grouped to- 
geUier; aofaible in 3 pts. of water. 

AcR&TBS OT Mbboost. — Mercurotu oeetote, 0*HK)* Hhg, [Hhg » Hg* » 200], is 
obtained by precipitating mereurons nitrate with a soluble acetate. It forms anhydrous 
miesieeoiis lainiiup, roanngly soluble in water. Heat decomposes it into metallic mer- 
cny, carbonic anhymide, and acetic add. 

MercMric .Adxtate, OH"0^Hk [or C^H'C^.H^O], is prepared by dissolving red oxide 
of meieazy in warm acetic acid. It czystallises in br&liant micaceous laminse, soluble 
in their own weight of water at 10^, and somewhat more soluble in boiling water. 
Alcohol and ether decompose it, separating mercuric oxide. 

Jeeiate of Mereurttmmonitimf (XBEH)*. (NJB[*Hg) + H^O, is obtained by a^tating 
recently pireeipitated mercuric oxide with a solution of acetate of ammonium. It cxys- 
tslfises in rhomboidal plates^ tcit soluble in water, insoluble in alcohol. At 100° it 
giies offfirom S O to 81 per cent of its weight, and is conyerted into acetate of tetrarner- 
cmammomum, CGEH)' (NHg«). 

AoRATB OF KiGXBL ciystallises in apple-green prisms, slightly efflorescent^ soluble 
IB 6 pta. of cold water, insoluble in alcohol. The solution is decomposed by hydro- 
Biiipluxrie acid, which dirows down sulphide of nickel. 

AcaETATK OF PoTAssiuic. — Abmfll aeetaU. 0"H«O«K [or C*IP(^JKO], (Terra 
foUata Tartari, Arcanum Tartari, Tartarus regeneratus, Bldttererde^ geUaiterte 
WemsteinertU). • 

This salt esosts in the juices of many plants. It is prepared by dissolving carbonate 
of potassinm in acetic acid. VHien brown yinegar is used for the purpose, the car- 
bonate of potaasium should be added by small portions, so as to keep the solution 
coostantly add. The olgect of this precaution is to avoid the formation of coloured 
products by the contact o£ free alkaU with the foreign matters in the yinegar. Pure 
acetate of potasdnm is a white salt, difficult to crystaUise, very^ soluble in water and 
ddiqueeoent, soluble also in alcohol, and predpitated by ether from the alcoholic 
section. Carbonic add gas, passed into a solution of the salt in absolute alcohol, 
throws down carbonate of potasdum, and liberates acetate of ethyl. The salt melts 
bdow a red heat, forming a limpid oil, which solidifies in an extremely deliquescent 
mass on cooling. It respires a very high temperature to decompose it, and then gives 
off acetone, empyreumatic oil, and mflammable gases, and leaves a reddue of carbonate 
of potassium mixed with diaiooaJL Heated with excess of hydrate of potasdum, it 
yielda carbonate of potasdum and marsh gas : 

C*H«0«K: + KHO - OH* +C0^« 

Heated witii arsenious anhydride, it yidds cacodyL (SeeAnsBNiDBSOFMBTHTL.) Chlo- 
rine, passed into the aqueous solution of acetate of potasdum, liberates carbonic anhydride, 
and fixrms a bleaching liquid, which however loses its decolorising power on exposure 
to the air. When an electric current is passed through a strong aqueous solution of 
acetate of potasdum separated into two parts by a porous diaphragm, hydrogen alone 
is evolved at the negative pole ; while, at the podtive pole, there is evolved a gaseous 
uixtare of methyl and carbonic anhydride, together with acetate of methyl and a small 
quantily of oxide of methyl. The prindpal decompodtion is represented hy the 
equation; 

C«H*0* - CH» + C0« + H, 

the acetate and oxide of methyl being secondary products. (Kolbe, Ann. Ch. Pharm. 

box. 267.) 
Aeid AeetaU or JHaoetate of Totauiim, C»HWK.C^*0«, [or C^B^C^MO + 

When the normal acetate is evaporated with an excess of strong acetic acid, this 

TOU L C 



18 ACETIC ACID. 

acid Mlt IB deposited in needles or lamin*, or by fdow evaporation in long flattoied 
prisms, apparently belonging to the rhombic system. It is very dehqnescent, melts at 
148®, and decomposes at 200<^, giving off crystallisable acetic aoid. On thu property 
is founded an easy method of obtaining the crystallisable acid 

Diacetate of potassium }fi formed when the normal acetate is distilled with bntroe or 
valerianic add ; but neither of these adds decomposes the salt thus produced. Hence, 
when butyric or valerianic add is mixed with acetic add, a separation more or lew 
complete may be effected by half neutralising the Uquid with potash, Mid distilling. If 
the acetic a<ad is in excess, diacetate of potassium alone remains behind, the whole of 
the valerianic or butyric add passing over, together with the remainder of the acetic 
acid. If; on the contrary, the other add is in excess, it passes over, unmixed with 
acetic add, and the residue consists of diacetete of potassium mixed with butyrate or 
valerate. By repeating the process a certain number of times, either on the ac^ 
distillate or on the add separated firom the residue by distillation with sulphuric aad, 
complete separation may be effected. (Liebia Ann. Ch. I'Jiw™-!™: ?£^ . 

AnhydrJL Dia^tate of Potassium, 2C«H»5«K.C*H»0« [-JK:0. 2C»fl»OT is pro- 
duced by dissolving melted acetate of potassium in acetic anhydride at the boiUng 
heat, or by the action of potassium on acetic anhydride. Forms colourless needlea 
very soluble in water, less deliquescent than normal acetate of potassium. It is de- 
composed by beat» giving off acetic anhydride. (Gerhardt, Ann. Ch. Phys. [3] 
xxxvii 317.) 

AcBTATB OF SiLVBB, C*H*0*Ag. — Obtained by precipitating nitrate of silver with 
acetate of sodium. Crystallises from boiling water in thin, flexible lamins ; soluble 
in 100 pts. of cold water. 

AcBTATB OF SoDiuM, C«HH)«Na [or C^J^O^JfaOJ] Terra foUata tartari crystal- 
ligabiUa^ Terre folUe mmirale, — ^Prepared either by dissolving carbonate of so- 
dium in acetic acid, or by decomposing acetate of calcium with sulphate of sodium. 
Forms large transparent prisms bdonging to the monoclinic system. Ordinary 
combination: oo P. [oo Poo] . OP . —P; more rarely with oo Poo, +P, + 2Poo . 
Batio of the axes : a\ hie^ 0*8348 : 1 : 0*8407. Angle of the axes ^ 68^ 16'. In- 
dination of the faces : oo P : oo P in the plane of the orthodiagonal and prindpal axis 
» 95^*30; — P: +P, forming the obtuse edges of the pyramid +Pin the plane of 
the oblique diagonal and prmdpal, axis ^ 117^*32; ooP: OP^^ 75^*35. Cleavage 
paniHel to OP and oo P. (Oerhardt^ Traits i. 725.) The crystals contain 3 at. 




. . p -^ ^ ,. o , boiling 

heat, contains 0*48 pts. water to 1 pt. of salt, and boils at 124^*4. The salt is less 
soluble in alcohol, it has a bitter, pungent, but not disagreeable taste. 

Acetate of Stsontivx crystallises like the barium-salt in two different forms, con- 
taining different quantities of water. The salt deposited at 15^, contains 4*23 p. c. 
water (? 4C'H'0*Sr + H'O), and that which is deposited at low temperatures con- 
tains C^"0^ + H'O. The latter forms prisms belonging to the monoclinic system, 
<»P: ooP«124<'54'; ooP . ooPoo « 107° 33' ; OP : P oo -1630-12. Cleavage 
indistinct, paralld to oo Poo . 

Acetate of Tnr. — Boiling acetic add dissolves tin slowly, with evolution of hy- 
drogen ; the hydrated protoxide dissolves easily in the boiling add, and the solution 
evaporated to a syrup and covered with alcohol yidds small colourless crvstals. Hy- 
drated dioxide of tin also dissolves in acetic acid, and the solution yields a gummy 
mass when evaporated. Bichloride of tin forms a crystalline compound with glacial 
acetic acid. 

Acetate of XTrahiuic. — Uraruma Acetate^ obtained by evaporating a solution of 
oxide in acetic acid, crystallises in green needles grouped in warty masses. 

Uranie Aoetate, or AcetaU of Uranyl, C«H«0«(UK))* [ « C*H*0*.lPO^, is ob- 
tained by heating uranie nitrate till it begins to evolve oxygen, dissolving the yellow- 
ish red mass, which still contains nitric add, in warm concentrated acetic aad, and 
evaporating to the crystallising point ; all the nitric add then remains in the mother 
liquid. From a very concentrated, or from an add solution slightly cooled, the salt 
separates in beautifal rhomboi'dal prisms, C*H*0»(U*0) + HK), belonginff to the mo- 
nodinic system ; boiUng water decomposes them with separation of uranie hydrate, but 
the solution yields the same crystals by evaporation. A more dilute solution cooled 
bdow 10° deposits square-based octahedrons containing C*H'OXn'0)-f | HK), or 

* Uranyl, U*0, U a moDatomlc radtcle,*8appoted to exist In the uranie compoundi. f See Dianicii.) 




ACETIC ANHYDRTOE. 19 

fC^SPO^(VH>)+SBK>. They ave off i of their witer Bt 200^^, and the rest at 275^, 
Irnnag the yeDowiah red anhydrous aalt. 

Unoie acetate comhinea with tbe acetates of the more basic metals, formixig double 
aeetates. The ammomttm, poiasaium, and sodium salts are obtained by adding the 
weMttM of the eaxbonates to a solntion of nranic acetate^ till a precipitate is formed 
flouiatiDg of a uranate of the alkali-metal, rediasolTing this precipitate in a slight 
eieesi of aeetie acid, and cooling the solntion till it crystallises. The other double 
Mits of this group are obtained h^ boiling the carbonates with nranic acetate, tiU the 
vhole of the nranic oxide is precipitated, redissolving the precipitate in acetic add, 
and emporating. The tead and cadmium salts consist of 1 at. of nranic acetate combined 
vith I at of the monobasic acetate, their formnk being CH«PbO> . C*H*(UK))0* 
+ tHH} and C*HH)dO*.C*H»(tJK))0« + | H*0. All the rest contain 2 at. nranic 
aeetiAe with 1 at. of the monobasic metol, their general formula being CHIiiO'. 
3(^H'(nK))0* + nBH). Host of these salts crysUllise with facility, the potassium 
and sihfr udts in the quadratic S3rstem ; the somum salt forms regular tetrahedrons. 
The strontium and calcium salts are yery soluble in water, and difficult to czystaUise. 
The sodhim salt is anhydrous ; the rest contain water of crystallisation. (Worth eim, 
J. pr. Ghem. Trrfr 209; Weselsky, Ghem. Ghiz. 1858, 390.) 

AcBt^TB OF Yttbiux, Oil*0*Y + H*0. — Bhombo'idal prisms with trihedral snm- 
mita They are permanent in the air at ordinaijr temperatures ; ^ve off their water, 
and become opaque at 100^ ; diBsolve in 9 pts. of cold water, and in a smaller quantity 
of boiling water; also in alcohol (Berlin.) 

AsxtxTB or Znro, C*H»0*Zn + |H*0,or2C«H»0«Zn + 8H«0 [ = CiPZnO«+ 3HO]. 
— Obtained by diasolTing either the metal, the oxide, or the carbonate in acetic ado. 
ClyBtanises in nacreous efflorescent laminse belonging to the monodinic system (K opp's 
EiyrtiJkgraphie^ p. 310). Ordinary combination : OP. ao P. « Poo . + P . + 2Pao , tne 
&ee OP predominating, a: 6 : c » 0*4838 : 1 : 0'87. Indination of axes » 46^30'. 
ladioation of feces, ooP: oo P in the plane of orthodiagonal and principal axis = 
1120 36'; ooP.OP-112<» 28'; OP: ooPoo =118° 30' ; OP: Poo ==80°; OP: +P 
a 750 3()r^ CleaTBge paralld to OP. The salt dissolyes yery readily in water. At 
100° it melta, grves off its water with a littie acetic add, then solidifies, and does not 
Uqueff again tul heated to 190° or 196°, at which temperature anhydrous acetate of zinc 
saUimes in nacreous scales. At higher temperatures, complete aeoomposition ensues. 
(Larocque, Becneil des Tray, de la Soc. Fharm. 1847-64.) 

ACVm ACKDff CUBSTIT U VIOIV VSOSVCTS OF> — ^The following adds 
(which will be more folly described hereafter), are deriyed firam acetic add by substi- 
tstion: 



'^""^'^ "^"SJo 



H 



Bihiomacetie add ^^"^^lo 

CUoncetieadd ^^^^^^^^jo 

TrichUnacetie add . . • • . Hi^ 



lodaoeticadd . . . . . ^^^HC^ 



cwio; 

0*HI«Oi 



IHniod-flcetio add ..... ^'^nc^ 

Thiaoeticadd ^^'^js 

The brominated and ehlorinated adds are produced by the direct action of bromine 
and dilotine on acetic add ; the iodated ados by the action of iodide of potasdum on 
bromacftate and difaromaoetate of ethyl ; and thiacetic add by treating glacial acetic 
add with pentasulphide of phosphoros (p. 11). All these adds are monatomic, 
Uke aeetie acid itself conespond to it in nearly all their reactions, and are formed 
vpon. the same type. 

ACmna Arnnsna. CHH«0* » (G>H*0)*0. Anhydrous Aoeiie acid; 
Oxide of Acetyl : Aeetaie of Acetyl.— {QeThArdt, Trait^ i. 711.) 

This compound is obtained : 1. By the action of ^xychloride of phosphorus, P0C1\ 
00 acetate ^potasdum. The acetate depriyed of water by fusion, is introduced into 
a tubulated retort, and the o^chloride of phosphorus admitted through tiie tubulus, 
drop by drop. A yudent action takes placie, the mixture becoming yery hot without 

2 



20 ACETIC ANHYDRIDE. 

the application of external heat, and a liquid distilB over, which is the chloride of 
acetyl, while tribaaic phosphate of potassium remains in the retort: 

SCWKO* + POa« - PO*K« + 3(C*HH).C1). 

If now this liquid be ponred back again three or four times into the retort» so that 
it may remain for some time in contact with the acetate of potassium, that salt being 
also in excess and pretty strongly heated, a farther action takes place between the 
acetate of potassium and the compound C'H'O.Cl, the result of which is the forma- 
tion of acetic anhydride : thus, 

C«H»KO» + C«H«0.a - Ka + C^H«0«. 

The acetic anhydride enters into combination with the acetate of potassium, and a 
considerable degree of heat is required to destroy this oom^und and cause the anhy- 
dride to distil over. The distillate is more or less contaminated with acetic acid and 
chloride of acetyl ; but on redistilling the crude product, these impurities pass over at 
the commencement, before the temperature rises to IZ7^'6, after which the pure 
anhydride distils over. — 2. By the action of terchloride of phosphoms on acetate of 
potassium. When the liquid chloride is added drop by drop to the acetate of potas- 
sium (about 1 pt PCI' to more than 2 pts. of the acetate), the action begins without 
application of heat, and chloride of acetyl, amounting in quantity to about half the 
chloride of phosphorus used, distils over mixed with a small quantity of chloride of 
phosphorus. On heating the residue after this action has ceased, acetic anhydride 
distik over free from chloride, and in quantity equal to about a third of the chloride 
of phosphoms used. The product contuns a small quanti^ of a phosphorus-compound, 
which causes it to impart a brownish colour to nitrate of silver ; but it may be freed 
from this impurity by a second distillation with acetate of potassium. — 3. By the 
action of chloride of benzoyl, CHH).G1, on Aised acetate of potassium. The first 
products of the action are cmozide o^potas8ium and acetate of benzoyl, CHK)* : 

c»HK). CI + o^mco* - Ka + otpoI ^• 

But if the acetate of potassium is in excess, and the mixtore is heated somewhat 
above the temperatore at which the original substances act upon each other, a farther 
action takes pUoe, and a colourless liquid distils over, which is acetic anhydride, while 
benzoic anhydride remains in the retort in combination with benzoate of potassium. 
These new products are formed by double decomposition between 2 atoms of the 
benzoic acetate : 



gjC'HK))^ _ C»HK)) Q . C«H«0)o 
'^IC'H'Oj" " C'HK)} " + C^'Op 



4. By Hie action of chloride of acetyl, CH'OCl, on dry benzoate of sodium. The reaction, 
which takes place without the aid of heat, is precisely similar to the preceding. 

Acetic anhydride is a colourless, veiy mobile, strongly refracting liquid, having a 
powerful odour, similar to that of the hydrated acid, but stronger, and recalling at the 
same time that of the flowers of the white-thorn. Sp. gr. 1*073 at 20^*6, which is 
nearly that of the hydrated acid, C^^O' + HK), at its greatest density. Boiling 
point 137^*5 under a pressure of 760 mm. Vapour density » 3'47 (by calculation 3*581 
for a condensation to 2 volumes). 

Fuming sulphuric acid becomes heated by contact with acetic anhydride, carbonic an- 
hydride being given off and a coi\jugated acid produced, which forms a gummv salt with 
lead. Potassium acts violently on acetic anhydride, evolving a gas whidi does not 
take fire if the potassium be introduced by small portions at a time. The liquid, after 
a while, soUdifies into a mass of needles, consisting of a compound of acetic anhydride 
with acetate of potassium (p. 33). An oily substance is also produced, having a veiy 
pleasant ethereal odour. Finely divided jpine acts upon acetic anhydride in a similar 
maimer, but less energetically, and only when heated in the water bath ; hydrogen 
gas is then ffiven off, and a soluble salt formed, which is deposited in microscopic 
crystals on the surface of the metal, and greatly retards the action. On satorating 
the excess of acetic acid in the residue with carbonate of sodium, the ethereal 
odour above mentioned is perceived. The hydrogen evolved, if collected immediately, 
has the same odour, bums with a bluish fiame, and the product of the combustion 
renders lime-water turbid ; but after passing through potassium, it is inodorous, and 
when burnt vields nothing but pure vapour of water. 

Acetic anhydride does not combine immediately with vxUer, but when poured into 
that liquid, fiills to the bottom in oily drops which dissolve after a while, if the liquid 
is heated or agitated. It absorbs water from the air, and must therefore be kept in 
well closed vessels. 



ACETIC ETHEES. 21 

Aeetie anhydride eombingi -with dldekjfdes. With ordisary aldehyde, it fomiB a 
hqind oompoaiid, C'H'O'. OH^O (G-enther), and a similar oomponnd with TaleraL 
CHW. G^'*0 (Guthrie and Kolbe) ; also irith bitter ahnond oiL(Geiither). 

AciTOBXsiaoM^ or JtenoACOBnc Amhidbidx, OH"0* >■ nrg^sofO. AeetaU of 

Betuoil, BenzoaU of Asetyl, — Obtained by the action of chloride of acetyl on benzoate 
of ■odinm. HeaTy oil smelling like Spanish wine. Neutral to litmns. £)il8 at 120^ C. 
and is lesolyed into acetic and benzoic anhydrides (p. 35V Besolved into aeetie and 
bGisDie adds by boiling with water, and more quickly witii alkalis. 

AcRO-GiKXAiac AiTHTDRiDB, G*HH).CfH'0.0. Acetate of Cinnamyl^ jv. — A yery 
zostaUe product obtained by the action of chloride of acetyl on dnnamate of sodium. 
Oil hearicr than water, something like the preceding compound. 

AcRO-cuxDOC Afstsbtob, CHK> . C**H"0 . O. Acetate of Cumyl, — Besembles 
the neeeding eompoonds. In the moist state it quickly turns add, and yidds beautiful 
laBiiufr of enminic add, the odour of acetic add Ixecommg perceptible at the same time. 

AdTO-BAXJCTiJC Akhtdbidb, OHH) . C*H*0'.0. Acetate of Sali^l, ^c— Salicylate 
of sodium n strongly attacked by chloride of acetyl, eyen at ordinaiy temperatures, 
the mixture lique^ring at first, but becoming perfectly hard in a few seconds. The 
product diflsolyes with efferyescence in carbonate of sodium, the uohydride being con- 
verted into acetate and salicylate of sodiunu (Gerhardt, Trait^ ilL 319.) 

ACBTIC JTHBIf These compounds are the acetates of the aloohol-radides, 
and may be diyided into the following groups : 



AcsTATn OF AixTL, (?HH).C*H*. — ^Prepared by treating acetate of silyer with iodide 
(^ allyl, and rectifjring once or twice oyer acetate of silyer. It is a colourless liquid, 
lighter than water, hftying a pungent, aromatic odour, and boiling between 98^ and 
100^. Boiling potash decomposes it into acetate of potassium and allyl-alcohoL 
(Oahonrs and Hofmann, Chem. Soc Qu. J. z. 322.) 

AcBTATB OT Amtx., or AcsTATH o» pBNTYL, CH'O'.O'H". — This compound is 
slowly produced when amylic alcohol is left in contact with acetic add, and may be 
ennyeniently prepared by distilling 2 pta. of acetate of potassium, or 3 pts. of de- 
hydrated acetate of lead, with 1 pt^ of strong sulphuric add, and 1 pt. of amylic 
alcohol, agitating the distillate witn milk of hme, then dehydrating oyer chloride of 
ealdum, and recnfying. It is a transparent, colourless liquid, of sp. gr. 0*8572 at 21^, 
and boiling at 133*3^, under a pressure of 27" 8'", with a platinum wire immersed in 
it Tapoinvdensity 4*458. Odonr ethereal and aromatic, like that of acetate of 
cthyL It is insoluble in water, but dissolyes in alcoholy ether, and fuael oil. It is 
decomposed yeiy slowly by aqueous potash, but quickly by alcoholic potash, yielding 
amylic alcoh<d and acetate of potasdum. Chlorine passed through it at 100^, conyerts 
into di-chlorifuUed acetate of amyl, CH^CIK)^ and this, by the action of chlorine in 
sunahine, is conyerted into a higher chloiine-compound. 

AcsKATB OF Benzti^ C^H'O'.CH*. — ^Produced by treating 2 yol. benzyl-alcohol with 
a mixture of 1 yoL sulphuric add and 4 or 5 yol. acetic add, or by boiling chloride of 
benzyl with alcoholic acetate of potassium. Colourless oil, heayier than water, and 
haying a yery agreeable odour, like that of pears. Boils at 210^ C. Boiled with 
potash-ley, it yidds acetate of potassium and benzylic alcohoL (Cannizzaro, Ann. 
Ch. Pharm. Ixxxriii 130.) 

AcxTATB OF Ethtl. Aeetto ether, EthyUo Acetate^ Eamgdtker, Eeewfumhtha, Ea- 
meaures JEtJ^loxyd, Ether acitique. C*H«0* = C«H»0*.0»H». or &IP(^.O^H*0. 
(Lanragais, Joum. d Scayans, 1759, 324; Th^nard, M^. d'Arcueil, i 153; 
Dumas and Boullay, J. Pharm. xiy. 113 ; Liebig, Ann. Ch. Pharm. y. 34 ; -r^r. 
144 ; Gm. yiiL 493 ; Gerh. i. 743). — Disooyered by Lanragais in 1759. It is formed 
by heatinff alcohol with acetic acid, or with an acetate and strong sulphuric add, 
or by A\mtt\\\T%^ ethyl-sulphate of calcium or potassium with glacial acetic add The 
best mode of preparing it is to distil a mixture of 3 pts. of acetate of potasdum, 
3 ptsL of absolute alcohol, and 2 pts. of sulphuric acid ; or 10 pts. of acetate of sodium, 
6 pts. of alcohol, and 15 pts. of snlphunc add ; or 16 ^ts. of dry acetate of lead, 
44 pts. of alcohol, and 6 pts. of sulphuric add. The add is first mixed with the 
alooho], and the liquid poured upon the salt reduced to fine powder. The mixture is 
then distilled to mryness, the heat being moderate at firsts but increased towards the 
end of the process. The product is purified by digesting it with chloride of ealdum 
and ractiiying the decanted liquid 

c 3 



22 ACETIC ETHEES. 

Ajoetate of ethyl is a ooloorless liquid, haying a pleasant ethereal odour. Sp. gr. 
0-9 1 046 at 0° (K o p p) ; 0*93 2 at 20^ (G 6 s s m a n n). Boils at 74^*3, when the barometer 
stands at 760 muL (Kopp). VapoiuHdensity 3*06 (Boullajand Dnmas). It dis- 
solves inll or 12 pts. of water, at ordinary temperatures (Mohr, Arch. Pharm.[2] Izr. 1), 
in all proportions of idcohol and ether. It hwrna with a yellowish flame, giving off the 
odour of acetic acid, and leaving that add in the liquid state. It is permanent when 
dry, but in the moist state gradually decomposes into alcohol and acetic add. The same 
decomposition takes place more quiddy under the influence of alkalis. Heated with 
strong sulphuric ado, it is resolved into oxide of ethyl and acetic add. Hydro- 
chloric acid converts it into acetic add and chloride of etii^l. 

Action of Chlorine on Acetate of Ethyl, (Malaguti, Ann. Ch. Phys. [2] xx. 
367; ibid. [3] xvi. 2, 68; Leblanc, ibid. [8] 197; Cloes, ibid. [3J xvii 804.,— 
When acetate of ethyl is introduced into a bottle flUed with diy chlorine gas, in the 
proportion of 1 atom acetate of ethyl to 8 atoms chlorine, and the action allowed to 
go on, first in the shade and afterwards with continually greater exposure to sunshine, 
a number of chlorinated compounds are formed in which 2, 3, 4, 6, 6, 7i and 8 atoms 
of hydrogen in the acetate of ethyl are successivdy replaced by an equal number of 
chlorine-atoms. It is however not always possible to obtain the particular compound 
required, the compounds C*H*01K)*, C*HCrO', and C*C1"0«, being the only ones that 
can be produced with certainty. Other products are also formed, among which are 
acetic add, trichloracetic add, and sesquichloride of carbon. If the acetate of 
ethyl is at once exposed to sunshine in contact with chlorine, an eiqplosion takes place, 
attended with deposition of charcoal. 

Diohlorinated Acetate o^ Ethyl, C*H*C1'0*, is the product obtained when the acetate 
of ethyl is kept cool and in the shade during the action of the chlorine. On distilling 
the product to separate the more volatile portions, till the boiling point rises to 110^, 
washing the brownish residue with water, and drying it over lime and sulphuric add, 
the compound is obtained as a transparent colourless oil, of sp. gr. 1*301 at 12^. It 
smells somewhat like acetic add, has a peppery taste, and produces irritetion in the 
throat. It is slowly decomposed by water, yielding hydrcdiloric and acetic adds. 
C*H«aK)*+ 2HK) - 2C*H*0«+ 2HC1; slowly also by aqueous potash, but quickly by 
alcoholic potash, yielding aoetete and chloride of potassium. (Malaguti) 

THohlorinated Acetate of Ethyl, C«HK)1K)*, was obtained by exposing the di- 
chlorinated compound for some time to the action of chlorine in a bottle, cov^ed at the 
upper part with black paper, so that the light fell only on the lower part of the liquid. 
It resembles the preceding compound, but cannot be distilled without alteration. It 
18 isomeric with trichloraoetate of ethyl, CK21H)'.CH*. See Tbichlobagbtio Aom. 
(Leblanc) 

Tktrachlonnated Acetate of Ethyl, C*K*CI*0\ was obtained by exposing the di- 
dilorinated compound to the sun in autumn, in bottles filled with dry cnlorine. After 
rectification, washing, and drying, it forms an oil of sp. ^. 1*486 at 26^. It is de- 
composed by potash, yielding diloride, acetete, and tndiloracetato of potassium 
(Leblanc). The five-chlorine compound, C^H'Cl^O', was obtained in the same 
manner as the preceding, excepting that the gas above the liquid was protected from 
the action of the solar rays ; tne etx-chlorine comoound 0*H'C1*C, by exposing the 
last compound to the sun for two days, in a bottle fiUed with dry chlorine. Sp. gr. 
1*698 at 23*5. The eeven-chlorine compound, C^HCl'C?, was produced by exposing ue 
dichlorinated compound in bottles filled with dry chlorine, to the sun for some months 
in winter. It forms rather soft crystals, insoluble in water, sparingly soluble in cold 
alcohol of ordinary strength, very soluble in ether. They melt ).*elow 100^, but do not 
appear to be volatile without decomposition. An oilv Uquid isomeric with this com- 
pound, and having a sp. gr. of 1*692 at 24-6°, is obtamed by exposing trichloracetete 
of ethyl to chlorine in the shade, as long as any action goes on. (Leblanc) 

Perchlorinated Acetate of Ethyl, O^OIK)', is prepared by exposing di- or tri-chlori- 
nated acetate of ethyl to the brightest summer sunshine, and at the same time heating 
it to 110°; even then the substitution takes ^lace veiy slowly (Leblanc). The pro- 
duct is distilled in an atmosphere of carbonic add, to remove free chlorme. It is a 
colourless oil, which remains liquid at a few degrees below (P, and has a strong pungent 
odour like that of chloral. Sp. gr. 1*79 at 25°. Boils, with partial decomposition, at 
245° (Leblanc). When its vapour is passed through a tube filled witii fragments of 
glass, and heated to 400°, it is partly converted into the isomeric compound chlor- 
aldehyde, C*C1K)' (Malaguti). In contact with water or moist air, it is gradually 
decomposed, yielding trichloracetic and hydrochloric acids. A similar decomposition 
is instantly produced by strong aqueous potash (Leblanc) : 

C*C1K)« + 2H»0 « 2C«HC1»0« + 2HCL 



ACETIC ETHERS, 28 

Ajnmonia, either paaeons or diaaolred in ^water, acta strooglj on tiid oompound, pro- 
dndng sBl-ammonue and trichloreeetamide (Malagnti) : 

C*C1«0» + 2NH« « 2Ha + 2C*H»Ca«N0 
WUh absolute alcohol, the compound becomes strongly heated, and ia completely oon« 
Toted into hydiodilorie add and trichloiacetate of ethyl (Malagnti) : 

OCPO* + 2C«H«0 - 2HC1 + 2C*HH:aH)«. 

When exposed for a long time to the action of chlorine, it yields crystals of sesqni- 
chkffide of carbon. (Leblanc) 

Perdilonboetie ether may be regazded as a tnehloraeetate of pentaeldorethyl^ 
G^C^H)*. CH}P ; and in like manner, all the preceding compounds which contain more than 
3 atoms of dilorine, may be riewed as trichloracetates of e^l-radides, in which the H 
is more or leas replaced by Q: e.y. pentachloracetic ether, C*]a"Cl*0« = C*C1»Q».C^"CI«. 
Some of tbeoa ai^)ear however to oe susceptible of isomeric modifications. 

AcBz^n OF Mbthtx., CH*0* « 0^*0 . OH'. Methtflic Acetate, Essiasaurer 
HoUSiher. (Dumas and P^ligot (1836), Amu Ch. Phys. lYiiL46.->Weidmann 
and Sehweiaer, Poffi. xliii. 693. — H. Kopp, Ann. Ch. Pharm. It. 181. — Gm. viii. 
484; Qerh. L 741.)-pThis compound occnzs ui crude wood-yinegar (Weidmann and 
Sehweixer). The Uqnid called Mther lignotua or Spiritus pyroaceticuB appears to be 
impare aoetate of methyL 

FreparaUon. — 1. Two pts. of wood-spirit are distilled with 1 pt of glacial acetic 
add and 1 pt. solphuric add; the distiUate is shaken up with chloride of «*ftH»T"', 
the acetate of m^^l tiien rising to the top ; and this product is freed from sul- 
pfanoas add hj agitation with quicklime, and from wo<Ml-spirit by 24 hoTin' con- 
tact with chlonde of caldum, which takes up the latter substance (Bumas and 
Peligot). — 2. When 1 port of wood-spirit is distilled with 1 pt. acetate of potas- 
simn and 2 pta. of solphunc add, acetate of methyl passes over first) then sulphurous 
add, aeedc add, methyl, and a small quantity of methylic sulphate. The first recdyer 
most therefore be removed as soon as sulphurous add begins to escape ; its contents 
sfaakoi up with water; and the s^wrated ether rectified over chloride of calcium and 
quicklime (Weidmann and Schweiser). — 3. A mixture of 3 pts. wood-spirit, 14^ 
pis. dehydrated aoetate of lead, and 5 pts. sulphuric add is distilled ; the distillate 
IS shaken up with milk of lime ; and the stratum of methylic acetate which rises to the 
toi&oe is dehydrated by repeated treatment with chloride of caldum, then decanted 
from the lower liquid, and rectified. (H. Kopp.) 

Aoetate of meuiyl is a colourless liquid, having a venr agreeable odour, like that 
of acetate of ethyl, sp. gr. 9'0085 at 21*^; 0-9662 at (P (Kopp). Boiling point, 663^ 
under a pressure of 760 mm. (Kopp, Pogg. Ann. bdi 1) ; bSP under a pressure of 
762 mm. (Andrews, Chem. Soc (&. J. i 27). Vapour-dendty 2*663 (Dumas and 
Peligot), by calculation 2'664. Index of refraction 1*3676. (Delffs, Pogg. Ann. 
Wnri 470.) 

Aoetate of methyl diasolvei in water, and mixes in all poportions with alcohol and 
ether. The aqueous solution sufif^ but little decomposition by boiling. Solutions of 
caostie alkalis convert the compound into wood-spirit and an alkaline acetate. When 
poured on pulverised soda^limei, it is decomposed with violence, yielding a mixture of 
acetate and formate of sodium, and giving o£f hydrogen. In contact with strong sul- 
phuric add, it becomes heated, gives off acetic add, and forms methylsulphuric add. 
with chlorine it forms a number of substitution-products. 

DieUormaied Acetate of Methyl, G^H}1K)*, is formed by passing diy chlorine gas 
through aoetate of methyl, assisting the action by a gentle heat towards the end. It 
is pnnfied like the corresponding ethyl-compound. It is a colourless neutral liquid, 
having a pungent odour ; its taste is sweet at first, but afterwards alliaceous and burning. 
8p. gr. 1*26. Boils between 146^ and 148^, but begins to decompose and give off 
Hsmes at 138^. It bums with a yellow fiame, edged with green at the bottom. It is 
decompo s ed slowly hj water, quickly by aqueous potash, and violently by alcoholic 
potash, yielding formic, acetic, and hydrochloric adds : 

C»H*C1K)> + 2H»0 - CH»0« + C«H*0« + 2HCL 

This compound is isomeric if not identical with dichlorinated formate of ethyl. 
(MaJaffuti, Ann. Ch. Phys. [2] Ixx. 379.) 

TricUorhuLUd Acetate of Methyl, C»H»C1H)*, is obtained by pasdng chlorine very 
slowly into aoetate of methyl, as Ions as any decomposition takes place, and purifying 
the product by repeated fractional distillation. It is a colourless oil^ fiquid,. heavier 
than water, boiling at 146^, and distilling without decomposition. It is decomposed by 
caustic pota^, yielding diloride and formate of potassium, and chtoromethylate, CHCl : 

(7H»a"0» + 2K«0 « 2KC1 + 2CHK0« + CHC1. 

4 



24 ACETIC ETHERS. 

It 10 iflomerio bat not identical with trichlonCetate of methyl, CKjlHy. CH*, produced 
hy distilling -wood-spirit with trichloracetic acid and a small qosintity of sulphuric 
acid. (Laurent^ Ann. Ch. Phjs. [2] Ixxiii. 26.) 

PerohlorituUed Acetate of Methyl, CHUl'O^ (Cloez, Ann. Ch. Fhys. [3] zviL 297, 
311.)— This componnd, which appears to be identical with perchlorinated formate 
of ethyl, is proanced by exposing acetate of methyl to the action of chlorine in 
sonshine, as long as the gas continues to be absorbed. It is a colourless liquid, having 
a suffocating odour and a disagreeable taste, which soon becomes intolerably add, from 
decomposition. Sp. gr. 1*705 at 18^. Boils at about 200^, with partial decomposition. 
It is quickly decompmed by water and by moist air, yielding hydrochloric^ carbonic, and 
terchloracetic acids : 

C«C1W + 2HH) = 8HC1 + C0« + C*HCI»0«. 

Similarly by the fixed alkalis in solution. With aqueous ammonia, it forms tri- 
chloracetamide, together with chloride and carbonate of ammonium: 

C«C1«0« + 6NH« + 2H«0 - N.H«.CK)1«0 + 8NH*C1 + CO" (NHV 

With alcohol it forms hydrochloric add, trichloracetate of ethyl, and monochlori- 
nated formiate of methyl : 

C*a«0« + 2C*H*0 - 2Ha + C«C1«0«.C«H» + C«H*C10« 

Similarly with wood-spirit it yields trichloracetate of methyl, and monochlorinated 
formate of methyl. 

The Tapour passed through a red-hot porcelain tube is decomposed into chloraldehyde 
and chloro-carbonic oxide (phosgene) gas : 

C«C1»0« - (yci*o + COCl\ 

AcBTATB OF OcTTL, CHK)'. C^E}", — Prepared by possinff hydrodiloric add gas 
through a mixture of acetic add and odylic (caprvlic) alcohol ; or, better by Ss- 
tilling a mixture of octylic alcohol, acetate of sodium, and sulphuric add. It is a 
liquid of yezy agreeable odour, insoluble in water, boiling at 190^. (B ouis, Compt. rend. 
xxxvuL 937.) 

AcET^TB OP pHxanrz^ CH'O.CH*. — Produced by the action of diloride of acetyl 
on acetate of phenyl : also by boiling an alcoholic solution of phosphate of phenyl 
with acetate of potassium. Alter all the alcohol has eyaporated, the temperature of the 
mixture rises rapidly, and acetate of phenyl distils oyer in the form of an oily liquid. 
It is heayier than water, and slight^ soluble in that liquid. Boils at 190^. Boiling 
potash decomposes it, yielding acetate of potasdum and hyctate of phenyL (S c r ug h am, 
Chem. Soc. Qu. J. yii. 241.) 

AcBTATB OP Tbtbtl, or AcBTATB OP BuTTL, CHK)*. C*H». — Obtained by heating 
iodide of tetryl with a slight excess of yery drf acetate of silyer in a sealed flask 
at 100^: — also by distilling in an oil-bath equiyalent quantities of acetate of po- 
tasdum (recently ftised) and tetryl-sulphate of potassium : 

C«H»0« K + SO*.KC*H» « C«H«0«.C*H» + SO«.K» 

AcBTATB OP Tmttl, or AcBTATB OF pEOPTL, CHW.CH^. — Obtained by distilling 
(propylic) alcohol with a mixture of acetic and sulphuric add. Besembles acetate 
of ethyL Boils at 90<^. (BertheloU 

It is a colourless liquid of agreeable odour. Sp. gr. 0*8845 at 16° C. Boils at 
114°. Vapour-density 4*073 (calculation, 4*017). iJ^iling potash conyerts it into 
acetate of potassium and tetiylic alcohol. 

a. Biatomlo Aoetlo BUien* (Glyeolie Ethers,) — ^These compounds are deriyed 
from the diatomic alcohols or glycols by tne substitution of 1 or 2 at. acetyl (C'H'O » Ac), 
for 1 or 2 at h^dr(^en. They are related to the glycols in the same manner as the 
monatomic acetic ethers just described are related to the monatomic alcohols. The 
following haye been obtained : — 



MonoaceUte of Ethylene ^^"^h'^O* 
Diacetate of Ethylene ^^a ^' \ 0* 

Diacetate of Propylene ^^^*^'' \ 0* 



Diacetate of Butylene ^^^' \ O" 
Biacetate of Amylene ^^^^ 1 ^' 
Diacetate of Benzylene ^^*J[' I O* 

The diacetates are produced by the action of acetate of silyer on the chlorides, 
bromides, or iodides of the seyeral diatomic alcohol-radides : e. g. 



ACETmS. 35 

BroiDiite of S at. acetate of Diaeetate of 

ctlijlene. aUTor. ethylene. 

M Qooaoetate of ethylene is obtained by heating acetate of potaflsinm with an alco- 
bolie sofaition of bromide or chloride of ethylene, or by heating in a sealed tabe a 
nuxtnre of 1 at. hydrate of ethylene and 1 at. acetic anhydride : 

«'^T|o.MC^)..o - ^^y^So..<^5o 

An these oompoonds when distilled with potash are converted into the oorre- 
nonding diatomic alcohols. They will be more fully described in connection with 
these scTeral alcohols. 

S. TMatonDte beetle BChersi Aoetliis. (Berthelot, Ann. Ch. Fhys. [3] 
Z1L277; 0m.iz.496; Gerh. iiL 950; Berthelot andBe Luca» Ann. Ch. Phys. 
[3] liiL 433). — Compoonds obtained by the nnion of 1 at. glycerin, C^HK)*, with 1, 
is or 3 sL acetic add CH^O', with elimination of an eqnal nnmbeor (riP atoms of water. 
They may be reeaided as glycerin, CHK)*.H', in which 1, 2, or 3 at. hydrogen are 
rqplaeed by aceM. 

MonoacetiH^ G*H>K>« » G^*0".H'.O^H'0, is produced by heating a mixture of 
g jy o e r iu and glacial acetic add to 100° for 24 hours. SUght traces are also formed 
by mere contact of the liquids at ordinary temperatures. It is a neutral liquid, haying 
a slightly ethereal odour. Sp. gr. 1*20. Mixed with half its bulk of water, it forms a 
dear liquid, whidi becomes turbid on the addition of two or more Yolumes of water; 
but the aoetin does not separate from it, and the emuldon continues opalescent eyen 
after the addition of a large quantity of water. Treated with alcohol and hydrochloric 
add, it forms gjlycerin and acetate of ethyL It mixes with ether. 

Diaeetm, also called Jeetidin, (rH«0» = C«H*0».H.(C»H»0)« « C»H»0« + 2CPH*0« 
~2HH), is obtained by heating gladal acetic add with excess of glycerin to 200^ for 
3 hours; by heating the same two liquids together at 27S°; by heating glycerin to 
200° with acetic add diluted with an equal bulk of water ; and by heating to 200° a 
mixture of 1 pt of glycerin with 4 or 5 pts. of acetic add. It is a neutral odori- 
ferous liquid haying a sharp taste; sp. gr. about 1-85. Boils at 280°, and distils with- 
out alteration. Assumes a yisdd consistency at— 40°. It becomes slightly add by 
prolonged contact with air. 100 pts. of it saponified with baryta, yield 52*4 pts. of 
^lyoerin and a quantity of acetate of barium corresponding to 66*4 pts. of acetic add ; 
calculation requires *52'3 glycerin and 68'2 acetic add. With alcohol and hydro- 
dilorie add it yields glycerin and acetate of ethyL It dissolyes in ether and in benzoL 

Tnaatin, frH"0* «C*HH)».(C?H»0)» - 0»H»0« + 3C«H*0« - 3 BPO. — Obtained 




iponified 

43-1 glycerin; by calculation it should be 82*6 acetic add and 42*2 glycerin. It is^ 
iDBoluble in water, but soluble in dilute alcohol. 

A compound of acetic add and glycerin, probably triacetin, appears to exist in cod- 
liyer oil (De Jongh, Berz. Jahresber. 1843), and in condderable quantity in the oil 
obtained from the seeds of Euonymua europaus (Schweizer, J. pr. Ghem. liii. 437). 
Acetic acid was also obsenred by Cheyreul among the product of uie saponification of 

&tB. 

Jeetoeilorkydrin, C»H»C10» = C«H«0« + C»HK)« 4 HCl - 2HK), is obtained by 
pasaiflg hydrochloric add gas to saturation into a mixture of acetic add and glycerin 
iieated to 100°, and satnnting the li<|uid with carbonate of sodium, after leaying it 
at rest for seyeral days. This process yields the compound mixed with dichlorhydrin. 
It is also obtained, together with the following compound, by the action of cmoride 
of acetyl on ^ycerin. It is a neutral oil, smelling like acetate of ethyl and yolatilising 
at about 250i°. 

jieetadufAlor]^drin,(?BKJlH)* « 0"IPO« + C»H*0« + 2HC1 - 3H*0, is obtained by 
adding chloride of acetyl to glycerin externally cooled, as long as any action takes 
place, distilling the product, and purifying the distillate obtained between 180° and 
160P, l^ agitation with water and then with an alkali, drying with chloride of cal- 
dum and ouicklime, and fractional rectification. It is a transparent neutral oil 
luring a reneshing ethereal odour, sparingly soluble in water and distilling at 205° 
without decomposition. (Bert helot and De Luca.) 

Diaeetochlorhpdrin, C'fl"C10* = C«H»0» + 2C»H*0* + HCl - 3H»0, is obtained 
by the action of chloride of acetyl on a mixture of eqnal yolumes of glycerin and 



26 



ACETINS — ACETONE. 



gladftl acetic acid. It is a neutral liquid which Tolatilises at 245^. (Berthelot and 
DeLuca.) 

Similar compounds are produced by the action of bromide of acetyl on glycerin. 
By treating glycerin with a mixture of chloride and bromide of acetyl in equal numbers 
of atoms, aceiochlorbromhydrin, C»H«ClBrO* - C»H«0« + C»H*0* + HCl + HBr - 
3 H'O, is obtained as a neutral colourless liquid, smeUin^ like acetate of ethyl and 
bromide of ethylene, boiling at 208°, and distilling without decomposition. It is 
somewhat coloured by exposure to light. (Berthelot and De Luca.) 
The formulae of all these compounds may be deriTod ^m that of a triple molecule 
HHO 
of water HHO. By replacing 8 at hydrogen in this formula by the triatomic 
HHO 

H 

radide, glyceryl C*H', we obtain glycerin H(CH')0. Bepkdng 1, 2 or 3 at H in 

H O 

this formula by acetyl (CH'O » Ac), we obtain monoacetin, &c ; and, lasdy, the re- 
placement of one or two molecules of jperoxide of hydrogen (HO), by chlorine in the 
rormulae of monoacetin and diacetin gives the acetooilorhydiins. Thus : 



Monacetin. 



Aeetoehlorhydrin 



Acetodichlorhydrin 



H O 

Ac(0»H»y"0 
H O 

H O 

Ac(C»H7"0 
CI 

a 

Ac(C5«H»)'"0 

a 



Br 
Acetochlorbromhydrin . Ac(C«H»)'"0 



7 



Diacetochlozhydrin . 



Triacetin . 



Ac O 

. Ac^C"H>y"0 



(CPm" 



. Ac\CTH7"0«. 



AOBTXra. A compound formed from acetic acid and mannite in the same manner 
as acetin from acetic asid and glycerin. (Berthelot, Compt rend, xxxviii. 668.) 

AOBTOmrBB- A hydrometer graduated for determining the strength of com- 
mercial acetic acid according to its density. (See Acbtic Accd.) 

ACarOVa. C*H*0»C*H'O.CH* [or C*H^O^. PyroacOie spirit, Eanggtut, 
BretiMBuiggeist (Gm. ix. 1 ; xiiL 462 ; G er h. L 700 ; iii. 943 ; ir. 906).— This compound 
has long been known as a product of the destructiTe distillation of acetates (p. 28). It is 
also produced by ^assins the yapour of acetic add through a red-hot tube ; by heating 
gum, sugar, tartaric acid, citric add and other vegetable substances in contact with 
lime ; and by heating dtric acid with permajganate of potassium, or with a mixture of 
binoxide of manganese and dilute sulphuric add. (r^an de St Gilles, Compt 
rend, xlvii 555.) 

C«HK)' + - C^H) + SCO* + HK). 

Citric add. 

It is prepared : 1. By distilling acetate of barium or acetate of caldum at a mode- 
rate heat, the metal then remaining in the form of carbonate : 

2C»H»BaO« « C«H«0 + bO«Ba*. 

Acetate of barium when div and pure, yields a perfectly oolouriess neutral distillate, 
in fact pure acetone. The caldum-salt requires a higher temperature to decompose it, 
and the distillate is in consequence contaminated with an empyreumatic oil, called 
dumtuitif C^'H^K). — 2. By distilling in an iron retort or (quicksilver bottle, a mixture 
of 2 pts. of acetate of l^id and 1 pt of pounded quicklime, rectifying the product 
sevenl times over chloride of caldum, and finally distilling over the water>bath. 

Acetone is a limpid, very mobile liquid, of sp. gr. 0'792 at 18^ (Liebig), 0*814 at 0^ 
(H. Eopp). Itdoes not solidify at - IS^'* Boils at 56<' (Dumas), at 56-3<' (Kopp) 
under a pressure of 760 mm. Evaporates quickly, produdng a considerable degree 
of cold. Vapour-density 2*0025 (D umas). It has an agreeable odour, and a biting 
taste like that of peppermint It is reiy inflammable, and bums with a white flame, 
without smoke. 

Acetone mixes in all proportions with water, alcohol, ether, and many compound 
ethers. It does not dissolve potash or chloride of caldum. It dissolves many cam- 
phors, fats and resins. 

Acetone forms definite compounds with the alkaUns bisulphites. The potassium 
salt, CHH) + SO* (KH), and the sodium-salt, C»H*0 + SO»(NaH) crystallise in 
nacreous scales (Limpricht). The ammonium-salt^ CH'O + SO*(NH*H,) is de- 
posited on mixing an alcoholic solution of bisulphite of ammonium with acetone, in 



ACETONE. 27 

ibling eholesterin, which quickly aggregate into a heavy dyetalline 
powder. (Stideler.) 

▲eetone was legarded by Kane aa an alcohol, CH^.H.O, containing tiie radicle CH^ 
which he called meaUyl, According to thia riew, howerer, the oxidation of acetone 
ehonld yield prodncta oontainins C*, jnat as the oxidation of common alcohol, CH*0 
yielda alddi jde and acetic add containing C; hut no such products are obtained. 
A maie pfrobable view of the compoaition of acetone is that of Cnancel, who regards it 
as aldehyde ooapLed with methylene, CH^O.CH', or, which comes to the same thing, 
that of mihardt and WiBiamaon, who regard it as aldehyde in which the basic hy- 

drogen is replaced by methyl; Q-gt \ • This Tiew is quite in accordance with the 

deeompoaition of acetates into acetone and carbonates. For acetyl may be regarded as 

a oomponnd of methyl with carbonic oxide; [C'H'O = GH". CO.] ; and it is easy 

CH* CO ) 
to concerre that 2 atoms of acetate of barium -^ [0, may decompose in such 

a manner that the CO of the one may unite with the two atoms of barium and 
the two external atoms of oxygen, to form carbonate of barium, while the methyl 
ranains in combination with the other atom of acetyl, forming acetone : 

Acetate of barium. CailMnate Acetone, 

of barium. 

Tlie same view is strengthened by the &ct (discovered by Williamson) that when a 
mixture of acetate and valerate of barium is heated, an acetone is formed containing 
acetyl coupled with tetiyl (C«H*), or valyl (C*H'0) with methyl: thus 

^^H».CO) f. ^ C*H».CO> rt CO > ^,^ CHK)) 
Ba P + Ba r "^ Ba^^ ^ C«H» { 

DeeomponihfU of AceUm$, — 1. Acetone passed in the state of vapour through a red- 
hot tube, d^oeits charcoal and is convert^ ioto a peculiar oil called dumasir^, which 
generally passes over together with acetone in the distillation of acetates. 

2. Acetone is decomposed by chlorine^ a portion of its hydrogen being replaced by 
that element ; but it is not possible in this manner to replace the whole of the hydro- 
gen by chlorine; even a mixture of chlorate of potassium and hydrochloric acid does 
not inipesr to be capable of replacing more than two of the hydrogen atoms lij chlorine. 
The higher ehlorinated acetones, may however be obtained by we action of chlorine, 
or the mixture just mentioned, on otiier organic bodies. (See Chlo&acbtomes, p. 29.) 

Chlofriru^ in presence of alkalis, converts acetone into chloroform : 

C^H) + 12 Cl + H«0 « 2CHC1" + C0« + 6HCL 



in presence of alkalis, acts in a idmilar manner, producing bromoform : but 
iodine forms only a dark pitchy mass. 

4. Ifydrookhnc aeid gaa is absorbed in large quantity by acetone, and according to 
Kane, ^elds chloride of meeityl (or chloropropylene) CH^Cl. Hydriodic add gas 
passed into acetone fonns, according to Kane, iomde oi mesityl, CH'I, which distils 
over w ith the hydriodic acid ; iodide of pteleyl C*H'I (or rather tri-iodomesitylene, 
OH'l*), which remains suspended in the residual liquid, in the form of yellow scales ; 
and meaityl-hypophoephorous acid, CH'O.PHO, which separates in silky needle«i as 
the liquid cools, f riedel (Compt. rend. xlv. 1013) stated that a solution of hydro- 
chloric add gas in acetone yielded, when heated to 100°, acetic acid and chloride of 
methyl (2C«H«0 + 4HC1 - C«H*0* + 4CB:«a), and similarly with hydriodic acid ; 
hot he has since admitted that these results were obtained with impure acetone con- 
tainii^wood-spirit. 

6. With peniaehloride of phosphorus^ acetone ^elds chloropropylene, CH*C1, boiling 
at about 30^ and methjfiehloracetol, a compound isomeric wiui chloride of propylene, 
CH*C1'. This body treated with silver-salts, ammonia, etfaylate of sodium, or alco- 
holic potash, is resolved into hydrochloric add and chloropropylene, identical with the 
body obtained by the action of alcoholic potash on C'H'C1^ Hence it ajipears that 
acetone is related to the propylene series. (Friedel, Ann. Ch. Fharm. cxii. 236.) 

6. Strong niirie acid acts violently on acetone, giving off copious red fumes, and 
lianning mesitie aldehyde, CH^O, and nitrite of pteWl, C'H'NO'. [or rather trinitro- 
mesitir&ne, CH*(NO')^, together with oxalic and cyanuric acid (Kane). By 
droppiiig acetone into nuning nitric add contained in a flask externally cooled, and 
addOng water as soon aa the action ceases, a heavy oil is obtained, which explodes with 
violeooe when heated, giving off red fumes. (Fit tig, Ann. Ch. Fharm. ex. 45.) 

7. Acetone mixed with strong sulphuric acid becomes heated, and, according to the 
quantity of add presentand the rise of temperature which takes place, forms either 



n 



28 ACETONK 

oxide of meritjl, CE}*0, or meeitylene, CH", together with mesil^Lmlphiirie add, 
SO^.CH'.H, and sulphnrouB add. (According to Kane, the composition of mesilylaul- 
phniic add ia C*H*0,H0,8€^^ ana there iB formed at the same time another add 

8. <$hidaljpAo0p£?r»0 add fonns with acetone a dark brown mass, partly oonsisting 
of medtylphosphoric add. (S. a n e.) 

9. A BOiution of phoaphorita in acetone turns add when kept for some weeks, and 
more quickly when heated, even in perfectly air-tight vessels. According to Zeise, the 
change consists in the formation of three peculiar adds, to which he gives the names, 
phosphacetiCf acephotgenic and acephorio adds ; but their nature and compodtion have 
not been dearly made out. Products of like nature are obtained with sulphur. Sulphide 
of phosphorus forms with acetone a peculiar add, and an oil which hus a powerful 
odour but no add reaction. (Zeis e.) 

10. A solution of ammonia in acetone yidds, by spontaneous evaporation, a colour- 
less syrupy reddue^ whidi gradually chanses into an alkaline liquid, consisting of 
acetoninej CH^N*, an organic base, which bears to acetone the same relation that 
amarine bears to bitter-aLmond oil : 

SCmH) + 2 NH« - C»H»*N» + 8HK). 

The non-basic compound first formed is perhaps isomeric with acetouine. (S t a d e 1 e r, 
Ghem. Gaz. 1853, 241.^ 

11. By the action ox ammonia and sulphur on acetone, Zeise obtained a number of 
products, which however do not present any definite characters. (Gm. iz. 11.) 

12. By the simultaneous action of ammonia and h^drosulphurie aeidf acetone is 
converted into thiaoetonine, a sulphuretted base consisting probably of G'H'NS*. 
It crystallises in shining yellowish rhombohedrons, having an alkaline reaction, 
sparingly soluble in water, but dissolving with facility in alcohol, ether, acetone, and 
dilute adds. (Stadeler.) 

13. When 1 volume of acetone is mixed with 1 voL disvlphids of carbon and 2 vols, 
aqueous ammonia^ laminated crystals, resembling ice, form in the liquid after a few 
days ; but these gradually disappear, and are suooeeded by laige yellow ciystals, which 
are insoluble in water, sparingly soluble in ether, but dissolve, with decomposition, in 
warm alcohol and in boiling hydrodiloric acid (Hlasiwetz, J. pr. Ghem. IL 365). 
Hlasiwetz asdgns to these crystals the improbable formula CH^'N'S*. Stiidder, on 
the other hand, regards them as the hydrosulphate of an organic base, cardo^Aiaoe^onin^, 
CH^'N^', and represents their formation by the equation, 

3CH-0 + 2NH" + CS« = C"H'«N«S» + 8H«0. 

The formula C**H*"N*S'. H'S agrees pretty nearly with the analytical numbers ob- 
tained by HladwetE. A cold alcoholic solution of the crystals forms with dichloride of 
platinum a brownish yellow, amorphous predpitate consistinff of C**H*'N%'JE*tCl' J^, 
and with mercuric chloride a white precipitate, whidi, according to Stadder, is merdy 
Hg'Gl'S mixed with a small quantity of hydrochlorate of carbothiacetonine. 

14. Acetone heated with a mixture of hydrocyanio and hydrochloric aeid, is con- 
verted into acetonie acid, C«H"0* (Stadeler): 

C«H«0 + CNH + 2H«0 - OEP0« + NH". 

15. Acetone distilled with diehromaU of potassium and sulphuric acid, gives off 
acetic and carbonic adds, but no formic add : 

C»H«0 + 40 = C«H*0« + C0« + H*0. 

16. Caustie alkalis, such as hydrate of potassium and quick lime, exert a dehydra- 
ting action on acetone, several products b^ng formed, according to the proportion of 
water abstracted. Lowig and Wddmann, by subjecting acetone to the action of 
hydrate of potassium, obtained a dark brown mass, consisting chiefly of xylite-oil, 
C"H»K), which boiled at 200°, together with a resin which they call xylite-resin, 
Volckel, by leaving acetone for some time in contact with quidc lime, also obtained an 
oil boil^ above 200^, which he regarded as xvlite-oiL But, according to Fit tig 
(Ann. Ch. Pharm. ex. 32), the products obtained by the action of quick hme in dosed 
vessels, are oxide of mesityl, CH^^O^ boiling at 131^, and a liquid isomeric or iden- 
tical with phorone, (?BP*0. It must *lso be noticed that Schweizer and W eidm a n n 
(J. pr. Chem. xxiii. 14) obtained xylite-oil, and likewise xylite-naphtha, C**H"0*, by 
the action of potash and of strong sulphuric acid on a compound produced from crudo 
wood-spirit, which those chemists called xylite, assigning to it the improbable formula 
(y£P(A, but which was probably nothing but somewhat impure acetone. On the 
whole it appears that the action of alkalis on acetone is similar to that of sulphuric 
acid (p. 52), consisting in an abstraction of the dements of water. The products 



ACETONE. 29 

obtained by the action of theae dehydnting agents on acetone may be arranged as fol- 
lows^ aceording to their boiling-points : 

Botllng-potnt. 

Xylite-naphtha . . CP«H«0« = 4C»H«0 - BPO . . IIO^ to 120o 

Oxide of Hesityl . CH»0 - 2Cra«0 - H«0 . . „ 131<» 

Hentylene . . 0»H" - 3C»H«0 - SBPO . . 1659 „ 160° 

Phorane? . . C'H'H) - 8CTa«0 - 2H«0 . . 210<> „ 220° 

XyUte-oil . C»*H"K) - 4 C«H«0 - 8BP0 . . above 200<> 

Tapoor of acetone passed over heated hydrate of potassinm or potash-lime is resolved 
into manh-gas ana carbonic anhydride : 

CmH) + 2KE0 - CO*K* + 2CK*; 

or if the heat is not yeiy strong the chief prodncts are acetic acid, formic acid and 
fajdrogen: 

C^«0 + 2KB0 + H«0-C*H»K0«+CHK0«+ 6H. 

17. Sodium is violently attacked by anhydrous acetone, but without evolution of 
bydrogen, and hydrate of sodium is separated in white flakes. The liquid gradually 
•sBomes a pasty consistence, and the sodium becomes coated with oxide, so Uiat it no 
longer acts perceptibly on the acetone. On distilling the mass, undecomposed acetone 
passes over first, and afterwards a watery liquid collects in the receiver, covered with 
a yelknrish oiL On pouring the distillate into a basin, so that the undecomposed 
acetone may evaporate, the watery layer solidifies in a white ciyBtaUine mass, from 
which the oal may be separated by pressure between paper. The crystids consist of 
l^nie of pinaeane, CWH) + 7 HH), and the oily liquid is pkorone, C^E}*0. The 
pinacone is produced by the abstraction of 1 at. oxygen from a doulale molecule of 
acetone : 

20^*0 + 2Na - Na«0 + C^>«0 ; 

and the anhydrous pinacone thus formed appears to take water from another portion of 
the acetone, oonTexting it into phorone : 

3 CHH) - 2 H«0 - (m}*0. 

By heatinff the crystals of hydrated pinacone in a narrow class tube, a viscid liquid 
is obtained which absorbs water rapidly from the air, and is reconverted into the 
dystalline hydrate. This liquid appears to be anhydrous pinacone ; but it is difficult 
to ezpd sU the water (Stadeler, Ann. Ch. Pharm. cxi 277). Pittig (ibid. ex. 23) 
assigns to the hydrated crystals, the formula CH'O •*• 3H*0, regarding them as the 
hydrate of paraceiane, a compound isomeric with acetone, which he also states is ob- 
tained in anli^drous crystals, by the action of ammonia on acetone. Fitti^s formulte 
do not, however, agree with the results of analysis so well as Stadel^s (see PmAcoioi); 
moreov e r it is yerv unlikely that sodium should act with violence on acetone, without 
abstracting a portion of its oxygen. The action of ammonia on acetone, produces, ac- 
cording to Stkdeler, not a crystalline compound, but a liquid organic base, acetonine 
(p. 32). 

18. Dry dieJdoride of plaHnum dissolves in acetone with evolution of heat, and 
ibrms a brown solution, which, when evaporated, gives off hydrochloric acid, and leaves 
a resinous mass, containing amoxig otner products, a yellow crystalline substance 
called aeecklaride of plaHnum or eSoropUiHnite of mewtyl, G^>«0 J^*G1*. (?) This 
compound may be obtained in larger quantity, bv triturating dichloride of platinum 
with acetone to the consistence of a thick paste, leaving the mass in a close vessel till 
it liquefies and ultimately forms crystals, washing these crvstals with acetone, and 
parifjring them by orstallisation from boiling acetone. Acechloride of platinum thus 
obtamec^ is yellow, inodorous, sparingly soluble in water, alcohol and ether, more 
readily in aqueous chloride of potassium or sodium. Gold acetone dissolves ^ of it ; 
boiling acetone a little more. The aqueous solution reddens litmus. The compound is 
decomposed and dissolved by potash, forming a brown solution. When boiled with 
water, it deposits a black substance called aceplatinow oxides probably 0^*0. The 
same substance is deposited on boiling the mother-Hquor of adchloride of platinum. 
The adchloride yields by distillation a residue of carbide of platinum, PtO. (Zeiss, 
Ann. Ch. Pharm. zxxiiL 29 ; 6m. ix. 31.) 

SvBSTXTunoir-PBODucTS OF AcBTONB. Ckloraeetones. — ^Each of theatoms ofhydro- 
gen in acetone may be replaced by chlorine, giving rise to six chlorinated acetones. The 
first oi these compounds is obtained by the action of nascent chlorine on acetone ; 
the second by that of chlorine or the oxides of chlorine on acetone ; the third and 
fourth by the action of chlorine on crude wood-spirit, probably containing acetone ; 
the fifth and sixth can only be obtained by the action of chlorine or the oxides of 
chlorine on other organic compounds. 



30 ACETONE, 

Monoehloraedone, CHK710, ia obtained by the action of a feeble dectnc euiTent 
(from three Bunsen's cells) on a mixture of acetone and hydrochloric acid, the 
chlorine set free at the positive pole from the hydrochloric acid, acting on the acetone 
and taking the place of 1 at hydrogen. It is an oily, colourless liquid, which, when 
separated from the watery solution and rectified, boils at 117^, has a sp. gr. of 1*14 at 
14^, and vapour-density ^ 3*40. Its vapour acts strongly on the nose and eyes, pro- 
ducing a copious flow of tears. (Biche, Compt rend. xuz. 176.) 

j5icMoracetone, CH^CIH) (Kane's meniie chlorat)^ is produced bypassing dry chlorine 
into anhydrous acetone, or better, according to StSdeler, by mixing acetone in a capa- 
cious flask with twice its volume of strong hydrochloric acid diluted with an equal 
bulk of water, and adding pulverized chlorate of potassium by small portions. It is 
an oily Hquid of sp. gr. 1-381 (Kane); 1*236 at 90<^ (Fittig). Boils at 116*5<' rSta- 
deler); at 121^*5 (Fittig). Vapour-density 3*2. Its vapour smells like chloro- 
form at first, but, after a few seconds, attacks the nose and eyea with violence. The 
liquid blisters the skin like cantharides, producing wounds wmch are difficult to heal 
(Liebig, Kane, Fittig.) It is insoluble in water, but mixes in all proportions with 
alcohol and ether. 

THchloraoetone^ C'H'CIK), is obtained by the action of chlorine on wood-spirit. 
When chlorine ^ is passed into ordinary (unpurified) wood-spirit, crystals are formed 
consisting of C*M^*C1K)* {chhromentate of mtthylene), but if the action of the chlorine 
be fiirther continued, the crystals disappear, and an oily liquid is formed, which is 
terchlorinated acetone. It is heavier than water, has an extremely pungent odour, 
and cannot be distilled without decomposition. (Bonis.) 

JHraehloracetonef CHKIi^O, is obtained by dissolving the ciystals just mentioned 
in wood-spirit and passing chlorine through the solution. It is an oily very volatile 
and pungent liqui(£ whi^ blisters the skin. When exposed to moist air, it forms 
crystals containing C'H'Gl^O + 4 H'O, which melt at 35^, and dissolve in water, alcohol 
and ether, forming solutions which are not precipitated by nitrate of silver. The oystals 
distilled with phosphoric anhydride yield the original anhydrous compound. This 
and the preceding compound are doubtless formed from acetone contained in the wood- 
spirit (Bouis, Ann. Gh. Thjs. [3] xxi 111.) 

Pentackloraoeione, CHCIK), is obtained by the action of a mixture of chlorate of 
potassium and hydrochloric acid on several organic compounds, viz. kinic, citric, 
gallic, pyrogallic, catechucio and salicylic acids, sAao kinone, muscular fiesh, albumin, 
indigo and tyrosin. The best mode of preparing it is to add a considerable quantity 
of chlorate of potassium to a boiling solution of kinic acid, and then add strong hydro- 
chloric acid in such portions that chlorine and chlorous acid may be continually 
evolved. The distillate is concentrated by rectification over chloride of calcium. It 
then, if tolerably pure, solidifies into a crystalline hvdrate when covered with water 
at 4^ or 5^. If no solidification takes place, the proauct is contaminated with other 
oils, and must be purified by figitating it with ice-cold water, and heating the de- 
canted and darified liquid to 60^ ; the greater part of the oily impurities then separate 
out. To purify it completely, it is converted into the ci^stalline hydrate as above men- 
tioned, and the crystals are pressed between paper. The pure anhydrous compound 
may be obtained by melting the crystals in a glass tube, whereupon they separate 
into a watery and an oily liquid, the latter, which is undermost, being pure anhydrous 
pentachloracetone. It is a colourless rather mobile oil, having a burning aromatic 
taste, and an odour like that of chloral. Sp. gr. between 1*6 and 1*7. It remains 
liquid at —20^ and boils at 190°. The hydrate, which crystallises in rhombic tables, 
contains 4 atoms of water. Water dissolves ^ of its volume of anhvdrous penta- 
chloracetone, and on the other hand, this compound takes up a certain quantity of 
water without change of appearance ; but it then becomes turbid at the heat of the 
hand, like hydrated conine. Pentachloracetone dissolves readily in alcohol and ether. 
The alcoholic solution mixed with alcoholic potash deposits chloride of potassium 
together with scaly crystals, probably consiBting of dicnloraceiaU of potassium, and 
the solution is found to contain formic acid : 

C*HCPO + H«0 = CHCa* + c«H»ca«o« 

Chlorofonn. Dichloracetlc 
add. 

and: CHa» + 2 H*0 = 3 HCl + CHK)». 

(Stadeler, Ann. Ch. Pharm. cxi. 277.) 

Hexachloracetonet CCl'O (discovered by Plantamour, who assigned to it the formula 
(CGl'K)*), is obtained bv the action of chlorine in sunshine on an aqueous solution of 
citric acid. It is an oilv liquid of peculiar pungent odour, sp. gr. 1*75 at 10°, and 
boiling between 200° and 201°. It makes transient grease spots upon paper, m- 
dually reddens litmus paper, and forms with water, at temperatures not noove ^, a 



ACETONES. 81 

a^gtalliiM liydnte, CPCPO + KH), which melts at a temperatiEre abore 15^, with 
Mpazatkn of an oil. 

Bromacetone, CH'JfrO, is produced similarlj to monochloracetone» tiz. by the 
action of a feeble electric cunent on a mixture of acetone and hydrobromie add. It is 
eoloaxleSB when first prepared, but turns brown in a fbw minntes, and is decomposed by 
difltiDatioii, the greater portion howoTer passing orar between 140^ and 146°. Its ya- 
poor irritates the eyes so strongly that the spiUing of a few drops renders the air of 
a room unendurable. (Bi ch e.) 

lodeetbms aiqpears ako to be fanned in small quantity by the electrolysis of a mix- 
tare of acetone and hydiiodic add. (Biche.) 

Mtthylaeetone^ C*H*0 « (?K\CBF)0, — When crude commercial acetone, 
or, better, the birown liquid which floats on the to^ of it, is dehydrated with diloride 
of ealdum and then subjected to fractional distillation, pure acetone jpasses over below 
60° and the distillate which is obtained between 60^ and 130°, yields, after about 
thirty fractionations, three distinct compounds, viz. methylacetone, boiling between 75° 
and 77°, ethylacetone, G*H>«0, between 90°, and 95° and dumasin, G*H^*0, between 
120° and 126°. fFittig, Ann. Ch. Phaim. ex. 18.) 

Methylacetone u a colourless liquid of sp. gr. 0*838 at 19^ 0. haTing the odour of 
acetone, misdble in all proportions with water and aloohoL It combines with add sul- 
phite of sodium, fbnning a crystalline compound, 2 C^H^aSO' + 8 HH), which is yeiy 
aoinhlein water. 

Etkvlaeetone, CVO ^ G^*(C^>)0.— Transparent, colourless liquid, smelling 
fkintly like acetone, sparingly soluble in water, but misdble in all proportions with 
akohal,spLgr.0<842atl9°. Boils between 90° and 95°. With acid sulphite of sodium 
it fbcms tae compound 2G*H*NaS0' + 3 HK), which crystallises in colourless nacreous 
lamins veiy soluble in water. (Fit ti g.) 

ACBTOMBS or MWSOMWB* This tenn is applied to a class of compounds 
which, like that just described, are composed of an add-radide united with an 
alcohol-radicle. Nearly all the acetones at present known consist of the radide of 
a&ttyacid combined with one of the corresponding alcohol-radides; their ceneral 
fonnnla being OH*™+^. OH*"—* O. where m may be either greater or less ttian n. 
When in»0, the acetone becomes an aldehyde, H.C"H*"'>0 - OH>>0; the 
aeetonee may therefore be regarded as alddiydes in which 1 at hydrogen is re- 
placed by an aloohol-radide. 

Acetones are either amfle or compound. In the simple acetones, m « n— 1, so that 
their goieralformula is 0-»H«»-". t>H«»->0. » C*"-»H^«0; thus, acetic acetone, for 
for which » n2, is CH'.CH'O. The simple acetones are produced br heating the 
barium or ealdum salts of the fktty adds, 2 atoms of the salt being decompomd in 
soeh a manner that the acid radicle of one of them is resolved into the next lowest 
aloohol-radicle and carbonyl (CO), so that a carbonate of ealdum or barium is formed 
at the same time : 

OH»"-»0)>^^C0.O-»H»-«)^ OH»^'0) ^ C0>^, 
Ca P+ Ca J^"0-»H«->{ + Ca^^' 

The formation of acetic acetone or methyl-acetyl (p. 26) by the decompodtion of 
acetate of barium, is a particular example of this process. In like manner, propione 
or eih^-propionyl, 0*H*.C»H*0, buiyrone or tntyl-butyryl, C'H'.C^H'O, valerone or 
tetf^-wujfi, OH'.G^HK), are produced by tiie decompodtion of the propionates^ butyrates 
Talentes^ &e. 

These simple acetones were the onl^ ones known, till Williamson in 1851 (Ohem. 
Soa Qn. J. ir. 238) showed that, by distilling a mixture of the barium or ealdum salts 
of two different &tty adds, acetones may be obtained in which an add radide is as- 
sociated with an alnmol-radide which is not the next bdow it in the series \m greater or 
less than n~l] : these are the so-called compound or interme^te acetones. If the 
adds whose salts are distilled together contain j> and ^ atoms of carbon, the decom- 
position may be represented by the equation : 

WH«^«0) rt ^ C0.Oi-»H*i-> > n OH»»- »0> CO > ^ 
Ca p+ Ca p'"Oi-»H*»->J"*' Ca«P' 

or, since it is indifferent which of the add radicles we suppose to be decomposed, the 

formulaoftheaoetone thus produced may also be ^_iW^_i[. Thus a mixture of 

acetate andTalerate of ealdum yields by distillation either meiMfl-valyl, CH'.C'H'O, or 
teir^-^Kriyi, C*H».C«H»0, dther. of these formulie bdng equal to CWa»0. Posdbly 
two isomeric oompoimds having these formulae, may be produced together. If one of 

CO TT) 
the mixed salts is a formate, A > O, the alcohol-radicle separated from it is reduced 

to an atom of hydrogen, and the acetone becomes an aldehyde. (See Axj>Bini>B8.) 



32 ACETONES, 

The compound acetones are also produced, together with the simple acetones and 
other prodncts, when a calcium or barium salt of a fatty acid is distilled alone. ThuB 
the distillation of butyrate of calcium yields, besides butyrone and a small quantity of 
butyral, a considerable number of hydrocarbons (Bert helot, Compt. rend, xlfii. 236); 
andomongtheee, methyl andethyl appear to occur, and give rise to the formation of ethyi- 
huiyryl, C*H*.C*H'0, and methyliutyryl, CH».C*H'0. (Friedel, Compt. lend, 
zlvii. 553.) 

The following is a list of the acetones, or ketones, at present known, which are de- 
rived from the fatty acids : 



Methyl-acetyl (Acetone) . 
Methyl-butyryi 
Ethyl-propionyl (Fzopione) 
l-butyryl . 



Ethvl-butyiyl 
Methyl-yalyl . 
Trim-butjpyl (Butyrone) . 
Metliyl-oenanthyl 
Tetryl-valyl (Valerone) 
Amyl-capronyl (Capronone) 
Heptyl-capiyl (Caprylone) 
Octyl-pelargonyl (t^elargonone) 
Laurone .... 
Myristone . . • 
Falmitone or Maigarone . 
Stearone .... 



C«H«0 -CH» .C*H«0 
C»H»0 - CH": .OffO 
C»H»0 = C'H'.C'H-O 
C«H»K)- C«H».C*H»0 
C«H»0= H».C»H»0 
C'H"0 « C»H^C*H'0 
C»H»«0 « H».C'H»>0 
C»H»0 « 0*H».0»H»0 
C"H«0 « C«ff>.C«H"0 
C»H«»0 » C'H» C«H"0 
C»'H"0 « C»H".C"ff^O 
C"H*«0 « C"H». C»*H»0 
C»HMC - C»»H«'. C"H"0 
C«»H«0 = C»H". C»*H»»0 
C«»H«0 - C>'H» C»"H»0 



Some of the compounds in this table are isomeric, e, g, propione and butyracetone. 
Among the higher terms of the series, the number of such isomeric compounds is doubt- 
less yery great, though but few of them haye yet been obtained. 

These bodies, with the exception of acetic acetone, haye not been much studied. 
Their reactions, so &r as they are known, resemble those of common acetone already 
described. The lower terms of the series unite with the acid sulphites of the alkali- 
metaJs, generally forming crystalline compounds. The best mode of purifying the 
acetones is to shake them up with a strong aqueous solution of acid sulphite of potassium 
or sodium, and distil the resulting solid compound with potash. The acetone then 
passes oyer pure. 

But little is known respecting acetones belonging to other series of adds. Two 
haye been formed containing the radicle benzoyl, yiz. benzophenone^ or ^henyUhemoyl^ 
C^H^'O a C'H^.C^K), the acetone of benzoic acid, obtained by heating benzoate of 
potassium ; and methyUbenzoyl, OHK) » CH'.O'H^O, obtained by distiYling together 
equivalent quiintities of acetate and benzoate of calcium (Friedel). Benzophenone 
treated with nitric acid yields nUroberusophenone^ C"H'(NO')'0. 

The calcium-salt of camphoric add, which is dibasic, yields by dry distillation an oily 
liquid called j^horone, which has the constitution of an acetone : 



" r 



Campborate of Phorone. Carbonate of 

calcium. calcium. 

and suberate of calcium, OH**0*Ca*, yields in like manner tuberone^ CH'^O, mixed 
with other products. These are the only two acetones of dibasic acids yet disooyered. 
(Gerhardt, Trait^ iy. 640.) 

^ JLC8TOVZVX. G"H"N'. — ^Produced by the action of ammonia on acetone (p. 28), 
either when a solution of ammonia in acetone is left to evaporate spontaneously to a 
syrup, or when acetone saturated with ammonia is heated to 100^ in a sealed tube. 
It is a colourless liquid, having a peculiar urinous odour, a burning taste and alkaline 
reaction, easily soluble in water, alcohol, and ether. It unites with acids, forming salts. 
The axalaU C»H"N«.C*H«0* + BPO crystallises feomahot saturated alcohoHc solution 
in delicate colourless prisms, which are soluble in water, insoluble in ether, give off half 
their water at 100^, tiie rest between 116° and 120°, and decompose at a higher tem- 
perature. The ehloropltUinate, C*H**N*.HCl.PtCl*, forms lustrous, orange-coloured, four- 
sided prisms with oblique terminal faces. It is soluble in water, also in boiling alcohol 
containing hydrochloric add; insoluble in ether. (Stadeler, Ann. Ch. Pharm. cxL 308.) 

iLOBTOmrxxiA. C'H'K. — A compound obtained by treating acetate of am- 
monium or acetamide with phosphoric anhydride : 

CH'O'.NH* - 2H*0 = (PH»N ; and C«H»NO - H*0 « C^«N. 
Acetate of ammonium. Acetamide. 



ACETON YL — ACETYL. 33 

It » idantical wiih eyanide of methj], obtained by diHtillfng cyanide of potasftinm with 
Bwtlytanlphate of potaagnm. (See Ctaiodb of Mbthti^T * 

OdortotUmUriU^ CO'N, or cj;anideof trichlorometh^l, GCl'.GN, is obtamed.by dis- 
tiSiiig tcichloraeetate of ammonium or trichloiaoetamide -with phosphoric anhydriddL 
It IB a liquid boiling at 81^ ; of sp. gr. 1'4441. With boiling potash, it yields ammonia 
and trichloracetate of potassium. 1% is Tiolentiy attacked by potassium. - 

mil lIWi 111 CH^.— ^A hy^thetical radicle 'sopposed b^ Hlaaiweta to exist in the 
TcUov ctyirtidtf Ibumed by the action of ammonia andbianlplude of carbon on acetone, 
blaaweti asdgna to theee ciyatala the fbrmnla GKIP^'S*, and regards them as ml- 
picemmaie of aoeiomd with mlpAocarbofutie of stdphaoetonyl ^ 2(C*H".2CNS) + 
2C"H*%.(7H<N^. Stadeler^a new of the constitution of this compound (p. 62), is 
Dodi mcTO probable. 

JkCnosiRb. The name giTen by Gerhardt to the hypothetical radicle C*H" or 
Cfi*, origmaUj called acetyl, and supposed by some chemists to exist in acetic acid and 
its denritiTea. (See Acbttl and Vintl.) 

AearaXTTbrn Kolbe's name for the radicle CH^O or C*JB*(^, usually called 
acetyl, iHiich flee. 

ACMTUMMoi^* Syn. of Acetyl-urea. 

ACSnx. CTEPO or C*H^O\ Aoetoxyl, Othyl.—A radicle not yet isolated, 
but BDppofled to exist in acetic add and its derivatiyes, the rational formula of acetic 

acid being; on this hypothesis, ^ > 0, and that of acetic anhydride, nzH*0 ( ^* 

The reason fop assuming the existence of this radicle in the acetic compounois is, 
that the fiumula to which it leads, affords the simplest representation of the most im- 
pcdant reaetions of acetic add and the other bodies of the series. Thus, when acetic 

add -a- V O 18 treated with a metallic oxide or hydrate, the basic atom of hydro- 

gm is lepiaoed by a metal, and an acetate of that metal -j^ > is produced. On 

treating the same compound with pentasulphide of phosphorus, F^S^ the external atom 

of oiygen is replaoed by sulphur, and thiacetic add, n- [S is formed ; and by the 

action of pentaehloride of phosphorus, the group HO is replaced by d, and chloride 
of acetyl 0^'O.Gl is produced. (See Acbtio Acm, and Acids, p. 44.) 

F<Nrmeriy, bowerer, acetic add, and the other members of the same group, were sup- 
posed to be derired from the radide CH* or C*B*; and to this the name acetyl was 
oc%iDaUy applied. Thus, anhydrous acetic acid was regarded as a trioxide of this 
rM&le, Tiz. C*H*,0*, and the hydrated acid as a compound of this oxide with water, 
riz. C*H*0*MO. &C. To applv the same name to two different radicles would of 
eoazse create concision ; hence the terms acetoxyl proposed by Kolbe, and othyl (ab- 
breriatioii of oxygen-ethyl) by IWilliamson, for the xadide C^'O. Most chemists, 
howeyer, are of opmion, mat the radide supposed to exist in acetic acid and its deri- 
TBtiyes, is most appropriatdy designatedby the term acetyl; and accordin^y, this term is 
now generally applied to the group 0*11'0, while C^H", whidi more properly belongs 
to anotlier series of compounds deriyed from alcohol, ether and ethylene, and haying 
a leas intimate distant relation to acetic add, is caJled by a different name. (See 
AcaiosiL and Vdttl.) 

Acetyl, CETO is regarded by Kolbe as a compound or conjugate radicle, 
eontaimng methyl and carbonyl, yiz. CH',CO ; and in like manner, propionyl, C'H'O, 
is regarded as a compound of ethyl: CH^CO; bulyiyl, 0*H'O, as a compound 
of trityl : CH^.CO, &c. each radide of a fatty add being supposed to contam the 
next lowest aloohol-radide associated with carbonyL This yiew, which has been 
adopted hy Gerhardt, in his " Traits de Chimie Oiganique" is based ujpon the fact 
that certain methyl-compounds may be obtained from acetic add and its deriyatiyes, 
and the oontruT ; similar transformations likewise taking place in the other terms 
of the series, ll^us, a solution of acetate of potassium subjected to electrolysis, yidds 
methyl and cazbonie anhydride : 

CH".CO I Q ^cH»+ C0« + H 

Cyanide of methyl boiled with aqueous potash giyes off ftmmonia and forms acetate 
of potassium: 

CmCKj. KHO + H*0 - ^^-^^JO + NH»; 



Cyanide of 



*■.— i 



methyl Acetate of 

potauium. 

Vol. L D 



84 



ACETYL. 



and acetate of ammoniiini (CH*.CO).NH^O, treated wiih.pho0p]ioric anhydride, giTea off 
2H^0, and is reduced to cranide of methyl, CH'.CN. Hanh-gas, or hydride of methyl, 
CH'.H, is prodnoed by the decomposition of acetates (p. 12) ; and caoodyl Aa(C'B-*)\ 
by the decomposition of acetic acid. The formation of acetone or methyl-aoetyl, 
CH'.CH'O, m>m acetates, and the' correroonding transformations of propionatee, 
yalerates, &c. (p. 26), is another example of the same kind of decomposition. Again 
it has been shown by Wanklyn (Ghem. Soc. Q. J. zi. 103), that sodium-ethyl 
subjected to the action of carbonic anhydride is oonyerted into propionate of sodium : 

C«H».Na + C0« - ((?H».CO).Na.O ; 



Sodium- 
ethjl. 



Propionate ofaodium. 



and in like manner, acetate of sodium may be prepared from sodium-methyL 
Lastly, many organic compounds, such as sugar, starch, alcohol, and acetone, which 
are conxertible into acetic add by oxidation, may also, under the influence of chlorine, 
or bromine, be conyerted into bodies belonging to the methyl-series, yiz. chloroform, 
C(HC3.*).C1, and bromoform, C(HBr').Br. It must be obeyed, howeyer, that the 
representation of acetic acid as a methyl-compound applies chiefly to a state of transi- 
tion, just as the add is being produced from or conyerted into a body belonging to a 
different series, and exhibiting different chemical relations ; so long as we are concerned 
with the transformation of one acetyl-compound into another, such as that of acetic 
add into chloride or bromide of acetyl, or of the chloride into acetic anhydride^ the 

C*H'0) 
formula ^ V is suflident for the representation of all the changes which take 

place. 

The hydrogen in acetyl may be partly or whoUy replaced by other elements, yiz. 
chlorine, bromine, &c. ; and hence anse the conjugate or deriyatiye radides, hromaceiyl, 
ehhraeeijflt &&, which, like acetyl itself are hypouietical, not haying yet been isolated. 
The following table exhibits a general yiew of the compounds of acetyl and of the 
radides deriyed from it by substitution. 



Bromide of Acetyl 

Chloride 

Iodide 

Hydride 

Hydrate 

Oxide 

Peroxide 

Sulphydrate 

Sulphide 

Nitrides 



Hydrate of Bromacetyl 

Nitride . • 

Hydrate of Dibromacetyl 

Nitride . . • , 

Hydride of Tribromacelyl 

Hydrate of Chloracetyl 

Nitride • 

Chloride of Trichloracetyl 

Hydride 

Hydrate . 

Nitride . 

Phosphide 

H^dnte of lodacelyl 

Nitride . 

Hydrate of Di-iodacetyl 

Nitride 

Hydride of Tri-iodacetyl 



Bromide of Acetyl, C«H«0 



C*HH).Br 

c«H»o.a 

CH'O.I 

C«H«O.H 

C«H«O.H.O 

(C«H»0)«.0 

OTPO.O 

CB*O.H.S 

(C«HK))«.S 
fC«H«O.H«.N 
. (C«H«0)«.H.N 
lc«H»O.C»H».H.N 
&c. &c. 

C»H«B rO.H.O 

C«H«B rO.H».N 

CHBr*O.H.O 

C«HBr«O.H».N 

C«Br»O.H 

C«H«C10.H.O 

C«H*aO.H«.N 

CK)1«0.C1 

C»C1«0.H 

CH31«0.H0 

C«a«O.H«.N. 

C«C1«0.H«J>. 

C«H*IO.H.O 

C»H«IO.H.N 

C«HPO.H.O 

C«HI«O.H«.N. 

CW).H. 



Aldehyde 
Acetic add 
Acetic anhydride 

Thiacetic add 
Thiaoetic anhydride 
Acetamide 
Biacetamide 
Ethyl-acetamide 

Bromaeetic add 

Bromacetamide 

Dibromacetic add 

Dibromacetamide 

Bromal 

Chloracetic add 

Chloracetamide 

Chloraldehyde 

Chloral 

Trichloracetic add 

Trichloracetamide 

Trichlorace1rn>hide 

lodacetic acid 

lodaoetamide 

Di-iodacetic acid 

Di-iodaoetamide 

lodal 



_ — . , .^ ^ „ ^ ^ x;.Br. — ^Prepared by slowly adding glacial acetic add to 

pentabromide of phosphorus in a tubulated retort» distilluig, and rectifying : 

C«H«O.H.O + PBr».Br" « C«H"O.Br + HBr + PBr«0. 
It is a colourless liquid, boiling at 81°. When exposed to the air, it ftimes strongly 
and immediatdy turns yellow. It colours the skin yellow, and is said to impart to it 
the odour of phosphuretted hydrogen ; but this must arise from impurity. Water 



r 



ACETYL. 35 

deeomposes it into aoetie and hydzobFomic acids. (Bitter, Ann. Ch. Phann. zcr. 

Chloride of Acetyl. CH'O.GL — ^Prodnoed by the action of oxyehloride of phoe- 
phom on acetate of potaaainm : 

8{0«H»O.K.O) + FOOT - 8C«H«0C1 + PO*K» ; 

or in tiie aame manner as the preceding componnd, by ^^igtiHi'Tig glaxnal acetic acid with 
pentachlodde of phosphoroa : 

c*h»o:h.o + pa«.a«. - c*h»o.ci + hci + pa«o. 

Gerhard t, who discoTered this componnd (Ann. Ch. Phys. [3] zxzvii. 294), pre- 
pand it by adding oxyehloride of phosphorus, drop by drop, to jEhsed acetate of 
[j ii tiiBinin A brisk action then takes place, and sufficient heat is produced to cause 
die chloride of acetyl to distQ over into tne receiver, which must be well cooled. The 
^irtpl«<» may be fieed from excess of oi^chloride of phoephoms hj re-distillation orer 
leelate of potaasimn, then distDled by itself and the Hqnid which passes oyer at 66^ 
eoUeded apart The re-distillation oyer acetate of potassium is, howeyer, attended 
with some loaa, in oonseqnenee of the formation of acetic anhydride. 

C*BPO.Cl + C*HK).K.O - (C«HH))K) + KCL 

For this reason. Bitter recommends the preparation of chloride of acetyl by the action 
of pentachloridie of phosphorus on glacial acetic acid, the product being thereby ob- 
tained in Iwger quantity and more essily purified. 

Chloride c? acetyl is a colouriess, yery mobile, strongly refiracting liquid, of speciflo 
cnrity 1-125 at 11<=>, 11305 at (P, and 1-1072 at ie9 (Kopp). BoOs at 66^. Vaponr- 
deosity, 2*87 (G-er h ar d t) : by calcnlation (2 yoL) e 2'718. It fumes Bl^tly in the air, 
and has a pungent odour like that of acetic and hydrochloric acid. The yapour at- 
tacks the eyes and respiratoiy organs yeiy stron^y. 

Chloride of acetyl is decomposed with explosiye yiolence by water, yielding acetic 
and hydrochloric acids : 

C«HH)a + H«0 = C»H*0« + HCL 

AmmrtnU acts strongly upon it, forming acetamide : 

C»H»0.C1 + H*N « CH'O.H'.N + HCL 

Shnihriy with phenylamine, it forms phenylacetamide C^H*O.CfH'.H.N. Distilled 
with acetate of potassium, it yields acetic azmydride : 

C«HK).KO + C«H»0.a - (C«H"0)»0 + KCi ; 

•ad with hesnate of potassium it forms benzoate of acetyl or acetate of benzoyl : 

C'HK).K.O + C«HH).a - CH«O.C^«0.0 + KCl ; 

ud similariy with the salts of other adds. With thiacetate of lead, it forms chloride 
of lead, and probably also thiacetic anhydride : 

0*H»OJTt).S + Cm*0,Cl - (C«H»0)«S + PbCL 

When it is heated with zinc in a sealed tube, the metal is strongly attacked ; and a 
black tany subtance is formed, from which water dissolyes chloride of zinc, and sepa- 
ratei a hqoid haring an ethereal odour. 

Hydride of Acetyl, See Aldshtds. 

Iodide of Acetyl. C*H*O.I. — Obtained by the action of iodide of phosphorus on 
aoetie anhydride (Guthrie, PhiL Mag. [4] xiy. 183), or on acetate of potassium; 
(Cab oar I, Compt. rend. zliy. 1253). After being shaken vp with mercury and re- 
diftilled, it forms a transparent colourless liquid, of sp. fi;r. 1*98 at 17°. It boils at 
108° (Guthrie) ; between 104<> and 105° (Cahours). It fumes strongly in the air, 
haa a reiy pungent odour, and an intensely sour caustic taste. 

^ Iodide of acetyl is partially decomposed by distillation. Water decomposes it with 
▼iolenoe^ finroung hymodic and acetic adds. It acts strongly upon alcohol, forming 
Ketate of ethyL It is decomposed by zinc and by sodium at ordinaiy temperatures, 
tin by mercury in direct sunshine, iodide of mercury being formed, and little or no 
pomanent gas being giyen off. 

Peroxide of Acetyl. C*H*0.0. — Biscoyered by Brodie in 1858 (Proceedings of 
the Boyal Society, iz. 861.) It is obtained by mixing acetic anhydride and peroxide of 
lanun, in equiyalent proportions, in anhydrous ether. The mixture must be effected 
Toy graduaUy, as it is attended with great eyolution of heat. The products are 
acttate of banum and peroxide of acetyl, the latter remaining dissolyed in the ether : 

(C*H»0)«.0 + BaO = C«H»O.Ba.O + C»H«0.0. 

D 2 



I 



36 ACETTLOUS ACID— ACHMITE. 

The ethereal solution, after filtration from the acetate of barium, is carefully diBtHled 
at a low temperature, and the remaining liqnid is washed three or four times with 
water till the wash-water ceases to be acid. The residue is peroxide of acetyL 

It is a -viscid liquid, extremely pungent to the taste, the sniallest portion placed upon 
the tongue boming like cayenne pepper. It is highly explosiye ; a single drop placed 
upon a watch-glass and heated, (explodes with^ a loud report, shivering the guiss to 
atoms. It is a powerful oxidising agent, immediately decolorising sulphate of indigo, 
conyertine protoxide of manganese into peroxide, and yellow prussiate of potash into 
red prossiate. Barytarwater poured u^n it^ is instantly oonyierted into peroxide of 
barium, with formation of acetate of banum. ^ 

Aeetyl'Urea. (See Ubbas (Compound) and Gabbamidb.) 

ACaTT&OUB ACZB. AXASSYBIC ACSB. Lampio add, Etherio add. 
An add supposed to be produced by the slow combustion of ether or of alcohol, 
and under certain circumstances by the oxidation of aldehyde. When ether ia 
repeatedly distilled, or allowed to fall in successive drops on a solid body heated to 
about 1299, 80 that its vapour may come in contact with the air at a high temperature, 
a disagreeable pungent odour is produced, supposed to be that of aldehydic acid.. 'The 
compound possessing this odour is formed in larger ^quantity, when a spiral of fine 
platmum wire, previously heated to redness, is suspended over a basin jDontaining 
ether, and the whole covered with a bell-jar. The wire then continues to glow, 'the 
ether underaoing a slow combustion without flame, and an acid liquid is formed, 
which mns £>wn the sides of the bell-jar, and may be collected in a vessel placed 
below. This liquid is colourless, has a very sour taste, and gives off a pungent vapour 
which excites tears, and causes great oppression when inhaled. The same compound 
is obtained, according to liebig, by heating oxide of silver with aqueous aldehyde ; 
part of the silver is then reduced, while the other portion remains m solution in the 
form of aoetylite of silver, and by decomposing this sUver^salt with sulphuretted 
hydrogen, the acid may be obtained in the fi^e state. It is, however, very liable to 
decompose, as aJso are its salts. When the silver-salt is boiled with baryta-water, 
silver is reduced and acetate of barium remains in solution. 

2C*H»AgO + 2BaH0 - C«H»BaO + C»H*BaO* + 2Ag + H»0 

,, ^ y , -^ > , — -^ ^- , -^ 

Aldehydateof Hydrate of Aldehjrdate Acetate of 
•ilrer. bariuin. of banum. barium. 

Gerhardt (Traits L) is of opinion that the so-called aldehydic or aoetylous acid is 
merely a mixture of aldehyde and acetic acid, the aldehydate or acetylite of silver being 
in fact merely aldehyde in which 1 atom hydrogen is replaced by silver. 

AOBZULBA XZULBVO&ZOX (3/tZ^/<>t/.)— The ash of this pknt has been 
analjjTSed by Way and Ogston. 100 parts of the diy herb left 13*45 per cent, ashes con- 
taining in 100 parts 80*37 parts of potash, 13*40 lime, 8*01 magnesia, 0*21 sesquioxide of 
iron, 2*44 sulphuric anhydride, 9*92 silica, 9*36 carbonic anhydride, 7*13 phosphoric 
anhydride, 20*49 chloride of calcium, and 3*63 chloride of sodium. 

AOBBUUIXC ACZD. An add said to exist in millefoil (Achillea MiUrfoUum). 
It crystallises in colourless prisms, soluble in 2 parts of water at 12^ *5. With the 
alkahea it forms salts which are easily soluble in water, but sparingly in alcohol The 
solutions are precipitated by neutral acetate of lead, whereas the free acid is precipi- 
tated by the basic acetate only. The potassium, sodium, and oilcium salts are otb- 
tallisable : the ammonium and magnesium salts diy up to amorphous masses. The 
quinine salt is said to be obtained in fine crystals grouped in stars, when its aqueous 
solution is mixed with alcohol, then boiled and left to cool slowly (Zanon, Ann. Ch. 
Pharm. Iviii. 31). Neither the acid nor its salts have been analysed. L. Gmelin, 
(Handbook, x. 207) su^^ested that this acid might be impure malic acid. According 
to Hlasiwetz (J. pr. (Shem. Ixii. 429) it is aconitic acid. 

AOBZXiXJUDi. A bitter substance of unknown composition, extracted by Zanon 
from millefoil. It forms a hard, yellowish brown extract, having a peculiar odour and 
bitter taste, easily soluble in water and in boiling alcohol, sparingly in cold alcohol 
and insoluble in ether; but on treating it with a few drops of any acid, it becomes 
easily soluble in ether; it dissolves also in ammonia. It is said to be useful as a 
remedy against fever. 

(See DiOFTASB.) 

A mineral first distinguished by Strom. It has a brown-black or 
red-brown colour on the outside, blackish or dark greyish green on the fractured sur- 
fiices; in thin fragments it is translucent, and exhibits a yellowish-brown colour. 
Sp. gr. 3*43 to 3*53. Scratches glass. Melts to a black bead before the blowpipe. 
It crystallises in oblique four-sided prisms with tnincated lateral edges andveiy 
sharp four-sided terminal faces, the edges of which correspond with the lateral edgee 



ACHROITE^ACIDIMETRY. 37 

of the oblique prifim. It has four desyagea, two parallel to the rides of the oblique 
pcjgm, and the other two leas obrionB parallel to the tnmcatioxui of the acute latcoral 
edgesL Aecording to the analyses of Berzelios and Kammelsbei^, its composition is 
2feaA0»+ FeO^. 2SiO' {Si = 21-5 . - 8) or 2Na«0.3SiO» + 2(Fe^O»,3SiO«) 
(Si » 28*5 . O » 16.^ It occurs, though rarely, embedded in granite at £ger, and in 
fljemte, near Pongnna in Norway. 

▲ name giyen to the colourless Tariety of tourmalin. 
xa. A name giyen by Breithanpt to a doubtM mineral, 
hitherto fbund only in decomposed orstals (trigonal dodecahedrons^ which occur in 
association with TseuTian from Yilui (riluite) : tiiey are perhaps denved from helvin. 

A1" Itm^— ' '^^ , ACZCH&ratSDaSv &c. (See OxTBBOiiiDBS, Oxtohloeidbs, 

AOBGUEXTBrn {Jcieular Biamutht NeedU ors,) a natiye sulphide of bismuth, con- 
taimnff also sulphides of copper and lead. The formula assigned to] it by Dana is 
(3Ck# + Biff^ -¥ 2(3J%i9 -i- BiS^) showing it to be analogous to Boumonite, with 
which it IB uomorphoua. 

It oocnrs embedded in white quarts, and accompanying gold, at Bereso^ in Siberia. 

^jiipA — ^iiii^ fj^Q determination of the quantity of real add in a sample of 
faydrated add, is a problem of frequent occurrence, both for scientific and for technical 
puiposes. As the specific gravity of a mixture of add and water always increases 
with the pr o portion of* acid present, and as, moreorer, a certain specific gnudty 
always corresponds to a certain strength, provided no foreign substances are present, 
it fellows that if the specific gravity corresponding to each particolar percentage of 
real add has once been accuratdy detemuned and tabulated, the strength of any 
giTsn sample of aqueous add may always be determined by taking its speofic gravity 
and refeiTingto the tables. (See SxTLPEirBic, Nitbio, Hydbochlobio Acid, &c.) This 
method is in fiict much used, the density being generally taken with the specific gravity 
bottle for sdentific puiposes, and with the hydrometer for commercial estimations. 
This method, however, necessarily supposes that the add £b pure ; the presence of any 
foreign sabetanoe, such as nitrate of sodium in nitric add, cream of tartar and ex- 
tractive or colouring matter in vinegar, &c would altogether destroy the accuracy of 
the result. Moreover, in some adds, tiie specific gravity varies so little for consider- 
able di£%rence of strength, that a yery slight inaccuracy of observation entails a large 
enor in the result. In acetic add. for example (p. 11), an increase of strength amount- 
ii^ to 1 per cent, produces on the average, an increase of density not exceeding 
D-0034. for these reasons it is essential, especially for technological purposes, to adopt 
some ready and exact method of determining the strength of an acid, independently 
of its specific eravity . 

The strengu of an add may be estimated : 

a. By FciumeMc ancdysia, tLat is by ascertaining the measured quantity of a standard 
alkaline solution required to saturate a given volume of the add. (See Analysis, Volt;- 

MB'IIUC) 

5. By Weight mudyris, • This mode of estimation might be conducted in various 
ways : fior instance, by conyertmg a eiyen quantity of the hydrated acid into a neutral 
salt of potaarium, sodium, barium, kad, silver, &c. dther by saturation or precipita- 
tion, weighing the salt thus formed, and calculating the quantity of add from its 
known composition. This method is indeed constantly adopted in scientific chemistiy ; 
bat is for the most part too tedious for technical purposes. A quicker method is to 
deco m po s e a known vreight of the add with an excess of add carbonate of sodium or 
potasnum, and estimate hy weight the quantity of carbonic anhydride evolved. The 
quantity of real add in the sample of hydrated add is then easily calculated ; for each 
atom of a monobasic add, expels 1 atom of carbonic anhydride (CO* » 44,) and each 
atom of a dibasic add expels two atoms of carbonic anhydride (2C0' » 88) : this 
win be seen from the fbUowing equations : 

For hydiodilQiic add : 

CO«NaH + CIH « ClNa + C0« + H»0. 
GO* : C!1H - 44 : 36-5 

For aeetie add : 

GO^aH + 0«H»0«.H » CJ«H«0*.Na + C0« + H«0 
CO* : CJ«H«0«.H • 44 : 60 
For sulphmie add : 

2CQ*NaH + S()*H» = SO^a« + 2C0« + 2H»0 
2C0« : S0^« - 88 : 98 - 44 : 49 

Suppose^ for example, that 13*5 grm. of hydrated sulphuric add thus treated with 

D 3 



38 



ACIDIMETRY. 



Fig.l. 



acid carbonate of flodinm, eliininate 1*4 grains of carbonic anbydride. The quantity 

49 
of real add (SO^H*) in the 12'5 grm. is then 1*4 x j7 « 1*47 gmu and the 

quantity of real acid in 100 parte of the hjdrated acid wiH be given by the equation : 

X - 1*47 X i52 - 1089. 

lo'O 

A oonyenient apparatuB for these determinations is a small liffht glass flask {fa, 1) of 
aboutlOO cubic centimetres (3 or 4 oz.) capacity, having a lipped edge, and fitted wi^ a 
cork perforated with two holes. Into one of these apertures is fitted a bent tube a, carry- 
ing a diying tube 6, filled witli chloride of calcium, and into the other, a narrow tube c, 
reaching nearly to the surfeuse of the liquid, and bent at an obtuse angle above the 
cork. A convenient quantity of the acid whose strength is to be determined, having 
been weighed out in the flask, a quantity of add carbonate of sodium or potassium 
more than suffident to neutralise the add, ib placed in a small test-tube about an inch 
long, and having its lip slightly turned over, so that it may be suspended by a thread. 
This tube is then let down into the flask by the thread* but not low enough to oome 
in contact with the add ; the thread is fixed in its place bv inserting the cork into the 
neck of the fiask, and the whole apparatus is weighed. The orifice of the bent tube r, 
is then dosed with a plug of cork or wax, the cork of the flask loosened sufBdently to 

allow the short tube ^, containing the alkaline carbonate 
to drop into the add, and the cork immediatdy tightened. 
The carbonate is now decomposed by the add, and carbonic 
anhydride escapes through the diying tube, the chloride of 
calcium retaining any moisture that may be carried along 
with it. When the dfervescence ceases, the flask must bo 
warmed to ensure the complete removal of the carbonic 
acid from the liquid, and after it has cooled, the plug must 
be removed &om the bent tube tf, and air drawn through 
the apparatus by applying the mouth to the extremity 
of the chloride of cidcium tube, in order to remove all the 
icarbonic anhydride remaining in the flask, and replace it 
by air. The whole is then again weighed, and the loss of 
weight gives the quantity of carbonic anhydride which has 
escaped. At the completion of the experiment, a piece of 
blue litmus paper must be thrown into the liquia in the 
flask; if it remains blue, the determination may be con- 
sidered «caet : but if it is reddened, there is still free add 
in the flask, showing that the quantity of carbonate intro- 
duced was not sufSdent to decompose it. In t£at case, a second small tube (K>ntaimng 
alkaline carbonate must be introduced as before, the apparatus again weighed, 
and the whole process repeated. The second loss of weight added to the flrst, gives 
the total quantity of carbonic anhydride evolved. 

Another form of apparatus for these estimations, devised by WOl and Fresenius, is 
shown in^. 2. ▲ and b are two small flasks, having strong nedu turned over in a 

lip. Each of them is dosed with a tight-fitting 
cork pierced with two holes. Through the cork of a 
there passes a straight tube a, readiing nearly to 
the bottom of the fiask ; a tube c, bent twice at 
right angles, passes through both corks, termi- 
nating just below that of a, but reaching nearly 
to the bottom of the fiask b ; a straight tube d 
also passes through the cork of b, termmating just 
below it. The tube a is dosed at the extremitv b 
with a plug of wax. The add to be estimated is 
weighed oat in the fiask A ; the other fiask b is filled 
to about one-third with strong sulphuric add ; and 
the whole apparatos Ib connected in the manner 
shown in the figure, the proper quantity of add car- 
bonate of sodium being introduced into ▲ in a 
short test-tube, suspended by a thread in the manner 
described with the former apparatus. The whole 
apparatus is then weighed, tne cork a loosened, so 
as to allow the tube containing the carbonate to fiill into the acid, and the cork im- 
mediately secured. Carbonic anhydride is now evolved, and is obliged to pass through 
the sulphuric add in b, whereby it is completely dried. As soon as gas ceases to 
escape, the flask a is immersed in water at about 5(P or 60° C. till the fr^sh 
evolution of gas thereby occasioned ceases. The wax-plug is then loosened, to 




Fig. 2. 



n » 




ACIDS. 39 

pKfoit the solpluiiie acid in b £rom being foicdd into ▲, in oonseqiienoe of diminiBlied 
pnomre in liiat Tessd; the apparatus is remoTed finnn the hot water; and air is 
nAed thromgh the tabe d as long as anj taste of carbonic acid is peroeiyed. Lastly, 
the ^jpaiatoB, -when quite cold, is re-weighed, and the loss of weight giyes the qnantily 
of carbonic azdijdride evolTed. 

This appantus is mneh hesner and more bnlliy than that before described, and 
docs not a^pttr to possess any adTontage orer it Mohr points oat, as a sonrce of 
inaeeoracy in its use, that the large ani&oe of the two flasks, being heated during the 
eipegiin ent» is not likely, on cooling, to condense exactly the same quantity of moisture 
as was attached to it before. 

It is of the ntmost xmpoitanee that the add carbonate of sodinm or potassinsv used in 
these determinations, be <^mte pure and free from neutral carbonate. Tne acid carbonates 
grre a white precipitate with chloride of mercury, and the neutral carbonates a red-brown 
precipitate ; bat ihia test will not indicia the admixture of a small quantilr of neu- 
tral carbonate with the acid carbonate. A more certain test of purify is to weigh out two 
equal portions of the add carbonate, ignite one in a platinum crudble, and determine the 
quantity of carbonic anhydride giyen off from the other by the action of the add in the 
spparatos represented in Jig. 2 (See Alkauxbtrt). The quantity of neutral carbonate 
of Bodiom remaining after the ignition should be to that of the carbonic anhydride 
erndred as 53 to 44 ; and that of the neutral carbonate of potassium to the carbonic an- 
hydride as 69 : 44. ^ 

If the add carbonate is not j^rae enough to giye a white predpitate with ddoride of 
mercoiT, it should be at once rejected. Oommensial add carbonate of sodium, which will 
stand that test^ may be farther purified by triturating it to a uniform powder, coTering 
it with an equal weight of cold distilled water, leaving it for 24 hours, then washing 
it two or three times on a filter with a small quantity of odld water, leaving it to 
drain, and drying it by exposure to the air without heating. Acid carbonate of potassium 
may be pur&ed by recryBtaJlisation. (For further details on Addimetry, see Dio- 
tionary of Jrts^ MamufaetureSf and Afmes, new edition, toL i. p. 23.) 

JLOTMMm Salts of hydrogen. The following properties are common to the most 

important adds, — 

1. Solubility in water. 

2. A sour taste. (In those adds which possess the most strongly marked characters, 

this prop er ty can be perodyed only after dilution wim a large quantity of 
water.) 

8. The power of reddening most organic blue and yiolet colouring matters (for ex- 
ample, litmus), and of restoring the original colour of substances which haye 
beeti altered by alkalis. 

4. The power of decomposing most carbonates, causing efferyescence. 

6. The power of destroying; more or less completely, Sie characteristic properties of 
alkalis, at the same time losing their own distinguishing characters, and 
forming alkaline salts. 

The last is the only one of these properties which can be considered essential to 
adds ; indeed, comparatiyely few acids possess them alL Moreoyer, there are many 
sabstanoes which possess, in a greater or less degree, all these properties, but which 
are nerer included among adds; of these it will besuffident to mention itium (sulphate 
of potasdum and aluminium). Alum is soluble in water ; its solution has a taste 
which, though not purely sour, approaches much more nearly to sourness than that of 
many adds (benzoic add, for example) ; its solution also reddens Htmus, causes brisk 
efferyesoence with alkaline carbonates, and neutralises completely the alkalinity of 
potash or soda, forming an alkaline sulphate. 

In order to get a more exact idea of what it is which essentially constitutes aciditr, 
it may be usenil to condder briefly the opinions which haye successiyely been held 
upon the subject by the chemists of past times. 

In ordinary language, aeid is equivalent to sour; and in both Greek and Latin, the 
idea of *' sourness" was expressed by almost the same word as that used for "vinegar," 
the only add known to the andents (thus, Crr, i^6s, sour; i^cs, vinegar: Lat. acidua, 
soar ; aeetum^ vinegar). It does not> however, appear that very great importance was 
at any time attached to sourness as a characteristic of adds from a chemical point of 
view. The number of known adds was flrst increased by the labours of the Arabian 
chemists * ; and the solvent power which many of them exert on substances which 
are insoluble in water, seems flrst to have caused them to be regarded as a special 
dasB of substances. Thus, Geber (middle of the eighth century), who was acquainted 

* AliBott an ttM historical itatemcDtt eoDUined in thli article, for which no reference (a glren, are 
■ade on che mitboflty of Ko p p, ** Geschlchte der Chemte," 4 toU. 8to. Brtuuwick, 1848« 47. 

n 4 



40 ACIDS. 

with nitric add imd with an impure kind of sulphuric add, speaks of these bodies 
under the common name of aqua diasolutiva. The idea of conoBiYeneBBi cor at 
least a kindred idea, whidi may perhaps be expressed with tolerable accuracy as that 
of chemical activity^ seems to have been long connected by chemists with the idea of 
addify. For example, Van Helmont (Hred 1677 to 1644^ attributed the active 
properties of quick-lime to a peculiar acid, which he supposed limestone to obtain £rom 
the fire during burning. Stahl ^lived 1660 to 1734), who supposed the earthii and 
alkalis to have the same qualitatiye composition (see Art At.Vat.t), represented the 
alkalis as containing, in larger proportion than the earths, an add prindple to which 
they owed their sreater diemical actiyily ; and even as lately as 1764, a similar idea 
to that of Van Hdmont was applied by M ey er to explain a lai^ number of phenomena. 
This diemist endeayoured to explain the different properties of the caustic and car- 
bonated alkalis and alkaline earths, by supposing the former to be combinations of the 
latter with a substance which he called aoidum pingtte (fatty add), because, as he 
thought, fat-like properties could be perodyed by the sense of touch in its combinations 
with alkalis (caustic alkalis). The idea that coirosiyeness is the most important cha- 
racteristic of adds, was also plainly uppermost in the mind of Lemery, when (1675) 
he attributed the properties of ad<u to a sharp-pointed form of their smallest partides. 

That the properties of adds are, in some important respects, opposed to those of 
alkalis, was perodved at a comparatively early period. This opposition of properties 
was in fact the basis of the medical theory of the latro-chemists (from the first quarter 
of the 16th century to the middle of the 17th century). . According to them, the con- 
stituents of the human body had, some of them an acid, the rest an alkaline nature ; 
the undue preponderance, or want of addity or of alkalinity was the cause of disease, 
the condition of perfect health being a particular relation between these two opposing 
qualities. Otto Tachenius, a chemist of this school, gave, in 1668, as the essential 
diaracter of an acid, its power of combining with alkalis to form salts ; and accord- 
ingly he induded silica among adds. Boyle was well acquainted with the properties 
which are now considered most distinctiye of adds. He characterised aads by the 
solvent power which they exert on various substances with various degrees of ener^ ; 
by their power of precipitating sulphur and other substances from solution in alkau ; 
by their power of changing the blue colour of many plants to red, and the red of many 
others to bright red, and of bringing back to their original colour tliose which have been 
changed by alkali ; and lastly by their forming with alkalis so-called neutral salts, at 
the same time losing the properties just mentioned. This enumeration of the dia- 
tinctive qualities of acids difi&rs in no important respect from that given at the be- 
ginning of this artide. 

Various suppositions have been made, from time to time, in order to account for the 
properties possessed in common by the most strongly marked adds. In order to un- 
derstand these, it must be borne in mind that the distinction which most chemists are 
now accustomed to make between adds and salts, dates only from the time of La- 
voisier, that is, from the end of the last centuir; and that, till his time, adds, alkalis, 
and the substance^ now by preference called salts, were all induded under the common 
term ealfe. But since the adds then known were comparativdy few, and, as was 
natural, were those of which the add properties are most evident, the apparent dif- 
ference between acids and other salts was much greater then than it is now. 

The first theory of the constitution of adds was propdsed by Becher in his "Phydca 
Subterranea," published in 1669. Ho attributed the common properties of adds to 
their containing a common principle of acidity {acidum primiffenium)f formed by the 
union of primitive earth * and water, and supposed that the distinguishing characters 
of each acid were due to the particular substance which it contained mixed with the 
primitive acid. 

The ideas of Lemery regarding adds have already been referred to. 

He was followed by Stahl, who, in 1723, revived and extended Becher*s theoiy. 
The following may be taken as a summary of Stahl*s views: — The essential pro- 
perties of all saline substances are: to affect the sense of taste, or to have sapidity; 
to be soluble in water ; and with regard to other chief properties, such as specific 
gravity and fixity, to be intermediate between water and pure earth. In some salts 
the saline properties, are very marked, in others they are less prominent, and in some 
they are barely perceptible. Those substances which are most saline, acids and 
alkalis, have a great tendency to combine with bodies which have not saline pro- * 
perties, and to impart such properties to them. Hence we may condude that some 
substances are in themselves essentially saline, while others exhibit saline properties 
merdy because they contain a substance essentially saline as one of their constituents. 

* Acoordtng to Becher there were three primitlTe earths, — the vttrffiabte, the combaitfble, and the 
mrreurial, — which were the cause* respectively of ftisibilitr, of combustibility, and of Tolatillty ( thus 
correipooding to what the alchemists understood by salt, sulphur, and mercury. 



ACmS. 41 

We Brest fcgafd as belonging to the fanner ckM those bodies which not only 
{MMBesi nfine propertiee (taste, solnbility, &e,) bat which can impart these properties 
to other bodies by combining with them, and which, when separated &om their 
eombinatioDS, recover their original qualities. Hence, aJl acids and alkalis, fixed and 
Tolatile, bqnid and solid, must be considered as essentiallj saline. But, comparing 
these bodies among themselyes, we find that eren they possess saline properties in yeiy 
ranooB degrees. It appears, therefore, that there is only aTery small number of actual 
primitiTe salts, or rattier that there is only one such substance, which is a constituent 
of an other saline bodies, and is the cause of their saline properties. It is obvious 
tiiat this sabstanee must be souf^t amcmg bodies which most distinctly and most 
inranably manifest saline properties, and which are, at the same time, most simple in 
their eompoeition. Following this rule, we may at once exclude neutral salts, as being 
lesolraUe into more simple saline substances ; again, alkalis are more subject to 
alteratioa and to loss of their saline properties than acids ; tiiey must, therefore, bo 
cxchided. Of adds, we may select mineral acids as the most energetic Lastly, of all 
rameial adds, viiriolte (sulphuric) is the most active, has the greatest solvent powers, 
adheres most forcibly to the matter dissolved, is the most deliquescent, See. &c. Ao- 
earding^, adds must be considered as the basis of all other sahne bodies, and vitriolic 
add as Uie basis of all adds. (Macquer^s Dictionnaire de Chimie [1st. £dit. pub- 
lished anonymously, Paris, 1766l[Artides "Adds" and *<Sel; " Kopp, iiL 16 ; also 
Ene^rdopMie, ou Dictionnaire raisonn^ des Sdences, des Arts, et des Metiers, * * 
mis en ordre et public par MM. Diderot et D'Alembert, t. xLv. [NeufchAtel, 1766] 
Artide " 8el et Sels." The chemical part of this work was bv Malouin). 

Sodi were the ideas respecting ados and the cause of acidity, which, with unim- 
pcncant variations, were held by almost all chemists until tiie rise of the antiphlogistic 
system of chemistij. (See Goxbustion.) But before the downfedl of the older 
system, chemists had begun to have more exact notions than formerly of what were 
dementazy bodies* and to fed the necessity of conddering as elements all bodies which 
they eould not decompose. Hence, although Stahl regarded sulphuric add as a 
aeeoodary prindple, formed by the union of the primitive prindples of earth and 
water, and the other acids as compounds of sulphuric add with various substances, 
many of the last uph(dders of the phlogistic theory regarded most of the inorganic 
adds as simple substances. For instanee, phosphoric and sulphuric adds were sup- 
posed to be elements which, when combined with phlogiston, formed phosphorus and 
ml|A«y reapectivdy. Sulphurous add was one of the few inorganic adds which were 
lesnded as compounds ; it was supposed to be sulphuric add combined with less 
pl^giston than was needed to convert it into sulphur ; or, what was the same thing, 
to be solphur deprived of part of its phlogiston. 

But all previous ideas about adds were gradually superseded by those of L a vo isi er. 
Having found, ej^)erimentally, that carbonic, nitric, phosphoric, sulphurous and sul- 
phuric adds, all contained the then newly-discovered substance — oxygen (discovered 
Aj^gost 1st, 1774), Lavoider conduded that oxygen was a constituent of aJl acids, — 
that it was the addifying principle. (Lavoisier, Traits ti^mentaire de Chimie 
(1st edit. 1789), i. 69 etpasnm; Kopp, i 308 ; also iii. 17.) 

He first proposed this theory of acids in 1778 ; and, although adds were known in 
^udi no oxygen oould be detected, nearly all chemists continued for about thirty 
years to consider the assumption, that aridity was in every case due to the presence of 
oi^gen, as a necessary part of the antiphlogistic doctrine. Berthollet, indeed, as early 
as 1789, pointed out that hydrosulphuric and pmssic adds contained no oxygen ; but 
it was not till about 1810, aiter Davy's and Gi^-Lussac and Th^nard's researches on 
mnristie and oxy-muziatie adds (hydrochloric add and chlorine) that chemists generally 
began to admit the existence of adds free from oxy^n. The condudons drawn from 
these experiments were confirmed by Gky-Lussac's discovery of hydriodic add in 1814, 
and by his examination of pmssic add inr 1816. From this tune, most chemists re- 
eognued two dasses of adds — tiiose containing oxygen (oxygen-adds), and those 
containing no oxygen (hydrogen adds). Attempts, however, were still made to dis- 
eorer a constituent common to all adds, to which their common properties oould be 
ascribed. Thus, on the one hand, Berzelius continued till 1820 to assert the necessary 
existence of oxygen in all adds ; while, on the other hand, some chemists maintained 
that all adds contained hydrogen as an essential constituent. 

The latter opinion was advocated by Davy. "Hia ideas about adds appear to have 
been essentially the following-: — ^No one substance ought to be regarded as the addi- 
fying prindple ; the chemical properties of adds, as well as of other bodies, depend 
not oniy on the nature of their constituents, but also on their corpuscular arrangement. 
The so-called hydrated adds are the only true acids, and have a constitution similar 
to that of their salts. Hydrated chlonc acid is a ternary compound of chlorine 
oiygen, and hydrogen, analogous to chlorate of potassium, which is a ternary compound 



42 ACIDS. 

of chlorine, oTvgefa, and potassium. The whole of the oxygen may be remoyed from the 
add, and it will remain acid ; the whole of the oxygen may be remoyed from the neutral 
salt, and it will remain neutraL We haye no proof that in either of these bodies 
the oxygen is divided between the chlorine and the other oonstitaent, or that either of 
them oontaiiis so-called anhydrous chloric acid. Similarly, there is no proof that sul- 
phates or nitrates contain anhydrous Bulphnric or nitric acid. Hydrated snlphoric and 
hydrated nitric acids are the lane acids, and ore temaiy compounds, like the sulphates 
and nitrates. (Davy, Journal of Science and the Arts, i 286 — 288 ; also Gilbert's 
Annalen, Hv. 377—381 ; Phil. Trans. 1815, 212, 213; 218, 219; also Kopp.) 

In 1816 Dulong proposed the theory, since known as the binary or hydrogen-theoiy 
of acids. He endeavoured to show that all acids were similar in constitution to hy- 
drochloric acid ; that they were all compounds of hydrogen with a radicle which was 
in some cases simple (as in hydrochloric and h^driodic acids), in other cases compound 
(as in hydrocyamc, oxalic, sulphuric, and nitnc acids). His view of the constitution 
of these acids may be ej^iressed by the following formula : — 

Hydrochloric acid S(€T) 

Hydriodic jEr(/) 

Hydrocyanic B(CN)atH(Ov) 

OxaUc H(C^O') 

Sulphuric SlSO") 

Nitric hInO^ 

Salts, according to tius theory, were represented as compounds of an add-iadide 
with a metal instead of with hycbogen ; thus : — 



Hydrochloric acid . , ff{Cl) 
Chloride of potassium , K (C^ 



Nitric add , . . H (NO^ 
Nitrate of potassium . K {ifO^) 



Dulong^s theory resembled Davy's in so &r as it restricted the term acid* to sub- 
stances containing hydrogen (Irrdrated adds), and assigned an analo^us constitution 
to adds and their sfdts, but differed from Davy's theory in representmg the atoms of 
every add as arranged in a spedflc manner : namely, all the atoms except hydrogen 
as grouped together to form a compound radide. 

These views did not attract much attention till they were applied by Liebig, in 
1837t to explain the constitution of several organic acids, and of the various modifi- 
cations of pnosphoric add (Ann. Ch. Fharm. xxyi. 170 ; Ann. Ch. Phys. Ixviii 70.), 
and although the^r are explained and discussed in a large proportion of the Manuals 
of Chemistry published during the fifteen or twenty years fbUowing that date, they 
have never been generally adopted. Until a comparativdy recent date, almost all 
chemists continned to regard oxygen-adds as a dass of bodies essentially ctistinct from 
hydrogen-acids and from metallic salts. Confining the name of oxygen-adds to the 
substances now known as Anhtdbides, they regarded oxygen-salts as bodies formed 
by the direct union of adds with metallic oxides, and recoenised no essential distinc- 
tion between actual hydrated adds (adds in the sense of Davy and of Dulong) and 
mere solutions of the anhydrides in water. 

An important extension in the then existing views respecting adds resulted from 
the discovery announced by Berzelius, in 1826 (BerzeL Jahresb. vi pp. l^etseqX 
that certain metallic sulphides, such as those of arsenic and antimony, were cajpable 
of xmiting with the alkaline sulphides so as to form well-defined salts perfectly 
analogous to those formed by the combination of the corresponding metallic oxides 
with the alkalis. From this time, the existence of three new classes of adds (and 
corresponding saltn) was recognised, namely, acids in which the oxygen of ordinary 
adds was replaced by sulphur, or by the anidogous ^ements, selenium and tellurium. 

We owe the ideas of the nature of adds, now very generally entertained, chiefly 
tothe advance of organic chemisty, which has brought t(^ light a veiy large number, not 
only of new adds, but of new substances of all kinds, whose chemical relations cannot be 
adequately expreissed upon the system formerly universally adopted, of regarding all 

* KotwithsUndfng the more itrlct use, which wu made by both Davy and Dulong, of the word 
add, Tery many chemist* ftlll uie It to express bodies belonging to two very different cla«sei : acids and 
anhydrides. Thus the bodies HCl, HN(P. HSSO«, NSO», SO^ are all of them flrequenily called acids, 
although the first three possess marked resemblances among themselves and equally marked differences 
from the other two. Again, the bodies H*SO^ and SO' are often called by the same name, sulphuric 
acid, although thev cannot be obtained in any case by the same process, and although, when caused to 
act upon one and trie same substance, thev almost always give rise to products essentially unlike. This 
confusion between acids and anhydrides dates firom the earliest knowledge of the latter class of bodies, 
and was caused by the fact that the anhydrides which were first discoTCred immediately produce acids 
when thev come in contact with water. Thus, Lavoisier, by burning phosphorus in oxygen, obtained phos. 
phorlc anhydride, bat since the solution of 'this substance In water contained phosphoric acid, he suppouNl 
the anhydride to be the acid, and regarded the real phosphoric acid as a combination of phosphoric acid 
and water. Similarly, sulphuric acid was looked upon as containing ** drv sulphuric acid *' (sulphuric 
anhydride) and water ; and ail other acids, even those of which the anhydrides were unknown, as nitric 
and hydrochloric acids, were, in like manner, regarded as compounds of a hypothetical anhydride (oftea 
called "real acid ") with water. 



ACIDS. 43 

eomptmnd bodies as Ibrmed by the union of two molecoles possessing o^^KMite electro- 
diemieal chsracterB} or of two groups, which, in their turn, have a siimlar binary confiti- 
tation. Among the new theories wnich were the earliest to be thus introduced into the 
■denee, was the " Theory of Chemical Types," which represented chemical compounds 
as combiDations of the elementary atoms held together by the attraction exerted by 
each atom npon all the rest, and capable of exchanging one or sereral atoms of one 
dement for an eqnal number of atoms of another, so as to produce new substances, 
built up after the same plan or type as the original compounds, though one or more 
of tiieir atoms was of a different nature. According to this yiew, adds and metallic 
salts were regarded as bodies of the same class : each add and its corresponding 
sahs were regarded as compounds formed upon the same type, and differing only 
&om the fact of the add containing hydrogen in the place of the metal contained 
in the saltsi It wiU be seen that this manner of representing the mutual relation of 
adds and salts differed but little from that of Davy. 

Another result of the progress of oiganic chemistzy which helped to modify the 
older notions on these subjects, was the acquisition of more consistent ideas than had 
prenoosly existed of the relatlTe weights of different substances which are chemically 
eomparaCle with each other. Thus it was discoyered that an atom of water con- 
tained twice as much hydrogen as an atom of hydrochloric add, and therefore, that 
the so-called monobasic adds, or adds containing the same quantity of hydro^n as 
hydiocfaloric add, could not be compounds of wtJUir with anhydrous adds, as had been 
hitherto supposed. The disooreiy by Gerhardt in 1852 (Ann. Ch. JPhys. xxxvii. 
286) of the uihydrides corresponding to sereral monobasic acids, and the fatct of their 
atomic weights bdng found to be double the atomic weights of the hypothetical 
anhydrides of the older theoiY, confirmed the same condusion. 

It is now dear that adds do not form a class apart, distinguished from other sub- 
stances by something essentially different in their nature ; they are, on the contrary, 
nothing more than a particular class of salts. The definition of adds as seUts of 
y^drogen, first dearly enunciated by Gerhardt*, and repeated at the head of this 
artide, is an accurate statement of the relations which exist between adds and other 
ehemieal substances. This definition is, however, obviously insuf&dent, without 
A previous answer to the question — what is a salt? For this we must refer to the 
artide Salt. In that artide also the properties which adds possess in common with 
other salts, and which characterise them as belonging to that class, will be most suit- 
ably discussed. In the remainder of this artide we shall consider the distinguishing 
properties of adds as such, and the mutual relations of the prindpal classes into 
which adds may be divided. 

The mode in which adds most frequentiy react with other substances is by double 
decomiwdtion, in which they exchange their hydrogen for metals, or for radicles 
possessing, to a certain extent, metallic functions. The following reactions are all of 
this kind : namely, their reactions — 

1° "With metals, — 

Zn« + mSO* « H? + Zn«SO*. 
3° With metallic oxides, sulphides, and salts generally, — 

KHO + Ha - BPO + Kca 
KHS + Hca = H«S + Kca 

Pb«0 + 2HC1 « HK) + 2Pba 
Fe«S + H'SO* « H«S + Fe«SO* 
2NaCl + H^O* = 2HC1 + Na«0* 
KNO» + H«SO* = HNO« + KHSO* 

2P With the hydrates of alcohol-radicles,— 

C»HMLO + HCa - HH) + CHH3L 



Hydrate of Chloride of 

ethyl. ethyl. 

4^ With various metallic compounds, — 

C«H»Zn + HCl = C«H».H + Zna 



Zinc-ethyl. Hydrid«rof 

ethyl. 

KH«N + Ha = H"N + Ka: 



Potauamine. 

• Prfeis de Chimto organlque (Peril, 1814) 1. 70; Introdactlon k made de 1e Chimle par le Sytttoe 
Unitalre (ParU, 1848). 103. On the similar characters of acids, or hydrogeo-salu, and of metallic salta 
la general, and on the important differences between them and the anhydridet, oomp. Laurent, M^hode 
de CUmta, pp. 49—56, or CaTendltb Society's translation, pp. 39 to 45. 



44 Acros. 

With some rabstanoes adds anito direcUj : namelj — 

1^ With ammonia and its analogaes, — 

NH« + Ha - NHH3I 
PBP + HI « PH*I 
2NC^' + ffiSO* » (NC^« H«SO«. 

Aniline. Solphate of inUlneL 

2^ With some hydrocarbons, — 

C»H« + H«80«-.C*H-S0* 



Ethylene. Sulphovlnle 

add* 

C»H« + Ha - 0»HTa 



Propylene. Chloride of 

trltyl. 

Reactions such as the abore can be prodnced by all veQ eharacterised adds. The 
minority of adds can also prodnoe other reactions of Tarions kinds, some of which are 
chaxactezistic of indiyidnal adds, while others are common to a considerable number, 
and therefore serve for their division into dasses. The rational formnlae by which 
the various adds are commonly represented, indicate the nature of their lAo/li'tig 
reactions, and hence to the class to which they bdong. 

Ozygen-adds form by far the most numerous and important dass of adds. We 
may tiuce acetic add as a special erample, and show how the double deoompodtions 
which it is capable of undergoins, in common with the other adds of this dass, lead to 
the choice of the rational formme by which ozygen-adds in general axe usually re- 
presented. 

1. When acetic add is converted into an acetate by acting upon it with an oxide, 
metal, or any other substance, it loses hydrogen. This may^ represented by writing 
one atom of hydrogen in its formula apart £i^m the rest : U^H^O* » G*H'0*,£L 

2. By percblozide of phosphorus acetic acid is converted into diloride of acetyl, and 
loses one atom of oxygen and one atom of hydrogen. To ei^ress this, we must 
write the formula of acetic add thus ; CfH'O.HO. 

3. By the action of pentasulphide of phosphorus, acetic add loses half its oxygen, 
and becomes thiacetic add, 6(C«H*0*) + P«S» - 6(C«H*0S) + PW. 

The rational formula derivable from this reaction is CH^O.O. 

Combining these three expresdons, we come to divide the formula of acetic add 

into three parts H, C*HK) and 0, and to write it ^^*^ 0, or H.C«H*0.0, or in some 

similar way. This formula indicates beforehand, all the most frequent double de- 
oompodtions of which acetic add is capable ; viz. the separation of one atom of 
hydrogen, the other atoms remaining together (formation of acetates); the sepajration 
of one atom of hydrogen and one atom of oxygen, leaving the group C*HK) (forma- 
tion of chloride of acetyl, of aoetamide &c) ; tiie separation of one atom of oxygen, 
leaving the remaining atoms combined (formation of thiacetic arid, &c) 

The large number of adds which resemble acetic acid as to their leading double 
decompodtions, recdve similar rational formulse ; that is to sav, rational formuhe con- 
sisting of three parts : namely (1) one or more atoms of hydrogen, (2) one or more 
atoms of oxygen or sulphur, (3) a radicle, nearly always compound and containing 
oxygen, sulphur or a similar dement. Thus, writing the rational formula of acetic add 

H ^» ""^^ write that of benzoic aoid -a 0, of pyruvic acid -a O, of 

oxalic add m 0*, of phosphoric add ^, O*, of thiacetic add ^ S, of sulpho- 

CS CN CI 

carbonic add -g, S*, of sulphocyanic add ^ S, of hypochlorous add ^^ 0. 

If in any of these formula we replace the radide b^ its equivalent quantity of hydro- 
gen (see £!quivalents) and the sulphur (where it occurs) by its equivalent of 

oxygen, we obtain the formula of one, two, or three, atoms of water -a 0> ^s O', 

or ^, O*. Moreover, the decompositions of which water is susceptible are essentially 

quite similar to those of acetic add. Thus, when converted into a hydrate by thea c- 
tion of a metal or of an oxide, water loses one atom of hydrc^n — K + H'O = H + HKO, 
or CaH) + HK) « CaHO + HCaO ; oxychloride of phosphorus converts water into 
hydrodiloric add, removing from it one atom of hydrogen and one atom of oxygen. 



ACIDS. 45 

3S*0 -I- POGH -> 3Ha + PO^H*; lastly, pentasulphide of phoephoros ooBTerts it 
into h7dro8ii]^lrazic add, lemoviog i^m it one atom of oxygen : — 6BH> + P^* « 
SEP8 -t- PK)*. It IB in this sense that water is taken as tiie i^pe, or standard of 
eoaqniisoBl fbr acetic add and all other adds which undergo similar double deoom- 
fffifilifffiiti 

AnothfT dafls of adds are^ in the same way, referred to the type hydrodiloric add, 
HCL These acids are sosceptible of only one kind of double decomposition : their 
atoms axe separable into only two ^ups, hydrogen and a radide. Hydrobromic add 
HBr, l^ydnooip add H7, hydrocyanic add HON, are of this daas. 

These is still a third class of adds whidi may be referred to the type ammonia, 
KH". Snfrinfmide, C^^'NO', cyanic add (earbimide), CONH, and snlphocyanic add 
(snkhocaiinmide), CSNH, are adds of this kind. Under the influence of metallic 
oxides, and hydrates th^ part with one atom of hydrogen, and take up in exchange 
an atom of metal : 

2(C*H»N0' ) + AgH) « 2 ((yH*AgN0') + H»0. 

Swfrinhnldft. ' ▲rgento-succini- 

mide. 

CHNO + HKO = CKKO + IPO. 



CfBBle Cyanate 

add. of potaadunu 

When boiled with dilute adds, they break up into two groups, a carbonised radicle 
on the one hand (which combines wilL oxygen or with oxygen and hydrogen deriyed 
from the water of the dilute add), and the gioup HN (whidi combines with two atoms 
of hydrogen) on the other hand. 

CHNO + H«0 = CO.O + HN.H». 

Cjmic Carbonic AmmoDla 

add. anhydride. 

C*H*NO« + 2BP0 - C*H*0».H«0« + HN.H« 

1 — ' * 1 " 

Saocinlmlde. Succinic acid. 

These reactions show that the rational formulse of these adds must consist of three 
psits ; an atom of nitrogen, an atom of hydrogeo, and a radide composed of the 

!Q4VT*f\2 
H 

that of cyanic add N.H.GO, or N j ^. The substance called by Oerhardt nitride of 

beosoyl, soJ^hophenyl and hydrogen (C'H^'SO'K) is another add deriving from the 
^pe ammonia. Its decompodtions have not yet been much studied, but its be- 
haTiour with metallic oxides and its formation from ammonia by the succesdye action 
of the chlorides ofsnlphophenyl and of benzoyl (C*H*S0^C1 and CHKX}!) require that 
its lational formula should be composed of the four parts N, H, C*H*SO* and C'HK). 
Knee the constituent atoms of this add are separable into four groups, it is evidently 
« i a ee | >itible of undoigoing even more numerous decompositions than dther the adds 
deronng from the type HH), or those previously mentioned as deriving from the type 
HH*, whoae atoms are separable into only three groups. 

In regard to their ehemeal conttUuHon, we may thus divide adds into three prin- 
cipal rlttfinriT, which haye the same mutual relations of formation and decomposition 
IS hydiochloiic add*, water, and ammonia, and whidi may therefore be regarded as 
doivin^ from tiiese bodies as types. 

Bnt^ in the same sense as some of the adds whidi we have been Conddering, are 
fanned from two, or from three atoms of the same type (from HK71*, H^O', H'O*, ^.), 
there are certain others which are formed from two or more atoms of two (or perhaps 
three) different types; £>r example, sulphuric add SO^H*, deriyes from the type 

m[ 0*, tiius ^ m' [ 0*, while sulphamic add, SO'H'N, and chlorhydrosulphuric add, 
SCraCI, derire lapectiyely from the double types ^^j and ^^|; thus ^^^*^ | 

— solphamic add; ^ ^ ^ O ( ^ dibrhydrosulphuric add. Adds of this kind may 

he called, finr tiie sake of distinction, intermediate adds. The so-called amic acids 
(tee Aioc Aodb) afford the most numerous and best known illustrations of this 

* Sineo tha icaeHons of the addi of the firit claii are alio poitesMd by those of the second and third 
daises. It is plain that. If we hare regard to theie reactions only, all acids may be referred to the type 
i^drodUorie add. To. this extent, but no ftirtber, the hydrogen-theory represents correctly the cou- 
itttatioBoraU ~ 



46 ACIDS. 

class. Like snlphamic add, they derire from, the type mQ [• They can gire rise to 

two kinds of double decomposition ; that is, they can deoompoee either as hydrates 
(derlyatiyes of water), or as amides (deriTatives of ammonia), according to the naton^ 
of the body with which they react. In like manner, chlorhydrosnlphnric acid and 
analogons substances can decompose either as hydrates or as chlorides (deriTatiyes of 
hydrochloric add). 

Another way in which adds may be dassifled has reference to their btuieiiy: they 
may be diyided into monobasic, dibasic, and tribanc* adds. Q-raham was the first 
to call attention to the existence of polybasic adds in his paper on arsenic and phos- 
phoric adds (FhiL Trans. 1833, 26S ; Phil. Mag. iii. 451, 469}. The distinctions 
which he establiahed between monobasic and polybadc adds, had reference merely to 
the composition of their salts. In 1837 Liebi^ (Ann. Ch. Pharm. zxri 138; Ann. 
Gh. Phys. Izyiii 35) showed that tartaric, citnc, meoonic, and some other organic 
adds were polybasic, but he pointed out no new general characters of polybasic acids, 
nor any new way of fli««nngniHTn'ng them £rom monobasic acids. Gerhardt (Pr^ds de 
Chimie Organiqne (1844), i. 71 — 84) was the first to connect the basidty of adds 
with other &cts than the composition of their metallic salts, and he and Laurent (Ann. 
Oh. Phys. [3] xviii. 266 ; M&hode de Chimie, 62—76, or Cayendish Society's Transla- 
tion pp. 50 — 62) first placed the question on its present footing. 

Mono-, di-, and tri-basic adds may be defined, in a few words, as containing respec- 
tiydy, one, two, and three atoms of hydrogen replaceable by other metals, or by com- 
pound groups of analogous function. Tms definition, taken by it»el^ is, howeyer, 
obyioudy insuffident to dedde the basidty of any particular add, since, by properly 
multiplying or diyiding its formula, we can represent it as possessing whateyer basidty 
we please. Hence, before we can dedde what the basidty of an add is, we must 
know its atomic weight, and conyersely, in order to fix the atomic weight of an acid 
we require to know its basidty: in other words, the determination of its baddty and 
the determinatibn of its atomic weight are the same thing. • 

To dedde eithto of these points, we must take into consideration the general beha- 
yiour of the add with other bodies, and the natnre of its deriyatiyes. The following 
are the most important general differences shown by adds of different degrees of 
basidty : — 

a. Each monobaeic add a. Each dibasic acid can a. Each tribasic add can 
can form but one ether, form two ethers; one of form three ethers; one of 
This is neutral in its pro- them neutral, the other them neutral, the other two 
perties. Twoydlnmes oiits add. (Thus, sulphuric add. (0.^. phosphoric add 
yapour contain only one acid forms sulphate of ethyl forms phosphate of ethyl 
Tolume of ethyl, or alcohol- and ethyl-sulphuric add.) and monethyl- and diethyl- 
residue. Monobasic adds Two yolumes of the yapour phosphoric adds.) Two yo- 
do not form add ethers. of the neutral ether con- lumes of the yapour of the 

tain two yolumes of ethyl neutral ether contain three 
or alcohol-residue. yolumes of alcohol-residue. 

b. Monobasic addacasmot b. Dibasic adds can 6. TWdoMcaddscanform 
form stable, weU-defined form, with each metallic three salts with the same 
add salts, or salts with base, a neutral salt and an metallic base, two of them 
two or more metallic bases, add salt, which last is add, and one neutraL 

exactly intermediate in They can also form double, 
composition betweeen the triple, and hybrid salts, 
neutral salt and the free 
add. They can also form 
weU-defined double salts 
containing two metallic 
bases, as well as hybrid 
salts containing two or 
more metallic bases in in- 
definite proportions. 

0. Monobasic adds cannot c. Dibasic adds can form c, 
form double or multiple double ethers, that is, 
ethers, that is, ethers con- .ethers containing two kinds 
t4uning two or more kinds of alcohol-residue. (Ex- 
of alcohol-residue. ample, double oxalate of 

ethyl and methyl.) 

* It li 'probable that tetralMsic acids also exist, bat none bave yet been much inrestlgated : pyro* 
phosphoric and silicic adds seem to be such. 



ACIDS. 



47 



The aboTa distinctionfl apply to adds of all kinds, fiom whatever type they derire. 
Hie loQowiiig apply only to adds which deriye from the type tDater (oxacids). 



dL Each fMonoftosie oxacid d. Each dibastc oxacid 
can Sum a chloride, in two can forma chloride, in two 
Tohunes of the Tsponr of TolmneB of the Taponr of 
wliidi is contained only one which are contained ttpo 
ToltaaB of chlorine. £ach Tolmnes of chlorine. Di- 
fodi chloride can take np basic oxacids can also form 
in atom of oxygen and an chlorides which contain, 
atom of hydrogen in ex- in two Tolnmes of vapour, 
diaage fiv an atom of ddo- only one yolnme of chlo- 
Bna to le-fbnn the normal rine, and are exactly inter- 
aeid, — -hot there ia no com- mediate in composition 
pound intermediate in com- between the chlorides last- 
possdon between the chlo- mentioned and the normal 
ride and the nosmal add. adds ; that is, they can 

take up an atom of chlorine 
in exchange for an atom of 
oxygen and an atom of 
hydrogen, to form chlorides 
containing two yolnmes of 
chlorine in two Tolnmes of 
Taponr; or they can take 
up an atom of oxygen and 
an atom of hydrogen in 
exchange for an atom of 
chlorine, to re-form the 
normal add. Thus, sul- 
phuric add, SO^H^ forms 
chloride of sulphuiyl or 
chlorosulphuric aldehyde 
S0K:;1*, and the intenne- 
diate oom^xmd chlorhy- 
drosulphunc add, SO'HCL 

i. lionobaaio oxadds, by e. IHbasic oxadds, by 

MBCtinff with MwtnAwi*, or reacting with ammonia, or 

its deriTati-veB, form nea- its dariyatiyes, form neu- 

tial amidge» in two yolnmes tral amides, in two yolumes 



d. Each irihaeic oxadd 
can form a chloride in two 
yolumes of the yapour of 
which are contained three 
yolumee of chlorine. 



e. Tribaeio oxadds, by 
reacting with ammonia, or 
its deriyatiyes, form neu- 
tral amides, in two yolumes 
of the yapour of which are 



of the T^omr of ▼hich is of the yapour of which are 

"^^^f*^ only one yolnme containea two yolumes of oontainecf three yolumes of 

of nitrogen. There are no nitrogen. Intermediate in nitrogen. Intermediate in 

coBipoBndB intermediate be- composition between these 

tweoi theoe amides and the amiaes and the oorre- 

CQETCspooding adds. spending adds are com- 

pounds, generally add 
(amic adds), in two yo- 
lumes of the yapour of 
whidi is containea but one 
volume of nitrocen. For, 
example, oxiuie add, 
CO^H', forms neutral ox- 
amide^ CH)«H*N*, and the 
intermediate compound 
Qxamic add C*0'H"N. 



/. iionohaaie oxadds do f, Dihanc oxadds form 

not form add compounds acid compounds (conjugate 

(Khcalied oonjn^te adds) adds) m reacting with 

by neacting wil^ hydro- hydrocarbons or other nou- 



composition between each 
of these amides and the cor- 
responding add, there may 
exist two add compounds, 
one monobadc and contain- 
ing in two yolumes of va- 
pour two yolumes of nitro- 
gen : the other dibasic and 
containing in two volumes 
of yapour only one volume 
of nitrogen. iFor example, 
dtric add, OHK)», forms 
with phenylamine (aniline) 
neutral dtrophenylamide, 
C«HH)^Ph"N», (Ph - Cm» - 
phenyl), and the interme- 
diate monobasic dtrodiphe- 
ny lamic add, C«H»0*Ph«N« ; 
the dibade dtromonophe- 
nylamic add, C«a»0«PhN, 
has not yet been discovered. 

/. Tribasic oxadds form 
add compounds by reacting 
with hydrocarbons or other 
neutral substances. For 



48 ACIDS. 

caibona, or other neutral traL substances. For ex* example, phosphoric acid 
substances. ample, sulphuric add re- reacts -with glycerin to form 

acts with benzene to form phosphoglyceric acid. 

sulphobenzidic (phenylsul- 

phurous) acid, and with 

glycerin to form snlpho- 

glyceric acid. 

(Compare Odline, Chem. Soc Qu. J. xi 127.) ^ , 

In addition to Siese, other properties of acids might be mentioned, which are con- 
nected more or less intimately with their basicity; but, notwithstanding the number 
of comparatively Tery well-defined characters which they severally possess, it is im- 
possible to establish any absolute distinction between monobasic and dibasic, or between 
dibasic and tribasic acids. There are many adds, which, in relation to a particular 
set of reactions, have the properties of monobasic adds, but^ in relation to another set 
of reactions, bdbave like cubasic adds; others, again, appear from one point of view to 
be dibasic, while from another point of view they seem to be tribasic. This will ap- 
pear more distinctly by considering what decree of generalit}^ belongs to each of the 
differences we have pointed out between adcb of different basidties. 

a. Number of ethers. Perhaps the only exception to this law is afforded by phospho- 
rous add, whidi forms three ethers, one of them containing, in two volumes of vapour, 
three volumes of alcohol-residue, although, as regards its metallic salts, it is only 
dibasic. 

6. Number of metaUio salts. Acetic and formic adds, which possess in a special 
decree most of the characters of monobasic adds, form, each of them, two potassium- 
and two sodium-salts. 

0. MuUwle ethers. Ko exception to this law is known so far as regards mono- and 
di-basic acids. Tribasic adds ought by analogy to form ethers oontaimng two or three 
kinds of alcohol residue ; none such have yetbeen obtained, but there is no reason to 
suppose that they might not easily be formed. 

d. Number ofchloruUs. Some acids, which according to a, i, and o would be classed as 
monobasic, form chlorides containing two volumes ofduorine, as well as intermediate chlor^ 
adds. For in8tance,Wur tz ' s ehlorwecPacityle oMorS, C«H«C1*0 (Ann.Ch. Phys. p] xlix. 
60) reacts with one atom of water to form chloracetic add, C^*C10' ; and this, with 
a second atom of water, forms glycollic add, C^H^O*. These three bodies are there- 
fore related in the same way as chloride of sulphuirl, chlorhydrosulphuric add, and 
sulphuric add. Again, lactic add, CSCO', a homofogue of glycollic add, is decom- 
posed by pentachloride of phosphorus, giving chloride of lactyl, CH^CPO, whidi re- 
acts with alcohol to form chloropropionate (chlorhydrolactate) of ethyl^ C^H*C10^ 
(Wurtz, Ann. Ch. Pharm. cvii. 192) ; that is to say, the ether of an add intermediat-e 
between chloride of lactyl and lactic add. The intermediate add itself is produced 
CH^CIO^ by the action of chloride of lactyl on water. (Ulrich, Chem. Soc. Qu. J. 
xii. 23 ; Ann. Ch. Pharm. cix. 268.) So £Eir then as their chlorides are concerned, 
glycollic and lactic adds resemble dibasic and not monobasic adds. (See also ob- 
servations on e.) 

In the case of tribasic adds, no intermediate chloradds are known, such as would 
correspond to chlorhydrosulphuric add and other derivatives of dibasic acids. It is 
probable that each tribasic add can form two such compounds, that phosphoric add 
(PH'O*), for example, can form chlorhydrophosphoric acid (PH*C10',) dibasic?) and 
dichlorhydrophosphoric acid* (PHCIK)', monobasic?) 

«. Number and nature of amides. Some monobasic acids form amides containing, in 
two volumes of vapour, two volumes of nitrogen. For instance, acetic acid forms 
acediaminSj C'H*N^ between which and acetic add CH^O', acetamide C^H^NO is 
exactly intermediate, (just as oxamic acid, C^^O', is intermediate between oxamide, 
O^H^N^O^ and oxalic add, C*RK)*) ; acetamide, however, is neutral, not add, in its 
properties. 

Certain other adds, generally considered monobasic, form amides oontainiug one 
atom of nitrogen, which possess some of the properties of acids. Thus glycolUc add, 
C*H*0', forms glycoooU, C'HfN^O', a substance capable of acting as an acid, and pos- 
sessing the same relation of composition to glycolhc add, that oxamic acid does to ox- 
alic add, or acetamide to acetic acid. The so-called benzamic, toluamic, cuminamic. 
&c adds, are substances of a similar constitution : they are to oxybenzoic, oxycuminic, 
&c acids what glycoooll is to glycollic acid. In short, glycollic and similar adds, 
though in the strict sense monobasio are diatomic; that is, they form but one salt 

* Chlorhvdrocalpbarie acid if formed; when nilphorlc anhydride fi brought in contact with drj 
hydrochloric acid (SO*-|-HCl a SHCIO'). Similarly, a liquid, which probably conUtiiB one or both uf 
the compounds mentioned in the text, is farmed when photphoric anhydride u exposed to dry hydro- 
chloric acid (r30»+8HClBFH>C103+PHClsO«~?) 



ACIDS, 49 

viA Meli metallic base— are monobasie sjb regards their metallic salts, — ^bnt resemble 
dibasie adds ao fu as reeards their other deiiyatiYes (chlorides and amides). 

/ FbrmaHon of comipUx adds. The difference in respect of acidity between oom- 
poDnds fbnned by the reaction of monobasic and of polybasic acids on neutral sub- 
stuMB, is a paiticalar case of a general role which was first announced by Gerhardt 
rPi^ev de Chim. Organ. L (1844) 102 ; Gompt. rend. Trav. Chim. 1846, 161) in the 
nDoving fonn ; ^ « ^ + & — 1, where B denotes the basicity of the body resulting from 
the the reaction, h and V the basicities of the reacting substances (me basicities of 
ilkilineorDeiitnl sabstanoes, and of mono-, di-, and tnbaaic acids beine estimated re- 
speetiTel;^ as 0, 1, 2, and 3). Strecker (Ann. Ch. Fharm. IxviiL 47)8howedthat the 
nle admitted of a somewhat more extended application in the form £ » 6 + V — o^, 
i^ere wa denotes the nmnber of atoms of water which separate in the reaction. Pir ia 
(Ann. €3l Pharm. xcri 381), observing that, when more than two substances reacted 
upon eadi other, the number of atoms of water formed was usually one less than the 
nvmber of reacting substances, eicpressed the role of basicity in the following form, 
B^h -^V •\' If -¥ . .. . — (w— 1), (n being the number of reacting substances). 
In all these ezpreesions, one substance only is regarded as the essential product of thd 
reaedon, bat^ if we take into consideration the basicity of all the products (water, 
faydiochloiic add, &c. as well as more complex substances) and r^iard water as s 
monobasic * acid, wb amve at the following expression — Th» sum of the basicities of 
tktfroduets of a reaeHon is equal to the sum of the iasiciiies of the reacting bodies. 

Examples: — 

HCl + KHO « KCl + H«0 
1 4- « + I 



TP80* + KHO « KHSO* + H«0 
2 + =. 1 +1 

H«SO* + KHO ■». KHO « K«SO« + HK) + H»0 
Bttidtiea 2 + + » +1+1 



Aeetataof 
add. Atodbol. ethyl. 



Cm*0» + C«H«0 = C*H»0» + HK) 
1 .^ t» + 1 

Aectamide. 



C^«0» + NH» - C»H*NO + H*0 
1 + = +1 



Aoetochlor- 
hjrdrobrom. 
Gl7<cerin. bydrin. 

C*H«0* + Ha + HBr + cSw = 0»H»OKaBr + H»0 + H«0 + H^ 
al+l+l+0« +1 + 1+1 

FlKMpluaildew 

'P0N»H«' + H«0 + H«0 + H«0 =.H*PO* + NH« + NH« + NH» 
Btsicifies +1+1 + 1» 8+0+0+0 

The application of the rule of basicity to substances which, like glycollic acid, are 
Bonatomic in some relations but diatomic in others, or, like phenyUc alcohol (carbolic 
add), are intermediate between neutral bodies and acids, often leads, as might be ex- 
pected, to eontiadictoiy results. It must be looked upon, not as a law uniyersally true, 
bat as a rale applicable to the minority of cases, and always dependent on our defini- 
tions of acidify and basicity. (Gomp. Kekul^ Ann. Ch. Pharm. cri. 130.) 

It hM been pointed out by B eke toff (Bullet de TAcad^mie de St. P^tersbourg; zii. 
369) that this law, in- any of the forms yet given to it, gives contradictory insults 
when applied to the three following reactions, which nevertheleBS are strictly com- 
parable with each other. 

* IT water be also cooddend at a momacfd btue, the acfditif of baaes (or the nnmber of atomi of acid 
vfth whtcfa tbey reset, — a property correlatlTe with baskHjf,) !• usueDy conformable to' the following 
into:. Tie jMM iff the admUu ^ the products qf a reaction iM equal to the turn of the oddities qf the 
rvMoift. The reprcMotation of water at a monobatlc acid and at a monadd bate expreitet the i^t 
tttt It tetily takea dp 1 atom of an electro-potltlTe, or of an electro-negatiTe radicle in exchange for an 
a:om of bydmm. or. an electrt>.potitire amd an electro-negati«« radicle In exchange for the two atomt 
efiifdraMD. The repreaentatlon of water at a dlbatie acid (or at a diacld bate) exprettet the posti- 
bm^ ofiv^adna both atmnt of hydrogen by the tame radicle (formation of anhydridet). Thit re- 
■lirMniii tbonfoot anfreqiwnt, certainly Uket place lett readily than the replacement of 1 atom of 
IfdrogcD oDtyTor than the replacement of the two by radldet of dlflbreot electro-chemical qualitlet, 
Bkber view, toverar, U evidently entirely relaiiv;. 

You I. E 



60 ACIDS. 

Benxoie Bensoato 

actd. Alcohol. of ethyl. 



1. cmK>* + C«H«0 « C^»»0* + H^O 
Basicities 1 -i- » 4- 1 

Aceto- 
Beniolc Acetic bensoic 

add. acid. anhydride. 



2. C^«0« + C«H*0« - C»H"0« + H«0 
Basicities 1+1 0+1 

Methyl. 
Methylio ethyl 

Alcohol alcohol. ether. 



8. C«H«0 + C«HH) = C»H»0 + HK) 
Basicities 0+0 0+1 

According to tiie conTcntions which have been made above, the sum of the basicities 
of the products of the first reaction is equal to the sum of the basicities of the re- 
agents, but in the second reaction it is less, and in the third it is ^;reater. The 
obviously artificial character of the law of basicity, which is sufficientiy shown 
by these instances, induced Beketoff to propose to compare the whole quantity of 
replaceable hydrogen in the reagents witn that in the products, instead of merely 
comparing their basicities, or the number of atoms of hy(bx>gen which are easily re- 
placeable by basylous radicles. If the so-called t^ical formulss (see Fobxulx, 
IIationaii) are employed in writing the above reactions, it at once becomes evident 
that in each case the whole quantity of replaceable hydrogen is two atoms, both in the 
products and in the reagents ; ana in all regular double decompositions, the whole 
number of atoms of replaceable hydrogen remams similarly unaltered (For an aooonnt 
of all that is important in Beketofifs paper, and for an extended criticism of the 
law of basicity, see Kekul^ Lehrbuch d. organisch. Chemie, pp. 210 — 219.) 

A general classification of adds according to their composition cannot yet be given. 
There are but few elements which are known to form more than two or three distinct 
acids ; and, although many remarkable relations can be pointed out among the acids 
formed by different elements, these relations are more important as inucations of 
analogies among the elements, than as serving for the classification of the acids them- 
selves.* There is, however, one element — carbon — which, in combination with hy- 
drogen and oxygen, forms a very large number of acids, the best known of whichy 
generally exhibit, when compared together, certain gradations of chemical composition 
and properties, in accordance with miich they can be arranged in a number of homo- 
logous series, (See Homology.) The most important of these series are the fol- 
lowing: — 

a. Monobasic acids represented by the general formula C'H^O'. 

Formic acid CH«0*, Capioic acid O^>«0« 

(Enanthylic „ CH"0«, 

CapiyUc „ C«H»«0», 

Pelaigonic „ C»H»»0«. 

Rutic or capric „ C"H»0«, 
&c 

The adds of this series are found in various vegetable and animal products ; several 
of them occur in combination with glycerin as the chief constituents of most natural 
solid and liquid fats. The first four have been found in mineral waters (Scheerer, 
Ann. Ch. Pharm. xcix. 267). Thev are produced artificially by a great variety of 
processes, the most important of wnich are the following : 

1°. The oxidation of the alcohols C»H^+«0 

C«H«0 + 0» - C«H*0« + H»0. 



Acetic „ 


C«H*0«, 


Propionic „ 


C»H«0», 


Bu^rrio „ 


C*H»0«, 


Valeric „ 


OH"0*, 



•If 



Ethyl- Acetic 

alcohol. add. 



2^. The decomposition of the so-called nitriles, or cyanides of aloohol-radides, of the 
formula 0"H*»- *N, by alkaline hydrates. 

C»H«N + 2HH) - C»H«0« + NH«. 



-r 



Acetonltrlle Propionic 

or cyanide acid, 

of ethyl. 

• For an able exposition of nearly all that can yet be laid on this point, see Odllng, PhfL Maff. sviii. 
8G8 : also a lecture on ** Adds and SalU," delivered by the same at the Royal Institution, 80th March. 
1860, Chemical News, I. Sao. 



r 



ACIDS. 61 

1^. Tlie o(niil)matioii of thepotasBimn- and sodinm- compounds of the alcohol-radicles 
D'H^'*'' with carbonic anydride. 

(?H»Na + C0« = C«BPNaO«. 



«- 



Sodinm- Propionate 

ethjL of sodium. 

4®. The oxidation, destrnctiTe distillation, fermentation, or putre&ctiTe decompo- 
sition of complex oiganic compoonds. 

When a fixed-alkalino, or alkaline-earthy salt of one of these acids is snbjected to 
diy distiUation, a carbonate and an acetone are generally produced. These products 
ire foimed by the decomposition of two atoms of the salt. 

Hie drf distillation of a mixtoze of the fixed-alkaline, or alkaline-earthy, salts of 
teo acids of this series giyes rise, in like manner, to a carbonate and to an acetone 
intermediate in composition between the two acetones corresponding to the acids 
enpkyed. 

When one of th^ salts is a formate, a similar reaction takes place, but an aldehydo 
is then produced instead of an acetone. 

In some cases the diy distillation of salts of these acids produces (besides acetones) 
aldehydes, or isomeric compounds (butyral, Taleral ) and hydrocarbons. (See Albb- 

STUBS, ACSTOHBS.} 

When distilled with excess of alkaline hydrate, they give hydrocarbons of the 
fiinnnla OH"*'**' (hydrides of alcohol-radicles) and alkaline carbonate. 

(?H»KO« + HKO - CK«0« + OH*. 

Acet. potaa- Hydrida 

dum. of methyl. 

With pentachoride of phoshorus they produce chlorides of the formula OH^~'OG1 ; 

^' c*H*o« + pa» « c«H»oca + pooi» + Hca 

Aoetle acid Chloride 

of acetyl. 

Tbsff ilkaline salts distilled with azsenioos anhydride giye compounds of axsenio 
with the aleohol-radides. (See Absenio.) 

Subjected to electrolysis, they give carbonates, alcohol-radicles, hydrogen and hy- 
dwcartons of the form OH*» and OH*»+». 

Under the influence of chlorine (or bromine) they lose one or more atoms of hydro- 
gen, and take up in exchange an equivalent quantity of chlorine, forming chloracids 
'^lose general properties usually resemble closely those of the normal acids from which 
they are formed. 

(?HW + Cl« - C«H«C10« + Ha 

' — , — ' * , — — ' 

Acetic acUL Cbloracetlc 

acid. 

w + Br« -= C*H?Br*0« + 2HBr. 
> , ' 

Dlbroma 
acetic acid. 

„ + a* - C»HC1«0» + 3HCL 

Trichlor- 
acetic acid. 

& Acids represented by the formula C'H^O*, di-atomic^ but usually monobasic. 
Tke adds of Uiis series differ from those of series a by containing three, instead of 
two, itomfl of o^gen. 

CJarbonic acid CH«0«, 

GlycolHc „ C«HK>», 

Lactic , C»H«0», 

Butylactic „ C*H»0«, 

ValerQlactic„(Buttlerow). . . . C»H>«0«, 

Lendc OWK>», 

These adds are formed 

1®. By the reaction of the protochloro- or protobromo- deriTatiyes of the acids of 
Kries a with hydrates. 

0*H»C10» + HKO - C«H*0« + KCSL 

Cbloraoetlc GlycoUle 

add acid. 

B 2 



52 Acros. 

2^. Br the ozidatioii of the diatomic alcohols, C>H*> * *0* (glycols). 

C*H«0« + 0« - C«H*0» + HK). 

Glycol. GlycolUe 

•cid. 

8®. By the ozidatioii of certain amides of animal origin (glycoool and faoi 

eepecially bj nitrons acid. 

C»H»NO« + NHO« - C«H*0« + N« + H*0. 

^ , — -^ * — . — ' 

Glycoool. OlyeolHc 

acid. 

4^. By fermentation. 

The acids of this series are decomposed by heat into anhydrides and ▼! 
the case of carbonic acid, this decomposition tiJces place at the ordinazy tern 

With pentachloride of phosphorus, they produce diatomic dilorides of th 
OB[^-*OC1«; e.g. 

C?WO* + 2KJP = C«H*0C1* + 2P0C1« + 2HCI 

v« — r-^ ^ r— ^ 

Lactic add. Chloride of 

lactyl. 

Lactic acid heated ^th hydriodio add prodnces water, iodine and prop 
(Iiautemann) : 

C»H«0» + 2HI - C^«0« + H*0 + P 



Lactic add. Pit^ionlc add. 

This win probably be £rand to be a general method of oonyerting addi 
b into the oorresponcung adds of series a. 

e. Dibasic adds represented hj the formula CH^^-^O^ The adds of 
repiesent the adds of series b, in which 2 at. hydrogen are replaced by an 
of oxygen. 



OxaHc add . . . C«BPO« 



]S£alonic „ 

Sncdnic „ 

Lipio „ 

Adipic „ 



Fimelic acid . . . C". 
Suberic „ . . . Gf 



Anchoic „ . • . C! 
Sebadc „ . • • G" 



. C»H*0« 
. C*H«0* 

These adds are, for the most part, products of oxidation. They are solid a 
temperatures, and are not Tolatile without partial or complete decompositi* 
of tnem are decomposed by heat into carbonic anhydride and a monoba 
series a. 

C«H*0* - C«H<0« + C0«. 



MaloDic acid. Acetic acid, 
(jeyeral of them also produce acids of series a, when ftised with excess c 
hydrate; the reaction is accompanied by erolution of hydrogen (G< 
Suberic and sebadc adds heated with a great excess of baryta^ lose the c 
of 2 at. carbonic anydride and yield the hydrocarbons 0*H** and C^*'; 
bable that other adds of this series would be decomposed in like manner i 
treated. TRiche.) 

Pentachloride of phosphorus reacts on the adds of this series, produc 
the corresponding anhydrides, which are afterwards conyerted by exec 
chloride into chlorides of the formula C»H«»-*0«C1* ; *. g. 

1°. c*H«o« + pa» - c*H*o» + 2Ha + poa». 

N , -^ > r— ' 

Sacdnic Socclnic 

acid. anhydride. 

2°. C*H*0« + PC1» » C*H*0*C1« + POCl* 



Succinic Chloride of* 

anhydride. tucdnyl. 

There is a certain number of adds which do not enter into any of these ti 
but which are related to certain members of them in the same way that th< 
longing to the .different series are related to each other. For instance, glyc 
CHH)\ differs from glycollio acid, G*H«0*, in the same way that the ki 
from acetic add, C^H^';. namely, b^ containing one more atom of oxy 
just as bromacetic add when boiled with oxide of silyer produces bromide oi 
glycollic add — 

C«BPBrO* + HAgO - C«H*0« + AgBr 

Bromacetic Glycollio 

add. add. 



ACIDS. 



S3 



bomaeJ^ooIlie add, wlieii similarly treated, yields bromide of ailTer and gljozjlio 
aeid(Perkin and DuppaX — 

C*H*BrO« + HAgO = C*H«0« + AgBr. 



Bromo^lrcoUIo 



Olyoxjlie 



Similuiy, Uieie is the same difference between glyceric add, CH'0\ (bomologoos 
vith gl^Qzylic add) and lactic add, G"H*0*, that there is between lactic add and 
propionic add, CHH)*. Again, malic and tartaric adds, C^H*0* and O'H'O', 
differ from succinic add ty containing respectiyely one and two atoms more oxygen 
asd thej can be eonyezted into socdnic add by heating them with hydriodie aad^ in 
the ssDie wajr that lactic add can be conyerted into propionic acid (Schmidt); moreoyer, 
dibnmoaiiccinie add is decomposed, when boiled with oxide of silyer, into bromide 
of Bilker and tartaric add, jnst as dibromacetic add is decomposed under similar 
dreomstanees into bromide of silyer and glyoxylic add (P erkin and D npp a ). The 
SUM rdatum that exists between malic and succinic adds exists also between their 
homnlngnfis, tartronic and malonie-adds CH^O and C'H^O\ but in the case of 
these adds, the conyerdcm of one into the other has- not yet been effected. There is 
little doubt that these adds — 'glyoxylic and glyceric, tarteonic and malic, snd tartaric 
— rop r ooc nt homologous series ronning parallel with the three first described, but of 
which the other terms are as yet unknown. 

The relation of all the series of adds, of which we haye yet spoken, to each other 
and to tile alcohols homologous with common alcohol, glycol, and glycerine, is shown 
in the following Table, giying the general formulte of each series. It will be seen 
that of the formulas written one aboye another, each contains one atom of oxygen 
more than the formula next aboye it, and that of the formulse written in the same 
horizontal line^ each contains two atoms of hydrogen less, and one atom of oxygen 
more, than the one directly to the left of it. miere known, a special illustration of 
each geneoral formula is giyen« 



Mooatomie. 


Alcohols. 


Acids. 


C»H*i+«0 
Fropyttc^ (PH*0. 


Monobulc* 


Propionic, C»H«0« 
and acids of lerlet a. 


OH»n-»03 
PyniTic CSH^Oa? 


C»Haa-*0< ^ 


Diatomic. 




OHOQS 

Lactic, C^fWfi 
and acids of series b. 


Dibasic. 


Malonic, C?WQ* 
Succinic. C^HfiO^ 
and adds of series e. 


;C«Ha»-*0» ' 
Mesoxalic, CHSQ' 


Triatomic. 


CaBSii4-tO> 
Glyoerin, CB^OS 


CaH«"0« 
Glyceric, CH^O* 


C«H*i-«0» 

TartTODic, C»H<0» 
MaUc, C4H«0» 


Tribasic. 


'cnH«i»-«0* 


Tetntomie. 


C*B*ta-l-tO« 


GoH«H^O> 


C«H«ii-»0« 
Tartaric, C4H«0« 


Citric, CfiR^Or 



Another series of adds is represented by the gemenX formula OH'^^-'O*. They 
am mmobasic like the adds of series a, but differ from these by containing 2 atoms 
las hydrogen combined with the same quantify of carbon and oxygen. None of 
them haye yet been reiy thoroughly inyestigated, and the empirical composition eyen 
daome of them is still open to discussion.. The terms of this series hitherto more or 
k« known are — 



add 



Acrylic 
Ciotonie 
Angelic 
Pyrolerebie ,« 
DamaTmie » 



II 






Campholic add 
Monngic „ 
Hypogseic „ 
OlJo 
Brassio 



If 



E 3 



»t 



C"ffH)* 
C»»H«0« 

CisHMQ" 



64 



ACONITIC ACID. 



Thd following dibasic acids represented by the general formula C"H 
related — so far at least as composition is concerned — to the last series^ : 
manner as the acids of series c are related to those of series a. 



Fumaricacid 
Gitraconici 
Itaconic > acids 
Mesaconic) 



C*HW 



Terebic . 
Camphoric 



O 



There are still two other series of adds, presenting the same mutual i 
the series a and b, seyeral terms of which have been yery folly studied. T 

1. Monobasic acids of the general formula OH*"""^'. 

Benzoic acid , CH^O* 

ToluyUc „ (?H»0« 

Cuminic „ C'«H'*0« 

2, Diatomic acids of the general formula C'H^-H)'. 

Oxybenzoic acid C'II*0* 

Oxytoluylic „ (?H?0* 

Phloretic „ OH^K)' 

Oxycuminic „ C*«H"*0* 

The position which a few of the yet remaining organic acids occupy 
to the series already recognised can be indicated with tolerable certaint; 
greater number are stiU so imperfectly known that they cannot be indue 
classification which is not entirely articifial and empirical — G. 0. F. 

ACOVZTZO ACZD. C«H«0« -(^'^^'^^'JO' [or C"J5r«0'«]. E^ 

CUridio Acid, (Gm. xii 408; Gerh. ii. 110; iii 960; iy. 922.)— An 
in the roots and leaves of monkshood (Aconitum Napdlus) and other aeon 
the herb of Delphinium Consdida^ collected after flowering. It is also prod 
metamorphosis of citric acid under the influence of heat. It exists in the 
aconitate of calcium, which crystallises out on evaporating the juice, and 
of its insolubility may by freed from the colouring matters and other im; 
washing with wat«r and alcohoL The aconitate of calcium is then dissolved in 
nitric acid, and the fllterod liquid is precipitated with acetate of lead. Th 
of lead, after being well washed, is decomposed by hydrosulphuric acid, tl 
of lead filtered o£^ and the solution which contains the aconitic acid is evi 
dryness, and the residue treated with ether, in which the acid dissolves, 
impurities. 

To obtain it from citric add, the acid is treated till it ceases to give off h 
vapours; and the residue dissolved in alcohol is treated with hydrochloric ad* 
aconitic ether is formed, and separates on addition of water, as an oily li< 
by treatment with potash is converted into aconitate of potassium. T 
next converted into a lead salt, and the add is liberated by hydrosulphuiii 
the preceding process. 

On evaporating the ethereal solution, it is left as an amorphous mass, t 
in water, alcohol, and ether. When heated to 160^ it is converted into an 
which is itOGonio acid, C«H«0« « C*H«0* + CO*. It is distinguished fr 
add by being more soluble in water, and from maldc acid by not crystallis 

Aconitic acid is tribasic, and forms three classes of salts, viz. C^H'M'O*; C£ 
and C'H*(MK*)0'. The aconitates of ammonium, potassium, sodium, mag 
zinc, dissolve readily in water ; the rest are insoluble or sparingly soluble. ' 
aconitates form with solutions of lead and silver, white flocculent predpitate 
not become crystalline either by ebullition or after prolonged immersion in 
whereas the lead and silver precipitates formed by fiunaric and malei 
crystalline. 

With ammonium and potassium^ aconitic acid forms salts, corresptmdin^ 
the three formulse above given; with sodium^ a disodic and a trisodic salt. 
ofoaldumy C*H'Ca*0* + 8H*0 ? occurs in large quantity in extract of aconi 
also be prepared by dissolving lime in aconitic acid, or by precipitating 
calcium with aconitate of sodium. It dissolves in 99 parts of cold water, m 
in boiling water. The solution evaporated at a gentle heat, and withou 
yields a gelatinous mass which dries up to a gum ; but if a few ciystals of 
introduced into the solution, the whole is deposited in delicate crystals. J 
manganese^ C*H"Mn*0* + 6HK), is obtained by boiling the acid with cj 
manganese. Small rose-coloured octahedrons, sparingly soluble in cold wat4 
taie of lead^ 2C*H*Pb"0« + 3H*0, is sparingly soluble in boiling water, ai 
fi'29 per cent, water at UO^,— Aconitate of silver, C^»Ag»0«. Nitrate of s 



r 



ACONITINE. 55 

pMC^tited by tii« free acid, but with the alkaline aoonitates it fbnns a white, 
juuMphoaa, spaiinglj aoloble precipitate^ which is partly zedaced to the metallic state 
by boiling with water. 

Je(nuiate of Etkyl^ CHXG^'VK)*, is prepared by diasolyiii^ aconitic acid in fiye 
timee its weight of absolate aloonol, and saturating the solntion with hydrochloric 
add. On addition of water, the ether separates in the form of an oily layer. 

It is a colonrlees liquid, haying an aromatic odour, and yeiy bitter taste. Boils at 
USP, and has a density of 1074, at 14^ 

Jamitamlic add or Phenyl-acomtamio add, C»«HWO* = q j^^^*^)"''^^''^" 

!-M"TT4 
■n , three of the hydrogen-atoms in the am- 
monium being replaced by the triatomic radicle, aoonityl, and the fourth by phenyl. 
It is obtained by the action of water on the (not yet isolated) compound, C"H*N0*C1, 
prodooed by treating citzanilic (phenyl-citramic) acid with pezchloride of phosphorus; 
probably thus : 

CWH"NO» + 2Pa» - C>*HW0«C1 + 2P0a« + 3HC1; 
>— — , — — ' 
Citranllic add. 

and C»«H*NO«a + H«0 = C«H^O« + Ha 

When 1 at. citramlic add is mixed with 2 at perchloride of phosphoros, added 
hj small portions, and the action is assisted at intervals by a gentle heat, the whole 
di9B<^Tes, forming a yellow liquid; and on treating this liquid with water, hydro- 
chloric acid is evolyed, and aconit&nilic acid separates in the form of a soft substance, 
which, by solution in hot water and cooling, may be obtained in small yellow needles, 
but cannot be rendered colourless eren by repeated crystallisation. The add dissolyes 
^)aring^y in water, easily in alcohol, and Tery easily in aqueou^ ammonia ; and the 
ammoniacal solution mixed with nitrate of silver, yields rose-coloured flakes of the 
nlver-saU, CP-H»AgNO*. (Pebal, Ann. Ch. Pharm. xcviii. 83.) 

Jeonitodiaml or Diphenyl-aeoniUhdiamide, C'«H>«N«0« - N« (C«H»0«.y"(C^7.H, 
is prodoced (together with aconitanilide), by the action of aconitic add upon aniline : 

cmny + 2(yRV « C»«H"N«0« + 3H«0. 
also by the aetion of ozychlorodtric add upon aniline : 

C^HK?1« + 2C«H»N - C»H"NK)» + 3H«0 + 2HC1. 

It is insoluble in water, veiy sparingly soluble in cold alcohoL From solution in a 
large quantity of boiling alcohol, it oystallises on cooling in slender, pale yellow needles. 
(PebaL) 

JemntanOids or TriphmyUaeonito-trtamide, C»*H«N»0« « N»(C"H»0«)'''((>H»)».H«, 
appears to be formed simultaneously with aconitodianil, by the action of aconitic add 
or oxycblorodtric add on aniline : 

C«H«0- + SC-H'N - C«<H«»NK)* + 3H»0 
and C*BK)«C1« + 8C«H'K i» C"H«NK)» + 8HK) + 2H(X 

It is an amorphous substance, insoluble in water, but reir soluble in cold alcohol, and 
is thereby easily separated from aconito-dianil. (PebaL) 
The amides of aconitic acid have not yet been obtained. 

ACNMRTIHB. C"H«NO* [or C"-ff*'A'0"]. (Geiger, Ann. Ch. Pharm. viL 269 ; 
Horson, Pogg. xliL 176; t. Plant a, Ann. Ch. Pharm. Ixxiv. 245.)— The alkaloid 
eontained in the Aconitum Napdlus, and probably in all the acrid aconites. It is 
obtained by exhausting the leaves with alcohol, saturating the extract with milk 
of ^i^f*^ separating the lime by sulphuric add, evaporatins the filtered solution of 
sulphate of acontine at a gentle heat to expel the alcohol, then diluting with water, 
aaa trcating the solution with carbonate of potassium, which precipitates impure 
aoonitine. The product is purified by redissolving it in alcohol, treating the solution 
with animal charcoal, reconverting the base into sulphate, again decomposing this 
•alt with hydrate of lime, and treating the predpitate with ether, which dissolves 
nothing but the aconitine. 

Pure aoonitine is depodted from solution in dilute alcohol in white pulverulent 
grains, or sometimes in a compact, vitreous, transparent mass. It is inodorous, but has a 
penistent^ bitter, and acrid taste. It dissolves sparingljr in cold water, and in 60 
parts of boiling water, forming a stron^^Iy alkaline solution. It is very soluble in 
aleohol, less in ether. At 80^ it melts mto a vitreous mass, without loss of weight ; 
at 120^ it tnma brown, and at a higher temperature suffers complete decomposition. 
It is disBolTed without colour by nitric add. Sulphuric* adi^ ooliouis it first yellow, 

B 4 



56 ACONITYL — ACROLEIN. 

tJien Tiolet ; tmctuie of iodine formB with it a kermes-colonred precii)itate. 
tensely poiBonous, ^ of a grain sufficing to kill a sparrow in a few minutes, 
a grain killing it instantly. 

The salts of aoonitine do not crystallise readily. They are not delique 
dissolve easily in water and alcohol. The solutions yield a precipitate of 
with alkalies. The hydroehlorate, C"H<»N0'.2HC1, is obtained by passing d 
chloric acid gas over dry aconitine. Its solution is not precipitated by c 
platinum, but yields a white precipitate with chloride of mercuiy, yellow wit 
of gold, and also with picric acid. 

CH'O' ; the triatomic radicle of aconitic add and its d 

A name given by Laurent to the hydrocarbon, OH*. (See A 

C»H<0 [or C*H*0^. (Redtenbacher, Ann. Ch. Pha 
114; Oeuther and Cartmell, ibid, cjdi I ; Hiibner and Geuther, ibid. 
Gm. iz. 365; xii. 660; Gerh. i. iy. 779, 914.)— This body constitutes the a 
ciple produced by the destructire distillation of ffttty bodies, resulting in faci 
decomposition of fflycerin. It is also produced by the action of platinum-b! 
a mixture of acid chromate of potassium and sulphuric acid on allyl-aloohol, bei 
the aldehyde of the allyl series. (Cahours and Hofmann.) (See Aixtl 

Acrolein is best prepared by distilling in a <capaeious retort a mixture ol 
and add sulphate of potassium, or phosphoric anhydride. When phosphoric i 
is nsed, the distillate consists entirely of acrolein ; but the contents of 1 
are very apt to froth over. With acid solphate of potassium, the distillation 
but the acrolein is contaminated with acrylic add, sulphurous add, and o 
ducts. The distillate is collected in a receiver kept very cold, and provi 
a long discharge-tube passing into the chimney in order to cany off the 
which are intenselj^^ irritating to the e^es. To purify the acrolein, it is digc 
oxide of lead, which removes the acid impurities, then rectified in the wi 
dehydrated over chloride of calcum, and again rectified. As acrolein oxid 
rapidly by contact with the air, all these operations must be conducted with 
of dry carbonic add gas passing throueh the iq)paratus. (Bedtenbacher.' 

Hiibner and Genther distil 1 pt. of glycerin with 2 pts. of add sulphate off 
over an open fiame, the bottom of the flask being protected by wire-gan 
quantilr^ of oxide of lead being placed in the receiver to neutralise the add 
According to these chemists, the process consists of two stages, the add si 
potassium first dissolving in the glycerin, forming glvcerosulphate of potass 
elimination of water, so tiiat the fiiist portion of the distillate consists ohiefljp 
with but little acrolein ; but, afterwards, when the liquid becomes more con 
the glycerosulphate is decomposed, and acrolein passes over with only a smal 
of water. This latter portion of the distillate is subsequently purified as ii 
bacher^s process. 

Acrolein is a colourless, limpid, strongly refracting liquid, lighter than v 
boiling at 62^4 (Hiibner and Genther). Vapour-density 1*897. Its va| 
intensely irritatuig, that a few drops diffused tluough a room are suffident 
the atmosphere insupportable. It bums readily with a dear bright fiame. Il 
in about 40 parts of water, and very readily m ether. The solutions are 
first, but grskdually torn add by contact with the air. 

Acrolein cannot be preserved long, even in dosed vessels, as it chax 
taneously into a fiooculent substance called by Redtenbacher disacryl, and m 
into a resinous substance, disaeryl-resin. It sometimes solidifies immedii 
being prepared, even in sealed tubes. It undergoes the same transformat 
water, wmch at the same time becomes changed with acrylic, formic and ac 
Vapour of acrolein passed through a redrhot tube is decomposed, with foi 
wi^er and deposition of charcoal. 

Caustic alkalia convert acrolein into resinous products. By oxidising a 
converted into acrylic add. It reduces oxide of silver with considerable' 
of heat, forming acrylate of silver, which remains dissolved. Nitrate of sl 
with aqueous acrolem a white curdy predpitate (probably C*H*AgO) which, 
gradually decomposes, yielding metallic silver and acrylate of silver. On 
few drops of ammonia, and boiling the liquid, the silver is immediat^sly re< 
not in the specular form bb with aldehyde. Nitric acid attacks acrolein 
converting it into acrylic add. Btrong sulphuric acid blackens it, giving off t 
anhydride at the same time. With chlorine and broinins, it forms hea^ 
gether with hydrochloric or hydrobromic add. Perchloridc of phosphi 
violently on acrolein, forming dichloride of allylene C»H\C1* (see Aixtl 
another oily liquid which appears to be isomeric with it. With acetic am 
unites directly, fermingthe compound C'H*O.C*H"0*, which is identiciU 



ACRYLIC ACID. 57 

mpeci vith the oompoiiiid resnltmg from the action of acetate of dilTer on dichloride 
of alljlene (Hnbner and Gent her), and may therefore be regarded as diaeetate of 
ailjlene (0»H7'.(0»H«0)«.0». 

AcroUm-miinumia. C«*H«N«0« « C»*H>«N«0« H«0. Acrolein acts ationgly on 
ammoniis fbinning a solid compound (first obtained by Bedtenbacher) : 

4Cra*0 + 2NH« « C>«H*N*0« + HK). 

It k best prepared by gradually adding a saturated solntion of ammonia-gaii in alcohol 
to an aleoh<mc or ether^ solnhon of acrolein, and precipitating by addition of ether. 
It IS a white or yeUowish, amoiphous, odonrless compound 'vmich turns brown at a 
gentle heat and b^ins to decompose at 100^, giving off volatile basic products. In 
the moist state it dissolves readily in cold water and warm alcohol ; less in hot water. 
It diasolTSB readily in addi, and is precipitated therefrom by alkalis and alkaline 
caibonates. Hence it appears to be a base. Its solution in hydrochloric acid forms 
with dichloride of platinum, a light yellow precipitate containing, when dried at 100^, 
C«H»!S»0». 2HCL 2PtCl«, or C«H»»NO.HCa.Pta« . (Hiibner and Geuther.) 

Acrolein with Acid. Bulpkite of Sodium, — When acrolein is poured into in aqueous so- 
lution of acid sulphite of sodium, its odour is destroyed, and by evaporation over the 
water^bathf a brown deliquescent syrup is obtained which does not deposit crystals, 
and from, which neither acrolein can be separated by boiling with carbonate of sodium, 
nor salphnroas acid by boiling with sulphuric add* (Hiibner and Geuther.) 

HydroekloraU of Acrolein^ CH^O.HCL Produceil by passing dry hydrochloric 
acid gas into anhydrous acrolein in a vessel surrounded by cold water. The viscid 
product, washed and dried over oil of vitriol in vacuo, yields hydrochlorate of acrolein 
as a mass of velvetv czTstal^ which melt at 32^ into a thick oil, having the odour 
of rancid fiit. It is insoluble in water, but readily soluble in alcohol and ether, on 
the eraporation of which it remains as a thick oiL It is resolved by heat into 
acrolein and hydrochloric add. It is not apparently altered by boiling with water, 
or 1^ the action of dilute solutions of the alkalis. Heated with ammonia to 100^ in a 
sealed tube, it yields chloride of ammonium and acrolein-ammonia. Strong hydro- 
chloric acid decomposes it, settingthe acrolein free ; a similar action is exerteid by 
dilute sulphuric or nitric add. Hydrochlorate of acrolein in alcoholic solution does 
not combine with dichloride of platinum, and very slowly reduces a boiling ammo- 
niaeal solution of nitrate of silver. 

Gaseous hydriodio acid passed into acrolein exerts a violent action, attended with a 
hissing noise like that of Md-hot iron plunged into water. The product is a resinous 
bo^ which is insoluble in alcohol, etner, adds and aJkalis, gives off iodine when 
heated, and yields a small quantity of free iodine to bisR^phide of carbon. 

Mbtacsouok. Hydrochlorate of acrolein heated with hydrate of potassium gives 
off hydrogen, and yields an oily distillate, which solidifies in magnificent colourless, 
needle-shaped crystals, consisting of metacrolein, a compound isomeric or more pro- 
bably polymeric with acrolein. It is lighter than water, has an aromatic odour, and 
a cooling taste with burning after-taste. It melts at ^0^, solidifies at about 46^, or 
volatilises a little before melting, so that it may be distilled with vapour of water. 
By heat, it is dianped into common acrolein. It is not affected by dilute alkalis, 
bat when heated with mineral adds it is changed more or less into acrolein. In 
a stream of dry hydrochloric add gas, it melts and is converted into the hydrochlorate 
of acrolein above described. Hence it is probable that the compound so named is 
realW a hydroeklorate of metacrolein, perhaps C«H"0'.2HCL 

^^riddaie of Metacrolein is produced by passing dry hydriodie acid gas over meta- 
crolein, as a heavy yellow Uquid which resembles the hydrochlorate in taste and 
appearance, and after washing in water, shows a tendency to cxystallisc at ordinary 
temperatures. When placed over oil of vitriol, it decomposes, turning brown and 
giving off iodine. 

Hydriodie add gas acts violently upon acrolein, produdng a resinous substance 
which is insoluble in alcohol, ether, adds and alkalis, and gives jap iodine when. 
heated or when digested with bisulphide of <!arbon. (Geuther and Cartmell.) 

AOMTKEO AOI]>. C»H*0*«C«H»O.HO (or C'^^O*). (Gm, ix. 369; Gerh. 
783 ; iv. 914.) AcroUio acid^Tins acid, discovered by Bedtenbacher, is produced bv 
the oxidation of acrolein. The best agent to employ is oxide of silver, which, when di- 
gested with acrolein, yields a deposit of metallic silver, and a solution of aciylate of 
nlver. This salt is decomposed by hydrosulphuric acid, and the acrylic add thus set 
free is purified by rectification. It is necessary carefullv to cool the vessel during the 
decomposition of the silver salt; otherwise^ the heat develoi)ed is so great that an 
expk>6ion results. The add is likewise obtained by the action of chromic add on 
oxide dT allyl. (Hofmann and Cahonrs.) (SeeAixTL.) 



58 ADIPIC ACID. 

When ponfied, it is a eolourless liquid, of an agreeable, slightly emp 
odour. It ifi mifldble with water in aU proportiona, and its boiling-poin 
mediate between that of fonnic and acetic acids. 

It is a monobasic acid, its salts haring the formnla, CWH«M)0«. Th< 
resemble the formates and acetates, and are generally rery soluble in water. 

AcrylaU of Sodium. 2C»(H*Na)0« + 6H*0, is obtained by saturating the 
carbonate of sodium and evaporating. It crystallises in transparent prunns. 

AcrylaU of Barium. C*(H*Ba)0*, is also a soluble salt. 

Acrylate of Silver, C'(H*Ag)0*, forms white needles, having a silky li 
Teiy soluble in water. 

AcrylaU of Ethyl is obtained, though not in the pure state, by distilli] 
add, or its sodium or barium-salt with alcohol and sulphuric acid. (Kedten 

ACTZVOUITB. A variety of Hornblende (q. v.) 

See BiAicoMB. — A9AM AMTIVB SPAS. See Co: 



at or ASOFTSX* A piece of tube of more or less conical f 
to elongate the neck of a retort, and to connect it with a receiver. 



(See Cohesion.) 

K&ATS. (See Suite.) 

roVB B9AMm (See OBELBMm and Saussubitb.) 

A compact impure felspar, better known as petrosHex. 
from jaspar, which it otherwise much resembles, in being fusible before the 

ASZPZCAOXB. C^»0* = 0« |9^^I[or(7"5^0»-(7»«J5r"0«.2J5rO] 

acid forminff the fifth term of the series CH** - '0^ the lowest term of which is o 
CB.H}*, and the highest at present known, sebadc acid, C"H**0^. It is pi 
the action of nitric acid on oleic add, suet, spermaceti, and other fatty bodiei 
pare it, tallow or suet is boiled in a capadous retort with nitric add of ordinal^ 
whidi must be frequently renewed, and the distillate poured back till the fa 
disappears and crystals separate on cooling. The liquid is then evaporatec 
water-bath till it solidifies in a crystalline mass on cooling ; this mass is w 
funnel, first with strong nitric acid, then with dilute nitric acid, and lastly 
water; and the acid is finallypurified by ciystallisation trom boiling water (M i 
Other adds of the same series are doubtless formed at the same time ; but 
to Malaguti, the crystals obtained in the manner just described have all 
appearance, excepting the very last Wirz (Ann. Oh. Pharm. dv. 267) ol 
acid, together with several other members of the series, by the continued actio 
add on the solid fatty acids of cocoa-nut oil The action is continued i 
weeks till the mass solidifies to a crystalline magma. This product is r< 
water into a mixture of several adds of the above series, and a heavy oil 
adds are separated one from the other by fractional crystallisation from 
alcohol, and lastly by fractional crystallisation of the silver-salts. (See Ancb 

The add separates from its aqueous solution in crystalline cmsts compos 
white, opaque, nemispherical nodules, which appear to be aggregations of small 
According to Wirz, these crystals dried at 100° contain water of crystallisa 
formula being 20«H'«0* + H*0 [anaL 462, 46*4 and 47*8 p. c carbon, 6 
p. c hydrogen ; calc 46-4 and 7*0 H]. At 140° they melt and give 
leaving the anhvdrous add CH**0* [analysis, 48*2, and 48*3 0; 6*8 ai 
calc. 49. 3 and 6*8 H] ; which soon afterwsrds sublimes in long slender n 
sublimed acid gave by analysis 49*6 and 6*6 HI. 

100 parts of water at 18° dissolve 7*73 of the crystallised add: a h( 
which deposited nystals abundantly on cooling, still retained 8*61 pts. of 1 
100 pts. at 18° (Wirz). The add dissolves very readily in hot alcohol and 

The adipates, O'H'MK)^ are for the most part soluble in water and cryi 
insoluble in alcAiol. The ammonium-BaM crystallises in needles (Laurent,! 
The barium-salt dried over sulphuric acid, forms opaque warty masses not 
water of crystallisation (Wirz). The strohtium-sftlt forms microscopic m 
taining 2C^«Sr«0* + 3H*0 (Laurent). The calcium^alt resembles the I 
in appearance, but contains 1 atom of water rC*H"CaO* + H*0] which ii 
between 100° and 200° fWirz). The siiver'Salt, C«H»Ag*0<, obtained by pr 
the ammonium-salt with a considerable quantity of nitrate of silver, i 
powder. 

Adi^ of Ethyl, C^O* (C^*)« obtained by saturating the alcoholic 
the add witii hydrochloric acid gas, \s a yellowish oil of sp. gr. 1*001 at 2( 
boilfl^ with decompodtion, at 230°. It has a strong oaour of apples a 




ADIPOCERE— AESCULIC ACID. 59 

csoatic tiMte. Chloiine decomposes it| giTing off hydrodhloiic add and fonning a 
liseoofl mass. (MalagntL) 

AMFOOSRB. (From adeps^ &t; and eera, -wax.) A peeollar wliite substance, pro- 
duced bj the decomposition of animal matters under the influence of moisture and in 
situations from which the air is excluded. It was first found bj Fourcroy in the Cimeti^e 
des Iitnocenis at Paris. A number of coffins had been piled one upon another, and 
lemained interred for about 20 years. The bodies were found compressed, as it were, 
at the bottom of the coffins, and oonyerted into a soft white substance resembling 
dieese, which bote the imprints of the linen in which they had been wrapped. This 
matter endoeed the bones, which were broken on the slightest pressure. It was 
fixmd to eonsiat diiefly of maigarate of ammonium together with the margaxatea of 
potaanam and caldum. 

(See Fklspab.) 

(See Edblfossitb.) 

or ABCnnuor* (Handwort d. Ghem. i 169.) A mineral of the 
angite family, occurring in the neighbourhood of Sreyig in Norway, sometimes in reiy 
large and well-defined crystals belonging to the monodinic system, and haying the 
general diaxacter and dearage of augite. Colour greenish-black to leek-green. Lustre 
Titreoua* The edges exhibit yarioua degrees of translucence, down to complete 
op§a.tj, Sp. gr. 3*43 to 3'60. Hardness about that of orthodase. The mineral con- 
tains a considerable quantity of iron, partly in the state of protoxide, partly of sesqui- 
oxide, besides alumina, lime, magnesia, and soda, sometimes ako protoxide of man- 
ganese and potash, associated with silica, and sometimes with titanic add. The 
fiKmula is not perfectly established, but it is probably of the general form, 

8(M«O.SiO») + «(M«0«.3SiO«) = 3M«SiO« + «M'Si«0« 

TAJTTBMBm (See Cabbonio Acn> and Water.) 

(See Mbtbobttb.) — ABBOBXTS. (See PrBAsoTBiin.) 

(Handwort. d. Chem. i. 192.) A mineral occurring at Miask in 
file Ural, and consisting, according to HartwaU's analysis, of 56 titanic acid, 20 
sovonia, 15 cme oxide, 3'8 lime, 2*6 ferric oxide, 0*5 stannic oxide (making together 
97*9), but according to Hermann's more recent analysis, of 25*90 titanic acid, 33 '20 
eolumbic add, 22*20 eerie oxide, 5'12 oerous oxide, 5*45 ferrous oxide, 6*22 oxide of 
lanthanum, 1-28 yttria, and 1*20 water (« 100*57). By its oystalline form and 
properties, as well as by its chemical constitution, it appears to be dosdy related 
to Pc^ymignite, Folycrase, Euxenite, &c 

AaBCVXanw or BSCiriATXar. C*H*0\ or C^H'O^. A product of the de- 
eompodtion of aesculin, discoyered in 1853 b^' Buchleder and Schwartz (Ann. Ch. 
Pharm. IxxzyiL 186; Ixxxviii. 366), and independently by Zwenger (ib. xc. 63). 
It is obtained; 1. By boiling lesculin with hydrochloric or cUlute sulphuric acid. The 
liquid on cooling depodts a crystalline mass which, when washed with cold water, 
dissolTed in hot alcohol, and treated with acetate of lead, yields a lead-compoimd of 
aeaculi^tin from which the latter ma^ be separated by hydrosulphuric acia.—2. A 
cold saturated solution of ssculin mixed with emulsin (the fermenting principle of 
street almonds) and left in a warm place, deposits after a while, small ciystals of 
cscnletin. 

Asculetin forms shining needles or scales which are bitter, sparingly soluble in 
cold water and alcohol, more soluble in the same liquids when warm, but nearly in- 
BoluUe in ether. The aoueous solution is fluorescent like that of sesculin (q. vX but 
in a orach less degree ; tne fluorescence is howeyer considerably exalted by addition 
of a small quantity of carbonate of ammonium. 

When gradually heated, it giyes off 6*64 p.c water at 100, melts aboye 270^, and 
then distils with decompodtion. Hydrochloric acid dissolyes it without alteration ; 
nitric add conyerts it mto oxalic add. It is also decomposed by hot concentrated 
sulphuric add. It dissolyes in alkalis, forming solutions of a fine gold-yellow colour ; 
its solution in boiling aqueous ammonia deposits on cooling a yellow substance, which 
decomposes rapidly in contact with the air. .Sscoletin imparts a dark green colour 
to feme salts. It reduces nitrate of silyer at the boiling heat ; predpitates red oxide 
of copper from cupricssJts dissolyed in potash ; and forms with acetate of lead a yellow 
predpitate containing C*H*Pb*0*. 

AMBCUJbEC JELCTD* Obtained as a wbite precipitate by boiling saponin (a 
substance contained in the horse-chesnut and in many other plants) with dilute hydro- 
chloric or sulphuric add, or by boiling saponin with potash-ley and decomposing the 
xesolting eescnletate of potasdum with an add. It is insoluble in water, but soluble 
in alodholy and is depodted therefrom in granular crystals on cooling. Nitric acid 



60 AESCULIN-AGALMATOLITE. 

transforms it into a yellow resinons nitro-componnd. It is but a weak a^ 
alkaline SBecnlateB are soluble in water, and ciystallifle from solution ii 
The formula of sscnlic acid, according to Fremj (Ann. Ch. Phjs. [SJ lyiii 
C»H«*0". BoUey (Ann Ch. Pharm. xc 211), who calls it sapogentn^ asf 
the formula C"H**0^ According to Bochleder and Schwars (Ann. d 
Izzxviii. 367) it is identu»l with chinovatio acid CH**0'. 

AMACUZaM or BSCmLZV. C^^R^O'*, or C**H*'0». (Gerh. iv. 29 
wcrt d. Chem. L 196.) A crystalline fluorescent substance obtained from 
of the horse-chestnut {AesctUus Hippocaatanum) and of other trees of tl 
Aescultts and Pavia, It was first observed by Frischmann, more closely inyest 
Trommsdorff the younger in 1835 (Ann. Ch. Phann.xiT.198), afterwards by Bo 
and Schwarz (ibid. Ixxxvii 186 ; Ixxxviii 166), and by Zweneer (ibid, a 

The aqueous extract oiTthe bark is precipitated with acetate of lead ; the p 
is washeo, suspended in water, and decomposed by hydrosulphuric add ; and 
is filtered at the boiling heat. Or better : the aqueous extract is mixed wit 
of alum and excess of ammonia ; the liquid filtered to separate the fawn-col( 
cipitate of alumina mixed with the colouring matter of the bark ; the yellowi 
neutralised with acetic acid and evaporated to diyness ; the residue consisti 
sulphates and acetates of potassium and ammonium, boiled with a little stroi 
to extract the SBSCulin ; the alcoholic filtrate evaporated till it crystallises 
flesculin thus obtained, is purified by pressure between bibulous paper, and rec 
tion. (Bochleder, J. pr. Chem. IxxL 414 ; Chem. Otsz. 1868, 96.) 

Aescnlin forms colourless, needle-shaped crystals. It is inodorous, ha 
taste, is sparingly soluble in cold water and alcohol, more soluble in the sai 
at the boiling heat, and nearly insoluble in ether. 

Aeflculin is coloured red by chlorine ; it forms a yellow precipitate with i 
of lead, and reduces the protoxide of copper to suboxide, like glucose. It me 
and decomposes at a somewhat higher temperature, yielding various produ 
which is a small quantity of sesculetine. ^iled witli hydrodiloric or dilute 
acid, it is resolved into sesculetin and glucose : 

CJ«iH"0" + 3H«0 « Cra«0* + 2C«H>*0« 

The aqueous solution of esculin is highly fluorescent (see Lxoht), the refli 
being of a sky-blue colour. Nearly the same fluorescent tint is ffldiibited 
ftision of horse-chestnut bark. The colour is however slightly modified by ti: 
of another fluorescent substance, pavHn^ recently discovered by Prof. St ok 
Soc. Qu. J. xi. 17). The latter is separated from eeeculin by its greater sc 
ether. Its solution exhibits a blue-green fluorescence. Aesculin and paviii 
exist together in tlie barks of all species of the genera AbcuIus and Pav 
being however more abundant in the former and paviin in the latter (et 
The fluorescence of both aesculin and paviin is augmented by alkalis, but de 
acids. 

(See Cbtyim) 

LBT1IIJ«» &c (See Ethbb, Ethti^ &c.) 

An old pharmaceutical term applied to various mineral pi 
of black colour or approaching thereto : e, g. Aethiops antimoniaUs ol 
tritnratinff together mercury, smphide of antimony, and sulphur ; AetMop 
black o^e of iron ; Aethiop9 mtneraliSf black sulphide of mercury obtaine 
rating mercury with sulphur; Aethiopa narcotieua (or hypnoiicus,) sulphi< 
cury obtained by precipitation ; AeiMopaper se, the grey powder obtained h 
impure mercory to the air. 

ABTBOXnUUnr. The yellow colouring matter of the flowers otJi 
Linaria, 

(See Chbmtcal Afstnitt.) 

(See Aphtonitb.) 

[from SyoXfiOf an image ; and xtOos^ stone] ; 
This name was originally given to a soft mineral or rather a numl 
minerals used by the Chinese for carving grotesque flgures and idols. The 
vary in colour m>m greyish-ereen to yellow and red ; thev are aU more i 
and unctuous to the toudi and capable of being cut and polished. 
The Chinese agalmatolites are of three kinds : viz. 

1. Hydratod silicates of aluminium and potassium : 

a. 9SiO«.3Al<OMK*0.3HH) « eaiC^.SAPO'.lKO.ZHO 
6. 3SiOMAl*0».M*0.1H«0 - SdiO'.ZAP.dMO^.dllO 

* M denotes potauiuin, todlain, cAlcium, magneiium, ttc 



AGAR-AGAR— AGARICUS. 



61 



1 Hjdimted aQieates of aluminium. 

a. 9SiO«.aAl*0».6H«0 - ZSiO^.lAPO^.ZffO 
b. l£SiO'.4Al<0*.4E:>0 » ^aiC^.%APO^jmO 

8. Hjdntad mKcattew of mAgnednxn: 

16SiO«.12MgH).4H«0 = bmC^.^MgOJlHO 

Then an also Beyoral European minerab -which in composition and physical oha* 
aeter dosely resemble the Chinese agahnatolites. 
4. AnhnatoUte from Magyag in HtDogaiy has the same composition as the Chinese 

niiiienX Ij ^ 

A. Agahnatolite, from Ochsenkopf in the Saxon HaiZi and Onkom from Posseggen 
in SalzbiD]^ haTe a composition expressed bj the formula : 

9SiO«.8AlW.22lP0.3HK) « eSi(^,ZJPO'.2M0.3SO. 

6. MotAer o/Diaspore, a mineral in which the diaspore of Schemnits in Hnngaiy is 
inteigrown, has the composition 2, a above. 

7. Pan^hiU from. Canada has a composition corresponding to the fonnnhi : 

9SiO*.8Al*0».3MK>.4jHK) = ^aiC^.ZJPC^.MO.^HO 

8. DmiUrSriie^ from Diana and other localities in St. Lawrence oonntj, New York, 
appears uso to haTO a oonstitation resembling that of the agahnatolites. 

9. JusoImi which is a hydrated silicate of aluminium, containing 

{2SiO*«Al*0«.2H«0) - 4.aiC^,ZJPC^.%H0, 

OMtdj ic s cmb les the agahnatolites in physical character. 

10. NeoUit, from Eisenach and other localities, containing 

©SiO»jaW.3MH).HK)- 6Aa".l^a".3if0.1^0, 

also fonns masses resembling agalmatolite. 

All these minerals hare a sp^ific grayity ranging from 2*75 to 2*85 ; rarely as high 
ss 2*90. In TitiT-^JTift— , they are interaiediate between gypsom and calcspar. They are 
mare or less translncent, nnctnons to the touch, do not adhere to the tongue, and 
are easily canned and wioaghL 

The tniA ag^dmatolites are 1, a; 4, 5, S, and 7 : the rest may be zegazded as allied 
KpedtB. (Handw. d. Chem. L 375.) 

(See TuBQVOiSB.) 

or Bengal Isinglass: a dried sea-weed from Singapore, consisting 
of amall transparent colourless strips, is almost completely soluble in water, and forms 
a laige qoantity of thick, tasteless, and odourless jelly. 

(See AxAximr.) 

A genns of the order Fungi, Many fungi, especially of the genus 
Jgarinu are oonmionly used as food, and it is remarkable that the amount of nitrogen 
eonfeained in their dried substance exceeds that in peas and beans, which are generally 
ngarded as the most nutritious of all articles of food. 

The following table exhibits the percentage of nitfoffen and of ash in Tarious species 
of fkmgi, as detomined by Schlossberger andDoppi ng (Ann. Ch. Fharm. lii. 106 to 
120). The plants were dried at 100^ 0. The qruintily of water ayeraged about 90 
parean^ 

jfg aricMt dfitcicfius 
n 




f» 



glutmoiUB 
canthardlut 



Itrogoii* 


Aih. 


4-68 . 


6*9 


7*26 . 


. 19*82 


4*61 . 


4*8 


4*25 . 


9*5 


8*22 . 


. 11*2 


6*34 . 


9-0 


4*7 . . 


, 6*80 


616 . 


5*2 


4*46 . 


80 


819 . 


31 



ft 

Boktui aitrena 
I/geoperdon eekinaium 
JMmorua/omentarnu 
Jknaiea quermna . 

ThiS ash eontains a laz*^ prroor t ion of phosphates. The solid tissue of Amgi, for- 
msfly regarded as a peculiar substance, fungvn^ is nothing but cellulose: it may be ex- 
tracted by treating the fungi successiTelY with water, weak sod^-ley, hydrochloric acid, 
and alcohol. Agancs were fbund by Schlossberger and Dopping to contain mannite and 
fermentable sugar, but no starch. The acid contained in aearics and other ftmgi was 
formerly supposed to be of peculiar nature, and called hdetic orfxmgio acid; but it 
has been shown by Bolley ana Dessaignes that many agarics contain fhmaric add, some* 
associated with malic, citric, and phosphoric acid. 



62 AGATE —AGROSTEMMINE. 



the mountain mUk^ or mountain meal, of 
mans, is one of the purest of the native carbonates of lime, found chiefly in thi 
rocks, and at the bottom of some lakes, in a loose or semi-indurated form. 

The name of mineral agaric, or fossil meal, was also applied by Fabioni to i 
a loose consistence found in Tuscany in considerable abundance, of which brid 
made, either with or without the addition of a twentieth part of clay, so light i 
in water, and which he supposes the ancients used for making their floatii 
This, howerer, is yery different from the preceding, not being eyen of the c 
genus, since it appears, on analysis, to be a hydtated silicate of magnesium mi 
lime, alumina^ and a small quantity of iron. Kirwan calls it argwo-murite. 



A mineral, whose basis is calcedony, blended with yariable pr 
of jasper, amethyst, quartz, opal, heliotrope, and camelian. Ribbon agate o 
alternate and parallel layers of calcedony with jasper, or quartz, or ameth] 
most beautiful comes from Siberia and Saxony. It occurs in porphyry and 
Brecdated agate ; a base of amethyst, containing fragments of ribbon agate, c< 
this beautiful yariety ; it is of Saxon origin. — Fortification agate, is found h 
of yarious imitative shapes, imbedded in amygdaloid. This occurs at Obt 
the Bhine, and in Scotland. On cutting it across and polishing it, the interi( 
parallel lines bear a considerable resemblance to the plan of a modern fortifio 
the yery centre, quartz and amethyst are seen in a splinteiy mass, surroundc 
jasper and calcedony. — Mocha stone. Translucent calcedony, containing darl 
of arborisation, like vegetable filaments, is called Mocha stone, from the place, i 
where it is chiefly found. These curious appearances were ascribed to deposi 
or manganese, but more lately they have been thought to arise from mineralif 
of the ciyptogamous class. — Moss agate, is a calcedony with variously coloun 
cations of a vegetable form, occasionally traversed with irregular veins of r« 
Dr. M'Culloch has detected, what Daubenton merely coi^ectured, in mocha i 
agates, aquatic confervse, tmaltered both in colour and form, and also coated 
oxide. Mosses and lichens have also been observed, along with chlorite, in vej 
An onyx agate set in a ring, belonging to the Earl of Powis, contains the ch 
a moth. 

Agate is found in most countries, chiefly in trap rocks and serpentine, 
nodules of agate,, called ^eodes, present interiorly crystals of quartz, colo 
amethystine, having occasionally scattered crystals of stilbite, chabasite, and 
mesoty^. These geodes are very common. Bitumen has bc^n found by J 
in the inside of some of them, among the hills of Dauria, on the right ba 
Ghilca. The small geodes of volcanic districts occasionally contain water 
cavities. These are chiefly found in insulated blocks of a lava having a 
fracture. When they are cracked, the liquid escapes by evaporation ; it is 
stored by plunging mem for a littie in hot water. Agates are artificially coJ 
immersion in mettdlic solutions. Agates were more in demand formerly than s 
They were cut into cups and plates for boxes ; and also into cutlass and sabr 
They are still cut and polished on a considerable scale and at a moderati 
Oberstein. The surface to be polished is first coarsely ground by large mil 
a hard reddish sandstone, moved by water. The polish is afterwards given c 
of soft wood, moiBtened and imbued with a fine powder of a hard reatripol 
the neighbourhood. M. Faujas thinks that this tripoli is produced by the d 
tion of the porphyrated rock which serves as a gangue to the agates. The 
employed agates for making cameos (see Calcedont). Agate mortars are 
an^tical chemists, for reducing hard minerals to an impalpable powder. 

The oriental agate is almost transparent, and of a vitreous appearance. Th 
tal is of various colours, and often veined with quartz or jasper. It is mo2 
in small pieces covered with a crusty and often running in veins through 
flint and petrosilex, from which it does not seem to differ greatiy. Agates 
prized when the internal figure nearly resembles some animal or plant. — U. 

AOBDOX&. A name applied by Gaventou to a crystellisable substanc< 
from liquorice-root ; identical with asparagin. (Henry and Pliss on.) 

AOflTBSITB. Syn. with BisicvTrrB. 

iikOftOBTBiacm. A crystalline basic substenoe obtained from th 
the corn-cockle {Agrostemma Githago), The seeds are exhausted with wet 
acididated with add ; the acid is concentrated by evaporation and mixed with 
and the dried precipitate is treated with alcohol. 

Agrostemmin crystallises in pale yeUow scales which are but slightiy 
water, but very soluble in alcohol, to which they impart an alkaline react! 
decomposed by boiling potash, with evolution of ammonia. 



AIR— ALANINE. 



68 



a. 


A. 


. 87-31 . 


36-39 


• • * 


4-81 


. 23-73 . 


16-70 


. 10-70 . 


5-43 


. 2-79 . 


1-70 


. trace . 


2-29 


. 6-46 . 


6-61 


. 3-63 . 


3-68 


. 6-04 . 


— 


. 2-66 . 


. 2-78 


. 8-61 . 


. 21-71 




Tb» sahihate, dtloio-aiixate and cfakroplatiiiate of agroetemmine are OTBtaUisable; 
and phoB^a^fbnDB a bulky pi«cipitate. (Schulse^ ^m. Ch. Pharm. Ixviii 360.) 

Sjn. with AcicuiJTB. 

_ The term "air" (Latin, aer) is now exdnaiyely employed to denote the com- 

poDCDt gases of the earth's atmosphere. Amongst the older writers on science, we find 
the void *'air'* made use of to designate the gaseous or aeriform condition of a body; 
thu carb<»ie add gas was called " fixed air/' hydrochloric acid gas *' marine add air/' 
hjdiogen gas ** inflammable air/' &c. (See Athosphxse.) 

AJVOA BSFTAV8 (Creeping Bugle). (Handw. d. Chem. i. 385.) This plant, 
mvn on the even ground of the Lechthal, yielded, when gathered in the beginnmg of 
June, 84*3 p.c water, and 10*4 p.c. ash (a) ; that which grew on the chain of hills ad- 
jounng the valley, yielded at the end of June, 81*6 p.c water and 9*5 p.c ash (6). 

Potash 

Soda .... 

Ijime .... 

Magnesia . 
Sesquiozide of iron . 
Manganoeo-manganic oxide 
Phosphoric anhydride 
Sulphuric . 
Chloride of potassium 
Chloride of sodium . 
Silica. 

, (See Efidotb.) 
(See AcBTOKB.) 
(See AcHSOTB.) 

A variety of arsenical pyrites. 
(See MAiroANSSB-GLAXcB.) 

ITSB* Grantdar gyptiffm, Albdtre gypseux. The tecbnical name for 
granular g yp s um or sulphate of calcium. Alabaster is among the several varieties of 
gjpsum "^mat marble is among carbonates of calcium, and like marble is used for sculp- 
ture, especially for objects of small dimensions. The hard, fine-grained, snow-white, 
tzanalnoent alabaster fiom Yolterxa near Plorence, is especially valued for these purposes. 

JkabAJUTB* (See Diopsmi.) 

A&ASnra. C^'NO>. (A. Streeker, Ann. Ch. Pharm. Ixxv. 29 ; Gm. ix. 
434; Oerh^i. 678.) An organic base obtained by heating aldehyde-ammonia with 
hydrocfanic acid in presence of excess of hydrochloric acid. 

C*H»0«.NH« + CNH + Ha + H«0 = C'H'NO' + NH*C1. 

To prepare it, an aqueous solution of 2 pts. aldehyde-ammonia is mixed with aqueous 
bydioeyanic acid containing 1 pt. of the anhydrous acid, hydrochloric acid is added 
in excess, and the mixture is Doiled and afterwards evaporated to dryness over the 
water-bath. The residue consisting of hydrochlorate of alanine and a laige quantity 
of sal-ammoniac, is digested in a Uttle cold water, which leaves the greater part of 
the sal-smmoniao undissolved ; the solution of hydrochlorate of alanine is boiled with 
hydrate of lead, added in small portions as long as ammonia continues to ^cape ; the 
Uqnid is filtered ; and the dissolved lead is precipitated from the solution by sulphu- 
leited hydrogen. The filtered liquid yields crystals of alanine by evaporation, and 
in additional quantity may be obtained from the mother-liquor bv addition of alcohol. 
Another and better method is to treat the mixture of hydrochlorate of alanine and 
■d-ammoniac with alcohol and ether, in which the former only is readily soluble, con- 
centrate the solution by evaporation, and remove the hydrodiloric acid by boiling with 
Iqrdrate of lead. 

Properties. — Alanine Cfystallises on cooling from a hot saturated solution in colour- 
IsM needles having the form of oblique rhombic prisms united in tufts. They have 
a peariy lustre, are hard, and grate between the tee^ At 200°, it sublimes and falls 
down agun in fine snowy crptals ; when rapidly heated, it melts and sufiers partial 
decomposition. It dissolves in 4*6 pts. of water at 17°, and in a smaller quantitv of 
hot water ; it is very sparingly 8oliu>le in cold alcohol, and quite insoluble in ether. 
The aqueous solution has a sweet taste, does not affect vegetable colours, and forms no 
pKcipitates with any of the ordinary reagents. 

Alanine is isomeric with ttrethane^ ladbamide, and saroosine ; from the two former 
it ii distinguished by not melting below 100° ; from the last by being soluble in water, 
ttid by its Dehavionr with metallic oxides. 



64 ALANINE^ALBUM GR^CUM. 

Pecompotiiiofu, — Alanine is not altered by boiling with dilute adds, or 
It diaaolyeB in strong sulphuric acid, and the solution does not blacke: 
Fused with hydrate of potassium, it gives off hydrogen and ammonia 
cyanide and acetate of potassium. When its aqueous solution is boiled w 
of lead, it is resolyed into aldehyde, carbonic azmy dride, and ammonia : 

0»H^0« + « 0^*0 + CO* + NH». 

The aqueous solution is also decomposed by nitrous acid, with erolutiox 
and formation of lactic acid : 

C"H*NO« + NO»H = C"HW + 2N + H«0. 

* 1 ' ' r— ' * r— ' 

Alanine. Nitroas Lactic 

acid. acid. 

Compounds of Jlanine. — ^Alanine acts both as a base and as an acic 
directly with acids, and when boiled with metallic oxides forms oompoun( 
of alanine witib 1 atom of hydrogen replaced by a metaL With hyaroehi 
forms two compounds, viz. 2C'H'N0'.HC1, obtained by treating alanine wit] 
chloric acid gas, and CH'KO'.HCl, produced by evaporating a solutioi 
in excess of hydrochloric acid. Botn these compounds di^lve readi] 
sparingly in alcohol; the latter is veiy deliquescent, but may with some 
obtained in crystals. On mixing a solution of alanine in hydrochloric acid 
of bichloride of platinum, and evaporating, the chloroplatinate, 2C'H7NO 
crystallises in slender yellow needles, soluble in wa ter and alcohol, ant 
mixture of alcohol and ether. Nitrate of alanine, (?H*NO«,HNO« is i 
evaporating a solution of alanine in dilute nitric acid, in long colourless ne 
deliquesce in damp air, and dissolves veiy readily in water; less in alcoli 
they torn yellow and decompose. Stdph^ of alanine is vei^ soluble in 
remains as a syrupy mass when its solution is evaporated ; it may be i 
cold alcohoL It is not precipitated from its aqueous solution by alcohol, bi 
of ether and alcohol separat«i it in the form of a thick ffmip. 

The copper-compautM of alanine, 20'H'GuNO* + H'O ciystallises fron 
of alanine which has been boUed with cupric oxide, in dark blue needles 
rhombic prisms. It forms a dark blue solution in water, but is nearly 
alcohoL The crystals remain unaltered at 100°, but at 120° they giv 
and are reduced to CHKhiNO* assumingat first a lighter blue colour, an( 
cmmbling to a bluish-whito powder. The eilver-compoundf CH'AgNO*, 
in a similar manner, and separates as the liquid cools, in small yellow ne< 
in hemispherical groups. They assume a darker colour when exposed t 
also when heated to 100° in the moist stato ; but when dry they sustain 1 
jature without alteration. A solution of nitrate of silver mixed with ala 
by spontaneous evaporation, colourless rhombic tables, which are decompoi 
with slight detonation, and leave a residue of spongy silver. A teat 
CH'FbNO'.PbHO, is obtained in colourless glassy needles, by boiling i 
lead in aqueous alanine, and evaporating and cooung the solution. It : 
cipitated in radiating crystals, on mixing the aqueous solution with aL 
crystals dried over sulphuric acid, give off water and crumble to a powc 
no longer completely soluble in water. 

(See Inttun.) 

A white, crystalline, resinous substance extracted from gutt 
alcohol or ether. It is best obtained by treating gntta pacha with ether, 
ing the resulting extract with alcohol which dusolves a yellow resin, a 
white substance to which Fayen gives the name of alban. After recrystalli 
absolute alcohol, it forms a white pulverulent mass, which begins to melt 
perfectly fluid and tranroarent between 175° and 180°, and contracts stron 
ing. It dissolves with facility in oil of turpentine, b^izol, solphide of ca 
hot alcohol, and chloroform, and separates from tiie solutions m the cryst 
The crystals are wetted by watery liquids. They exhibit with sulphuric aci 
reactions as native gutta percha. (Pay en, Gompt. rend. xxxv. 109.) 

A&BSVa. A name given by Yolckel to a white substance which, a 
his observations, remains undissolved when melam ia boiled with wate 
assigns to this substance the composition C^* H*N^*0^ (Aim. Ch. Phys. [2] 

(See Apofetlijtb.) 
Soda-felspar. (See Fslspab.) 

NLBOVBI* An obsolete name for the excrements of the do 
used as a remedy in medical practice. The substance contains about 79 ] 
phosphate of calcium. 



ALBUMIN. 65 

(6eth. br. 433; Lehmann, Physiological ChemiBtxy i. 330; also 
Zooehemie in Gmelin's Handbuch, Bd. viii. Pelouze et Fr^m j, Tftiit^ de Ghixnie 
gen^nle, vi 67.) Albumin ia the chief and characteiistic constituent of white of egg 
and of the senmi of blood, and occnis in all those animal substances which supply 
the body et indiyidnal parts of it witii the materials required for nutrition and 
RDOTitieo. It forms about 7 p. e. of blood and 12 p. c. of white of egg ; it is a principal 
ooDstitiient of chyle, lymph and of all serous fluids. It occurs also in the juice of 
flesfa, in the brain, the pancreas, the amniotic liquid, and generally in a greater op 
Mnaller quantity in all the Hquids (transudates^ effused from the blood-vessels into 
the edfauar tissues of the oigans, into the caTities of the body, or on to the surface. 
It is inmd in the solid excrements of man and of other animals^ the quantity in- 
creasing in disorders of the mucous membrane of the intestinal canal. It is not 
found in nonnal urine^ but is present in that liquid in many states of disease, espe- 
cially in aflections of the respiratory ofgans, which interfere with the process of 
oxidation. 

Albomin exists in two very distinct modifications, -viz. the soiuile form, in which 
it always oeoirs in the animal body, and the insoluble form, into which it may be 
bvooght by the aetion of heat» as when white of egg or blood-seram ia boiled. These 
twD modiflcatioas of albumin are identical in chemical composition, the difference 
betwee n them being due, partly, perhaps, to peculiarity of molecular aggregation, but 
diiefly to the presence df certain mineral salts which are always associated with the 
adabie yazietj. In fiict, albumin does not occur in the amm^l body in the free 
states but in the form of an alkaline albuminate ; white of egg, serum, and all liquids 
whidi eontain albumin, leave, when incinerated, an ash chiefly consisting of alkaline 
evbonate. Insoluble albumin does not appear to exist in the living animal orgaiiism, 
unless indeed, fibrin may be regarded as coagulated albumin, which is by no means 
imptobabie, inasmuch as there is no exact method of distinguishing between the two. 
^PrepttraUofU — Albumin may be prepared either from white of egg, or from blood- 
senna. White of e^ consists of transparent thin-walled cellules, enclosing an alkaline 
aofaition of albuminate of sodium. On beating it up with water, the cellular sub- 
stanoe separates in pellideSr while the albuminate of sodium remains in solution, 
together with chloride of sodium and phosphate of calcium. To remove these mineral 
aabstanoea, the liquid, after being filtered from the cellular substance, is mixed with 
a small qna&titj of snbacetate of lead, which produces an abundant precipitate (an 
excess of the lead-salt would redissolve it). Tiie mass, after being washed, is stirred 
up with water to the eonsistence of a paste, and carbonic acid gas is passed through 
the liquid. The albuminate of lead is thereby decomposed, carlwnate of lead remains 
sDspended in the liquid, and the albumin in the free state remains dissolved. The 
sedation is filtered through paper previously washed with dilute acid, and, as it still 
retains traces of lead, it is treated with a few drops of aqueous hydrosulphuric acid, and 
caatioosly heated to 60^, tiU it begins to show turbidity ; the first fiocks of albumin 
thus precipitated carry down the whole of the sulphide of lead. When the liquid 
which after filtration is perfectly colourless, is evaporated in large capsules at 40<^, 
a residue is obtained consisting of pure soluble albumin (Wurtz, Ann. Ch. Phys. 
[3] xii. 27)* The same method applied to the albumin of blood-serum does not yield 
a pure prodaet* 

To obtain pure albumin in the coagulated state, white of egg, diluted with an equal 
balk of water, filtered, and reduced to its original vdume by evaporation at 40^, is 
mixed with a strong solution of potash, whereby it is soon converted into a translu- 
eent, yellowish elastic mass. This is divided into small portions and exhausted with 
eold water as long as the water removes any alkaU, the whole being kept as much 
as possible fitmi eontact with the air. It is then dissolved in water or boiling alcohol, 
ana the solution is precipitated by acetic or phosphoric acid. The precipitate, after 
washing leaves no appreciable residue when mcinerated. (Lieberkiihn.) 

Pnperties, — Soluble albumin, dried in the air, forms a pale yellowish, Iranslucent 
mass, easily triturated and reduced to a white powder* The specific gravity of the 
albfirain of the hen's egg, from which the salts nad not been removed, was found by 
C. Schmidt (Ann* Ch« Pharm. xi. 166-167), to be 1-3144, and after calculating 
for the elimination of the salts, the density of pure albumin was found to be 1*2617. 
It beeomes electric by friction, and is tasteless, inodorous and neutral to vegetable 
eolourB. It swells in water, assuming a gelatinous appearance ; it does not dissolve 
freely in pure water, but very readily in water containing any alkaline salt. After 
being dried in vacuo, or at a temperature below 60^, it may be heated to 100^ with- 
out passing into the insoluble modification. Soluble albumin dried at 60^ loses 4 p. a 
water at 140°, remaining, however, soluble in water. 

The aqueous solution of albumin deviates the plane polarisation of a ray of light 
to ibe left. It becomes opaline at 60°, begins to deposit the albumen at 61° to 63°, 

Vol. L F 



66 ALBUMIN. 

and at a temperature a little hi^er the whole ooagnlates in a maM. When Ttay 
dilate, it becomes tnrbid without coagulating ; but if the liquid be then concentrated 
bj evaporation, it depoeita the albumin in p«llicleB or flocks. 

Coagulated albumin is white, opaque, efastic, and reddens litmua (Hruachaueri 
Ann. Ch. FharnL zItL 348). When dried, it assumes a yellow colour, and becomes 
brittle and translucent like horn. When immersed in water, after dicing, it gra- 
dually absorbs about five times its weight of the liquid, and resumes its primitire 
consistence. 

When coagulated albumin is boiled in toater for about 60 hour% it gradually dis- 
appears, being transformed into a subetance soluble in water, and consisting^ ac- 
cording to Hulder and Baumhauer (J. pr. Chejn. xx* 346 ; xxzl 295), of triaxide 
of protein, C"H"NK)» (C - 6098 p. c. ; H - 6-69 ; O and S - 601 ; N « 27-32). 
Coagulated albumin, heated to 160° with a small quantity of water in a sealed tube, 
graoually forms a limpid solution, which has no longer the property of coagulating by 
heat. (L. Gmelin.) 

Albumin is insoluble in alcohol and in ether. Strong alcohol added in lazce ezcera, 
precipitates albumin fi?om its aqueous solution in the same state as when it is 
coagulated by heat; but the precipitat e p roduced by a small quantity of weak 
alcohol redissolyes completely in water. Wnen alcohol is added to a somewhat dilute 
solution of albumin, so as to render it slightly opaline, the liquid after a while, 
solidifies in a jelly, which, howerer, is a^un liquefied by heat. Coagulated serum, 
or white of egg, may be made to dissolye in aloonol by the addition of a little aUcalL 
(Scherer.) 

Ether shaken up with a solution of albumin ooagnlates but a small portion of it ; 
if^ however, the albuminous solution is concentrated, it thickens so much as to appear 
coagulated. Albumin is not acted upon by oils either fixed or volatile. 

Nearly all acids precipitate albumin m>m its solutions. Nitric add precipitates 
it with peculiar facility, and may therefore be used as a test of the presence of 
soluble sibumin. Strong hydrochloric acid aided by heat dissolves coagulated albu- 
min, forming a blue or violet solution, which turns brown when boiled in an open 
vessel, and according to Bopp (Ann. Ch. Pharm. Ixix. 30) yields chloride of am- 
monium, leucine, tyrosine, and oUier products of unknown composition. With aqua 
regia^ albumin yields both chlorinated and nitro-compounds. 

Strong sitlphuric acid coagulates albumin by the heat which is evolved when the 
two liquids come in contact Dilute sulphuric add precipitates albumin after some 
time only, not however combining with it» as the add may be completely removed 
from the precipitate by washing. 

Tribasie phosphoric acid, acetic, tartaric, and most other orsanic acids do not fbnn 
precipitates in moderately concentrated solutions, of albumin ; but when either of these 
acids is added in excess to a highly concentrated solution of serum or white of e^, the 
liquid solidUies in the cold to a jelly which liquefies like gelatin when heat^ and 
again forms a'gelatinous mass on cooling. The aqueous solution of this jellv remains 
perfectly tran^arent when boiled, but it is precipitated by a neutral salt of either of 
the alkali-metals. (Lieberkiihn.) 

When a small quantity of acetic acid is added to white of effg or serum, so as just 
to saturate the alkali, and the liquid is then largely dilutedwith water, flocks of 
albumin are deposited after awhile. If the supernatant liquid be then decanted, 
and the precipitate treated with a small quantity of solution of nitre or common 
salt, it immediately dissolves, and the solution is coagulated by boiling. (Scherer.) 

Serum or white of egg mixed with a certain quantity of common salt or other 
salt of an alkali-metal, forms a liquid precipitable by phosphoric, acetic, tartaric, 
oxalic, lactic add, &c. Conversely, a solution of albumin Tor other albuminoidal sub- 
stance) in acetic acid is predpitated by the salts of the alkali-metals. The predpi- 
tation is greatly facilitated bv heat, and Likewise takes place with ^;reater fiunbty 
as the proportion of salt added is greater. The predpitate dissolves in pure water, 
with greater fadlity in proportion as less heat has been applied in piodudng it; 
the s(9ution is not coagulated by heat. It is soluble also in acetic acid, phospnorie 
acid, and even in alcohol, provided it has not been altered by desiccation, or by 
contact with the air. The aqueous solution is predpitated by certain salts, ferro- 
cyanide of potassium, for example. 

Dried soluble albumin suspended in acetic, tartaric, or dtrie acid, swells up and is 
converted into coagulated albuinin, which may be completely freed from acid by 
washing. Acetic, tartaric, and tribasie phosphoric add dissolve coagulated albumin 
when heated with it. Arsenious acid does not combine with albumin. Chlorine and 
bromine precipitate albumin. 

Alkalis do not in general predpitate albumin from its solutions; but a strong 
rolution of potash added in considerable quantity to a solution of albumin, forms a 



ALBUMIN. 67 

gebtinoiia maa of allnimizuite of potassiiim. Dilatd solntioiui of potash and soda 
mix vith JtlKntnin in all proportions, and on boiling the liqnid, an alkaline snlphide is 
fiomed. When albumin is heated with hydrate of potassium melted in its water of 
ojstallisation, the water being renewed as it evaporates, ammonia and hydrogen 
an erolred, leucine and lyrosine are produced, together with oxalate, butyrate 
Talerate, &c of potassium. Alkaline carSonates added to a solution of albumin preyent 
its coagulation by heat. Coagulated albumin digested at a gentle heat wititi nenla^ 
carbonate or acid carbonate of sodium, displaces Qie carbonic add, and forms with the 
alkali a eompoond, which, after washing, is perfectly neutral to test paper, but leayes 
when incinerated a considerable quantity* of alkaline carbonate. 

Albomin sabjected to dry SstillaUtm yields water, carbonate of ammonium, 
hjdroffolphate of ammonium, Tolatile alkalis of undeterxnined composition, empyreu- 
Datic oils, ^Icc Coagulated albumin putrifies when left in contact with water, yielding 
Tslerie and bntTric acids, a crystalline body having a penetrating odour, an oily 
add, and a anbetance which dissolres in hydrochloric add, producing a liquid of 
beautiiul yiolet colour and jielding tyrosine, together with other products (Bopp, Ann. 
Ch. Phaim. Ixix. 30). The oxygen of the air has no action on serum or white of egg. 
Seoenfly extracted serum left for a fortnight in contact with oxygen in a tul^ 
ftr"^*^C over mercury absorbs but a yeiy small quantity of the gas, and does not 
IbflB carbonic acid. 

Albumin distilled with a mixture of peroxide of manganese and stUphurie acid 
jieldB acetic, propionic, butyric, and benzoic aldehydes, t<^ether with formic, acetic, 
MbfriCy Talenc, and benzoic adds, and probably also propionic and caproic acids. 
Keuly the same products are obtained by distilling albumin with eulphurio acid and 
add ekromate of potassium, this mixture yielding in fact, hydrocyanic add, a heavy oil 
having the odour of cinnamon, cyanide of tetz^l (valeronitrile), also benzoic, acetic 
and TO.tyric adds, with smaQ quantities of formic, caproic and propionic adds, and of 
benzoic and propionic aldehydes (Guckelberger, Ann. Ch. Pharm. Ixiv. 39). Al- 
bomin does not decompose oxygenated water, 

Cowiposition of Mbumin, — Albumin obtained from various animal fluids exhibits 
the same composition, as shown by the following analyses : — 

From White qfEgg. 

/ * , 

Duniu 

Mulder. Sch^rar. and Cahours. Rilling. Wurtz. LleberkOhn. 

Caibon . 63*4 . . 54*3 . . 63*4 . . 63^4 . . 629 . . 63-3 

Hydzogen . 7*0 . . 7*1 . , 7*1 . . 7*0 . . 7*2 . . 71 

Nrtiogen . 16-7 - . 15'9 . . 16-8 16-6 . . 16-7 

•• •. •• .. .. MA X 

1-7 to 1*8 1-8 




8al 



Wurtz's analyais was made with soluble, the rest with coagulated albumin. Mulder 
sopposes that albumin contains also 0*4 per cent, phosphorus. Most of the preparations 
with which the above analyses were made, contuned small quantities of phosphorus 
in the fizEm of phosphate of caldum. 



Caiton 
Hydrogen 
Kitxogen 
Oxysen • 
Sulfur . 



JPhmt Koodsermm, 

r " ' ' All ^ 

Dumat and Cahoun. Mulder. Rtiling: Scberer. 



68*3 

7-1 
16-7 



6Z'6 . . 63-4 . , 63-1 
7-3 . . '71 . . 70 
16-8 . . 16-6 . . .. 



1*3 . . 1-3 



64-5 
70 
16-7 



Mu]dar Biqyposes that blood-albumin contains also 0*3 per cent, phosphorus. Billing 
foond the amount of sulphur in eight analyses to vary fix>m 1*29 to 1'39 per cent 



Sdierer. Weideabtuch. Baumhauer. 



/ -• » 



a b e d e 

Carbon . 54'2 . . 641 « . 540 . • 53'3 . • 54*3 
Hydrogen . 71 . . 72 . . 7*0 . . 70 . . 7*1 
Nitrogen . 16-5 . . 16*8 . . 15*8 . . 16'7 . . 15*8 

Oxyeen 

So^hiir • • «..• •• • 

4 from a hydrocele ; b from a congestion-abscess ; e from pus ; d from flesh of 
poultry ; e from the flesh of fish. 

From thme and other analyses, liebig deduces the formula G^'W^^S'O^ : Mulder, 
CrH»«T««SO": laeberkiihn, C«fl'»>N"SO« Each of these formulro gives numbers 

F 2 



^ I 



68 ALBUMIN. 

Agreeing nearly with the analytical tesulta. Mulder regards albondn as a eompoond 
of (hypothetical) protein vith (hypothetical) aulphamide, tiz. : 



Protein. Sulphamide. 

Liebigf 8 formula is intended merely to express in a simple form certain relations 
between albumin and other animal substaiices. laeberkuhn, on the other hand, 
regards his formula as actoalLy expressing the composition of the molecule of albumin 
as it exists in the metallic albuminates {q, v.) 

According to Lebonte and Goumoens (J. Pharm. [3] xxiy. 17) albumin is not 
a pure proximate element, but a mixture of two bodies, one of which is insoluble in 
glacial acetic acid, while the other dissolves in that acid and is precipitated therefrom 
by potash. 

The properties of albimiin -vary in some degree with the source from which it is 
derived. The differences may in some cases be attributed to the presence of different 
mineral substances ; but in others they are of such a nature as rather to point to 
the existence of different modifications of albumin. Thus, Fr^my and Yalen- 
ciennes have found (Ann. Ch. Phys. [3] L 138) that the albumin of the eggs of 
certain tribes of birds of exhibits peculiar modifications. That from the eggs of 
different species of gallinaceous birds always exhibits the characters above described ; 
but the eggs of swinmiing and wading birds yield an albumin which, when diluted 
with 3 measures of water, is not coagulated by heat, but is precipitated by nitric acid ; 
and the albumin from the eggs of predaceous bird^, and of some kinds of perchio^ 
and climbing birds is neither coagulated by heat nor precipitated by nitric ad£ 
The composition was, however, found to be the same in all cases. 

Blood-albumin exhibits the same reactions as that from white of egg, excepting that 
the latter when boiled gives up part of its sulphur in the form of sulphuretted 
hydrogen, which blood-ubumin does not; nevertheless coagulated white of egg 
appears to contain more sulphur than blood-albumin. 

Paralbumin, — Scherer found in a liquid obtained from a case of ovarian dropsy, 
a substance resembling albumin, but differing from it in not beins completely preci- 
pitated by ebullition, even after addition of acetic acid, and in dissolving in water 
after being precipitated by alcohol. MetaUmmin is the name given by the same 
chemist to another supposed modification of albumin, likewise obtained frrom a pa- 
thological fluid, which . exhibited similar peculiarities to the preo^ling, and was 
fruther distinguished by giving no precipitate with hydrochloric acid, or with ferro- 
cyanide of potassium after acidulation with acetic add. 

Other substances more or less resembling albumin are: ghhtdin or erystaUin 
existing in blood-globules and in the crystalline lens of the eye ; JuBmatocrygtaUin^ a 
crystalline body obtained from blood, and vitdUUf ftTiating in the yolk of eggs (see 
these substances). 

Quantitatiife Estimation of Albumin, — The best mode of precipitating albumin 
from alkaline liquids (serum, for example), for (quantitative estimation, is to neutralise 
or slightiy acidulate the liquid with acetic acid, and then coagulate the albumin by 
boiUng. The precipitate thus obtained is flocculent and may be easilv collected on 
a filter and washe(^.the liquid passing through perfectiy clear, whereas if the albumin 
be coagulated by heat alone, it is veiy apt to dog the filter. Another reason for 
using &e acetic add is, that mere boiling does not predpitate the albumin completely 
from alkaline solutions. The precipitated albumin, after being thoroughly washedf, 
may be dried in vacuo over sulpnuric acid or in a current of warm air. 

Uses of Albumin. — Albumin is much used for darifying vinous and syrupy liquids, 
inasmuch as, when boiled with them, it coagulates, aiid takes hold of the colouring 
matter and other impurities, thereby removing them, and canying them to the bottom 
or to the surface of the liquid, according to its density. In cookery, white of esg 
is employed for this purpose, but in large operations, such as sugar-refining, the 
serum of blood is used. Albumin is applied to a considerable extent for fixing 
colours in calico-printing ; it is also used in photography. Its property of forming aharS 
compound with lime renders it very us^Ful for making cement for laboratory pur- 
poses and for mending broken earthenware. A paste made of white of egg and 
slaked lime, acquires after a while the hardness of stone. 

Albuionatbs. (Lassaig^e, Ann. Ch.Phys. [3]lxiv. 90; Lieberkilhn, J. Pharm. 
[3] xxxiii 398 ; Lehmann, Physiol. Chem. i. 382; Gerh. iv. 447.) — Albumin is a 
weiEik acid, and apparentiy dibasic Its compounds with the alkalis are soluble and 
are obtained directly by treating albumin witn caustic alkalis or alkaline carbonates. 
The other albuminates are insoluble and are obtained by predpitation. 

AJUnminaU of Barium, CH^^^BaN^SO" + H*0 (?) — A solution of albuminata 



ALBUMIK 69 

of pfftinrinin in dilute alcohol fomui with baziiimHnlts, a precuutate which dries 
«p to a white powder, insohible in water, alcohol and ether, white of egg mixed 
with eauBtie hazTta^ strontia or lime^ fozma an inaolable compound, whichbecomea 
Ttrj hard whea drr. 

MbmminaU of Copper, C**Hi»Ca'N»SO« -i- HH) (?) — Obtained in like manner 
Ibnna when diy, a ^reen, brittle mass, insoluble in water and alcohoL Acids deoo- 
loriae^ bnt do not dusolTe it (Lieberknhn). Aoooidin^ to Laasaigne, double albu- 
miuatfm of eoj^wr with potassium, or barium, or calcium, may be obtained by 
heatiog hydrate of copper with solution of albumin and solution of potash, baiyta or 
lime, lliere is also an albuminate of copper and magnesium which is insoluble 
and has a lilae eolour. 

ASbmmbuUe of Lead is a white insoluble salt, obtained by mixing the solution of 
■iTytrntii and snbaoetate of lead; it is soluble in excess of the lead-salt, and is decom- 
posed by all adds. 

Mtreurie jUbwminate is a white substance obtaioied by precipitating corrosive 
sublimate with albuminate of sodium (white of egg). It is insoluble in pure water, 
bat soluble in saline liquids ; for this reason, when white of egg is used as an antidote 
in cases of poisoning br coRosiTe sublimate, endeaTours should always be made 
to prodnoe Tomiting; ouierwise a portion of the mercuric albuminate may remain 
diasdlTed ia the gastric juice, whi ch contains chkride of sodium. 

JUmmintUe of Fotassium, C«H»'«?N»SO« + H«0. — Prepared by mixing a con- 
oentrated solution of white of egg with strong potash-ley, and washing the result 
log gelatinous mass with cold water, as long as any alkali dissolves out^ then dissolving 
the residae in boiling alcohol, and precipitating by ether. After diying, it is no longer 
eohible in boiUne alcohol or in water. The aqueous solution is not coagulated by 
boiling or by addition of aloohoL With a smaU quantity of acetic, tartaric, citric 
or plusphorie add, it yields an abundant white precipitate easily soluble in excess of 
aeuL These cfaaraetess axe the same as those of casein ; henoe^ Gkiriiardt considers 
it probable that casein ma^ be really albuminate of potaasiunL. 

AlbmfmtmaU of Sodium is contained in blood-serom and in white of egg, together 
with chloride of sodiom and phosphate of calcium. Seram and white of egg have 
a slight alkaline reaction,, are more soluble in water than pure albumin, and when 
bailed, coagulate in a gelatinous mass, not in flakes. After boiling, the filtered liquid 
is mors a&aline than before, and still contains albinyfiate of sodium, whereas the 
eoagufaim is f^ fiom alkali. Hence^ Gerhardt thinks it probable that serum 
and white of egg contain an acid albominate. of sodium, C^Hii^NaN^^O**, 
which is decomposed Inr heat into the neutral albuminate^ and free albumin which 
separatee from the liquid. This view is, moreover, in accordance with the composition 
of dried white of egg, which, according to Lehmann^s analysis, contains 1*6 per cent. 
of soda, the finmula CP*H"»NaN*^90«" + HK) requiring 1*8 per cent White of egg 
or serum treated with strong caustic soda, yields a eelatinous mass nearly insoluble 
in eold water, and doselv resembling the compouna produced under the same dr- 
cnmstanoobypotash. This gelatinous salt appears to be the neutral aHmminate of 
ModhtM, CH'^fNa'N'^BO'' + SPO. It contains, according to Lehmann, 3*14 per cent. 
soda (by caleulation 8*7). 

AHmmnuOe of SUver, C»BP>*Ag»N»«SO« + HH) (?) — Obtained by precipitatioa 
White, floccnlent, blackens when exposed to light. 

Ai^mmifUMte of Ztne, C«H"«Zn«N»feO" + H*0 (?>— White powder insoluble in water, 
aloobol, and ether. 

AXSmnar, VBOarABSa. (Gerh. iv. 444; Handw. d. Chem 2*« Aufl. ii. 
147.) — Most v^etable juices contain a substance which appears to be identical in 
co mp osition and properties with the albumin of blood or of white of egg. The 
same compound appears also to exist in the solid form in certain parts of plants, 
e^wdally in the seed. Vegetable juices containing albumin deposit it, when heated 
to 66^ or 70^, in flocks, which are often coloured greenish by diforophyll, and contain 
&tty and waxy substances mechanically enclosed. To remove these matters, the 
ooagnfaim must be washed, first with water, then with boiling alcohol and with ether. 

^bumin is especially abundant in the juice of carrots, turnips, cabbages, and 
the green stems of peas, but it is more easily prepared from potatoes, by cutting 
them into slices, covering them with very dilute sulphuric add (of 2 p.e.), leaving the 
liquid to itself for 24 hoars, then adding fresh potatoes, and repeating the same 
opcfation onoe more, afterwards neutralimng the solution with potash, and boiling. 
A considerable quantity of albomin is then deposited in thick white fiocks. 

Wheat-flour also contains a condderable quantity of albumin, which may be ex* 
tneted widi cold water. For this porpose, the water which runs off in washing the 
paste €fi wheat-flour for the preparation of gluten (q, «.) is left at rest till the starch 

F 3 



70 ALBUMINOIDS. 

is completely deposited; the dear liquid is then heated to the boiling point, where- 
upon it depoeits a small qnantily of albnmin ; on eTapoiating the solution a laiger quan- 
tity is obtained. 

Oleaginous seeds likewise contain albumin, which may be extracted by beatins 
the seeds with water into an emulsion, extracting the &t by agitation with ether, and 
the albumin by boiling. 

When sweet almonds which have been fi?eed from their euTelopes are reduced 
to a pulp by rasping, and the pulp is digested for a few minutes in boiling water, 
the sugar, g^um, and the greater part of the legumin contained in the almonds enter 
into s^ution; and on depriving the residue of fatty matter by means of ether, 
nothing is left but coagulated albumin, exhibiting the same characteni as coagulated 
white of egg. 



b e 



Carbon . 640 . 637 . 61*9 to 620 . 63-1 . 62*0 

Hydrogen . 7*8 . 7*1 . 6*9 . 7*0 . 7-2 . 68 

Nitrogen . 16*8 . 16-7 . 18-4 . . . . . . . 

Oxygen 

Sulphur 0-97 . 079 . 1-0 . 0*77 

a, albumin from rye,analysed by Jones (Ann. Ch. Pharm. xl. 66) ; b, from wheat- 
flour, by Dumas and Oahours (Ann. Gh. Phys. [3] tL 809); r, from wheat-flour 
by Boussingault (ibid. [2] Ldli. 226); d, from potatoes byBiiling (Ann. Ch. 
Pharm. Mil. 306) ; e, from peas b^ Billing; /, ^, fix>m rye, by Mulder. 

Vegetable albumin is distinguished fh)m legumin (yegetable casein) by being 
coagulated by heat, and not precipitated by acetic add. It exhibits the same 



actions as animal albumin with adds, allcalis, tannin, chloride of mercuiT, &c. Tho 
mode of its occurrence differs, however, remarkably from that of animal albumin in 
this respect, that it is always foxmd in plants in neutral or add liquids, whereas animal 
albumin exists only in alkaline liquids (p. 26). 

The albumin of sweet almonds is remarkable for the fadlity with which it decom- 
poses, and by its property of acting as a ferment, and determining the metamorphosis 
of amygdaliii, salidn, and other organic bodies. This altered albumin is distingnished 
by the terms emidsian and synapittae {q, v.) 

The myrosin of mustard-seeds likewise resembles vegetable albumin. Lastly, the 
diastase of germinated barley, beer-yeastf and totne-l^ are likewise albuminoidal 
substances in a state of alteration. 



Oonin. (Handw. d. Ohem. 2*« Aufl. i. 404.) — The name given bj 
Gouerbe to the substance of the cells which enclose the white of birds' eggs. It is 
obtained by exposing white of egg for a month to temperature between 0^ and— 8^, in 
the form of a white filmy substance, which when dried is whiter translucent in thin 
laminse and easily friable. It does not contain nitrogen, and consequently does not 
evolve ammonia when heated. It is insoluble in water, whether hot or cold, but swells 
up in hot water, forming a gummy mass. It is not acted upon by alcohol, ether, or 
acetic acid. Nitric and sulphuric acids decompose it. It dissolves in hydrochloric 
acid, and on adding water to the solution, a white powder is predpitated. It dis- 
solves in caustic potash, forming a solution which is rendered turbid by adds, but not 
predpitated. 

A&BVBSIirozsS. Protein-compounds, JSlutbilder. (Gerh. iv. 430; Handw. 
d. Chem. 2** Aufl. ii. 120.) — This term is applied to a <uass of compounds which 
play an important part in the functions of animal and vegetable life. Three of them, 
alfmmin, casein, 9XidL fibrin are distingnished by well-marked characters. 

Fibrin separates spontaneously in the solid form from blood, soon after its removal 
from the living body ; albumin is contained in the serum or more liquid portion of 
the blood, and separates fh>m it as a coagulum on the application of heat; and 
casein is contained in milk, ttom. which it may be separated, not by heat, but by the 
addition of an acid. The same substances are found in plants, viz. fibrin, in the grain 
of wheat and other cereal plants ; albumin in most vegetable juices, and casern (or 
legumin) in the seeds of the pea^ bean and other leguminous plants. 

The other bodies of this dass are less distinctly characterised ; indeed, most of 
them appear to be mere modifications of the one or other three above-mentioned: 
thus, synionin, the essential constituent of the muscular fibre, dosely resembles 
blood-fibrin ; viteUin, a substance occurring in the yolk of eggs, is scarcdy distin- 
guishable from albumin; and globulin and hamatacri/stallin, two substances con- 
tained in the blood, resemble albumin in the property of coagulating by heat. 

Moreover, albumin, fibrin, and casein, though clearly distinguished from one 
another by the different conditions under which they pass from the liquid to the 



ALBUMINOIDS. 71 

solid stslOy nereiiheleflB posseBS many chaiacten in eommon. Tliej all disBolTO in 
oostie potash or aoda^ and when boiled with thoae alkalis, yield solutions from which 
leids precipitate theja in a more or less altered state, and at the some time eliminate 
hjpdrGSQlphniic add. When subjected to dij distillation, they all give off ammonia 
(or oompoond ammonias). Th^ all decompose and putrefy with great &cility when ex- 
posed to moist air» and in that form are yeiy actiye as fermenia ; thus, yeast, wine-less, 
jitrfjMw, ice^ are merely albnminoidal substances in a peculiar state of dedomposition. 

All albununcids treated with oxidising agents, such as mixtures of peroxide of 
flumgaDCse or acid chromate of potassium and sulphuric acid, yield the same products, 
TUL aeids and aldehydes of the acetic and benzoic series (see Albdvin, p. 67). — Albu- 
mindds dissolre in Tery strong hydrochloric acid, forming a solution which is yellow 
if kept ftom contact with the air, but assumes a fine blue or violet colour on exposure 
to the air. — ^A solution of mercury in an equal weight of nitric acid imparts to these 
bodies a Teiy deep red colour, this test serving to detect the presence of 1 part 
of albumin in 100,000 ports of water. 

AD the albuminoids exhibit the same or nearly the same constitution. In the 
firing oiganism, albumin, fibrin, and casein are constantly being converted one into 
the other. The casein of milk supplies the material for the formation of albumin 
and fibrin; and conversely, albumin and fibrin are conyerted into casein. Indeed, 
the analyses of different bodies of the class do not differ from one another more than 
analyses of the same body from different sources or by dififerent experimenters. They 
eontain 50 to 54 p. c. carbon, about 7 p. c. hydrogen, 15 to 17 p. c nitrogen, about 25 p. c. 
ozjgen, and from 0*9 to 1*8 sulphur. Accoiding to some analyses, however, fibrin 
oootains rather less carbon and more ziitrogen uian albumin. Albumin and fibrin 
have been supposed by some chemists to contain also a small quantity of phosphorus 
88 an organic constituent, but its existence is not well established. Most albuminoids 
are associated with small quantities of mineral substances, including phosphate of cal- 
rioBi, which cannot be separated from the organic matter by acids. 

This great similarity of composition and properties exhibited by these bodies has 
led to various views of the relation between them. Mulder supposed that all the 
ilbuminoids contain the same organic group, G^H^^O*, which he cabled, prottin^ 
combined with different quantities of sulpnur and phosphorus, and that the con- 
Tcraian of one of these bodies into the other depends upon the assumption or elimina- 
tion of nnall quantities of one or both of those elements (see Pbotsin). Mulder 
also stated, that when an albuminoid is treated with caustic alkali, the sulphur and 
TtboK^tufroB are removed and the protein remains. The researches of other chemists 
hsve shown, however, that this view is untenable. Neither of the albuminoids 
contains phosphorus, and the proportion of sulphur appears to be the same in them 
all: at ail events, fibrin and egg-albumin, which perhaps exhibit the greatest dif- 
ference of physical and chemidal properties, do not differ perceptibly in amount of 
snlphur. Moreover, the sulphur of albuminoids cannot be completely extracted by the 
action of alkalis, so that the existence of the so-called protein is merely hypothetical. 

Gcriiazdt was of (pinion that all the albuminoids are identical, not only in com- 
posxtioD, bat in chemical constitution, and that they differ from one another only 
m moleenlar aznuigemezit, and by the nature of the mineral substances with whidi 
they are associated; in &ct, that they contain a common proximate element which, 
Hke many other oiganic compounds, is capable of existing in a soluble and in an 
insoluble modification. Designating this common element by the name albumin, he sup- 
posed that white of egg and serum consist of add albuminate of sodium (p. 99), which is 
separated by heat into free albumin and neutral albuminate of sodium, the latt^ remain- 
ing disBolyed ; that casein, which is soluble and non-coagulated by heat^ consists of 
nntral albmninate of potassium, from which the organic compound may be precipitated 
by neutralising the alkali with an add ; and that fibrin is albumin in the insoluble state, 
more or leas mixed witii earthy phosphates. This view is in accordance with the &ct 
that fifarin and caadn may be oissolyed in neutral potassium-salts (better with addi- 
tion of a little canstic alkali), forming a liquid which coagulates by heat, and deflects the 
plane of polarisation of a luminous ray to the left, like albumin ; and that fibrin and 
albumin, diasolyed in a certain quantity of caustic alkali, exhibit the characters of 
sdbble casein. Nevertheless, it is possible to obtain the albuminoids in some cases 
whol^, in othen yezy nearly, free from mineral matters, and neyertheless exhibiting 
their distingnishing characteristics. Moreoyer, it is certain that all these bodies 
contain tiie same proportions of carbon, nitrogen, and sulphur. 

Strecker (Huidw. d. ChenL 2** Aufl. ii. 124) eappoaee the albuminoids to be 
eoDoposed of a great number of radides (a supposition m accordance with the variety 
of their prodncts of decomposition) ; that the greater number of these radides are the 
aaaia in aU — hence their great similarity, — but that each contains one or more 
sneh radiclea pecnliar to itsdt Thus, when casein is oonyerted in the animal body 

F 4 



72 ALCOHOL. 

into albumin and fibrin, it mfty take the radides required for that transformatioa 
from the other constituents of the milk, viz. the fat and the sugar. (See Aiadkin, 
BiiOOD, Cassin, Cbystaluhb, Fibsih; Globulin, Hjematocbtstaliik, LBOUimr, 
Milk, Yitbllin.) 

AXMUWUMOWMb This term is applied by Bouchardat to a product of the decom- 
position of animal fibrin by Tery dilute hydrochloric acid (see Fibbik), and by Mialhe, 
to a peculiar substance into which he supposes albumin to be oonyerted by the action 
of the gastric juice before it is assimilated. 

A&CAXBASAfl> Very porous yessels of slightly burnt clay used in hot climateB 
for cooling water and other liquids. The liquid oozes through the pores and stands 
on the outside of the yessel in a sozt of dew, which rapidly evaporatee^ especially if 
the vessel is exposed to a current of air, and thereby cools the Uquid. 

A&CBSBVZlb&A VmbOASZS. 100 pts. of the fresh plant contain, acoarding 
to Sprengel : 76*0 pts. water, 10*3 pts. extractable by water, and 7'8 by dilute potash- 
ley; 5*6 woody fibre and 1'66 ash free from carbonic acid. The ash contained in 
100 pts. ; 30*6 potash, 2*4 soda, 33 '6 lime, 4*9 magnesia, 0*9 alumina, 14*4 silica, 
4*4 sulphuric anhydride, 5*4 phosphone anhydride, B-6 chlonne, and traces of the 
oxides of iron and manganese. 

AX«COBO&. C»H*0 = C*H».H:.0 [or C*H*0' « C^B^O.HO.]. This compound, 
which is the spirituous or intoxicating principle of wine, beer, and other fermented 
liquors, may be regarded as the hydrate or hydrated oxide of ethyl, or sjb a molecule of 
water, HHO, in which half the hydrogen is replaced by the radicle ethyl, CH*. It has also 
been regarded as a compound of ethylene and water, CH'.H'O. 

History. — Intoxicating drinks produced by fermentation of vegetable juices contain- 
ing sugar, have been known from the earliest times ; but it was not till the twelfth 
century that the method of obtaining pure spirit of wine or hydrated alcohol from 
these Uquids by distillation, was discovered by Abucasis ; and the dehydration of this 
liquid was first partially effected by means of carbonate of potassium by Baimond 
Lullins in the thirteenth century. The mode of obtaining perroctly anhydrous alcohol 
was afterwards discovered by lK>witz. 

Formation. — I. By the decomposition of glucose (grape-sugar) under the influence 
of ferments, that is to say, of nitrogenous organic substances, such as ^east, which are 
themselves undergoing decomposition. The sugar is then resolved mto alcohol and 
carbonic anhydride : 

(XB«0« - 2C»H*0 + 2C0«. 

Other kinds of sugar, cane-sugar for example, as well as starch, woody fibre and 
other vegetable substances, also yield alcohol under the influence of ferments, but they 
are first converted into glucose. 

2. From ethylene or defiant gas, by addition of the elements of water : 

C«H« + HK) = C«H«0. 

Olefiant gas briskly agitated for a long time with strong sulphuric acid, is absorbed, 
and on diluting the uquid with water and distilling, alcohol passes over. This mode 
of formation, first observed byHennel (Phil. Trans. 1826, p. 240), has lately been con- 
firmed and fully examined by Berthelot(Ann. Ch. Phys. [3] xliii. 885). As olefiant 
gas can be obtained from inoi^anic materials, it follows that alcohol may be produced 
without the agency of living organisms. 

Preparation. 1. 0/ HydraUd or Aqueous Alcohol. — ^When wine and other liquids 
which have undersone the vinous fermentation are distilled, alcohol passes over t(^ther 
with a considerable quantity of water ; and by subjecting the product to repeated dis- 
tillations, spirit is obtained continually richer in alcohol, because the alcohol, being 
more volatile than the water, passes over in larger quantity than the latter. But it is 
not possible to remove the whole of the water by simple distillation. The residue of 
the custiUation, if continued long enough, is notMng but water containing small quan- 
tities of acetic acid (produced by oxidation of the sdcohol) and fiisel oil. Portions of 
these impurities also pass into the rectified spirit. The greater part of the acetic acid 
however, and a considerable portion of the fusel oil are left in the residues of the 
several distillations. The last portion of the acid is easily removed by distillation 
over a small quantity of carbonate of potassium or wood-ashes : and the fasel oil, 
which adheres more obstinately, and imparts a very unpleasant odour to the spirit, is 
best removed by adding to the spirit about 0*7 of its weight of coarsely powdered 
charcoal, leaving the mixture to stand for several days, and stirring it repeatedly, then 
decanting and distilling. Bone-black or blood-charcoal may also he usea. 

2. Of Anhydrous or Absolute Alcohol. — ^Alcohol cannot be completely dehydrated by ' 
distillation, because, at the boiling-point of pure alcohol (78^ G.^, the vapour of water 
possesses a considerable tension. The most highly rectified spirit obtained by fhiei 



ALCOHOL. 73 

dislalbitioA, BtQl letains about 9 per cent, of water. The last portioiiB of water 
niHt be KSioTed by the agency of some substance which has a poweirol attraction for 
it Caibooate of potassimn, chloride of calcinm, and qiiick lime, are the sabstanoes 
Bost commonh' used for ihis poipoee, more rarely acetate of potassium, sulphate of 
copper, and other salts. 

0. Sy Carbonate of Ii>ta$sium. — ^Highly rectified spirit is shaken up with ignited 
esibonate of potassium, which forms a watery or pasty layer at the bottom* The 
akohd, whose density is thereby lowered to 0'815, is poiLted off into a t^iMtiTli'ng yessel 
containing tvioe the quantity of palyerised and recently ignited carbonate of potassium, 
kft to stand for 24 hours, and then two-thirds of it are diatilled off (Lo wi tz). This 
method does not however remove the last minute portions of water. — b. A more com- 
pfetd dehydration is effected b^ chloride of caicium. The salt fused or dehydrated by 
a beat of 400^ C. ia added in tiuck lumps to twice its weight of spirit containing 90 per 
cent of real alcohol ; and the mixture left for some days in a closed vessel and occa- 
mooaJlj shaken up^ after which it is distilled in a retort over a fresh quantity of fused 
diiorioB dT ealduuL The retort is heated in a sand or oil bath with its neck directed 
upwwpda to prevent the contents &om spirting over. When the quantity of alcohol 
is laige^ a second treatment with chloride of calcium is necessaiy to effect complete 
dehjthation. 

c By QmetltTne, — ^A retort is two-thirds filled with small pieces of quick lime, and a 
quantity of 90 per cent, spirit poured in sufficient to nearly cover the lime. The lime 
aooD slakes and becomes heated ; the miztoze is left to digest for some hours ; and the 
anbydnras alcohol is then distilled off in the water^bath. The distillation must be care- 
inDy conducted, otherwise the distillate will be contaminated with lime. Alcohol con- 
taining fusel oil acquires a very unpleasant odour when treated with lime. This is by 
hr the easiest method of obtaining absolute alcohoL 

d. When aqueous alcohol is enclosed in a bladder, and exposed to warm air, the 
water gradnalh' percolates through the bladder and evaporates, and absolute alcohol is 
left inside. (Sdrnmerins.) 

Akohol may be regarded as anhydrous if sulphate of copper previously burnt white 
does not acquire any blue colour when immersed in the aJconol m a close vessel (Cas- 
soria), or if it forms a perfectly deaf nuxtnre with benzol (Gorgeu). It is doubtful 
however whether either of these tests will indicate the presence of a veiy minute 
quantity of water. 

/Vopertusf . — ^Alcohol is a transparent, colourless, veiy mobile liquid, having a strong 
lefraeting power. Its specific gravity, according to ICopp (Pogg. Ann. Ixxii. 1), is 
0-792 at 20^ ; or 0-7989 at 16-5^ or 0-8095 at 0^. If its volume at 0° C. be taken for 
unity, the volume at any temperature i9 is given by the formula: 

tr = 1 + 0-00104139i + 00000007836^ + 0000000017618<«. 

and therelore lor the temperatures : 

09 C. 6^C, lOoC. 15° C. 20° C. 25<>C. ZO^C. 

the vohimes of a given quantity of alcohol are as the numbers : 

1-00000 1-00523 1-01052 101585 102128 102680 1*03242 

Alcohol has never been reduced to the solid state, but becomes viscid at very low 
temperatures, as when it is surrounded with a mixture of solid carbonic acid and 
ether under an exhausted receiver. It boils at 78*4^0. (173*1° Fah.) when the baro- 
meter stands at 0-76 met (Gay-Lussac, Kopp.) Vapour-density » 1-613 (Gay- 
Lussac) ; by calculation, for a condensation to 2 volumes, it is 1-591 when referred to 

air as unity, and 23 when lefetred to hydrogen as unity ( 5 «» 23. j 

Akohol has an enlivening odour and a burning taste, and .when unmixed with water 
exerts a poisonous action. It is a very slow conductor of electricity. 

Deeonmoeiiums, 1. By Seat. — ^Alcohol- vapour passed through a red-hot glass or por- 
edain tuoe jrields carbonic anhydride, water, hydrogen, marsh-gas, olefiant gas, naphtha- 
lin, empyreomatic oil and a deposit of charooaL K the tube he filled with fragments of 
pumice-stone, the solid and liquid products consist of nalphthalin, benzol, hydrate of 
phenyl, acetic add (?) and aldehyde, together with a number of solid compounds of not 
veiy ddlnite character, some of them smelling like musk, others like garlic (Berthelot, 
Ann. Ch. Phys. [3] xrriii. 285). Alcohol-vapour does not undeigo decomposition at 
300® C. in a tube containing fragments of porcelain, but gives off gas even at 220^, if the 
tube contains spongy platinum. (Beiset and Mi 11 on, Ann. Ch. Phys. [3] viii. 280.) 

2. By EUetrtciUf, — Absolute alcohol scarcdy conducts the voltaic current, but when 
pottth or potassium is dissolved in it, decomposition takes place, hydrogen being 



74 ALCOHOL. 

erolTed at ihe negative pole and aldehyde-xeBin fonned at the podtiTe pol< 
(ConnelL) 

3. By Oxygen, — Alcohol is very inflammable, and bnins in the air ^th a dnUbh 
flame, yielduig water and carbonic acid. It does not readily deposit soot, eren vhen ti 
snpply of air is limited, bnt absolute alcohol deposits it more readily than ordioary^iii 
Aloohol-Tapour mixed with air explodes by contact with flame or by the deetrie spaxli 

Imperfect Combttsiion, — When alcohol or its Taponr comes in oontaet with air, ai 
at the same time with platinnm or certain other metals, an imperfect oxidation of tl 
alcohol takes place, the metal being generally heated to redness, and the alcohol bei 
oonyerted, partly into carbonic add and water, partly into aldehyde, acetic add, fSmrn 
add, aoetal, and a peeoliar oom^nnd having an exeessiyely pnngent odoor. &m 
metals exdte this action at ordmary temperatures, others only when more or 1< 
heated; bat in all cases the action is more powerftd aa the metal is more finely divid 
and oonseqnentiy exposes a laiger surfiice to the alcohol-vaponr. The most powei 
action is exertea by plaiinum black. When this snbstanoe is shalien on paper m( 
tened with alcohol, it makes a hissing noise and becomes red-hot» sometimes sett 
Are to the alcohol, or else oontinning to glow, and indndng the slow combnstion ab 
mentioned. If the platinum be previonidy moistened with a small quantity of wa 
or at once covered completely with alcohol, the ignition is prevented, and the a 
combustion induced with greater certainty. If a number of watdi-glasses oontaii 
moist platinum black, be placed above a cush containing alcohol, and a bell jar opei 
top inverted over them, the alcohol turns sour in a few weeks, and is found to con 
alaehyde, aoetal, acetic add, and acetic ether. 

This action of platinum black affords an excellent means of discovering thepresi 
of alcohol in the air or in watery liquids. The liquid, neutralised, if necessary, ' 
alkali, to prevent the escape of volatile adds, is introduced into a retort, into the : 
of which, and near the bulb, is thrust a littie boat containing platinum black, am 
each side of this boat is placed a piece of litmus paper, in contact with the platu 
The retort is then gently heated in the water-bath, when, if alcohol is pre 
its vapour will be converted into acetic add by contact with the platinum black 
the paper will be reddened (Buchheim). [Other volatile oiganio liquids might 
a similiar action.] 

Spongy platinum and dean platinum wire act in a similar manner to platinum 1 
but not so quickly. If a coil of platinum wire be placed round the wick of a c 
lamp, the alcohol set on fire till the wire becomes red-hot» and the flame then 1 
out, the wire will continue to glow and the alcohol-vapour to bum slowly, prod 
acetic add, aldehyde, &c The same effect is produced by a ball of spongy plat 
This is the lamp tnthoutflame, or fflow lamp of Sir H. Davy. 

4. By Chlorine, — Chlorine eas is rapi^y absorbed by alcohol, imparting t 
yellow colour and causing considerable nse of temperature, which, if tne liqtdd 
posed to ligh^ may even cause it to take flre. At the same time it rapidly ab 
hydrogen, which is partiy replaced by chlorine, thereby producing hy<uochlori 
aldehyde, acetal, acetic add, acetate of ethyl, chloride of ethyl, and finaJly cblora 
mixture of these substances, freed by washing with water from the soluble oonsti 
was formerly called heavy hydrochloric ether. The formation of these aeyeral p: 
is represented by the following equations : 

C"H«0 + 2 a » 0«H*0 + 2HC1 

> r-— ' > r— ' 

Akobol. Aldehjde. 

OE*0 + 6 a - C»HC1»0 +8HCa 



Aldehyde. Chloral. 

C«H*0 + Ha - OHK31 + H*0 



AloohoL Chloride of 

ethjl. 

C«H*0 + B?0 + 4a - C«H*0« + 4Ha 



Alcohol. Acetic acid. 

C*H«0 + C»H*0< « C*H«0*.C*H» + HH) 



>— » -^ ^- . — ^ 



Alcohol. Acetic add. Acetate of ethyl. 

Acetate of ethyl may also be formed by the direct action of chlorine on the 
thus: 

2 C*H»0 + 4a - C«H»0«.C«H» + 4 Ha 
The acetal, which is probably formed at the beginning of the procesA^ accord] 
equation : 

3C«H«0 + 2 a - C«H"0« + H*0 + 2Ha, 



ALCOHOL. 75 

is fir the mosl port sabseqiientlj oonTerted into aoetie acid': 

C*H"0» + 4HH) + loa - ZCm*0» + IpHCl. 

'When the sction of the chloiine is continued for a long time, chloral is always the 
principal product. 

Chlorine in pireeence of alkalis, conyerts alcohol into chloroform and carbonio 
anhydride i 

c«H«o + sa + o - CHa« + chci + cx)«. 

ThB same products are formed by distilling dilute alcohol vith hypochlorite of cal* 
eiiiB (efaloriae of Ume, bleaching powder). (See Chlobofobm.) 

Bromime acts upon alcohol in a simiLar manner to chlorine, producing bromal, hydzo- 
bromie acid, bromide of ethyl, bromide of carbon, formic acid, and oUier products not 
jet tbostrag^y examined. Iodine is at first dissolved by alcohol without deoompoei- 
tkn, and txroaa a brown solution ; but after a while, hymiodic acid is produced, and 
actinff upon a portion of the alcohol, forms iodide of ethyL An aloohoHc solution of 
pi^n tzested with iodine yields iodoform and iodide of potassium, the former of whicdi 
co m pooads may be separated by water. 

9. GUorieacid^ in uie concentrated state, sets fire to alcohol ; when diluted, it forms 
icede acid, the action being sometimes attended with eyolution of chlorine. Perehlo' 
fie add mixes with alcohol without decomposition at ordinary temperatures, but the 
hquid when heated first gives off alcohol, then ether, and ultimately white yapoura 
■molKwg like cnl of wine, tiie residue at the same time turning black. 

10. Strong Nitrie acid decomposes alcohol, with great evolution of heat and brisk 
ebollition, a mixture of various elastic fluids, the ethereal nitrtme ga$ of the older 
diendsCB, being evolved and an acid liquid remaining behind ; if the nitrie acid is 
dihite, the action does not take place without i^lication of heat. Part of the nitric acid 
unites direetlT witii the alcohol, forming nitrate of ethyl, but the greater part is reduced 
to nilzous acid which then forms nitrite of eth^l (nitrous ether) with a portion of the 
akohol, while the remainder of the alcohol is oxidised andoonverted into aldehyde, aoetie 
arid, formic add, saccharic acid, oxalic add, glyoxal, glyoxylic add, and glycolUo add, 
tog^er with water and carbonic anhydride, which escapes as gas, together with nitric 
oxide and the vapours of the more volatile among the compounds just mentioned. The 
formation of ^yoxal, glyoxylic add, and glyoollic adds is represented by the equations : 

C*H«0 + 80 = C*EPO« + 2HH) 

Alcohol. Gljoxal. 

C?HH) + 30 =» C«H*0« + H«0 

Akokol. OljooUic add. 

C*H»0* + O + HK) « C^*0* 



-T- 



lie 



GlyoouL Gljonrl 

If urea be added to the mixture of nitric add and alcohol so as to decompose the 
mtrous acid as fast as it is formed (see Ubba), the chief product of the action is nitrate 
of Hhyl NCCH*. Hydrocyanic add has also been obserred among the products ot 
the action of nitric add upon alcohol. 

When strong alcohol is heated with red faming nitric add (containing nitrous add) 
and nitrate of silver or mercuric nitrate is added, white Aimes are given ofl^ containing 
aldehyde and other oxidised products, and a aystalline deposit of fUminate of silver 
or meremy is formed, its production being due to the action of the nitrous acid on the 
alcohol: e.g. 

C«H»0 + 2N0«Hg « C«N«Hg«0« + 3H*0 

AlcoboL Mercuric Fulmtnata 

nitrite. of mercury. 

But when a solution of mercury in nitric add free from nitrous add is added at a 
temper a t ur e below 100^ C. to alcohol of sp. gr. 0.944, no action takes place at first; but 
on raising the temperature to 100^, a white crystalline precipitate is formed, which is 
a compound of mercuric nitrate with a nitrate of ethyl in which the whole of the hydro- 
gen is replaced by mercuiy (Sobrero and Selmi; Oerhardt): 

2N0^ + 3 Hg*0 + CJ«H*0 - NO^.NO«(C»Hg») + HH) + 3 H«0 

CryiUlUne compooiuL 

11. Sulphuric acid forms with alcohol, a number of products varying in quantity 
according to the proportions in which the two liquids are mixed, their degree of con- 
centration, and the temperature to which the mixture is exposed. 



76 ALCOHOL. 

Strong snlphimc acid mixes with alcohol, prodnciiig consideTable eTohtion of heal 
and fonns etnjl-sulphuric or snlphovinic add, the acid being at the same time brongl! 
to a greater atote or dilation : 

C«H».H.O + SO*.H» - SO^H.C«H» + HH) 

^ ,_^ , ' 

Alcohol. Etbyl-sulphorle 

add. 

When the strongest snlphnric acid (sp. gr. 1*825) is digested for some time at 
gentle heat, with excess of absolute alcohol, more thaii half the sulphuric acid is co 
Terted into ethyl-sulphuric acid. If the acid or the alcohol is diluted with vater, a co 
siderable quantily of the sulphuric acid remains unaltered. Sulphuric acid oontaini 
1 at. water (SO^U'.HK)) forms ethyl-sulphuric acid only when heated. As the fern 
tion of etbyl-sulphuric add is necessarily accompanied 'by that of water, a ceiti 
portion of the sulphuric add must always remain unconverted into ethyl-snlphu 
add. 

Formation of Ether, — ^A mixture of 1 pt. alcohol, and from 1 to 2 pts. strong sulp] 
ric add heated in a distillatory apparatus, boils between 120° and 14(^ C, at first gir 
off ether, together with more or less undecomposed alcohol, l^en at 140^ ecaroely a 
thing but ether, at 160° ether and water, — and at length when, in consequence of 
decompodtion of the alcohol, the proportion of sulphuric acid has become excess 
and the temperature rises above 100°, the mixture blackens and gives off defiant 
togeUier with sulphurous add and other products hereafter to be mentioned. If h 
ever the alcohol be allowed to flow constantly into the vessd in a thin stream, so a 
maintain the proportion of 5 pts. alcohol to 9 pts. sulphuric add, the temperature 
mains constant at about 160°, no sulphurous add or olefiant gas is formed, but 
alcohol, as fast as it is supplied, is given off again in the form of ether and water. 

The alcohol converts a molecule of sulphuric add into ethyl-sulphuric add and w^ 
mi ftbove * 

C*H».H.O + BO\W - SO*.C«H».H + HH> 

AlcohoL Sulphurie Ethjl-tutphuric 'Water, 
acid. acid. 

and the ethyl-sulphuric add coming in contact with another molecule of alcohol, j 
ether and sulphuric add : 

SO*.C*H».H + C«H».H.O - (C*H»)«0 + SO*H«. 

Etbyl-tulphuric Alcohol. Ether. Sulphuric 

add. acid. 

The sulphuric add thus reproduced acts in like manner upon another molec 
alcohol, and in this way the process continues as long as the supply of alcohol i 
up. Etheriflcation is therefore a continuous process, a given quaotil^^ of sul] 
add being capable of etherifying a very large quantity of aloohoL The water, 
ever does not all pass off as it is formed, so diat the sulphuric add becomes oonti 
though slowly weaker, and consequently a continually larger quantity of alcohol 
over undecomposed with the ether and water. 

The explanation just given of the process of etheriflcation is due to Willis 
(Chem. SoG, Qu. J. iv. 106, 229). Its correctness is strikingly exhibited 1 
analogous reaction which takes place between common alcohol and amyl-sulpburi 
When amyl-alcohol is dissolved in sulphuric add, amyl-sulphuric add is produ< 

C»H»>.H.O + SO*H« - SO*.C»H".H + H«0. 
Now, on heating this mixture and passing a stream of ordinary alcohol throug 
above, ethamylic ether, or oxide of ethyl and amyl passes over first, then c 
ether, and ethyl-sulphuric add remains behind in place of amyl-sulphuric add 

SO*.C»H".H + C»H».H.O « C»H».C»H".0 + SO*H« 

Amyl-tulphuric Alcohol. Oxide of ethyl Sulphuric 

acid. and amyl. acid. 

The sulphuric add thus reproduced acts upon the ethyl-alcohol in the maziner 
described, the products being ethyl-sulphunc acid, ether, and water. The same ' 
are obtained by distilling a mixture of ethyl-alcohol and amyl-alcohol with s 
add. 

The formation of ether from alcohol was formerlv regarded as a simple pi 
dehydration. Ether being regarded as C*IPO and alcohol as its hydrate, C*j 
it was supposed that the sulphuric acid simply ab8tract«d the water and left t 
Against this view, however, it must be alleged that the quantity of water gi^ 
the distillation is very nearly equal to the whole quantity supposed to be f 
from the alcohol, which could not be the case if it were retained by the sulph* 
Moreover, the molecule of ether referred to the same vapour-volume aa "that o 



ALCOHOL. 77 

C'iPO', ii not C*H*0, bat C*iP*0*; or, according to the atomic weights adopted in 
thia vori^ alcohol being CH'O, ether is C*H^*0. For these reasons, Hitscnerlieh, 
Batzdhu^ and other diemists haTe regarded the action of snlphnric add upon alcohol 
as ^wntaistrCfeUon^ or caUdyHe oeHon, a mode of expression which simply states the fiwt 
vitboat ei^Iaiiiing it. 

Anotlwr objection to the Tiews jnst mentioned, is that they take no account of the 
finmation of ethyl-sulpburic acid. That this, however, is an essential step in the process 
of etheriftcation is shown by the fact that, on distining amixture of alcohol and strong sul- 
phuric add, the quantLtjr of eth^l-sulphuric add constantly diminishes as the ether passes 
over, and that, if the add be diluted so far as not to form ethyl-sulphuric add, the mix- 
tnrppeUb no etber by distillation. Liebig therefore supposed that the ethyl-solphuric 
add IS resolTed at a certain temperature (120^ to 140^ C.) into ether, sulphuric acid, and 
aulpfanrie anhydride : 

2(C*BP.H.SCH) =- C*H»0 + SO«H» + S0« 

and that the sulphuric anhydride, unitine with water also present in the mixture, re- 
produees sah>huric add. But ethyl-sulphuric add when heated alone giyes off, not 
ether hat alcohol, even when heated to 140° or above in sealed tub^ ; but when 
heated with alcohol, it immediately yields ether. We are therefore led to regard the 
loxmation of ether as a resolt of the mutual decomposition of alcohol and ethyl-ralphuric 
add, in the manner already explained. 

When alcohol and strong sulphuric add are heated together in sealed tubes, the 
alcobol bdn^ in excess, a layer of ether Ibrms on the top of the liquid, but no ethyl-sul- 
l^raric add is found in the lower stratum. If the sulphuric add is in excess, no ether 
» fonned (Grab am , Chem. Soc Qu. J. iii. 24). In the former case, it is probable that 
ethyl-fluj^huric add was first formed, and afterwards converted by the excess of alcohol 
into ether and sulphuric add. Add sulphate of potasdum (Graham) and various other 
sulphates heated with alcohol in sealed tubes, also etheri^ it more or less completely, 
the sulphate being in some cases converted into a basic salt. The alums, namely 
common alum, anmionia-alum, potassio-ferric sulphate, and potassio-chromic sulphate 
heated with an equal weight of 98 per cent, alcoho], etherify it completely. In sll 
these cases, the sulphate appears to give up a portion of its sulphuric add, which then 
acts on the alcohol as above. (Reynoso, Ann. Ch. Phys. [3] xxviii. 385.) 

FormiUicm of Oi^fiani gat, — When 1 pt. of alcohol is nested with 3 or 4 pts. of 
strong sulphmric add, the mixture begins, between 160° and 180° C, to blacken and 
thidben, swells up considerably and gives off olefiant gas C^\ together with variable 
qnantitiea of sulphurous anhydride, carbonic anhydride, carbonic oxide, oil of wine, 
acetic add, acetic ether and ^srmic add, and a black reddue is ultimately left con- 
sisting of a peculiar add called thiomelanic add and free sulphuric add. £y pasdng 
alcohol-vapour through a boiling mixture of 10 pts. of strong sulphuric aad and 
3 pta. of water, olefiimt gas and water are obtain^ with scarcdy any coloration of 
the mixture or fonnation of secondary products : 

CTI*0 - C*H* + H*0. 

12. Sulpkurio anhydride, SO*, is dissolved by absolute alcohol, with evolution of heat, 
and Ibrms neutral sulphate of ethyl SO^(C^*)*. When the vapour of the anhy- 
dride is passed into abeolute alcohol, crystals of sulphate of carbyl, G'H^280', are 
ibimed, together with ethionic, isethionic, ethyl-sulphuric and sulphuric acids. 

18. Fkotphoric add mixed with alcohol at ordinaiy temperatures, converts part of 
it into ethja-phoephoric add. A mixture of phosphoric acid with a small quantity of 
alcohol 27^^ olefiant gas but no ether ; but if the alcohol is in excess, ether is first 
given ofl^ then olefiant toB and a thick add distillate probably consisting of neutral 
phosphate of ethyl, P0*.(U'J1*)*. Phosphoric anhydride absorbs the vapour of an- 
hj^droos alcohol, forming ethyl-phosphonc acid PO^C*H*.H*, and diethylphosphoric 
add, PO*.(CH*)^H. Jreenie acid acts veiy much like phosphoric add, proaudng 
ether and ethyl-arsenic add. Boric anhydride (vitrefled boric add) in the state of 
powder heated with absolute alcohol, gives off olefiant gas and leaves boric add. 

14. HydrochUmo add sas is absorbed in large quantity by alcohol, and the eolation 
when heated gives off chloride of ethyL The same compound is obtained by distilling 
alcohol with strong hydrochloric add, or with a mixture of common salt and sulphuric 
add; but iHien a mixture of hydrochloric add with a large excess of alcohol, dther 
anhydrous or hydrat«d, is heated to 240° in a sealed tube, ether is formed as well as 
cfaknido of ethyl, these two liquids forming a layer on the surface, while the lower 
stratum consists chiefly of water and hydrochloric add. The ether results &om the 
action of alcohol on the chloride of ethyl abeady formed : 

C«H».C1 + C»H».H.O - ipWfO + Ha 



1 



78 ALCOHOL. 



The same tnmflfomiatioii takes place, though dowly, even at lOO^' C. (A. Reynoso^ 
Ann. Gh. Phjs. [3] zlviii. 886.) 

16. ^Sjuij metallic ckloridefBictnipontJi^^ acid* 

UEodncing ether and chloride of ethjL Chloride of zine oonyerts anhjdiona alcohol 
into chloride of ethyl with a small quantity of ether. With hydrated alcohol, it yields 
at 166^0^ ether and oil of wine, the qnantilr of which increases as the distillationgoes 
on ; hydrodiloric acid is also given otE, and basic chloride of zinc remains. Vfhea. 
didiloride of tin is distilled witii a considerable qnantity of alcohol, ether and chloride 
of ethyl pass over between 140^ and 170^, afterwards a componnd of chloride of et&yl 
with dichloride of tin. (Knhlmann, Ann. Oh. Pharm. zzxiii. 97, 192.) 

Omtallised protochlonde of tin distilled with alcohol yields ether, but no chloride 
of ethyl (Karehand) ; the same decomposition takes place in a sealed tube at 240^. 
CiystaUised chloride ofman^aneee and protochloride of iron also etherify alcohol com- 
pletely when heated with it in sealed tabes to 240^; the chlorides c^ cadmium^ nickd^ 
and cobalt partially ; in all these cases, the etheriflcation takes place without blacken- 
ing of the contents of the tube, and with little or no escape of gas when it is opened 
(B ey noso, Ann. Gh. Phys. [2] zlviiL 386). The formation of eUier in these reactions, 
may be explained by the following equations, given by Williamson for the case of 
chloride of zinc: 

C«H».H.O + Zna ■= C«H».Zn.O + HCl. 
C«H».H.O + HCa - C«H».a + H*0. 
C«H».a + C«H».Zn.O « ((?H»)«0 + ZnCL 

With seeqtdchloride of iron, alcohol yields ether and chloride of ethyl between lS(fi 
and 140^., afterwards hydrochloric acid and water, the residue consisting of sesqui- 
chloride of iron mixed with sesquioxide. With chloride of aluminium, chloride of 
ethyl is given off between 170^ and 200^, afterwards hydrochloric acid, and alumina is 
left behind. Trichloride and pentachloride of antimony convert alcohol into chloride 
of ethyl, with a little ether, tlie residue consisting chiedy of oxychloride of antimony. 
Protochloride of platinum boiled with alcohol of sp. gr. 0*813 to 0-893 is converted 
into a black explosive powder called detonating platinum-depoeit, 0"M*PtK), the liquid 
acquiring a strong acid reaction and the odour of chloride of ethyl : 

CHH) + 2PtCl - C«H«Pt«0 + 2HCL 

The chloride of ethyl is formed by the action of the hydrochloric acid on another por- 
tion of the alcohoL (Zeise.) 

Asolution of 1 pt of dichloride of platinum in 10 pts. of alcohol of sp. gr. 0*823, dis- 
tilled to ^ yields aldehyde, chloride of ethyl, and hydrochlorie acid^ The residual 
dark brown liquid deposits a considerable quautitv of the black detonating powder 
just mentioned, and retains in- solution the so-called inflammable chloride of platinum, 
C«H*Pt«Cl«, according to Zeise, or C«H»Pt«Cl«, accorcQng to Liebig. Its formation 
is represented by one of the following equations : 

2C*RK> + 2PtCl« «- C^*Pt*Cl« + C«H*0 + HK) + 2Ha (Zeise.) 

Aldehyde. 

8C*H«0 + 4PtCl« - 2C«H^«a« + C«H*0 + 2H«0 + 4HCL (Liebig.) 

^^ — I — ' 

Aldehyde. 

The formation of &e black deposit is not an essential part of the reaction, and in- 
deed takes place most abundantly when the dichloride of platinum contains proto- 
chloride. 

Mercuric chloride, HgCl, dissolved in alcohol ia slowly reduced to mercuious chloride 
Hg>CL Potaah added in excess to the alcoholic solution heated to 60^C., forms an amor- 
phous ^ellowprecipitate containing carbon, hydroffen, oxyeen and mereuzy, the hydrogen 
being in smaller proportion than in alcohol This precipitate heated to 200^, explodes 
without leaving any residue ; heated in the moist state, it decomposes less violently, 
yielding mercury, water, and acetic acid (Sobrero and Selmi). Gerhardt and 
Werther did not succeed in preparing this compound. 

16. Trichloride of phosphorus reamly decomposes alcohol, forming chloride of ethyl« 
hydrochloric acid, tnbaac phosphite of ethyl and phosphorous acid. (B 6 champ 
Compt. rend. xL 944.) 

6(C«H».H.O) + 2 Pa« - 3C^»a + 8 Ha + PO».(C«H»)« + PO».H». 

17.^ With pentachloride of phosphorus, the products are chloride of ethyl, hydro- 
chloric and ddorophosphoric acid, J?CI*0 : 

C*H».H.O + PCI».C1« - C«H»C1 + Ha + pa«.o. 



ALCOHOL. 79 

I& PaUanUfkitU ofpiotpkoruSf on the other band, oonTerto alcohol, not into two 
flcpante mlphidee^ but into the single compound mereaptan, or anlphide of ethyl 
andhydiogen: 

^CTPJBLO) + P«» - 6(C«H».H.S) + PW. 

Theae last two reactions iQnstrste in a strildng manner, the difference between mon- 
atomie and diatomic elements or radicles. In the former, the sin^e atom of oxygen 
in alcohol is replaced hj two atoms of chlorine, one of which unites with the ethyl, 
and the other with the hydrogen of the alcohol, foiming two perfectly distinct chlorides; 
whereas in the latter, the oi^gen of the alcohol is replaced by 1 atom of tiie diatomic 
element, snlphnr, which being indiTisible, binds together the ethyl and hydrogen 
into one single molecule of mereaptan. f Compare page 11.) 

19. Hie bromidm and iodides at phosjmoms, hy wgen, and the metals, act lilce the 
cfaloridea. J^droftvoric add appears to cony^ alcohol into fluoride of ethyl. 

20. Poiasnum and todium rapidly decompose absolute alcohol, 1 atom of hydrogen 
being erohred and its place snpphed by the metal ; the resulting compound is an ethyl- 
ate rf p o tassiu m (C*H'KO) or ethylate of sodium, which crystSlises from the saturati^ 
solution. The same compound appears to be formed by dissolving hydrate of pot-assium 
or sodinm in absolnte alcohol: 

C*E*M,0 + KHO « C«H».K.O + HK) 

Hie ablution thus obtained exhibits in many cases the same reactions as that which is 
produced W dissolying the metal in alcohol. 

21. Alcohol heated with hydrate of potassium (or sodium) yields hydrogen gas and 
an acetate: 

C*H«0 + KHO - C«H»KO« + 4H. 

To pndaee this decomposition, a mixture of equal weights of the alkaline hydrate and 
ponnded quick lime is moistened with alcohc^ the excess of alcohol driven off at 100^, 
toad the mixture gently heated -without access of air. Hydrogen is then evolved, 
together with a snmU quantity of marsh gas, and the residue contains acetate of potas> 
Mum, -which, at a hi^er temperature, is resolyed into marsh gas and carbonate of 
polas8inm(p. 17). 

22. Alcohol-vapour passed over anhydrous baryta heated nearly to redness, yields 
defiant gas, marsh gas and hydrogen, with a residue of carbonate of barium. 

23w Gaseous chloride of cyanogen is readily absorbed by alcohol, but does not decom- 
pose it immediately. AJter a few days however, or more quickly if a little water is 
present or if the kquid is heated to 80^, chloride of ammonium separates out, while 
chloride of ethyl, caroamate of ethyl (uretiiane) and carbonate of ethyl remain in solu- 
tion. The urethane and carbonate of ethyl are formed in the manner r^esented by 
the two following equations : 

C*H«0 + CNCa + H*0 « C»H^O« + HCl 

Urethane. 
20B«0 + CNCl + H«0 - CO«(Cra»)« + NH*C1 

- ,1, _ -* 

T 

Carbonate of 
ethyl. 

The diknide of ethjd results from the action of the hydrochbric acid, produced as in 
the first equation, on the aloohoL (Wurtz. Ann. Ch. Pharm. Ixxix. 77.) 

24. Mnny oryaiKic acids when heated with alcohol convert it into compound ethers, 
with elimination ^ 1, 2, or 8 atoms of water, according as the add is monobasic 
dibaaicvortzibaaic: s.y. 

C«H».H.O + C5*HK).H.O - C^»O.C*H».0 + HK) 



AkdioL Acetic acid. Acetic ether. 

2(C«H».H.O) + CO*.H».0« - CO*(C»H»)*0« + 2HK) 
Alcohol. Oxalic acid. Oxalic ether. 

8(0^*.H.O) + CyHK)*.H'.0; - G^*0\(0«Hy.q » + 8H«0 

Alcohol. atric add. Citric ether. 

'With some acids, e.g, acetic and bnlyric acids, the transformation is easily effected ; 
with others, as oxalic and hippuric add, it takes a considerable time : in other cases 
again, as witii baozoic add, no ether is formed when the add and the alcohol are merely 



80 ALCOHOLATES— ALCOHOLOMETRY 

distilled toffether; bat on passing hydrochloric gas into the alooholic solution of ti 
acid, the euier is qtiiddy ibrmed. In this caae, chloride of ethyl is first ionned az 
afterwaidfl decompoeed by the organic acid. Other strong minonl adds, such is st 
phuric add, also facilitate the formation of these compound ethers. 

Many poWbasie oisanic adds form add ethers wnen digested with alcohol ; th 
tartaric add forms ethyl-tartaric add C*B.K)\C*R*JR)0*, 

The anhydrides of monobadc adds qnickly convert alcohol into the oonespondi 
ethers. (See Dictionary of Arts, Mant^acturea, and Mines,) 

Co mp ounds of Alcohol. Alcohol has a tcit strong affinity for Vfoter^ and mi: 
with it m all proportions. The mixture is attended with slight OTolation of heat, i 
also with contraction of yolume, which gradually increases till the mixtore oonts 
116 pts. water to 100 pts. alcohoL Strong alcohol absorbs moisture from the air. 
abstracts water &om the moist parts of the animal body, and coagulates them if t 
are of albuminous nature ; hence its use in the preservation of anatomical preparati( 
From the same cause it destroys life in the veins. 

Alcohol dissolves iodine and bromine ; also sulphur and phosphorus in small qi 
titles. Gases for the most part dissolve in alcohol more readily than in water. I 
Gasbs, ABSOBPnoir of.) Salts are, generally speaking, less soluble in alcohol tha 
water ; indeed many salts quite insoluble in alcohol are easily soluble in water ; 
the alkaline carbonates and sulphates. Chloride of mercury is, however, an excq 
to the eeneral rule, being more soluble in alcohol than in water. Inorganic oompoi 
sparingly soluble in water, are, for the most part, quite insoluble in alcohol ; so ukc 
are efflorescent compoundis. But all deliquescent salts, excepting carbonate and ] 
phate of potassium and a few others, are soluble in alcohol 

Since alcohol does not dissolve all compounds which are soluble in water, it fo 
that many substances, when dissolved in alcohol, do not exhibit the same rea< 
towards other substances aa when dissolved in water. Thus many adds, whei 
solved in absolute alcohol do not redden litmus or decompose carbonate of barii 
calcium, probably because the resulting caldum or barium salt would be insolu 
aloohoL 

Alcohol readily dissolves resins^ ethers^ essential oils, fats, alkaloids, many ot 
acids, and in general, all substances containing a larger proportion of hydrogen. 

AxooHOULTBs. Alcohol unites in definite proportion with several salts, fc 
crystallisable compounds, which however have but little stability and are alm( 
decomposed by water. These compounds were first obtained by Grraham. (Gri 
Phil. Map. Ann. iv. 265. 331 ; Einbrod^ Ann. Ch. Pharm. Ixv. 115 ; Cho- 
ibid. Ixxi. 241; Lewy, Compt. rend. xxi. 371; Bobiquet, J. Pharm. [3] 
161.) 

Nitrate of magnesium dissolved in alcohol forms, on cooling from a boiling be 
tion, a dystaUine mass like marsarin, containing 3CH'0.N0'Mg. 

Fused chloride of calcium dissmves in absolute alcohol, and the solution if aorr 
with ice, deposits aystals containing 2C'H'0.CaGL This compound subjected 
distillation yields nothing but carburetted hydrogen. If the aJoohol oontains i 
quantity (about 1 per cent.) of water, the solution yields by evaporation aomel 
ciystalline mass, sometimes a syrup, which driesup in vacuo to a wMte am* 
mass. Both the crystals and the syrup contain 20*^*0.30801 + H*0. 

Chlorids of zinc forms with absolute alcohol a crystalline compound wbicli < 
0*H"O.ZnC!l, and yidds when heated, alcohol, chloride of ethyl, hydrochloric f 
oxide of zinc, but no ether. 

JDichloride of tin and absolute alcohol, brought together in a vessel immei 
freezing mixture, unite immediatdy, and on evaporating the solution in vac 
sulphuric add and sticks of potash, crystals are formed containing 4G^S*OJ 
The crystals are very soluble in alcohol. They distil at 80^ almost without d 
sition (Lewy.) By cooling a mixture of 11*5 pts. of anhydrous alcohol, and 
of dichloride of tin in a fri^rific mixture, Bobiquet obtained a white powde 
when dissolved in alcohol, yielded by evaporation in vacuo over sulphuric acid 
containing 20«H»0.SnCl*. 

With &ryta, alcohol forms the compound 20*HH).BaK). which is obtained 
ing anhydrous baryta to absolute alcohol, filtering, and again adding baryta, 
alcoholic solution be then boiled, the compoimd separates in the &nn. of a 

Eredpitate which redissolves on cooling. Water added to the solution 'thn 
ydrate of barium. (Berthelot^ Ann. Ch. Phys. [3] xlvi. 222.) 
The following substances also form crystalline compounds with alcohol : seaqi 
of iron, protochloride of iron nitrate of caldom, and protochloride of m 
(Graham.) 



ALCOHOLOMETBY. 



81 



He alcohol in all these oompounds may be regarded as analogous to water of czys- 



ICfcltliBM. This name is frequently appHed to the organic baMB pro- 

dneed by the aiibstitation of alcohol-radicles for thenydrogen in ammonia; such, as 
eCfaylamme, pheoylamine^ &c. (See Axxnes.) 



r. (Alooamiirie,) The yalne of spizitnons liqnors depends 
iqMrn the qaantity of alcohol which they contain. This may be determined in yarions 
ways : Tis. by the specific ffrtmtj of the mixtore, by its boiling-point, by the tension of 
its npoor, by its rate of expansion, and by estimating the proportion of carbon contained 
in it b^^ combustioa with oxide of copper. But of all these methods, that which depends 
upon the density is almost always employed for practical pniposes, other methods being 
TCSoited to only when the mixtnre of alcohol and water is associated with foreign 
snhiitsingei^ sneh as sugar, or colonring matter, or salts, in sufficient quantity to produce 
a material alterstian ^ the density. 

To determine the amount of alcohol in a spirituous liquor by its density, it is neces- 
suy to know beforehuid the density corresponding to each particular proportion of 
ifeohol and water. If these liquids were capable of mixing without alteration of 
Tofamieh the spedSc gravity of each particular mixture might be calculated fiom the 
{Bopartkms of aloohd and water contained in it, and the known specific gravity of 
absohite aloohoL This however is not the case, the combination of alcohol and water 
being attended with a contraction of volume varying in amount with the temperatore. 
For this reason the specifie gravity of each mixture of alcohol and water must be 
determined by direct esperiment, and the results collected in tables. 

The importanoe of this object for the purposes of revenue induced the British 
gorenunent to employ Sir Charles Blagden to institute a very extensive and accurate 
sedes of expeanments on the density of spirit of various degrees of strength. The 
determiiiatioiDa^ which were made by Gilpin under Blagden's oireetion, were first pub- 
Ivfaed in 1790, afterwards twice repeated to obtain greater accuracy, and published in 
the Fhiloeophical Transactions for 1794. 

The ^eofie gravity of the mixtores of alcohol and water was determined by accu- 
latelv wpighJTig a quantity of the liquid in a flask having a long nairow neck, and 
filled with it up to a certain maik, the weight of an equal quantity of distilled water 
having been pccviously ascertained. In this manner, the spetnfic gravity of 40 mixtures 
was detennined, each at 15 difierent temperatures. The standard alcohol used to mix- 
when the vater was not absolute, but had a specific gravity of 0*82514; for oonve- 
nienee however, it was supposed to be a 0*826, a corresponding deduction being 
made fi»m aU the numbers in the table. 



Tabls I. — Showing the Specific Gratfiiy of various mhhires of Jlcohol (of Specifie 
Gratiiy 82500 ai 60^ Fakr,) and Water at different Tpmperatwres^ the Specific Gra- 
tis of water at 60^ Fakr, hkng 100000. 



- 


Tbe 
pore 


100 

craiotof 

spirit to 

5 gr. of 

water. 


100 

graintof 

spirit to 

lOgr.of 

water. 


100 

grains of 

•pfrit to 

\l gr. of 

water. 


100 

grains of 

spirit to 

lOgr. of 

water. 


100 

grains of 

spirit to 

S5gr.of 

water. 


100 

grains of 

spirit to 

30gr. of 

water. 


100 
grains of 
spirit to 
3ftgr.of 

water. 


100 

grains of 

spirit to 

40gr.of 

Water. 


100 

grains of 

spirit to 

45gr.or 

water. 


100, 

grains of 

spirit to 

Mgr.of 

water. 


SOF. 


-83896 


-84995 


•85957 


•86826 


•87685 


88282 


■88921 


•89611 


•90064 


90568 


•91023 


U 


83672 


84769 


85729 


86587 


87357 


88069 


88701 


89294 


89839 


90346 


90811 


40 


83445 


84539 


85507 


86361 


87184 


87838 


88481 


89073 


89617 


90127 


90696 


45 


83214 


84310 


86277 


86131 


86905 


87613 


88266 


88849 


89396 


89909 


90380 


M 


82977 


84076 


86042 


85902 


86676 


87384 


88030 


88626 


89174 


89684 


90160 


55 


82736 


83834 


84802 


85664 


86441 


87160 


87796 


88393 


88945 


89468 


89933 


60 


82500 


83599 


84568 


86430 


86208 


86918 


87669 


88169 


88720 


89232 


89707 


65 


82262 


83362 


84334 


85193 


85976 


86686 


87337 


87938 


88490 


89006 


89479 


70 


82023 


83124 


84092 


84961 


86736 


86461 


87106 


87706 


88264 


88773 


89262 


75 


81780 


82878 


83851 


84710 


86496 


86212 


86864 


87466 


88018 


88638 


89018 


80 


81530 


82631 


83603 


84467 


86248 


86966 


86622 


87228 


87776 


88301 


88781 


85 


81291 


82396 


83371 


84243 


86036 


86757 


86411 


87021 


87590 


88120 


88609 


90 


81044 


S2150 


83126 


84001 


84797 


86518 


86172 


86787 


87360 


87889 


88376 


95 


80794 


81900 


82877 


83753 


84650 


86272 


86928 


86642 


87114 


87654 


88146 


100 


80648 


81667 82639 


83513 84038 


86031 


86688 


86302 


86879 


87421 


87915 



Vol. L 



O 



82 



ALCOHOLOMETEY. 



Tablb I. (continued). 



Heat 


100 

grains of 

spirit to 

55gr.of 

water. 


100 

grains of 

tpirit to 

GOgr. of 

water. 


100 

graint of 

spirit to 

65gr. of 

water. 


100 

grains of 

spirit to 

70 gr. of 

water. 


100 
grains of 
spirit to 
75 gr. of 

water. 


100 

grains of 

spirit to 

80gr. of 

water. 


100 

grains of 

spirit to 

86gr.of 

water. 


100 

graint of 

tpirit to 

90gr.of 

wateir* 


100 

graint of 

tpirit Co 

95gr.of 

water. 


10 

grain 

•plrh 

lOOgr 

wan 


30° F. 


•91449 


•91847 


•92217 


•92563 


•92889 


•93191 


•98474 


•93741 


•93991 


•942 


35 


91241 


91640 


92009 


92355 


92680 


92986 


93274 


93541 


98790 


940 


40 


91026 


91428 


91799 


92151 


92476 


92783 


93072 


93341 


93592 


938 


46 


90812 


91211 


91584 


91937 


92264' 


92570 


92859 


93131 


93382 


986 


50 


90596 


90997 


91370 


91723 


92051 


92358 


92647 


92919 


98177 


934 


56 


90367 


90768 


91144 


91502 


91837 


92145 


92436 


92707 


92963 


982 


60 


90144 


90549 


90927 


91287 


91622 


91933 


92225 


92499 


92758 


930 


65 


89920 


90328 


90707 


91066 


91400 


91715 


92010 


92283 


92546 


927 


70 


89695 


90104 


90484 


90847 


91181 


91493 


91793 


92069 


92333 


925 


75 


89464 


89872 


90252 


90617 


90952 


91270 


91569 


91849 


92111 


923 


80 


89225 


89639 


90021 


90385 


90723 


91046 


91340 


91622 


91891 


921 


85 


89043 


89460 


89843 


90209 


90558 


90882 


91186 


91465 


91729 


919 


90 


88817 


89230 


89617 


89988 


90342 


90668 


90967 


91248 


91511 


917 


95 


88588 


89008 


89390 


89763 


90119 


90443 


90747 


91029 


91290 


915 


100 


88357 


88769 


89158 


89536 


89889 


90215 


90522 


90805 


91066 


913 



Heat. 


96 

grains of 

spirit to 

100 gr. of 

water. 


90 

grains of 

spirit to 

100 gr. of 

water. 


86 

graint of 

tpirit to 

100 gr. of 

water. 


80 

graina of 

spirit to 

lOOgr.of 

water. 


75 

graint of 

spirit to 

100 gr. of 

water. 


70 

graint of 

spirit to 

lOOgr.of 

water. 


66 

graint of 

spirit to 

100 gr. of 

water. 


60 

graina of 

spirit to 

lOOgr.of 

water. 


66 

graint of 

tpirit to 

lOOgr.of 

water. 


60 

grain 

tpirit 

100 gi 

wat 


30° F. 


•94447 


•94675 


•94920 


•95173 


•95429 


•95681 


-95944 


•96209 


•96470 


•967 


35 


94249 


94484 


94734 


94988 


95246 


95502 


95772 


96048 


96315 


965 


40 


94058 


94295 


94547 


94802 


95060 


95328 


95602 


95879 


96159 


964 


45 


93860 


94096 


94348 


94605 


94871 


95143 


95423 


95703 


95993 


962 


50 


93658 


93897 


94149 


94414 


94683 


94958 


95243 


95534 


95831 


961 


66 


93452 


93696 


93948 


94213 


94486 


94767 


95057 


95357 


95662 


959 


60 


93247 


93493 


93749 


94018 


94296 


94579 


94876 


95181 


95493 


958 


65 


93040 


93285 


93546 


93822 


94099 


94388 


94689 


95000 


95318 


956 


70 


92829 


93076 


93337 


93616 


93898 


94193 


94500 


94813 


95139 


954 


75 


92613 


92865 


93132 


93413 


93695 


93989 


94301 


94623 


94957 


952 


80 


92393 


92646 


92917 


93201 


93488 


93785 


94102 


94431 


94768 


951 



Heat. 


46 

grains of 

spirit to 

100 gr. of 

water. 


40 

grains of 

spirit to 

lOOgr.of 

water. 


65 

graint of 

spirit to 

100 gr. of 

water. 


30 

grains of 

spirit to 

lOOgr.of 

water. 


95 

graint of 

spirit to 

lOOgr.of 

water. 


90 

grains of 

spirit to 

lOOgr.of 

water. 


16 

grains of 

spirit to 

100 gr. of 

water. 


10 

graint of 

tpirit to 

Mfogr.of 

water. 


6 
graint 
tpirit 
100 gr. 
watei 


30° F. 


•96967 


•97200 


•97418 


•97635 


•97860 


98108 


-98412 


•98814 


•9933 


35 


96840 


97086 


97319 


97556 


97801 


98076 


98397 


98804 


9934 


40 


96706 


96967 


97220 


97472 


97737 


98033 


98373 


98795 


9934 


45 


96563 


96840 


97110 


97384 


97666 


97980 


98338 


98774 


9933 


50 


96420 


96708 


96995 


97284 


97589 


97920 


98293 


98745 


9931 


66 


96272 


96575 


96877 


97181 


97500 


97847 


98239 


98702 


9928 


60 


96122 


96437 


96752 


97074 


97410 


97771 


98176 


98654 


9924 


65 


95962 


96288 


96620 


96959 


97309 


97688 


98106 


98594 


9919 


70 


95802 


96143 


96484 


96836 


97203 


97596 


98028 


98527 


9913 


75 


95638 


95987 


96344 


96708 


97086 


97495 


97943 


98454 


9906 


80 


95467 


95826 


96192 


96568 


96963 


97385 


97845 


98367 


9899 



ALCOHOLOMETRY. 83 

Gt^Ein's tables do not giTO diiectlj the quantity of absolute aloohol contained in spirit 
d aaj giTen densitf . In this Tespect, however, they have been oompleted by the 
ezpcnmenta of Tralles, who in 1811 (Gilbert's Annalen, zzzviii 386), determined 
the spedile gravity of alcohol, dehydrated as completely as possible by means of 
fhlorioe of calcimn, and likewise the strength of Gilpin's standard spint, having a 
epeciAe gravity of 0*825 at 60^ F. He found that the specific gravity of absolute 
aieohol at 60^ F. compared with that of water at its maximum density is 0*7939 (or 
07M6 compared with water at 60^) and that GHlpin's standard spirit contains in 100 
pflitB by weight, 89'2 parts of anhydrous alcohol, and 10*8 parts of water. Proceeding 
upoB ^eae d^ta, Tralles calculated the proportions of absolute alcohol and water con- 
tained in Bfixit of various densities ; the results are given in Table 11. p. 83. 

The prcNDortions of aloohol in spirit of wine may be expressed either by weight or by 
Tolnme. The ibnner mode of expression is by fiu the simpler and more definite, 
becane tbe pcoportion b^ weight is independent of the temperature, whereas the 
pnpofftioD by Tolume varies with the temperature, being affected by the different 
rates of expansion of aloohol and water. For scientific purposes, therefore, the 
Btzeogth of spizit is always expressed in percentage by weight In commerce, 
on t£s eontruT, the method by volume is always adopted, spirit being generally 
boQg^t and sold by measure, not by weight. It becomes theiH?fbre necessary to know 
bow to caleolate the composition 1^ volume from the composition by weight and the 
o b stti ied mpedRc gravity. 

Let 8 be the spedfle gravity of the spirit (mixture of alcohol and water) : a the 
qoanftiity of aloohol in 100 puts by weighty and tiierefbre 100 - a the quantity of 
water; Pthe volume of the sjpit referred to a unit of volume, such that a quantity 
of water which fills it is the unit of weight (s. y. if the weight is eiq»rfossed in grammes, 
V is measored in cubic centimetres) then : 

100 « r . 8 

If thai, tiie specific sravity of anhydrous alcohol at the observed temperature com- 
pared with water at l£e same temperature be s, the volumes of alcohol and water con- 
tained in the spirit are : 

-• and 100 — a 

and oonsequflntly, the p rop o r t ions of alcohol and water in 100 volumes of the spirit 
axe: 

« 100 8 . i, , 1. , 

- • -fs- ■> 0. •» volumes of alcohol. 

and: (100— a) ■ -^ ■- (100 — a) i9 volumes of water. 

For example : fiom the table p. 86 it appears that spirit containing 77 '09 per cent of 
alcohol by weight has at 60® F. a n>. gr. of 0*8555, merred to water at the same tem- 
perature^ and the specific gravity of absolute alcohol referred to the same standard is 
0*7946 : henoe the percentage of alcohol by volume is : 

8555 
77-09 • j^ - 83*00 

and the peroentage by rolume of water is : 

(100 — 77-00) . 0-8555 - 22*91 . 0*8555 » 20*60 

the whole beii^ measured at 60® F. 

The volumes of aloohol and water thus obtained amount together to more than 100, 
in the preceding example to 103*60 ; and acooidingly, if 83*00 measures of aloohol be 
mixed with 20*60 measures of water, both at 60® F., the mixture, after it has cooled to 
60® F., win fill exactly 100 measures, and the spirit thus produced will contain 
83 volumes per cent of alcohol. (Bespecting the contraction which takes place on 
mixing aloohol and water in various proportionSi see Eudberg, Pogg. Ann. xiii. 196 ; 
also ICopp» ibid, liii 356.) 

When tne volume per cent in a mixture, of alcohol find water is given, the weight 
per cent is found from the equation : 

a.r-5 

This, aeeording to the table (p. 85)spirit containing 68 volumes per cent of alcohol 
has a ^ gr. of 0*8949 at 60® F. Hence the weight per cent of alcohol is : 

7946 

**-**• 8949 "• ^^'^ 
thai is to say : 100 lbs. of this spirit oontain 69*38 lbs. of alcohol and 39*62 lbs. of water. 

2 



84 



ALCOHOLOMETRY. 



The specific gravity of aqneous alcohol may be determined by any of the ordinary 
methods ; either by weighing in a specific gravity bottle, or by means of the hydrometer 
(See SpBocno Q&^vrrr and Htdbombteb) and thence the percentage of anhydrons 
alcohol by weight and by volume may be determined by means of the preoedins formulas 
and the tables to be given hereafter. To facilitate these determinations, hydrometeirB 
are constracted with scales marking directly the percentage of alcohol by volume, and 
sometimes also by weight, of the spirit in whida they are immersed. Such instni- 
ments are called AiJOOHOLOicBTBBa. Three of them are in nse, vi& the alcoholometer 
of Tralles, which gives the percentage volume for the temperature of 60^ F. 
» 12} B. a 15| C. ; Gkiy-Lussac*s alcoholometer, which likewise indicates percentage 
by volume at 15^ C.; and Meissner^s, which gives percentages both by wei^t 
and volume, the latter for the temperature of 14^ B i- 17*5^ 0. 

As the scales of these instruments are constructed for different temperatures, they 
cannot be expected to agree exactly ; but the differences arising from, this cause are 
trifling. Greater discrepancies however arise from the different experimental data 
upon which the scales have been constructed ; that of Tralles beinff founded on the 
exact and extensive observations of Gilpin, and Meissner^s on experiments of his own. 
Gay-Lussac has not stated on what experimental data his observations are founded, 
but his numbers agree very nearly with those of Tralles, the differences never exceed- 
ing ^ per cent for the same specific gravity. 

The following table gives the percentages of anhydrous alcohol both by weight and 
volume of mixtures of alcohol and water, according to their specific gravity as determined 
hj Tralles from the observations of Gtilpin ; also the specific gravities as detonnined by 
Chiy-Lussac They are deduced from Tralles' numbers by multiplying by 1*0009. 
The corresponding indications of the hydrometers of Beck, Baume, and Cartier, are 



likewise added. 
















Tablb 11. 








Volumac 

per cent. 

accord- 


WeightB per cent. 


Specl6c grsTftlei 
according to Gilpin 


Spedflc grarities 
•coording to Gay- 


Degreeior 


Degreeiof 
Baom^'B. 
Hydro- 
mety. 


Degrees of 
Cartier*! 
Hydro- 
meter. 


inf to 
Trdlei. 




At 60° F.alftf C. 


Luuac at W^ C. 


droroeter. 








1-0000 


1-0000 


0-0 


10 


11 


1 


0-80 


0-9986 


— 


^- 


— 


_ 


2 


1-60 


9970 


—. 


— 


... 


^_ 


3 


2*40 


9966 


— 


— 


>— 


_ 


4 


3-20 


9942 


— . 


1-0 


_ 


_ 


6 


4-00 


9928 


— . 


1-2 


11 


12 


6 


4-81 


9916 


.— 


1-4 


-.— 


— 


7 


5-62 


9902 


.^ 


1-6 


.— 


— 


8 


6-43 


0890 


-~ 


1-9 


— 


... 


9 


7-24 


9878 


.^ 


21 


-i^ 


_ 


10 


8-06 


9866 


1-0000 


2-3 


12 


-. 


11 


8-87 


9864 


— 


2-6 


._ 


_ 


12 


9-69 


9844 


— 


2-7 




13 


13 


10-61 


9832 


-^ 


2-9 


— 


.i_ 


14 


11-33 


9821 


— 


8-1 


^— 


^^ 


15 


12-16 


9811 


_ 


8-3 


.— 


.... 


16 


12-98 


9800 


— 


8-6 


13 


... 


17 


13-80 


9790 


._ 


8-6 


_ 


«_ 


18 


14-63 


9780 


..^ 


3*8 


.. 


, - 


19 


16-46 


9770 


— 


4-0 


— 


14 


20 


16-28 


9760 


„_„ 


4-2 


^^^ 


_ 


21 


1711 


9760 


.-. 


4-4 


_— 


... 


22 


17-96 


9740 


^ 


4-6 


m^ 


.... 


23 


18-78 


9729 


^■^* 


4-8 


14 


^_ 


24 


19-62 


9719 


.— 


4*9 


_- 


.^ 


25 


20-46 


9709 


~. 


61 


.- 


_ 


26 


21-30 


9698 


..- 


6-3 


— 


16 


27 


2214 


9688 


_ 


66 


_ 


^^ 


28 


22-99 


9677 


— . 


6-7 


m.^ 


... 


29 


23-84 


9666 


» 


6-9 


16 


^.. 


30 


24-69 


9666 


0-9666 


6-1 


.. 


.... 


31 


26-66 


9643 


m^ 


6-4 


._ 


... 


32 


26-41 


9631 


- 


6-6 


— 


— 



ALCOHOLOMETRY. 



85 



Table U, (eonHnued), 



JToiiaMi 
urecBC 




SpecUfe GniTltiei 


Soeciflc Oravitiei 


Degreeeof 
Bnck't 


Degrees of 


Degreeeof 


eOBOCQ« 


Wcighu per cent. 


aeeording to Gilpin 


according to Gat- 


Cartler'ft 


Baumi't 


iBKtO 




■t60»F.Bl9|C. 


Lussac at lb'* C 


Hydro* 
meter. 


aydrom 
meter. 


Hydro- 
meter. 


33 


27-27 


0-9618 


0-9656 


6-8 


16 


16 


S4 


2813 


9605 


_ 


7-0 


16 




86 


28-99 


9592 


9595 


7-2 


...• 


- 


M 


29*86 


9579 


^^ 


7-5 


.i_ 


^^^ 


37 


30-74 


9565 


•^ 


77 


^^ 


, ^ 


38 


81-62 


9660 


_ 


8-0 


1 


17 


39 


82*50 


9536 


— 


§-3 


17 




40 


33-39 


9619 


9623 


8-6 


^mmm 




41 


84-28 


9603 


.1. 


8-0 


^_ 




43 


36-18 


9487 


-^ 


9-2 


... 


18 


43 


86-08 


9470 


_ 


9-5 


18 




44 


86-99 


9452 


_ 


9*8 


..^ 


^■^ 


46 


37-90 


9435 


9440 


10-2 


... 


^i^W 


46 


38-82 


9417 


... 


10-6 


19 


19 


47 


39-76 


9399 


^^ 


10-9 


... 




43 


40-66 


9381 • 


mm^ 


11-2 


_ 


•_ 


49 


41-50 


9362 


— 


11-6 


— 


— 


60 


42-62 


9343 


9348 


11-9 


20 


20 


61 


48-47 


9323 


... 


12-3 






62 


44-42 


9803 


«. 


127 


.._ 


^^^ 


63 


45-36 


9283 


^^■ 


131 


21 


^_^ 


64 


46-32 


9262 


— 


13-5 




21 


66 


47-29 


9242 


9248 


18-9 


_ 




66 


48-26 


9221 


.^ 


14*3 


22 


_^ 


67 


49-23 


9200 


.^ 


14*8 




22 


68 


50-21 


9178 


^_ 


15-2 


23 




69 


51-20 


9156 


— 


15-6 




— 


60 


52-20 


9184 


9141 


16-1 




23 


61 


53-20 


9112 


.M 


16-5 


24 




62 


54-21 


9090 


m^ 


170 




M-H* 


63 


56-21 


9067 


.^ 


17-5 


25 


24 


64 


66*22 


9044 


9141 


18-0 


25 


24 


66 


57-24 


9021 


9027 


18-4 




25 


66 


59-27 


8997 


^^ 


18-9 


26 


._ 


67 


59-32 


8973 


m.^ 


19-4 


..^ 


... 


68 


60-38 


8949 


_ 


200 


27 


26 


69 


61-42 


8925 


— 


20-5 




— 


70 


62-50 


8900 


8907 


210 


28 


27 


71 


63-58 


8875 


_ 


21-5 






72 


64-66 


8850 


»i» 


22-1 


^.^ 


_ 


73 


65-74 


8824 


_ 


22-6 


29 


28 


74 


66-83 


8799 


._ 


23-2 


^^^^ 




76 


67-93 


8773 


8799 


23-8 


80 


29 


76 


69-05 


8747 


.. 


24-4 






77 


7018 


8720 


•_ 


260 


81 


30 


78 


71-81 


8698 


•. 


26-6 






79 


72-45 


8664 


— 


26-2 


32 


— 


80 


73-69 


8639 


8645 


26-8 


_ ^\ 81 


81 


7474 


8611 


_ 


27-4 


83 


w»M 


82 


75-91 


8683 


... 


28-0 


34 


32 


83 


7700 


8665 


... 


287 






84 


78-29 


8526 


^_ 


29-4 


85 


33 


86 


79-50 


8496 


8602 


30-1 






86 


8071 


8466 


— 


80*8 


36 


84 



o 8 



86 



ALCOHOLOMETRY. 



Tablb IL {continued). 



Volumm 
percent 




Specific Gravitlef 


Specific GraTitlei 


DegreMof 


Degrees of 
Bainn6*t 
Hydro- 
meter. 


1 

D^greaof 

Cartier'* 

Hydro- 

meter* 


accord- 
ing to 
Traltei. 


WelghU pOT cent 


according to Oil- 
pin at 60o«l5|oa 


itccording to GmA 
Luuac at I5<> C. 


Beck's Hy- 
drometer 


87 


81*94 


0-8436 


0-8602 


81*6 


87 


86 


88 


83*19 


8406 


— 


82*2 


... 


— > 


89 


84-46 


8373 


— 


33*0 


88 


36 


90 


86-76 


8340 


8346 


83*8 


- 


,^_ 


91 


87-09 


8306 


— 


34*7 


39 


37 


92 


88-37 


8272 


— 


86-6 


40 


38 


93 


89-71 


8237 


— 


36-4 


41 


— 


94 


91-07 


8201 


— 


37*3 


~. 


39 


95 


92-46 


8164 


8168 


38-2 


42 


40 


96 


93-89 


8126 


— - 


39-2 


48 


— 


97 


96-34 


8084 


— . 


40-3 


44 


41 


98 


96-84 


8041 


— 


41-6 


46 


42 


99 


98*39 


7996 


— 


42-7 


46 


43 


100 


10000 


7946 


7947 

• 


43-9 


47 


^— 



The Tise of thiB table may be extended to intermediate numbers by interpolation. 
Thna, if it be required to find the composition by yolume of a miztore of 60 lbs. of 
anhydroTis alcohol and 60 lbs. of water, we find from the table that : 

49'23 p. e. hj weight corresponds to 67 p. c bj yolume 
and: 60* 2 „ ,. 68 

and 



M 



t» 



difference 



0-98 



Hence, to find the fraction which must be added to the number 67 togiye the percent- 
age required, we haye the proportion : 

0-98 : (60 - 49-23) » 1 : « 
77 



which giyes: 



iii-*»» 



Whence it appears that 100 yolumes (measured at 60^ F.} of a spirit containing equal 
weights of alcohol and water contain 67*8 yolumes of alconol, also at 60^. 

Again, let it be required to find the composition of a spirit haying at 60^ Fahr. the 
specific grayitj 0*8966, compared with water at the same temperature; this number is 
intermediate between the numbers 8949 and 8973 in the third column of the table, 
which correspond to the yolume per centages 67 and 68 ; hence the proportion: 

8973 - 8949 : 8973 - 8966 » 1 : x 



which giyes 



*"24"' * 



that is to say, 100 measures of spirit of sp. 0*8966 at 60° Fahr. contain 671 measures of 
anhydrous alcohol. 

Meissner^s results are giyen in his "Araometriein ihrer Anwendung auf Chemie und 
Tecknik," Wien, 1816. Th. ii 27. They differ somewhat from the preceding. 

TjkBLB IL a. — Spedfie Gravity {according to Meistner) of Hydrated Jkohol containing 

in 100 parts : 



Alcohol 


By Weight. 


By Volume. 


Pai|^. 


At«l°C. 


AtlT-S^C. 


At 900 C. 


At 17*S*» C. 


F 

100 


0-791 


0-793 


0*791 


0*798 


96 


0-806 


0-801 


0*809 


0*811 


90 


0-818 


0-822 


0-824 


0*828 


86 


0-831 


0-836 


0*839 


0*843 


80 


0-843 


0*847 


0*864 


0*867 


76 


0-866 


0-869 


0*867 


0*869 


70 


0-868 


0-870 


0*880 


0*883 



ALCOHOLOMETEY. 



Bj Weight. 




Tabui n. a. (oontmued). 



At 17-6' C. 



0*883 
0-896 
0-906 

0-917 
0*928 
0-939 
0-948 
0-968 
0-966 
0-971 
0-977 
0-983 
0-991 
1*000 



By Volitmo. 



At 80° C. 



0-893 
0*906 
0-917 
0-928 
0-938 
0-947 
0-966 
0*963 
0-969 
0-976 
0-981 
0-987 
0-998 
1-000 



At I7-6' C. 



0-896 
0-907 
0*919 
0-930 
0*940 
0*949 
0-968 
0-964 
0-WO 
0*976 
0-980 
0-986 
0-993 
1-000 



>591% t^^ 



JlsiU it given hy Fowne$ (Haxraal of Chemistry, 3zd 
€fraoUie$ being taken at 16-6^ C. or 60 Falir. 



nrcmtagt 
bjr Wright. 




0-098 X 



o-eo-4'3r 

0-9930 
0-091'* 

o- 




0-08S4 
0-9809 

0-984:1 

0-981i( 

0-978d 
0-9778 

0-9728 

0-97l« 
O-07O4 
0-9891 
O-0«78 

O-90^^ 
0-98^5 
0-9638 

0-98S3 
O-9099 

0'9^^^ 
0-9^7B 



Ptfomtage 
by weight. 



Spedfle OrsTitj. 



34 


0-9611 


36 


0-9490 


36 


0-9470 


87 


0-9462 


38 


0*9434 


89 


0-9416 


40 


0-9396 


41 


0*9376 


42 


0-9366 


43 


0-9336 


44 


0*9314 


46 


0-9292 


46 


0-9270 


47 


0-9249 


48 


0*9228 


49 


0-9206 


60 


0*9184 


61 


0*9160 


62 


0-9136 


63 


0-9113 


64 


0*9090 


66 


0*9069 


66 


0-9047 


67 


0-9026 


68 


0-9001 


69 


0*8979 


60 


p-8966 


61 


0*8932 


62 


0*8908 


63 


0*8886 


64 


0*8863 


66 


0*8840 


66 


0*8816 


67 


0-8793 



Pereentage 
by weight. 



68 
69 
70 
71 
72 
73 
74 
76 
76 

77 

78 

79 

80 

81 

82 

83 

84 

86 

86 

87 

88 

89 

90 

91 

92 

93 

94 

96 

96 



Spedfle Grai 



0*8769 
0*8746 
0-8721 
0-8696 
0-8672 
0-8649 
0*8626 
0*8608 
0*8681 
0*8667 
0-8633 
0-8608 
0-8483 
0-8468 
0-8484 
0*840S 
0*8382 
0*8367 
0-833] 
0*830£ 

0-827S 
0-8264 
0-822e 
0-819{ 
0-8175 
0-814( 
0*81 li 
0-808< 
0*806] 



97 


0-8031 


98 


0-800] 


99 


0-7961 


100 


0*7931 



e 4 



88 



ALCOHOLOMETRY. 



It 18 often necessa^ to take tlie specific graTitj of spirit at a temperatoze different 
from the standard. Li tiiat case, the percentage of alcohol may be determined hy means 
of the two following tables, giyen by Tralles. 



Tablb m. — Bpeeifio Chravity of Spirit of different gtrengths at Tsm^peraturei fn>m 
Z(P Fahr, to IWP Fahr. that of Water at 39'83 Fakr. being - 10000. 



Quantity of 
Alcohol at 


Temperaiuret (Fahr.) 

• 


60OFahr. 
inperceau 


• 






40°. 45*>. 
























ages by. 


80°. 


88°. 


50°. 


55<». 


60°. 


65°. 


70°. 


75°. 


80°. 


85°. 


90P. 


95«. 


100°. 


Volume. 



































SISWB 


iOOOO 


10000 


10000 


sftISM 


9996 


9991 


9686 


9980 


9974 
990f 


9967 




9951 


9941 


9991 


6 


9988 


9929 


9929 


9928 


9926 


9998 


9919 


9914 


9908 


9894 


9816 


9877 


WJDO 


9«57 


10 


9879 


9878 


9871 


9869 


oautt 

iWOD 


9069 


9857 


9851 


9844 


9837 


9898 


9820 


9610 


9800 


9789 


1ft 


9887 


98S5 


9693 


9819 


9814 


9808 


9809 


9795 


9787 


9777 


9768 


9758 


9747 


9785 


9788 


20 


9790 


9786 


9780 


9n4 


9767 


9759 


9751 


9749 


9739 


9791 


9710 


9696 


9685 


9679 


9658 


95 


9756 


9748 


9789 


9781 


9791 


9710 


9700 


9689 


9G76 


9664 


9650 


9687 


9699 


9607 


9S9I 


80 


9719 


9706 


9697 


9685 


9679 


9659 


9646 


9689 


9618 


9608 


9587 


9571 


9555 


9588 


9591 


85 


9678 


9668 


9644 


9699 


9614 


9599 


9583 


9566 


9550 


9538 


9515 


9497 


9479 


9461 


9449 


40 


9613 


9597 


9560 


9569 


9545 


9598 


9510 


9499 


9478 


9454 


9435 


9416 


9896 


9876 


9366 


45 


9589 


9581 


9508 


9484 


9466 


9446 


94^ 


9407 


9887 


9367 


9347 


9896 


9805 


99»4 


9268 


60 


9458 


9454 


9415 


9895 


9875 


9855 


9335 


9814 


9998 


9979 


9951 


9929 


9807 


9185 


9169 


55 


9358 


9888 


9318 


9997 


9976 


9955 


9284 


9919 


9191 


9169 


9147 


9195 


9102 


9079 


9056 


60 


99IV8 


9988 


9219 


9191 


9169 


9148 


9126 


9104 


9089 


9069 


9086 


9018 


8990 


8867 


894} 


65 


9148 


9199 


9101 


9080 


9058 


9085 


9018 


8091 


B96B 


8045 


8991 


81198 


8875 


8851 


8fl96 


70 


9095 


9004 


8889 


8960 


8987 


8914 


8892 


8869 


8846 


8893 


8799 


8775 


8751 


8727 


8709 


78 


8900 


8878 


8856 


8888 


8811 


878S 


8765 


R749 


8719 


8695 


8671 


8646 


8699 


8596 


8978 


80 


8768 


8746 


8798 


8701 


8678 


8654 


8631 


8608 


8584 


8660 


8585 


8511 


8487 


8469 


9487 


85 


8fi87 


8604 


8581 


8558 


8536 


8511 


8488 18464 


8440 


8416 


8899 


8367 


8848 


8318 


8998 


90 


8472 


8449 


8496 


849618380 


8356 1 8339 | 8308 1 8984 1 8960 


8235 ' 8211 1 8186 I 8161 


8186 



Tablb TY.-^Volumee of Alcohol of Specific Gravity 7939 (UfiO^ Fahr, which toould be 
contained at 60^ Fahr, in 100 meaeures of Spirit exhibiting at the several TemperO' 
turea (Fahr.) stated ai the heads of the columns the following apparent Specific Gra- 
vities as determined trith a Glass vessel or instrument. 



Volumei 

of 
Alcohol. 


80°. 


iffi. 


40°. 


45°. 


50°. 


65°. 


60°. 


66°. 


70°. 


75°. 


80°. 


85'». 




5 

. 10 

15 

90 


9994 
9924 
9868 
9893 
9786 


9997 
9996 
9869 
9829 
9789 


9991/ 

9929 
98G8 
9890 
9777 


QOQB 

9H96 
9867 
9817 
9779 


9997 
9925 
9865 
9613 
9766 


9994 
9922 
9861 
9807 
9769 


9991 
9919 
9857 
9602 
9751 


9987 
9915 
9859 
9796 
0743 


9981 
9909 
9M45 
9788 
9785 


9976 
9908 

9889 
9779 
9793 


9970 
9897 
9681 
9771 
9713 


9969 
9889 
9693 
9761 
9701 


95 
80 
85 
40 
45 


9759 
9715 
9668 
9609 
9585 


9745 
9705 
9655 
9594 
9518 


9787 
9694 
9641 
9577 
9500 


9729 
9688 
9697 
9560 
9489 


9720 
9671 
8612 
9544 
9464 


9709 
9668 
9598 
9527 
9445 


9700 
9546 
9583 
9610 
9427 


9600 
9688 
9567 
9493 
9406 


9678 
9619 
9551 
9474 
9888 


9666 
9605 
9535 
9466 
9869 


9668 

9690 
9518 
9438 
9360 


9640 
9574 
9500 
9419 
9399 


50 
55 
60 
65 
70 


9449 
9854 

9949 
9140 
9091 


9481 
9385 
9280 
9120 
9001 


9418 
9816 
9210 
9W9 
8960 


9383 
9295 
9189 
9078 
8956 


9374 
9275 
9168 
9056 
8986 


9354 
9254 
9147 
9034 
8918 


9335 
9284 
9126 
9013 
8899 


9815 
9913 
9105 
8999 
8870 


9994 
9199 
9088 

MMQ 
WUSr 

8847 


9274 
9171 
9061 
8947 
8825 


9958 
9160 
9089 
8924 
8801 


i989 
9198 
9016 
8901 
8778 


75 
80 
85 
90 


8896 
8764 
8698 
8469 


8875 
8743 
8601 
8446 


8854 
8721 
8579 
8493 


8839 

8556 
8401 


8810 
8676 
8583 
8379 


8787 
8658 

8510 
8855 


8765 
8681 
8488 
8339 


8748 
8609 

8465 
8809 


8790 
8585 
8441 
8985 


8697 
8569 
8468 
8969 


8678 
8588 

8894 
8988 


8649 
8514 
8370 
8914 








B 


^■Ducn 


ons roi 


1 A Br A 


US iNtnoMBirr. 




To be 


dedocU 


id from 


the Spc 


clflc Gr 


aTttles. 


~\ 


To be added to the Spedflc Orartt 


let. 




-5 1 


-4 1 


-8 1 


-« 1 


1 -« 


1 +1 1 +9 1 +9 1 +8 1 


•4-4 



ALCOHOLOMETRY. 89 

Ib UUe HL the spea&c g;raTity of the spirit is supposed to be compared with that 
cfwMtet at the w»«-"'Tniiyn density, and to be conected for the ez^aiision of the yessel 
or iBstrament with which the determination is made. These densities maj be lednced 
to those compared with water at 60^ F. (as in Table II.), by multiplying them all by 

1-0009. 
To find by means of this table the strenfi;th of a spirit, when either the specific 

gsrity or the temperatnre is not given ezac^ as in the tables, we proceed by interpo- 
tion as in the ealcnlations connected with Table II. (p. 85.) Bat of neither tempe- 
ntnre nor specific graTity is exactly given in the table, the (alcolation is made as in 
the IbDowing example. Let it be required to find the strength of a spirit of sp. gr. 
0-9321 at 77*^ F. 

Spedflc Gnvity _.^ 

ftr cut. of Alcohol. ae75op. at8(PF. Dilferanoe. 

45 9867 9347 20 

50 9272 9251 21 

Biflcrence T ""95 96 

Hence the sp. gr. for 77^ F., and for : 

OA 

45 p. c alcohol is 9367-2 x -^ - 9359 

o 

50 „ 9272-2 X ^ - 9263-6 





Difference - 95*4 

Galling this difiTerenoe 95, it follows that to each 1 per cent of alcohol there corre- 
^xmds at 77^ F. a difference of 19 in the specific graTity, and consequently the Tolume 
per eentk of aloohd corresponding to the specific grayity 9321 is 

^, 9359 - 9321 .. ^ 38 , ^ , „ ^ 
45 + jg 45 + ~ — 47 YOL p. c 

lliis resnlt shows that the spirit in question, when cooled down to the normal tern- 
peratme of 60® F. contains in 100 measures, 47 measures of absolute alcohol; this is 
not, howerer, the actual proportion by Tolume at 77°, because alcohol and water ex- 
paod at different rates. 

Table TV. exhibits in the same manner as Table III. th^ strength of spirit according 
to its specific gravity, but on the supposition that the specific gravity is determinea 
with a glass instrument, and is not corrected for the expansion of tiie glass : hence 
the expression " apparent specific gravity." 

If the specific gravity of a sample of spirit has been determined at one temperat ur e 
and its volume measured at another, the amount of alcohol in it may be calcmated as 
in the following example : 350 quarts of spirit are measured out at 75° F., and the 
nedfic gravity determined with a glass instrument at 65° F. is 0*8609. By Table lY. 
the stzengtii of this spirit is 80 per cent, that is to say, 100 volimies of it measured at 
60^ F. contain 80 voL of alcohoL By Table III. the specific gravities of spirit of 80° 
percent forthe temperatures 60° and 75° are 8631 and 8560. Consequently the volumes 
of a given weight of the spirit at 60^ and 75° are as 8560 : 8681, and therefore the 350 

quarts of nnrit would, if cooled to 60°, measure 350 x ~--t <■ 347*12 quarts; and this 

8631 

volume of liquid at the strength of 80 per cent contains 277*7 quarts of real alcohoL 

To ensure perfect accura^, the expansion of the vessel in which the R>irit is measured 

ought to be taken into account; but for commercial purposes, to which calculations of 

this kind diiefly apply, this correction is too small to be of any importance. 

The quantity of alcohol of 60° F. in 100 volumes of spirit of the same temperature 

is called the strength (Starke; force), of the spirit ; and the quantity of alcohol of 60° F. 

in 100 volumes of spirit of any given temperature is called the real amount of alcohol 

(wahrer Alkokoigehalt; Rieheue), Thus in the example just given, the strength of the 

077.7 
■pirit i. 80. Imt the re.1 ««onnt of dcohol i. ^^ X 100 - 79-3. 

The f<Aowing Tables, Y. and YL, exhibit the strength and the real amount of alcohol 
of a sample of spirit according to the indications of the alcoholometer and the ther- 
mometer. If^ for example, the alcoholometer marks 75 per cent in a spirit whose 
temperature is 50° F., we find firom line 16, column 6, of Table Y. that the strength 
of the spirit is 767, and from the corresponding place in Table YL that its real amount 
of alcohol is 77*1 per cent 



90 



ALCOHOLOMETRY. 



Tablb '^.^Skowmg tk$ Amount of JJcoM which a ginm •aimpU of Bjtmi would 
contain at 60^ F. acoordmg to the indication of a glass Mooholometsr, immersed init 
at any oUm' temperature. 



ll 


Strength of the Spirit, when teeted bj the Alcoholometer at the following tempenturct. 


0» 


9» 


40 6« 


8» 


10«> 


ia» 


14« 


169 


18» 


20» 


2r» 


94 B. 


Indlctt 
Akoh 





9-6 


ft 


7*6 


10 


12-5 


16 


17-6 


90 


29-ft 


2ft 


27-6 


80 C. 


89 


86-6 


41 


46'ft 


60 


64*6 


69 


68*6 


68 


79-6 


n 


81-6 


86 F. 





OS 


0*4 


0-4 


0*4 


0-4 


0-2 





^^ 


_ 


^^ 


^^ 


^ 




ft 


S-4 


ft-ft 


ft-6 


ft'ft 


6-4 


6-9 


6*0 


4-7 


4-4 


41 


8-7 


8-2 


9*5 


10 


11-9 


ll'l 


11-0 


10-9 


10-7 


10-4 


10-1 


9-7 


9-2 


8-8 


8-8 


7-8 


7*8 


1ft 


17*8 


17-4 


17-0 


16*ft 


160 


15-6 


16-1 


14-6 


14-0 


18-4 


12-8 


19-9 


11-6 


ao 


94*7 


98*9 


98-1 


9S-8 


21-7 


90-9 


90-2 


19-6 


16-8 


18-0 


17-2 


16*6 


16-7 


25 


81-9 


80>1 


88-9 


980 


871 


26*1 


25'9 


94*4 


28*6 


22-6 


21-6 


20-7 


19-8 


80 


866 


86*4 


84*8 


888 


83-8 


31-8 


80-2 


29*2 


99-8 


27-8 


90-3 


26-8 


94*3 


Sft 


41*4 


40-4 


89-8 


88*8 


87*8 


36-9 


86-2 


84-2 


83-2 


82-2 


81*2 


809 


29-1 


40 


46-1 


4ft*l 


44-1 


48-1 


49*1 


41-9 


40-2 


89*2 


88-2 


87-2 


86-2 


3.V9 


84*9 


4ft 


60-8 


60-0 


49-0 


481 


471 


46-9 


46-9 


44-9 


48-2 


42-8 


41-3 


40*4 


89*4 


CO 


ft6'6 


64-7 


68-9 


68-0 


620 


61-1 


60-2 


49-8 


48-4 


47*4 


46-5 


46*» 


44-6 


ftft 


00-4 


69-5 


68-7 


67-8 


66-9 


66-1 


66-2 


64-4 


68-6 


62-6 


61-6 


60-7 


49-7 


60 


66*9 


64-4 


68« 


69-7 


61-9 


611 


60*2 


69-4 


66-6 


67-6 


66-7 


66*8 


64-9 


69 


70H) 


69-8 


68-ft 


67-7 


66-9 


66-1 


66-2 


64-4 


63-6 


62-7 


61-8 


60-9 


69-9 


70 


74*8 


74*1 


78-4 


79HJ 


71-8 


71-0 


70-2 


69-4 


68-6 


C7-8 


66-9 


66-1 


66-9 


76 


797 


79-0 


789 


77-4 


76-7 


7*9 


76-2 


74-4 


73-7 


72-8 


72-0 


71-2 


70-8 


80 


84*4 


83-7 


880 


89-8 


81-6 


80-9 


80-2 


79-4 


78-7 


779 


77-2 


76*4 


75< 


Sft 


89*1 


88*6 


87*8 


87-9 


86*6 


86-8 


86*1 


84-5 


83-7 


88-0 


82*8 


81*5 


80-8 


90 


98*7 


98*9 


99-6 


99H) 


91*4 


90-8 


90-1 


89-6 


88-8 


88-2 


87-6 


86*8 


86-1 


95 


96-9 


97-7 


97-1 


96^ 


96-1 


99-6 


96-1 


94-6 


94-0 


93*4 


92-8 


92-8 


91-6 


100 










_■ — • 


100-1 


99-6 


991 


96-5 


96-0 


97-6 


97-2 



Tablb YL — Showing the Beal Amount of Jlcohol in Spirit at different Temperatures 

according to the indications of a glass Alcoholometer. 



iontof the 
olometer. 


Real Amoant of Aloohol at the following Temperaturee. 


0" 


2° 


4« 


6« 


8» 


10° 


12° 


14° 


Ifio 


I80 


9tf» 


fSP 


94»R. 


P 

1< 





9-6 


6 


7-5 


10 


12-5 


15 


17*5 


90 


22-5 


25 


27-6 


80 C 


32 


86*6 


41 


45'5 


60 


54*5 


69 


63-6 


68 


72'6 


17 


81-6 


86 F. 





0-8 


0*4 


0-4 


0-4 


0-4 


02 




^^ 


^^ 


^^ 


_ 






ft 


ft-4 


5*5 


6*5 


ft'ft 


6-4 


5-2 


6-0 


4-7 


4*4 


4-1 


8-7 


8*2 


2-5 


10 


11*1 


11-1 


11-0 


10-9 


10-7 


10*4 


10-1 


9-7 


9*2 


8-7 


8-3 


7*8 


7-3 


1ft 


17*7 


17-4 


17-1 


16-4 


160 


15*5 


151 


14-5 


14-0 


13*4 


12-8 


12*2 


11-5 


20 


24-9 


94-0 


28-1 


22*4 


21-7 


21-0 


90*2 


19-5 


18-8 


18-0 


n-i 


16-4 


15-6 


29 


81*8 


80-2 


29*2 


28-2 


»r2 


26-2 


252 


24-3 


28-4 


22*5 


216 


207 


19-8 


80 


37*0 


857 


34-6 


83*4 


32-4 


31*3 


802 


29-2 


28*2 


27-2 


96*2 


25*2 


24*2 


85 


42*0 


407 


89*6 


38-S 


37*4 


36-2 


85-2 


84*1 


33-1 


32-1 


31-0 


80-0 


28-9 


40 


466 


45-5 


44-5 


434 


42-3 


41*2 


40-2 


89-1 


88-0 


870 


86-0 


850 


»9 


4ft 


61-5 


50-4 


49-4 


48-3 


47-3 


46*2 


46 2 


44*2 


43-1 


42-1 


411 


40-0 


89-0 


60 


66-8 


65-8 


64*3 


53*3 


62*3 


51*2 


60-2 


49-9 


48-2 


47-1 


46-1 


450 


44-« 


65 


61*2 


60-2 


69-2 


68*2 


67*2 


56*2 


55*2 


64*2 


58^ 


62*2 


61*9 


60-9 


49-9 


60 


66-2 


69*2 


64*2 


63-2 


6i-2 


61*9 


60*2 


89-2 


68*2 


67*2 


56-8 


55-8 


54-S 


66 


71-1 


70-1 


69*1 


68*1 


67-2 


66-2 


66-2 


64-2 


63-8 


62*8 


61-8 


60-8 


69-3 


70 


76-0 


76 


741 


73-1 


72-1 


711 


70-2 


69-3 


68-8 


67-3 


66*4 


65-4 


64-4 


75 


60-9 


79-9 


79*0 


78*1 


77*1 


76*1 


75-2 


74-3 


78-8 


72-8 


71*4 


70-4 


69*4 


80 


85*7 


84-9 


839 


83-0 


B2-0 


81*1 


80-2 


79-3 


78-3 


774 


7C-4 


75-6 


745 


85 


90-5 


89*6 


88-8 


87-9 


87*0 


86-1 


85*2 


84-3 


83-4 


83-4 


81-5 


80*6 


79-6 


90 


950 


94*1 


93-5 


92-7 


91-9 


91-0 


90*2 


89-3 


88-4 


87-5 


86^ 


857 


84-8 


95 


99-6 


986 


96*0 


97*4 


96-5 


95-8 


95-2 


94-3 


93-5 


997 


91-9 


91*1 


90-2 


100 




— 


-~ 


— 


^~ 


100-8 


100-2 


99-6 


990 


96-3 


97-6 


969 


95*7 



The scale of Tralles* alcoholometer is constmcted as follows. Suppose the cylindrical 
or prismatic stem of the instrument to be divided into a number of equal parts, of 
arbitrazy length ; and let v be the volume of that portion of the neck between two 
consecutive mvisions ; V the volume of liquid of sp. gr. 1, displaced hy the alcoholo- 
meter, and P the weight of the alcoholometer; then 

p - r. 1. 

If now the division to which the instrument sinks in this liquid be mailced 0, the 
divisions being numbered upwards therefrom, and if the instrument be immerBed in 
spirit of specific gravity n to the mark «, we have 

P- (r+ n«)«, 
which equations give, 

F-(r+nt;)«,orn-- ^j--lj =-' -j- 



ALCOHOLOMETRY. 



91 



The arbitnzy quantity v is fixed by TralleB at such a magnitude that 

n =. 10000 • ^^ 

"Saw he 60^ F. tlie q>eeifle gnmty of water compared with that of water at its mazi- 
mim dendtj (Table L) is 0*9991 : hence tea the diyiaion in whieh the instroment 
sinks in pore water at 60^, we find, 

1^0-9991 
»- 10000 . -5:5^51; »• 

Again, spirit of 80 per cent has at 60^ F. the spi gr. 0'8631 : hence, for the diTision 
to whidi the instrument sinks therein, we have 

1—0-8631 

* ^^^^ • -0^8631 ^^®7' 

and in like manner the Tables of the other diyisions of the scale may be fonnd : they 
are giyen in Table YIL 

To endnate an alcoholometer by means of this table, the instroment is first im- 
mened in pure water at 60^ F., and the point of the stem to which it sinks is marked 
9. It is next immened in spirit of known strength, and the point marked to which 
it sinks wlien the liquid is at 60^ F. Thus if spirit of 90 per cent be used, the num- 
ber of the diTiflion will be 

1-0-8340 
« - ^^^ ' 0-8340 - 2002. 

The interral between these two marks is then to be diTided into 2002—9 *i 1993 
equal part% and the divisions continued upwards as fiur as 2697, which coiresponds 
to absolute aloohoL The percentages in the first column of Table YIL are then 
marked on the scale by the side of the numbers of the diyisions in the second 
column. 

To Toriff the scale of an alcoholometer already divided, the spedfic gravities of a 
nmnber of samples of spirit varying in strength by nearly equal intervals between 
and 100 per cent may be determined 1^ any of the ordinary methods ; the correspond- 
ing strength found srom Tables L, II., or TTT. ; the temperatures of them all then 
rrauced to 60^ F» ; and the alcoholometer immersed in them in order to ascertain 
whether its indications agree with the strengths so determined. The intermediate 
points may be tested by comparison with the numbers in the columns of Table VII. 
■ "tHflerences." 





Tabui \iL--AleoholomeUr-3calefor Volumes per Cent at 6(P F. 




Anoant 
of Alcohol 


Length of 

bBmericd 

part of 

Stem. 


DliRsr. 


Amount 
of Alcohol 

by 
Volume. 


Length of 
Immerted 
pert of 
Stem. 


Differ- 
encei. 


Amount 
of Alcohol 

by 
Volume. 


Length of 

immerted 

part of 

Stem. 


Dlflbr^ 
encca. 


ySL.. 





9 




22 


277 


11 


44 


688 


19 


1 


24 


16 


23 


288 


11 


46 


608 


20 


2 


39 


16 


24 


299 


11 


46 


628 


20 


8 


54 


16 


26 


310 


11 


47 


648 


20 


4 


68 


14 


26 


321 


11 


48 


669 


21 


6 


82 


14 


27 


332 


11 


49 


690 


21 


6 


95 


13 


28 


344 


12 


60 


712 


22 


7 


108 


13 


29 


366 


11 


61 


736 


23 


8 


121 


13 


80 


367 


12 


62 


768 


23 


9 


133 


12 


31 


380 


13 


63 


782 


24 


10 


146 


12 


82 


393 


13 


64 


806 


24 


11 


167 


12 


33 


407 


14 


66 


830 


24 


12 


169 


12 


34 


420 


13 


66 


864 


24 


13 


180 


11 


Z6 


434 


14 


67 


879 


26 


14 


191 


11 


36 


449 


16 


68 


906 


26 


15 


202 


11 


37 


466 


16 


69 


931 


26 


18 


213 


11 


38 


481 


16 


60 


967 


26 


17 


224 


11 


39 


498 


17 


61 


984 


27 


n 


236 


11 


40 


616 


17 


62 


1011 


27 


19 


246 


10 


41 


633 


18 


63 


1039 


28 


20 


266 


10 


42 


661 


18 


64 


1067 


28 


21 


266 


10 


43 


669 


18 


66 


1096 


29 



92 



ALCOHOLOMETRY. 



Tablb YII^(c(miinued). 



Amoimt 


Length of 




Amomt 


Length of 




Amount 


Length of 




of Alcohol 


ImmerMd 


Diflbr- 


of Alcohol 


immened 


Dlfferw 


of Alcohol 


Immened 


Differ. 


by 


pert of 


enoes. 


b7 


part of 


ences. 


by 


part of 


encee* 


Volume. 


Stem. 




Volume. 


Stem. 


^ 


Volume. 


Stem. 




66 


1125 


29 


78 


1514 


86 


90 


2002 


47 


67 


1154 


29 


79 


1550 


36 


91 


2050 


48 


68 


1184 


80 


80 


1587 


37 


92 


2099 


49 


69 


1215 


31 


81 


1624 


37 


98 


2150 


^1 


70 


1246 


81 


82 


1662 


38 


94 


2203 


53 


71 


1278 


82 


83 


1701 


39 


95 


2259 


56 


72 


1310 


32 


84 


1740 


39 


96 


2318 


59 


73 


1342 


32 


85 


1781 


41 


97 


2380 


62 


74 


1375 


33 


86 


1823 


42 


98 ' 


2447 


67 


76 


1409 


34 


87 


1866 


43 


99 


2519 


72 


76 


1443 


34 


88 


1910 


44 


100 


2597 


78 


77 


1478 


35 


89 


1955 


45 









The following is a mmilar table for percentages hy veight. 

Tablb YJIL-^Akohohmeter-ecaU for Weighta por Cent, at 60<' F, 



Amount 

of 

Alcohol 

bjWeight 




1 
2 
8 
4 
5 
6 
7 
8 
9 

10 
11 
12 
13 
14 
15 
16 
17 
18 
19 
20 
21 
22 
23 
24 
25 
26 
27 
28 
29 
30 
31 
32 
33 
84 



Length of 

Immened 

part of 

Stem. 



9 
29 
46 
64 
82 
98 
114 
130 
145 
159 
173 
187 
201 
214 
227 
240 
252 
264 
277 
291 
304 
317 
330 
343 
357 
371 
386 
402 
419' 
435 
452 
469 
487 
507 
527 



Dlflbr- 
enoet. 



19 

18 

18 

18 

16 

16 

16 

15 

14 

14 

14 

14 

13 

13 

13 

12 

12 

13 

14 

13 

13 

13 

13 

14 

14 

15 

16 

17 

16 

17 

17 

18 

20 

20 



Amount 

of 

Alcohol 

by Weight. 



35 
36 
37 
88 
39 
40 
41 
42 
43 
44 
45 
*46 
47 
48 
49 
50 
51 
52 
53 
54 
56 
56 
57 
58 
59 
60 
61 
62 
63 
64 
65 
66 
67 



Length of 




Amount 


Length of 




immened 


DiflSBf. 


of 


Immened 


DIlTer- 


part of 
stem. 


encet. 


Alcohol 
byWelgfat. 


part of 
Btem. 


eneee. 


547 


20 


68 


1411 


31 


568 


21 


69 


1442 


31 


589 


21 


70 


1473 


31 


610 


21 


71 


1505 


32 


633 


22 


72 


1536 


31 


655 


22 


73 


1568 


32 


677 


22 


74 


1600 


32 


700 


23 


75 


1632 


32 


724 


24 


76 


1664 


32 


748 


24 


77 


1697 


33 


772 


24 


78 


1730 


33 


797 


25 


79 


1763 


33 


822 


25 


80 


1796 


33 


847 


25 


81 


1830 


34 


873 


26 


82 


1865 


35 


899 


26 


83 


1901 


86 


925 


26 


84 


1938 


87 


951 


26 


85 


1975 


37 


978 


27 


86 


2012 


87 


1005 


27 


87 


2050 


38 


1033 


28 


88 


2088 


38 


1061 


28 


89 


2126 


38 


1089 


28 


90 


2165 


39 


1117 


28 


91 


2204 


39 


1145 


28 


92 


2254 


40 


1173 


28 


93 


2286 


42 . 


1202 


29 


94 


2329 


43 


1231 


29 


95 


2372 


43 


1261 


30 


96 


2415 


43 


1290 


29 


97 


2458 


43 


1320 


30 


98 


2503 


45 


1350 


30 


99 


2549 


46 


1380 


30 


100 


2697 


48 



AlCOHOLOMETKY. 



TuvHH otber hjdiometan or anametera ue also lued for 
UliDg Uk apedfii! gnrit^ and ascettaiiiitig tile atrength of 
^aiiti. SkMfa h^^ometei' ia tii« ons nsed in leT;iiig tha . 

nirit dn^ in this eoontrj. Thii inatnuDeDt luu a four- ^ 
ndfd itam 6, diTided into 11 equal parts, and fitting into a 
Inn ball a, vbich carriea at the bottom a small conicu stem e, ^ 
toimiiatuig in ■ peai^afaapad loaded bolb. It is olio pro- | 
Tided Tith 9 dicolarveightii, numbered 10, 20, 30,10,60,60, 
TO^ 80, 90, hanng slits 'bj vhich the; flt into the stem. The ^ 
i»tniiM!iit is a4JDat«d so as to float with the zero of the scale ■ 
niinriding with the imrfkM of the liquid in spirit of apedfic ^ 

gnvit; 0825 at 60°F. vhich is the " ttandaid aUohol" of the 
eictse (p. 82). Inireaker spirit it will not aiiili bo low ; and if 
the density of the liquid be ninch greater, it wUl he neceasar; 



gather with the natnber on the scale which is at t£e lerel 
ri tbe liquid, gires, hj meKoa of a table provided for the 
pmpoae, the amount of proof spjrii ia the sample, proof 
■rant bone, according to Act of Parliament, mch as at 61° 
f ihr. wei^s 4J " mwJi ss an equal bulk of water, or in other 
weida haa a H«cifie gravit; of 0-923077 at £1°, or 0-919 at 
60° P. 

When spirit ia said to be SO per cent (for sismple] oion 
Jfif, tho meaning ia, that 100 msasnrea of this spirit, 
rfwn ditnted with w«cr, wunld ^dd 130 measures of proof 
B[irit; on the other hand, spirit SO per cant btUmi pret^ 
cCTlaiiw in 100 measares, 100—30 or 70 meaaniM of proof 

It is often required tc find the qnaniitj of water which mmt be added to spirit 
(ootaiiung a gcren percentage of alcohol in order to rednce it to a lower pCTCentoge. 
If the actual and re(]iiiiedBiiKmnta are given in wei^ts per cent, a and a', the wei^t 
'Of water to be added to 100 Ihs of sfdril to r«dae« ue percentage of alcobcJfrom 
a to ■*, is giren hj the ^«porCioa : 

100 4- «: a - 100 : »', 



9 e 



Thence I - loo/^ — 1 1 
tuning SO lbs. 
rcent., the qua 

"(S-') = 



If Pbethevagbt, and 5 the specific graTJ^ of l^e tpirit we have: 
P - 100 & 
andif to this we add tDTolnniM of water, the wei^t of which will hIm be w (its 



mpl^ to reduce spirit of BO Tolnme« p. c. to spirit of 40 Tolnmes p.e. w« find, 
I . 0-eeiO - 0-8639) - 108-99 






n 



94 



ALCOHOLOMETRY. 



The Tdnme of diluted spirit produced by the mixture is 

V 



100^ 
1/ 



80 



In the example just giyen, 100 • j^ » 200 yolumes, less tiierefore than the sum of 

the Yolumes of the li<|uids mixed* 

On the principles jost explained, the nnmhen in the following table are calculated. 
It must be observed, however, that the specific gravities are given as determined bj 
Oay-Lussae, and correspond to 16° G. on which account the rosult of the calculation 
just given does not agree exactly with the number in the table. 

The original volumes per cent, of the spirit are placed at the tops of the columns, 
and the percentages to which they are to be reduced in the first column of the table. 
Thus to find how much water is required to reduce spirit of 76 per cent to 40 per cent 
look in the column headed 70 for ^e number on a level with 40 in the first column ; 
we thus find that 77*68 volumes is the quantity of water required: 

Tablb IX. — Showing the quantity of Water reauired to reduce 100 ffolwnea of a 

stronger Spirit to a Spirit of lower strength. 



86 


90 


86 


80 


76 


70 


66 


60 


66 


60 


6-66 


















80 


13-79 


6-88 
















76 


21-89 


14-48 


7-20 














70 


3106 


2314 


16-36 


7-64 












65 


41-63 


3303 


24-66 


16-37 


8-16 




^ 






60 


63-66 


44-48 


86-44 


26-47 


17-68 


8-76 








66 


67-87 


67-90 


48-07 


38-32 


28-63 


19-02 


9-47 






60 


84-71 


73-90 


63-04 


62-43 


41-73 


31-26 


20-47 


10-36 




46 


106-34 


93-30 


81-38 


69-64 


67-78 


4609 


84-46 


22-90 


11-41 


40 


180*80 


117-84 


104-01 


90-76 


77-68 


64*48 


61-43 


88-46 


26-66 


36 


163-28 


14801 


132-88 


117-82 


102-84 


87-93 


7308 


68-31 


43-69 


30 


206-22 


188-67 


171-06 


103-63 


136-04 


118-94 


10171 


84-64 


67-46 


26 


266-12 


246-16 


224-30 


263-61 


182-83 


162-21 


141-66 


121-16 


100-73 


20 


366-80 


329-84 


304-01 


278-26 


262-68 


226-98 


201-43 


176-96 


160-65 


16 


606-27 


471-00 


436-86 


402*81 


368-83 


334-91 


30107 


267-29 


233-64 


10 


804-64 


763-66 


702-89 


661-21 


601-60 


661-06 


600-69 


46019 


399-86 



A similar but much more extended table for this purpose is given by Oay-Lussac. 
(See Haudworterbuch d. Chem. i. 604.) 

To determine what quantity of a weaker spirit must be added to a stronger one to 
produce a spirit of given mean percentage, we proceed as follows. 

Let t; be the volume of alcohol in 100 measures of the stronger spirit, 8 its specific 
gravity, and P its weight. Also let V^ be the volume of the weaker spirit added, 9^ its 
percentage of alcohol, 8^ its specific gravity, and Pi its weight; and lastly, let V^ be 
the volume of spirit resulting from the mixture, v^ its percentage of alcohol, 8^ its spe- 
cific gravity, and P, its weight. Then : 



P - 100 5 : Pi « FiSi : P, - P + Pi 

or 100 8 + VxS^ = VA • 
The quantity of alcohol contained in this mixture is, 



(!)• 



'' + Ioo*x 



But since the mixed spirit is to contain V^ volumes per cent of alcohol, thia quantity 
of alcohol is also represented by 

Hence the equation : 

Ta^a » 100 tr + FiVi . . . («), 

And eliminating Ta between the equations (1) and (2), we have, 

100 5f+ Fi-Si 



«. 



fa >i 100 « + VxVx 



ALCOHOLOMETRT. 



96 



iteee veobtsm: 



F- 



100 - iSf - 100 iSf 
^9 

fa 



Hie immentor of this fraction is the qoantity of wtAeat which most he added to 100 
foifaimes of the stronger spirit to prodnee a spirit of the requied* strength. The de- 
Bominstor maj be written in the fonn, 

ind is therefore the Tolmne of water which mnst be added to -^ Tolomes of spirit oon- 

taioing v^ per cent of alcohol to bring it to the percentage v^. 

To determine the amount of alcohol in spiritnons Hqnors, snch as wine or beer, con- 
taining foreign matten^ as Tolatile oils» sugar, mndlage, saline substances, &c., the 
Jkpad may be distilled, and the distillate, which will be free from the fixed imparities, 
mtj be treated b j the methods already described. Volatile oils are for the most part of 
TtttAj the same specific grarity as alcohol, and the small quantities of them A*^«i-i«g 
in rinoos liquors do not make any essential difierence in the specific grarity. 

Other physical chazacters haye also been resorted to for determining the strength of 
apiiitDoos hqnors^ tis. the boilinff-point, Taponr-density, rate of expansion, &c. 

The boiknff'poitU of hydrated alcohol has been proposed by Groning as a means 
of dstctminiqg its strength. For this purpose, he has constructed tiie following 
taUe. 

Percent, 
or AloohoL 

40 
46 
60 
60 
60 
66 

According to Dalton, alcohol of 43 per cent boils at 84° C. 

J. J. Pohl (Doiksehriften d. math, naturw. Classe d. Wien, Akad. IL abstr. 
Wjen, Akad. Ber. 1860 ; Marz. 246 ; Jahresber. 1860, 466) has also determined the 
boiling-point of hrdrated alcohol of various strengths. He finds that, at the commence- 
nent^the ebullition, the thermometer remains constant for a short time, then slowly 
rises a little, and afterwards remains constant for a somewhat longer time (from 4 to 
16 seeouds whm 14-6 gims. of liquid were used). The temperatures at the second 
•tatioiiaiy interfal axe giren in the following table (Bar. at 760 mm.) 



F\BrC8nC. 


BoOlngw 


«rAloolMl. 


Point. 


6 


. 96-3 C. 


10 


. 92-9 


16 


. 910 


20 


. 891 


26 


. 87-6 


SO 


. 86-2 


86 


. 860 



Boiling. 


Percent. 


BoHing. 


Point. 


of AlcoboL 


Point. 


841 C. 


70 


80-9 G 


83-4 


76 


80*3 


831 


80 


79-7 


82-2 


86 


79-4 


81-9 


90 


79-0 


81-6 


96 


78-4 



Pifcenlsse 
orAkohoL 




1 
2 

3 

4 
6 
6 



Boiling. 
Point. 


PercCTitase 
of Alcoh^. 


loo-ooo C. 


7 . . . . 


98-79 


8 . . . . 


97-82 


9 . . . . 


96-86 


10 ... . 


96-90 


11 ... . 


9602 


12 ... . 


94-21 





Boiling. 
Point 

93-480 C. 

92-70 

92-03 

91-40 

90-88 

90-27 



The presence of sugar in the liquid up to 16 p. c. appears not to exert any pexvep- 
^le influence on the boiUng-point (a mixture of 10 pts. alcohol with 16 sugar and 76 
vater boiled at the same temperature as a mixture of 10 alcohol and 90 water). 

Instruments, called EUnUUoKopes, for directly ascertaining the strength of hydrated 
ikohol by its boiling-point, haye been constructed l^ Broissard-Yidal and by Conaty. 
(See a report on these mstniments byB esprets, P ouille t, and Babinet, Complrend. 
uvii 874. A description and figure of a Yidal-instmment are giyen in the Pharm. J. 
Tnas. rii. 166.) Ur e (Pharm. J. Trans, rii. 166 ; Pharm. Centr. 1847, 422) by means 
of an iastroment similar to Conatv's (which is merely an ordinary thermometer, haring 
s moreible scale which can be shifted so as to correspond with the yariations of the 
yuometer, and has the percentages of alcohol marked on it) has determined the boil- 
ing-points of hydrated aioohol as follows: 



96 



ALCOHOL-RADICLES. 



Boiling. 


Specific 


Boiling. 


Foinu 


Onrlty. 


Point. 


. 81-40 0. 


0-9665 . 


. S5'3<> 


. 821 


0-9729 . 


. 87-2 


. 82-6 


0-9786 . 


. 88-8 


. 83-3 


0-9850 . 


. 91-3 


. 841 


0-9920 . 


. 94-4 



SfMcifle 
Gravity. 

0-9200 . 

0-9321 . 

0-9420 . 

0-9516 . 

0-9600 . 

Silbermann lias propoAed to determine the strength of hydrated alcohol bj its rate 
of expansion by heat, and has constmcted an instrument for the piirpose (Compt rend, 
zxvii. 418). A thermometer is filled up to a certain mark mih tne spirit at 26^ C. and 
after this uqnid has been exhausted of air by the air-pump, an observation is made 
of the amoimt by which it expands when heated to 50^ 0. The amonnt of alcohol ia 
then found by means of a sciede graduated by direct observation upon a number of 
samples of spirit of known strength. The indications of this instrument aie not sen- 
sibly affected by the presence of sugar or salts in the liquid. 

Another instrument for the same purpose haa been constructed and described by 
Maki n. (Chem. Soc Qu. J. ii. 224.) 

For fnruier details on alcoholometry, see the new edition of Ur^s Dictionary o/Arts, 
Manufactures and Mines^ toL l pp. 44-64. 



The radides which, when they replace half the hy- 
drogen in a molecule of water form alcohols, are capable of uniting, though not directly, 
with chlorine bromine, iodine, cyanogen, oxygen, sulphur, &c., with the ruUdes of acida, 
and with metals : in short they e^iibit in their chemical relations the character of 
electro-positLYe elements or metals. Only a few of them have yet been isolated; and 
of these, dl but one (allyl) belong to the first series of alcohob mentioned in the 
preceding artide, and are represented by the general formula OH^'*'^, or C^H^'*'*. 
They are obtained : 

1. By the action of sodium, potassium, zinc, &c, at high temperatures, on their 
iodides or bromides. In this manner ethyl was first isolated by Frankland. — 2, By 
the dectrolysis of the adds of the series OJBC'O*. The general formula of the decom- 
position is^ 

C-H*-0« = 0-»H>-> + C0« + H. 

In this manner, acetic add, C*H*0^ yields methyl, CH* ; valeric add, G*H**0*, yields 
tefeylor butyl, C*H*; caproic acid, C*H"0', yiel<u amyl, C*H"; and oananthyHc add 
C'H"0' yidds hexyl or caproyl, C"H". — 3. Some of these radides, viz. trityl or propyl, 
tetiyl, am^l and hexyl, are also found among the products of the dry distiUation of 
Boghead Gannd coaL (Qr. Williams, Chem. Gaz. 1857, pp. 29 and 95.) 

Methyl and ethyl are gaseous at ordinary temperatures ; trityl, tetrv!, amyl, and 
hexyl, are liquids, the first boiling at 68^ C, the second at 108^, the third at 155®, and 
and the fourtili at 202^. They do not unite directly with any of the dementaiy bodies, 
and it has not yet been found possible to reproduce from them, by direct union, 
any of the bodies of the methyl, ethjl series, ^ At the moment of isolation, how- 
ever, from their iodides by the action of metais, they exhibit a strong tendency to 
unite with the metal: in this maimer, zinc-ethyl, C*H*Zn and zinc-methyX CH'Zn, are 
formed by the action of zinc on the iodides of those radides. 

The constitution of these bodies has given rise to considerable discussion. The 
formulsB OH?, 0"il\ &c, originally assign^ to them by FrankUnd and Kolbe, repre- 
sent their vapours as condensed to 1 volume, whereas the usual mode of condensation 
in organic compounds is to 2 volumes (see Atomio Yolxtkb). For this reason, and 
likewise because all organic compounds whose formulae are well established, are found 
to contain even numbers of hvdrogen-atoms, Q-erhardt (Oompt. chim. 1848, 19 ; 
1849, 11) proposed to double the formuhe of these radides in the free state, making 

CH* ) CH* ) 

them 0^* or q^, [ , O^H'* or ^s^s [ ^ This duplication of the formulsB was after- 
wards supported by H of mann (C^em. Soc. J. iii. 121) on the ground that the boiling- 
points of the consecutive terms of the series of these bodies differ by about 47^ O., an in- 
terval more than double of that which generally ooiresponds to a difference of OH' in 
bodies of the methyl, ethyl, trityl series, &c. But the decisive argument in &vonr of the 
double formulffi is afforded by the experiments of Wurtz, yrho has shown that by the 
action of mixtures of the iodides of these radides (iodide of ethyl and iodide of tetiyl, 
for example) with sodium, or by the electrolysis of a mixture of the potassium-salts of 
two fatty adds, e. g, acetate and oenanthylate of potassium, compound radicles are ob- 

CH* ) CH* ) 

tained, viz. ethyl-tetryl, ^^j^Lmethyl-hexylQag,,^ &c; and moreover that when 

these mixed radides are compared with the simple radides with double formulse, a 
regular gradation of physical properties is observed as the number of atoms in the 
molecule increases. This will be seen from the following table. 



ALCOHOLS. 



97 



Ethjl-tetzjl . 
Ethjl-amyl 
MetbjI-liezyl . 
Tetijl . 
Tetzyi-amyl . 
Amyl 

Tebyl-hexyl . 
BeKjl . 



Formula. 



CTH" 



C*H" 

;cH» 
;c*H» 

Off* 

;c*H" 

OH" 

C*H» 

OH" 

:c«H»» 



Specific 

Gravity at 

6<»C. 



0-7011 

0-7069 

? 

0-7067 
0-7247 
0-7413 

? 
0-7574 



Tapour.Densitj 



Observed. 



3-053 
3-522 
3-426 
4-070 
4-466 
4-966 
4-917 
5-983 



Calculated. 



2-972 
8*466 
3-466 
3-939 
4-423 
4-907 
4-907 
6-874 



BoHing- 
Point. 



62«C. 

88« 

82? 
106 
132 
168 
166 
202 



It 18 defir that if the Bimpler foramls of tetryl, amjl and hexjl wore retained, the 
aioeofdanee between the gradation of properties and increase of atomic weight which 
theprecedmg table exhibits would be completely lost. 

^ewed in this light, the formation of the simple radicles is strictly analogoos to 
that of the mixed radicles, as will be seen from the following equations : 

C»H*I + OH1 + ZnZn = 2ZnI ¥ C»H*.OH» 
and 2C«H»I + ZnZn = 2ZnI + C^H^.C^H*. 

A&CMIO&B. The term alcohol, originally limited to one substance, viz. spirit of 
vine, is now applied to a considerable number of oiganic compounds, many of which, 
in their external characters, exhibit but little resemblance to common alcohoL The 
alcohols are all compounds of carbon, hydrogen, and oxygen. They are divided into 
several homologous groups, but their rational formulae may all be derived from one, 

tvo^ or three molecules of water, ^VO, ;m[0^ xrsfO', by substitution of an or- 

ganie radicle containing hydrogen and carbon for half the hydrogen in the type. 
Alcohols are accordingly monatomic, diatomic, or triatomic, e.g. Ethyl-alcohol 

(monatomic) = H [^* — Glycol (diatomic) « ^ H*[^'» — Glycerin (tria- 

A. »foiimtOfnii> Aloohols. Of these there are several series, containing radicles 
whose genoal formuIiB are C»H"« + \ OH*» - », C"H*»-', C"H*»-7. 

1. Alcohols of the form C-H«- + *0 = OH'"*'| q. These alcohols, of which 

nine, or perhaps ten, are at present known, are intimately related to the fatty acids (p. 
60). To every alcohol of this series there corresponds an acid of the series C"H*°0*, 
wrtucfa may be formed from the alcohol by oxidation, being substituted for H^ The 
fcXUjvring table exhibits the names and formulse of these alcohols, together with those 
of those of the corresponding acids : 



Alcohols, 



H 



Methyiie or protylic . 
EithjDC or deutyHc . 
Piopylie or tritylic . 
Bnty lie or tetiyUc . 
Amylic or pentylic 
Gapzoylic or hexylic . 
OBnanthyEc or heptylic 
Gapiylic or octylic . 
Cetylie . . 
Cootylie . 

Keliajlie > • 
VolL 



■!" 



CH^O 

CH'O 

C»H»0 

C*H»«0 

C»H"0 

CH'H) 

C"H"0 
C«H»0 



Aci 


ds, H 


. CH«0« 


Formic . 


Acetic 




. C«H*0« 


Propionic 




. C»H«0« 


Butyric . 




. C*HK)« 


Valeric . 




. G»H>«0« 


Caproic . 




. C-H'20» 


(Enanthylic . 




. CH"0« 


Capiylic 




. C»HW0« 


Palmitic « 




. C»«H«0« 


Cerotic . 




. c«^»«o« 


Melissic . 




, . C"H«K)« 



98 ALCOHOLS. 

These alcohoLs are also designated as Hydrates, or Kydrated Oxides, of Methyl^ 
Ethyl, Sec, or as Methylate, EtkylaU, Tritylaie, ^c. of Hydrogen. The numerical terms 
protyl, deutyl, trityl, &c. were proposed by Gerhardt They are in most cases pre- 
ferable to the older names : but the terms, methyl, ethyl, and amyl, are too much con- 
secrated by use to be discarded. 

Methyl-alcohol, or wood-spirit^ was first recognised as a compound similar in nature 
and constitution to common alcohol by Dumas and PeHgot in 1835. In the following 
year, the same chemists showed that ethal (cetyl-alcohol), a substance first obtained 
from spermaceti by CheTreul in 1823, is also of alcoholic nature. Fusel-oil was re- 
cognised as an alcohol somewhat later by Cahours and Balard. Cerotyl-alcohol and 
melissyl-alcohol were discovered by Brodie in 1848 ; octyl-alcohol by Boms in 1851 ; 
tetryl-alcohol by Wurtz in 1852 ; ttityl-aloohol by Chancel in 1852, and hexyl-alcohol 
by Faget in the same year. 

Methyl-alcohol is found among the products of the distillation of wood. Ethyl- 
alcohol and the four following alcohols are produced by fermentation of sugar, 
(C*H"0*), perhaps in the manner represented by the following equations : 

CffK)* = 20«H«0 + 2C0« 

Ethyl, 
alcohol. 



2C«H«0« « 2C'H«0 4- C«H«0 + 4C0« + HK) 

Trityl- Ethjl- 

alcohol. alcohol. 

C«H>K)« - C*ff«0 + 2C0« + HK) 



Tetryl- 
alcohol. 



3Cm"0« « 2C»H»K) + C»H»0 + 600* + 3H«0 

Amvl- Ethyl- 

aloohoL alcohol. 

2C^»0« - 0»H>«0 + C»H"0 + 4C0« + 2HK> 

Amyl- TrttyU 

alconol. alcohol. 

5(>H»K)« = 4C*H"0 + lOCO* + 6BP0 

Ami 
alcot 



Aznyl- 
>nol. 



8C^'«0« « 2C«H"0 + 6C0» + 4n'0 
Hexyl- 
alcohol. 

Oetyl-alcohol is said to be obtained by saponifying castor-oil with potash, and dis- 
tilling the resulting ricinolate of potassium with excess of the alkali at a high tempe- 
rature. The ricinoHc acid is then converted into octyl-alcohol, sebate of potassium, 
and free hydrogen : 

QwQUQt + 2KH:0 s= C^»K) + C"H»«K*0* + 2H 

Ricinolic Octyl- Sebate of 

acid. alcohol. potassium. 

Bonis (Compt. rend, xriii. 141). Other chemists, however, who have examined 
this reaction, state that the alcohol produced by it is not octylic, but heptylic. Ac- 
cording to Stadeler (J. pr. Chem. Ixxii. 241) two reactions ts^e place simultaneously, 
the one giving rise to the formation of heptylic alcohol, sebate of potassium, and 
hydride of methyl (marsh gas), the other to the formation of methyl-cmanthyl, an acetone 
isomeric with caprylic aldehyde, CH^K), and free hydrogen ; thus : 

Ci«H"0« + 2KH0 = C'H»«0 + C'»H»«KW + CH'.H 

Blcinolic Heptyl- Sebate of Hydride 

acid. alcohol. potassium. or methyl. 

Ci«H«*0» + 2KH0 « CH'.CH'K) + C'^ff^K^O* + H* 

Ricinolic ' Metbvl- Sebate of 

acid. oenantByl. potassium. 

According to Dachauer, on thecontraijr (Ann. Ch. Pharm. cvi. 270), the products 
of the distillation are methyl-cenanthyl and octylic alcohol, the formation of this al- 
cohol differing from that of methyl-oenanthyl only by the elimination of two atoms of 
hydrogen instead of four. It does not appear that Stadeler actually observed the evo- 
lution of marsh gas. 

Cetyl-alcohol (or ethal) is obtained by decomposing spermaceti (which consists chiefly 
of oetin,(^K**0^) with alkalis, palmitic acid being formed at the same time : 

C«H"0« + KHO B C"H"0 + C»«H"KO» 

Cetia. CetTl- Palmitate of 

alcohol. potassium. 



ALCOHOLS. 99 

In the same manner, cezotyl-alcoliol is formed from Chinese^waz, and melissyl- 
aktthoi from beea-wax. 

C"H»0« + KHO = C«H«^ + C«TJ"KO« 

Cbinete- CerotyU Cerotate of 

wuL. alcohol. potusium. 

Some of these alcohols have also been formed from the corresponding hydrocarbons 
OH^, e.y. common aleohol from olefiant gas, (?K*, and trityl-alcohol from tritylene, 
CH', by difisolvijig these gaseons hydrocarbons in strong sulphuric acid, and decom- 
Dosiiig the resolting ethyl-solphnric or trityl-salphuric acid by distillation with water. 
Methyl-^cohol has been formed from marsh-gas, CH^ by exposing that compound to 
the action of chlorine in sonshine, whereby chloride of methyl is obtained, and decom- 
poBiDg this body with aqueous potash (Bert he lot, Compt. rend. zIt. 916) : 

CH«C1 + KHO = CH*0 + KCl 

The first eight alcohols of the series are liquid at ordinary temperatures. Methylic 
and ethylic uoohols are mobile watezy liquids ; the others are more or less oily, the 
Tiscidity increasing with the atomic weight. Cetyl-alcohol is a solid fat: cerotylic 
and m^iasylic alcohols are waxy. 

Oxidising agents convert these alcohols into aldehydes, C"H'"0, or acids, OH^O^ in 
each ease with elimination of one atom of water : 

OH*»*K) + O « OH*»0 + H«0 
and C*H«-+K) + O* - C-H^-O* + B.H) 

These changes take place on exposing the alcohols to the air, especially in contact with 
pbtinum-black, and more quickly on distilling them with a mixture of dilute sul- 
phnric add and chromate of potassium. The alcohols are also conyerted into fatty 
acids by heating them strongly in contact with soda-lime (a mixture of quick lime 
with caustic soda) ; e.^, am^'l-alcohol thus treated yields valerate of sodium. 

The alcohols of this senes contain one atom of hydrogen replaceable by metals or 
eompoond radicles. Hany of them, when treated with potassium or sodium, give off 
hydrogen, and form solid compounds containing 1 atom of the alkali-metaJ, e,ff, 
etbTlate of sodium, CH^NaO. Id. this respect the alcohols partake of the nature of 
adds. — The oompoonds thus formed are easily decomposed, and are not easily ob- 
tained in a definite form. 

On treating these potassium- or sodium-alcohols with the iodide of an alcohol-radicle, 
iodide of potassium or sodium is precipitated, and an ether is formed, that is to say, 
a compound deziTed from an alcohol by the substitution of an alcohol-radicle for the 
banc atom of hydrogen : thus ethylate of sodium with iodide of ethyl yields ethylic 
ether ((?H»)«0, and with iodide of amyl, ethyl-amyl ether, (?H».C*H".0 (p. 76), 

The alcohols are also converted into ethers by the action of strong sulphuric acid 
chloride of adnc, fluoride of boron, and other powerful dehydrating agents, at a certain 
temperature. The ultimate change is represented by the equation : 

2(o^-jo)-HK)-gg::;jo 

Alcohol. Ether. 

For the intermediate steps of the process see page 76. This particular change takes 
place only between certain limits of temperature, e, g. for the etnerification of common 
aleohol by sulphuric acid, the limits are 140^ and 160^ C. At higher temperatures, a 
farther dehydration takes place, and a hydrocarbon OH^ is obtained : 

i,g, common alcohol heated above 160® with strong sulphuric add, yields olefiant gas 
0»H*. 

With the greater number of adds, alcohols yield eomptmnd ethers ; that is to say, 
■alts in which the basic hydrogen of the acid is more or leas replaced by the radicle of 
the alcohol With monobasic adds, only neutral ethers are formed: thus common 
ileobol heated w^ strong aeetie add yields acetate of ethyl, with elimination of 
vater: 

The formation of these ethers is greatly assisted by the presence of strong sulphuric 
or l^rdroehloric add, to take up the water. They are commonly prepared dther by 
distilling the idoohol with sulphuric add, and a salt of the other add (e,ff. acetate of 
ethyl, by d igfilling alcohol with sulphuric add and acetate of sodium), or by passing 

H 2 



100 ALCOHOLS. 

hydrocUoric acid gas into an alcoholic aolntion of the acid. The former method is 
applicable to the more yolatile ethers, the latter to those of higher boiling-point 

With dibasic and tribasic acids, the alcohols generally form acid ethers or alcokolie 
acidst that is to say, compounds in which only a portion of the basic hydrogen of the 
acid is replaced by the alcohol-radide. Thus, when amyl-alcohol is mixed with buI- 

C*H**) ^SO*V' ) 

phuric acid and the mixture kept cool, amyl-sulphurie acid, ^ f ^^* ^' C»H".H { ^ 

is produced: 

In like manner, phosphoric acid, and amyl-alcohol yield amyl-phosphoric acid, 

PO*.C*H".H». 

Hydrochloric, hydrobromic, and hydiiodic acids convert the alcohols of this series 
into chlorides, &c., of the alcohol-radides, with elimination of water : 

^^H*l^ + ^^ " C«H«-*> a + H*0 ^ 

A similar transformation is effected by the chlorides, bromoides, and iodides of phos- 
phorus: e,ff, 

^h"{^ + pa*.a» = c»H»ci + Hci + pocp 

Amyl- Penta- Chloride Oxychlo- 

alcohol. chloride of of amyl. ride of 

phosphoruf. phoipborua. 

With the chlorides of acid radides, the alcohols form compound ethers, hydrochloric 
acid being at the same time eliminated : 

cf* jo + CTBPo.a - g^.'Ojo + Ha 

N , > , ' > , 

Ethyl- Chloride of Bensoate 

alcohol. benaoyL of eihyL 

Persulphide of phosphorus transforms the alcohols of this series into mercaptans 
(sulphur-alcohols) : 

6C-H«»+« + P«S» - 60-H«-+*S + PK)» 

2. Alcohols of the form OB>0 « H 1 ^ convertible by oxidation into adds 

of the form OU^-K>\ 

Only one term of this series is at present known, viz. : — 

AUyUalcohol or Hydrate of Myl, C»H"0 - ^'g* \ 0. 

This alcohol was discovered by Cahours and Hofmann in 1856. It is con- 
verted by oxidising agents into aciyHc aldehyde or acrolein, CHK), and acrylic 
acid, C*H^O', and moreover exhibits all the transformations of the bodies of the pre- 
eedinff series (see At.t.tl). It is probable that to every acid of the series C"H^-*0" 
(angeKic, terebic, oleic acid, &c^, there corresponds an alcohol of the form OHM). 
These alcohols are isomeric with the aldehydes of the preceding series ; e. g, allyl- 
alcohol with propionic aldehyde. 

8. Alcohols of the form C»H«»-«0 «^"^'*|o. Only one alcohol of this kind 

is known, viz. : 

Campholf or Bomean Camphor, C'*H"0 « tt [ 0. It is a solid substance which, 

when distilled with anhydrous phosphoric add, yields the hydrocarbon, CH'* a 
C^'H^O— KK). It forms neutral ethers with stearic and benzoic adds. 

4. Alcohols of the form OH^^-K) ■■ n [ ^» *^^ corresponding to adds of 

the form OH*»-*0* Three of these alcohols are known, viz. : 
Benzyl-alcohol, or Hydrate of Benzyl, C'H»0 ^^g'l ^ 

CumyUalcohdl, or Hydrate of Cumyl, C"H><0 «^"^**| O 
Bycoeeryl^deohol^QxHydraU of aycoceryl, C»"H*0=^*"2*1^ 



ALCOHOLS. 101 

Boayl-alcoho] vas discovered by Cannizzaro in 1863 ; cmnyl-alcoliol by Erant in 1864 ; 
thcie two alcofaob are obtained by treating the corresponding aldehydes (bitter- 
almand oil and cnminol) with an alcoholic solution of potasn : 

2C'H«0 + KHO « C*H»0 + C'H*KO« 

•" , - >^ f »x *- ^ -* 

HTdrlde of B«niy|. Benzoate of 

benzoyl. lUoobol. poUMium. 

MoreoTer, the aldehydes themselves may be formed from acids, by distilling a mix- 
tme of the caldimiHHdt of the acid irith formate of calcium, thus : 





Benzoate of Formate Hydride of Carbonate 

ealcium. of calcium. ofbenxoyl. ofcalclam. 

Henee it appears that these alcohols ma^ be formed from the corresponding acids. 

Bmz^lie and cnmylic alcohols are liqmds which volatilise without decomposition. 
Thej are conyerted into aldehydes and acids by the action of oxidising agents ; they 
form compound ethers when treated with a mixture of sulphuric acid and other 
(njcen-aads {e.ff. acetate of bensEyl, C*H'0'.C'H\ is formed by treating benzyl- 
aleohol vith a mixture of sulphuric and acetic acids), and yield the chlorides of the 
coTTCaMmding radicles when treated with hydrochloric acid ; thus chloride of benzyl, 
C^H'U is obtained by treating benzyl-alcohol with strong hydrochloric add. 

With snlphurie acid or chloride of zinc, they yield resinous masses, which are 
pobebly hydro-carbons analogous to olefiant gas: anhydrous boracic acid converts 
baii]rl-alooh3l into benzyl-ether (CrH')*0. They do not appear to form conjugated 
acids like ethyl-solphniic acid. By caustic potash, at high temperatures, tney are 
ooDTOted into the corresponding acids and hydrides of the alcohol-radides ; e.g. : 

3(CH'.H.O) = (7H«0« + 2(CH'.H) + HH) 

Beuzyl-alcohol. Benxoic Hvdride of 

acid. benzjl. 

S^eoeexyl-alcohol was discovered bj Warren DelaRueand Hugo Miiller,in 1859 
(Pkoc Baj, Soc X. 298). It exists in the form of a natural acetic ether in the exuda- 
tion from an Australian plant, the Ficus nUnffinoaa, This ether is readily obtained 
in beautiful ciystals, and when treated with sodium-alcohol, yields acetic add and 
If eooeiylic alcohol, in feathery crystals resembling caffeine or asbestos. Treated with 
nitric add, it yidds an add whidi appears to be sycocerylic acid ; and with chromic 
acid, it yields a product which is probably the corresponding aldehyde. 

5. Alcohols isomeric with the last, but differing from them in forming conjugated 
acids with sulphuric add, phosphoric acid, &c., and in not being converted into acids 
and aldehydes by the action of oxidising agents. Two of these alcohols are known, 
m: 



Htnfi-aleohol, orEydraU of Phenyl, CWI^O = ^"^ | O 
Cn^fl-akohol, otHydraU of Creayl, CHK) « ^^[o. 



The farmer was identified as an alcohol by Laurent^, in 1841 ; the latter was disoovered 
liy Williamson and FairUe, in 1864. 

Both of these compoundis occur among the ^xroducts of the destructive distillation of 
ooal, and are seiMzated by fractional distillation. Phenyl-alcohol is also produced by 
the destructive distillation of salicylic acid : 

CH«0» = C^»0 + C0» 

I%coyl-alcohol is solid and crystalline at ordinary temperatures, mdts at 36^, and 
distils without decomposition at about 186^. Cresyl-alcohol is liquid at ordinary 
temnentures. 

lliese alcohols are easily decomposed by potasdnm and sodium, like common alco- 
hols, hydrogen being evolved, and compounds formed analogous to ethylate of potas- 
simn. They exhibit more dedded add characters than any of the preceding alcohols : 
phenyl-alcohol indeed is sometimes called phenic or carbolic acid : it forms a series of 
nlti, called phenates or carbolates, containing 1 at. metal in place of the basic hydrogen. 
These alcohols are not converted into simple ethers or hydrocarbons by heating with 
solphunc add. Strong nitric add converts them into nitro-adds, e, g, phenyl-iiloohol 
into tiinitzoeaibolic or picric add, C«H*(NO>)*0. 

h3 



102 ALCOHOLS. 

With pentachloride of phoflphoms, thej yield a chloride and a phosphate of the 
radicle together with hydrochloric acid : e.g. 

4(C«H».H.O) + PC1«.C1» - PO*(C*H»)« + C«H»C1 + iHQ 

Hydrate of Phosphate of Chloride 

phenyl. phenyl. of phenyl. 

With the chlorides of the acid radides, they form compound ethers, thus : 

C^».H.O + C'H*0.C1 « (7H»0«.C*H» + HCl 

Hydrate of Chloride of Benioate of 

pbenyU benzoyl. phenyl. 

6. Alcohols of the form C"H*»-»0 = ^"^^^Jo. Two only of these bodies are 
known, yiz. : 

Cinnamio alcohol^ Hydrate of Oinnamyl, or Styrone, C*H**0 « h(^ 

Choleaterin C»H"0 - ^ ^^fo 

Styrone is obtained b^ heating styradn (cinnamate of cinnamyl), with caustic alkalis ; 
cholesterin is found in the bue and other products of the animal economy. Styrone 
is converted by oxidising agents into cinnamic aldehyde, C^HK), and cinnamic add, 
CH'O', and forms with fuming sulphuric acid a coig'ugated acid, the barium-salt of 
which is soluble in water. Cholesterin heated with strong sulphuric acid gives i^ 
water and forms a resinous hydrocarbon, C^^ (Zwenger, Ann. Ch. Pharm. Ixv. 
6). Heated to 200^, with acetic, butyric, benzoic, and stearic acids, it forms com- 
pound ethers, with elimination of water, thus : 

Stearic Cholesterin. Stearate of 

acid. cholesterin. 

7. Saliffenin, CHK)*, aa alcohol of the salicyl-series, and Anuic alcohol, O'H'H)*, 
produced by the action of alcoholic potash on hydride of anisyl, OH'O^H, are 
probably monatomic ; if so, they must contain oxygen-radicles, their rational formulae 

being ^'^gjo and ^^'^hI^' ^^* ^^^ ^^^ *^ ^ diatomic alcohols, ^*|o« 
and n> [ ^* Their reactions are not suffidently known to decide the question. 
B. IMatomlo Alooliols, or Olyeols. C»H>^sO' « ^^^'^^| O*. These com- 

"ITS 

pounds, discovered by Wurtz, are derived from a double molecule of water, n-sO*, in whidi 

half the hydrogen is replaced by a diatomic radide OB>. Four of these have been 

obtained, viz. Ethylene^lyool, or HydraU of Ethylene, C«HK)« = ^^'^^[o',iVopy- 

lene-glycol, CHH)*, ButyUne-glycol, C*H'*0*, and Amylme-glycol, C»H»«0". The 
simme name glycol is espedaUy applied to the first of these, just as the term alco- 
hol IS espedaliy applied to hydrate of ethyl, the most important of the monatomic al- 
cohols. 

Glycol is obtained by treating iodide of ethylene with acetate of silver, whereby di- 
acetate of ethylene is formed : 

Iodide of 8 at. acetate of Diaoetate of 

ethylene. silver. ethylene. 

and heating the distilled diacetate of ejthylene with potash, whereby it is decom- 
posed, like other compound ethers, yidding acetate of potassium and hydrate of 
ethylene : 

(C^.).jO. . 2(KH0) - <^:j0. . (C^^IJo. 

It was discovered by Wurtz in 1856. The other bodies of the series are obtained by 
similar processes. They are oily liquids, which distil without decomposition. They 
contain two atoms of basic hydrogen, one or both of which may be replaced by metds 
or other radides. 
Glycol treated with sodium yidds monoaodic glycol, C^'(NaH)0^ and this com- 



ALCOHOLS. 103 

pound, ibsed irith excess of sodium, yields disodic glycol^ C*H^NaK)'. By treating 
mooosodic glycol with iodide of ethyl, the prodact with potaasium, and this piquet 
a^sain with iodide of ethyl, the componnds C»H«(C«H*.H)0«, C*H*(C?H».K)0*, and 
C^H^CrH*)*©*, are sacoesaiTely obtained. The la?t ia isomeric with acetal, but not 
identical with it (p. 3^ inasmuch as it boils at a temperature 20^ below that compound. 
Dehydrating agents^ such as sulphuric acid and chloride of zinc, do not act upon the 
glycols in the same manner as upon the corresponding monatomic alcohols. Ethyl- 
alcohol, (XS\H.O, acted upon by sulphuric acid, or chloride of zinc, at certain tempe- 
ratures; is conyerted into ether, (CH*)K), a second atom of ethyl being introduced in 
j^ace of the remaining hydrogen. If glycol were acted on by these reagents in the 
same manner, the result would be a glycolic ether containing (C'H*)'0*. Instead of 
this, the change which takes place is a simple abstraction of water, and the resulting 
compoond is aidehyde, 0*M*0, a body of isomeric composition, but only half the atomic 
wdght: 

C«H«0» - HK) = C«H<0. 

Similar results are obtained with the other glycols. The aldehydes may therefore 
be regarded as the ethers of the diatomic alcohols ; and their mode of ibrmation from 
these ala>hols difiers from the etherification of the monatomic alcohols in the same 
manner as the oonyersion of dibasic acids into anhydrides difiers from that of mono- 
basic acids, — ^the latter being converted into anhydrides by duplication of the radicle : 
e.ff. acetic acid « OH*O.H.O ; acetic anhydride » (OH'0)K), whereas dibasic acids 
pass to the state of anhydrides by simple abstraction of water, e.g. SO^Hf — H*0 » SO*. 
(Wurtz, Compt. rend. xlyiL 346.) 

By treating diatomic akohols, first with hydrochloric acid and afterwards with 
potash, oompounds are obtained isomeric with the aldehydes, and resembling them in 
some €»F their properties, but difiering in others ; thus, ethylene-glycol, heated in a 
sealed tnbe with hydrochloric acid, yields monochlorkydric glycol, CHH^O, a compound 
intermediate between ^col and chloride of ethylene, CH^CP, and formed frx>m glycol 
by the snbatitation of CI for 1 atom of peroxide of hydrogen : 

(?H*.H«0» + HCl = C^H^.HO.Cl + H^O; 

and this compound, treated with potash, yields oxide of ethylene, a body isomeric with 
acetic aldehii^e: 

0"H*.HO.a + KBO « CH^O + H^O + KCl. 

This oxide of ethylene resembles aldehyde in being miscible with water, and in form- 
ing a crjTBtalline compound with acid sulphite of sodium ; but difiers from it by boiling 
at a lower temperature, and by not forming a crystalline compound with am- 
monia. Sinular results are obtained with propylene-glycol. (Wurtz, Compt. rend. 
xlriiL 100.) 

The glycols corresponding to the other series of monatomic alcohols, have not yet 
been obtained ; but several diatomic compound ethers containing benzylene, C'H*, have 
been produced, viz. the acetate, valerate, and benzoate, CH*. (C^*0)'.0*, &c. ; the 
metfajlate, ethylate, and amylate, CH«.(CH")*.0», &c; the sulphate, SO*.C'H«, and 
the saecinate, (rE:C*K*0*.0\ The diatomic alcohol, CTBL'.H^O^, corresponding to 
those compound ethers, has notyet been obtained, not being produced when the ethers 
are decomposed by alkalis. (W. Wicke, Ann. Ch. Phaim. cii 363.) 

C. THatonlo Alooliols» or Olyoertns. The general formula of these compounds 
m [ O*, the radicle OH*»- ' being equivalent to three atoms of hydrogen. One 

term of the series haB long been known, viz. ordinary glyjeerin, C*HH>* « H"[^** 

the sweet oily liquid obtained in the saponification of fats. It was first shown to oe a 
tziatomic alcohol by Bert helot, in 1853. (Compt rend. xxxviL 398.) 

The neutral fats of the animal body, stearin, palmitin, olein, &c., consist of glycerin, 
in whidi three atoms of hydrogen are replaced by acid radicles; and by heating 
^yoerin with adds in different proportions, a large number of compounds may be 
formal, in which L {, or the whole of the replaceable hydrogen is thus replaced, 
the formation of these compounds being accompanied by the elimination of 1, 2, 
or 3 atoms of water. Thus, with stearic acid, C"H"0^ the following compounds 
are obtained: 

Honostearin - C«H«0* = C^>0» + C'^H-O* - H«0 - h1^^mo|o«. 
Distcarin - C*H»0» « C»H«0« + 2C»H«0« - 2H»0 - h.(cS«0)»1^* 

5SSf°.te«riB)t - ^^"•^ " ^^^ + ^C'^H"^' - »^'- (i^')'!<^'- 

H 4 



IS 



104 



ALCOHOLS. 



Freciflely similaF actions take place on heating glycerin with hydrochloric, hydio- 
bromic, or hydriodic acid ; but to refer the resulting compounds to the same type, it 
is best to write the formula of glycerin thus : C'H*(HO)', representing it as a compound 
of glyceiyl with 3 at peroxide of hydrogen : then the compounds just mentioned may 
be represented as glycerin in which 1, 2, or 3 at peroxide of hydrogen are replaced 
by CI, Br, I, &c Thus: 

Monochlorhydrin - C^'aO» « C»HK)" + HCl - IPO « C»H»Cl(HO/ 

Bichlorhydrin « C»H«C1K) = C»H"0» + 2HC1 - 2HH) « C^»C1«(H0) 

Tricblorhydrin « C^KKH* « C»H«0' + 3HC1 - 3HK) 

Biomhydrodichlorhydrin - C«H»Cl»Br« C»H"0» + 2HC1 + HBr - 3H»0. 

The chlorhydrins and bromhydrins are likewise produced by treating glycerin with 
either of the bromides or chlorides of phosphorus. (See Gxtcerin.) 

By treating glycerin with the chloride of an acid radicle, or by passing hydrochloric 
acid gas into a solution of glycerin in the corresponding acid, compounds are formed 
which may be regarded as glycerin, in which the peroxide of hydrogen is replaced 
partly by chlorine and partly by the peroxide of the acid radicle ; thus with acetic acid 
[Ac - C^H'O] : 



Acetochlorhydrin » C*H»aO« = C»H»0« + C«H*0» + 
Diacetochlorhydrin « Cff »C10« « C«H*0» + 
Acetodichlorhydrin « C*H«aK)« - C«H»0» + 



HCl - 2HK) « 

C»H»Cl(Ac0XH0). 
2C"H*0« + HCl - 3H«0 « 

C»H».a(AcO)« 
C*H*0« + 2Ha - 3H»0 « 

C«H».Cl«AcO. 



(For fiirther details, see Acetins, p. 25.) 

All these compounds, when heated with caustic alkalis, or with metallic oxides and 
water, reproduce the acid and the glycerin ; thus stearin heated with caustic potash, 
yields glycerin and stoarate of potassium : 

(0^^).|0. . 8KH0 . C^ljO. . z(0-^'\0) 

Glycerin may also be formed synthetically in a similar manner to glycol* "riz. Irjr 
heating tribromhydrin, C*H*Br", with acetate of silver, whereby triacetin, U"H'AcK)* is 
formed, and heating this compound with solution of caustic baiyta. The other 
gfycerins have not yet been obtained in the free state, but the acetate of ethyl-glyeerin 
(U*H»)'"Ac*0* appears to be obtained, together with glycol, by the action of iodide of 
ethylene on acetate of silver. 

D. Alooliols not inolnded la ajiij of tbo preeodiBff groupo. — Berthelot 
has shown that a considerable number of substances, not usually classed as alcohols, 
nevertheless possess one essential character of those bodies, viz. that they unit4> with 
acids, producing neutral compounds, the formation of which is attended with elimina- 
tion of water; and these compounds, when heated with alkalis, reproduce the sub- 
stances from which the^ have been formed. The bodies in question are chiefly of 
a saccharine nature, viz. Mannite, C*H*20*.H*0, the sugar of manna; Dtdcin, 




Phycite^ C*H"0*, a sugar obtained from certain lichens, and from the Protococctts tni/- 
garis, — Orcin, C'H'O', a sweet crystalline substance, existing in the lichens which 
yield archil and litmus ; Trehalose, C«H^»0», also a kind of sugar ; Glucose, C*H"0«, 
and Meconin, C**H><^0\ an acrid crystallisable substance, obtained from opium. The 
following are examples of the compounds formed : 

C^«0» + 2C«H*0« - 2H«0 a C»H'«0» 

Mannlte. Acetic acid. 

C^»K>» + 4C>»H»0« - 2HK) « C^H»«0" 
Mannlta Stearic acid. 



C«H»0* 
Maouite. 


+ 6C"H*0» - 
Stearic acid. 


6BP0 « C"*H"«0" 


Fhjcite. 


+ 2C»H«0« - 
Benzoic acid. 


2HK) - C«»H«0» 


(?) 


C«H»0« 
Pbjrcite. 


+ 6C'H'0» - 
Benioic ac*d. 


6H«0 = C"H*0" 


(?) 


C^»K)« 

Glucose. 


+ 2C»«H"0« - 
Stearic acid. 


3H«0 = C**WK>^ 




C"H»»0* 
Moconln. 


+ 2C"H«»0» - 
Stearic add. 


2H«0 « C«H»0«. 





ALDEHYDE. 105 

The eompoands fiinned by all these bodies, exceptiiiff the last two, with acidB, readily 
jield ihe original saccharine substance and the acid. The compounds formed with 
gineose are not very definite, and not easily decomposed ; but when treated with dilute 
solphnric acid, thej yield the original acid and a fermentable sugar, which reduces 
copper salts. (Berthelot, Compt. rend. zIL 462; zlTii. 262.) 

AZASBTBB. C*H*0 « C«HK).H. [or Cfi^O* = dPO.HO]. Acetic aldehyde, 
Hjfdride cf Acetyl (Gm. yiii 274; xiii. 437; Gerh. i. 658). — A volatile liquid 
produced, by the oxidation and destructire distillation of alcohol and other oiganic 
eompovnds. It was first obtained in an impure state by Dobereiner, who called it 
IjUfkt axyyen ether, and waa afterwards prepared pure and thoroughly examined by 
Liebig (Ann. Ch. Pharm. xir. 133 ; xxxvi 376). The name aldehyde ia an abbrevia- 
tion of alcohol dehydroyenatunif inaamuch as the compound may be r^arded as alcohol 
depriTed of two atoms of hydrogen. 

Formaium^ — 1. In the oxidation of alcohol, either by slow combustion in contact 
with platumm-black, chromic oxide, &c, or by the action of chromic acid, nitric acid, 
chlorine water, or a mixture of sulphuric acid and.peroxide of manganese (see Axconoi., 
pi 74). — 2. Wben the yapour of alcohol or ether is passed through a tube heated 
to dull redness ; also in tne slow combustion of ether. — 3. In the decomposition of 
acetate of ethyl, and probably also of other ethylic ethers, by a mixture of sulphuric 
add and acid chroma te of potassium. — 4. By heating acetal with glacial acetic acid to 
between 150^ and 200^ G. for two days. Acetic ether and alcohol are formed at the 
same time, and on distilling the mixture, aldehyde passes over below 60^ : 

Acetal. Acetic Aldehyde. Acetic Alcohol, 

acid. ether. 

abo by >»Aft*ing acetal with acetic anhydride : 

C^»K)« + C^H'K)* « C*H*0 + 2C*H»'0». 

A fewdnps of liquid are also obtained boiling above 150^, and probably consisting of 
a compoond of aldehyde with acetic anhymide (Beilstein, Gompt. rend, xlviii. 
1121). — 5. By heating ethyl-sulphuric aeid or one of its salts with a mixture of sul- 
phune acid and peroxide of manganese. This formation of aldehyde is said to take 
place under circumstances which altogether preclude any previous formation of alcohol 
(Jacquemin and Liis-Bodard, rlnstitut, 1867, p. 407). — 6. When hemp-oil is 
passed through a gun-barrel heated to low redness, a liquid is formed containing a 
large quantity of aldehyde, together with alhehydic or lampic acid (Hess). — 7. By 
the dry distillation of lactic acid, lactic anhydride, and lactates with weak bases, such 
as lactate of copper, carbonic oxide being given off at the same time : 

CR'H)* = 2C"H*0 + 2C0 + 2H*0. 

— , — ' " — , — •' 

Lactic Aldehyde, 

acid. 

8. Lactic acid and the lactates also yield considerable quantities of aldehyde when dis- 
tilled with sulphuric acid and peroxide of manganese (Stadeler, Ann. Gh. Pharm. 
Ittix. 333). — 9. In the decomposition of animal albumin, fibrin, casein, and gelatin by 
a mixture of sulphuric add and peroxide of manganese, or bichromate of potassium 
(Ouckelberger), also of v^table fibrin by sulphuric acid and peroxide of manganese 
(Keller). — 10. By the dry distillation of a mixture of acetate and formate of caldum 
in equal numbers <^ atoms (Li mpri ch t. See Aldbhtdbs, p. 1 1 1 ; also Acbtonbs, p. 31 ). 

C»H«GaO« + CHGaO« = CWO + CG»Ga«. 

Acetate of Formate of Aldehyde. Carbonate 

calcium.' calcium. of calcium. 

I^'eparaium. — 1. Two pts. of 80 per cent alcohol are mixed with 3 pts. oil of vitriol 
aod 2 pts. water, and distilled into a receiver kept at a vezy low temperature. The 
mixture is gently heated till it begins to froth slightly, and the distillation is interrupted 
as soon as the liquid which passes over begins to redden litmus, which it does when 
the distillate amounts to 3 pts. The distillate, consisting of aldehyde, alcohol, &c., is 
mixed with an equal weight of chloride of calcium, and distilled (the receiver being 
constantly kept veiy cold), till 11 pt. has passed over, and this distillate is again 
rectified with an equal weight of cnloride of caldum till f pt. has passed over. This 
last portion is anhydrous, but contains alcohol and certain compound ethers as well as 
aldehyde. To punfy it^ 1 vol. is mixed with 2 vol. ether, the mixture surrounded with 
oold water, and dry ammoniacal gas passed into it to saturation ; the gas is absorbed 
npidly and with great evolution of heat, and the aldehyde separates out in crystals of 
aldehyde-anunonia. These crystals are washed three times with absolute ether and 
dried as above. (Liebig.) 



103 ALDEHYDE. 

2. A mixture of 1 pt. 80 per cent, alcohol and 2 pts. wat«r ia saturated with 
chlorine gas (being kept cool all the while), and the liquid distilled, as soon as it has 
lost the odour ofchlonne, till ^ has passed over. That which distils oyer afterwards 
is alcohol, which may be collected in a separate receiver and again treated with chlorine 
as above. The first distillate is again freed from water by repeated distillation so far 
as to admit of its being saturated with ammonia as aboye, and yields a very large 
crop of crystals. (Liebig.) 

3. One part of alcohol of sp. gr. 0*842 and 1 pt of bichromate of potassium are in- 
troduced mto a capacious tubu^ted retort and 1| pt. oil of vitriol admitted by drops 
through the tubulus. The heat evolved by the chemical action which ensues is suffi- 
cient to begin the distillation, but towards the end, heat must be applied from without. 
A large quantity of carbonic acid gas is evolved, and the aldehyde condenses in the 
well cooled receiver, contaminated with only a small quantity of acetic acid and other 
substances, so that the distillate may be immediately mixed with ether, and ammoniacal 
gas passed through it as above (W. and R Bodgers, J. pr. Chem. xl. 248). The 
modes of formation 5, 6, and 8, above given, may aUo be advantageously used for the 
preparation of aldehyde. < 

To obtain the pure anhydrous aldehyde from the aldehyde-ammonia formed by • 

either of these processes, a solution of 2 pts. of the aldehyde-ammonia in 2 pts. water, 
IB distOIed in a water-bath at a gentle but increasing heat, with a mixture of 3 pts. 
sulphuric acid and 4 pts. water, the distillation being interrupted as soon as the water 
in the bath begins to boil, and the receiver kept as cold as possible, The hydrated 
aldehyde which passes over is dried by contact with coarse lumps of chloride of cal- 
cium in a well aosed vessel, and then rectified in a water^bath, at a temperature not 
exceeding 30^. 

Properties. — Aldehyde is a thin, transparent^ colourless liquid, having a pungent 
suffocating odour. Its specific gravity is 0-80002 at 0^ (Kopp); 0*80561 at 0^ 
(Pierre). It boils at 20*8^ when the barometer stands at 760 mm. fKopp) ; at 
22^, with ihe barometer at 758*2 mm (Pierre). Vapour-density 1*532 (Liebig) ; (by 
calculation, 1*520, for a condensation to 2 vol.) It does not redden Utmus, even when 
it is dissolved in water or alcohol. 

Aldehyde may be regarded either as the hydride of acetyl^ C^H'O.H, or as the hv' 

drate or hydrated oxide of vinyl^ H [^' I^^ cb^°^cal ^^ctions may for the most 

part be explained equally well on either hypothesis; but according to the recent 
observations and calculations of Kopp, the formula C^*O.H, is most in accordance 
with the observed atomic volume of aldehyde, which is between 56*0 and 56*9, the 
calculated atomic volume being 56*2, as deduced from the first formula, and 51*8 as 
deduced from the second. (See Atomic Volume : also Graham's Chemistry, 2nd Ed. 
vol. ii. p. 581.) — ^Aldehyde is isomeric, but not identical, with the oxide of ethylene, 
C*H*.0, recently discovered by Wurtz. 

Aldehyde mixes in all proportions with water, alcohol, and ether. A mixture of 
1 pt. aldehyde and 3 pts. ' water boils at 37°. Chloride of calcium added to the 
aqueous solution separates the aldehyde, which then rises to the surface. 

Aldehyde dissolves sulphur and phosphorus, also iodine, forming a brown solution. 

D17 sulphurous acid gas passed into anhydrous aldehyde surrounded with cold 
water, is rapidly absorbed, 11 pts. of aldehyde absorbing 9 pts. of the gas, with 
increase of volume. The absorption-coefficient of aldehyde for sulphurous acid gas is 
1*4 times as great as for alcohol, and 7 times as great as for water. (Geuther and 
Cartmell, Ajon. Ch. Pharm. cxi. 17.) •■ 

Decompositions. — 1. Aldehyde is very inflammable, and bums with a blue flame. — 
2. When kept in close vessels, it is often converted into a less volatile liquid, or into 
two crystalline bodies, which are isomeric modifications of aldehyde (p. 109). — 3. In Tea- 
sels containing air, it absorbs oxygen, and is converted into acetic acid ; the action is 
greatly accelerated by the presence of platinum black. — 4. Chlorine-water and nitric 
add also convert aldehyde into acetic acid. — 5. By strong sulphuric acid, it is thickened 
and blackened, also by phosphoric anhydride. — 6. When an aqueous or alcoholic 
solution of aldehyde is heated with potash, it becomes yellowish and turbid, and a 
red-brown resinous mass, the resin of aldehyde, separates on the surface, the liquid at 
the same time emitting a spirituous and disagreeably pungent odour. The solution is 
afterwards found to contain formats and acetate of potassium. This is the most 
characteristic reaction of aldehyde. — 7. When vapour of aldehyde is passed over red- 
hot potash-lime, acetate of potassium is formed and hydrogen evolved : 

C*H*0 + KHO « C«H»KO« + 2H. 

8. Potassium Tor sodium) acts on aldehyde in the same manner as on alcohol, hydro- 
gen being evolved and aldehydate of potassium, C'BPKO, produced. — ^9. When an 



ALDEHYDE. 107 

•qveoiis eolation of aldehyde is heated with oxide or nitrate of silver^ mixed with s 
imdl quantity of a$nmonia^ tlie silTer is reduced, forming a beautiful specular coating 
on the side of tlie vessel, and acetate of silver is formed in the solution. This reaction 
■ffiods an extremely delicate test for aldehyde. — 10. Chlorine gas in contact with alde- 
hyde, botli beiiu; dry, decomposes part of the aldehyde^ forming chloride of acet^ which 
then unites with the nndeoomposed aldehyde, forming the compound, C'HH}.&H'0C1. 
— II. When diy hydrochloric acid gas is passed into anhydrous aldehyde surrounded 
by a freezing mixture, the gas is absorbed and the liquid separates mto two layers, 
the lower consisting of water saturated with hydrochloric acid, and the upper of oxy- 
chloride of eihyUdcne, C<HK3K) (A. Lieben, Compt lend. xlyi 662) : 

2C?H*0 + 2HC1 « (ySHSlH) + WO. 

Aoecoding to Genther and Cartmell (Ann. Ch. Fharm. crii. 13 ; Froc Roy. Soc 
X. 110) the first product of the action is the body, C^"G1H)^ which, when gently 
heated in an atmosphere of carbonic add, splits up into aldehyde, CH^O, and 
C*HK]3*0. The compound CH'Kn^K)^ may be ri^garded as a triple molecule of alde- 
hyde ((XHTK)*), haying one atom O replaced by Cu^. — 12. Aldehyde mixed with twice 
its bulk of absolute alcohol, and saturated in the cold with hydrochloric acid gas, 
yields the compound OH*C10, which, when treated with ethylate of sodium, forms 
SfCetal (p. 3 ). --- 13. "^th pcntachloride of phosphorus^ aldehyde yields chloride of 
ethylidene,,(?H*Cl*, and with pentabromide of phosphorus it yields bromide of ethyli- 
dene, U*ll^i*, which is conyerted by ethylate of sodium into acetal (p. 4). — 14. Chloro- 
carbonic oxide (phoseene gas) conyerts aldehyde into chloride of vinyl, CH'Cl, with 
evolution of hydrochloric add and carbonic anhydride. (Harnitz Harnitzky, Ann. 
Ch. Fhaxm. cxi 192.) 

c«H*o + coa« a. c*H»ci + Ha + co«. 

15. Hydriodic acid gas appears to act upon aldehyde in the same manner as hydro- 
chloric add, but the product is very unstable. — 16. When aqueous aldehyde is satu- 
rated with hydrosulphuric acid gas, a visdd oil is formed, consisting of hydrostd- 
fhaU of aoetyl-mercaptan: C^'H^'S » SH*6C<H«a On treating this oil with strong 
nydroddorie or sulphuric add, hydrosulphuric add escapes, and a white crystalline 
mass remains, consisting of acetyl-^ncrcaptan, CH^S, a compound related to aldehyde, 
in the same manner as ethvl-mercaptan, CH^S, to aloohoL — 17. (hfanic acid vapour 
evolved from cyannric ada is quietly absorbed by anhydrous aldehyde at 0°; but 
even at ordinaiy temperatures the mixture becomes heated, gives off carbonic anhydride, 
and ultimately froths up and solidifies into a mass consisting of trigenic acid, C^H^NK)', 
together with small quantities of cyamelide, aldehyde-ammonia, and other products 
(Liebig and Wohler) ; 

C*H*0 + 3CNH0 = C*ffNH)» + C0« 

AumHTBAiBS. — Aldehyde may be regarded as a monobasic add, inasmuch as it 
contains one atom of hydrogen replac^ble by metals. Thus, when potassium is 
gently heated with aldehyde, hydrogen is evolved, and aldehydate of potassium, 
CH'KO, produced : and oy evaporation in vacuo this salt may be obtained in the 
solid state. — Aldehydate of silver, CH'AgO, is produced when oxide of silver is 
heated with aldehyde and ammonia. The most important of these salts is the am- 
monimn-salt : 

Aldehydate of Ammonium, AldehydcTammonia, Acetyl-ammonium^ O^H^O.NH* a 
<?H»0 JTH*, or Oxide of Vinyl and Ammonium, C«BP.NH*.0. — Ammoniacal gas 
passed into pure aldehyde combines with it, giving off heat, and forming a white 
oystalline mass. If the aldehyde be previoiuly mixed with ether, the compound 
separates in distinct crystals; the finest are obtained by mixing a concentrated 
akoholic solution of aldehyde-ammonia with ether (Liebig). — The crystals are acute 
rfaovnbohedions with terminal edges of about 85^, often truncated with the faces of 
ancvther riiombohedron (G-. Rose) ; they are transparent, colourless, shining, stronsly 
refractive, of tiie hardness of common sugar, and veiy friable. The compound melts 
between 70^ and 80° C, and distils unaltered at 100°. In the state of vapour or in 
aqueous solution, it reddens turmeric paper. Its odour is ammoniacal, but has like- 
wise the character of tuipentine (Liebig). — ^It dissolves veiy easily in water, less 
easily in alcohol and ether. 

Aldehyde-ammonia is veiy inflammable. In contact with the air, especially if also 
exposed to light, it becomes yellow, and acquires an odour resembling that of burnt 
animal substances. By distillation it may again be obtained in the colourless state, 
and leaves a brown rcddue, which is soluble in water, and contains acetate of am- 
monium and another ammoniacal salt Even the weaker acids, such as acetic acid, 
separate the aldehyde from the compound. Sulphuric acid and potash act upon it in 






108 ALDEHYDR 

the Mine T«*tw»^ u upon aldebyde. Its aqneons solntiafii, digerted with oxide of 
silver, redaces part of Uiu oxide and diMolres the rest, forming aldehydate and acetate 
of tiller mixed with ammonia, from which the oxide of silver is precipitated by baryta- 
water, and reduced when the liquid is heated, while acetate of boriom remains in 
solution. 

Aldeh jde-ammonia treated with hydroenlphoric add yidds tkialdine, C*H"N9 : 

3(C«HK).NH*) + 3BPS = C«H»*NS» + (NH*)«S + 3H«0. 

Similarly, with hydioselenie add, it yields seUruddine, C^^^Se*. With bisulphide 
of carbon it forms carbotkUddine : 

2(C«H»0.NH*) + C8» « C»H»«3rS« + 2H«0 

s— ., > , ' 

AUebjrde. Cvbo- 

CDinoDla. tliialdioe. 

Aldehyde-ammonia heated with hydrocyanic and hydrochloric adds yields alanine: 1 

C»H«O.NH» + CNH + HK) + Ha « CBTSO* + NH*CL ] 

>-' — , ^ ' — . — ' * • 

Aldehyde- Hydro- Alanine. , 

iimiDonia. cyanic 

add. 

But when a mixture of aldehyde-ammonia and hydrocyanic add, with snffident hydro- 
chloric add to give it a distinct add reaction, is left to itself for some time, in a doeed 
vessel, espedal^ in sunshine, colourless needle-shaped crystals are formed, consisting 
of hydrocyaruUdine, (?H**N* : 

8(C«H*0.NH») + 3CNH + 2HC1 = O^VSi* + 2NHH:J1 + 3H*0. 

Aldehyde-ammonia heated in a sealed tube to 120° G. is decomposed, and yields two 
layers or liquid, the upper consisting chiefly of aqueous ammonia, with small quanti- 
ties of other volatile bases, while the lower, which remains behind on Hiatilling at 
200°, contains a substance which has the composition C**H**NO, and mav be regarded 
as an aldekydate of tetravinylium : s CH'O.N(CH')\ Its formation is represented 
by the equation : 

6(C*H»0.NH^) - C»»H»*NO + 4NH» + 4HK). 

By treating this compound with baryta-water, the group (>Jtl"0 is replaced by HO. 
and hydrate of tetravinylium is formed. 

C*HK).N(C«H»)* + BaHO = C*H«O.Ba + N(C«H»)*.H.O. 

(Babo, J. pr. Chem. Ixxii. 88 ; Chem. Gaz. 1858, 136.) 

Concentrated aqueous solutions of aldehyde-ammonia and nitrate of silver yield, 
when mixed, a fine-grained white predpitate, probably consisting of NO'Ag. 
2(C*H*0.NH*). It dissolves very sparingly in alcohol, easily in water. 

BulphiU of Aldehyde-ammonia, or Stdphite of Vinyl-ammonium, C*H"^NH*)O.SO* — 
(C'H'.NH*).SO'. — Sulphurous add gas passed into a solution of aldehyae-ammonia in 
absolute alcohol is rapidly absorbed ; and if the liquid be kept cool, sulphite of alde- 
hyde-ammonia is deposited in small white prisms, which may be washed with alcohol 
and dried in vacuo. This compound is isomeric with taurin, CH'NO'S — a substance 
produced by the metamorphosis of a sulphur-add contained in the bile — ^but possesses 
very different properties. It is soluble in water and in aqueous alcohol, very 
sparingly in absolute alcohoL The crystals decompose slowly in the air at ordinary 
temperatures, turn brown and lose weight at 100° and are completely decomposed at 
higher temperatures, leaving a spongy carbonaceous residue. Adds decompose them, 
liberating aldehyde and sulphurous anhydride. When strongly heated with potash- 
lime, they give off ethylamine (Qossmann, Ann. Ch. Phann. xd. 122), or rather 
perhaps mmethylamine : 

C«H".NH*.SO» + KHO « C«H^ + SO*.HK. 

CoKPouin) OF Aldbhtdb wtth Acbtic Anhtdridb, C*H'*0*=C*H*0*.C*H*0. — 
When 1 at. acetic anhydride and 1 at., pure aldehyde are heated together in a sealed 
tube to 180° C. for about 12 hours, they unite and form a liquid compound which may be 
freed firom unaltered aldehyde and acetic anhydride by fractional distillation, further 
purified by washing the portion which passes over above 140° with hot water, and dehj- 
orated over chloride of calcium. It then boils at 168°. It has an alliaceous odour and 
slight acid reaction, probably arising firom decomposition during distillation. Heated 
with hydrate of potassium, it yields acetate of potassium, giving off the peculiar odour of 
aldehyde when similarly treated. This reaction diHtinguishes the compound from Wuitz'a 
acetate of ethylene (acetate of glycol), C«H*(C«H»0)«.0» with which it is isomeric: for 
that compound heated with caustic alkalis, yields hydrate of ethylene (glycol), with- 
out aoy odour of aldehyde. (Gent her, Ann. Ch. Pharm. cvi. 249.) 

Aldehyde appears to form similar compounds with benzoic and succinic anhydrides. 



ALDEHYDE. 109 

GOMPOUND OF AxJiVETDE IHTH ChLORIDB OF ACSTIL, C*HH710*«C*H*0.C'B[*0CL 

—Chloride of acetyl and aldehyde heated together to 100^ for three hours in a 
•eakd tabe, iinit€ and form a liquid which diatils completely between 90^ and 140° C. 
and yields bj fractional distillation a considerable (quantity of liquid, boiling between 
120° and 124°. This liquid is lighter than water ; is yeiy slowly decomposed by cold 
water, more quickly by hot water ; and dissolyes easily in dilute potash, forming 
ehbride and acetate of potassium, and yielding free aldehyde which is partly i«sinisea 
by the potash. Moist oxide of silyer also decomposes it, forming chloride and acetate 
of nher. (Maxwell Simpson, Compt.-rend. xlvii. 174.) ' 

The same compound is pzoduced, according to Wurtz (Ann. Ch. Phys. [3] xliy. 68), 
t<^gether with chloride of acetyl, by introducing perfectly diy aldehyde into a large 
Tcssel filled with dry chlorine. Its formation is due to the union of the chloride of 
acetyl first produced with the remaining aldehyde (compare p. 106). Wurtz, how- 
erer, regaids it as a double molecule of aldehyde (C*H"0'), having 1 at H replaced by 
ehbrine. 

Modifications of Aldbhtdb. — ^Aldehyde ts susceptible of four isomeric modiflca- 
tioDi^ two liquid and two solid. 

a, Idqmd nuH^fications. — 1. Pure aldehyde sealed up in a tube changes in the 
eonree of a few weeks into a liquid, which has a pleasant ethereal odour, boils at about 
81°, and do longer forms a resin with potash ; it may be exposed to the air without 
ozidiriiig, and floats on water without mixing. (L i e b i g ) 

2. Pore aldehyde mixed with about half its bulk of water and a trace of sulphuric 
or nitric add, and cooled to 0° C, changes into a liquid which is no longer miscible with 
water, and after being purified by agitation with water, and rectification over chlo- 
ride of caldum, boils at 125°. It has a peculiar aromatic burning taste, and is 
aokble in alcohol and ether, sparingly also in water. Its vapour-density is 4*683, 
which for a condensation to 2 volumes, corresponds to the formula C*H*K)'. When 
left to itself or in contact with water, it readily changes into an acid, and then becomes 
miscible with water ; occasionally also crystahi separate from it at the same time. 
When heated with a small quantity of sulphuric or nitric acid, it is converted into 
ordinaiy aldehyde. (Weidenbusch, Ann. Ch. Pharm. Ixvi. 166.) 

b. Solid modifications, — 1. Solid and fusible Maldekyde, — Anhydrous aldehyde, en- 
dosed in a tube, together with pieces of chloride of calcium, for two months in winter, 
yielded long ti^nsparent prisms, which, howerer, disappeared again after a fortnight, 
■0 eom^etdy that not a trace of them could be perceived in the liquid. — These crys- 
tals max at -i- 2° C, forming a liquid which solidifies at 0°, and boils at 94°, giving off 
a vapour whose density is 4 '61 67. In the fused state, this substance has an ethereal 
odour ; more agreeable and less pungent than that of aldehyde ; its taste is some- 
what burning. Its bums with a blue flame ; its vapour passed through a red-hot 
tabe yields a combustible gaseous mixture, and a small quantity of a Hquid having 
an empyreumatic oc|pur. Oil of vitriol blackens the crystals slowly in the cold, imme- 
diately when heated. The ciyst«lB may be heated with potash-ley for some time with- 
out becoming coloured^ and solidify again on the surface as the liquid cools. When 
heated with aqueous nitrate of silver, th^ throw down the silver in the form of a 
grey powder, not as a specular coating. When dissolved in ether, they do not absorb 
ammoniacal gas but remain unaltered. (Fehling, Ann. Ch. Pharm. xxvii. 319.) 

Oeuther and Cartmell (Ann. Ch. Pharm. cxi. 16) have obtained a similar modi- 
tion, by saturating common iddehyde with sulphurous add gas, dissolving the result- 
ing liquid in water, saturating the acid with chalk, distiUiiig, and treating the dis- 
tillate with potash, which separates the remaining common aldehyde in the resinous 
fonn, and leaves the modified aldehyde in the form of a clear liquid, which boils at 
124° C, like the modification obtained by Weidenbusch, and solidifies at 10°, starting 
into crystals which also beein to melt at 10°. 

2. Solid and infusible Metcddehyde. — ^Anhydrous aldehyde kept for some time in a 
sealed tube or well stoppered bottle, frequentlv deposits transparent, colourless, four- 
sided prisms, which traverse the whole Hquia like a network. The crystals remain 
■olid at 100° C, but at a stronger heat sublime undecomposed, in the form of transpa- 
rent, colourless, shining, rather hard needles, which are easily pulverised, inodorous, 
combustible, scarcely at all soluble in water, but easily soluble in alcohol and ether 
(Liebig). — ^Fehling, by exposing pure aldehyde to the cold of winter for several 
wedu, once obtain^ the same crystals, mixed^ however, with a larger quantity of 
the erystala b. They are hard and easy to pulverise ; at 120° they sublime without 
pevious fusion. When they are suffered to evaporate in the air, the vapour condenses 
m line snowy flakes (Liebig). Heated for some time to 180° in sealed tubes 
they are leoonrerted into ordinary aldehyde. (Geuther, Ann. Ch. Pharm. cvi. 262.) 

Alobhtdb-bbsin. — A resinous body obtained by heating aldehyde with potash, either 
tn aqueous or in alcoholic solution, especially the latter. It is also formed in solutions 



110 ALDEHYDES. 

of the alkalis in alcohol, and in acetal, when kept fbr a long time. Aocoidinff to 
WeidenbuBch (Ann. Ch. Fharm. IztL 153) itia a substance of a fieiy orange ocHonr 
which is reduced by diying at 100^, to a powder, haTin|F a paler tint. It dissolves in 
alcohol and ether, sparingly in water, scarcely at all in alkalis, partially in strong 
sulphuric add, from which it is precipitated by water. When pnrified as completely 
as possible, it contains 76*4 per cent of carbon, and 8*0 per cent, of hydrogen : its 
formation is accompanied by that of acetic, formic and acetylous [?] acid ; at the 
same time a punsent odour is eyolyed, proceeding from, a peculiar substance which 
adheres obstinatdy to the resin. This substance is oily and volatile when first pro- 
duced, but soon thickens, even when alone and still more quickly under the influence 
of nitric acid, and is converted into a golden-yellow, viscid resin, which .«mells like 
cinnamon, dissolves in alcohol and ether, and sparingly in water, and is different fiom 
the true aldehyde-resin. 

AlABBnSS. A class of organic compounds intennediate between alcohols 
and acids. They are derived from alcohols by abstraction of 2 atoms of hydrogen, 
and are converted into acids by addition of 1 atom of oxygen : thus in the fktty acid 
series: 

C-H«-+«0 - H« = C'H^O, and OH»-0 + = OHK)« 

Alcohol. Alddiyde. Aldehyde. Add. 

Aldehydes may be regard d as derivatives : 1. Of a molecule of hydrogen HH, half 
the hydrogen being replaced by an ozygen-radide : e,g, benzoic aldehyde or bitter- 
almond oi^ C'H*0 -* (7H*0.H.— 2. Of a molecule of water, half the hydrogen being 

replaced by a monatomic hydrocarbon, e.ff. benzoic aldehyde » rr f O; acetic alde- 

hydfi B n; V ^' — ^-OftL molecule of water, in which the whole of the hydrogen is 

replaced by a diatomic hydrocarbon: e.ff, acetic aldehyde « (C^^y'O. According to 
this last view, which is strongly corroborated by the action of sulphuric acid and 
chloride of zinc upon glycol (p. 102), the aldehyaes are the ethers or anhvdrides of 
the diatomic alcohols, and are related to them in the same manner as the dibasic an- 
hydrides to the dibasic acids ; thus 

Type H*0* Type H«0 

Sulphuric add ^^2 0* Sulphuric anhydride S0».0 

Glycol ^»|^' Aldehyde CmO. 

The following are the aldehydes at present known. 

1. Aldehydes of the form OH*-0 = ^^""""jo - C^E^OJR. 



Acetic aldehyde 
Propionic „ 
Butyric „ 
Valeric „ 
(Enanthylic „ 



C*H*0 

C»H«0 

C^H-O 

C»H»«0 

CH^O 



Capiylic aldehyde [?]. . (?H>«0 

Enodic „ . . C"H«0 

Laurie „ . . C*«H«0 

Palmitic „ . . C»*H«0 



2. Aldehyde of the form OH«"-«0 « ^^^'^jo « C^«-«O.H. 
Aciylic aldehyde^ or Acrolein, C*H*0. 

8. Aldehyde of the formG"H«-*0 « ^^"'gjo « OH*»-*0.H 
Campholic aldehyde, or Camphor, C^'R^'O, 

4. Aldehydes of the form OH*»-^ » ^^*^|o «OB>-K).H. 

Benzoic aldehyde, or Bitter-almond oil, C^'O. 
Cuminic aldehyde, or Oil of Cumin, O'BS), 

6. Aldehyde of the form C-H*»-»0 - ^^*' gjo, or C-H«^>O.H. 
Cinnamic aldehyde, or Oil of Cinnamon, CEPO. 

6. Aldehydes of the form C-H*-^« = C-H«-^> q^ ^^ C-H«*-*0».H. 

Salicylic aldehyde, or Salicylous add, C»H«0*. 
Anisylic aldehyde, or Anisylous add, C'H'O*. 



ALDEHYDES. Ill 

The aldehydes tSonespondiiig to known alcoholB may all be fbrmed from thoM 
iloobols by oxidation, either by ezposuie to the air in contact with platinum-black, or 
bf distillation with a mixture of (ulnte snlphnric acid and peroxide of manganese or 
acid ehromate of {wtaasinm. Aldehydes may also be prepared &om the corresponding 
aods by a general process, Tic by distilling a mixture of the barinm-salt of the acid 
with an eq[iuYaleDt quantity of formate of buium, thus : 

Benzoate of Formate of Hydride of Carbonate 
bariua. bariam. benzoyU oft>ariiim. 

(Limpricht) Ann. Gh. Fharm. zcvii. 368 ; Piria, Ann. Ch. Phys. [8] xlyiii. 113). 
This process is a particular case of Williamson's method of producing compound ace- 
tones (p. 31). 

Streril aldehydes, as benzoic, acetic, propionic, butyric, &c. are produced by the 
distillation of albumin, fibrin, casein, and gelatin with peroxide of manganese and 
Bolphnric acid. Some are formed in the destructive distillation of orgamc acids, as 
atfUe aldehyde from lactic acid, cenanthylic aldehyde from ricinolic acid. Caprylic 
aldehyde is said by some chemists to be produced (together with the corresponding 
alcohol), by distilling ricinolic acid with excess of potash. According to Bonis 
(Conpt rend. ilJiL 603), a new add, C^^H^^O', is formed at the same time : 



Ricinolic Caprjlio 

add. aldebjde. 

But according to Malaguti (Cimento, iy. 401), the acid formed is sebadc acid 
thns: 

CWH"<0« + 20 « C"H»«0 + C»«H>"0* 



Ricinolic Caprylic Sebacic 

add. aldehyde. acid. 

This deoomjposition is supposed to take place simultaneously with that by which 
oetyfie (capirhc) alcohol is produced (p. 97). The aldehyde might indeed be pro- 
dneed by oxidation of the aloohoL According to St adeler, on the othier hand (J. pr. 
Chem. IxTxiii. 241), the product OH"0 thus formed is not caprylic aldehyde, but 
methyl-cenanthyl, CH^.CH^'O, a body isomeric with it (p. 97). 

Many aldehydes are obtained directly from plants, eitiier existing ready formed in 
the plants, or being given off as rolatile oils on distilling the plants with water. Thus, 
benzoic aldehyde constitutes the essential part of bitter-almond oil, cinnamic alde- 
hjde of cinnamon oil, cuminic aldel^de oi Eoman cumin oil, and salicylic aldehyde 
or saHcyloos add, of oil of spinea. Oil of rue consists prindpally of euodic aldehyde, 
mixed with a small quantity of lauric aldehyde (0. G-. Williams, Proc. Koy. Soc. ix. 
167). It was formerly supposed to be capric aldehyde. Benzoic aldehyde is also pro- 
dnced by the action of nascent hydrogen (eTolved by the action of zinc on hydrochlo- 
lie add) on cyanide of benzoyl, hydrocyanic being formed at the same time : 

CrH*O.Cy + HH « (?H«O.H + CyH. 

This mode of formation corresponds with the representation of aldehydes as hydrides 
of add radicles. 

All the known aldehydes (except palmitic aldehyde, which is a fatty solid) are 
fiqiiidB, which Tolatilise without decomposition. They are yeiy prone to oxidation, 
bong conyerted into adds more or less quickly by mere exposure to the air. In con- 
seqoence of this tendency to oxidation, they easily reduce the oxides of the noble 
metals (see p. 106). Hany aldehydes are conyerted by hydrate of potassium, espe- 
cially in aleonolic solution, into the corresponding alcohols, and the potasdum-salt of 
the oonrespondSng add : thus, with bitter almond oil : 

2CrH«0 + KBO = CHK) + C*H*KO« 

Bensoic Benxyl- Benxoate of 

aldehyde. alcohol. potassium. 

Cominie aldehyde and anisylic aldehyde are decomposed in like manner. The al- 
dehydes of the first series (corresponding to the fatty acids) and acrylic aldehyde, are 
not decomposed in this manner: acetic aldehyde treated with potash yields acetate 
and formate of potassium and a brown rednous mass. 

All aldehydes form definite, and for the most part crystalline, compounds with the 
tod Rilphites of tiic alkali-metals, e. g, bitter-almond oil with acid sulphite of sodium. 



112 ALDEHYDES. 

C'H«O.SO«NaH « ^*| S0« + H»0 « Na.C'^»l ^' "*" ^^' '^^ eompounds 
are for the most part soluble in water and alcohol, but insoluble in saturated solutions 
of the alkaline bisulphites. Hence by shaking a liquid containing an aldehyde with 
excess of such a saturated solution, the aldehyde may be completely separated in the form 
of a crystalline compound. This is an excellent method of purifying those volatile oils 
which haye the constitution of aldehydes. The acid sulphites of potassium and sodinm 
are, generally speakine, the best adapted for this purpose, as the compounds which l&ey 
form with the aldehydes are much less soluble in the solution of the sulphite than the 
corresponding ammonium-compounds, and therefore crystallise more readily. From 
all these compounds, the aldehyde may be set free by the action of the stronger acids^ 
or by neutralisation with an alkaline carbonate, and may then be obtained in the pure 
state by distillation. 

The (Udehydes of the first series combine with ammonia, forming crystalline com- 
pounds like aldehyde-ammonia, C^H^O.NH', (p. 106), and yaleral-ammonia, 0»H»«O.NH». 
These compounds treated with sulphuretted hydrogen yield sulphur-bases, like thial- 
dine, C«H»«NS«, and yaleraldine, C»»H"NS«, thus : 

3(C»H»«0.NH») + 3H*S - C"H«NS« + (NH*)«S + 3EP0. 

Heated with hydrocyanic and hydrochloric adds, they yield bases similar to the last, 
but containing oxygen in place of sulphur : e. g.: 

C»H«*J0.NH» + CNH + CIH + HK) = C«H"NO« + NH*C1. 

>*- — , — ^ 

Leucine. 

Acrylic aldehyde appears also to combine directly with ammonia^ forming a white 
amorphous compound. 

The remaining aldehydes yield with ammonia pecuMar amides called hydramides, 
the formation of which is attended with elimination of 3 atoms of water, e. ff. 

3(C'H*.0) + N*H* = ^Cm'y + 3H*0 

Benioie Hydrobenxa- 

aldehyde. mide. 

Z{CR*0*) + liPH* =r N'CC'H'O)* + 3H«0 

Siilicylic Salhydramide. 

aldehyde. 

Aldehydes also combine with anhydrous acids (anhydrides), forming eompoonds 
which are isomeric, but not identical with the diacid glycol-ethers. Thus acetic alde- 
hyde unites with anhydrous acetic acid, forming the compound, C-H*O.C^H*0*, isomeric 
with acetate of ethylene, C'H*.(C*H*0)*.0' ; — also with anhydrous benzoic and succinic 
adds. Yaleral forms with anhydrous acetic, and benzoic adds, the componnda 
C*H"O.C*H«0» and C*H'»0.Cte'O», isomeric with acetate and benzoate of amylene, 
0»H'«.(C«H«0)«.0« and C»H»».(C'H»0)'.0«. These compounds heated with caustic 
alkalis yield acetates, benzoatos, &c., of the alkali-metals, and reproduce the original 
aldehydes, whereas the acetates, benzoates of ethylene, amylene, &c., under the same 
circumstances, yield glycols, or hydrates of ethylene, amylene, &c (Geuther, Ann. 
Ch. Pharm. cyi 249; Guthrie u. Kolbe, ibid. cir. 296.) 

The caldum and barium-salts of certain monobasic organic adds, butyric and yalerie 
adds, for example, yield by dry distillation, together with acetones (p. 31), compounds 
isomeric with the aldehydes, but distinguished &om them by not combining with am- 
monia: these compounds are called butt/ralj valeral, &c (Chancel, J. Pharm. [3] 
yii. 143; Limpricht, Ann. Ch. Pharm. xc 111.) 

Many of the aldehydes are susceptible of polymeric transformations. Acetic alde- 
hyde exhibits three or four such modifications (p. 108) ; and benzoic aldehyde is yery 
apt to pass into the solid substance benzoin, C'^H'^O*. 

The acetones or ketones are aldehydes in which the basic atom of hydrogen is re- 
placed by an alcohol-radide, thus : ^ 

Acetone . ^^j . ggOJ 
yalerone«g:i:jo.O;H;0| 

Valeracetone - C*^-) ^ _ C'H'O) ^^ C«H») ^ .. C^H»0) 
vaieracetone - CH*J ■" " CE*\ ^^ C*H»J ^ — C*H» } 

A&BXBS. The generic name applied by L. Gmelin, in his Handbook, to the alde- 
hydes, the latter term being by him restricted to acetic aldehyde. In Gmelin's system, 
the term indudes seyeral organic anhydrides and other compounds not generally re- 
garded as aldehydes. (Handb. yii 192.) 



r 



ALEMBIC— ALIZARIN. 113 

U An apparatus for distOIation, mnch used by the older cheimBta. It 
toaatia of a bodj a, to which is adapted a head b, of conuad shape, and having ita 
ertezsal cinnimferenoe or haae depre^ed lower than -^ . 

the neck, so that the ti^qis whidi nae and are oon- ^ ^* 

doved against the sides, run down into the circular & 
ehuoel fonned hj its depressed part, whence they / 
pass throng the noee or Beak c, into the leoeiyer a. l^/^^\ |j\^ 
xlie alem^ is now searoelj nsed in the laboratoiy, 
being snpeneded Inr the retort, which is simpler and 
leas expeBsire. Nerertheless, the alembic has its 
•drastages. In particniar the residues of distilla- 
tions maj be easilj cleared out of the body a; and in 
<*xpenments of sublimation, the head is yeiy con- V.«.«x^ d^ 

tenient to receiTe the dry podncts, while the more <> 

volatile portions pass OTer mto the leoeiver. Glass 
aleinbics are now nsed in some manufactories of sulphuric acid for effecting the final 
eondensition of the acid. 




■T* A nam egJY en by the alchemists to one of the double 
chloiideB of mercniy and ammonium, 2(NH^CLHgCl) + H'O, also called Salt of wisdom, 

(See Chbtsobbbtl.) 

(Powder of). The alchemical name for the ozychloride of anti- 
aitty, produced bj throwing the chloride (butter of antimony) into water. 



I — A hydrated silicate of alumina, occurring in New Jersey, and crys- 
talHshig, sometimes in right, sometimes in oblique prisms. The following analyses of 
it hsTe been giren by Hunt and Crossley : 

Silica 62-16 6200 

Ahimina 26*08 26*42 * 

Sesquioxide of Iron .... 1*94 1*64 

Magnesia 1*21 6*39 

Potash 10*69 10*38 

Water r92 6*27 

100 . 100*00 



(See NuTBrnoN.) 

An acrid, bitter extract, probably a mixture of several compounds, 
4]]itained from the water-plaintain (Jlisma PUmtago) ( J a c h, fiepert Pharm. iv. 1 74 ; 
fi 246.) 

^^-^^Tft^ftTfTlfflMt A crystalline substance, sometimes deposited on the 
inner snr&foe of the bark d Mixta aromatica. The crystals are white and capillary, with 
a slight aromatic taste and tiiie agreeable odour of the plants They sublime undecom- 
poaed between 70° and 80°G., but at higher temperatures they melt and form a brown 
sabatanoe. ThOT are insoluble in cold, but soluble in warm water, forming a neutral 
sofaitiini, which depoeits the crystals unaltered ; so likewise does the distillate obtained 
from this solution. They dissolre readily in alcohol of 80 per cent, in ether, oil of 
tupentine, caustic potash, carbonate of potassium, and caustic ammonia. Nitric acid 
of ap, gr. 1*2 does not dissolye, but merely colours them yeUow. (Handwort d. 
Ghem. i 431.) 

AXaOLABlO AOUK Obtained by Schunck by the action of nitric acid on alizarin, 
and shovn by Wolff and Strecker to be identical with Laurent's phthalic acid (which 
see.) 



C"H«0* + 2I£K) [orC»fl^*0»+4J5rO]. Xwrarwacw?.— A red colour- 
ing matter obtained from' madder. It was first prepared by Bobiquet and Colin 
(Ann. CL Phys. [2] zxziy. 226), who obtained it by digesting poxmded madder with 
wikt«r at 16° or 20° C, exhausting the gelatinous extract thereby obtained with alcohol, 
tad treating the alcoholic solution, after concentration, with dilute sulphuric acid. A pre- 
cipitate was thereby obtained, which, when washed, dried, and sublimed, yielded aliairin 
in long brilliant needles^ haying the red colour of natiye chromate of lead. Alisarin is 
ideatical with Bunge's madder-red (J. pr. Chem. y. 362), and with the somewhat impure 
•Mtii^ eoA>ran<efvi^«; obtained from madder by Pers OS and Gaultierde Claubry 
(Ann. Ch.Phys. [2] xlyiii 69), and has been prepared in the pure state by Schunck 
(Ann. Ch. Pharm. Ixvi 174), by Debus (ibid. Ixy. 361), and by Wolff and Strecker 
(ibid. Ixxy. 1). It appears not to exist ready formed in madder, but to be produced 
hj the decomposition of rubian and rubeiythric acid. (See Maddbb.) 

Vol. I. I 



114 ALIZARIN. 

Preparation aeeording to Wolff and Strecker. — Madder is ezhansted with bolHiifr 
water; the decoction is precipitated by salphnric add; and the washed precipitate 
while yet moist, is boiled with a concentrated solution of alumina in hydrochloric add, 
which dissolves the colouring matters, and leaves a dark brown residue. The solutiozi 
mixed with hydrochloric acid deposits red flakes, consisting of alizarin, more or less 
contaminated with purpurin and resinous matters. This precipitate is dissolred in 
alcohol, or in dilute ammonia^ and the solution is treated with hydrate of alumins. 
which unites with the colouring matters ; and the alumina-componnd thus formed is 
boiled with carbonate of soda, which dissolves the purpurin and leaves the alizarin in 
combination with the alumina. Lastly, this compound, after being freed from resinous 
matters by digestion in ether, is decomposed by hot hydrochloric acid which dissolves 
the alumina; and the alisarin thus separated is washed, dried by single ea^MMure to 
the air, and purified by repeated crystidlisation from alcohol 

According to Schwartz (Bull, dela Soc industr. de Mulhouse, I860, Ko. 135), the 
purest alizsrin is obtained by subliming on paper an alcoholic extract of madder having 
at least 36 times the colouring power of the root itsell According to Plessy and 
Schutzenberger(Gompt. rend, xliii. 167), when an extract of madder prepared with 
wood-spirit, is triturated with a tenfold quantity of water, and heated to 260^ in a 
closed vesselj^the water on cooling becomes filled with ciystals of alizarin ; and the 
f ased extractive mass remaining at the bottom of the vessel, yields, when again treated 
in the same manner, an additional quantity of very pure alizarin. 

Anderson, by treating opianic acid (0'*H*^* = alizarin + 2HK)) Wiili sulphuric 
acid, obtained a colouring matter (probably alizarin), which yielded all the madder 
colours with alumina and iron mordants. (Edinb. PhiL Trans, xxi. 1, 204.) 

Alizarin in the anhydrous state fonas red prisms, inclining more or less to yellow, 
according to the size of the crystals. It combines with 2 at. water, forming scaly 
crystals like mosaic gold. These crystals give off their water at 100 *^0., becoming 
opaque and of a darker colour. At 216^ the compound sublimes, yielding a crystalline 
subUmjfte of the same composition as alizarin dried at 100^ ; neverthelesa a consider- 
able quantity of charcoal is always left behind. 

The following are the mean results of the analyses of alizarin dried between 100^ 
and 120^ or sublimed : 

Caleuiation, Boblqoet. Schuodc. DebilB. Rocbleder. 

IOC . .120 68-96 69-72 69*4 68*96 67*93 

6H . . 6 8*46 3*74 40 3*78 8*77 

3 0. .48 27*69 26*54 26*6 27*26 2 8 80 

C»HH)» 174 10000 100*00 100*0 10000 100^^ 

Shtrock atttgna to crjitalllsed alisarin the formula C^*H^O* -f 8H0 Armrdioff to the fominla 
CieH<03, alisatin if doselr related to Laurent's chloronapthalle acid, Ci0H>ClO>. The latter, when 
hoiled with nitric acid, yielda phthalic and oxalic acid, like alitarin (vtf . ^.). 

Alizarin dissolves but sparingly in water, even at the boiling heat ; but acooiding to 
Flessy and Schiitzenberger (he. cit.) its solubility is much increased by heating to 
higher temperatures in close vessels, 100 pts. of water dissolve 0*034 pt. of alizarin 
at 100® C. ; 0*035 at 150^ ; 0*82 at 200<^ ; 1*70 at 226^ ; and 3*16 pts. at 260^. 

Alcohol and ether dissolve it, forming yellow solutions. It is not decomposed by 
hydrochloric acid. Strong sulphuric acid dissolves it, forming a brown solution from 
which the alizarin is precipitated by water in orange-coloured flakes. Nitric acid at 
the boiling heat dissolves it, with evolution of red vapours, forming phthalic acid and 
probably also oxalic acid (Wolff, u. Strecker): 

C»H«0" + H«0 + 40 « C«H*CH + C»H*0* 

^ r— ' ^ , ' V , » 

Alizarin. Phthalic Oxalic 

acid. acid. 

It is also converted into phthalic acid by boiling with ferric chloride or mtiate 
(Schunck). Chlorine converts it, when suspended in water, into a yellow substance 
which dissolves in alkalis without much colour, and yields a colourless sublimate when 
heated. 

Alizarin dissolves in caustic alkalis and in alkaline carbonates, forming deep purple 
solutions, from which it is precipitated by acids in orange-coloured flakes. The ammo- 
niacal solution gives off all its ammonia by evaporation, and forms with the chlorides 
of barium and calcium purple precipitates which become nearly black when dry. The 
potash solution is completely decolorised by lime-water, a precipitate being formed 
containing 2C"H«0».3CttHO, or 2C»H*0'.S{CaO,HO), Wth baryta, in a similar 
manner, two compounds are formed, viz. 2C"H»0'.3BaHO and C"H«0».2BaH0. Alu- 
mina decolorises an alcoholic solution of alizarin, forming a beautiful re<l lake. An 
ammoniacal solution of alizarin forms with salts of magnesium, iron, copper, and silver. 



ALE ALL 115 

fnipla precipitAt66 with a tqiI or bluish iridescence. The silyer precipitate becomes 
icdaeed after some time. The alcoholic solution of alizarin forms yriih. an alcoholic 
loktion of acetate of lead, a purple precipitate containing 4C'»H*PbO*.3Pb*0, or 
2C»S*PbO'.3PbO, according to Schunck, and 3C"H«0».2Pb«0, according to Debus. 

(See PDanjTB.) 

jileaH, LauffensaU, The word alkali is used in Tuious senses. In 
its most reatricted, bat most usual sense, it is applied to four substances only : hydrate 
of potasshim (potash), hydrate of sodium (soda), hydrate of lithium (lithia), and hy- 
drate of ammonium (which may be supnposed to exist in the aqueous solution of ammonia). 
In a mors geserml sense, it is applied to the hydrates of the so-called alkaline earths 
(bsiyta, stiontia, and lime), and to a large number of organic substances both natural 
snd sitifidal, wiiich are more folly described in the articles Alkaloids and Ajtxosjjju- 
sasBS. The first four bodies are sometimes spoken of as alkalis ^proper, when it is 
wi^cd specially to distinguish them from the other alkalis. 

As the iiidiTidiial alkalis are described with sufficient detail in the articles specially 
dervitedto each, we shall confine this article to a discussion of those properties which 
they an possess in common ; in order, as fur as possible, to define the essential nature 
of alkalinitr, and to point out upon what grounds this or that particular body is classed 
as sn alkali. These objects wiU probably be best attained by tracing the most im- 
portant of Che snceessiye steps by which the word alkali, which was at first the name 
of a single substance, has come to be the generic name of an indefinite number of bodies. 

The tenn alkali was first used in chemistiy to designate the soluble part of the ashes 
of plants, especially of sea-weed (carbonates of sodium and potassium). It was, how- 
em; soon extended to seyeral similar substances which were obtained by other pro- 
eesses : for instance, to salt of tartar and to carbonate of potassium, obtained by heat- 
ing nitre with charcoal. The substances obtained by these processes, and by others 
of like nature, were regarded as identical, or at most, as mere yarieties of the same 
substance. Alkali was, therefore, not yet used as a generic name, but as the specific 
name of a particular substance. The character which was chiefly depended upon for 
distingnishing alkali from other substances was the property of efferyescing with acids. 
This piTope r ty was supposed to be characteristic of, and essential to, alkaline bodies, 
till after the middle of the 18th century. Another property of alkali which was early 
obeerred was its opposition to adds, and power of destroying their most distinctiye 
charaeten. On account of its possessing these properties, carbonate of ammonium, 
which had been known since uie thirteenth centuiy, was, from the beginning of the 
serenteenth century, regarded as a kind of alkali. The power of alkaU to change many 
TEgirtable colonrs was recognised at a later period than the properties aboye mentioneo, 
hat was well known to Boyle, who also knew that colours which had been thus altered 
eookl be restored by acids. 

It wraa fint clearly established in 1736, by Duhamel, that there exis^d two essentially 
dlstiiiet kinds of fixed alkali From this time, three kinds of alkali were recognised, 
— regetable alkali, mineral alkali, and yolatile alkali, corresponding respectiyely to 
potas£, soda, and ammonia, or to their carbonates. 

We haye already said that, far on in the eighteenth century, the power of efferyes- 
cing with acids was regarded as an essential property of alkalis. Boyle had indeed 
obeerred, in 1684, that yolatile alkali could be obtained by distillation oyer quick lime 
in a condition in which it no longer efferyesoed with adds, although it retained all its 
other usual prupert iea. But, notwithstanding isolated obseryatious of this kind, non- 
c fltfrie seing alkalis were regarded ra^er as subordinate yarieties of the ordinary 
alkalis than as essentially different substances. 

Moreoyer, it was known at a yery early date, that quick lime altered some of the 
p ro per t i es of alkali. This alteration was expressed by calling alkali, which had hot 
been acted on by lime, mUd^ and alkali which had been so acted on, caustic. The 
eflect of the lime was ascribed by Basil Valentine (latter half of the fifteenth century) 
to heat {^ die Hitse ans dem lebendigen Kalk ") which it imparted to the alkali. And 
the idea that lime in burning combined with an actiye principle — " matter of fire " -— 
which it gaye out again partiaUy to water (when shJced), and completely to alkali, 
remained long dominant. Van Helmont (circ. 1640) regarded the substance taken up 
by K»M» as akind of sulphuric acid, whence the heat eyolyed in the action of water on 
qoick lime. Meyer, as recently as 1764, supposed the lime-salt of a peculiar acid, 
addum pinantj to be formed during the burning of lime, and that when this salt was 
treated wiu a mild alkali, a corresponding alludine salt (caustic alkali) was obtained. 
The gieaay feel of the caustic alkalis suggested the name of the add which Meyer 
si^^XMed them to contain.* 

• It k a rcn«rkabl« inuatratlon of the change which takef place in the ideas attached to the tame 
word, that both Van Helmoat aiwl Meyer should have attribntrd what we coniider an exaiuuon of the 
•tkmbmt p f o pe ity to the agency of an add. (See Aciua, lee p. 4a) 

X 2 



116 ALKALI. 

The trae nature of the diffisrence between caustic and mild alkaliB was disooTered 
by Black in 1765. Black's investigation of this subject occopies so important a place 
in the history of general chemical thecvy, that it is worth wlule to consider a little in 
detail his experiments and the condnsions he derived from them. 

His first observation was that qnick lime, when deadened by e xpus ure to air, became 
heavier, not lighter, as was to be expected, if the change which took |^ace consisted 
in the escape of fire-matter. He made a similar observation in the case of magnesia 
(a snbstance wluch he had previonsly found to be distinct from. lime). He fonnd fozther 
that«magnesia, in the state in which it effervesces with adds, lost considerably in 
weight when calcined, and that it then no longer effervesced with adds, althongh it 
formed with them falts exactly similar to those of effervescing Tnsgnesia, In ordw to 
find oat what was \^o substance which effervescing magnesia lost when caldned, he 
repeated the calcination in a retort connected with a well cooled reodver. In this 
experiment, he obtained nothing but a small quantity of water ; it occurred to him, 
however, that a gas might have escaped, and that this gas might be the same as that 
which is evolved during the solution of magnesia alba (effervescing magnesia) in adds. 
Following out this supposition, he came to the condnsion that the eiServesdng mag- 
nesia which is predpitated by a mild alkali from a solution of caldned (not efiervesdng) 
magnesia in add, could obtain the 01s, which caused it to effervesce when dissolved, 
from no source except the alkali. Hence he conduded further that the mild alkalis 
contain the same gas as is expelled from magnesia alba by calcination ; that, when 
they combine with adds, this gas is separated and causes effervescence ; and that, 
when a magnesia salt is predpitated by a mild alkali, the gas leaves the latter and 
unites with the magnesia, in cembination with which it is predpitated. These con- 
dnsions were verified by the following quantitative experiment. A weighed quantity 
of magnesia alba was caldned ; it then dissolved in sulpnuric add without effervescence. 
The solution was predpitated by mild vegetable alkidi (carbonate of potassium), the 
precipitate washed, dried, and weighed : its weight was almost exactly the same as 
that of the original magnesia alba, and it behaved in every respect like that substance. 
On a further examination of the gas, whiclw^xpelled by adds from the mild alkalis 
and lime, and from magnesia alba. Black fo^^^^to be the same as that which is formed 
during fermentation, and gave it the name^Hrmr. 

From the sum of his observations, Black deOjU^ed the following general condnsions. 
The effervescing earths and alkalis contain fix A air, which can be expelled from the i 

former by heat, though not from the latter, bunlirhich is expelled from both by adds ; ■ 

the alkalis and earths are caustic when tiiey eont^^ no fixed air, and therefore l^eir 
causticity does not depend on the presence of any peculiar constituent, but is a pro- s 

pcrty possessed by them in a state of purity ; quick lime renders the alkalis caustic, | 

not by imparting to them any prindple of caustidty, but by the removal from them 
of fixed air ; lasUy fixed air partially neutralises the alkslis by combining with them, 
insomuch as it destroys their causticity. 

Two of the most important effects which the adoption of Black's theory had upon I 

the received ideas of alkalinity were that it caused chemists to perceive (which they 
had not done before), a necessary opposition between the causticity of an alkali and 
its power of effervescing with acids, and caused the term alkali to be transferred from 
the carbonated to the caustic alkalis. 

Besides the substances to which the name alkali was first given, it was soon per- 
ceived that certain kinds of earth possessed, in some degree, alkaline properties ; that 
is to say, the power of effervescing when acted on by acids, and of neutralising their 
add properties. Earths which possessed these qualities were called terrts absorbenteSf 
or terrtB rJcalina, and were long supposed to owe their peculiarities to the prraenoe 
of alkali as one of their constituents. 

It is not easy to make any precise statement as to the degree of similarity or of 
difference which was supposed to exist betweep these bodies and alkali proper. The 
difficulty arises partlv from the fact, that, until they had acquired some icfea of the 
principles of chemical analysis, chemists had no sure means of ascertaining the iden- 
tity or individuality of chemical substances, and hence often called different bodies by 
the same name, or, on the other hand, gave different names to the same substance 
when obtained by different processes ; partly also, from the word alkali having been 
used formerl V as now in various senses : by Lemeiy, for instance, to indude aU sub- 
stances which effervesce with acids ; by Stahl, to indude all those which neutralise 
acids ; by many others, however, to denote none but the substances now known as the 
Alkaline carbonates. This uncertainty in the use of the word is not surprising, when 
we remember that our present more extensive knowledge does not enable us to point 
out any one difference of fundamental importance between the alkalis and the alkaline 
earths. The different solubility in water of their carbonates probably furnishes a more 
exact distinction than any other single property. This character was pointed out by 



ALKALI. 117 

Babaiiiel in 1736, as a generic difference. He distinguished earths from alkalis hj 
the property -vfaich the latter have of precipitating the fonner from their solutions, 
and the alkaline earths from others by their capability of completely neutralising acids. 
These distinctions have, for the most part, been ever since retained. 

It is not necessary to discuss with much detail early ideas relating to the ultimate 
eonstitixtion of the alkalis and alkaline earths. A similarity of constitution between 
the eazths and metallic calces was soon suspected ; in consequence of which Neumann, 
befefe the middle of the eighteenth centoxy, endeavoured to get a metal from quick 
lime. By the later |>hlofi;istic chemists, both alkalis and earths were, like metallic 
cakes, regarded as sunp& bodies. Lavoisier, though he regarded metallic calces as 
eompoandfl, continued to class the alkalis and earths among elementaiy bodies, inas- 
much as there waa no known means of decomposing them. He considered it probable, 
howereTy that they contained oxygen, and suggested that the earths might be oxides 
cf metala which had a greater affinity for oxvgen than carbon, and therefore could 
not be reduced. Hanj attempts were made by Lavoisier's followers to verify these 
SBppositions ; but their uniform failure seemed almost to have px>ved the elementaiy 
nature of the bodies in question, when, in 1807, Sir Humphry Davy succeeded in re- 
ducing potash and soda by the galvanic current. The composition of volatile alkali 
(aBanooia), was approxnmvtely ascertained by Berthollet in 1785. After the discovery 
of oxygen in the fixed alkalis, it was long supposed by Davy and Berzelius that am- 
monia also contained oxygen. The idea that aqueous ammonia contained the oxide of 
m eompoond metal, which likewise existed in the anmionia-salts, was suggested by 
BeneliiiB in 1820. (See Amxoiouk.) 

In the present state of chemical theory, the relations of the alkalis to other sub- 
stances lead to the representation of them as hydrates, or as water in which haJf the 
hydrogen is replaced by a metal, or compound radicle. (See Ttfbs.) 

The earliest addition made by modem chemistry to the old list of alkalis was morphia, 
di a coyered in opium by Sertiimer in 1805, but first fully described by him in 1817. 
This was the &r8t organic alkali, or alkaloid which became known ; but, when the 
general attention of <memi8ts was directed to its existence, it was soon found to be 
one of a very numerous class of compounds (see Alkai.oids). Of late years, a huge 
munber of bodies, possessing many points of resemblance to the natural dkaloids have 
been obtained by artificial processes. The constitution of these artificial alkalis is 
Himflar to that of hydrate of ammonium: they represent hydrate of ammonium in 
'vfaidi hydrogen is replaced by an electro-positive radicle (in most cases a hydrocarbon), 
(see AMMomnx-BASBs), or in which nitrogen is replaced by phosphorus, arsenic, or 
antinKHiy. 

The fcDowing properties are common to the mineral alkalis and to many of the 
nsganic alkalis. 

(1) They are more or less soluble in water, the alkalis proper much more so than 
the alkaline earths. (2) They neutralise completely the strongest acids, and with 
veak acids form salts possessing in some degree, alkaline properties. (3) Their aqueous 
•ohitions exert a caustic or corrosive action on vegetable and animiU substances. (4) 
Precipitate the heavy metals from most of their acid solutions as hydrates or as oxides. 
(5) And alter the tint of many colouring matters ; for instance, they turn Utmiis, which 
has been reddened by add, blue, they turn turmeric brown, and syrup of violets and 
jnfasion of red cabbage, green. The extent to which the various alkalis dissolve in 
vster appears to determine the degree in which they possess the last three properties 
(3, 4, 5), the most soluble possessing them in a greater degree than the rest The action 
oo eolonring matters appears to bdong to all metallic hydrates which are soluble in 
-vmter, and is possessed by the hydrates of lead, silver, and mercury, in a degree cor- 
ro^jonding to their slight solubility. 

(For iiirther historical details concerning alkalis and alkaline earths, see Kopp, 
Oesefaichte der Chemie, vols, iii and iv.)i — G« C. F. 

^ Trl^ ^ ^- ■ — ■■■■o^ is the determination of the amount of real alkali in alkaline 
mixtures and liquids, such as the commercial carbonates of potassium and sodium, 
(commonly called potash and soda), in wood-ashes, solutions of caustic and carbonated 
alkalis, &c. This estimation, like tiiat of the strength of acids, may be made either 
by volumetric or by weight-analysibk 

The Tolumetric method ef alkalimetry is merely a particular case of the general 
method of "Analysis by Saturation," described in the article Axaltbis, Yoxtthbtrio 
(which see). The valuation ef an alkali by the amount of a standard acid solution 
which it will saturate, was first introduced by Descroizille, afterwards peifected 
by Gay-Luseac, and still farther by Mohr. (Lehrbuch der chemisch-analytischen 
Titrirmethode, Braunschweig, 1855.) 

Instead of the sulphuric or hydrochloric acid generallv used for the purpose, Mohr 
xeconunends oxalic acid, because it oin be weighed with greater accuracy than any 

l8 



118 ALKALIMETRY. 

liquid acid, and becauBe itd standard solution may be kept for any length of time with- 
out change. To obtain it pure, the commercial acid, which is genersliy oontaminated 
with the oxalates of potassium and calcium, is finely pounded, and treated with a 
quantity of lukewarm water sufficient to dissolve only a portion of it ; the solution is 
filtered and left to crystallise ; and the crystals are collected on a filter and dried in 
the air, till they no longer adhere to each other or to the paper. The add is thus 
obtained pure, and containing exactly CH'O^ + 2HH), the atomic weight of which 
is 126. 

The standard solution is best made of such a strength that 1000 cubic centimetres 
(1 litre), shall contain exactly one |-gramme-atom (i,e. 1 atom expressed in ^-grammes) 
of the acid. This is efiected by dissolving in water ^ » 63 grammes of tiie ciystals, 
and diluting the solution to the bulk of 1 litre. 1000 c c. of this solution contain one 
|-gramme-atom of add : hence 2 c. c. contain 1 milligramme-atom of add, and 
saturate 2 milligramme-atoms of a caustic alkali (KHO or NaHO), 1 milligramme of 
an anhydrous alkali (K«0 or Na*0), or of an alkaline carbonate (CO»K« or CO»Na«.) 

To estimate the value of a sample of commerdal potash or soda, 3 or 4 grammes of 
it are first ignited in a platinum crucible in order to determine the amount of water 
contained in it. The residue is then dissolved in water ; a few drops of litmus are 
added ; and the standard add is gradually added from a burette till the first appearance 
of a purple-red or wine-red colour. This takes place when a Uttle more than half Hie 
alkaline carbonate is decomposed by the oxalic add : for the first portions of carbonic 
add disengaged by the oxalic add, imite with the remaining portion of alkaline car- 
bonate to form add carbonate, and it is only when half the alkui has been neutralised 
in this way that the carbonic add is actually set free and reddens the litmus. After 
this stage has been attained, the oxalic acid must be very cautiously added till the 
purple-red produced by the carbonic acid, just passes into a bright yellowish-red, in- 
dicating the presence of free oxalic add, and showing that the whole of the alkali is 
neutralised by that acid. Each c c of acid thus employed corresponds to 1 milli- 
gramme of caustic alkali, or to one |-milligramme of alkaline carbonate, t. e. to 0*040 
grm. caustic soda (NaHO), 0-056 grm. caustic potash (KHO), 0'069 grm. carbonate 
of potassium (CO'K^), and 0*053 grm. of carbonate of sodium. The amoimt of caustic 
alkali or alkaline carbonate is then found by a simple proportion ; thus : 

100 : 5*3 : : number of c. c. employed : amount of carbonate of sodium. 

By operating on 100 times the f-milligramme-atom (e,g. 6*0 grms. of carbonate of 
potassium, or 5*3 grms. of carbonate of sodium), all calculation is saved : for as this 
amount, if perfectly pure, would require 100 c. c of add for its saturation, the number 
of c. c. actually required indicates at once the percentage of alkaline carbonate. The 
burettes commonlv used contain 50 c. c, and are graduated into half c. c ; so that by 
operating on 50 times the |-milligramme-atom, the number of divisions employed in- 
dicates the percentage. 

In operating upon alkaline carbonates in the manner just described, it is difficult to 
notice the exact moment when the wine-red colour of the litmus due to the presence 
of free carbonic acid, changes to the light red produced bv oxalic or other strong add. 
For this reason Mohr recommends the following, called the residual method. The 
standard add is added till the colour of the litmus is distinctly bright red ; the solu- 
tion is then heated to boiling, and a sUght excess (^5 to 10 c c.) of add is added. 
The hot solution is freed from carbonic add by agitation and by arawing air throng 
it by means of a glass tube, and then neutralised with a standard solution of caustic 
soda (Analysis, Volumstbio), till the colour just changes from red to blue. Since 
the acid and alkaline solutions neutralise each other, volume for volume, it is only 
necessary to deduct the number of cubic centimetres employed of the latter from, 
that of the former, and calculate the amount of alkali from the reddue. In esti- 
mating the strengtJi of caustic alkaline solutions, this residual method is of course 
unnecessary. 

To determine the proportion of caustic alkali and alkaline carbonate in a mixture of 
the two, two equal portions of the solution must be taken : one of them treated with 
chloride of barium, whereby the alkaline carbonate is converted into chloride, and car- 
bonate of barium is precipitated. The liquid is filtered and the quantity of caustic 
alkali determined in the filtrate as above. The second portion of the solution is 
neutralised with the standard add, without previous treatment with chloride of barium, 
and the total amount of alkali, existing both in the caustic state and as carbonate, is 
thereby determined. The first result deducted from the second, gives the quantity of 
alkali^ existing as carbonate. 

If it be preferred to make these estimations with the ordinary English weights and 
measives, the standard solution of oxalic add may be made by dissolving 63 grains 
(f-grain-atom) of the crystallised add in water and diluting the solution to lOOO 



ALKALIMETRY. 



119 



Fig, 6. 



^ at 60° F. This quantitT of the solution will then neatraluse 1 gndn- 

itom of a eaDstie aUuli (40 grains of soda NaHO, or 56 grains of potash KSO ), and 
l-grain-atom of alkaline carbonate (69 grains of 00%^ or 63 grains of CO'Na')i and by 
opezatiDg on ^ of these quantities of the substance to be tested, the percentages viU 
be given at onoe by the numbCT of grain-measures of the standsid add employed. 

A eonveiiient method of estimating by -volumetric analysis the proportion of potash 
and soda in a caustic mixture of the two, has been kindly commimicated to the Editor 
by Mr. Jc^in Dale of Combrook, near Manchester. It depends upon the fact that 
acid tartrate of potassium, though moderately soluble in water, is but yery sparingly, 
if at all, aolidde in a liquid containing acid tartrate of sodium. The method is as 
foOovB : Add to the mixture a standarcL solution of tartaric acid till an add reaction 
just hewmtgii peceeptible ; the alkalis are thereby converted into neutral tartrates ; 
then add a saoond quantity of tartarie add equal to the first, so as to convert them 
into add tartrates : the whole (or nearly the whole) of the acid tartrate of potassium 
then separates. Next filter off the solution of add tartrate of sodium, and add a 
standaro. solution of eanstie soda till the. liquid just exhibits an alkaline reaction. 
Hie quantity of the soda solution thus added is equal to the amount of soda present 
in the mixture. — ^The quantity of tartaric add required to form add tartrate with the 
sodsy subtracted from the total quantity added to the mixture of the two alkaHs, gives 
the quantitT required to form acid tartrate with the potash ; and thus the amount of 
potash is determined. This method would scarcely be applicable where sdentific 
aecuzacy is required ; but, for rapid estimation in commercial practice, it is found to 
give good results. 

AUu^^anetry by Waght-amdyna. — The proportion of alkali in the commerdal car- 
bonates of notassium and sodium may be estimated by determining the quantity of car- 
bonic anhyoride evolved when the carlbonates are decomposed 
by an add: for 22 parts of carbonic anhydride (CO*) corre- 
spond to 69 parts of carbonate of potassium (CO'K*), and to 
Z5 ports of carbonate of sodium (CCKN'a'). The apparatus 
em^oyed is the same as that described in the article AciDX- 
USTBT ; but the method of using it is slightly different A 
weighed quantity of the carbonate to be examined is dis- 
solved in warm water in the flask a, and a quantity of hydro- 
diloric or dilute sulphuric add more than suffident to 
decompose the carbonate, is placed in a short test-tube 5, 
which IS carefully introduced into the flask, so that it may rest 
agiainst the side. The apparatus having been then weighed, 
the extremity of the tube o is dosed by a plug of wax, and 
the flask is tilted so that the add may run over into the 
alkaline liquid. When the evolution of gas ceases, the flask 
is heated to complete the decomposition ; the wax plug is 
removed and air ^wn through the apparatus to remove the 
carbonic add remaining in it ; and the flask after cooling is 
again weighed to ascotain the loss of carbonic acid. At 
the condusion of the experiment, a piece of blue litmus-paper must be thrown into the 
flask, to try whether the liquid is acid ; if not, more add must be added, and the pro- 
cess repeated. 

The apparatus of Will and Fresenius {fig, 6) may also be used. The alkali dis- 
solved in water is then placed in the flask ▲, and 
strong snlphttrie add in b; and the whole appa- 
ratus is weighed; the tube a 6 is dosed with a 
'wx plug; and suction is applied by the mouth at 
the end of the tube c?, so as to draw a few bubbles 
of air firom ▲ into b. On discontinuing the suction 
the pressure of the air forces a small quantity of the 
add in b into the flask a, whereby a portion of the 
alkaline carbonate is decomposed. This process is 
r^eated as long as any gas continues to be evolved, 
after which the flask ▲ is heated, and the experi- 
ment completed in the manner just decribed. 

Xf the alkaline carbonate contains any caustic al- 
kali, which may be known (in the absence of sul- 
phide), by its solution having an alkaline reaction 
after the addition of excess of chloride of barium, 
another equal portion must be mixed with about one- 
thiid of its weight of carbonate of ammonium, and 

3 parts of quarts-sand (to prevent caking), and heated till the water and ammonia are 

X 4 




Fig,^; 




120 ALKALOIDS. 

expelled ; tlie diy residue 19 then decomposed as abore. The excess of alkaline caiv 
bonate obtained in the second determinaUon is due to the caustic alkali in the sample, 
which is converted into carbonate bj ignition with the carbonate of ammonium ; and 
from it the amount of caustic alkali is easilj calculated ; thus for soda : 
CO»Na« : 2NaH0 [or CO'.NaO : NaO.HO] « 106 : 80. 

The sulphites, hyposulphites, and sulphides of the alkau-metals, which often occor 
in commercial samples of alkali, especiiJl^ in ** baU-soda," introduce errors both into 
the Tolumetric and the weight-analyBes : into the former, by neutralising a portion of 
tlie test-acid, and into the latter by OTolving sulphurous acid or sulphuretted hydro- 
gen, which would be estimated as carbonic acid. When the amount of alkali is to be 
determined by the volumetric method, these compoxmds may be decomposed by igniting 
the substance with chlorate of potassium, whereby they are aU converted into sulphates. 
For the carbonic acid estimation, they ma^ be oxidised by adding a small quantity of 
neutral chromate of potassium to the solution in the flask, before commencing the de- 
composition. 

The carbonates of the earths, which would introduce similar errors, may be removed 
by dissolving the alkaline carbonate in water and filtering. 



Organio Jlkalis^ Organic Bases. — ^At the banning of this oentnrv* 
the only substances in which alkaline properties had been recognised were potash, 
soda^ ammonia^ and the alkaline earths (see At.kat.t). In 1817i Sertiimer drew 
attention to the existence in opium of a* substance whose alcoholic solution acted upon 
vegetable colours like the solutions of the alkalis, which combined directly with acids, 
forming neutral salts, soluble in water, and giving the usual reactions of the adds 
from which thev were formed ; and which was precipitated from solutions of its salts 
by the mineral alkalis. To this substance, Sertiimer gave the name morphine, and 
in consequence of its possessing the properties just mentioned, regarded it as a kind 
of alkali. After the discovery of morphine, it was soon found t^t many vegetable 
products which had been long known as exerting marked physiological ^ects (e. g. 
cinchona bark, nux vomica, tobacco, &c), contained similar alkaline principles. The 
nimiber of such natural alkaloids now loiown is very great, and indudes many sub- 
stances which cannot in any strict sense be termed alkalis, but which are connected by 
such insensible gradations (between intermediate terms) with substances decidedly 
alkaline, that they must be regarded as possessing essentially the same chemical 
nature as the latt^. Since 1848, a great number of organic alkalis have been obtained 
artificially. Some of these rival potash and soda in the degree of their alkalinity, 
while in others the existence of alkaline properties is barely perceptible. 

The only property which is possessed by all alkaloids, whether natural or artificial, 
is that of combining directly with acids to form salts possessing a certain degree of 
stability, and capable, when dissolved in wat-er, of producing the ordinary phenomena 
of saline double decomposition. Those alkaloids, whose salts possess any considerable 
degree of stability, generally exhibit, when dissolved in water or alcohol, an alkaline 
reaction with vegetable colours. 

Most of the natural alkaloids contain carbon, hydrogen, nitrogen, and oigrgen, and 
are, at ordinair temperatures, solid, and not volatile without decomposition. Some 
natural alkaloids contain carbon, hydrogen, and nitrogen only; these are, for the 
most part, liquid at ordinary temperatures, and can be distilled without decomposition. 
The greater number of the artindal alkalis are composed of carbon, hydrogen, and 
nitrogen ; some, however, contain oxygen in addition. In both natural and artifidal 
alkaloids, hydrog^en may be replaced by chlorine, bromine, iodine, peroxide of nitrogen, 
&c Alkaloids have also been obtained artifidally, in which nitrogen is replaced by 
phosphorus, arsenic, antimony, or bismuth. (See Phosphinbs, Absinbs, &c) 

Most of the alkaloids, as they are obtained in the free state, correspond in compo- 
sition to ammonia, NH», rather than to the fixed alkalis ; that is to say, they form 
salts by direct union with acids, without elimination of water or any other sul»tance. 
In order to make them strictly comparable to the fixed alkalis, they require, like am- 
monia, the addition of HK) to their formulse : l^ey may then be considered as hydrates 
of compound radides analogous to ammonium. A few alkaloids, however, are known 
which, when dehydrated as far as possible, correspond precisely to the fixed alkalis ; 
e.g. hydrate of tetrethylium, C»H"NO = C«H»N.H.O. These bodies, for the most 
part, resemble potash and soda very dosely in properties. 

The constitution of most of the artificial alkaloids is tolerably well known. The 
processes by which they are obtained show that they must be considered as ammonia, 
or as hydrate of ammonium, in which the hydrogen is replaced wholly, or in part, by 
8 compound radide generally composed of carbon and hydrogen (see Amidss, Ax- 
MONiUM-BASBs). The phosphorus, arsenic, &c. alkaloids are similarly relat^ to 
phosphide, arsenide, &c. of hydrogen, PH",A8H*, &c The constitution of the natural 



ALKALOIDS. 



121 



alkala'di xb^ as jet, Terf imperfecUj understood. They are probably, like tbe artificial 
alkalii^ denvatiTes of ammonia; but it is unknown by what radides the hydrc^en is 
xiqdseed. 

The following is a list of the most important nitrogen-aJkaloids, natural and arti- 
fieia], which are now known. 

1. Alkaloids comparable to ammonia, forming salts by direct union with adds. 



Aeediamine 
? Aoetonine 
Aeetjlaznine. 
Aeonitine 
Alanine 

Alkabid 
Alkaloid 



Formula. 
. C*EP]SP 

(See YDrsuaaim.) 

. CH'NO' 






jUkaloid 
Alkabid 
AlHamine . 

Bihzomdiallylamine . 

Ethjidibcomdialljlamine 
Amazine 

Dieihylamazine . 
Ammdine 
Amylamine • • . 

IMamylamine 

Biethylamylamine 

Hethylethylamylamine 

Triamylamine . 
Ajiiline. (See Fhsntlaionb.) 
ABiaine 
Aridne 



0»ff«NO 

C"H"NO 

(XB'N. 

OH'Bt'N 

C«BP«Br«N. 

0»H»N«. 
C»H*N»0 
C»H'«N. 
C"H»N. 

C"H"]Sr. 



Source or Mode of Formadon. 

. Acetamide heated in hydrodiloric add gas. 
. Action of ammonia on acetone. 

. Aconitum NapeUus. 

. Hydrochloric and hydrocyanic acids on 

aldehydammonia. 
. Nitrous ether on creatine (Bessaignes). 
. Di8tillationofethylcyanamide(Cahours 

and Cloez). 

> From aldehydammonia (B a b o). 

. Tribromide of allyl on ammonia 

. Potash on hydrobenzamide. 

. Strong adds or alkalis on cyanamide. 



Atrapme 
Asonaphtylamine 
Aaophenylamine 
Bebinne 



Benzidine 

Boberine 
S^ndne 

Ethylbrudne 



C«HWO« 
C»H"l!nO* 

C"H»«N» ■ 



. C«H»NO* 
. C»H«»N«0*. 



Caffeine .... C^^«N<0« 
OajaoyUmine. (See HExruLiazra.) 
Capiylamine. (See OcrrLAJiizaL) 
Cirbomide. (See Ubba.) 

^*">^f yl*™™^^ or > c«jp70N» 
Cjantriphenyldiamine . ) 

Carbothiii&ine . . . Ciff-liPS' 



• Action of heat on anhishydramide. 
. Cinchona bark. 

. Asparagtts officinalis^ and other plants. 
. Atropa belladonna, Ikttura Stramonium, 
. Keduction of dinitronaphtalene. 
. Beduction of dinitrobenzine. 
. *' Bebeent," a spedes otNectandra, British 
Gxdana.- 

. Bedudng agents on azob^ndde and on 

azoxibenzide. • 
. JBerderis vulgaris, 
. Sirychnos nux vomica^ 8, Ignaiii, & 

Colubrina, 



• Tea, coffee, &c. 



. Bichloride of carbon on phenylamine. 
• Sulphocarbonic anhydride on aldehycU 



Cetylamine. 

Tricetrlamine . 
? CSididonine 
Cindionidne 

Cindumidine 

Methyldnchonidine 
Cinchonine 

Uethyldnchonine 
Codeine . • 

Ethyloodeine 



C«H"N. 

C»H»»N»0« 

C"H"N*0 

0«H"N»0 

C"H»*N»0 
C"H»N«0. 
C"H"NO» 
C«H»NO«. 



ammonia. 



. Chelidoniitm mt^'iu. 

. Isomeric transformation of dnchonine or 

of dnchbnidine. 
. Cinchona bark. 

. Cinchona bark. 



. Opium. 



122 



ALKALOIDS. 



Name. 

Colchiceixie . 

Gollidine 

C!onhydiine . 

Conine 
Ethyleonine 
Hetnyloonine 

Gotamine 

Conmaramine 

Creatine 

Creatinine • 

Ciyptidine . 

Cuinidine • 

Cjranamide . 
Amylcyanamide 
Diamylcjanamide 
Diethylcyanamide 
Ethylcranamide 
Metnylcyanamide 
Hethylethylcyanamide 

Cyanetfaine . 

(^anetholine 



Formula. 



Cyaniline 

Cyanocmnidine . 
C^anomelamine . 
C^ranotoludine 

Diphenine • 
Diphenylformyldiamine 

Ethylamine . 
Biethylamine . 
Triethylamine . 
Ethylenamine . 
Bie&iylenamine . 
Phenylethylenamine 
(orDiphenyUbiethyleni 
Triethylenamine 

Flavine • 
Fuiforine 

Glycocoll 
Glycosine 
Glyoxaline . 
Oiianine 

Hannaline . 

Hydiocyanhannaline 
Sannine • • 

Hexylamine. 
Trihezylamine . 



? Jervine 
Lepidine 

Leucine 



Lophine 
Lntidine 

Melamine 



. C«H**1TO»> 
. C^"N 
. CfH>'NO 
. C«H"N 
. C»«H>*N. 
. OTBP'N. 
. C>*H"NO«* 
. 0»H^0» 
. C*H»N»0« 
. C*H»N»0 
. C»ff»N 
. 0^»«N 
. CH«N» 
. C^»»N«. 
. C"H«N«, 
. C»H>«N». 

. o»Bra«. 

. C«H<N*. 
. C«H»N». 
. C»H»*N« 
. C«H»NO 

. C^ff^N* 

. C»H*N< 
. C»H>«N» 
. C"H>"N« 

. C»«H»«N« 
. C"H»«N» 

. C*H»N. 
. C«H"N. 
. C«H»N« > 
. C*H»*N« J 
. 0»H«N . ) 
amine C»«H:»«N»?{ 



ao aw or Mode of Formatio n. 

Colckieum autumnale, 
. Bone-oiL 

. Hemlock (Conium fnaeulatum), 
. Hemlock {Conium maculatum). 



. Oxidation of narcotine. 

. Redaction of nitxo-coiimarine. 

. Jnioe of flesh. 

. Action of acids on creatine. 

. Coal-tar. 

. Beduction of nitro-comine. 

. GafieouB chlor. of cyanogen on ammonia. 



. Fotasaimn on cyanide of ethyL 
. Chloride of cyanogen on ethjlate oi 

Bodium. 
Do. on phenyUunine 

(anuine.) 
Do. on comidine. 

Do. on melaniline. 

Do. on toluidine. 

. Redaction of dinitrazobenzide. 
. Chloroform on phenylamine. 



. C"H»»N«0 
. C»»H»«N«0« 

. C«H»NO« 
. C^«N«) 
. 0»H*N«J 
. C»H»N»0 

. C"H»«N«0 
. C»«H'*N«0 



. C»H>W 

. C^H^^NW 
, C»«H*N' 

. C^'«NO« 

. C"H>«N" 
. C'H'N. 



. Bromide of ethylene on ammonia. 

. Bromide of ethylene on phenylamine. 
. Bromide of ethylene on ammonia. 

• Redaction of binitrohenzophenone. 
. Forforamide, boiled with potash. 

. Ammonia on chlor- or bromacetic-acid. 
. Ammonia on glyozaL 
. Qoano, &c 

. Seeds of jRyantMnJSTafma^ 
. Hydro(gramo add and hannaline; 
. Seeds of PegoMim Hartnala ; also oxida- 
tion of hannaline. 

. Solphite of ananthylsodiom distilled with 
lime. 

. Verairum album, white hellebore. 

. Coal-tar; also qoinine and cinchonine 

distilled with potash. 
. Hydrochloric and hydrocyanic acids in 

▼aleral ammonia. 
. Distillation of hydrobenssamide. 

• Bone-oiL 



• • . CH'N' . Action of heat on cyanamide. 
• According to unpubliibed analjrtet by Matthietsen and Fofter. 



F 



Meoiplitli^laiiiine . 
Xetfaylamxne 

BimethTlainiiia . 

Tnmethjlamixie. 
Xtthyhnsmiiie 

Xetdmdine . 
XoiphiDe 

BuiTlmoipliixie . 

Keujlmoiphine 

Kaf^tylamioe 

EthjlnapthTlamme 
Nuoeuie • 
Naiootine 

Kluplitylainiiie . 
Oetylimiiie . 

FipfTCTIiC • 

PuTQline 



Pdosiiie, or CisMmpciline 

Pheojlamine 
AxDjlphenjIainiiie 
DiamylphenyUunine 
Dicthjlphenylamine 
Bioetylphenylaiiuxie 
Cety^enylamme 
EthylamylphenTlJimme 
Ethylphenylamine 
Xethjlamjlphenylamiiie 
Methylethylphen^lamme 
Hethjlphenylamine 
Xxxpoeiiylaimne . 

TmylphenyUmine 
(FhenyUcetylaxmne 

Fbtilidine .• • 
PiooIijM 
Piperidine . • 

Amylpiperidine . 

£UiTlpiperidme . 

Meuylpipeiidine 
fPiperme , . 
fto^Iamine. (See 
^noine 

Qnnidiie 

Qonidine 
Qnimne 

Etbylquimne 

H^liylqiiiiiiiie . 
Qoiiioleuie . 

Amyltjuinoleiiie • 

Etliylquinoleiiie 

Hetfaylqainoleino 



ALKALOIDS. 

Formula. Sonrca or Mode of Fonnatlon. 



123 



. C»BP*N» 
. CH»N. 

. C»H"NO». 



. 0»H"NO'»l "P^™- 



Gyananilide (cyanophenylamine) and 

phenyUunine. 
Gnloriae of cyanogen on naphtylamine. 



Creatine or creatmine heated with oxide 

of mercniy. 
Chloride of cyanogen on tolnidine. 
Opinm. 



Bednction of nitronaphfylene. 



Tobaooo. 

Bednction of dinitronaphtylene. 



. C"H«N 

. C*H«NO« 
. C"H^ 

. C»H«NO« 
. C'H'N. 

. C»«H«^. 
. C»«H»»N. 
C^H^N. 
. C«H*N. 
. C"H«N. 
. C»H"N. 
. C«H»*N. 
. OB^N. 
. C^-N. 
. C»H>*N 



• Opium* 

. DistiJlat of bituminous shale of Dorset- 
shire. 
. Cisaamj^doB pareira, L. (Antilles). 
. Beduetion of nitrobenzene^ &c 






(C^»N. 

or 
C»«H'"N« 
C«H»N . 
C^'N. 
C»H"N 
C>*H«N. 
C^"N. 
C^'«N. 
C"H*N«0« 

. C»H*N«0» 



. Sulphite of cinnamyl-ammonium distilled 
with lime. 



. Bednetion of nitrophtalene. 

. Coal-tsr. 

. Fipexine distilled with potash. 



. Pepper (Piper mgnm^ P. longum\ 

• Bone^nL 

• Isomeric transformation of quinine, or of 
qninidine. 






. C"«H»NK)*. 
. C»»H«N«0». 
. C^'N. 
, C^ffrN. 
. C"H"N. 
• C»«H«!N. 



Quinine or Cinehonine distil with potash. 



* According to unpublbbed analrset by MatthieMen nod Foster. 



124 



ALKALOIDS. 



N«ne« 

Sarcine 
Sarcocdne 
Sinamine 
Ethylfiinamme . 

Sinapine 
Sinapoline • • 

Sincaline . 
Sparteine 

Stiychnine • 



Tetrylamine (Fetimne) 

Thebaine 

Theineu (See CAnoMB.) 

Theobromine 

?Xliiacetonine 

Thialdine • • 

Thiosanime • 

Ethvlthiosanimine . 

Toluidine (Toln^lamine) 
Biethyltolnidine 
Ethjltoluidine . 

Tritylamine . 



FormuUu 
. C»H*N*0 

. OH«N« 
. C»«H"NO« 
. C»H'«NO 
. C«'H«N«0« 



Off»N 
C"HnNO» 

0»H>»NS* 
C«H>«NS* 
C*HWS 
C«H>«N«S 



CR*NH). 



Urea (Carbamide . 
Alljlurea . . . 
Amylnrea . 
Diallylurea. (See SmAPOLms.) 
Diethylurea . . . C»H»*N«0. 
Diphenylurea. (See Fulyimb.) 
Ethylallylnrea . . . C«H»»N«0. 
Ethylamylnrea . . . C"H»«N«0. 
Ethylpipezylnrea 
Ethylnrea . 
Memylethylnrea 
Hethylpipeiylnrea . 
Methylures 
Naphtvlnrea 
Phenylallylnxea 
Phenylurea 
Kpeiylurea ... . CTB[»«NK). 
Supliallyliirea. (See TmofliKAiaNE). 
Tolylnrea .... 0»H»«N»0. 



CTB[»«N»0. 

C«H*N'0. 

C*H»N«0. 

C'H^^N'O. 

C«H«NK). 

C»H»«NK). 

C"ff*NH). 

CH'NK). 



Valeraldine . 
Veratrine 
?Vinylamine . 



C»*H«NS« 
C«H«N»0 
C«H»N 



So orce or Mode of Fonnat lop. 

Jnice of flesh. 

Baryta-water on creatine. 

Oxide of mercoiy on thioainamine. 

Ethylthiosinamine heated with hydrate 

of lead. 
White mustard. 
Hydrate of lead in oil of mustard (sul- 

phocyanate of allyl). 
AUcalis on sinapine. 
Spariium soopariwn, L, {Cy tints seopO' 

ritu, Linck.) 
8tryehno9 nux vonUca, 8, Iffnain, 8, oolu- 

brina. 

Bone-oil. - 
Opium. 

Cacao-beans. 

Ammonia and hydrosulphnric add on 

acetone. 
Hydrosnlphurio acid on aldehydam- 

monia. 
Ammonia on snlphocyanate of allyl (oil 

of mnstard.) 
Ethylamine on snlphocyanate of aUyL 
Bedoction of nitiotolnene. 



I^rdrosnlphnric acid on Tsleral ammonuL 

Verairujn album. 

Chloride of ethylene on ammonia. 



2. Alkaloids comparable to hydrate of ammoninm, fanning salts by combining with 
adds and eliminating water. 



Name. 



Formala. 



Amylinm. 

Hydrate of Methyldiethylamylinm C»*H»NO. 

Tetramylinm C*H*»NO. 

Triethylamylium C»H«rNO. 



If 



Brudnm. 
Hydrate of Ethylfamdum 



C»H«N«0». 



ALKALOIDS. 125 

Formuln . 

ConiimL 

Hydrate of Biethylconiiim C^^^^O. 

Methylethylooniixm C»H"NO. 

Et^leniimi. 

HydzateofTrimethylethjlemum C^ff^O. 

Ethrliain. 

Hydrate of Methyltrieihyliiim (?H»KO. 

Tetrothylium C^"NO. 

Metbylinm. 

Hydrate of Tetramethylium OH^'NO. 

NiootiimL 

Hydrate of Ethylnicotiiim (7H"N0. 

Methylnicotiran C»ff>NO. 

Fhenylinm. 

Hydrate of Ethyltriplienyliiiiii C**H*«NO. 

^ MethTlethylamylophenylinm . . . C"H*»NO. 

Trietiylplienylium C"H«'NO. 

Pipenyliimi. 

Hydrate of IMethylpipeiyKum C^"NO. 

Pyridine. 
HydiateofEthylpyridlne CH^'NO. 

Stryehniixm. 

Hydrate of Amylstrydmium C*^"NK)». 

Efchylst^dminm 0"H«N»0*. 



ti 



TdTlium. 



Hydrate of 



TriethyltolyKum C»*H»NO. 



Tliere axe some sabstancee not induded in tHe aboYO list^ sach as acetamido, 
CH^KO, acetonitrile, U*il"N, &a, vhich poaaefls the most important properties of 
alkaloids to quite as great an extent as some of the bodies there enumerated, bat 
vfaich, in moat of their relations, are associated with other well defined groups of com- 
pounds^ and are in consequence seldom classed amon^ alkaloids. On the other hand, 
this list contains some bodies, such as urea and its deriTatiTea, which also find their 
places in other daases, but which had long been regarded solely as alkaloids before 
their relations to other compounds were disooyered. This inoonsiBtency is unaToidable. 
There is not in nature any sharp distinction between alkaloids and other substances ; 
henee, in determining whether particular bodies ought, or ought not, to be classed as 
alkaloids, we must sometimes decide by reference to customaiy usage, or other circum- 
stanees equally arbitrazy. — G. C. F. 

AttaloidSp deteettoB of* In elieiiileo-laffttl lawestlirationi. — The certain 
detection of the poisonous alkaloids in chemico-legal inyestigations involyes their sepa- 
ration, in a state of purity, &om the substances with which they are mixed. When, 
as is oAen the case, a yeiy small quantity of an alkaloid is contained in a laige quan- 
tity of a oon4>licated mixture of animal or yegetable matter, its accurate separation 
is a problem of considerable difficulty. The first chemist who gaye a systematic 
method of proceeding in such cases was Stas (Bulletin de I'Acad^mie Boyale de M^e- 
cine de Bdgiqae, xi. 304 (1861) ; Ann« Ch. Pharm. Ixxxiy. 379 ; Phaim. [3] xxii. 
281% and vie method which he proposed continues to be the one most generally 
employed. His process consists in the successiye and systematic use of yarious 
solvents, such as dilute acids, alcohol, and ether. 

The method of canying it out is as follows : When an alkaloid has to be sought for 
among the contents of the stomach or intestines, the substances to be examined are 
tzeated with twice their weight of pure absolute aJoohol, to which from 0'5 gramme to 
2 grammes of tartaric or oxalic acid (the former is preferable) haye been added, and 
the niixture is heated in a flask to between 70^ and 75^ G. (When an entire organ, 
such as the liyer, heart, or lungs, has to be examined for an alkaloid, it must first be 
diiided aa finely as possible, then moistened with pure absolute alcohol, squeezed, and 
afterwards washed with alcohol till all the soluble constituents are removed. The 
liquid thus obtained is treated in the same way as a mixture of suspected matter and 
alcohol.) When quite cold, the mixture is filtered, the insoluble part washed with 
strong alcohol, and the alcoholic solution eyaporated either in yacuo, or in a rapid 
nurent of air at a temperature not exceeding 35^ C. 

If the residue left on eyaporating the alcohol contains fat or other insoluble matter, 



126 ALKALOIDS. 

it must be filtered agam throngh a filter wetted with distilled water, the filtrate must 
be evaporated nearly to dryness in yacao oyer sulphmic add, and the residue ex- 
hausted with cold absolute alcohol. The alcoholic solution is once more evaporated 
at the atmospheric temperature, either in the air, or better in vacuo, and tiie acid 
residue of this evaporation is dissolved in the smallest possible quantity of water. To 
the solution so obtained, pure, powdered acid carbonate of potassium or of sodium is 
added very araduaUy until there is no more effbrvescenee. The neutralised solution 
is shaken with from four to five times its bulk of pure ether, and then allowed to settle. 
When the layer of ether has become perfectly dear, a little of it is decanted into a 
glass capsule, and left to spontaneous evaporation in a very diy place. I^ after the 
evaporation of the ether, disht streaks of liquid appear on the side of the capsule, 
and run together slowly to we bottom of it, a liquid and volatile alkaloid is probably 
present, fi this be the case, the warmth of the hand will be sufficient to cause the 
contents of the capsule to exhale a disagreeable smell which, according to the nature 
of the alkaloid, is more or less sharp, choking, and irritating. If these indications 
are wanting, the alkaloid, if anv is present^ is probably solid and non-volatile. Ac- 
cording to the nature of the alkaloid, as indicated by this preliminary trial, Stas 
recommends different processes for its farther purification. 

A« 7%e alkaloid is liquid and volatile, — In this case 1 or 2 cub. cent, of strong 
solution of caustic potash or soda are added to the contents of the flask, from which 
the small quantity of the ethereal solution was taken, and the whole is again well 
shaken. After standing for a suffident time, the ether is poured of^ and the residue 
is again shaken three or four times with fresh quantities of ether. The ether^ 
liquids so obtained, containing the alkaloid in solution, are united and shaken with 
1 or 2 cub. cent, of a mixtmre of 4 parts by weight of water and 1 part of sulphuric 
acid ; after being allowed to stand, the ether is poured ofi^ and the add liquid is 
washed with a second quantity of ether. 

As the sulphates of the volatQe alkaloids are soluble in water, but almost all 
insoluble in eUier, the alkaloid sought is contained in the dilute sulphuric add, in tha 
form of pure sulphate *, while the animal matter which the ether may have taken up 
from the alkaline liquid together with the alkaloid, remains still dissolved by it 

In order to obtain the alkaloid from the solution of its sulphate, the latter is mixed 
with a strone solution of caustic potash or soda; the mixture is well shaken, and then 
exhausted with pure ether, which dissolves the alkaloid together with ammonia. The 
ethereal solution is allowed to evaporate f at as low a tmperature as possible, and 
in order to remove from the reddue the last traces of ammonia, the vessel containing 
it is placed for an instant in vacuo over sulphuric add. The alkaloid then remains 
in a state of purity, with its characteristic chemical and physical properties. 

B. The alkaloid is solid and fixed,— Ji on evaporating a small quantity of the ether 
with which the Uquid neutralised by acid carbonate of sodium has been mixed (see 
above), there is no sign of the presence of a volatile alkaloid, the liquid must be fiu> 
ther examined for fixed alkaloids as follows. Caustic potash or soda is put into the 
flask containing ether and the neutralised solution, the mixture is again vigorously 
shaken, the ethereal layer is poured off as soon as it is clear, and the wateiy alkaUne 
liquid is several times washed with a oondderable quantity of fresh ether. The ether 
now contains the free alkaloid in solution ^, and on evaporation leaves either a solid 
residue or a colourless milky liquid containing solid particles in suspendon. The 
smell of this residue is disagreeably animal, but not shaip ; it colours red litmus- 
paper permanently blue. 

In order to obtain the alkaloid in the crystalline state, a few drops of alcohol are 
poured into the capsule containing it and allowed to evaporate. Usually, however, 
it is still too impure to crystallise in this way. When this is the 'case, a few drops of 
water made very slightly add by sulphuric add, are poured upon the residue left by 
the evaporation of &e alcohol, and made to come in contact with the whole of it by 
properiy inclining the capsule in various directions : the alkaloid is thus diasolvea, 
while the fatty impurities remain adhering to the capsule. The acid solution, which, 
if the last operation has been well performed, is dear and colourless, is poured ofi^ the 
capsule is washed with a few drops more of the acid water, the washings are mixed 
with the first solution, and the whole is evaporated over sulphuric acid to about 
three quarters of its bulk. A saturated solution of pure carbonate of potassium 

* Solpbate of eemine being not quite insoluble In ether, a little of thlt alkaloid maj remain In the 
etherMU solution ; the greater part, however, is always in the aqueous add solution. 

t \t amine be present, a great part of it will evaporate with the ether. 

i ir menkme has to be sought for the liquid should be shaken with ether t'mmediatefy after being 
neutrallsetCwith carbonate of sodium, and the ether should be poured off as quickly an possible, for. If 
the alkaloid have time to separate in the crystalUoe form, scarcely any of it is dissolved by the etlier. 
(Otto.) 



ALKALOIDS. 127 

11 added 10 the TCmumng liquid, and the mixtnre is trented with absolute alcohol, 
vfaich disBolTee the liberated alkaloid, but leaTea undisaolyed the sulfate and 
exeees of carbonate of potaasium. On evaporating the alooholic solution, the alkaloid 
is obtained carTstallise^ and in a state to snow its cfaaraeteiistic reactions. 

According to Otto (Ann. Ch. Pharm. c. 39) the above process of purifying the 
fixed alkaloids may be advantageoualY modified as follows. Instead of decomposing 
the impure tartrate oar oxalate bj acid carbonate of potassium or sodium, and m)tain- 
ing a solud)(Mi of the free alkaloid in ether; as deeeribed in the first part of this 
azlLcle, the salt dissolved in a small quantity of water is washed with ether, as long as 
^ ether is ocdoored by it and leaves a residue on evi^poration, and aftervoards the 
fidntion is neutralised bj carbonate of sodium and ether added to dissolye the 
alkaloid as already described. On evaporating the etheceal solution thus piepaxed, 
the alkaloid is left in a state of ^reat purity. Or, the aeid sulphate of the alka- 
loid maybe £xmed and washed with ether, as in the process for purifying a yolatile 
alkaloicL 

Another method of detecting; and separating the oij^nie alkaloids from mixtures of 
other substances has been given by Sonnenschein (Ann. Gh. Phaim. ciy. 45). 
This method is founded upon the property which the alkaloids possess, in common 
^th ammonia, of giving precipitates in an acid solution of phosphamolybdate of 
tpdhtm : it is yery easy cdf execution, and seems to give ygpj accurate results. 

Phosphomohrbdate of sodium is thus prepared. The yellow precipitate obtained 
bj mixing acid solutions of molybdate of ammonium and phosphate of sodium is 
^1 washed, suspended in water, and heated with carbonate of sodium tUl it is 
completely dissoWed. The solution is evaporated to dryness, and the residue ignited 
till all ammonia is expelled : if any reduction of molybdic acid take place during 
the ignition, the product is moistened with nitric add and again ignited! It is then 
heated with water, nitric acid added till the solution has a strongly add reaction, 
and the gold-yellow solution thus obtained is diluted till 10 parts of the solution 
contain 1 part of solid residua It must be carefully preserved from contact with 



This reagent is applied to the separation of the alkaloids in the following manner. 
The whole of the organic matter to be examined is repeatedly exhausted with yery 
difaite hydrochloric add : the extract is evaporated at a heat of 30^ C. to the consis- 
tence of a thin syrup, then diluted, and leit for some hours in a cool place before 
filtration. The filtrate is predpitated by excess of phosphomolybdic acid, the predpi- 
tate collected on a filter, uiorougfaly washed with water containing phosphomolybdic 
and nitric adds, and introduced while moist into a fiask. Caustic baryta is added, 
to a distinct alkaline reaction : and the flask having been fitted with a deliveiy- 
tube which is connected with a bulb-apparatus containing hydrochloric add, heat is 
gradually applied, when the ammonia and yolatile organic bases distil over, and are 
collected in Uie hydrochloric add. The residue in the fiask (containing the non- 
yoimtile alkaloids) is freed from excess of baryta by a current of carbonic anhy- 
dride, carefully evaporated to diyness, and extracted with strong alcohol. On 
eraporating the alooholic solution, the bases are commonly obtained in a state 
of such parity that tiiey will at once exhibit their characteristic reactions : occa- 
sionally, however, they require to be farther purified by recrystaUisation from alcohol 



A process has been employed by Graham and Hofmann (CheuL Soc Qn. J. v. 
173 ; Ann. Ch. Pharm. Ixxxiii. 39; Pharm. J. Trans, xi. 504) for the detection of 
strychnine in beer, which might doubtiess be employed with equal advantage for the 
detection of other alkaloids in large quantities of liquid. It consists in leaving the 
liqaid to be examined in contact with about a fortieth of its weight of good animal 
chflzcoal for a day, the whole being frequentiy shaken, collecting the charcoal on a 
filter, washing it once or twice with water, and then boiling it for half an hour with 
aleobol, which dissolves out the alkaloid. The alcoholic solution is evaporated, 
the residne is made alkaline by the addition of a few drops of potash or soda, and 
then shaken up with ether, wUch, when poured off and evaporated, leaves the oi^ganic 
base with its characteristic properties. 

Schulze (Ann. Ch. Pharm. dx. 177) has indicated the add liquid obtained by 
dropping pentachloride of antimony into aqueous phosphoric acid as a very delicate 
reagent far certain alkaloids, and as a substance which may probably serve for the 
separation of the alkaloids in general 

When an alkaloid has been separated in a state of purity by one of the above 
processes, or hr any other, its chemical and physical properties must be carefully 
observed in order to determine its individual character, and the reactions obtained 
sbrmld in eveiy case be controlled by comparison with those given by a pure speci- 
men of the substance suspected. 



128 ALLANTOIC AND AMNIOTIC LIQUIDS. 

From what has been stated above relative to the abeoiption of the alluiloids bj 
animal chaicoal, it is evident that that substance shonla never be employed to 
decolorise a solution previous to its being examined for poisonous organic bases. The 
emplovment of baflic acetate of lead for the same purpose rtiould also be avoided, 
since it not only introduces a poisonous metal into the substance to be examined, but 
the sulphuretted hydroeen, which is required to remove the lead, is apt to combine 
with some of the organic matters present, forming compounds which, in contact with 
the air, give rise to highly coloured and disagreeably smelling products, veiy difficult 
afterwards to get rid of. (St as.) 

For further detals concerning modifications of Stas*s process, and for some methods 
which are not mentioned in tms article, the reader is referred to the article on tibe 
same subject in Liebig, Poggendorff, and Wohler's ** Handworterbuch der reinen nnd 
angewandten Chemie," 2naedition, i 464 ; and for the reactions of the individual 
alkaloids, to the various articles in thia Dictionary in which they are specially de- 
scribed. — G. C. F. 



IT. The commercial name of two different plants. Ihis alkanet oon- 
sists of the leaves and roots of the Lawaonia inermis^ which grows wild in the Levant. 
The leaves pulverised and made into a^ paste with water yield a yellow dye. The 
root, which contains a red pigment, is used aa a cosmetic 

False alkanet (Orcanette, Radix alcanna spurus) is the root of Anchusa tinc' 
toriOy which grows in France, Spain, Italy, Hungary and Greece. It is inodorous, 
has a faint^ somewhat astringent taste, and colours the saliva. It is uaed in dyeing 
to produce a very brilliant violet and a grey ; and for this purpose, linen or cotton 
goods previously prepared with alum-mordants for violet, and with iron-mordants for 
grey, aro dipped in an alcoholic extract of the root. It is also used for dyeing silk, 
but not for wooL The colouring matter is called Anchusin (which see). 

and AULAS8ZW. (See Arsenidbs of Mbthtl.) 

A mineral which appears to be an intimate mixture of homstone 
and silicate of manganese, perhaps also with carbonate of manganese. 

Syn. of DiopsiDB and Auoitb. 

(See Obthttb.) 

A&&AVTOZO and ABCVZOTZO XiZQinEDS. The fcetus of most mammi- 
ferous animals is enveloped in two membranes, the outer of which is called the 
allantoiSt and the inner the amnittm. The space between the two is connect'Cd by a 
duct with the urinary bladder of the foetus, and contains a liquid called the allantoic 
liquid, which is in fact the urine of the foetus. The amnium at first lies close upon 
the foetus, but gradually separates and becomes filled with a liquid in which the 
foetus floats suspended by the umbilical cord. This liquor is the liquor amnH. 

The allantoic liquid is especially distinguished by containing alfantoin, together 
with albumin, alkaline lactates, chloride of sodium and phosphates, and sometimes 
glucose. The amniotic liquid contains albumin, pyin, a substance rosembling mucus, 
extractive matter, and in some instances glucose, together with alkaline dilorido, 
sulphates and phosphates. 

These liquids have been investigated by many distinguished chemists, but the most 
exact analyses of them are those which have been recently made by Schlossberger 
(Ann. Ch. Pharm. xcvi. 67, and ciii. 193), and by Majewski (Dissert, de Substan- 
tiarum, &c, Dorpat, 1858; J. fur Chem. Ixxvi. 99). Majewski's results are as 
follows : 

Both liquids, in the earlier stages of development of the embryo of cows and sheep, 
are clear and colourless : at a later stage, the amniotic liquid of the cow becomes 
gummy and yellowish, also turbid; in sheep and swine on the contrary, it alwavs 
remains clear and colourless, and never becomes gummy. The allantoic liquid 
becomes yellower with age, and at last reddish yellow, but remains dear, excepting 
in swine, in which it is always turbid. Both liquids generally exhibit an alkaline 
reaction. 

In both liquids, the solid constituents, organic and inorganic, increase for the most 
part in quantity as the development of the foetus progresses. In the human foetus, how- 
ever, the quantity of solid matter in the amniotic liquid decreases considerably towards 
the time of birth (see table). The same result was obtained by Vogt and by Scherer. 
the latter of whom found 2*416 per cent, of solid constituents in the amniotic liquid 
in the fifth month of gestation, and only 0*852 at birth. 

The amniotic liquid retains its albumin up to the period of maturity of the foetus, 
but (as appears tram investigations on the numan embryo) this amount decreases in 
the later period of the development of the embryo, and this diminution appears to be 



ALLANTOIC AND AMNIOTIC LIQUIDS. 



129 



eaooeeted with the fonnation of the placenta. In the amniotic liquid of the cow, the 
albumin may be recognised l^ its orainary properties in the earlier sta^ of derelop- 
BMDt, but afterwardB the liqnid becomes gummy and no longer exhibits the nsnal 
medon vith nitric acid. The same result was obtained by Schlossbeiger, (p. 130). 

Hie allantoic liquid increases in quantity and consistence as the development of 
the onlnTO adTanoes ; it is always dear (excepting in swine) and resembles saturated 
vnae. the allantoic liquid of swine contains iron and a peculiar compound of lime 
and albnmin. 

In both liquids^ the quantify of sugar gradually increases from the earliest period 
of fietal life, and is greiftest a short time before birth. Sugar appears however to be 
nreseat only in the yegetable feeders : in human embryonic liquids it cannot be 

Hie quantity of inorganic salts increases as development advances. Both liquids 
OQotain chlorides, phosphates and sulphates, the quantity being greater in the 
aSanftoie than in Uie anmiotie liquid. 

Tbe following table exhibits a summary of the quantitative results obtained by 
Majewski: 

In 100 parts. 













y 


-" — ^ 




Bjasi-. 


AjBlte 


cmc 


9p«. 


Warn. 


tiolid 
nil». 


Or- 
■aale. 


Inor. 
gaale. 


Alba- 
Bin. 


SofV. 


UfMU 


FlOA 


S08 


W*« 


{ 


17 


1-00S9 


99-357 


0*649 


0*459 


0*184 




0-14S 










» 4-«l 


{ 


AltaDMb 


19 
69 


1-0018 
1006d 


99^460 
98-900 


0*540 
1*010 


0*400 
0-650 


0-140 
0*370 


0*105 


0-063 
0-141 


0*10 
0*40 


0*0047 


0-0051 


%; 


. H-9 




Amta 


61 


i-ooi; 
i-OOik 


98-945 

m-i«7 


1-055 
1-878 


0*685 
1-198 


0-370 
0*675 


0*115 


0-114 
0*449 


0-301 
0*500 


0-0078 
0-0356 


0-0061 
0-0069 




• l»-lt| 




AI^Mofc 


163 
119 


1-0069 
1-0100 


96-515 
97-453 


1*485 
1-547 


0-917 
1-671 


0*568 
0-876 


0-170 


0-171 
0-641 


0-370 
0606 


0-0148 
0*013? 


Oi)034 
0-0x75 




m 111-18 




Aranta 


6S7 
835 


1-0064 
1-0097 


98-660 
97-380 


1*349 
1*6S0 


0-905 
0-960 


0*435 
0*660 


0*S41 


0-196 
0-667 


0-475 
0*780 


O-0817 
0HM98 


0-006 
0-OSK 




. »-is 




Amain 

AJlMMQii 


675 
9S 


1-0047 
1-OlOk 


98-97P 
97-310 


1*03 
1*69 


0*600 
1*800 


0*430 
0*890 


0*091 


0-104 
0*555 


o-mo 

0*330 


0-018 
QrOm 


0*009 
0-033 


dCmm, 


m H-tt 


I 


ABWiM 


1«U 
643 


1-0064 
1-OlU 


98*554 
98*858 


1*446 
8*148 


0*876 
S-S38 


0-570 
0-804 


0-097 


0*191 
0*605 


0-198 
0*645 


oa&i 

0*011 


0-011 
<h097 




» SI— 17 




AlbmMfe 


699 
ISM 


1-0076 
1-0163 


98-076 
96*160 


1-9M 
3*840 


1*171 
S-767 


0*753 
1-073 


0-115 


0*301 
0-648 


0M16 
0*857 


0*016 
0-038 


OK>n 
0-llS 


i55L{ 


lateMlBM 


■eh 

p 


M 




1-0049 


95-405 
98-490 


3-595 
1-510 


0*95 


5*600 


9*188 

0-357 


^ 


0*380 






5!s:{ 




A-nfaw 


60 
19 


1-0064 
f0096 


98-114 
97*580 


1-886 
MIO 


1*148 
1*705 


0*638 
0*715 


0*561 


trace 
naec 


0*140 
0*858 







SehloBibager found in the embryonic liquid of cows the following quantities of 
water and inorganic salts : — The ages oi the foetus were : of (a) 30 weeks ; (6) 18 
weeks ; (c) 16 weeks ; {d) 7 — S we^ ; (e) 5 weeks, and (/) 3 weeks : 







Water. 


Aib. 


Soluble 
Salu. 


Insoluble. 
SalU. 




(^ 


97-18 










b. 


97-28 


0-72 


0-694 


0026 


Amniotic 


c. 


98-96 


1-02 


100 


002 


liquid. 


d. 


98-67 


» 








e. 




0-89 


0-86 


003 




1/ 


9812 








I11«««MJ> ! ^' 


97-33 


0-93 


0-91 


0-02 


liianiDie 
liquid. 


« 


98-76 
97-36 


0-73 
0-71 


0-70 


003 



The liqaids, even in the fresh state, exhibited an alkaline reaction, and effervesced 
bri^ly with acids : and they all exhibited the reactions of sugar, the amniotic liquid 
of tf containing 0*092 per cent, of that substance, and the allantoic liquid of the same, 
0-464 per cent Schloesberger did not find urea in the amniotic liquid. 

The albmninoidal substances of both liquids exhibited differences of character 
amcMigprt themselves, and many unusual reactions, indicating the presence of com- 
pouids intermediate between albumin casein, mucus and pyin. The reactions ob- 
served by Schloesberger are giren in the following table: 

V0L.L K 



ALLANTOIC AND AMNIOTIC LIQUIDS. 



boiling wid 
on^dditiM. 
ofacatioacid. 


Amniotic liquid of a and i;. 


Allantoic liquid of* and a 


0. Vitdd like vliito of egg : 
mixed easily witli vakr, and 
Bltered readilj. On boiling, 
became mora mobile, vith 
Bcarcel; perceptible tnrbidit;. 

bidilj, the liqmd renmining ™- 
cld. Od boiling, small flocks 

the protein-substance remained 
dissolved. On evaporation: Alms. 

perfecU? clear when boQed, 
either uone or wit^ acetic acid. 


6. HotTiwid; clear on boil- 
ing. Acetic acid produces 
slight turbidity, and redifsolTS) 
the flocks but slowly, even in ex- 
cess and at the boiling heat. 

e, COHgnlatei even vheo 
boiled alone, the coagulum being 
hut partially soluble in scetie 

Both 6 and e beceme Tsty 
turbid when boiled with chlo- 
ride of CBldum or snlphiil« of 

turbidi^ (arising in b most pro- 
bably fitjm carbonates) disap- 
pesiB on adding acetic acid 


Akobol 


a. ThroTB dami flocks aolu- 
c. No change. ' 


b. So change. 
e. Turbidi^. 


Nitric add. . 


c. No turbidity. Liquid does 
not become yellow on boiling. 


_ &. Scarcely perceptible turbi- 

c Fiecipitate and yeHov 
colour on boiling. 


Hga 


a. Slight turbidi^: small 
flakes on boiling. 

c. Turbidity. {WilhNO«Hg: 
copious precipitate). 


b. No change. 




a. Ho change. 

c. Turbidity only after addi- 


b. Ho change. 

c; Aftaaradolatioii:flodw. 


AceUte of 
lead. Baaic 
acetate of letuL 
TaimiQ. 






Alnm. 1 



ir. CH^'C, or CifA-'O".— Discovered by Vanquelin 
Buniva (Ann. Chim. zxiiii. 269) in the amniotic liquid of the cow* Lagsai 
(Ann. Ch. Phys. [3] ivii. 301) obtained it from the allantoic liquid of the cow, 
Wohler (Ann. Ch. Pharm. tix. 220) from the nrine of calves. It is formed 
flcially by treating uric acid with water and peroxide of lead. (Liebig and Wiil 
Ann. Ch. Pharm. zzri. 244.} 

OH'N'O' + ffO + 2FbO - C'H'NH)' + CPVO'; 

Uilc uld, AUnDtotn. CulMDiita 

ollud. 
or with a mixture offerricyanide of potassium and caustic potash. (Schl leper, 
Ch. Pharm. livii. 216.) 
CK'N-O* + SCTS'Fe'^ + 4KH0 - CH-N'O' + CK'O' -i- iOWTeK* + '. 



Uriel 



Fnilc,«l 



PrfparaHon. — Fnlverised uric add is suspended in water, nearly at the boilino; heat, 
and finely pounded oxide of lead is added by small portions, and with frequent stirring, 
till the last portions no longer turn white. The hquid Sit«red while hot deposits on 

lublB tdu the utDlnllTllqiiM wu mliad vlth allutcilc li<)uld. ' 



ALLANTOIN. 131 

(odii^ aptiJB of ftUantoiiii while urea lemainB in solution, and oxalate of lead is 
left Qo the filter. The two latter compounds are produced by the action of the excess 
ofperazideof lead on the allantoin. (LiebigandWohler.) 

<?H«NH)» + 2PbO + H*0 - 2CH*N«0 + C^H)*. 

, — — ' "« — , — ' 

Urea. Oxalate of 

lead. 

To obtain allantoin from tiie allantoic liquid, the liquid is evaporated to a fborth of 
its bulk, and the dyBtals which are deposited on cooling are decolorised with ani- 
nal durpoaL From calTes* urine, it is prepared by eTaporating the liquid to a syrup, 
and leaTiDg it at least for several days, tnen diluting with water; washing the deposit 
vith water to separate a quantity of gelatinous matter, chiefly consisting of urate of 
migBsnuii ; boiling the ctystaliine residue of allantoin and phosphate of magnesium 
vim vaterand animal charcoal; filtering at the boiling heat; ana addinga few drops 
of hjdvocblone add to the filtrate to retain in solution the small quantity of phos- 
phate of oagnesium dissolved in the boiling liquid. The allantoin is then deposited in 
CTfitdi OB cooling. 

Pn^trtm. — ^Allantoin forms shining colourless prisms, having a vitreous aspect, and 
bdoq^a^ aoeording to D auber (Ann. Ch. Pharm. had. 68), to the monodinic fiystem. 
It is tsBtdesB and without action on vegetable colours. It dissolves in 160 pis. of 
viter at 20° C, and in 30 pts. of boiling water. Alcohol dissolves it in larger quantity. 

DieompotUicms, — ^By dry distillation, allantoin is resolved into carbonate and cyanide 
of ammonium, a small quantitT of empyreumatic oil and a verj porous charcoal When 
gat^ heated with nitric or hydrocmoric add, it is converted into urea and allanturic 
acid. (Pelouze, Gerhardt) 

C*H«N«0" + H»0 = CH*1TO + C«H*NK)« 

f 

AllaDtnric acid. 

Heated with suljpkurie aeid^ it is resolved into carbonic add, carbonic oxide, and am- 
noai^ (Lisbig and Wohler.) 

C*HWH)« + SWO « 2C0« -I- 2C0 + INRK 

Boiled with btu^^ water ^ it gives off ammonia and predpitates oxalate of barium : 

C^*N*0« + 4BaH0 + HH) - 4NH" + 2C«Ba«0^ 

KBihliy with aqueous potash (LiebigandWohler). A solution of allantoin in 
cdd potash depodta all the allantoin unaltered, if immediatdy mixed with adds ; but 
intteowiwe of a day or two, it changes spontaneonsljr Into hydantoaU of potasnum 
(C*R'JSJS*0*^ and is then no longer predpitated by adds, gives off but Uttle ammo- 
ma what boded, and does not form mj oxalic add : 

C*H«N*0" + KHO = C^H'KN^O* ; 

Ifj the finther action of the alkali, the hydantoate of potassium is resolved into urea 
sod la&tanuzate of potassium : 

When the aqueous solution of allantoin is boiled with metallic oxides, compounds 
are fonned which may be called salts of allantoin. Some of them consist simply of 
alkatoin in which 1 at. H is replaced by a metal; thus, the cadmiwnroompouna is 
C*HHMKH)* : and the stiver-compound, obtained by mixing a solution of allantoin 
with nittate of silver and then wiUi ammonia, is C^H^AgN^O'. But most of them con- 
tab an eieess oi the metallic oxide ; thus, the zinc-compound is ZnK).2OH*ZnN*0', 
tad the lead-compound Pb*0.4C^H*FbNK)'. Theee compounds are insoluble or 
apanojdj soluble in water, and decompose at 100^ or a little above (Limpricht, 
Ann. uL Pfaaim. Ixzxviii 94). The silver^compound was obtained by Liebig and 
Wohler. 

When a solution of allantoin is boiled with excess of mercuric oxide, the filtrate 
heoomes milW on cooling, and after a while deposits an amorphous powder containing 
Hg«0.3C«H»HgN«O«, or bHgO.ZC*H^N*0^. Three other compounds are said to be 
obtained from the mother-liquor. Allantoin does not precipitate corrosive sublimate ; 
^ with mercuric nitrate, in a cold and very dilute solution, it forms a predpitate 
containing 3H^.4C^H»HgN*0«, or &^y0.2Cffl»JV»0». 

On this last pr o pert y is founded a method for the quantitative estimation of allan- 
toin, bj precipitation with a graduated solution of mercuric nitrate. The method is 
similar to Liebig's process &r the estimation of urea {q. v,\ but is applicable to 
the estimation of allantoin only in liquids not containing urea. To predpitate 
100 ams. of diy allantoin, C^H^^, requires 172 erms. of mercuric oxide : conse- 
qnentty 10 eab. cent of a graduated solution of mercunc nitrate containing 0*770 gnu. 

K 2 



132 ALLANTUBIC ACID— ALLOPHANIC ACID. 

mercnrie oxide, will pedpitate 0*448 gnn. aOaiitoiiL The liqmd shonld oouUiii a «oii- 
ridenble ezoesB oi the mercnrie ealK 



CFH^S*0^. — A product of the decomposition of aUmtoiB 
under the inflnence of nitric add, hydrochloric acid, or pooxide flf lead (p. ISl}: 
also obtained by treating nric acid with, nitric acid or chlorine. It is a white solid 
body, slightly acid, deliquescent, neariy insoluble in alcohol, and yields by distilla- 
tion a product containing hydrocyanic add, with a bulky residue of chareoaL With 
nitrate of silrer and acetate of lead, it forms white bulky predpitates, soluble in 
of these salts, and of allantuiic add. (Pelouze, Ann. Ch. Phys. [3] ri. 71.) 

sude of Antimony, (p. 871.) 

iCM3^ CH'WK)*? Obtained by mixing an aqueous solution of 
alloxantin with excess of hydrochloric add, boiling the liquid rapidly down to a small 
quantity, treating the pnlremlent mixture of allituric add and undeoomposed alloxaatin 
with nitric add to dissolre out the latter, and diasolring the reddue m 15 or 20 pts. 
of hot water. The solution on cooling depodts allituric add in the form of a bulky 
yellowish white powder. It diasolyes in strong sulphuric add, and is predpitsted from 
the solution by water. Its solution in ammonia yields allilurate of ammo ni um, by 
spontaneous CTuporation, in colourless shining needles. The add is deeompoeed \rf 
boiling with potash, with erolution of ammonia. (Sehlieper, Ann. Ch. Pham. 
ItL 20.) 

ASMSUWK SATXVUIC ( Garlic.) 100 pts. of the ash of the fresh plant yield 0*64 
p. c ash, containing in 100 parts : 12*17 carbonic anhydride, 4*82 sulphuric anhydride, 
2*18 phosphoric anhydride, 35*13 potash, a trace of soda, 2*75 chloride of sodium, 
5*74 carbonate of caldum, 6*89 carbonate of magnedum, 30*09 bade phosphate of 
caldum, 0*22 silica» and traces of the phosphates of magnedum and iron. 

A&&OOHXOITH1 A TBrietj of gamely flne-grained, maadye^ and of dark dingy 
colour. (See Gabmbt.) 

AUMMMVITB. 8yn. with Heboebtib. 

A&KOMOXVKXTa. Breithanpf s name for a mineral from Bndolstadt^ which, 
according to the analysis of GFemgross, appears to be merely sulphate of barium. 

AUEiOVBAVMi A hydrated silicate of aluminium, of a bkie and sometimes 
ffreen or brown colour, occurring masdre^ or in imitatiTe shapes, in a bed of iron-shot 
mnestone, or greywadce slate in the forest of Thuringia. It is transparent or trans- 
lucent on the ed^es, moderately hard, but yery bri&e. Eracture imperfectly con- 
choidaL Lustre vitreous. Specific gravity 1 *89. According to Stromeyo^s analysis, it 
contains 21*92 silver, 32*2 alumina, 3*06 ferric hydrate, 0*73 lime, 0*52 sulphate of 
caldum, 3*06 carbonate of co^)er, and 41*30 water. Bunsen found in a specimen from 
a bed of lignite near Bonn, nearly the same compodtion, with a slight admixture of 
the carbonates of calcium and magnedum, but no copper. The minnal appears from 
the analyses of Walchner, Berthier, Ghiillemin, and others, to vary oonsidembly in 
composition, but irrespective of foreign admixtures it agrees nearly with the formula 
A1^.3SiO* + 5HH). Schnabel (Jahreeber. d. Chem. 1850, s. 731), has» however, 
analysed seranl allophanes containing from 14 to 19 per cent of oxide of copper. 

AXAOV&aVXCAOZB. C^«NK)*-.^^'^'|o. Ureo<arbonie add. (Gm. 

ix. 266 ; Gerh. i 418.) By passing the vapour of cyanic add into absolute alcohol, 
Liebig and Wohler obtained in 1830 a peculiar ether, which they regarded as cyanate 
of ethyl ; but in 1847 (Ann. Ch. Pharm. lix. 291), they discovered that the substance 
thus formed was the ether of a peculiar add which they called allophanio add. 
This add contains the dements of 2 at. cyanic add and 1 at, water: 

C«H^NK)« - 2CB3TO + H«0. 

Its ethers are produced when the vapour of cyanic add comes in contact with the 
corresponding alcohols, and ti^ese ethers, treated with caustic alkalis, yield the cor- 
responding salts of allophanic add. The add itself is not known in the separate state ; 
when its salts are decomposed by a stronger add, it is resolved into carbonic anhydride 
and urea: 

C«H*N«0« - C0« + CH<N«0. 

In like manner the salts when healed in the state of aqueous solution, are resolved into 
carbonic anhydride, a carbonate, and urea. 

AJUophanate of Barium. — Obtained by dissolving allophanate of methyl or ethyl in 
baryta-water, whereby wood-spirit or alcohol is set free. The best method is to tri- 
turate allophanate of ethyl wiUi ciystals of hydrate of barium and baiyta-water, without 
applying heat^ till the ether disappears ; filter from the remaining baryta-erystals ; and. 



ALLOPHANIC ETHERS. 133 

Ki Mide tbe fflinte for some days in a closed yeesel; the barinm-salt then separates 
gradnglty in hard ajBtalline nodules and cmsts. The ciystaJs are separated from 
tbe Teasel imder the liq^nid ; the liquid quickly decanted ; any carbonate of barinm 
thatmaj have been formed, is sepanSted by elutriation ; and the crystals are washed a 
iew tiineB with a small quantity of cold water, and dried on paper at the temperatoie of 
the axe 

The bannm-salt has an aftaUne reaction. When heated alone, it does not 
give off a trace of water, bat erolTes monocarbonate of ammonium, and leaves cyanate 
at faaoivKL Its aqueous solution becomes turbid below 10(P G^ giyes off carbonic 
anhydiide wil^ eflferreseence, deposits all -the baryta in the form of carbonate, and 
afterward* ooastains nothing but urea in solution : 

2C^«BaN»0« + HK) = CX)«Ba« + C0« + 2CH*NK), 

Tfaas mah, vhen an add is poured upon it^ ia decomposed with brisk effervescence, 
yieldbig earbonie anhydride and urea ; even carbonic acid produces this decomposition, 
^^Mwg** dowly ; neither cyanic acid nor ammonia is formed. 

jSepktinaie of Calcium, — Prepared like the barium-salt, Ciystallisable. Sparingly 
aofaible in water. 

JBo p kt mate of PotoMtiuim, — A solution of allophanic ether in alcoholic potash quickly 
deposits this salt in laminn resembling those or chlorate of potassium. 

MinpkamaU of Sodium, — Obtained like the potassium-salt, or by triturating the 
faarimn-salt, without application of heat, with an equivalent quantity of aqueous sul- 
phate of sodium, and pouring alcohol upon the filtrate, which causes the sodium-salt to 
crystallise out in small prisms having an alkaline reaction. The aqueous solution of 
the aalt evaporated without heat in vacuo^ leaves the salt in the form of an iridescent 
gelatinous mass ; evaporated between 40^ and 60^ C. it leaves the salt partly unde- 
coB^Kwed, partly resolved into urea and carbonate of sodium. The aqueous solution 
mixed with nitric add gives off carbonic anhydride and deposits shining scales of 
ni&ate of urea. It does not predpitate chloride of barium, in the cold, but^ when 
hoatod with it^ fonna an immediate predpitate of carbonate of barium. 



-These compounds contain the elements of 2 at. cyanic add, 
and 1 at. of an alcohol, monatomic, diatomic, or triatomic^ e.ff, 

AUophanate of Ethyl . . . C*H"NH)» - 2CNH0 + (?H«0 
Allophanate of mhylene . . C*H!^0* » 2CNH0 + C>H«0* 
AUophanate of Glyceryl . . C»ff>NK)» = 2CNH0 + C»H"0« 

They are obtained by passing the vapour of cyaaio add into the alcohols. 

AUophanate of Amyl, C'ff^N'O' - C*H»(e*H»)NO«.— AmyUc alcohol rapidly 
absorbs the vapours poduced by the action of heat on cyanuric acid, the liquid, after 
a whDe, solidiQring mto a magma of cxystals, which may be purified by solution in 
boiling water. (Schlieper, Ann. Ch. Pharm. liz. 23.) 

Allophanate c^ amyl forms nacreous scales, unctuous to the touch, and without taste 
or odoor. It is insoluble in cold water, and its solution in hot water is neutral to 
vegetable colours, and does not predpitate metallic salts. It is very soluble in alcohol 
and in ether, and is predpitated from the solutions by water. It is not attacked by 
chlorine, biomine^ nitric add, or hydrosulphuric add. It melts at a gentle heat, and 
snblimea without alteration ; but its mdtmg-point is ver^ near that at which decom- 
poaition takes place. When heated above 100^ C. it boils, gives off vapours of amylic al- 
eohol, and leaves a residue of cyanuric add, 8C»H"N«0« - 8C*H>*0 + 2C»N*H*0«. 
DistOled with fixed alkalis, it gives off amyl-alcohol ^Schlieper). According to 
Wurtz (Compt rend. xxix. 186), hot potash-ley converts it into carbonate of potassium, 
amylamine, ud ammonia : 

Crff^NH)* + 4KH0 = 2C0*K» + C»H»«N + NH» + H«0. 

Allophanate of Eikyl^aeAttovhanio Ether, C*B?NH)^ » G^C>H')N*0*.— When 
the vapours evcdved from heatea OTanuiic add are passed into absolute alcohol, 
the Uqoid becomes very hot and gradually depodts crystals of aUophanic ether. The 
prodoet is washed with a small quantity of alcohol, then dissolved in a mixture of alcohol 
and ether, and left to czystsJiise b^ evaporation (Liebig and Wohler, Ann. Ch. 
Fbarm. IviiL 260 ; lix. 291). According to Debus, allophanic ether is likewise produced 
by the action of ammonia on dicarbonate of ethyUc disulphide. 

AlViphanin ether erf stallises in colourless transjparent needless, having a strong lustre. 
It is insoluble in cold water, but dissolves in boiling water and in alcohol, sparingly in 
ether. The solutions are neutral to test-papers, have no taste, and do not precipitate 
BMtallic salts. 

The ether dissolves in ammonia somewhat more freely than in water, and crystallises 

X 3 



134 ALLOPHANIC ETHERS. 

therefrom, apparently free from ammonia. It diBsolyes in dilate salphnne and nitne 
acid at the boilinsheat^ apparently -without deeampoaition. 

The crystalairlLeii heated in an open veesel melt and Tolatiliae, the Tapoora eofn- 
densing in the air in woolly flocks. 

Treated with cold alcohoUe potaah or baiyta-water, it yields a metallio allophanate 
and alcohol ; with a boiling Bolution of potash, itforms cyanurate of potassium. 

Allophanate of I^hyUne,C*B*JPO* ^^^^^Ao^. JUophanate of Glycol.-^ 

G^lycol (hydrate of ethylene) absorbs cyanic acid vapour with considerable fareei so 
that it 18 best to oool the liquid during the absorption. The product is a white mass 
which dissolves in boiling alcohol, and separates on cooling in eoloariass iih»"^"g 
lamins. It is soluble in water, and melts at 100° G. without decomposition, to a clear 
colourless liquid, which solidifies in the dystalUne form on cooling. At a stronger 
heat, it gives oif carbonate of ammonium, and a thick viscid liquid, while mnurie acid 
remains behind. Strong acids decompose it. With hydrate of barium, it behaves like 
the glycerin-compound next to be described; also with alcoholic potash. StRKig 
aqueous potaidi likewise decomposes it» without Honnation of cyanuric add. (Baeyer, 
Ann, Ch. Pharm. adv. 160.) 

Allophanate of Glyoeryl, (m>«N*0» - H^Srl^' ^^^^^^^^f^h' 

eerin. — Glycerin absorbs cyanic add vapour, and is thereW converted into a white 
stidnr mass, which dissolves in alcohol, leaving only a small quantity of eyamelide. 
The hot saturated solution, on cooling, deposits allophanate of glyceryl in hard crusts, 
composed of small translucent nodules. The crystallisation is often slow, especially 
when much glycerin is present ; hence it is best to wash the crude product with cold 
alcohol before dissolving it in hot alcohoL The nodules, ait<er rectystallisation from 
alcohol and drying at 100°, gave by analysis 83*6 per cent carbon, (*7 hydrogen, and 
16-5 N, the formula requiring 88*7 C, 5*6 H, and 167 N. 

Allophanate of glyceryl has neither taste nor smell, dissolves slowly but abundanthf 
in water, and wiui tolerable fiadlity in boiling alcohoL Heated in the dry state, it 
melts at about 160° C. to a colourless liquid, which solidifies in a gelatinous mass on 
cooling. On raising the temperature, a large quantity of carbonate of ammonium is 
evolv^ and the mass ultimately turns brown and emits an odour of burnt horn. 

It is not decomposed by dilute adds at ordinary temperatures, but strong nitric and 
sulphuric acids decompose it, with evolution of carbonic anhydride. 

When triturated with water and hydrate of barium^ it dissolves with &cilitf ; but 
the dear filtered solution deposits, after a short time, a bulky crystalline predpitato of 
carbonate of barium. The predpitation takes place even when the quantity <xF baryta 
is less than suffident to saturate the aUophanic add present, so that it does not appear 
possible to prepare allophanate of barium in this manner. A certain quantitv of that 
salt appears, however, to be formed, inasmuch as the liquid, after long stanoing, still 
deposits carbonate of barium when heated. If alcohol be added to the liquid containing 
an insuffident quantity of baryta, allophanate of ethyl is produced, probably by a 
catalytic action. AUophanate of glyceryl heated with baiyta-water, yields nothing out 
carbonate of barium, urea, and glycerin. 

In an alcoholic solution of potash^ allophanate of glyceryl cakes together to a stidcy 
mass, then gradually dissolves, the solution after a wmle depositing long needles 
which gradually change to small bulky masses of needles, apparently consisting of 
ethyl-carbonate of pottusium. (B aeyer.) 

Allophanate of Methyl, 0»H«NK)» - C*H»(CH^)NK)«.— Discovered by Bi chard- 
son in 1837 (Ann. Ch. Pharm. zxiii. 128), and oriffinally called ureo-<:arhoyuUe of 
methyl. When cyanic add vapour is passed into metSyl-alcohol, colourless crystals are 
obtained, which must be repeatedlv washed with water, and then dried at 100° C. When 
heated, they partly volatilise undecomposed, and are partly resolved into ammonia, 
methylene gas (?), carbonic anhydride, and cyanuric acid: 

30»H«NK)« - 8NH» + 8CH« + 8C0« + CTPIW. 

Heated with potash, the^ are decomposed in the same manner as the ethyl-compound. 
They dissolve readily in water, wood-spirit and alcohoL especially when heated, 
forming neutral solutions. 

Allophanate of Eugenic acid, C»*ff*NK)* « CH'CCwff'OJNK)*.— Eugenic 
add rapidly absorbs cyamc add vapour, forming a thick msss, whicn dissolves in hot 
alcohol and separates in long shining needles on cooling. At 100° C. it gave 67'0 — 
67-9 per cent C, 6'7—6-9 H. and 11-3 N (calc 67'6 G, 6*6 H and 11-2 N). It contains 
the elements of 2 at cyanic add, and 1 at eugenic add (2CNH0 + C^'H)*), and is 
therefore analogous in composition to the allophanic ethers. 

It is insoluble in water, sparingly soluble in cold alcohol, abundantly in hot alcohol. 



ALLOXAN. 135 

It wThihitB itioDg tondeney to erystaUise, so that eyen amall quantities of the aolution 
yield needlee of proport i onably conaiderttble length. It is very soluble in ether, is 
destitnte of taste and smell, has a silky lustre, and is permanent in the air. 

Strong adlda decompose it. Triturated wiUi water and hydrate of barium, it forms 
a stiff paste, consisting of engenate and allophanate of barium. Alcoholic potash does 
not appeiir to oonTert it into allophanate of potassium. When heated, it is resolyed 
into eugenic and cyanuric adds. (Baey er, Ann. Ch. Fhsrm. odr. 164.) 

See IflOXXBisic 



{Mhxanhydride, Laurent.) C*H«N»0*, or C^B^N'O^. 

Hittoijf. — Discovered in 1817 by Brugnatelli, who designated it Erythric acid: 
first completely inyestigated by Liebig and Wohler, in 1838 (Ann. Ch. Pharm. 
zxri. 256); more recendy by Schlieper (Ann. Ch. Pharm. Ir. 263). 

ForwutUon and Preparation, — Alloxan is one of the numerons products of the oxida- 
tion of uric acid. Its prepantion is a matter of some nicety. Liebig and Wohler 
{toe. eiL\ and Gregory (Phil Mag. 1846), prepare it by the action of nitric acid on 
uric ada : concentrated nitric add specific gravity 1*4 to 1*42), must be employed, and 
Qie temperature must not be allowed to rise above from 80^ to 36° C. The process is 
thus conducted. Prom 1} to 2 parts strong nitric acid are placed in a beaker or por- 
celain basin, sunounded with cold water, and 1 pt. uric add is added in successive 
small portions, with constant stirring, care being taken not to add a fresh portion of 
uric add until the action caused b^ the addition of the former portion has quite sub- 
sided. Carbonic anhydride and mtrogen are evolved with efieryescence, the action 
becoming gradually less violent as the operation proceeds ; and ciystals of alloxan 
gradually separate out. When the decompodtion is complete, the mixture is left over 
night in a cool place, and the crystalline magma is then thrown on a funnel plugged 
with asbestos or coarsely pounded glass, and the last portions of the mother-liquor are 
carefully removed by washing with ice-cold water, till the washings have only a faintiy 
add reaction. Schlieper recommends removing the alloxan as it forms, in order to 
withdraw it from the further action of the nitric acid. The crystals of alloxan are 
dried by standing on filtering-paper or a porous tile, and then purified by solution in 
the smidlest possible quantity of water at from 60^ to 80° C. ; the solution is filtered, 
and cooled tul it crystallises : by evaporating the mother-liquor at a heat not exceed- 
ing 50° C. farther crystals are obtained. The mother-liquor from these crystals, as 
wdl as that originally drained off^ still contains alloxan, which is best separated by 
bcang predonsly converted into alloxantin. For this purpose, Schlieper proceeds as 
follows: — The -mixed mother-liquors are nearly neutralised by carbonate of caldum or 
sodium — if the neutralisation were complete, the alloxan would be converted into 
alloxanic add — and | of the mixture are saturated with sulphuretted hydrogen, 
whereby sulphur and aJloxantin are precipitated, some dialuric acid being also formed 
by the further action of the gas. The remaining | is then added, the alloxan in which 
reconverts the dialuric add formed into alloxantin. The alloxantin, which separates 
out completely in 24 hours, is freed from sulphur by solution in boiling water and crys- 
tallisation. In order to convert it into alloxan, one half of it is boi^ with twice its 
volume of water, nitric add bein£ added drop by drop until the evolution of nitric 
oxide is perceptible, and the whole is heated in a water-bath until effervescence has 
ceased: small portions of the remaining half are then added successively, until a fresh 
addition produces no effeirescence, then a little nitric add, and so on till the nitric 
add is completely decomposed, a little alloxantin remdning in excess. The solution 
is then filtered hot, and 3 or 4 drops of nitric add added to the filtrate, which deposits 
crystals of alloxan on cooling. The total weight of alloxan thus obtained, should be 
about equal to that of uric acid employed. It is not advisable to operate on more than 
70 to 80 grm. nitric add at once. 

Schlieper prefers chlorate of potassium to nitric acid as an oxididng agent. Into a 
basin containing 124 grm. or 4 oz. of uric add, and 240 grm. or 8 oz. of moderately 
strong hydroduoric acid, he adds in succesdve portions, with constant stirring, 31 
grm. or 6 dr. pulverised chlorate. Heat is evolved, which must not be allowed to 
rise above a ccotain limit ; and a solution is obtained, containing only alloxan and 
iir«a (C*H<N*0» -f H»0 + - C*H*NK)* + CH*NK)). If proper care be taken, no 
gas is evolved. The solution is diluted with twice its volume of cold water, and de- 
canted after three hours from any undissolved uric add, which is heated to 50° with 
a littie strong hydrochloric acid, and oxidised by a fresh portion of chlorate. In order 
to separato tne alloxan from the urea, it is converted into alloxantin and reconverted 
into alloxan in the manner above described. 

The alloxan prepared hj the above methods contains 1 or 4 atoms of water of crys- 
ialUsation. Anhydrous dloxan is obtained by heating the monohydrated compoimd 

X 4 



136 ALLOXAN. 

to 150^ — 160^ C. in a stream of dry hydrogen : the tetrahydrated compoimd mwrt be 
first converted into the znonohydrate by very careful heating to 100^. (G-melin.) 

Properties. — Anhydrons alloxan is of a pale reddish colour, which is probably due 
to the action of heat. When aystallised, it contains 1 or 4 atoms of water of crys- 
tallisation. The crystals obtained by evaporating a warm aqueous solution, contain 
1 atom of water : they are oblique rhombic prisma, belonging to the monodinic system, 
having the appearance of rhomboidal octanedra truncated at the extremities ; th^ 
are large, transparent, and colourless, of a glassy lustre, and do not effloresce in the 
air. Liebig and Wohler regarded this compound as anhydrous. Those obtained by 
cooling a warm saturated aqueous solution are transparent, pearly crystals, often an 
inch long, belonfl;ing to the trimetric system : they effloresce rapidly in warm air, 
and when heated to 100^ are converted in the monohydrated compound. According 
to Gregory, there exists a third hydrate containing 2| atoms of water. 

Alloxan is readily soluble in water or alcohol, forming colourless solutions, whence 
it may be precipitated by nitric acid. Its aqueous solution has an astringent taste, 
and colours the skin purple after a time, imparting a peculiar and disagreeable smell. 
It reddens litmus, but does not decompose alkaline-earthy carbonates : neither does it 
attack oxide of lead, even on boiling. 

The following is the percentage composition of the three varieties : 

C*. . . 48 . . 88-8 

H». . . 2 . . 1-41 

N*. . . 28 . . 19-72 

0*. . . 63 . . 4607 

C*H»N«0*. 142 10000 

Calc Gm. 

C*H«N«0* . . 142 . . 88-76 . . 8866 

H»0 . . 18 . . 11-26 . . 11-35 

C*BPN«0* + aq. 160 10000 10000 

Gale. L.a. W. ^ Om. 
C*H«N«0* + H«0 . 160 . 74-77 . 78-6 . 7472 
8HH) . 64 . 26-23 . 26-6 . 26-28 

C*H«N»0* + 4 aq. 2l4 100^00 lOOM} 10000 

Decompoeiiiona, — I. By Heat, When heated, alloxan melts, and is decomposed, 
forming, besides other products, cyanide of ammonium and urea. (Handwb. d. Chim.) 

2. By EUctrolysU. — An aqueous solution of alloxan is decomposed by the voltaic 
current, oxy^n being evolved at the positive pole, and crystals of alloxantin formed 
at the negative pole. 

3. By Nitric acid. — Hot dilate nitric acid converts alloxan into paiabanic acid and 

carbonic anhydride : 

eHW»0* + - C«H«NK)« + C0« 

Purabanic ac. 

Further action of nitric acid converts the parabanio acid into nitrate of urea and car- 
bonic anhvdride. Monohydrated alloxan is scarcely attacked by heating with strong 
nitric acid. (Schlieper.) 

4. By Hydrochloric and Sulphuric acids. — When heated with these acids, alloxan is 
converted into alloxantin, which gradually separates, and the mother-liquor yields on 
'evaporation acid oxalate of ammonium. The decomposition goes through several 
stages : firsts alloxantin, oxalic and oxaluric adds are formed ; then the oxaluric add is 
decomposed into oxalic add and urea ; and the urea is finally resolved into carbonic an- 
hydride and ammonia, which last combines with the oxalic add. (Liebig and Wohler.) 

6. An aqueous solution of alloxan is decomposed by boiling into carbonic anhy^bide, 
parabanic add, and alloxantin, which separating on cooling : 

3C*H*NH)* = C0« + C«H*N*0« + C^WO» 

^ t ~' AllozoQtin. 
Furabanle 
acid. 

6. By reducing agents^ alloxan is converted into alloxantin. This deoompoeition is 
effected by protochloride of tin, sulphuretted hydrogen, or zinc and hydrochloric add 
(nascent hydrogen) : 

20<H«NK)« + H« = C^*N*0' + HH) 

the further action of the two latter reagents converts the alloxantin into dialuric add: 

O^WO' + H« + H«0 «- 2C*H*N^* 

^ , ' 

Dialarlc add. 



ALLOXANIC ACID. 137 

Tbt ame daeompMxtion ifl efieeted when an aqneons solntion of allozan ia boiled -with 
eseen of solphnrons acid. When, however, aqueons alloxan ia saturated with anl- 
pbiroiis anhjdride, and the aolntion eyaporated at a gentle heat^ it yields on cooling 
hige efflorceeent tables of a conjugated acid, which, by analysis of its potassinm-salt^ 
wpptan to contain the elements of 1 atom alloxan and 1 atom snlphnrons anhydride 
(Gregory^ When a cold satorated solntion of aqneons alloxan is treated with sul- 
vhnooB aetd in excess, ammonia added, and the whdLe boiled, thionnrate of ammonium 
isibiiiied: 

(yB?S*0* + NH« + SO»H» = C*H»N»SO« + HH) 

Tbionurlc 
acid. 

7. BjfJML aiialis and alkaline eariks, alloxan is converted into alloxanic acid : 

C*H*N»0* + H*0 = C*H*N«0» 

Alloxanic 
aekL 

Aqneoos alloxan gives with baryta- or lime-water a eradual white precipitate of allox- 
snate of barium or calcium : a similar action is produced by a mixture of chloride of 
faariam, or nitrate of silver, with ammonia. If the alkali be in excess, the precipitated 
aUoExuste contains mesoxalate, and the filtrate contains urea (Schlieper). By boil- 
ing with aqueous alkaliis alloxan is decomposed into mesoxaJic add and urea : 

C*H«N«0* + 2H«0 » C«H«0» + CH*N*0 

Metoxallc Urea, 

add. 

8w BvAmmtmia. — A solution of alloxan in aqueous ammonia turns yellow when 
goitly ounled, and on cooling forms a yellow transparent jelly of mycomelate of am- 
nonimn: the liquid retains in solution alloxanate and mesoxalate of ammonium and 
iii«a(Liebig): 

C*WNH>* + 2NH« - C«H<N«0« + 2H«0 

Myocmelic 
add. 

9. WiUhferrouB salts, aqueous alloxan gives a deep blue colour, but no precipitate 
vakm an alkali be sidded. 

10. When aqueous alloxan is heat«d with peroxide of lead, carbonic anhydride is 
etotrad, carbonate of lead precipitated, and urea is contained in the solution : 

C^HWO* + 4PbO + H«0 « CH*NK) + 2C0^Pb« + C0« 

11. When aqueous alloxan is gradually added to a boiling solution of neutral acetate 
of lead, mesGocalate of lead is precipitated, and urea remains in solution. When the 
lead-ecdutioa is added to the aUoxan-solution, alloxantin and oxalic add are formed. 

F. T. C. 

AUbOaEAVZO ACSD. OH<N<0^ » alloxan + H*0. 

iKs^.^Disooveied bvLiebig and Wo hler, in 1838 (Ann. Ch. Pharm. xxvi. 292), 
farther examined by Schlieper. (Ann. Gh. Pharm. Iv. 263, Ivi. 1.) 

Fomation and briparaHon, — ^oxanio add is formed when alloxan is brought 
into oontaet with aqueous fixed alkalis (see Axloxan), alkaline carbonates, or add 
eaxhonate of calcium (Stadeler). It is prepared by decomposing alloxanate of barium 
by solphmic addL The salt is suspended in a little water, and a slight excess of dilute 
sulphuric add added, with constant a^tation : 6 pts. salt require 1^ pt. strong sul- 
phuric acid, duly diluted. After digestion for some time at a gentle neat, the excess 
of solpfanrie add is removed by pure carbonate of lead, the excess of lead by sul- 
phuretted hydrogen, and the excess of gas by heat : the solution is then filtered, and 
er^nrated to a syrupy either over sulphuric add in vacuo, or at a temperature not 
exceeding 4(P C. 

^vperties, — Thus prepared, alloxanic add forms hard white needles, arranged in 
ndiated groups, or in warty masses : if it has been heated above 40*^ C. it crystallises 
vith difficulty, or not at all The crystals are permanent in the air : have a sour taste, 
Int a sweetish aftertaste ; are readily soluble in water, less readily, viz. in 5 to 6 pts. 
aloobd, still less in ether. The solution is add to litmus, readily decomposes car- 
bonates and acetates, and dissolves zinc, cadmium, &c., with evolution of hydrogen. 
Its composition is : 

C* . . . 48 . . . 800 

H* . . . 4 . . . 2-6 

N« . . . 28 . . . 17-6 

O* . . . 80 . . . gO-0 

C«M<NH> 160 100=0 ^ 



188 ALLOXANIC ACID— ALLOXANTIN. 

It is ft dibasio add, forming acid as well as nonnal salts : the formula of normal 
alloxanates is 0*WWNH)*, of acid aUozanates, CH'MKK)*. It also appears to form 
basic salts with some heavy metals. Alloxanates are mostly obtained by the action 
of aqueous alloxanic acid on metallic carbonates. The alkaline alloxanates are soluble 
in water: the normal salts of other metals are generally more or less insoluble, the 
acid salts readily soluble. They part with their water of crystallisation at temperatoiea 
Taxying firom 100^ C. to 160^ ; and require a stronger heat for their decomposition. 

The alloxanates have been investigated principally by Schlieper (^loc. cit). The 
only one which requires special mention is the normal bariufn^salt, which is employed 
for the preparation of alloxanic acid. It is obtained by mixing 2 vols, of a cold satu- 
rated smution of alloxan with 3 vols, of a cold saturated solution of chloride of barium, 
heating the mixture to 60^ or 70°, and adding gradually potash-solution, with constant 
agitation. Each addition of ^tash produces a white curdy precipitate, which soon 
redissolves: at last the precipitate remains permanent, and the liquid suddenly 
becomes filled with alloxanate of barium, which falls down as a heavy crystalline 
powder, and may be freed from chloride of potassium by washing with cold water. 
If too much potash has been added, a persistent curdy precipitate forms, consisting of 
basic alloxanate and mesoxalate of barium ; it must be redissolved by the addition of 
a litUe alloxan-solution. A less abundant^ but more certainly pure product is obtained 
by adding baryta-water to aqueous alloxanic acid. 

Deeamposiiions, 1. By Heat. — When heated, the acid melts with intumescence, 
becomes carbonised, and evolves vapours of cyanic add. Alkaline alloxanates are 
decomposed by heat into a mixture of carbonate and (^anide. An aqueous solution 
of alloxanic add is decomposed by boiling, carbonic anhydride being abundantly 
evolved, and two new bodies formed, one of which, Uucoturio €Kid, being insoluble in 
water, separates as a white powder when the solution, after evaporation to a syrup, is 
diluted with water; while tne other, difiuafif remains in solution, but may be preci- 
pitated by alcohoL The latter is formed in far the larger quantity. The composition 
of these bodies is not accurately established: Schlieper assigns to the former the for> 
mula 0«H»N«0«, to the latter, C»H*N*0«* or C^*N«0». Schlieper states that a third 
substance is also formed, soluble in water and alcohol, with uie formula C*H^NK)*. 
The alcoholic solution of alloxanic add is not decomposed by boiling. Allrtrr^Ln^f.^ m^ 
decomposed by boiling with water into mesoxalate and urea : 

C*HWO« + ffO « C»H»0» + CHWO 

2. When heated with nitric add, alloxanic add is decomposed into parabanic acid 
and carbonic anhydride : 

OH^W + O = C«H«N«0« + C0« + HH). 

3. AUoxanate of potassium gives a dark blue predpitate with ferrous-salts. (See 
Alloxan.) 

Alloxanic add is not decomposed by sulphuretted hydrogen, or by boiling with 
bichromate of potassium or bichloride of platmum. 

According to Omelin, the compound described by Vauquelin (M^m. du. Has. tiL 
26Z) by the names aeide purpurique blano or ur^pie suraxigenit (axuric add) is to be 
regarded as impure alloxanic add. — F. T. C. 



( Uroxin.) C»H*N«0» + 3HH) [or C*S*N*0^\+ ^SO]. 

History, — Probably firat noticed by Front; first described by Liebiff and Wohler 
in 1838 ; .farther examined by Fritzsche, who called it uroxin (J, pr. Chem. xiv. 237). 

Formation and preparation. — Alloxantin is formed in vanous reactions. 1. By 
the action of warm dilute nitric acid on uric acid.— 2. By the action of electrolysis, or 
of reducing agents on alloxan^ or by heatine it with water or dilute sulphuric add 
(see Aixoxan) : also by dissolving alloxan in dialuric acid. — 3. By heating dialuramide 
(uramil) with dilute sulphuric or hydrochloric acid, or thionurate of ammonium with 
a large quantity of dilute sulphuric acid. — 4. By the action of the air on dialuric acid. 
— 6. In the decomposition of caffeine by chlorine. (Rochleder.) 

The following are the most usual processes for the preparation of alloTantin. 
1. Dry uric add is added gradually to warm, very dilute, nitric acid, as long as it is 
dissolved, and the solution evaporated till it has an onion-red colour ; or dilute nitric 
add is added to 1 pt. uric acid in 32 pts. water, till all is dissolved, and the solution 
evaporated to two-thirds ; the crystals obtained in either case are purified by re-crys- 
tallisation firom hot water. — 2. Sulphuretted hydrogen is passed through an aqueous 
solution of alloxan, till a crystalline magma forms ; this is dissolved by heat, the pre- 
cipitated sulphur filtered off hot, and the filtrate crystallised. — 3. A solution of alloxan 
in dilute sulphuric acid is heated for a few minutes, when it becomes turbid, and de- 
posits crystals of alloxantin on cooling. — i. Dialurato of ammonium is evaporated at 



ALLOXANTIN. 



139 



t gentlfl heat with a luge exoees of dilate sulphuric add ; when dialiiric acid aystal- 
Hms oat, which im oooTerted into allorantin by the action of the air, without changing 
its ajstilline form. (Qregorj.) 

i¥op<r<ft».— The alloKantin obtained bj the aboye methods, contains 3 atoms of 
vater of ayBtalliBation, which it does not lose till heated to above 160*^0. Of the 
properties of anhjdrous alloTantin nothing is known. The ayBtals aro small, trabs- 
puent^ colonrleaB, or yellowish, oblique rhombic prisms, hard, but fery finable. In 
tboM prepared by methods 1, % and 8, the ang^ of the obtose lateral edge is 105^ : 
m the dunorphons crystals obtained from dialurate of ammonium, it is 121^. They 
redden litmus, but do not exhibit add properties in other respects. They are yeiy 
elightly soluble in cold water, more abundantly, but still slowly, in boiling water, 
frina idiieh solution the aHoxantin separates almost completely on cooling. The fol- 
lowing is iba percentage composition of anhydrous and hydratod aHoxantin. 



0» 



96 

4 

56 

112 



Cole. 

S5-8 

1-5 

2M 

41-8 



Cnntatt. 



96 

40 

56 

160 



Caie. 
29-81 

811 
17*89 
48-67 



L.aiid W. 

30'62 

816 

17-66 

48-67 



FritsiclM. 

8006 

8-04 

17*62 

49-38 



(ya^Hy 268 lOO^ CH*N«0'+8aq.822 10000 10000 10000 

JkeompoMtions, — 1. 3if heat, alloxantin yields a peculiar aystalline product. 

2. By oxiduing agents, alloxantin is coUTerted into alloxan. This change takes 
fiiee bIovIt, when its aqueons solution is exposed to the air, much more rapidly when 
It 10 bested with chlorine- water ; or when it is diffused in boiling water and a small 
qvtntitjr of nitric acid added. Selenious add also conyerts the hot solution of allox- 
intiB into alloxan, with separation of selenium. 

5. By reducing agents, e. g» sulphuretted hydrogen, a hot solution of alloxantm is 
eonreited into maluric add : 

CraWO' + H«S + H»0 " 2C*H*N»0* + S. 

Dialuric add, 

4. 'When boiled with excess of hydrochloric add, it is partly decomposed, and de- 
podli an cooling; a white powder of alliturie add, CH*!^* (Schlieper). At the 
■ante time, aTloran and parabanic add are formed, together with an add which 
Sdilieper esBs diUtarie aad, which he has not succeeded in isolating. 

6. With batyta-^ufoter, allnxnnfin giyes a yioLet predpitate, which, on boiling, turns 
white, and then disappears ; the solution contains alloxanate and dialurate of barium, 

Cra*N*0» + SBaHO = C*BXBa*NK)» + C*H«BaN*0* + H«0. 

Alloxanate Dlalarate Ba. 

Ba. 

6. By ammoma, alloxantin is oonyerted into purpurate of ammonium (murexide). 

C»H*NH>' + 2NH» = C«H»N«0« + H*0 

Murexide. 

This diange takes place dther in the wet or the dry way. In the dry way it occurs 
▼hen alloxantin is neated to 100^ G. in an atmosphere of dry ammonia (Gmelin) : or 
▼hen it is exposed at the ordinary temperature to air containing ammonia. ^ In the 
vet way, an aqneous solution of alloxantin is coloured purple-red by ammonia : the 
eoloiir oisappeaas on farther heating, or when left for some time in the cold. When 
nitric add u gradually added to Sie hot alloxantin-solution, so as to form alloxan, 
the addition of ammonia produces a deeper purple colour as the quantity of nitric 
acid, and oonaeqnently of RllATim, increases ; but the coloration ceases when the 
allmantin is entirely conyinted into alloxan. When a solution of alloxantin in tho- 
roog^ boiled water is mixed with ammonia, and boiled till the purple colour has 
dia^fwared, crystals of dialuramide (uramil) are deposited: the yellow mother-liquor 
beoomes purple by exposure to the air, deposits crystals of purpurate of ammonium, 
and finally ooagulates into a jelly of mycomelate of ammonium : 

0»H«N^O' + 4NH« - C*H»N«0« + C^HWO* + 2HH). 

Uramil. Hjoomel. 

ainm. 

The ibrmation of murexide depends upon the oxidation by the air of some of the 
nraaul whidi is dissolyed in the ammoma. When a solution of alloxantin in aqueous 
ammonia is repeatedly eyaporated at a gentle heat in an open yessel, the residue being 
eadi time dissolyed in iiniinnt^ ifi^ pnre oxalurate of ammonium is finally obtained : if the 
air be ezdnded, this substance does not form. 
7. Aqueous solutions of alloxantin and sal-ammoniac, both freed from air by boilings 



140 ALLOXANTIN— ALLYL. 

form a pinple-iwd mixture, which soon beoomee paler, and deposits oolonrlMa or 
reddish scales of nramil: the mother-liqiior oontaina aQo3can and hydrochloric add : 

CB«NW + WHKa - C*H*NK)« + C*H«N*0* + HCL 

Uramfl. 

Acetate or oxalate of ammoniom acts like the chloride. 

8. When aqueous *Tlmr>wfiii ig heated with oxide of silver, csibonic anhydride is 
evolTod, silTer reduced, and oxalnrate of sQver finmed : 

(m*NH)» + 4AgK) + H*0 - 2C»H»AgNK)* + 2C0« + 6Ag. 

Oulante tilTcr. 

From nitrate of silyer, *nnnr««»iii precipitates metallic silTer : the illtnte gi^es a 
white preeu>itate witii bazyta-water. Aqueous alloxantin dissohes mereorie oxide 
with erolntion of gas, probably forming merenrons alloxanate. By peroxide of lead 
allnrriitin is oonverted like alloxan. — 9. Aqneons alloxantin is decomposed by long 
keeping, eren oat of contact with air, and is conTerted into aUoxanic acid. (Gregory.) 

Tetrametkyl-Alloxantin, 0"H»^K)« - C\CH»)«NW + H«0.— This composi- 
tion is assigned by Gerhardt to a product of the action of chlorine on caffeine, disco- 
Tered by Bochleder (Ann. Ch.Phann. IxxL 1), also aMioSiAmaUeacid{^, v.) — F.T.C. 

(SeeMsTALS.) 
■VAUJMTMi (See TBZFsnim.) 

Aarfl, ProwienyL G*H*.— Berth elot and Be Lnea in 1864 (Ann. 
Gh. Fhys. [31 xliii. 267), by acting on glycerin with iodine and phosphonis, obtained 
the componnd 0^*1, which they regarded as todotrityUne, that is to say, tritylene, O^*, 
baring 1 at. H replaced hj^ iodine, but iriiich is now rather regarded as the iodide 
€il the radicle allyL Zinin, in 1866 (Ann. Ch. Fharm. xcv. 128) by acting on this 
iodide with snlpbocyanide of potassiiiiii, obtained a volatile oil, the snlphocyanide of 
ally], CH'.CyS, identical wiui Tolatile oil of mnstud, and afterwards (Ann. Ch. 
Pharm. xcri. 861) prepared the benzoate, acetate, &c. of the same series. Hofmann 
andCahonrs, in 1866 (Compt rend, xlu.217; more folly, FhiL Trans. 1867, 1; 
Ann. Ch. Fharm. ciL 286 ; Chem. Soc. Qo. J. x. 316), diBoorered allylic alcohol and 
prepared a great number of its derivatiYes. Lastly, Berthelot and Be Loca in the 
same year isolated the radical allyl, and prepared the dibromide and diniodide. The 
existeoce of this radicle in the oils of mustard and garlic was first demonstrated 
by Wert h eim. (Ann. Ch. Pharm. IL 289 ; ly. 297.) 

Allyl is the third term in the series of homologous radicles OH"-*, rinyl CH* 
being the second; it is the only ra dide o f the series that has yet been isolated. 

Allyl, in the free state, CH'* «> CH'.CH*, is obtained by decomposing the iodide, 
CH*1, with sodium at a gentle heat, and aftOTwards <i^«ta'1Hng the liquid product. It 
is a yeiy yolatile liquid having a peculiar pungent, ethereal ojoor, somewhat like that 
of horse-radish. Specific gravity 0*684 at 14. Boils at 69^ C. Vapour-density by ex- 
periment 2'92 , by calculation from the formula CH^* (2 vol.) 2*89. Allyl is but 
little attacked by strong sulphuric acid. Fuming nitric add changes it into a neutral 
liquid nitro-compound, soluble in ether and decomposed by heat. Chlorine acts 
stroiijgly upon it| hydrochloric add being evolved and a liquid compound formed 
heavier than water. Bromine and iodine unite directly wiu it, forming the com- 
pounds CH»Br« and CH»I*. (Berthelot and De Luca.) 

AS&T&-A&OOHOXN Hydrate of AUyl, CH*0 >- ^^|o.— Prepared by the 

action of ammonia on oxalate of allyl, oxamide being formed at the same time : 

( coy(CH')«o « + 2NH» - 2(CH».H.o ) + K«.(coy.m 

Oxalate of allyl. AUjl^oohoL Oxamide. 

Dr^ gaseous ammonia is passed into oxalate of allyl till the whole is converted into a 
sohd mass of oxamide saturated with allyl-slcohoL The latter is then distilled off in 
a bath of diloride of caldum, and rectified over anhydrous sulphate of copper. The 
alcohol appears also to be produced by Hi'arini'Tig benzoate or acetate of allyl with 
potash (Z in an. Aim. Ch. Pharm. xcri. 362). It is a colourless liquid, baring a 
pun^nt but not unpleasant odour, and a spirituous burning taste. It mixes in all pro- 
portions with water, common alcohol, and ether. It bums with a brighter fiame than 
common alcohol Boilinc-point 103^ C* It gave by analysis, 62*08 per cent C and 
10-43 H, the formula CH*0 requiring 62*07 C, 10*34 H, and 27*6 9 0. 

• One lample ofthe alcohol Tery careftillr prepared, was foand to boll between 90° and 100° C. TWa, 
bowerer, mar hare ariira from decompotitlon ; at all OTentt, the number 103O agrees witb the diflbr. 
ences generallj obterred In analogous ethyl and allyl*coropoands. (Hofmann.) 



ALLYL, BBOMIDES OF. 141 

iUljrl-Aleoihol 18 stran^y attraeti'd by phosphoric anhydride, a ooloniless gas, pro- 
bably C'H\ being given ofi^ vhich bums with a very bright flame. It is yiolently 
axi&ed by a mixture of acid ehromate of potassium and sulphuric acid, "with forma- 
tkm of allylic aldehyde (acrolein), CH^O, and acrylic acid, CH^O*. The same trans- 
foimation is effected, though more slowly, by platinum black. Potassium (or sodium) 
deeompoBes allyl-aloohol, with evolution of hydrogen and formation of a gelatinous 
mass of aUylate of potaasium, C"H^KO. Strong sulphuric acid acts on it in the same 
mamier aa on oommon alcohol, oonyertiiig it into allyl-sulphuric acid, C^^H.80^ 
With potash and disnlphide of carbon, it yields the potassiumnsalt of allyl-zanthic 

AXSn^ MBMKOmWB OV. The rnonohromide, C*H*Br, which is isomeric^ 
orperiiapB identical with bromotritylene, is obtained by the action of bromide of phos- 
phona on aHyl-alcohol (Hofmann and Cahours); or by distilling dibromide of 
txHykoe, CH'Br' (or hydrobromate of bromotritylene, CH'Br.HBrT with alcoholic 
potash (Cahours). Its specific gravity is 1*47, and boiling-point 62^ C. (Cahours.) 

The hydrobromate of this compound, or dibromide of tritylene, is produced when 
liomine is gradually passed into an excess of tritylene gas ; but when tritylene iiB 
paeaod into excess of bromine, a number of compounds are formed which may be re- 
gaidsd aa compounds of hydrobromic acid with bromide of allyl having its hydrogen 
mofe or leas le^aoed by bromine. (See Tstttlenb.) 

Dibromide of Ally l^^ CH'Br*. — Allvl unites directly with bromine, the com- 
bination being attended with evolution of heat If the action be stopped just as the 
liquid begins to show colour from excess of bromine, and to give off hycut>bromic acid, 
and if the liquid be then treated with potash, dibromide of allyl is obtained as a 
oystalline body, vei^ soluble in ether. It melts at 37^ C. and when once Aised, 
aomeiimes remains liquid at drdinazy temperatures. It may be volatilised without 
deeompoaition (Berthelot and De Luca). The allyl in mis compoimd takes the 
place of 2 at. H. 

Tribromide of Allyl, C^WBi*. — Obtained by gradually adding bromine to 
iodide of aDyl in a vessel surrounded by a freezing mixture. The mixture is left to 
itself till Ute next day ; freed from oystaUised iodine by washing first with alkaline and 
affcerwBids with pure water ; then dned and distilled ; the liquid which passes over is 
a^un washed and distilled, collecting apart that which goes over fnm 210° to 220 °C. ; 
the pmple liquid then obtained is cooled to 0° C. whereupon it solidifies in a ciys- 
talline maas ; the mother-liquor is drained off; and the product is fused and again 
rectified. By this method, tribromide of allyl is obtained as a colourless neutral 
liquid, of not unpleasant odour, specific gravity 2*436 at 23° C, boiling at 217° 
or 218°, and solidifying below 10°. By uow solidification, it yields shining prisms, 
which melt at 16°. (Wurtz, Ann. Ch. Fhys. [3] Ix. 84.) 

Alcoholic potash converts it into an etheroal suhBtance boiling at 135° C. Heated to 
100° i n a s ealed tube with alcoholic ammonia, it is converted into DihromaUylamine, 
N.H.(C'H3r)* (31 Simpson, FhiL Mag. [4] xvi. 257). The decomposition appears 
Id ooosist of two .stages ; in the first, the compound Cu^Br", is converted into CH^Bz*, 
and in the aeoon^ this latter is converted into dibromallylamine : 

C«H«Br" 4- NH« - C^<Br» + NH^r. 

}C^<Br 
C^«Br -H 2NH^r. 
H 

Diaeolyed in glacial acetic acid, and heated with acetate of silver to 120° — 125° C. 
for a week, it yulds bromide of sUver and triacetin (p. 25.) 

The ladide C^H* in this compound is triatomic^ roplacing 3 at hydrogen, as seen in 
the reaction just mentioned ; in other words the compoimd is formed on uie type H'.H'. 
Wmts has obtained two compounds (or perhaps only one) isomeric with it, by the ac- 
tion of bromine on bromotritylene, C^*J^. and on the isomeric body bromide of allyl. 
Theae oomponnda are perhaps formed on the type H^H', their rational formula being 
CH^Br^i*. The^ both have a s|>ecific gravity of 2*392 at 23° C, and boil at about 
195°; but they differ somewhat in odour and in their action on silver-salts, the 
former being more energetic in both respects than the latter (Wurtz). The action 
of bromide of bromallyl on ammonia is totally different from that of tribromide of 
ally], giving rise, not to dibromallylamine, but to the compound C'H'Br'.CH^Br'. 
(Simpson.) 



142 ALLYL-COMPOUNDS. 



Ckiorotritylene, CH^Cl, ii obtained like the bn>r 
mide, by the action of chloride of phoephoruB on allvl-alcohol, or by treating chloride 
of tritylene, C"H«.C1* (hydrochlorate of allyl-chlonde, C»H»CLHC1) with alcoholic 
potash. The last mentioned oomponnd treated with excess of chlorine yields sabsti- 
tution-prodncts similar to those obtained with the bromide. (See TbityIsnil) 



., I or, C»H« = (?H*.H.— Tritylene op propylene, the third 

term in the series of hydrocarbons O'Hh, is perhaps the hydride of allyl. 

AJXWlat ZOBZBBfl OV« The monoiodide (iodotritylene) CH% is obtained 
by f^ i V-illing glycerin at a gentle heat with diniodide of phosphoros ; 

2C«HW + 2PP = 2(?H»I + I«0« + 8HK) + 2L 

A quantity of tritylene-gas is giren of^ due to a secondair action, and a mixtare of 
oxygen-acids of phosphoras with iodine and nndecomposed glycerin remains in the 
retort Tri-iodiae of phosphorus may also be used, but the action is less regular. 
The distillate is purified bv rectification, the portion which passes orer at 100^ C. 
being collected apart (Berthelot and De Luca). Iodide of allylis idso produced by 
the action of iodme and phosphorus on allyl-alcohol. (Hofmann and Oahoura.) 

When first prepared, it is colourless, and has an ethereal alliaceous odour; but fay 
the action of air and light, it becomes coloured and then gives off irritating TsponixB 
Specific graTitv 1*789 at 160^ C. Boiling-j^int 101<'. It is insoluble in water, bot 
dissolves in alcohol and ether. By the action of zinc or mercuzy, and hydsocUozie 
or dilute sulphuric acid, it is converted into tritylene (hydride of dlyl) : 

C^»I + 4Hg + HCa « CH* + HgK31 + Hg^ 
and C«H»I + 2Zn + HCl = C«H« + ZnCl + ZS. 

Iodide of allyl is decomposed by silver-salts, iodide of silver being formed, and tlie 
acid radicle being transfened to the aJlyl.^ 

Diniodide of Allyl, C*H*P. — Obtained by dissolving 6 or 7 pts. of iodine in 
1 pt of allyl at a gentle heat. The mixture, which is liquid at first, soudifies after a few 
minutes ; and by triturating the mass with aqueous potash, then digesting in boiUng 
ether, and evaporating the ethereal solution, ike diniodide of allyl is obtamed in the 
crystalline form. It is decomposed by distillation, yielding iodine and a neatrai 
liquid. It is scarcely attacked by aqueous potash ; but alcoholic potash decomposes 
it, producing a liquid which smeDs like idlyl. It is not acted upon by mercury and 
hydrochloric acid. (Berthelot and De Luca.) 

Iodide of Mereurallyl, C*H*Hg'I, is obtained by agitating iodide of allyl wilJi 
metallic mercury. On oystallising the resulting yellow mass from a boiling mixture 
of alcohol and ether, nacreous scales are formed, which turn vellow when exposed to 
lights especially if moist. Th^ dissolve but sparingly in cold alcohol, and are nearly 
insoluble in boiling alcohoL Heated to 100^ G. they sublime in rhombic plates ; at 
135^ they melt, and solidify in a oystaUine mass on cooling. When quiddy heated, 
they decompose, yielding a yellow sublimate and a carbonaceous residue. The alco- 
hohc solution treated with oxide of silver, yields a strongly alkaline liquid, which 
when evaporated leaves a syrupy mass, probably consisting of hydrate of mercurallyl. 
(Zinin.) 

ASXWla, oacZBa OV> Allylic ether, (0"H*)"0, is produced by the action of iodide 
of aUyl on aJlylate of potassium : 

(?H»KO + C»H»I - KI + (C«H*)»0 ; 

also by the action of oxide of silver or oxide of mercuxy on iodide of aUyl : 

2C«H»I + Ag«0 « 2AgI + (C»H»)«0. 

A body having the same composition was obtained byWertheim (Ann. Ch. Phann. 
IL 309 ; Iv. 297), by acting on oil of garlic, (O'H')'S, with nitrate of silver, and dis- 
tilling the aystallme product thereby produced; also by heating oil of mustard 
(sulphocyanide of allyl), with fixed alkalis, e, g, with soda-hme. 

Oxide of allyl is a colourless liquid, lighter than water, and insoluble in water. 
It boils at 82<^ C. (Hofmann and Cahours) ; between 85® and 87® 0. (Berthe- 
lot and De Luca). It forms with sulphuric acid a conjugated acid yielding a 
soluble barium-salt. Nitric acid conyerts it into a nitro-compound heavier than 
water. With iodide of phosphorus, it yields iodide of allyl. Heated with butyric 
acid it is decomposed, with formation of butyrate of allvL (B. and L.) 

Ethyl-allyl-ether, C»HW0=C«H».C«H».0, is obtained by the action of iodide of 
ethyl on allylate of potassium, or of iodide of allyl on ethylate of potassium. It is a 
colourless aromatic, very volatile liquid, boiling at about 84® C. Similar compounds 



ALLYL, SULPHIDE OF. 148 

ue pmdneed hy tveaftiiig iodide of allyl with methylato, Amylate, and phenylate cyf 
potuinim (Hofmann and Cahonrs). Amyl-^yl^tker boils at about 120® C. 
(Berthollet and De Lnca.) 

Otide ofAllyl and Glyceryl, or Triallylin, C'*H»0» « [^C| 0«.— Iodide 

of aliyl digtillwi with potash and glyeerin yields this oompomid in the fonn of a liquid, 
lxH]iiig at 232^ C, soluble in ether, and haying a disagreeable odonr. (Bert he lot 
and De Luc a): 

(C"H»r.H».0» + C«H»I - 8HI + (Cra»r.C»H».0«. 

The fonnnla is tiiat of a triple molecule of water HK)*, in which 3 at H are replaced 
by the triatomic radide glyceryl, and the other three by 3 at. of the monatomic 
ndide aDyL 



Dr«4MLXiT8 OV. Acetate, oxalate, snlphate, &c. (See the 
■errenl acidsw) 

MXMiWTtH amunanm OV. Oa of garlic, GV«S-(C*H*)<S Tor C<^i9].»Thi8 
eofflpoQnd is produced by dJKtilling iodide of aUyl with protosnlphide of potassiiim : 

2C^»I + K«S - 2KI + (C^»)«8, 

and is oontained in the essential oils produced by distilling with watPT the leaves 
and seeds of Tarious plants of the liliaceous and cruciferous orders. It forms the 
principal constitnent of the oil obtained from the bulbs of garlic (Allium saiivum\ 
ftom which it was first obtained in the pure state by Wertheim in 1844 ; and it 
exists in smaller quantity in oil of onions (Allium eepa). It occurs also, together with 
10 per eent. of ott of mustard (sulphocyanide of aUyl), in the herb and seeds of 
Tuaapi arvense, passing oyer when these matters are bruised with water and dis- 
tilled. The leaves of AUiaria officiiudi» distilled with water yield oil of garlic ; the 
seeds yield oil of mustard (Wertheim). The bruised seed distilled after maceration 
in water, yields a mixture of 10 per cent oil of garlic, and 90 oil of mustard ; but the 
seed produced in sunny places yields onl^ the latter. The herb and seeds of ThUupi 
ammse yield a mixture of 90 per cent oil of ^lic, and 10 oil of mustard. The herb 
and seeds of ^eri$ amara likewise yield a mixture of the two oils ; and yeiy small 
quantities of the same mixture are obtained from the seeds of Capsella Bursa Pas* 
toris^ R^^hanus Bi^kamstrum, and Sisymbrium Nasturtium. (PI ess, Ann. Ch. 
Phaim. iTiii 36.) 

To obtain the whole of the mixed oils, the several parts of the plants, especially 
the seeds, must be macerated in water some time before distillation. For, in the 
seeds of 7%laapi aroense, for example, the oils do not exist ready formed ; the seeds, 
in &ct, emit no odour when bruised, and if before distillation with water, they are 
heated to 100^ C. or treated with alcohol, no oil passes over ; and if tiie seed be ex- 
hausted with alcohol, and the filtrate evaporated, there remains a czystalline residue 
SiixBd with mucus, which, when triturated with water and with the seed of Sinapis 
crwfMU, yidds, not oil of garlic, but oil of mustard. (Fless» Ann. Ch. Pluunn, 
IriiLSe.) 

Preparation, a. From Iodide of AUyl. — The iodide is cautiously dropped into a 
eoDoentrated alcoholic solution of sulphide of potassium, the liquid then becoming 
yery hot, and an abundant crystalline deposit of iodide of potaasium being forme£ 
As soon as the action ceases, the liquid is mixed with a slight excess of s^phide of 
potaasinm; water is then added, and the oil which rises to tiie surface is rectified. 

6. From Garlic. — ^The crude oil is obtained by distilling bruised garlic-bulbs with 
water in a laige still. The oil passes over with the first portions of water, the pro- 
duct amounting to 3 or 4 oz. from 100 pounds of the bulbs. The milky wi^er which 
passes over at the same time, contains a large quantity of oil in solution, and serves 
tberefine for cohobation. The crude oil is heavier than water, of dark brownish- 
yellow colour, and has a most intense odour of garlic. It decomposes at 140^ C. ; 
that is to say, somewhat below its boiUng-point, which is 150^, becoming suddenly 
h^at^t assuming a darker colour, and giving off intolerably stinking vapours, 
without yielding a trace of garlic oil; the residue is a black-brown glutinous mass. 
(Wertheim.) 

Preparation of the rectified oil. — ^The crude oil is distilled in a salt-bath (in the 
water-bath the distillation is slower) as long as anything passes o^&t. One-third of 
the crade oil remains behind as a thick dark-brown residue. The rectified oil is 
lighter than water, and of a pale yellow colour, or after two distillations, colourless, 
and smells like the crude oil, though less offensive. Does not evolve a trace of 
of ammonia when treated with hydrate of potash. It covers potassium with a liver- 
cokmred film of sulphide of potassium, depositing an organic substance, and giving 
off a small quantity of a gas which burns with a pale blue fiame. With fuming nitrie 



144 ALLYL, SULPHIDE OF. 

acid, oil of vitriol, hydrocUoric acid gas, dilute acids and alkalis, ooiroaiYe aablimate, 
nitrate of silyer, bichloride of platinum and nitrate of palladium, it behaves like pure 
sulphide of allyL Even after being several times rectified and dried with chloride of 
calcium, it exhibits a variable composition and a certain amount of oxygen, and 
must therefore contain, besides sulphide of allyl, an oxygen compound, probably 
oxide of allyl, the presence of which is indeed indicated by the reaction with potassium. 
(Wertheim.) 

Preparation qf^re Oil of Garlic or Sulphide o/AUyl. — ^The rectified oil is again 
rectified several tunes ; dehydrated over chloride of calcium ; decanted ; a few pieces 
of potassium introduced into it; and as soon as the evolution of gas thereby proauoed 
has ceased, the oil is quickly distilled off from the residue. The rectified oil appears 
to contain oxide as well as sulphide of ally], together with excess of sulphur, these 
impurities either pre-existing in the crude oil, or being formed from sulphide of allyl 
by the action of atmospheric oxygen, that portion of the sulphide which takes up the 
oxygen, giving up its sulphur to the rest. If the potassium be not suffered to 
complete its action before the liquid is distilled, it merely removes the excess of 
sulphur, but does not decompose the oxide of aUyl, and a distillate is obtained, con- 
taining from 65*17 to 64*76 per cent C, and 9*22 to 9*15 H. (Wertheim.) 

Properties. — Colourless oil, of great refracting power, and lighter than water. 
Boils at 140^ 0. May be distilled without decomposition. Smelfi like the crude oil 
but less disagreeably. It dissolves sparingly in water, readily in alcohol and ether. 





Calculattom. 


Wertheim. 


6C . 


. 72 . . 6316 . 


. 63-22 


lOH . 


. 10 . . 8-77 . 


8-86 


S . 


. 32 . . 28*07 . 


. 27-23 



(C*H»)»S . 114 . . 10000 . . 99-31 

Decompoeitions, — 1. Sulphide of allvl dissolves with violent action m/uminff nitric 
acid ; the solution when diluted with water, deposits yellowish-white flakes, and ia 
found to contain oxalic and sulphuric acids; according to HI as i wets (J pr. Chenu 
IL 355) oil of garlic treated with nitric acid, yields formic and oxalic adds. — 2. With 
cold oil of vitrioly it forms a purple solution, from which it is separated by water, 
apparently without alteration. — 3. It absorbs hydrochloric acid aas in large quan- 
tities ; the deep indigo-coloured mixture becomes gradually decolorised on exposoxv 
to the air, and imm^ately if gently heated or diluted with water. — 4. From nitrate 
of silver, it throws down a large quantity of sulphide of silver, whilst nitrate of silver 
and allyl remains in solution (Wertheim). It is not altered by dilute acids or 
alkalis, or by potassium. 

CoTnbifMtions, — Sulphide of allyl does not precipitate the aqueous or alcoholic solu- 
tions of acetate of nitrate of lead, or acetate of copper ; neither does it precipitate the 
solution of arsenious or arsenic acid in aqueous sulphide of ammonium. 

With solutions of ffold, mercury, palladium, platinum, and siltfer, it forms precipi- 
tates, consisting of a double sulphide of aUyl and the metal, either alone or associated 
with a double chloride. 

Gold-precipitate,— Svl^]dde of allyl forms with aqueous trichloride of gold, a beauti- 
frd yellow precipitate, which resembles the platinum-precipitate, but soon cakes together 
in resinous masses, and becomes covered with films of gold. 

Mercury-j^recipitate, — Alcoholic solutions of oil of garlic and corrosive sublimate 
form a copious white precipitate, which when left to stand for some time, and espe- 
cially if diluted with water, increases to a still sreater quantity. It is a mixture of 
the compounds a and b, which may be separated by continued boiling with strong 
alcohol, only the compound a being soluble therein. (Wertheim.) 

a. The iJcoholic filtrate, when left to itself or evaporated with water, and after 
washing and dxying, yields a white powder, agreeing in composition with tiie formula 
(C»H*)«S.2Hg«S + 2(C»H»a.2Hga), or 2(C»H*)«S.Hg«S.6HgCl (anal. 10-91 C, 1-61 H, 
63*67 n%, and 16-41 Ci :— <jalc 11-32 C, 1-57 H, 62*87 H§, and 16*70 Q). It blackens 
superficially on exposure to the son ; when heated, it gives off vapours smelling like 
onioiis,and yields a sublimate of calomel and mercury. When immersed in moderatelj 
strong potash-ley, it acquires a light vellow colour from separation of oxide of mercozy ; 
if this oxide be then removed by dilute nitric acid, there remains a white substance, 
probably — (C»H»)«S.2Hg«S. When distilled with sulphocyanide of potassium, it 
yields oil of mustard, together with other products. It is insoluble in water, and dis- 
solves but sparingly in alcohol and ether. (Wertheim.) 

h. The portion of the mercury-precipitate insoluble in hot alcohol contains the same 
constituents, and has the carbon and hydrogen likewise in the ratio of 6 : 5 at., bat is 
much richer in mercury. (Wert h e i m.) 



ALLYL. 14o 

TaSadntmrpttcipitate, — ^When rectified oil of garlic is gradually added to a solution 
of nitrate of palladium, kept in excess, a farown precipitate is formed, which appears 
to contain 2C*H'^.3Pd*S. — Chloride of palladium forms with oil of garHc a yellow 
|inapitat«^ probably consisting of the preceding compound mixed with ehlonde of 
paUaoium. 

Baitnym^preeipUate,— -Ol\. of garlic forms a yellow precipitate with dichloiide of 
piatiniuB. This precipitate is obtained of a finer yellow colour by the use of alcoholic 
lolntions; bat when strong alcohol is used, its formation is gradual, becoming instanta- 
Bcons boverer on addition of water. If the water be added too quickly and in too great 
quantity, the precipitate is yeUowish^brown, resinous, and difiicult to purify ; the addi- 
tioo of water must therefore be stopped as soon as a strong turbidity appears ; in that 
cue, if the oil of garlic is not in excess, a copious flocculent precipitate is sure to be ob- 
tained, resembling chloro-^Iatinate of ammonium. The precipitate is washed on the filter, 
first vith alcohol then with water, and dried at 100*^,0. — ^When heated considerably 
ahore 100°, it changes colour, and leaves sulphide of platinum in so porous a condition 
that it takes fire at a higher temperature, and continues to glow till it is reduced to pure 
platiniun. Faming nitric add decomposes and dissolyes the precipitate completely, 
jonniuig dichloride of platinum and platinic sulphate. When immersea in hydroeulphate 
of ammoniom, it is gradually conyerted into the kermes-brown compound next to be 
dMcribed. Aqueous potash and sulphuretted hydrogen haye no action upon it. The 
precipitate is nearly insoluble in water, and dissolves but sparingly in alcohol and ether. 
It gires by analysis 17*85 per cent 0, 2*87 H, 48'53 Pt, 1829 S, and 13*22 CI, 
▼hnioe Wertheim deduces the somewhat improbable formula, 3(C^'*S.2PtS) + 
2(CT[»CLPta«), which requires 17*77 C, 2*47 H. 48*88 Pt, 17*77 S, and 13*11 d. 

Kemut-brown compound, (0'H*)*S.2PtS, — Formed; together with dissolved sal- 
ammoniac, when the platinum-precipitate just described is left in contact and shaken 
m) irith bydrosulphate of ammonium. The brown compound heated to 100° C. emits an 
aUiaeeons odour, and gives ofif 4*88 per cent, of sulphide of allyl. The darker substance 
containing excess of platinum which remains, continues unaltered till it is heated to 
140^ C. Irat between 150° and 160°, gives off 5*17 per cent, more, therefore in all 9*55 
per cent, of sulphide of allyl, leaving a still darker compound of (CH*)^ with 3PtS. 
The kermes-browB compound is insoluble in water, alcohol, and ether. (Wertheim.) 

8Swr-precipitate^ — ^When a solution of nitrate of silver in aqueous ammonia is 
mixed with excess of sulphide of allyl, one portion of the compound resolves itself 
into oxide of allyl, which rises to the surface as an oil, and nitrate of ammonium ; but 
then is also formed at the b^inning a white or pale yellow precipitate, which perhs^ 
eoDsistfl of (CH*)^ + xAg^. For if it be immediately washed with alcohol, and 
dried between paper, it is resolved by distillation into sulphide of allyl and a residue 
of snlpfaide of silver. But if it remains half an hour immersed in the liquid, it 
asnnnes a continually darker brown colour, and is finally converted into black sulphide 
ofailTer. (Wertheim.) 



AIATA and BTBSOCHEH't VtTLntXBM OV> AUyl-mereaptany C*H"S a 
C*ii*HJS.— ^ftoduced by distilling iodide of allyl with sulphide of hydrogen and 
potaasinm: 

C"H»I + KHS = KI + C^H».H.S. 

It 18 a volatile oily liquid, having an odour like that of oil of garlic, but more ethereal. 
It boils at 90 °C. It is powerfidly attacked by nitric add, assuming a red colour, and 
yielding an acid analogous to ethyl-solphurous acid. It acts with &;reat energy on 
mercuric oxide, forming a compound CH'HgS, which dissolves in boikng alcohol, and 
leparates fix>m the solution in pearly scales resembling mercaptide of mercury. (Hof- 
mann and Cahours.) 

A&&T&. BraVBOCTAVJLTB OF. C^^S «- CNS.C*H>. ~ VolatUe oU of 
Mtuiard. (See Svlfuocyaxig Ethbrs.) 

AI&T&-0VSVBOCAXSAMZC, or BV&PBOBZVAPXC ACZB. C^BTNS* » 
^ 1 H * — ^^ ^^^ ^ °^^ known in the separate state, but its soluble 

salta, viz. those containing the metals of the alkalis and alkaline earths, are obtained 
hy treating oil of mustard with the hydrosulphates of those metals: e, g. 

C*H»NS + KHS « C^«KNS«, 

It may bo regarded either as composed according to the preceding formula, that is to 
ny, as hvdioeulphate of ammonium, NH\H.S, having 1 at^ H in the ammonium-mole- 
eole lepUced by allyl and two more by the diatomic radicle CS, or as a compound of 
iolphocyaoide of aUyl with solphide of hydrogen. The mode of formation leads 
dii^ly to the latter view. (See Sttlfhosxnafio Acid.) 
VouL L 



146 ALLYL. 



A&&T-«V&»BOCASBOVZC9 or AUbTlb^KaVTKZC AOZB. Sulphide 

of AUyl, Carhonyl, and Hydrogen, C«H«S*0 = S^j^^^^,.— Wlien aUyl-alcohol is 

treated with potash and disulphide of carbon, a salt is formed, which crystallises in 
yellow needles like xanthate of potassinm. (H o f m a n n and C a h o u r s.) 

AXiIiTb-BirXiVBinUO ACZB. O'RK'R.^O^.—SidjphaU of AUyl and Hydrogtn. 
(See SiiLFHtTBic Ethebs.) 

(See Carbamide.) 

. C*H'N « N.H».(C»H»), is obtained by the action of ammonia 
on iodide of allyl, or by boiling cyanate of ally! with strong aqueous potash^ 

CNO.C»H» + 2KE0 « CO»K« + N.ff(C>H*). 

If the alkaline distillate be condensed in hydrochloric acid, a saline mass is obtained, 
which when distilled with potash, yields, among other producta, a basic oil having the 
composition of allylamine. The platinum-sfdt, CH'N.HCLPtCl*, separated from 
solution by slow eyaporation forms magnificent crystals. 

DiALLTLAiONB, OH"N w N.H.(C*H*)', is formed, together with other products^ by 
the action of iodide of allyl on allylamine. 

DiBBOMALLTiAMiNB, C^H^Bi^N = N.H.(C«H*Br)*.— Produccd by the action of am- 
monia on tribromide of allyl (p. 141). 

2C«H»Br" + 6NH» = C«H*Bi«N + 4NH*Br. 

1 ToL tribromide of allyl is mixed with about 6 yoL of a solution of ammonia in weak 
alcohol, and heated to 100^ C. in sealed tubes for 10 or 12 hours ; the liquid is then 
filtered from the separated bromide of ammonium, and the filtrate mixed with a large 
quantity of water, whereupon it becomes turbid, and deposits dibromallylamine in the 
rorm of a heavy oil, wliich may be purified by dissolving it in hydrochloric acid, ersr 
porating to dryness at 100° C, redissolving in water, filtering to separate a small 
quanti^ of oil, again evaporating, and treating the residue with ether, in which the 
nydrochlorate is nearly insoluble. From the salt thus purified, the base is separated 
by distillation with potash. It is alkaline to test-paper, and forms a cloud with 
hydrochloric acid : it is however but a weak base, incapable of decomposing the salts 
of copper or silver. It cannot be distilled without alteration. It is but sparingly 
soluble in water, but dissolves readily in alcohol and in acids. It has a peculiar sweet 
and aromatic taste. It does not show much tendency to form aystallisable salts. 
The sulphate forms a gummy mass. — The hydrochlorate is a yellowish salt easily 
soluble m water and alcohol, sparingly in ether. It tastes like the base itself. It 
assumes a darker colotir at 100° C. ana sublimes partially at 160°. On adding nitrate 
of silver to the aqueous solution, the whole of the chlorine is precipitated as chloride of 
silver, but the bromine remains in solution. The chloroplatinate, C*H'Br*N.HCLPtCl', 
is an orange-coloured precipitate nearly insoluble in absolute alcohol Alcoholic solu- 
tions of dibromallylamine and chloride of mercury form, when mixed, a copious Tiiiite 
precipitate. (Maxwell Simpson, Phil. Mag. [4] xvi. 257.) 

Ethyldibromallylamine, C«H'^r*N «= N.C*H*.(C»H^r)*. — Obtained by enclosing 
dibromallylamine with a large excess of iodide of ethyl in a sealed tube, and heating 
the mixture to 100° C. for a considerable time. The excess of iodide of ethyl is 
then distilled off, and the remaining hydriodate of eth^lbibromaUylamine is dissolved 
in water and distilled with potash. It has a very bitter and pungent taste, smells 
like nutmeg, is insoluble in water, soluble in acids, and alkaline to test-paper. It is 
a stronger base than dibromallylamine, and precipitates oxide of copper from capric 
salts. (Simpson.) 

Tbiaixtlamine, C»H»*N « N.(C»H*)", is formed by the destructive distillation of 
hydrate of tetrallylium. 

TETBALLTLnjM, 0"H»N = N(C»H*)*.— The iodide of this base is the chief product 
of the action of ammonia on iodide of allyl The action takes place without the aid 
of heat^ a large quantity of the iodide dissolving after a few days* contact ; the solution 
afterwards deposits splendid crystals of the iodide, and sometimes becomes a solid 
mass. The separation of the crystals may be accelerated by adding a strong solution 
of potash, in which the iodide is completely insoluble. The iodide is purified by ex- 
posing it to the air till the potash is converted into carbonate, and then reczystaUising 
from absolute alcohol Treated with oxide of silver, it yields the hydrated oxide of 
tetrallylium, and the solution of this oxide mixed with hydrochloric acid and bi- 
chloride of platinum, forms a yellow salt containing N(C'H*)*Cl,PtCl'. 

IkiraUylaraonium, As(CH*)*.~-When iodide of allyl is digested with arsenide of 



ALL YL — ALOEa " 1 47 

potaasiimi, sereral liquid compounds are formed, having a reiy fetid odour, and at the 
sime time a solid crystalline body separates, which is Uie iodide of tetraUyl-arsonium. 
(Hofmann and Cahours.) 



C*H*. — A diatomic radicle which bears to allyl the same relation 
Oat ethylene CH*, bears to ethyl C«H*. It is not known in the free state, and only 
tvD of its oompoonds haye been prepared, yiz. the chloride and the acetate. 

Chloride of Allyl ene, C»H^C1«. -^CT-ofetwc^onV?.— Obtained by the action of per- 
diloride of phosphorus on acrolein (p. 56). To prevent the action from becoming too 
violent, the retort should be externally cooled, the perchloride of phosphorus covered 
vita a layer of oxychloride, and the acrolein added by small portions at a time. The 
propQitions are 1 pt acrolein to 3 ^ts. of the perchloride. The crude distillate is shaken 
0^ \rith water to remove ozychlonde of phosphorus, and further purified by digestion 
with chloride of calcium and rectification, the chloride of acrolein passing over at 
about 90^ C. It is a colourless oil, having a sweetish ethereal taste, and an odour like 
that of chloroform. Specific gravity 1 • 1 70 at 27 "5 C. Boiling-point (corrected) 84 "4° C. — 
Another oily liquid, apparently isomeric with chloride of allylene, is likewise formed 
by the action of p^ehloride of phosphorus on acrolein. 

Chloride of allylene is slowly oxidised by nitric add. Heated with aqueous nitrat<* 
of silver, it precipitates chloride of silver. Chlorine converts it into a crystalline com- 
pound, probably sesquichloride of carbon. Sodium has no action upon it Heated 
with ethylate of sodium, it appears to yield a compound corresponding to acetal 
(p. 3). Seated in a sealed tube with alcoholic potash, it appears to yield the 
same compound, together with chloride ofacryly CH'^Cl. Heated in a sealed tube with 
anifflonia^ it yields sal-ammoniac and acrolein-ammonia (p. 56). (Hubner and 
Oeuther, Ann. Ch. Pharm. cxiv. 36.) 

Acetate of Allylene, C»H"0* « (c^lm* \ 0\ Acetate of Acrolein^-^Viodvuied, 

1. By heatiiig in sealed tubes a mixture of 1 at. acrolein (CH^O), and 1 at. acetic 
anhydride (C*K*0*.) — 2. By heating 1 at chloride of aUylene with 2 at acetate of 
tSl\a in a sealed tube, first in the water-bath for several hours, then to 160^ 0. in 
aa oil-bath, reetlfying the product, and collecting apart that which passes over between 
l«Oand I6OO: C»H*Cl« + ((?H»0)«.Ag*.0« = (C«HK))».(?H\0« + 2Aga It is a 
eoloorless liquid, having a strong fishy odour, and very shaip taste. Specific gravity 
11)76 at 22^ C. ; boils at about 180°. It slowly reduces an ammoniacal solution of 
nifrate of silver. Heated with caustic-potash, it yields acrolein and acetate of 
potaasiiim. It may he regarded as a compound of 1 at acrolein with 1 at. acetic 
anhydride, C«HK).C^H*0». (Hiibner and Geuther.) 



Native anhydrous sulphate of zinc (See Suiphates.) 

(See Gahnbt.) 

OV. — ^Both sweet and bitter almonds yield by pressure a fixed 
oil, having a light yellow colour, an agreeable taste, but no odour. Specific gravity 0*918 
at 15°. It consists chiefiy of olein, with but little solid fats, and consequently requires 
a vay low temperature ( — 25^ C.) to solidify it It easily turns rancid. It dissolves 
in 25 pta. of cold alcohol, in 6 pts. of boiling alcohol, and mixes in all proportions with 
ether. 

Bitter almonds macerated with cold water and distilled, yield also a volatile oil, of 
fragrant odour, which is the hydride of beneoyl (CH'O.H). This oil does not exist 
ready formed in the almonds, but is produced by the action of an azotised body, 
etMdein, on the amygdalin contained m the fruit Sweet almonds do not contain 
emolsin, and therefore do not yield the volatile oiL (See Bsnzotl, Htdbtob of.) 

I. (See Alostic Acid.) 

The thickened juice of various species of aloe, a genus of plants belong- 
ing to the liliaceous order. It is chiefiy extracted from the Al^ aoocotrina in Arabia ; 
from Aloe epicata and A. lingviformie at the Cape of Good Hope ; and from A, vtdgaris 
or Hnttata in Barbadoes and Jamaica. The best sorts of aloes aro prepared by ex* 
fmii^ to the sun the juice which exudes spontaneously from incisions in the leaves ; 
mferior kinds are obtained by pressing the leaves. Aloes occurs in commerce in large 
red-brown masses, having a shming conchoidal fracturo ; in thin plates it is red and 
translucent; it is easily reduced to a yellow powder. It has an odour like that of 
■aifron, and a very persistent bitter taste. It dissolves completely in alcohol and in 
boiling water. It possesses active purgative properties, due to a crystallisable principle 

L 2 



\ 



148 ALGETIC ACID — ALOUCIII. 

aloin^ which is contained in it, and may be extracted in a st&te of pnritj from Bar- 
badoee aloes. 



C?*fl'^»0"? Pbfychromio Acid. Artificial Bitter of Aloes.-^ 
Produced by the action of nitric acid npon aloes, ditjsanunic acid being formed at 
the same tune (Schunck, Ann. Oh. Pharm. tttjt. 24; Izv. 236; G. J. Muldei; 
J. pr. Ghem. zlviii. 39). 1 ^art of aloes is gently heated with 8 pts. of moderately 
strong nitric add till gas begins to escape ; the vessel is then removed from the fire, 
and as soon as the disengagement of gas ceases, the solution is concentrated by era- 
poration, tUl a yellow powder separates, the quantity of which may be increased by 
addition of water. The aloetic acid is separated from the chrysammic acid in this 
powder by treatment with boiling alcohol, which dissolves the aloetic acid ; and m 
evaporating the solution, the add is obtained in the form of an orange-yellow powder 
having a bitter taste. It is but slightly soluble in water, but dissolves more freely in 
boiling water, forming a solution of a splendid purple colour, which is changed to 
yellow by nitric acid, but restored by alkalies. It is dissolved b^ ammonia^ potash, 
and soda, forming purple solutions. Strong nitric acid converts it into chrysammic 
acid. It is monobasic. The ten'vm-salt, C'H'BaN'O*, is a brown-red nearly msolnble 
powder, obtained by predpitating the aqueous acid with acetate of barium. The 
potassium-Bslt separates by slow evaporation in crystals of a fine ruby colour. Ac- 
cording to Schunck, the formula of aloetic acid is C^*H*NO^*; according to Mulder 
C* W^O". According to the formula above given, it is isomeric with dinitrobenzoie 
add. 

The alcoholic mother-liquor obtained in the preparation above described contains 
another acid called Aloeretic acid^ CH'ON* ? which, according to Mulder, is the firrt 
product of the action of nitric add on aloes. It is separated by neutralising vitii 
chalk, mixing the filtrate with acetate of lead, decomposing the lead-predpitate with 
hydrosulphuric acid, and evaporating. It is a brown amorphous mass, which when 
boiled with nitric add is converted first into aloetic, then into chrysammic add. 
(Mulder.) 

The name aloeretic add is also applied by Schunck to an add produced bv the action 
of alkalis on chrysammic acid, and called by Mulder chrysatric acid (whidi see). 



C^TffitQi^ or C"ir«0".--A crystalline bitter prindple obtained fiwn 
aloes : also called Bitter of aloes. It is prepared by mixing Barbadoes aloes with sand, 
to prevent agglomeration, treating it several times with cold water, and evaporation 
the aqueous extract in vacuo to the consistence of a syrup. It then separates in small 
crystals. The solution most not be heated to the boiling-pointi since aloin undeigoet 
alteration at 100^ C. 

According to Dr. Stenhouse (Phil. Mag. [3] xxxvii. 481), the Cape and Socotria 
aloes contain large quantities of foreign matters which prevent the crystaUisation of 
the alo'in ; he has succeeded in isolating the aloin, only by operating on the Barbadoes 
aloes. 

Pure alom separates from an alcoholic solution, in the form of small prismatie 
needles, grouped in stars, of a pale yellow colour. Its taste is at first sweet, then 
extremely bitter. It is much more purgative than aloes itself. In the cold, it is but 
slightly soluble in water and alcohol, but dissolves better when hot ; the solutions 
are ydlow and neutral to test-paper. Dried at 100°C. it contains C"H"0'. 

The caustic and carbonated alkalis dissolve aloin with a bright yellow colour. 

By digestion with concentrated nitric acid^ aloin is transformed into chrysammic 
add. Chlorine passed into an aqueous solution of aloin, produces a bright yellow 
precipitate, chloralotlf containing, according to Robiquet, C^^CIO*. Solution of 
chloride of lime colours aloin bright yellow, this tint passing rapidly to brown. 

Bromine added in excess to a cold aqueous solution of aloin produces a yellow pre- 
dpitate oi bromaloiny C"n'*Br*0'? which dissolves in boiling alcohol, and separates 
in shining yellow needles, grouped in stars, and much larger than the ciystals of aloin. 
It is less soluble in cold water and alcohol than aloin : the solutions are neutral. 



1 — C*IPO* ? An oily liquid obtained in very small quantitvifcy distil- 
ling aloes with half its weight of quick lime. It ia colourless, has a shar|rpenetnting 
odour, is insoluble in water, but mixes in all proportions with alcohol and ether. 
Specific gravity 0'877. Boiling-point 130°C. By contact with the air, or by the action 
of strong nitrie acid on chlorine water, it is converted into a brown-red liquid, hearier 
than water, and having a very decided odour of castorenm. Treated with oxide of 
copper or chromic acid, it yields carbonic add, water, and hydride of benzoyl (Ro- 
biquet, J. Pharm. [3] x. 167 and 241.) 

AliOVCBZi or A&VORI BWBTW is imported from Madagascar, where it is 



J 



ALPHENE — ALUMINIUM. 149 

obtaioed, araording to Yabnont do Bomare, from a tree called TimpL According to 
ochezs, torn Wintera aromatica. It is friable, whitish on the outside, black wit'Lin, 
has a marbled a^^earance, and a strongly aromatic, peppety, bitter taste. According to 
Bonastro (J. JPhann. x. 1), it contains 68'12 p. c of resin easily soluble in cold 
akohol, 20*4^ of resin sparingly soluble in cold alcohol, 1-58 essential oil, together 
vith small qoantities of free acid and ammonia-salt, besides earthy impurities. The 
sfuin^j soluble re8in.appearB to be of peculiar nature. 

Bi 8VI1PBIBH OV« (See Sxtlfhocyaiodb of Ammoniuic) 



A mineral haying the same composition as haryioedlcite, GCBaCa. 
[or JaO.CO* + CaO.CC^, but erystelHsing in obhque prisms, whereas baryto-calcite 
foims right rhombic prisms : hence carbonate of bfloinm and caldom is dimorphous. 
Alstomte is found on Alston Moor in Cumberland. 



(See Tellubede of Lead.) 

Syn. of AsPABAGiN. 

ACZ]>. C*H*SO*. — This acid, isomeric with ethylsulphuric or 
ealphoTiiuc add, is produced, according to Regnault (Ann. Ch. Fhys. [2] Ixy. 98), 
▼bim alcohol is heated with excess of strong sulphuric acid till olefiant eas begins to 
be eyolyed (between 160^ and 180^ C.) When equal parts of sulphuric acid and alcohol 
are used, nothing but sulphoTinic acid is formed, ana even iu the residues of the ether- 
preparation on the large scale, the latter is the only acid found. 

To prepare the barium-salt of althionic acid, the residue obtained in the preparation 
of ol^ant gas from 6 pts. sulphuric acid and 1 pt. alcohol, is saturated with milk of 
lime ; the filtrate, after eTaporation, is treated with oxalic acid to precipitate the lime ; 
the Hqnid again filtered and saturated with baiyta- water ; the excess of baryta preci- 
pitated by carbonic add ; and the filtrate evaporated, first by heat, and finally in yacuo, 
ajstallisation then taking place as soon as the liquid acquires a syrupy consistence. 
The salt when purified by recrystalHsation, forms spherules composed of small needles 
permanent in the air, and giving off 8*^9 p. c (1 at.) of water in vacuo. The formula 
of the oystallised salt is CH^BaSO^ + H^O. It is more soluble in water than the 
EaldioTinate of barium, and dissolves also in alcohol especially when hot 

rrom the aqueous solution of the barium-salt, the firee acid (the hydroeen-salt) may 
be obtained by precipitating the baryta with sulphuric acid, and from this the other 
lalta may be prepared by direct combination. The caicium-Bslt evaporated at the 
gentlest possible heat, solidifies completely in a mass, without crystallising. The 
copper^salt forms pale green, very thin rhombohedrons, having an acute angle of 60^. 
(Regnault) 

Hagnus (Pogg. Ann. xlvii. 523) was not able to find althionic acid in the residues 
of the preparation of olefiant gas, but only ethionic, isethionic, and sometimes also 
BoIphoTinic acid. 

AliOpMEMm Pear-shaped earthem vessels used by the older chemists for sub* 
liming. The^ are open at each end and fit into. _. 

one another m the manner shown in fy. 7. At ^^' * * 

the quicksilver works at Almaden in Spain, vessels cz^^^^^^ISr:^^ l&lT^'^'^'^tjil 
of this shape are used to condense the mercurial B^||j^p^i^llPl^a^«^l|gpi|l 
TapoQEB issuing firom the retorts. For this pur-. 

pose they az«laid in the form of a chain on a slightly inclined suHace called the 
dudd-bath, (See Hebcubt.) 



(See Suu'HATBS.) 

Compoonds <^ alumina with the stronger bases. 

A basic sulphate of aluminium, A1^0*.S0' + 9H0, found native 
at New Haven in America. It is a white, opaqiie, earthy mass, of specific gravity 
1*705, soluble in hydrochloric acid. Gives oa its acid at a red heat. (S tromey er.) 



Bymbcl, Al; Atomic weighty 13*75. — This metal occurs in a 
great variety of forms, viz. as oxide (alumina^ anhydrous, and hydrated, sometimes 
alone, but more generally associated with tne oxides of other metals, iron zinc, 
g^udnum, magnesium, &c ; — as sulphate and phosphate ; as silicate, which is the chief 
constituent of all olays, and in combination with other silicates, forms a vast number 
of minerals, especialfy the felspars ; also as mellitite, or honeystone, as fluoride of 
ahnninium and sodium in cryolite ; and in very small quantities in plants. 

Alumina was first shown to be a distinct earth by Marggrafir in 1754, having 
besa pterioosly confounded with lime. Oerstedt, in 1826, showed how to prepare 

L 3 



150 ALUMINIUM. 

the cMoride of alnminium by passing cUorine over a red-hot mixture of alumina 
and charcoal; and Wohler, in 1828 (Pogg. Ann. zi. 136) succeeded in eliminating 
the metal by igniting the chloride with potassium. It was thua obtained in the form 
of a grey powder intermixed with tin-white globules ariaing from partial fusion. It 
has lately been obtained in the compact form, and in much larger quantity, by 
H. Sainte-ClaiTe Deyille and others. 

Preparation, — ^The mode of preparation now adopted is the same in principle $a 
that of Wohler, depending on the action of sodium at a red heat on the chloride or 
fluoride of aluminium, or better, on the double chloride or double fluoride of alumi- 
nium and sodium. Sodium is used to effect the reduction in preference to potassium, 
partly because it acts more regularly and with less Tiolence, and partly because it is 
more easily prepared, and, having a lower atomic weight than potassium, a smaller 
quantity of it suffices for a given amount of chemical work. 

The process flrst adopted by Deville consisted in passing the vapour of chlofride of 
aluminium over sodium contained in a tube of iron or copper wiuch was kept at a 
dull red heat. Metallic aluminium was thus obtained, mixed with chloride of alumi- 
nium and sodium. The latter was. removed by waahing with water, and the metallic 
globules which remained were made to unite by heating them till they began to melt, 
and pressing them together with a pipe-stem. The mass thus obtained was then 
remeUed and cast into bars. Another method which promised to yield good results, but 
has not yet been perfected, was to reduce the chloride of aluminium by vapour of 
sodium. The mixture of carbonic oxide and sodium-vapour produced by heating a 
mixture of charcoal and carbonate of sodium (see Sodium) was conveyed into a huge 
earthen crucible by means of an iron tube passing through a hole near the bottom and 
reaching nearly to the other side ; and as the sodium and carbonic oxide burned and 
thereby heited the crucible, portions of chloride of aluminium were thrown in from 
time to time. The crucible when cold was broken, and the aluminium separated 
from the saline mass in the manner above described. 

The quantity of compact aluminium obtained by these methods was however con- 
siderably below the theoretical amount, a large portion of the metal being reduced in 
the fbnn of a fine powder which re-fused to unite into globtdes. This inconvenience 
may be obviated and much better results obtained by the use of fluor spar or cryolite 
as a flux. These fluorides assist the union of the particles, apparently by dissolving 
small quantities of alumina — ^produced by moisture adhering to the chloride, — ^which 
surround the partidee of metal at the moment of reduction, and, not being decom- 
posed by the sodium, prevent them from uniting into globules. The reduction may 
be performed in crucibles, or better, in a reverberatory ^imace. 

a. 400 parts of chloride of aluminium and sodium, 200 pts. of chloride of sodium, 
200 pts. of fluor spar or crvolite — the latter being preferable — all perfectly dry and 
flnely pulverised, are placed together, with 76 or 80 pts. of sodium, in alternate layers, 
in an earthen or iron cmcible, which is moderately heated till the action b^^ins, 
and afterwards to redness, the melted mass being stiired with an iron rod and after- 
wards poured out. If the process goes on well, 20 pts. of aluminium are thus 
obtained in a compact mass, and about 6 pts. more in globules encrusted in a hard 
mass. 

The aluminium thus obtained is, however, somewhat contaminated with silicon, 
derived from the earthy matter of the crucible, which is attacked by the sodium, by 
the aluminium itself, and by the fluorides in the slag. This evil may be corrected to 
a certain extent, but not completely, b^ lining the crucible with a paste composed of 
calcined alumina, or aluminate of calcium. If iron crucibles are used, the aluminum 
is found to contain iron. 

b. The reduction is performed with greater facility, and on a much larger scale, 
by heating the mixture on the hearth of a reverberatory furnace. 

The proportions used are : 

Chloride of aluminium and sodium . . .10 parts. 

Fluor spar or cryolite , . . .6 



Sodium . . . . . .2 



»f 



1} 



The double chloride and the cryolite or fluor spar are mixed in the state of powder 
with sodium in small ingots, and the whole is tlirown on the hearth of the furnace pre- 
viously raised to the required temperature. The dampers are then closed to prevent 
access of air. A vind action soon takes place, accompanied by evolution of heat, 
sufficient to raise the walls of the furnace and the mixture itself to bright redness ; 
and the mixture is almost completely liquefied. When the reduction is complete, the 
fused mass is run out through an aperture at the back, the slag escaping first, and 
then the aluminium fiowing out in a single jet, and collecting in one mass below the 
liquid slag. With a furnace having a hearth about 16 square feet in surface, about 



ALUMINIUAL 151 

16 lbs. of alnniimum may be obtained at one operation. The slag consists of two 
hjen, the appcr containing a larse quantity of common salt, while the lower, which is 
pasty vad leas fusible, consists chiefly of fluoride of alnminium. On pnlyerising this 
tatter and passing it through a sieve, an additional quantity of aluminium is obtained 
in fdoboks. The fluoride of aluminium may be used for the preparation of alumina. 

This process (which has been patented by JOLBousseau, Frires and M. Paul Morin, 
both in France and in this country, 1856, No. 1810) is peculiarly adyantageous in 
this TCBpeety that the reduced metal is yeiy little exposed to contamination with silicon. 
The iB^oduction of this impurity generally arises from the action of the sodium or of the 
dtg on the earthy matters of the Ycssels in which the reduction takes place. Now, 
when cnicibles are used and the heat is applied from, below, the part of the mixture 
in contact with the crucibles is necessarily the hottest, and consequently the action 
exoted on the crndble is considerable ; but when the mixture is fused on the hearth 
of a rererberatoiy furnace, with the flame playing on its surface, the coolest part is in 
contact with the hearth, which is therefore less acted upon. Moreoyer with the pro- 
portions above given, the whole of the fluorine is separated as fluoride of aluminium, 
a compound which exerts but little action on silieious substances. 

Pi^aratioK from Cryolite. — ^The pulverised mineral is mixed with half its weight 
of common salt^ and the mixture is arranged in alternate layers with sodium (2 pts. 
of eodium to 6 pts. of cryolite), in an earuien or iron crucible, a layer of pure cryolite 
being placed at top, ana the whole covered with common salt. The mass is rapidly 
heated till it melts completely, and then left to cool after being stirred with an iron 
rod. The ahmainium is generally found in large globules. Such was the method 
originally practised by Professor H. Kose in Berlin, and by Dr. Percy and Mr. Allen 
Dick in this country. It is now carried on, on the manufacturing scale, at Am&eville, 
Bear Bouen, by C. and A. Tissier. 

A peculiar apparatus for effecting the reduction of aluminium, either &om the 
double chloride or from cryolite, the object of which is to prevent loss of sodium by 
ignition, has been invented and patented by F. W. Gerhard (1858, No. 2247). It 
comists of a reverberatory furnace having two hearths, or two crucibles or reverbe- 
ratoiy furnaces placed one above the other, and communicating by an iron pipe. In 
the lower is plaoed the mixture of sodium with the aluminium-compound, and in the 
upper a stratum, of chloride of sodium, or of a mixture of sodium and cryolite, or of 
the slag obtained in a former operation. This layer when melted, is made to run into 
the lower furnace in quantity sufficient to cover completely the mixture contained 
therein, so as to protect it from the air. 

The chief inducement for using cxyolite as a source of aluminium, is that it is 
a natural product obtained with tolerable facility, and enables the manufacturer to 
dispense with the troublesome and costly preparation of the chloride of aluminium 
and sodium. But the aluminium thus obtained is less pure than that prepared from 
the double chloride by the method previously described. If earthen crucibles are 
used, the aluminium is contaminated with silicon, because the fluoride of sodium pro- 
duced by the decomposition acts strongly on the silieious matter of the crucible ; and 
if crucibles of iron are used, the aluminium takes up a portion of that metal. For 
these reasons, Deville is of opinion, that the best use of cryolite is as a flux in the 
preparation of aluminium from the double chloride. In that case, as already observed, 
the sUg consists, not of fluoride of sodium, but of fluoride of aluminium, which acts 
hot slightly on tiie containing vessel. 

Seduction of tUumnium by means of hydrogen or carbon, — Several attempts have 
been made, but with doubtful success, to separate aluminium from its compounds by 
means of the ordinaiy reducing agents. 

F. W. Gerhard decomposes fluoride of aluminium, or the double fluoride of alumi- 
niom and potassium or sodium, by subjecting it to the action of hydrogen gas at a 
red heat. The aluminium-compound is placed in a number of shallow dishes of glazed 
earthenware, each of which is surrounded by a number of other dishes containing iron 
filings. These dishes are placed in an oven previously heated to redness ; hydrogen 
gas is then admitted, and the heat increased. Aluminium is then separated, and 
hydrofluoric acid evolved, which is immediately taken up by the iron fllings, and 
thereby prevented from acting on the aluminium. To prevent the pressure of gas 
from becoming too great, an exit-tube is provided, which can be opened or closed at 
|deasnre by means of a stopcock. This process, which was patented in 1856 (No. 2980), 
is ingenious and was said to yield good results ; tlie inventor has however since returned 
U> the use of the more costly reducing agent, sodium (see above), which would seem 
to im^ that the hydrogen method has not quite fulfilled his expectations. 

Sir Frauds C. Knowles has patented a process (1857, No. 1742) for reducing alu* 
minium from its chloride by means of cyanide of potassium or cyanide of sodium, the 

l4 



152 ALUMINIUM. 

chloride, either in the fused state or in the form of yaponz being brought in contact 
either with the melted cyanide or its vapour. Puve alumina may be added to increase 
the product 

L. F. Corbelli, of Florence, states that aluminium may be obtained by mixing the 
impure sulphate (prepared by heating clay with strong sulphuric acid), with 2 pta of 
ferrocyanide of potassium, and IJ pt. common salt, and heating the mixture to whiteness. 
The metal thus obtained must howeyer be very impure, perhaps consisting chiefly of 
iron. The process was patented in this country in 1858 (No. 142). 

M. Cumenge, of Paris, obtains aluminium from the sulphide (Al^S*) either by heat- 
ing that compound in an atmosphere of hydrogen, or by heating it with alumina or 
sidphate of alimiinium, in such proportion that the oxygen contained in that com- 
pound shall be just sufficient to convert the whole of the sulphur into sulphurous 
anhydride : 

A1*S« + 2A1*0« - 3S0« + 12A1 
or APS* + A1*(S0*)» = 6S0* + 8A1; 

or, Isfitly, by decomposing the sulphide with an ordinary metal, such as iron, copper 
or zinc. This process is also patented (1868, No. 461). 

Preparation of Aluminium by Electrolysis. — The electrolytic reduction of alumi- 
. nium may be performed either in the diy or in the wet way. The reduction from 
fused chloride of aluminium and sodium was first effected in this manner by Sun sen 
in 1854 (Pogg. Ann. xciL 648^. The salt is introduced in a fused state into a red- 
hot porcelain crucible, divided into two parts by a porous earthenware diaphragm, and 
the extremities of the carbon poles of a Bunsen's batteiy of ten elements are introduced 
into the two halves of the fused mass. The metal is then reduced at the negative 
pole. The heat must be raised considerably above the melting-point of the cbuble 
chloride, otherwise the aluminium separates in the pulveruleut form. It is best to add 
fresh quantities of chloride of sodium during the reaction, and to raise the tempera- 
ture ultimately to the melting point of silver. The aluminium is then obtained in 
globules of considerable dize, which may be melted into one by throwing them into 
chloride of sodium melted at a white heat Deville adopts a similar method, using^ 
however, platinum instead of charcoal for the negative pole. 

The same method may be used for coating metals witii aluminium. Thus, if a bar 
of copper be used as the negative pole, and a bar of aluminium as the positive pole, 
tha latter dissolves as the action goes on, and is deposited upon the copper. 

Aluminium may also be reduced by the action of the current from the solution of its 
salts. Mr. Qtore has in this way obtained a deposit of aluminium on copper, and 
Messrs. Evans and Tilley have patented a process (1855, No. 2756), for coating metals 
with aluminium and its alloys, by electrolysing a solution of alumina mixed with 
cTjranide of potassium, the negative pole being formed of the metal to be coated, and 
the positive pole of platinum or aluminium, or of some other metal, such as copper, 
tin or silver, which is to be deposited together with the aluminium. The bath may 
also in some instances be composed of a mixed solution of aluminium and the other 
metal to be deposited. — ^M. Corbelli, of Florence, obtains a deposit of aluminium by 
electrolysing a mixture of rock-alum or sulphate of aluminium with chloride of calcium 
or chloride of sodium, the positive pole being formed of iron wire coated with an 
insulating material and dipping into mercury placed at the bottom of the solution, and 
the n^ative pole of zinc immersed in the solution. Aluminium is then deposited 
on the zinc, and the chlorine eliminated at the positive pole unites with the mercuiy, 
forminff calomeL This process is also patented (1858, No. 607). 

Of eSi the processes above described, the only one that has been successfidly applied 
to the production of aluminium on the large scale, is the decomposition of the double 
chloride or of cryolite by sodium. The electrolytic method is too expensive, excepting 
for producing a thiu coating of aluminium on other metals ; and the attempts which 
have been made to obtain ^uminium by means of the ordinary reducing agents, such 
as hydrogen and charcoal, do not appear to have led to very satisfactory results. At 
present, therefore, the progress of the aluminium manufacturo depends essentially on 
the economical production of sodium; and indeed the manufacture of aluminium has 
already given a great stimulus to that of sodium, and has led to considerable improve- 
ments in that process, and consequent reduction of cost (See SoDnmc.) * 

PKr(^a^n,— Aluminium may be purified from copper and iron by fusion with iiiti« 
in an iron crucible, the foreign metals being thereby oxidised, while the nitre lemains 

* When Deville commenced hli experiments in 1894, great hopes were entertained that Aliuninittn 
might be produced at a price sufficiently low to admit of a variety of useful ai>pIications. Hitherto thcae 
expectations have been but Imperfectly fulfilled, the metal being still too costly to be applied to other 
than ornamental purposes. Still, however, great progress has been made, the price, which in 1856 was 
U per OS., being now reduced to 5«.i and further reduction will doubtless be nude as the details of the 
manufacture are Improted. 



ALUMINIUM. 153 

intact Before introdiKuig the almnixiiiim, the inner svaface of the crucible should be 
veQ cuddised by the action of the nitre. Alnmininm containing zinc, may be freed 
from that metal bj melting the alloy in contact with the air. No method has yet 
been diaeoTered of porifying alumininm from siliam. 

AluminTTim is yery apt to retain portions of the slag in the midst of which it has 
been fcmned, causing the surface, when worked and polished, to exhibit a number of 
points of inferior lustre, which gradually became more and more conspicuous. The 
belt mode of purification is to melt the metal in an open black lead crucible for a con- 
sidaahle time, then remore it from the fire and stir it with an iron skimmer oxidised 
00 the 8Qi£ice, By this means, the whitish slaggy matter is remoyed, together with a 
smaJl portion of the aluminium, which may be set aside to be remelted. The metal is 
then cast into bars, and the whole operation repeated three or four times. 

[For further information respecting the preparation of aluminium, see De Alumu 
m'mi, par H. Sainte-Glaire DeyiUe, 8to. Pans, 1859; U Aluminium et lea Metaux 
MealhUf par C. et A. Tissier, 12ma Paris et Bouen, 1858 ; Chemical Technologyy by 
Biehsrdaon and Watts, yoL iy. pu 1 ; Urt^s Dictionary of Arts, Manufactures and 
Mine*, yoL L p. 120.] 

J^tjperties, — Aluminium is a white metal, with a faint tinge of blue. It takes a fine 
poliah, and its snrfaoe may be frosted, like that of silyer, by plunging it for an instant 
uto a -nxj weak solution of caustic soda, washing with a large quantity of water, and 
then digesting it in strong nitric acid. When pure, it is quite destitute of taste and 
odour. It is yery malleable and ductile ; may be beaten and rolled as easily as gold 
lad silTer, and <u«wn out into extremely thin wire. In this last operation, however, 
it becomes yery brittle, and requires to be tempered by cautiously heating it oyer a 
lamp. In elasticity and tenacity, it ia about equal to silyer. After fusion it is as soft 
as pore silyer ; bnt after hammering in the cold, it acquires the hardness of soft iron 
It u hi^y Booorous, a bar of the metal suspended by a thread and struck with a 
hard body, emitting a beautifully dear, ringing sound. It is yeiy light, being not much 
more than 2| times as heavy as water, and about 4 times lighter than silver. Its 
density after nxsion is 2*56, and after being hammered in the cold, 2 *67. Its melting- 
point IS intermediate between the melting-points of zinc and silver, but nearer to the 
fanner. It may he cast with the greatest ease in metallic moulds, and stiU better in 
moulds of sand. It may be fused without any flux ; indeed, the addition of a flux 
is rather detrimental than otherwise, the metal attacking borax and glass with 
Polity. Aluminium, heated in a closed vessel, does not exhibit the slightest tendency 
to volatilise. 

The electric conducting power of aluminium is eight times as great as that of iron, 
and about equal to that of silver; it conducts heat even better than silver. Its spedflc 
heat is very great, and hence, though Its melting-point is comparatively lo^ir, it takes 
a long time to liquefy. The melting together of small pieces of the metal may be 
&eflitated by shalong the crucible and pressing them together with an iron rod oxi- 
diied on the sur&ce. When slowly cooled from frision, it exhibits a crystalline 
stncture ; the crystallisation is, however, most distinct when the metal is impure. 
Aluminium precipitated from its solutions by electrolysis at low temperatures, crys- 
tallises in octahedrons, which appear to be regular. It is slightly magnetic. 

Aluminium does not oxidise in the air, even at a strong red heat ; neither does it, 
in the compact state at least, decompose water, excepting at a white heat, and even 
then butalowly (Deville). It is not attacked by sulphuretted hydrogen^ or even by 
wlphide of ammonium^ and consequently preserres its lustre in the atmosphere of 
luge towns^ where silyer is very soon tarnished and blackened. It may also be heated 
to redness in vapour of sulphur without showing any disposition to combine ; at very 
high temperatures, however, combination takes place. 

Almninium is not attacked by nitric acidy either dilute or concentrated, at ordinary 
temperatures, and very slowly even at the boiling heat ; neither is it acted upon by 
sulj^ric acid diluted to the degree at which that acid dissolves zinc ; but hydro- 
chloric acid, either dilute or concentrated, dissolves it readily, even at low temperatures, 
with evolution of hydrogen. The vegetabie acids^ such as acetic and tartaric acid, 
exert no perceptible action on aluminium ; a mixture of acetic acid and common salt 
exerts a somewhat greater action, because it contains free hydrochloric acid ; but even 
in this case the action is very slow, and not nearly so great as would exerted upon tin 
under similar drcnmstances. Aluminium would therefore be well adapted for culinary 
vessela, especially as the small quantity of alumina which might be formed from it by 
the action of certain acid mixtures would not exert any ^eterious action on the 
animal economy. 

The hydrates of potassium and sodium in the state of fusion do not act upon alu- 
minium, but their aqueous solutions dissolve it readily, forming aluminate of potassium 
or aodium, and giving off hydrogen. Ammonia acts but slightly on it. 



154 ALUMINIUM. 

A solution of common salt pp chloride of potassium ia also witbont action on alumi- 
nium, but the solutions of many otber cblorides dissolve it, and more readily, as the 
metals which they contain are higher in the scale ; even a solution of chloride of 
aluminium dissolves the metal, forming a basic chloride. Solutions of sulphates and 
nitrates^ on the contrary, do not act upon it. Hence in precipitating other metals upon 
duminium by electrolytic action, it is necessary to use acid solutions not containing 
hydrochloric acid or any chloride. In an acid solution of sulphate of copper, the 
aluminium quickly becomes coated with metallic copper. 

AlTiTwi'Tiinm may be fiised with nitre at a moderate heat, without undergoing the 
slightest alteration ; hence this process may be adopted for purifying aluminium from 
admixtures of other metals. If however the heat be raised till the nitric acid is com- 
pletely decomposed and begins to give off nitrogen, a new reaction takes place at- 
tended with incandescence, and aluminate of potassium is formed. 

Uses, — The lustre and whiteness of this metal, its unalterability in the air, and the 
fiicility with which it takes a frosted surface, render it well adapted for jewellery, for 
which purpose it is now much used. It also makes very bright reflectors. Its light- 
ness renders it useful for mounting astronomical instruments, especially sextants. It 
may also be used for making bjobJI weights, such as the diivisions of the gramme. 
Very delicate balance-beams have also been constructed with it. For culinary vessels 
it is adapted by its lightness and the little tendency which it has to become corroded 
by any of the liquids likely to come in contact with it. It is necessary however to 
observe, that this power of resisting t'he action of corroding agencies, and more espe- 
cially those of the atmosphere of large towns, is exhibited only by the pure metal 
Now, much of the aluminium of commerce is very impure, being contaminated with 
iron OP silicon, or not having been properly freed from slag. Aluminium thus con- 
taminated soon becomes tarnished, and much disappointment has been experienced 
from this cause by many who have used it for ornamental purposes. According to 
Deville, the impurities just mentioned are found to the greatest amount in the metal 
obtained from cryoUte (p. 162). 

General Characters and Reactions of Aluminium-compounds. — Aluminium forms 
only one class of salts, and into these it is supposed to enter as a sesqui-equivalent 
radicle, 2 atoms of aluminium taking the place of 3 atoms of hydrogen : Al' « H*. or 
All = H. Thus, the chloride of aluminium is (Al*)"'Cl*; the oxide (alumina) is 

(AIT'W*' the sulphate, (AI«)'«.3S0*, or ^^/^!]w[o«, &c. These formula are 

based upon the isomorphism of the aluminium-compounds with other compounds of 
corresponding character, which are known or supposed to contain sesqui-equivalent 
radicles: thus, alumina, the only known oxide of aluminium, is isomorphous with 
sesquioxide of iron and sesquioxide of chromium; and common potash-alum 
(Al«)'"K'(SO«j« + 12H«0, is isomorphous with iron-alum (Fe«)'"K'.(SO«)« + 12HK), 
and chrome-alum (Cr»)'"K'.(SO*)* + 12H*0. All these formulae may, however, be re- 
duced to others containing mono-equivalent radicles, the values of which are two-thirds 
of those of the corresponding sesqui-equivalent radicles. For instance, the aluminium- 
compounds may be supposed to contain a radicle (alumtnicum\ al = }Al b).13-75«» 
10*31. The formula of the chloride will then be alCl ; that of alumina, o/'O ; that of 
the sulphate al^SO* ; that of alum, alK,SO\ It is sometimes convenient to write the 
formulae in this manner. 

Most compounds of aluminium are colourless. The oxide, hydrates, borates, phos- 
phates, arseniates, and silicates, are insoluble in water; most other aluminium-com- 
pounds are soluble. All of these, excepting the silicates, are soluble in, hydrochloric 
and sulphuric acid, at least if they have not been strongly ignited. 

The aqueous solutions have an add reaction, and an astringent disagreeable tasfe. 
They are not precipitated by any fi?ee acid. With sulphide of ammonium and other 
soluble sulphides, they give a white gelatinous precipitate of trihydrate of aluminium, 
the formation of which is attended with evolution of hydrosulpnuric acid gas. The 
precipitate is insoluble in excess of that reagent, but soluble in caustic potash or soda. 
With solution of potash or soda^ the same gelatinous precipitate of the hydrate is pro- 
duced, soluble in excess of the alkali, and reprecipitated by boiling with sal-ammoniac, 
or by cautious neutralisation with hydrochloric acid. — ^With ammonia^ the same preci- 
pitate, insoluble in excess. — With alkaline carbonates, the same, carbonic acid being 
given off) and not entering into combination with the alumina. — y^iih ferrocyanids of 
potassium^ a white gelatinous precipitate, after some time. — 'WiiAi phosphate ofsodium^ 
gelatinous precipitate, closely resembling the hydrate in appearance, and dissolving 
with the same facility in hycGx>chloric acid and in potash. From these solutions it is 
precipitated in the same manner as the hydrate, viz. from the hydrochloric acid solu- 
tion by ammonia, and from the potash-solution by sal-ammoniac ; it is distinguished 



ALUMINIUM (ALLOYS). 155 

from tbe hydrate hffweret, b j its insolttbility in acetic acid, and bj exhibiting certain 
reietions of i^oephoric adid {q. v.) 

Most oomponnds of aluminium, when moistened with a small quantity of nitrate of 
cMt^ and ignited before the blowpipe, exhibit a fine characteristie blue colour. This 
duncter is best exhibited by placing a small quantity of alumina, precipitated as 
aban, OD ehaieoal or platinum-foil, heating it to redness, then moistening with nitrate 
of eobiit^ and igniting again. 

Qftantitativ$ Estimation of Aluminium. — ^Aluminium is usually precipitated in the 
farm, of hydrate by excess of ammonia or carbonate of ammonium, or better by sul- 
j^de of ammonium, because an excess of ammonia or its carbonate dissolves a 
email hit peroeptible quantity of the hydrate, which can then be reprecipitated only 
bj boiliiig the liquid till every trace of ammonia is expelled. The precipitate when 
ignited leaTCS anhydrous alumina, containing 63*26 per cent, of the metaL 

Afamumum may also be yeiy oonyenienf ly separated from its solutions by boiling 
▼ith ^kosviphite of sodium; alumina is then precipitated together with sulphur, 
^vlnle siuphnrous acid is expelled, and a sodium-salt of the acid previously combined 
with the alumina remains in solution : thus, if the aluminium exists in solution as 
sulphate: 

S»0»«A1* + 3SK)^a* « A1*0* + 8S + 3S0« + 3S0<Ka«. 

The liquid should be dilute, and must be boiled till it no longer smells of sulphurous 
add; the alumina then separates quickly in a compact mass, not at all gelatinous, and 
T«7 easy to wash. The sulphur mixed with it is very easily expelled by ignition. 
(G. Chancel, Compt. rend. xlvi. 987.) 

This mode of precipitation by hyposulphite of sodium, serves also to separate 
ahuniniam tram many metals, especially from iron, the latter metal being reduced to the 
ftate of protoxide, and remaining in solution as a sodio-ferrous hyposulphite. To 
eosnre complete separation, the solution must be nearly saturated, if necessary, with 
an alkalme carbonate, diluted to a considerable extent, and mixed with the hypo- 
nlpfaite while cold ; otherwise the alumina separates too quickly, before the iron is 
completely reduced to protoxide, and then carries some of the iron down with it. 
After the separation of the alumina, the iron is re-oxidised by nitric acid and preci- 
pitated by ammonia. (ChanceL) 

Almnioium may also be separated frx)m the alkalis and alkaline earths, by precipi- 
tatbn with amnxonia or sulphide of ammonium. In thus separating it from tne 
allralme earths, however, care must be taken to protect the solution from the air, 
otherwiie carbonic acid will be absorbed by the excess of ammonia, and wiU preci- 
pitate the alkaline earth together with the alumina. From barium, aluminium is 
most easily separated l^ sulphuric acid. 

Altoys of ^iTTw«-f«wfi- Aluminium forms alloys iidth most metals. With rnnc 
and tin it unites readily, forming brittle alloys ; with cadmium it forms a malleable 
aflov. With iron, aluminium unites in all proportions, forming alloys which are 
hard, brittle, and crystallise in long needles, when the proportion of iron amounts 
to 7 « 8 per cent. Aluminium containing iron dissolves m acids jnore readily than 
the pore metal. (Deville,) 

Aluminium ^oyed with even a small proportion of silver, loses all its malleability. 
An alloy containing 6 per cent, of silver may, however, be worked like the pure 
metal, and has been used for making knife-blades. An alloy containing 3 per cent, 
of silver is used for casting ornamental articles. It has the colour and lustre of silver, 
and is not tarnished by siuphuretted hydrogen. (D evi 11 e.) 

The alloys of aluminium and copper are of especial importance. One in particular, 
ccmtainisg 10 pts. of aluminium with 90 pts. of copper, called aluminium-brome, 
pcasesaes very remarkable properties. It is a definite compound, containing Cu*Al. 
It has the colour of gold, takes a high polish, is extremely hard, and possesses a 
tenacity equal to that of the best steel ; it is also very malleable. Another alloy con- 
taining only 2 or 3 per cent, of copper, is used for casting ornamental articles of large 
(dimension, intended to be chased. Aluminium may be easily plated on copper. The 
I^es of the two metals are prepared in the usual manner, and well rubbed with sand, 
^en placed between two plates of iron, the whole being well bound together, heated 
to low redness, and then strongly pressed. (Deville.) 

Alloys of aluminium may be prepared by heating a mixture of alumina and the 
oxide of another metal, such as copper, iron, or zinc, or a mixture of alumina with 
ctrbon and the other metal in the free state, granulated copper, for instance, the 
materials being all very finely divided, and mixed in atomic proportions ; or rather 
with the carbon slightly in excess. This method, due to a foreign inventor, has been 
P«ientedin this country in the name of E. L. Benzon (1858, No. 2753). 



156 ALUMINICJM. 

Amalgamation and Gilding of Aluminium, — ^According to Cailletet, alnminiam may 
be amalgamated by the action of ammonium-amalgam or sodium-amalgam and water, 
also when it is connected with the negative pole of the voltaic battery, and dipped 
into the mercury moistened with acidulated water, or into nitrate of mercury. — 
Ch. T iss i er (Compt. rend. xlix. 56), confirms this statement respecting the amalgamation 
of aluminium in connection with the negative pole of the batteiy, and adcb, that if 
the aluminium foil is not very thick, it becomes amalgamated throughout, and vciy 
brittle. The same chemist finds that aluminium may be made to unite with mercuiy, 
merely by the use of a solution of caustic potash or soda, without the intervention of 
the batteiy. If the surface of the metal be well cleansed and moistened with the 
alkaline solution, it is immediately melted by the mercuiy and forms a shining amal- 
gam on the surface. 

The amalgam of aluminium instantly loses its lustre when exposed to the air, 
becoming heated and rapidly converted into aluminium and metallic mercury. It 
decomposes water, with evolution of hydrogen, formation of alumina^ and deposition 
of mercury. Nitric acid attacks it with violence. (Tissier.) 

To aild aluminium, 8 grammes of gold are dissolved in aqua regia, the solution is 
diluted with water and left to digest till the following day, with a slight excess of 
lime ; after being well washed, it is treated at a gentle heat with a solution of 20 gnus, 
of hyposulphate of sodium. The filtered liquid serves for the gilding of aluminium, 
without the aid of heat or electricity, the aluminium being simply immersed in it, after 
having been well cleaned by the successive use of potash, nitric add, and pure water. 
(Tissier.) 

It is somewhat difficult to solder aluminium, partly because no flux has yet been 
found that will dean the surface without attacking either the aluminium or the solder, 
partly because the surface of the aluminium is not easily melted by metals more fusiUe 
than itself. An imperfect soldering may indeed be effected by means of zinc or tin, 
but a better method, devised by M. Hulot, is to coat the aluminium with copperj by 
the electrolytic method, and then solder in the ordinary way. (Devi lie.) 

Arsenide of Alwmtnlwin* (See Ahsbnides.) 

Borlde of Almnlnlmn. Boron unites with aluminium under the same drcmn- 
stances as silicon (p. 160), and alters its properties in a similar manner. 

Bromide of Almntnlnm, Al'Br', is obtained by the action of bromine on pulveru- 
lent aluminitmi, the metal beins in excess. By sublimation, it is obtained in white, 
shining laminae, which mdt at 90^, forming a mobile liquid which boils at about 265° C. 
It is decomposed when heated in contact with the air. It dissolves in bisulphide of 
cairbon, forming a solution which fumes strongly in the air. It dissolves in water, 
and the solution evaporated in vacuo over oil of vitriol, leaves needle-shaped crystals 
containing Al'Br' + 6HK>. With bromide of potassium, it forms the double salt 
KBr.Al^r". It absorbs ammonia and hydrosulphurio acid, forming compounds which 
are decomposed by heat (R. Weber, Pogg. Ann, dii. 254.) 

CbloHde of Alnmliiliuiit Al'Cl*. — The finely divided metal heated to redness in 
a current of diy chlorine gas, takes fire and is converted into the chloride, which 
sublimes (Wohler). The compound is also produced by passing diy chlorine over 
an ignited mixture of alumina and charcoal : and this is the method adopted for pre- 
paring it. Hydrate of aluminium precipitated from a hot solution of alum by an 
alkaline carbonate is made up into small pellets with oil and lampblack, and the mix- 
ture is strongly ignited in a crucible : the oil is then decomposed and an intimate 
mixture of alumina and charcoal remains. This is introduced into a porcdain tabe 
or tubulated earthen retort placed in a fiimace, and connected at one end with an 
apparatus for evolving chlorine, and at the other with a diy receiver. On raisins the 
heat to bright redness, and passing chlorine through the apparatus, cMoride of 
aluminium is formed and condenses in a solid mass in the receiver. 

A similar process is adopted in preparing the compound on the large scale. Alu- 
mina or clay is mixed with cool, pitch, tar, resin, or any organic substance that will 
decompose by heat and leave a considerable quantity of charcoal, and the mixtmv, 
after being well caldned, is heated to redness in a cylinder of earthenware or cast 
iron, through which a current of dry chlorine is made to pass. The vapours of 
chloride of aluminium pass into a condensing chamber lined with plates of glazed 
earthenware, on which the chloride collects in the solid state. If day containing 
a considerable proportion of iron is used in the preparation, it must first, after 
ignition with carbonaceous matter — whereby the iron is reduced to the metallic 
state — be treated with a dilute acid to dissolve out the iron, then washed and dried. 

Chloride of aluminium is a transparent waxy substance having a crystalline stmc- 
ture like talc. It is colourless when pure, but generally exhibits a yellow colour, dns 



ALUMINIUM (CHLORIDE— OXIDE 15Y 

periiaps to the presenoe of iron. It is ^ible in lai^e masses, and according to 
liebig, boils at aoont 180^ C. A small quantify volatilises immediately when heated. 
It iiimefl in the air, and smeHs of hydrochloric add. It is decomposed at a heat 
beknr redness by potassium or sodium, aluminium being set free. When it is dis- 
tilled with sulphuric anhydride, sulphurous anhydride and chlorine are giyen off and 
ndphale of aluminum remains. (H. Bose.) 

2Al«a« + 6S0* - Al\SO*y + 3S0« + 6CJL 

Chloride of aluminium is yery deliquescent^ and dissolves readily in water. The 
Bolutioo left to evaporate in a warm diy place, fields the hydrated chloride APCl'. 
6H^ in six-aided prisms. The same solution is formed by dissolving alumina in 
hydrochloric acid. The anhydrous chloride cannot be obtained by heating the 
hvdrated chloride, because the latter is thereby resolved into alumina and hydro* 
chloric acid. 

Chloride of Aluminium and Sodiumy NaCLAl'Cl', is obtained by fusing together 
the component chlorides in the proper proportions ; by passing the vapour of chloride 
of aluminium over iused chloride of sodium ; or by adding the proper quantity of 
chloride of sodium to the mixture of alumina or aluminiferous matter and carbon used 
for the preparation of chloride of aluminium, and igniting the mass in an atmosphere 
oi dry chlorine or hydrochloric acid, and condensing the vapour in the same manner as 
that of the simple chloride. It is a cxystalline mass which melts at 200^ C, and 
oyBtaDiseB on cooling. It is perfectly colourless when pure, much less deliquescent 
than chloride of aluminium, and bein^ quite fixed at ordinary temperatures, may be 
handled with fiuality. These qualities render it much more convenient than the 
simple chloride for the preparation of aluminium. When ignited with sodium, it 
yie&OB nearly the theoretical quantity (14 p. c.) of aluminium. 



If Al'F', is produced by the action of gaseous fluoride of 
silicon on aluminium. The product is at first mixed with reduced silicon, but this 
may be easily removed by digestion with a mixture of hydrofiuoric and nitric acids. 
Fluoride of aluminium then remains in a colourless mass of cubical crystals, which 
have but little refracting power. It volatilises at a bright red heat, is insoluble in 
water, and resists the action of all acids. (Deville, Compt. rend«xliii. 49.) 

fluoride of Aluminium and Potassium, SKF.AI'F', is obtained as a gelatinous pre- 
cipitate by Chopping a solution of fluoride of aluminium into a solution of fluoride of 
potaasium, till the hitter remains in only' slight excess. A precipitate of similar cha- 
racter, but consisting of 2KF.A1'F*, is obtained by stirring up a solution of fluoride of 
ahimininni with a quantity of fluoride of potassium not quite sufficient for complete 
saturation. Both precipitates dry up to white powders, and give off the whole of 
their floorine as hydrofluoric acid when heated with sulphuric acid. (Berzelius.) 

Fluoride of Aluminium and Sodium^ 8NaF.Al^. — ^Found native as Cryolite^ and 
prepared artificially by pouring hydrofluoric acid in excess on a mixture of calcined 
alumina and carbonate of sodium in the proportions indicated by the formula, then 
diyii^ and iusing the mixture. Ciyolite belongs to the quadratic or dimetric sys- 
tem. It is colourless and transparent^ softer than felspar, of speciflc ^vity 2*96, 
melts below a red heat, and forms an opaque glass on cooling : so likewise does the 
artificially prepared salt. It is found in large quantity at Evigtok in Greenland, but 
has not hitherto been discovered in any other locality. It is used, as already 
described, for the preparation of aluminium, and also in Germany for the manufacture 
of soda for the use of soap-boilers. 



of Jllufnlntnm, Al^*, is obtained by heating the metal with iodine or iodide 
of silver in sealed tubes. After repeated sublimation over metallic aluminium, it 
forms a snow-white crystalline mass, which melts at about 185° C, and boils at a tem- 
perature above the boiling-point of mercury. It resembles the bromide in most of its 
propertiea. With water it forms the hydrate A1^'.6HK), which may also be obtained 
uj dissolving hydrated alumina in h^driodic acid. It forms double salts with the 
a&aline iodides, and absorbs ammonia, forming a snow-white powder. It does not 
appear to combine with hydrosulphuric acid, ^eber, Pogg. Ann, cvii. 264.) 

OxlAe of ^i»»i»t«««w»- Alumina, Al^O', or APO^. — This, which is the onlv 
known oxide of aluminium, is formed by the direct combination of the metal with. 
oxygen. Aluminium in the massive state does not oxidise, even at a strong red heat ; 
but in the state of powder it bums brightly when heated to redness in the air or in 
oxygen gas, and is converted into alumina, 53 '3 pts. of the metal taking up 46*69 
pts. of oxygen to form 100 pts. of oxygen. The atomic constitution of alumina 
cannot be determined from this or any other direct experiment, because there is no 
other oxide of aluminium with which to compare it ; but it is inferred to be a sesqui- 



158 ALUMINIUM (OXIDE). 

oxide, because it is isomoiphous with the sesqnioxides of iron and chromium, and is 
capable of replacing those oxides in combination in any proportion. 

AliiTninji. occiirs native, and very nearly pure, in the form of corundum^ varieties of 
which, difitingoished chiefly bv their colour, are the $apphire^ 't'^i oriental topaz, 
oriental ameihi/st, &c. The colourless variety is called hyaline corundum. The crys- 
talline forms of these gems all belong to the rhombohedral or hexagonal system, Uie 
primaiy form being a rather acute rhombohedron. Ahimina in the crystalline state 
has a specific gravity of about 3*9, and is, next to the diamond, the hardest sub- 
stance known. An opaque variety of corundum called emery ^ wltieh has a brown- 
red colour, arising from oxide of iron, is much used in the state of powder for polish- 
ing glass and precious stones. 

Alumina is prepared artificially : 1. By precipitating a boUing solution of common 
alum (sulphate of aluminium and potassiimi), free from iron, with carbonate of am- 
monium, washing the precipitate with water, and igniting it to expel the combined 
water. — 2. By igniting sulphate of aluminium or ammonia-alum. In the former case, 
sulphuric anhydride is given off ; in the latter, that compound, together with sulphate 
of ammonium, and alumina remains : 

A1*.3S0* r, A1*0« + 3S0» 
and 2(A1«.NH*.2S0») «= A1*0« + (NH«)«.SO* + 8S0«. 

Alumina thus prepared is apt however to retain a small quantity of sulphuiie acid, 
and if the original salt contained iron, the whole of that impurity remains in the 
residue. — 3.* By digesting clays, felspathic rocks, or other minerals containing alumina 
in a strong solution of caustic potash or soda, assisting the action, if necessary, by 
boiling under pressure, or by heating the same minerals with kelp or soda-ash in a 
reverberatory furnace, and lixiviating the fused product with water. A solution of 
aluminate of potassium or sodixmi is thus obtained, a silico-aluminate of the alkali 
generally remaining imdissolved — and the alumina may be precipitated from the solu- 
tion as a hydrate by passing carbonic acid through the liquid ; by treating it with 
acid carbonate of sodium, or with neutral or acid carbonate of ammonium ; by saturating 
with an acid (using by preference the last vapours of hydrochloric acid evolved in the 
manufacture of that compound) ; by treating it with chloride of ammonium, where- 
upon, ammonia isitvolvea, chloride of potassium or sodium remains in solution, and 
alumina is precipitated ; or by mixing the solution of the alkaline aluminate with 
chloride of aluminium, the result being the precipitation of the alumina from both 
compounds : 

A1^>0» + A1«C1« « A1*0« + 3Ka 
* — I — 
Aluminate of 
poUssium. 

4. Bv mixing cryolite with rather more than f of its weight of quick lime, adding a 
small quantity of water to slake the lime, then a larger quantity, and heating the 
mixture by a current of steam. The products of this operation are fluoride of calcium 
and aluminate of sodium : 

Al*Na>F« + 3CaK) = 6CaF + Al^a«0» 



Cryolite. Aluminate 

of sodium. 

The aluminate of sodium is decanted from the heavy deposit of fluoride of calcium, and 
decomposed by carbonic acid as above. If any insoluble aluminate of calcium should 
be formed, it may be decomposed by digestion with carbonate of sodium. (Deville.) 
5. The slag obtained in the preparation of aluminium frx)m chloride of aluminium 
and sodium, with fluor-spar or dyolite as a flux (p. 150), contains about 40 per 
cent of fluoride of aluminium, together with soluble chlorides ; and the residue of the 
extraction of sodium by Beville's process (see Sodium), which consists in igniting a 
mixture of carbonate of soditmi, carbonaceous matter and chalk, contains about 14*5 p. c. 
carbonate of sodium, 8'3 p. c caustic soda^ and 29*8 p. c. carbonate of calcium. Now, by 
heating to redness a mixture of 6 or 6 pts. of the sodium-residue with 1 pt. of the 
aluminium-slag, freed by washing from the soluble constituents, and lixiviating 
the product after cooling, a solution of aluminate of sodium is obtained which may be 
decomposed by carbonic acid as above. (D ev il le.) 

Alumina prepared by an^ of the preceding processes contains iron. From this it 
may be purified by dissolving it in caustic alkali and precipitating the iron* by a 
stream of sulphuretted hydrocen (Deville). It may then be reprecipitated by car- 
bonic acid. The alumina tibus precipitated always contains a certain quantity of 

* This process, tlie Inrention ofM. Lp Chateller of Paris, is patented in thii coancxy tu the Mme of 
H. F. Newtoo, 1858, No. 1988, and 18A'j, No. 957. 



ALUMINIUM (OXIDES AND HYDRATES). 159 

ilkalme earbonftte, irhich cannot he removed by washing with water. It may, how- 
erer, be separated by digestion, with the aid of heat, in a small quantity of dilute 
hydrochloric or nitric add, or by digestion with chloride of aluminium in excess. 
(LeC ha teller.) 

Aitifldally prepared alumina is white, and if it has been exposed only to a moderato 
led heatk is Texy light and soft to the touch ; but after strong ignition, it cakes 
together, becomes so hard as scarcely to be scratched with a file, and emits sparks 
vhen stroek with steeL According to M. Bose (Pogg. Ann. Ixxiv. 430), the specific 
carity of alumina ignited over a spirit-lamp is between 3*87 and 3*90 ; after six 
Souls' ignition in an air fdmace, it is between 3*726 and Z'76 ; and after ignition in a 
ponxlain furnace, 3*999, which agrees Teiy nearly with that of native corundum. 

Alumina is infusible at all temperatures below that of the oxy-hydrogen flame ; but 
at that degree of heat» it melts into transparent globules which assume a crystalline 
glw c lur e on cooling. If a small quantity of chromate of potassium be added before 
foaon, the melted alumina on cooling retains a deep red colour, and resembles the 
DStaral ruby. When a mixture of 1 pt. of alumina and 3 or 4 pts. of anhydrous 
borax is exposed for a considerable time to the hi^h temperature of a porcelain fur- 
nace, the ahimina dissolves in the fused borax, and as the borax is volatilised by the 
heat, remains in crystals resembling corundum ; in this case also, the addition of a 
Toy small quantity of chromate of potassium causes the crystals to exhibit the colour 
of the ruby. This method is applicable to the artificial formation of a great number 
of crystalhsed minerals. (Ebelmeo, Ann. Ch. Phys. [3] xxii. 211.) 

Aiumina is not decompoeible by heat alone. Potassium at a white heat deoxidises 
it partially, forming an alloy of potassium and aluminium which decomposes water. 
It IS not decomposed by chlorine at any temperature, unless it be mixed with charcoal, 
in irhich ease a chloride of aluminium is produced. 

Anhydrous alumina is perfectly insoluble in water. After strong ignition, it is like- 
vise insohible in most acids, concentrated hydrochloric or sulphuric acid being alone 
able to dissolve it. In the crystallised state it is insoluble in all acids. It may, how- 
erer, always be rendered soluble by fusion with hydrate of potassium or sodium. 

Htdra-TES of ALxmiBiiult, or of Alttuina. These compounds are three in num- 
ber, viz.: 

Monohydrate .... A1«H0* or APO^MO. 

Dihydrate Al^HW „ AP0*.2H0. 

Trihydrate Aim'G* „ APO».ZHO. 

The numohydrate is found native as Diasporey a mineral which forms translucent 
granular masses of specific gravity 3*43, and crumbles to powder when heated, but 
does not give off the whole of it« water below 360^ C. It is insoluble in water, and 
eren in boiling hydrochloric acid. 

The irikydraU is the ordinary gelatinous precipitate, obtained by treating solutions 
01 aluminium-salts, alum, for example, with ammonia or alkaline carbonates ; it is also 
thrown down from the same solutions by sulphide of ammonium, the aluminium not 
entering into combination with the sulphur. When dried at a moderate heat, it forms 
a soft finable mass, which adheres to the tongue and forms a stiff paste with water, 
bak does not dissolve in that liquid. At a strong red heat, it parts with its water, and 
nndezgoes a very great contraction of volume. It dissolves with great facility in adds, 
and in the fixed caustic alkalis. When a solution of alumina in caustic potash is 
exposed to the air, the potash absorbs carbonic acid, and the trihydrate of aluminium 
is then deposited in white crystals which are but sparingly soluble in acids. 

The trihydrate of aluminium has a very powerful attraction for organic matter, and 
when digested in solutions of vegetable colouring matter, combines with aod carries 
down the eolouring matter, whidi is thus removed entirely from the liquid if the 
alumina is in sufficient quantity. The pigments called lakes are compounds of this 
nature. The fibre of cotton impregnated with alumina acquires the same power of 
retaining colouring matters ; hence the great use of aluminous salts as mordants to 
produce fast colours. (Sec Dyeino.) 

Trihvdrate of aluminium occurs native as GibbnUf a stalactitic, translucent, fibrous 
minenJ, easily dissolved by acids. 

JHkvdraU of Aluminium, A1«H^0», or A1<0«,2H»0.— When a dilute solution of diace- 
tate of aluminium is exposed for several days to a temperature of 1 00^ C. in a close vessel, 
the acetic add appears to be set free, although no precipitation of alumina takes place. 
Ilie liquid acquires the taste of acetic acid, and if afterwards boiled in an open vessel, 
gives off nearly the whole of its acetic acid, the alumina nevertheless remaining in 
sohition. This solution is coagulated by mineral acids and by most vegetable acids, 
by alkalis, and by decoctions of dye-woods. The alumina contained in it is, however, 
no longer capable of acting as a mordant. Its coagulum with dyed-woods has the 



160 ALUMO-CALCITK-ALUM-SLATE. 

colour of the inf^ion, but is tnuuilucent and totally different from the dense opaqiiA 
lakes which ordinary alumina fomm with the same colouring matters. On erapora- 
ting the solution to dryness at 100^ C. the alumina remains in the form of dihy- 
drate, retaining only a trace of acetic acid. In this state, it is insoluble in the stronger 
adds, but soluble in acetic acid, proTided it has not been previously coagulated in Sie 
manner just mentioned. Boiling potash converts it into the trihydrate (Walter 
Grum, Chem. Soc. Qu. J. yi. 225). The dihydrate is said to occur native at B^aux 
(B er t h ie r, Schw. J. xxxiv. 164). Hydrargyllite^ a mineral occurring in regularsix-sided 
prisms is also a hydrate of alummium, but its exact composition is not known. 
(G. Rose, Pogg. Ann. xlviii. 664; L 656.) 

Aluminates. — ^The hydrogen in trihydrate of aluminium, maybe replaced by 
an equivalent quantity of various metals ; such compounds are called aluminaUa. Ac- 
cording to Fr^my, a solution of alumina in potash slowly evaporated [out of oootMt 
of air ? ] deposits granular ciystals of aluminate of potassium, Al*EO*, or Al^O*, K^. 
Similar compounds occur native; thus SpineUia an iduminateof magnesium, Al'MgO'; 
Gahniiej an aluminate of zinc, Al'ZnO^. 

Osyren-Salts of Almnlniuin. — The general characters of these salts have ali^y 
been described (p. 164). The most important of them are the sulphate A1^(S0* » 
with its double sulphates, especially common alum, the sulphate of aluminium and 
potassium, and the silicates and double silicates. [For the detailed descriptions of 
these salts, see the several Acids.] 

Fbosplilde of Alnmlnliiin. — Obtained by heating pulverulent aluminium to red- 
ness in phosphorus vapour. It is a dark grey mass, which acquires metallic lustre bj 
burnishing, and is decomposed by water, with evolution of non-spontaneously in- 
flammable phosphoretted hydrogen. (W o h 1 e r.) 

SUicido of Almninlmn* — Aluminium combines readily, and in all proportioDa, 
with silicon. When strongly heated in contact with any sihcious substances, such as 
glass or porcelain, it reduces the silicon and unites with it. Nevertheless aluminium 
may be fused in glass or earthen vessels, without undergoing the slightest alteratiooi, 
provided no flux be used, because it does not then come into intimate contact with the 
substance of the vessel ; but the addition of a flux produces instant decomposition. 
The properties of the compoimd vair with the proportion of silicon. An alloy con- 
taining 10*3 per cent, of silicon, called east aluminium {fonte cTaluTninium) is grey 
and very brittle. A compound coiitaining 70 per cent, silicon, still exhibits me^ic 
properties. All the compounds of aluminium and silicon are much more easily 
altered by exposure to the air, or by the action of '*ids and alkalies, than either pore 
aluminium or pure silicon. 

Selenide of Aluinlntmn, Al^Se', or ^iSe'— I'roduoed with incandescence when 
aluminium is heated in selenium vapour. It is a black powder, which acquires a 
dark metallic lustre by burnishing, and is readily decomposed by water or by a moist 
atmosphere, with formation of alumina and hydroselenic acid. 

Bulpliide of Alrnnlntwin, A1*S', or APS*. — Sulphur may be distilled over alu- 
minium without combining with it ; but when thrown upon the red-hot metal, it is ab- 
sorbed with vivid incandescence (W o h le r). The sulphide may be prepared by passing 
the vapour of disulphide of carbon over red-hot alumina. It is fusible, decomposes 
water at ordinary temperatures, yielding hydrate of aluminium and hydrosulphuric add, 
and thus perhaps contributes to the formation of natural sulphur springs. (Fr^my.) 

AXiVMO-CAKCira. A mineral from Erbenstock, in the Saxon Harz, having 
the appearance of opal. Specific gravity 2*1 to 2*2, scarcely harder than mica. Con- 
tains, according to Kersten's analysis, 6*26 per cent, lime, 2*23 alumina^ and 40 
water. It is probably a mere residue of decomposition. 

AXiUM-SASTB.' A massive variety of aluminous schist, found in the neighbour- 
hood of tertiary lignites, as in several parts of the valley of the Oder, on the Rhine, 
in Ficardy, and other localities. It has not a distinct slaty structure, but is a soft, 
friable, usually dark brown mass. 

A&UBK-4IZJLTB. A clay slate, containing bitumen and sulphide of iron, gene- 
rally found in the transition-strata, but sometimes in more recent formations. It is 
found in the north of England and in Scotland, in Scandinavia, in the Han, in the 
Ural, the Vosges, the lower Rhine, and other localities. There are two varieties of it, 
-Hz. 1. Common, This mineral occurs both massive and in insulated balls of a greyish- 
black colour, dull lustre, straight slaty fracture, tubular fragments, streak coloured liko 
itself Though soft, it is not very brittle. Effloresces, acquiring the taste of alum. 

2. Glossy Alum-slate, A massive mineral of a bluish-black colour. The rents dis- 
play a yanety of lively purple tints. It has a semi-metallic lustre in the fraetnrey 



ALUNITE — AMARINE. 161 

•wJiielk 18 stnighty alatj, or nndnlating. There ifl a soft Tariety of it, approaching in 
ipppuaiiee to slate day. By eszposure to air its thidmess is prodigioosiy augmented 
tj the formation of a saline effloresence, which separates its thinnest pL&tes. These 
aftcnnuds exfoliate in brittle sections^ causing entire disintegration. 

ji&UfllTJif or AX1IJIK-8TOVSL A basie sulphate of aluminium and potas- 

finm, A1*K:2S0* + 3A1»H*0» or ^^ | 4S0« + 3(A1^0".3H«0), found chiefly in vol- 

euoc districts, tiz. at Tolfia^ near Ciyita Yecchia, at Solfatara, near Naples, at Puy do 
Oaicey, in AuTeigne, and other localities. Used for the preparation of Roman alum. 
It is either massive or crystallised ; the former is usually greyish white, and some- 
times red. It is translacent, easily frangible, scratches calcareous spar, but is scratched 
by floor spar. The crystals are genendly situated in the cavities of the massive sub- 
alanee, they are small, shining, sometimes externally brownish, their form is an obtuse 
ihomboid, variously modified. The crystals have the composition above given : the 
Tsriety contains in addition a considerable quantity of silica. 

Native sulphate of aluminium. (See Sulfhatbs.) 

A combination of mercoiy with another metaL (See Mrrcubt.) 

r. The process of extracting gold and silver from their ores 
by difisohing them out with mercuiy. (See Gou> and Silvbb.) 

flWflTiTC ACIB (fr^m dtftaxSs, 8ofif on account of its feeble acid reaction.) — A 
prodact of the decomposition of caffeine by chlorine ^see Caffbimb), discovered by 
Boehleder. Its composition is that of alloxantin, having the whole of its hydrogen 
replaced by methyl : O«(CH*)*N*0' + BPO. 

It forms transparent colourless crystals, which do not give oflf their water at 100° C. 
At a higher temperature, it melts and volatilises, leaving scarcely a trace of charcoal, 
but giving off ammonia, and yielding an oil and crystallised body. It slightiy reddens 
litmus, and raoduoes red stams on the skin, imparting to it an unpleasant odour, like 
allozantin. It reduces silver-salts like alloxantin. Nitric acid converts it into a ciys- 
taUine substance. When exposed to vapour of ammonia, it gradually assumes a deep 
Tiolet colour, and forms a compound which dissolves in water with the colour of 
mmexide : the solution yields a crystalline body, to which Boehleder gives the name 
matxoin. With baryta, potssh, and soda, it forms compounds of a deep violet 
eokiir. 



An organic base obtained by Letellier from the fly agaric {Agari'^ 
CH9 nvxarius, or Amanita mvscaria), and from. Affarictts btUbasuSt and supposed by him 
to be the poisonous principle of these agarics. According to Apaiger and Wiggers, on 
the other hand, the fl^ agaric contains a peculiar acid (muscaric acid), as well as a 
base, and it is to tlie acid that the poisonous aetion is due. (Handw. d. Chem, 2** Aufl. 
L 663.) 

AXABZVS. CH'^N*. Senzoline, Pikramiiij Hydru/re cTasobenzailine, — (L a u r n t , 
Ann. Ch. Phys. [Z] L 306 ; Fo wnes, Ann. Ch. Pharm. liv. 363 ; Gossmann, Ann. 
GL Pharm. xdiil 329 ; Gm. xii. 193.) 

This compound was discovered simultaneously by Laurent and by Fownes. It is 
isomeric wiui hydrobenzamide, from which it is generally prepared. 1. When hydro- 
benzamide is heated for three or four hours to 120° — 130° C, the vitreous mass, when 
eool, dissolYed in boiling alcohol, and excess of hydrochloric acid added, white crystals 
of faydrochlorate ofamarine separate out (Sertagnini). — 2. Hydrobenzamide is 
boiled for some hours with caustic potash, the resulting resin dissolved in dilute sul- 
pfamie add, the solution precipitated by ammonia, and the precipitate washed with 
water and crystallised from hot alcohol (Fownes). — 3. A solution of bitter-almond 
Ml in alcohol, when saturated with gaseous ammonia, solidifies in 24 — 48 hours into 
a crystalline mass. This is boiled with water, and saturated while hot with hydro- 
chloric acid, when an oily substance separates out, together with crystals of a peculiar 
add (see Bkkzimic Aced). The hot solution is decanted, and the residue again 
otiadted with boiling water, until all the hydrochlorate of amarine is dissolved out. 
The solution is precipitated by ammonia ; and the precipitate is washed, dissolved in 
boiling alcohol, mixed with hydrochloric add, and reprecipitated by ammonia : pure 
amarine then crystallises out (Laurent). — 4. When the dry compound of bitterv 
almond oil and add sulphite of ammonium is heated in a large retort to 180° — 200° 
with 3 or 4 times its volume of slaked lime, amarine and lophine distil over. The 
fiirmer, which collects partly in the receiver, partly in the lower part of the neck of 
the retort, is dissolved m alcohol, and purified as in the former process. (Gossmann.) 

Amarine crystallisee from alcohol in shinins six-sided prisms. It melts at 100° C. 
and solidifieB to a vitreous mass on cooling : "^en heated more strongly, it volatilises 

Vol. L M 



162 AMARONE. 

almost completely, ammonia being evolred : an oil smjelling like benzol distilfl over, and 
a sublimate collects in the neck of the retort, which Fownes calls wrobensdliney and 
which, according to Laurent, is identical with lophine. Amarine is inodorous, taste- 
less at first, but afterwards slightly bitter. It is insoluble in water, solnble in al- 
cohol and ether ; the alcoholic solution is strongly alkaline. Amaiine becomes stronslj 
electrical by friction. Unlike its isomer, hydrobenzamide, it exerts a poisonous action 
on animals. 

Amarine is readily attacked by bromine, hydrobromate of amarine being formed 
together with a resinous mass. When it is boiled with a mixture of sulphuric and 
chromic acids and water, a brisk action takes place, and benzoic acid is abundantly 
formed. Nitric acid acts similarly, but less yioiently. Fused potash does not attack 
it, save at a very strong heat 

Amarine-salta are formed by the direct combination of amarine with adds. Witii 
the exception of the acetate, they are all but slightly soluble. The hydrochloTaie^ 
C^*H*"N^HC1, crystallises in small shining needles, which effloresce in Tacua, or when 
heated to 100^. When hydrochloric acid is poured upon amarine, a colourless oil is 
formed, which gradually solidifies on drying, and may be drawn into threads when 
heated. It distils without decomposition, passing oyer as an oil which solidifies to a 
transparent mass. It is soluble in alcohol and ether. The ohlcroplaiijiate separates in 
yellow needles, when boiling alcoholic solutions of the hydrochlorate and of didiloiide 
of platinum are mixed together. Fownes found in it 19*8 per cent pUi-tTinm ; the 
formula PtCl.'C''H''N' requires 19*68 per cent. The aidphate cirstallises from an add 
solution in small colourless prisms resembling oxalic acid. The nitrate is obtained 
by treating amarine with hot dilute nitric acid ; a soft, amozphous mass is produced, 
which dissolves in boiling water, and on cooling deposits smaU crystals, which remain 
unaltered in vacuo. The acetate is veiy soluble, and yields on evaporation a gummy 
non-ciystalline mass. 

Diethylamarine, C"(C2H*)2H"N«. — Amarine heated with iodide of ethyl, 
yields a crystalline salt, which is the hydriodate of this base. The base itself is ob> 
tained by distUling the hydriodate with potash. It crystallises readily in oblique 
rhombic prisms, is nearly insoluble in water, but dissolves readily in alcohol and ether. 
It melts between 110° and 115^ C. but does not solidify again till cooled down to 
70^. At a stronger heat it decomposes. The hydrochlorate crystallises in oblique 
rhombic prisms. The platinum-saltf is a yellow powder, insoluble in water and in 
ether, but soluble in alcohol, from which it crystallises in small prisms. (Borodine, 
Ann. Ch. Pharm. ex. 78.) 

Diethylamarine treated with iodide of ethyl yields the hydriodate of another orstal- 
line base, probably triethylamaiine, which howeyer has not yet been analysed, and 
this base again treated with iodide of etliyl, yields a third crystalline base. (B o r o d i n e.) 

Trinitr amarine, C"H'*(NO«)«N« (Bertagnini, Ann. Ch. Pharm. IxxW 275).— 
This compound is formed from trinitrohydrobenzamide, with which it is isomeric, just 
as amarine is from hydrobenzamide. Trinitrohydrobenzamide is boiled with 1 toL 
caustic potash of 46^ Baum6, and 60 vols, water; the resulting brown resinous 
mass (which becomes brittle on cooling) is dissolved in hot alcohol ; a little ether 
added ; and the solution is predpitated by hydrochloric acid. The hydrochlorate is 
redissolved in alcohol, alcoholic ammonia added to the solution, and the predpitated 
trinitramarine is washed with water, and recrystallised from alcohol Trinitramarine 
is also obtained by heating trinitrohydrobenzamide in an oil-bath to 126^ — 130° C. 

It crystallises slowly from its alcoholic solution in white hard nodules. It melts in 
boiling water, and dissolves slightly, forming an alkaline solution. It is soluble 
in boiling alcohol or ether, most readily in a mixture of the two. A hot satur&ted 
solution deposits it on cooling as an amorphous powder. 

Its salts are but sHglitly soluble in wat«r. The hydrochlorate separates in small 
shining needles when hydrochloric acid is added to an alcoholic solution of trinitra- 
marine ; it is nearly insoluble in cold, slightly soluble in boiling alcohoL The nitrate 
crystallises in needles from boUing alcohoL An alcoholic solution of trinitramarine 
forms with dicMoride of platinum^ smaU, yellow, heavy nodtdes insoluble in alcobd; 
and with mercuric chloride, a somewhat crystalline predpitate.— F. T. C. 



C'«H"N (Laurent, Eev. Scient. xviii. 207, &c).— A compound 
formed by the dry distillation of azobenzoyl, benzoylazotide, or hydrobenzamide. The 
sublimate obtained by heating benzoylazotide is washed with ether, and then freed 
from lophine by boiling in alcohol containing hydrochloric acid ; the residue is washed 
with alcohol, dried, crystallised from boiling rock-oil, and washed with ether. It forms 
small, colourlt ss, inodorous needles, which melt at 233° C, and solidL^ to a radiated 
mass on cooling. It is insoluble in water, slighUy soluble in alcohol, more readily 
in ether. It dissolves in cold sulphuric acid, with a fine blood-red colour, which di*- 



AMARYL— AMBER 163 

a|ipean on idditioii of water, the amarone separating ont. It dissolres sparingly in 
hot nftrie add, and ciTstallises unchanged on cooling. It is not decomposed by bouing 
vitli alooholie potash. -F. T. C. 



A name given by Laurent to a substance which he afterwards found 
to be impure nitrate of lophine. 



ByjL with Sbtthbin-bittbb or Ficbo-ebtthbin, 

SjJL with ISiAMZDB. 

Compact Felspab. 

B. A variety of orthoclase, coloured green by eopper. It is 
finnd chiefly in the shores of Lake Hmen in Bussia, also in Norway. It is used fbv 
making trinkets. 

mtlM. Succin, EUcirum, Ambra flava^ Bematein, AgUteiii, gdbea Erdhare. — 
A hard brittle tasteless substance, sometimes perfectly transparent, but mostly semi- 
tranqnrent or opaque, and of a glassy surface | it is found of all colours but chiefly 
yellow or orange, and often contuns leaves or insects. Its specific gravity varies from 
I'Otto to 1*070 ; hardness 2 to 2*5 ; slightly brittle ; fracture conchoid^. It is susceptible 
of a fine polish, and becomes cdectric by friction : hence the word electricity (from 
4\iicr^, amber). When rubbed or heated, it emits a peculiar smelL It is insoluble 
in water and alcohol, though the latter, when hip;hly rectified, extracts a reddish colour 
from it It is soluble in sulphuric acid, to which it imparts a reddish purple colour, 
intiareprecipitatod on addition of water. No other add dissolves it, nor is it soluble 
in esBential or expressed oils without decomposition ; but pure alkalis dissolve it. 

Aceoidinff to Benelius, amber contains a volatile oil, succinic acid, and two resins 
aoluUein uoohol and ether. According to Schroetter and Forchammer, amber when 
decriTed by ether of all its sohible constituents^ possesses the composition of camphor 

The diy distillatioii of amber presents three distinct phases, characterised by the 
nature of the products. When submitted to the action of heat, amber softens, fdses, 
intanMsees considerably, and gives oiS succinic acid, water, oil, and a combustible 
g»L If now the residue {Coiopkony of Amber) be more strongly heated, a colourless 
oil passes over. Lastly, when the residue is completely charred, and the heat is raised 
tin the glass nearly fuses, a yellow substance sublimes of the consistence of wax. 

The oil thns porodaced is a mixture of several hydrocarbons. The more volatile portion 
wnich passes over between 110° and 260'-' C, is decomposed in the cold by sulphuric acid, 
andooloQied bhie by hydrochloric acid, and by chlorine ; the less volatile portion produced 
\jj a heat approaching redness, begins to boil at 140°, and then rises to 300° ; sulphu- 
ric and hydrochloric add and duorine do not al£er it. According to Pelletier and 
Walter (Ann. Ch. Phys. [3] ix. 89), these oils present the composition of oil of 
tmpentine, containing 88*7 percent of carbon, and 11*3 of hydrogen. 

The erade mixture of the two oils is used in pharmacy under the name of oil of 
amber, being in fact one of the constituents of Eau de LiicCf a preparation sometimes 
used as a remedy for the bites of venomous animals, and consisting of 1 part of oil 
of unber, 24 of iJeohol, and 96 of caustic ammonia. 

The wax-like solid which passes over in the diy distillation of amber is a mixture 
cf oil, yellow matter, a white crystalline substance, and a brown bituminous substance; 
these bodies are separated bv treatment with ether and alcohol. The yellow matter 
tffam to be identi<»l with chiysene (C 94*4, H 6*8). It is scarcely soluble in 
boiling alcohol and ether, is pulverulent rather than crystalline, and requires for 
fasion a temperature of 240° C. 

The white matter (suocisterene) is tasteless and inodorous, it is scarcely soluble in 
cold alcohol, but little soluble in ether, but more soluble than the yellow matter; it 
bmHs between 160° and 162°, and distils above 300°. Nitric add resinises it 
in the oold. It contains, according to Pelletier and Walter, 96*6 per cent, of carbon 
■nd 6*6 of hydrogen. 

When amber is treated with faming nitric add, a resin is formed (artificial musk) 
whidi ii soluble in an excess of nitric acid, and contains C^H^'NH)'. 

When powdered amber is distilled with a strong solution of potash, a watery liquid 
paasea over, together with a white substance which exhibits all the properties of com- 
■on camphor. 

Amber ooeors plentifully in regular veins in some parts of Prussia, espedally between 
ftjhnnicken and Grosa-Hubenicken. In East and West Prussia there is scarcely a 
tiSa^ where it has not been fbund and thence it extends into Mecklenburg and Hol- 
itaan and in fact along the whole Baltic plain. It has likewise been found in southern 
Germany, in France, Italy, Spain, Sweden and Norway ; also on the shores of the 

x2 



164 AMBERGRIS — AMBLYGONITE. 

Caspian, in Siberia, KamtschatJui, China, Hindoostan, Madagascar, North AmerieA 
and Greenland. In Britain it is thrown out by the sea on the shores of Norfolk, Suffiilk 
and Essex, and has also been found in the sands at Kensington. In the Boyal Cabinet 
at Berlin there is a mass of 18 lbs. weight, supposed to be the largest ever found. 

Haiiy has pointed out the following characters by which amber may be distin- 
Kuished from mellite and copal, the bodies which most closely i«semble it. Hellite 
IS infusible by heat; a bit of copal heated at the end of a knife takes fire, melting 
into drops, which flatten as they fall; whereas amber bums with spitting and frothing^ 
and when its liquefied particles drop, they rebound from the plane which reoeiTes them. 

Various frauds are practised with this substance. Neumann states as the common 
practices of workmen the two following : The one consists in surrounding the amber 
with sand in an iron pot, and cementing it with a gradual fire for forty hours, some 
0mall pieces placed near the sides of the vessel being occasionally taken out forjudging 
of the effect of the operation. The second method, which he says is that most generally 
practiced, is to digest and boil the amber about twenty hours with rapeseed oil, l^ 
which it is rendered both dear and hard. 

The chemical properties and mode of occurrence of amber leave no doubt of itj 
being the produce of extinct coniferse. It has been found encrusting or penetrating 
fossil wood exactly like resin at the present day, and enclosing the cones and leaves of 
the trees. Numerous insects, the inhabitants of these ancient forests have been em- 
balmed in it. To the tree which principally produced it, Goppert gives the name of 
Pinites sticcini/erj but there was probably more than one species. Amber is often 
stated to occur in the brown coal beds of Northern Germany, but Goppert stat^ that 
he knows of no instance of this, the substance found in those beds being retinite. 
(Handw. d. Chem. 2te Aufl. ii. 972; Dana, ii. 466 ; Gerh. iv. 394). 

ABEBSROKZS. {Ambra^ Ambra grisea), is found in the sea, near the coasts of 
various tropical countries ; and has also been taken out of the intestines of the sperma- 
ceti whale (Physeter maorocephalus). As it has not been found in any whaks but 
such as are dead or sick, its production is generally supposed to be owing to disease, 
though some have a little too positively affirmed it to be the cause of the morbid 
affection. As no large piece has ever been found without a greater or smaller quantify of 
the beaks of the sepio octapodia, the common food of the spermaceti whale, interspersed 
throughout its substance, there can be litUe doubt of its originating in the intestines 
of the whale : for if it were merely occasionally swallowed bv the animal, and then 
caused disease, it would much more frequently be without these bodies, when it is 
met with floating in the sea, or thrown upon the shore. 

Ambeigris is fbund of various sizes, general^ in small fragments, but sometimes so 
large as to weigh near two himdred poxmds. When taken from the whale, it is not so 
hard as it afterwards becomes on exposure to the air. Its specific gravity ranges from 
0*780 to 0'926. If good, it adheres like wax to the edge of a knife with which it is scraped, 
retains the impression of the teeth or nails, and emits a £fit odoriferous liquid on being 
penetrated witn a hot needle. It is generally brittle ; but, on rubbing it with the nail, 
it becomes smooth, Uke hard soap. Its colour is either white, black, ash-coloured, 
yellow, or blackish ; or it is variegated, namely, grey with black specks, or grey with 
yellow specks. Its smell is pecuuar, and not easy to be counterfeited. At 62*2 C. 
it melts, and at 100 C. is volatilised in the form of a white vapour; on a red-hot 
coal it bums, and is entirely dissipated. Water has no action on it; acids, except 
nitric acid, act feebly on it ; alkalis combine with it, and form a soap ; ether and the 
volatile oils dissolve it ; so do the fixed oils, and also ammonia, when assisted by heat; 
alcohol dissolves a portion of it. 

The principal constituent of ambergris is ambrein (q. v.) Succinic and benzoic 
acids are said to be sometimes found among the products of its destructive distillation. 
Its inorganic constituents are carbonate and phosphate of calcium, with traces of ferric 
oxide and alkaline chlorides. 

An alcoholic solution of ambeigris, added in minute quantity to lavender water, 
tooth powder, hair powder, wash balls, &c communicates its peculiar fragrance. Its 
retail price being in London a guinea per oz. leads to many adulterations. These 
consist of various mixtures of benzoin, labdanum, meal, &c. scented with musk. The 
greasv appearance and smell which heated ambergris exhibits, afford good eriUria^ 
joined to its solubility in hot ether and alcohol 

It has occasionally been employed in medicine, but its use is now confined to the 
perfumer. Swediaur took thirty grains of it without perceiving any sensible effect. — U. 

AMBXiTOO VITB. A greenish-coloured mineral of different pale shades, marked 
on the surface with reddish and yellowish-brown spots. It occurs massive and arstaUised 
in oblique four-sided prisms. Lustre vitreous ; cleavage parallel to the sides of an 
oblique four-sided prism of 106® 10' and 77*^ 50' ; fracture uneven; fragments rhom- 
boidal; translucent; hardness as felspar; brittie; specific jgravity 3*0: intomescea 



I 



AMIC ACIDS 165 

vitli the blowpipe, and foses with a reddish-yellow phosphorescence into a white 
cnameL It oocara in granite, with green topaz and tourmaline, at Chursdorf and 
Aniadorf, near Pinig, in Saxony. A specimen from Arsndorf analysed by RammeLsberg 
gave 47*16 phosphoric anhydride, 88*43 alumina, 7*03 lithia, 3*29 soda» 0*43 potaah. 
and 8*11 ihioEine^ agreeing reiy nearly with the formula: 

(5A1*0».3P*0» + 5M»0.3P*0*) + 2 (A1«F» + MF.) 

(HandworL d. Chem. 2m Aufl. L 665 ; Dana, iL 409.) 

A — ^**™*— By digesting ambergris in hot alcohol, specific graTity 0*827, the 
peculiar anbatanoe, eiUled ambrein by Pdletier and Cayentx)u, is obtained. The alcohol, 
on oocJing, d^KMita the ambrein in Tory bulky and iiregojar crystals which still retain 
a verj eonaiderable portion of alcohol. Thus obtained, it has the following properties : 
— It is of a brilliant white colour, has an agreeable odour, of which it is deprived by 
xepeated solntion and oystallisation. It is destitute of taste, and does not act on 
Tegetable blnea. It is insoluble in water, but dissolyes readily in alcohol and ether ; 
and in mnch greater quantity in these liquids when hot than when cold. It melts at 
90^ C. (86° F.) BofleBing at 26*^ C. When heated aboye 100° C, it is partly volatilised 
and decomposed, giving off a white smoke. It does not seem capable of combining 
with an alkali, or of being saponified. When heated with nitnc acid, it becomes 
green and then yellow, eliminates nitrous gas, and is converted into an acid, which 
has been called ambrde acid. This acid is yellowish white, has a peculiar odour, 
veddena vegetable bines, does not melt at 100° C, and does not evolve ammonia 
when decomposed at higher temperatures. It ia soluble in alcohol and ether ; but 
flUigfatly so in water, iumbreate of potassium forms yellow precipitates with chloride 
of ealcinm, protosnlphate of iron, nitrate of silver, acetate of lead, corrosive sublimate, 
protochloride of tin and chloride of gold. (J. Pharm. v. 49.) 

Ambrein is perhaps impure cholesterin, which substance it greatly resembles in its 
properties. Pelletier (Ann. Ch. Pharm. vL 24) found it to contain 83*3 p. c C, 
13*3 H, and 3*82 O, which is nearly the composition of cholesterin : if this be so, 
ambreie add is probably identical with cholesterlc acid. 



A name applied to the ethers of the amic acids, e. g. oxamethane 
to «««»^*^ of ethyL (See Aiao Acms.) 

AM W U I ST. The amethyst is a gem of a violet ooloup, and preat brilHancy, 
said to be as hsord as the ruby or sapphire, from which it differs only m colour. This 
is called the oriental amethyst^ ana is very rare. When it inclines to the purple or 
rose colour, it is more esteemed than when it is nearer to the blue. These amethysts 
have the same figure, hardness, specific gravity, and other qualities, as the best sap- 
phires or nines, and come from the same places, particnlarly from Persia, Arabia, 
Armenia, and the West Indies. The occidental amethysts are merely coloured crystals 
of quarts. — U. (See QuAsn and Safphibb.) 

A variety of Hornblende (j. v.) 

Mountain flax. (See Asbestos.) 

By this name are designated a class of nitrogenised acids, which 
differ from the add ammoQinm-salts of polybasic adds by the elements of one or more 
atoms of water; and which, under oertam circumstances, are capable of taking up the 
elipfncnts of water, and regenerating ammonia and the original non-nitrogenised poly- 
haiie add. They bear a considerable resemblance to amides in their modes both of 
formation and of decompontion : bnt they differ from these bodies in possessing 
inTariable and dedded acid properties, and in not deriving from the type KH*. 

^th regard to tiieir constitution, amic acids are best regarded as deriving from 
the double type NH',HK). They represent this type in which 2, 3, or 4 atoms of 
hydngen are replaced by other radides, one of whicn must be the radicle of a polyba^io 
add: and they maybe divided into 8 classes, according as 2, 8, or 4 atoms of hydrogen 
are so replaced. In class 1, therefore, it is obvious that 2 atoms of hydrogen in 
the tjpe must be replaced by 1 diatomic acid radide ; in class 2, three atoms of 
hydrogen may be replaced by 1 triatomic, or by 1 diatomic and 1 monatomic add radide ; 
and so on. No amic add is formed by the substitution of an acid radide of less than 
2 atoms of hydrogen in the t^fpe: if 1 atom of hydrogen in NH',HH) be replaced bv 
<he ndide of a monobade add, the only result is the formation of the ammonium-salt 
cf that add, €.g,i 

AcetyU AeeCate of 

aiamoDium 

X3 



166 AMIC ACIDS. 

Neither can an amic acid be formed by replacing 2 atoms hydrogen in the type by 
2 monatomic acid radicles ; for when benzoic anhydride is treated with ammonia^ the 
2 atoms of benzoyl, each equivalent to H, do not remain combined, forming an amic add, 
bat separate, forming 2 distinct compounds, benzamide and benzoate of ammonium: 

(CH*©)'.© + 2NH« « N.CH»O.H* + CH'O.NH^.O 
Benzoic anhyd. BetiMxaide. Benioateof amm. 

But when a dibasic anhydride is treated with ammonia, the acid radicle, equiTalent to 
H^ being indivisible, is incapable of separating so as to form two distinct oompoonds; 
so that a single compound is neoessarily formed, the ammonium-salt of an amic add: 



Ml 



S0«.0 + 2NH« « NH«.SO«.H.O 
Sulphuric Sulphamate of 

anhyd. amm. 

Hence it follows that a monobasic acid \& incapable of forming an amic acid : in fact 
the possession of this property is perhaps one of the most Higfiti^iifthmg characteristica 
of polybasic acids. 

We now proceed to describe the modes of formation, properties, and reactions of 
amic acids, dividing them into 3 classes, according as 2, 3, or 4 atoms of hydrogen an 
replaced in the type. 

ClaB8 1. They represent the ty^e NHHH HHO in which 2 atoms of hydrogen aza 
replaced by one diatomic acid radicle : 



tu 



Sulphamic acid NH.H.SO<.H.O 

Carbamicacid NH.H.C0.H.0 



it 



Oxamicacid NH.H.CH)*.ttO 



Succimamic acid NH.H.OH*0«.K0 

They are formed — 1. By action of heat on the add ammoniam-ealt of a dibasic acid: 



lU 



C*0«.(NH*)H.O« - BPO - N.H».C«0«.H. 
Acid oxalate of amm* Ozamic acid. 

In some cases, s. g, comenamic acid, NH'.CHK)'.H.O, prolonged boiling of the am- 
monium-salt with water is sufficient. 
2. By action of ammonia on anhydrides : 



C"ff *0«.0 + NH» - NH».C"H'*0».H.O 
Camphoric Camphoramlc add. 



nphori 
ihyd. 



The best mode is to dissolve the anhydride in absolute alcohol, and to lead diy 
ammonia into the solution. The reaction takes place with 2 iftoms of ammonia^ an amate 
(if ammonium being formed. 

8. By action of ammonia on aeid salts of organic radicles : 

HI U 

C'H*0.(CH»)H.O« + NH" « NH«.C*H*O.H.O + CBP.H.0 

Acid talicylate of methyl. Sallcylamic acid. Methylic 

(Methyl-salicylic acid.) alcohol. 

4. By action of aqueous ammonia on ethers of dibasic acids. (Gerhardt^ Chim. 
org. iv. p. 668.) 



C»»H»«0« (C«H»)*.0» + NH« + H«0 « NH«.C»«H>«0«.H.O + 2/C«H».H.0\ 

Sebamicacid. \ Alcohol. / 

6. Imides, boiled with dilute ammonia» take up H'O, and form amic acids : some 
alkftlamides exhibit the same reaction : 



lU 



N.C*H*0«.H + H«0 = NH».0*H*0«.H.O 
Suocinimide. Succinamic acid. 



AMIC ACIDS. 167 



N.C*H*0«.Ag. + WO = NmC*H«0«.Ag.O 

Argento-ffuocini- Succinamate of sllrer. 

inlde. 

& Some prixnuy diamides, boiled with mineral adds or alkaliSj take up H'O, and 
foim amie adds^ or axnates of ammonium : 



N«.OH*0«.H* + HH) = NH«.C*H*0«.H.O + NH« 

Ifabiinide. Bfalamtc add. 

(A»paragine.) (A«partic add.) 

7. Some amic adds are farmed bj the action of hydrosulphuric add on nitro-conju- 
gated 



(?H*(NO«)OJa.O + 3H«S = NH'.(rH*O.H.O + 2BP0 + 33 
Nitrobenxote add. Ozybenzamic add. 

The add thus formed is commonly called benzamic acid ; an impoBsible name, as 
heosDie add is monobedc We regard it as the amic acid of ozybenzoic acid, 
t^^.H'.O*, a diatomic add, although it does not form add salts. Strecker regards 
tbis amie add as phenylcarbamic add, NH.C*H*.CO.H.O. 



CUui 2. Thej represent the type NHHH HHO in which 3 atoms hydrogen of are re- 
pbeed ; (a) by 1 tnatomic add radide, (b) by 1 diatomic and 1 monatomic add radide, 
(c) by 1 Hi«fi\min, add, and 1 monatomic basic radide. 

a. 3H orv r^piaeed by 1 triaiomie acid radicU: 

m m 

Phoephamic acid, NH.PO.H.O, formed by the action of ammonia on phosphoric 
anhydride: 

P«0» + 2NH« ^ 2(N.HPO.H.O) + H»0. 

b. 8H are replaced by 1 diatomic and 1 monatomic acidrTadide : 



Ml 



Benzoylnaicylamic add .... NH.0'H»O.C'H«O.H.O 

Sulpbophenyl-sucdnamic add . . NH.G*H*SO'.C«H<0'.H.O. 

Obtained by boiling eextain tertiazy amides with aqueous ammonia (Gerhardt and 
Chioisa): 



m 



SolphoplMnyl-niediia- Sulphophenyl-taoeinainateofainin. 



e. 8H are repiaeed by 1 batio monatomic and \ add diatomic radicle : 



Eihylozamie add NH.C«H».C*0«.H.O 

PhenylBulphamic (sulphanilie) add ... NH.(>H^SO<.H.O 

Fhenybncdnamic (sucdnanilic) add . . . KH.CmC<H«0*H.O. 

These oompounds (which may be called alkalamio adds) are obtained by the same 
xeaetiona that serre ix the formation of adds of dass 1, a primary amine being sub* 
stitoted Ibr ammonia: 

L By heating the add salts of organic alkalis : 



CH)«.N(CH«)H*.0« - H«0 = NH.CH».C«0« H.O. 

Add oxalate of me- Metbyloxamic acid. 

tbyUnin. 

Sb By aetion of primary amines on dibado anhydrides : 



C»ft«0».0 + N.C«E».H« » NH.C^» C«H«0«.H.O. 
lyrolartaric Phenjlamioe. Phesylpxrotartramic acid, 
mbjd. 

u 4 



16S AMIDES. 

8. Bj heating alkalimides with dilute ammonia: 

KC«H».C*H*0» + H'O = NH.O"H».C*H*0»SO. 

PbeujlmaUunide. PhenylmaUiinic acid. 

Class 8. They represent the Irpe NH'iH'O in which four atoms of hydrogen are 
replaced by other radicles, one of which must be a polyatomic acid radicle. The onlv 
known members of this class are a few phenyl-oompounds : phenylcitramic ad^ 



N.C«H*.C*H»O^H.O, is an example. 

There are also certain nitrogenised acids, which either exist ready formed in nature^ 
or are products of the decomposition of other compounds, which we may regard as 
amic acids. Thus glycoooll, C*H*NO*, is the amic acid of glvcoUic acid,C*H*O.H*0«, 
and maybe written KH'.C^H'O.H.O. Hippuric, choleic, and other acids may also be 
regarded as amic acids ; but their constitution is as yet but imperfectly understood. 

Amic acids are distinct monobasic acids : they form well defined salts, which are 
generally more soluble than those of the corresponding dibasic acids. They are mostly 
solid, ciystalline, not Tolatile without decomposition. When heated, many of them 
lose the elements of 1 atom of water, and are converted into imides: others arc decom- 
posed into a dibasic anhydride and a primary amine. When boiled with mineral acids 
or alkalis, they mostly take up the elements of 1 atom of water, and regenerate the 
corresponding dibasic acid, and ammonia or a primary amine : in some cases, the mere 
boiling of their aqueous solutions suffices for this reaction ; in others, fusion with soUd 
potash is required : 



NH.C«H».C^H*0*.H.O + H»0 « C^tf*0«.H».0« + N.OH'.H* 

FhenyUuccinamic acid. Succinic add. Phenyiamtne. 

With nitrous acid, many amic acids regenerate the corresponding dibasic add, with 
evolution of nitrogen : 



ii 



NH«.C*H*0».H.O + NHO« « C*fl*0«.H«.0« + N^ + BPO. 

Malamic acid. Malic acid. 

Like all decided acids, amic adds form ethers, t. e. salts of alcohol-radides. These 
amic ethers are sometimes called urethanes (or amethanes), the former name having 
been applied to the earliest discovered, carbamic ether. They are formed by the in- 
complete action of ammonia en the ethers of dibasic adds : 



C«0«.(C«H»)«.0» + NH» = NmC«0* C«H».0 + 0»H«.H.O. 
Oxalic etber. Oxamic etiier. Alcohol. 

They are isomeric with alkalamic acids. When boiled with water, acids, or alkalis, 
they are converted into dibasic adds, alcohol, and ammonia : 

NH«.C»0«.C«H".0 + 2HX) = C*0«.BP.O« + C«H».H.O + NH«. 

Oxamic etber. Oxalic acid. Alcohol 

Excess of ammonia converts them into primary diamides {q, v,) — F. T. C. 

Amio Bases. This name may be given to a dass of bodies produced by the action 
of ammonia on the oxides, or chloro- or bromo- hydrates of polyatomic alcohol-radides, 
and which are related to the polyatomic alcohols in the same way as the amic acids to 
the polyatomic aoids. Their leading properties may be expressed by representing 
them as derived from a combination of the types NH* and H^O. 

The following bodies belonging to this class are already known : 

Anisamine, CH'^NO - (^g? |^; tTpejII^ 

Dianisamine, C"H»»NO» = ^^^^'|o« 

Diglycolamine, CW»NO« = ^^H'^'jo^ 

Glyceramine, C»HWO« - ^^h^Mo« 

Diglyceramine, C»H"NO» = ^^h^'|o« 

Triglycolamine, O»H'*N0> -^ ^^) j^,; typo 3^^^ j 



*yP® 2(H«o{ 



} 



AMIDES. 169 

Ammonia, NHHH, is capable, nnder certain circumstances, of ex- 
Aanging each atom of its hjdrogen suocessiTely for a metal, or for a compound radicle, 
add or basic, — thus giving rise to a numerous class of compounds, all denying from 
the same type, KHHH. The earliest discovered of these compounds were some of 
ihox in wluch one atom of hydrogen was thus replaced, e. g. NHHK, which was re- 
guded as a compound of KH* (amidoffen) with potassium, N£[*K, and called amide of 
potaasiom, analogous to the cyanide, CNK. In process of time, compounds came to be 
oLcoTered, deriving £rom the type NHHH, in whicJi 2 or 3 atoms of hydrogen were 
replaced bj metals or compound radicles, to which the name amide in its ori^nal sense 
of a compound containing amidogen, NH", was plainly inapplicable ; accordingly these 
componnds were designated by other names, imideSy niirtles, &c, the introduction of 
▼hieh has caused considerable confusion, since they in no way indicate the common 
dEHTation of all these eompounds. 

Of late years attempts have been made, chiefly by Gerhardt, to remedy this confu- 
BOD, by assigning to this numerous class of compoimds a rational constitution which 
shall render evident their common derivation, and a nomenclature by which this con- 
sdtation is at once expressed. These attempts have been attended with considerable 
nuee» : and the dasisification adopted in this article is based upon that given by 
Gerhardt and Chiozza (Ann. Ch. Phys^ [3] xlvi.), certain modifications being 
introdneed where great-er clearness seems thereby to be attained. 

Since the hydrogen in ammonia is capable of bein^ replaced either by acid- or by base- 
radicles (simple or compound), the first obvious division of the compounds thus formed 
is one based upon the nature of the radicle which has been substituted for hydrogen. 
These compounds tbus fall into three great divisions : 

1. Ammonias in which 1 or more atoms of hydrogen are replaced by an aoid-mdicle. 
To this division we propose to confine the name of amides. In the case of each in- 
dividnal member of the dass, the generic name is preceded by a prefix, which indicates 
the particular add radide or resides contained in the compound, e,g. acetamide 
K.OT«O.H«, diacetamide N.(C»H«0)«H, &c. 

2. Ammonias in vhich 1 or more atoms of hydrogen are replaced by &z«f-radides. 
This division we call amines. For examples of the nomenclature of individuals, 
we may take potassamine^ N.K.H', ethylamine, N.C^^H', methylethylamine, 
K.CH".C»H».H, &c. 

8. Ammonias in which 2 or more atoms of hydrogen are- replaced by add- and 
Aflw-iadides. This division we call alkalamides. Examples are ethylacetamide, 
N.(?H».C?HK).H, phenyldibenzamide, N.C«H».(C'H»0)«. 

This primary classification enables us to perceive in compounds deriving from the 
type ammonia, NHHH, the same seriation of properties which was first pointed out 
hj Gerhardt in the compounds deriving from the type oxide, OHH. As in the latter 
ease, we have metallic oxides (bases) occupying the positive extreme, adds tiie negative 
extreme, while the middle place is filled up by salts, containing at once an add- and 
a base-radide ; bo in the former case, we have amines at the positive extreme, amided 
at the negative, and alkalamides between the two extremes. 

A fbruer ground for division is furnished by the fact that amides, amines, and 
alkalamides may derive firom 1, 2, or 3 molecules of ammonia, according as they con- 
tain monatomic, diatomic, or triatomie radides. Hence we have a further division of 
amides into 

1. Monanudes (or amides), deriving firom 1 mol. ammonia NHHH. 

2. Diamidea „ „ 2 mols. „ N^H'H^H*. 
8. Tnamides „ ,,3 mols. „ N*H«H»H». 

The same subdivision applies to amines and alkalamides. 

In eadi of these types, NHHH, N«H«H*H», N«H»H»H", one third, two thirds, or the 
vhole of the hydrogen may be replaced by acid- orbase-radides : hence arises a further 
division of amides, diamides, and triamides into : 

1. Primary, in wh. } of the hydrogen is replaced, NAHH, N*A"H'H«, N"A"'H»H». 

2. Secondary, in wh. } of the hydrogen is replaced, NA*H, N«(A")«H« N»(A'")«H«. . 

3. Tertiary, in wh. the whole of the hydrogen is replaced, NA», N«(A")«, N»(A"')». 

The nme subdivision applies to amines, and (partially) to alkalamides. 

Having thus indicated the general principles of classification which we adopt, \re 
BOW proceed to the more detailed consideration of amides, amines, and alkalamides. 
It is not our purpose to give a complete list of these compounds, but merely to cit6 a 
i»affident number of them to illustrate our classification ; and to enumerate the piiu'^ 
opal reactions by which the formation and decomposition of eadi group is effected. 



170 AMIDES. 

Amidbs. 
L Mommldes or Amides. 



1. Primary Amides, Thej represent 1 molecule of ammonia, in which I atom of 
hydrogen ia replaced by a monatomic acid-radicle (of a monobasic add) : 



Acetamide 
Fropionamide . 
Benzamide 
Cyanamide 
Snlphophenylamide 



N.C5«H«0.H» 
N.C»H*O.H« 

N.CN.H« 
N.C«H»80*.H«. 



They differ from the ammoniam-salt of their adds in containing the elnnent of 
I atom of water leaa : 

Acet. amm. AceUmlde. 

They are formed : 1. By the action of ammonia on anhydrides (Gerhardt). 

(CH»0)«0 + NH» - (rH»O.H.O + N.CTH-O.BP 
Benxoic anhyd. Bensoic acid. Benzamldt. 

2. By the action of ammonia (Liebig and Wohler), or of carbonate of ammonium 
(Gerhardt) on the chlorides of add-n^des : 

CNa + NH» « HCl + N.CN.H« 
Chloride of Cyanamide. 

cyaDOgen. 

This method is especially adapted to the formation of those amides which areinaolable 
or nearly so, in water. 

8. By the action of ammonia on ethers : 

C«H»O.C»H».0 + NH» = C«H«0 + N.C«HK).H« 
Acetic ether. Alcohol. Acetamide. 

This method is peculiarly adapted to the formation of soluble amidffl. Glycerides, 
with ammonia^ also yie^ an amide, and glycerin. (Berthelot) 

4. Some primary amides have specie methods of foimation : e. g, benzamide is 
formed by oxidising hippnric add with peroxide of lead : 

C^*NO« + 80 « N.CH*O.H» + 2C0« + H*0 

Primaiy amides are mostly solid and crystalline, easily fusible^ neutral to test paper, 
volatile without decompodtion. Some of them, e, g, acetamide, combine with aads: 
others e. g, benzamide, can exchange 1 atom of hydrogen for a metal, forming metallic 
salts, or alkahunides. Thej are generally^ soluble in alcohol or ether : some in water. 

SeacHoTu, — 1. Boiled with adds or with aUcalis (some with water), they take op 
HH) and regenerate the acid and ammonia, 

2. Treated with phosphoric anhydride, they lose H'O, and yield the oorrespondiitg 
nitrile. The same reaction frequently takes place when they are passed in the state d 
▼apour over caustic lime. 

N.C*H»O.H« - H*0 - N.CH* 

Acetamide. Aceto- 

nltrlle. 

3. Treated with petitachloride of phosphorus, they behaye as though they were 
oxides, yielding oxychloride of phosphorus, and the chloride of the radide which the/ 
may be supposed to contain, if deriyed from the type HHO (Gerhardt) : 

CH-N.H.O + Pa» « PC1»0 + HCl + (THW.a 
Beniamlde. Chloride of 

bcnasamyi. 

The chloride thus formed is readily decomposed by heat, frequently bdow 100^ C. 
into hydrochloric acid and the corresponoiDg nitnle, C'H^IsCn » HCl + N.CH' 
(aceto-nitrile^. 

4. With nitrous add they yield their corresponding add, with eyolution of nitrogen : 

N.CH'O.H* + NO«H - NN + BPO + (7H«0« 
Beniamide. Bensoic 

add. 

2. Secondary Amides, — They represent 1 molecule of ammonia, in which 2 atontf 
of hydrogen are replaced : (a) by 2 monatomic add-radides. (b) by 1 diatomic add- 
radide of a (dibasic add). 



AMIDES. 171 

§.B*tre replaced by 2 monatomic radides : 

PiaceUmide N.(CH»0)«.H 

Solphophenyl-benzamide .... N.G*H*SO'.CrH*O.H 

Thej are formed: 1. By the action of chlorides of acid-radicles on pzimary amides, 
cr their metallic salts (Gerhardt) :- 

N.C^»SO« H« + (?H»0.a = Ha + N.<>H»S0».C^»O.H. 

flolflio^iaiylamJde Chlorifle of SulphophenjI-beoiamlde. 

bensojl. 

2. Bj action of dry hydrochloric acid on primary amides, at a high temperature 
(Streeker): 

2(N.C«H»0.H?) + Ha » :NHHn + NjrC«H»0)*.H 
AcHamide. Diaoetamide. 

JkeiBe amides ai« readily selnhle in ammonia^ They exhibit acid properties, red- 
douD^ litmus, and exchanging their remaining atom of hydrogen for a metal : the 
metallic salts thus formed dissolve in ammonia, producing compounds which Gerhardt 
Rguds as dialValamidfw, but which, as they contain only monatomic radicles, it ia 
praiaps preferable to regard as monalkalamides containing a compound ammonium : 

N.C«ffSO*.C?H»O.Ag. + NH« - N.C^«SO« CTEPCNAgH' (monalkahimide). 

or N« C«H*SO«.C»H*O.Ag.H» (dialkahimide). 

Aceordiog to Gerhardt (Ann. Oi. Phys. [8] liii), pentachloride of phosphorus acta 
oo aeeoudary amides in the same way as on primary amides : 

N.CTff»so».crHK).H + pa» - pa«o + Ha + N(C'H»xc^»so«)a 

SnlplioplicnylbeDBainide. Chloride of ralphopbcnjl* 

bexamldyL 
md the dbkride fonned is decomposed by heat : 

N (c^»)(c^»so«)a - N.c^» + (>Hso«.a 

Benso- Chloride of 

nitrile. lulphophenyl. 

kB* an replaced by 1 diatomic radide. These are the bodies generally called 
imideSf being regarded as containing imidoyen, NH. Though we rgect this view of 
their eonstitotion, we retain the name for oonyenience sake. 

Carbimide (cyanic add) N.(CO)''.H 

Sucdnimide N.(C*H*0«)" • H 

Camphorimide N.(C"H"0«)''.H. 

Thej differ from the acid ammonium-salts of their adds by containing 2 atoms of 

vtterlesi: 

C*H*0*(NH*)H - 2H«D - N.C^H)».H 
Acid sQcciniite of flucctnlmide. 

ammontem. 

They are formed much more easily than secondary amides (a) : 

1. By heating the add ammomum-salts of dibasic adds. 

2. By heating primary diamides : 

N».C^<0\H* - NX««0«.H + NH». 
SoodiuuBide. Suoclnlmide.. 

3. By healing amic adds (Laurent) : 

N.a*H'*0«.H«.H.O - HK) + N.C»«H"0».H 
Camphonmfe add. Camphoilinlde. 

1 By heating dibadc anhydrides with ammonia: 

OHW.O + NH* - H«0 + N.C*HH)«.H 
Sucdnlc anhr- Sacdoimide. 

dride. 

Imides possess dedded add properties, and readily exchange their basic hydrogen 
for a metal ; carbimide in £ict is identical with cyanic add. 

BetfetionM, — 1. Boiled with adds or alkalis, they take np 2H'0 and regenerate the 
^iibasie add and ammonia : 

N.C*H*0«.H + 2H«0 - 0*H*0<.H» + NH«. 

BeooiidaiT amides (a) also exhibit this reaction. 
1 Boiled with mlnte ammonia, they form the ammonium-salt of the corresponding 

N.C«H«0».H + NH*.HO - N.C«H«0«.H«.NH^O 

Sucdnamate of anm. 



172 AMIDES. 

3. Tertiary Amides,— They represent 1 molecule of ammonia, in which all the 
hydrogen is r^laced : (a) by 8 monatomic^ (b) by 1 diatomic and 1 monatomic, (c) by 
I triatxxnic, aad-radide : 

a. H* are replaced by 3 monatoTiao radidea : 

Sulphophenyl-benzoyl-acetamide . . N.<>H»SO*.C»H»O.CHK). 

5. H' are replaced by 1 diatomic and 1 monatomic radicle: 

Snlphophenyl-Buccinamide . . . N.C^'SO^CC^H'O*)". 

They are formed by the action of chlorides of acid-radicles on the metallic salts of 
secondary amides (tertiaiy alkalamides) : 

N.C^-SO«.C'HK)Jlg + C^'O.Cl - AgCl + N.C^-SO«.C'H*O.C«H«0 
N.C*H*0*^ + (>H*S0«.C1 - Aia + N.C*H*0«.C^*SO«. 

Their reactions are bnt little known. Boiled witb dilute ammonia, the amides of dasB 
(fi) giye the ammonium-salt of the corresponding amic acid : 

N.C^H*0».C«H»SO« + NH«.H.O « NC*H*0«.C«H»SO«.H.NH*.0. 

Sulphophenyl-auccina- Sulphophenyl-ftucdaamate of 

mide. ammonium. 

c. H' are replaced by 1 triaiomie radicle. To this group, by their reactions and 
mode of formation, the following mineral compounds belong : 

N.(PO)'" . Gerhardt's biphosphamide (phoephorylamide) - PO*(NH<)H« - 3H«0 
N.N.'" . Free nitrogen (Nitroso-nitrile) = NO«.NH* - 2HK) 

N.(NO.r . Nitrous oxide. (Nitro-nitrile) = NO«.NH< - 2H«0. 

n. Btamldes. 

1. Prim aryJ) iami dee. — ^They represent 2 molecules of ammonia in which 2 atoms 
of hydrogen are replaced by 1 diatomic add-radide. 

Sulphamide N*.(SO«y'.H« 

Oxamide N«.(C«OV.H* 

Succinamide N«.(C*H*0«)''.H* 

Carbamide (urea) .... N\(COy.R* 

They differ firom the normal ammonium-salts of their acids in containing 2 atoms of 
mrater less * 

C«0*(NH<)« - 2HH) - N*. C«0«.H* 
Oxalate of Oxankide. 

ammoDiam. 

They are formed — 1. By the action of ammonia on ethers : 

C«OXC«H»)» + 2NH» - 2C*H«0 + N«.C»0*.H« 
Oxalic ether. Oxamide. 

2. By the action of ammonia on chlorides of add-radides : 

C^H*0«.C1« + 2NH« = 2Ha + N«.C*H*0«.H« 
Ctilortde of Succinamide. 

succlnyl. 

3. By heating normal ammonium-salts of dibasic acids (Dumas). 

4. By the action of ammonia on imides (Wohler) : 

N.CO.H + NH« « liP.CO.H* 

Carbimide. Carbamide. 

By the action of ammonia on dibasic anhydrides, not primaiy diamides, but omie 
add^, are generally formed. 

Many primary diamides exhibit decidedly basic properties, combining with acids 
and formmg de&iite salts: e.y, urea, asparagine, &c 

Reactions, — 1. Many of them, when heated, evolve ammonia and yidd imides. 

2. Boiled with adds or allLalis, they take up 2H^, and regenerate the add and am* 
monia: 

mC«0«.H« + 2BP0 = CK)*.H« + 2NH». 

3. With nitrous acid, they regenerate their dibasic add, with evolution of nitrogen 
(Piria^ Malaguti): 

N^.C^O'^.H* + 2N0'H - 2NN + C»0*.H« + 2H«0. 
Oxamide. Oxalic acid. 

Intermediate between primary and secondary diamides must be classed the bodies 



AMIDES. 178 

ktel7 diaooTered hj Zinin (Ann. Ch. Phys. [3] zliv. 57), which he describes as 
vrw in which 1 atom of hydrogen is replaced by an acid radicle O^iey are of course 
(tiamidffl^ in which 3 atoms of hydrogen are rephiced, 2 by a dia;tomic, and 1 by a mon- 
itoime xadide. 

Acetocarbamide (acetyl-urea) . , N'.CO.C'H^O.H* 
Benzoearbamide (benzoyl-nrea) . . N*.CO.C'H*O.H». 

Hmj are ibnned by the action of chlorides of acid-radicles on nrea: 
IP.CO.W + C*HH).Cl « HCl + N«.CO.C*H»OH» 

Carbamide. Cbloridn of Acetocarbamide. 

acetyl. 

Attempts to replace more than 1 atom of hydrogen in nrea by an acid-radide, have 
bitheito &iled. 

i These bodies are crystaUisable, and do not combine with addi. They are not 
Tdatiky being decomposed by heat into cyannric acid and a primaiy amide : 
8(K«.CO.C»H»0.H") « C'N»0*H« + 3(N.C2H«O.H«) 
Acetocarbamide. CyaQuric acid. Acetamide. 

Here too mnst be placed Gerhardfs phosphamide (Ann. Ch. Phys. [3] zyiii.) — 
IPJlJ^yjP, formed by saturating pentachloride of phosphorus with ammonia, and boil- 
ing witn water: 

PC1» + 2NH» + HK) = N'.PO.H* + 6HCL 

It diffen from monacid phosphate of ammonium by the elements of 3 atoms of water : 

FO*(KK*yE - 3H»0 = N«.PO.H». 

1 Secondary Di amides. — ^They represent 2 molecules of ammonia, in which 4 
atoms hydrogen are replaced by 2 diatomic acid-radicles, or by 1 diatomic and 2 
monatomic radidesL 

None of these have yet been formed. (Handwb.) 

8. Tertiary Diamides, — They represent 2 molecules of ammonia, in which all 
tbe hydrogen is replaced by acid-radicles, one of which at least must be dibasic : 

TrisMcinamide N»(C*tfO»)» 

Sucdnyl-disulphophenyl-dibenzamide . N«.(C*H*0*).(C«H*SO«)*(C'H*0)« 

The^ are formed by the action of chlorides of acid-radides on the silyer^salts of 
8eeon<uiy amides : 

2(N.C*H*0«.Ag) + C^H*0«.a« + N«.(C*H*0«)» 4- 2AgCL 

Argentosoocioamlde. Chloride Trltuc- 

of tuccinyi. dnamide. 

in. Trtamldes. 

1. Primary Triamides. — ^They represent 3 molecules of ammonia, in which 8 
atoms of hydrogen are replaced by a tnatomic add-radide : 

Phosphamide .... N».(PO)'".H«. 
Citramide N«.(OH»0*y".H«. 

They difSar from &e normal ammonium-salts of their adds by containing 35*0 less : 

CflB[K)'(NH*)« - 3H«0 = N».C"H»0*.H« 
Citrate of amm. Citramide. 

Phoqihamide is formed hj the action of ammonia on oxychloride of phosphorus : 
POCP + 6NH» = 3NHH31 + N».PO.H«. (Schiff Ann, Ch. Pharm. d. 300.) 
Citramide is formed by the action of ammonia on dtric ether : 

• C«a»0*.(C»H«)».0« + 3NH» = N».C«H»0*.H« + 3(C«H».H.O) 
Citric ether. Citramide. AlcoboL 

Heated with acids or alkalis, they take up 35*0, and regenerate their add and 
ammonia. 

1 Secondary Triamides. > They represent respectivdy 3 mols. ammonia, in which 

8. Tertiary Trtamides, (two-thirds and the whole of the hydrogen is replaced 
ly add-radides, one of which at least must be triatomic. 

No member of either of these groups has yet been formed. 

Oerhardt (Chim. oi*g. iy. p. 767) regards melam, C'H*N*, as a primaiy triamide^ 
N'.CN'.H* : and indeed we may admit the existence of a triatomic radicle, CN*, and 
Kgard hydrocyanic acid as tribasic, CNII': otherwise such compounds as ferro- 
cjaoide at potassium, C'N'FeK*, present the anomaly of bodies deriving from a triple 
^pe (H'd'), and yet containing only monatomic racudesL 



174 AMIDES. 

Akinb8. 
L Monmiwtnag or Amlniw. 

1. Primary Amines. — They represent 1 molecule of ainmoiiia» in which 1 atom of 
hydrogen ib replaced by a monatomic boae-radide, whether a metal or an organic 
radide. They are sometimee called amide-boBea. 

Potaasamine KKH* 



Platinamine . 
Methylamine . 
Ethylunine . 
Phuiylamine (Aniline) 



N.PtH«. 

N.CH».H« 

N.C»H*.H« 



Brimaiy amines contamiBaMiifitals are generally obtained by the action of ammonia 
on the metal or its oxide. %ncamiDa ia formed by the action of ammonia on nno- 
ethyl: ZnC*H» + NH" = RCH* + NZnH*.— When treated with water or adds, 
they are mostly decomposed, like primary amides, yielding ammonia and the hydrate 
of ike metal. 

Primary amines containing organic radicles are formed : 

1. By action of ammonia on hydrobromic or hydriodic ethers (Hof mann) : 

CH«I + im» - HI + N.CH».BP 
Iodide of MeChyUmlne. 

methyl 

2. By action of potash on cyanic or cyanuric ethers (Wurtz) : 

N.CO.CH» + K*BPO« « CO.K«.0« + N.CH».H« 

Cjanate of Carbonate of Metb jU 

methyl. potatiium. amine. 

3. By action of reducing agents, yiz. alkaline hydrosnlphates (Zinin), acetate of 
iron (B 6 champ), on certam nitro-coxgngated hydrocarbons: 

C^«(NO«) + H« - 2H«0 + N.C»H».H» 
MitrobenseDe. Pheujlamlne. 

Their formation is also observed in the dzy distillation of several nitrogenised organic 
substances. (For the various modes of formation of monamines in general, primary, 
secondary, and tertiary, see K^kul^, Lehrb. d. org. Chemie, pp. 451 — 466.) 

These primary amines are mostly liquid, boiling at a low temperature^ and volatile 
without decomposition. They strikingly resemble ammonia in all their propertiee: 
like it they have a strong alkaline reaction ; thev combine directly with acids, forming 
salts, whence they are expelled by the fixed aikaUs ; they precipitate metallic solu- 
tions ; with anhydrides, ethers, and chlorides of acid-radicles, they react predsely like 
ammonia (forming alkalamides, q.v.)^ and with hydriodic ethers they form «liMni^<w. 
With nitrous acid they yield nitrons ether or alcohol, with evolution of nitrogen : 

N.C*H».H* + 2N0«H « NN + 2H»0 + NO*.C»H» 
Ethylamine. Nitroui ether. 

N.C»H».H» + NO*H « NN + HH) + C«H«0 

Fhenylamine. Phenylle 

alcohol. 

In this group must also be included those amines whose radicle contains dilorine, 
bromine, iodine, or nitryl (NO'), substituted for 1, 2, or 3 atoms of hydrogen: e.g. 
Dichlorethylamine, N.C*H»CRH«, Chlorophenylamine, N.Cra*Cl.H«, Dichlorpbe- 
nyhunine, N.C«H«a«.H», Trichlorphenylamine, N.C»H«C1».H«, Nitrophenylamine, 
lf.C'H\(NO^).H', &c Their alkaline properties are less marked, the greater the num- 
ber of atoms of chlorine, &c they contain. They are formed mosuy either by the 
direct action of chlorine, &c. on amines, or by the metamorphoses of other coiyugated 
compounds. Nitrophenylamine is formed by the reduction of dinitrobepzene by 
hydrosulphate of ammonium, just as phenylamine results from the reduction of nitro- 
benzene by the same agent. 

2. Secondary Amines. — They correspond to 1 molecule of ammonia, in which 
2 atoms of hydrogen are replaced by two monatomic base-radides. They are sometimei 
called Imide-bases, 

Dimethylamine N.(CH»)«.H. 

Methylethylamine .... N.CH«.C«H».H. 
Ethylphenykmine .... N.(?H».0»H».H. 
They are formed by the action of hydriodic ethers on primary amines : 

N.CH».H« + CTa:»i m m + n.ch".c^.»h 

Methylamine. Iodide of Methylethylamine. 

ethyl. 



AMIDES. 175 

In pmwitiet and reafetioxis, they eloaelj resemble primaiy amines : but they are in 
geDoaf leaf TobtQe. 

We BntBt also regard as aeoondaiy amines two alkaloids, which have not yet been 
failed arttfciany: 

Piperidine N.(C»H»»)''.H. 

Conine N.(C"H")''JBL 

The diemieal relations of the radides contained in these componnds are as yet 
vnknovn to ns ; and we cannot detennina wh e fl w r ^17 toe abgfe diatOBrie ndittB% 
or vhether they aie BMida wp of two monatomic radicles. 



S. Tertiary Amines, — ^They represent 1 molectde of ammonia, in which all the 
liydrogen ia r(*placed : (a) by 3 monatomici {b) by 1 diatomic and 1 monatomic, (c) by 
1 triatomic base-radicle. 

0. H' lie replaced by 3 monatomic radicles (Nitrile-bases). 

Tripofassaiaine N.K' 

Tiimereoramine ^'^^ 

Trimethylaniine N.(CH»)* 

Hethyldiethylamine N.CH».(Cra»)*. 

Methylethylphenylamine .... N.CH».C*H».C«H». 

Those eontaining oiganic radicles are formed — 1. By the action of hydriodie ethers 
on aeeondaiy amines : 

U.(CH»)«.H + C«HM - HI + N.(CH»)« C«H>. 
DlnMChjUiniiM. Iodide of DlmelbjlethjbuniDe. 

ethyl. 

2. By the distillation of the salts of oiganic ammonimn-bases : 

N.(CTI»)*.KO « N.(C^»)» + C«H* + HH) 

Hydnte of Trietbyla- Stbylene. 

tetretbyllnm. mine. 

K(C»H»)M - N.(C*H»)« + C*H»L 

Iodide of 
tetrechyllam. 

3. By action of ethylate of potassiom on cyanic ether: 

N.CO.C*H» + (0«H»)*.K*.0« = N.(C«H»)« + CO.K«.0« 
Cj»Mto of ethyl. 9 mol. eChyl«to TrtcthyU- Carboneiaor 

of pocaumm. mlneL potaMimn. 

TUs reaction is analogous to that of hydrate of potassium on cyanic ethers. (See 



Terliaiy amines are generally similar in properties to primaiy and seoondair amines : 
tiiey ue kss Tolatile than either. They are however distingnished by one important 
nactioD, whiebi at the same time exhibits in the strongest lisht their analogy with 
the ^rpe from which they are derired. When acted npon by hydriodie ethers, direct 
combmation takes place, an iodide of an oiganic ammonium-base being formed: 

N.(C*H»)« + C«HM « N(C«H»)M 

Iodide of 
tetrethyliam. 

These iodides are usually crystalline, soluble in water and alcohol : when treated with 
ends of sihrer, th^ yield iodide of silyer, and a hydrate of the ammonium-base : 

2[N(C*H»)*.I] + AgH) + H«0 - 2AgI + 2[N(C*H»)*.H.O] 

Hydrate of 
tetreihyllam. 

These hydrates are dystalline and soluble in water : they are powerfol alkalis ; in 
some reactions they resemble the fixed alkalis, liberating ammonia from A^inTnAniiti>^i 
■Its, and decomposing ethe rs into acid and alcohoL Precisely, therefore, as ammonia 
(nitride of hydrogen) NH*, combines with hydriodie add (iodide of hydrogen) HI, 
fetming iodide of ammonium, NH*I ; so triethylamine (nitride of ethyl) y (C% *)*, 
eombmes with iodide of ethyl, C^*t forming iodide of tetrethylium, N(C^*)r[. 
Jvit as we haye the hypothetical compound ammonium, NH^ playing the part of 
potaasiam, sodium, and other metals, and replacing the basic hydrogen in adds to 
form salts-— BO we liAye the hypothetical compound tetrethylium, I<r(C'H*), performing 
predaely the same metallic ftmctions. The analogy could not be more complete. 

6. IP are replaced by 1 diatomic and 1 monatomic radicle : Hofmann's ethylene- 
phenylamine, N.(C»H*)<C«H». 



176 



AMIDES. 



c. H* are replaced bj 1 txiatbmic radide (Nitriles). 

Aoetonitrile (cyanide of methyl) N.(CTP)*' 

Propionitrile (cyanide of ethyl) N.(C"H*)J 

Benzonitzile (cyanide of phenyl) .... N.(C'H*)'". 

They are formed — 1. By the action of heat or dehydrating .agente {e.g. phoepboric 
anhydride) on ammoniacal salts of monobasic acids : 

C«H«0«.NH* - 2HH) - N.C"H». 
Acetate of amm. Acetonitrlle. 

These nitriles differ £rom primary amides in containing H*0 less. 

2. By the action of cyanide of potassium on sulphate of ethyl and potassiom (or a 
liomologous salt), or on hydriodic ethers: 



SO«.(C«H»).K.O« + CN.K 
Sulphate of ethyl 
and potaisluro. 



SO«.K«.0« + CN.C*H» 

Sulphate of Cyanide of 
potastiom. ethrl or 

propto^nitrlle. 



This mode of formation shows that nitriles may also be regazded as cyanides 
(N.C«H» - CN.CH«), denying from the type CIH : and it is in this light that they 
are usually considered. But, if we consider their formation from ammoniacal salts, 
and their behaviour when boiled with acids or alkalis, when they regenerate thnr 
acid and ammonia,— NC«BP + KBO + WO - C«H»0*K + NH",— we may fairly 
regard them as deriving irom the same type with amides. And we are led to consider 
them as amines rather than as amides, by the fact that, in one of them at leasts the 
radicle is clearly a basic one ; in propio-nitrile, N.CH*, the radicle is glyceryl^ the 
triatomic radicle of the triatomic alcohol, glycerin, CHMI'.O'. Moreover, that they 
resemble amines in the property of combining with acids, is shown by the componndb 
which G^rhardt obtained by the action of pentachloride of phosphorus on primaiy 
amides {a. v.) C^«NC1 = N.C'H» + HCl. 

In order to show the connection between nitriles and the acids from whose 
ammonium-salts they are formed, e.g, of acetonitrile N.C*H', with acetic add, 0^*0*, 
and acetic compounds generally, it may be observed that acetic compoundis may be 
represented as containing the triatomic radicle CH*. Thus acetic acid may be written 
(C»H»)".H.O«, deriving from the double type H*0« : acetamide, N.H.C«fi».H.O, de- 
riving from the double type NH" + H*0 : chloride of acetyl, CLC*H".0, deriving from 
the double type CIH + ff : acediamine, N^.CH'.H", deriving from the double type 
N«H«. 

We have already seen that, when an amine which contains* any replaceable 
hydrogen (primary or secondary amines), is treated with the iodide of an organic basic 
^radicle, the result is the replacement of the basic hydrogen by the organic radicle: 
but that when tertiary amines, in which aU the basic hydrogen is already replaced, are 
• similarly treated, the result is a direct combination of the iodide with tne amine. 
Hence we are enabled to class as tertiary amines many natural organic alkalis, which 
combine directly with organic iodides ; of whose constitution, as they cannot be formed 
artificially, we should oSierwise be ignorant. Among these are tiie following homo* 
logons alkalis, obtained by the dry di^illation of animal matter : 



Pyridine 

Picoline 

Lutidine 

Collidine 

Parvoline 



N.C»H» 

N.CTI* 

N.OTl" 

N.C»H". 



Also the numerous vegetable alkalis or alkaloids (quinine, strychnine, morphine, &c), 
which have been extracted from plants. The migority of these latter compounds 
contain oxygen-radicles : as many of them contain 2 atoms of nitrogen, it is possible 
that they must be regarded as diamines. How many radicles they may contain, ve 
have as yet no means of determining. 

IL Blamlaes. 

1. Primary Diamines. ) They represent 2 molecules of ammonia, in which 

2. Secondary Diamine8,\2 and 4 atoms of hydrogen are replaced by 1 and 2 
diatomic base-radicles. The only representatives of these groups are the compounds 
lately obtained by Hofmann, by the action of bromide of ethylene on ammonia ; they 
contain the diatomic radicle ethylene, C^H^ : 

Ethylenamine N«.(ci*).H* 

Diethylenamine N».(C«H*)«.H«. 



AMIDES. 177 

likqr are thus fbzmed : 

C?H<.Br» 4- N«H« ■=- 2HBr + N«.C«H«.H* 

Bromide EthjIeDamine. 

of ethylene. 

2C*H«Bi* + N*H« - 4HBr + N».(C%<)«.H« 

Di-ethylenamlne. 

latermediate between secondaxy and tertiary diamines, is Hofinann*s diplienjl- 
lannTlmnine, N» (CH*)'.CH.H, obtained by the action of chloroform on phenywunine : 
2(N.C«H*^ + CHOT = K«.((?H»)».CH.H + 3Ha. 

3. Tertiary JKamines, — ^They represent 2 mols. ammonia, in which all the hydrogen 
ia TCfilaced; (a) by 3 diatomic, (b) by 2 diatomic, and 2 monatomic base-radides. 

a, Hofioann has obtained triethylenaminei; N'.(C%')*, by the reaction : 

8C*H^r* + N*H» « 6imBr -h N».(C*H*)». 

In thifl groop may be daaaed the compoimda known as hydramidea : 

Benzhydramide (hydrobenzamide) . . • , N'.(C'^H')' 

Salhydramide N».(C''H«0)«. 

Thcj are obtained by the action of ammonia on certain aldehydes : 

SCTHK) -t- N«H« « 8H»0 + m(C»H*)» 

B^niolc al* Benshrdrft* 

defayde* midie. 

They are OTstalline, insoluble in water, soluble in alcohol, not Tolatile without 
decomposition. They are decomposed by hydrosulphuric acid, yiddiog solph-aldehydes. 
(Cabovrs.) 

l^.CCH*)' + 3H«S - WE* + 3Cm«S. 

The Tiew here taken of the constitation of hydrobenzamide is confirmed by its 
Ibfnnation from chlorobenzol, CH*C1^ and ammonia (Engelhardt), by the manner 
in which iodide of ethyl reacts upon it (Borodine), and by the existence of a number 
of bodies obtained from chlorobenzol^ which may be regarded as the methyhite^ 
ethylate, acetate, Talerate, benzoate, &c. of the diatomic radicle CH*. 

b, Hd&nann has obtained diethylene-diphenylamine, K*.(C*H^)'(G^*)', by the action 
of cfakEEide of ethylene on phenylamine : 

2(C«H*.C1*) + 2(K.CWB[».H') = 4HC1 + K«.(C*H*)*.(C^»)*. 

Here too should probably be classed cyanogen, or oialo-nitrile, NK)*, which bears 
the same relation to normal oxalate of ammonitim that acetonitrile does to acetate of 
ammonium: 

C«H»0*jra« - 2H«0 - N.C H«j 
also nitride of boron, K^. 

HL 

1. Primary. 

2. Secondary. 

3. Tertiary. 
The only triamine known is Erankland and Kolbe's CyanetUne, (?H**N', which, 

according to Ho&iann, should be regarded as tnglyceiylamine, N*«(G*b*)', a tertiary 
triamine. 



They represent 3 molecules of ammonia^ in which 3, 6, or 9 atoms 
of hydrogen are replaced by 1, 2, or 3 triatomic basic radicles. 



and Pfintamtnesg-r-We know but little of any complex ammonia- 
molecules of a higher order than the. triamines ; nerertheless it appears that under 
certain drcmnstanees, four, five, or even a greater number of atoms of ammonia are 
capable of eoalescing into a complex molecule. 

The only well characterised tetramines with wjiich we are acquainted are ylyeostne^ 
K*.C^*, a product of the action of ammonia on glyoxal, which may be regarded as 

N\C?k*)*, and hexamethylenaminey N*»CfH", formed by the action of ammonia on 

diozymethylene, which maybe written N*(CH*)» (Buttlerow, Bullet, de la Soc. Chim. 
de Paris, i. 221.) There are also some natural bases containing 4 at. nitrogen, e. q, 
caffine, C^»«N*0*, and ikeobroTnifie^ C'II*N*0», but we know nothing of the radicl'ed 
which they contain. 
Vol. I. N 



17S AMIDES. 

Pentamines appear to be produced by the action of anunoma on oertain metallia 
oxides. Some of the ammoniacal compoondfl of cobalt appear to be of thia character ; 
but further inyeatigation is necessary to give accurate ideas of their oonstitatioD. 

Phosphines, Absinss, Stibinbs. — In connection with the basic deriTatiTes of 
ammonium, we must also mention a class of bodies derived from pho^horetted hydrogen, 
PH*, arsenetted hydrogen, AsH", and antimonetted hydrogen, SbK', by the substita- 
tion of alcohol-radicles for the hydrogen. All the compounds thus formed, are basic, 
like the alcoholic deriyatiyes of ammonia^ and form salts of exactly analogous charac- 
ter. Up to the present time, however, the only phosphines, arsines, and stibines, that 
have been obtained are those in which the whole of the hydrogen in the type ia 
replaced by an equivalent quantity of an alcohol-radicle, e. g, : 

Triethylphosphine P(C«H»)" 

Trimethystibme Sb(CH»)" 

These bases have not yet been obtained by direct substitution from the hydrides of 
phosphorus, arsenic and antimony; but they are produced, either by submittinff a 
metiulic compound of phosphorus, arsenic, or antimony to the action of the iodmea, 
bromides or chlorides of the alcohol: radicles, e.g,i 

Na'As + 8C»H»I - SNal +' Afl(C*H»)« 
Triaodic Iodide of Triethyl- 

•neDide. ethyl. anino. 

or, better in most cases, by treating the metallic compounds of the alcohol-iadides 
with the iodides, bromides, and chlorides of phosphorus, aiaenic and antimony; thos, 

SCBPZn + Pa« » SZnCl + P(CH»)« 

Zlnc-methyl. TrlmethjI. 

phofphiD^ 

These compounds, when treated with the bromides or iodides of the alcohol-radidea, 
behave exacUy like the corresponding nitrogen-bases, producing the bromides or 
iodides of bases containing 4 at. of the alcohol-radicle and belonging to the ammoniTua 
type : e, g.i 

ViC^n^y + C'ffl . P{C»H»)«I 
Triethyl. Iodide of Iodide of 
pboepnine. ethyl. ethylphoe* 

niuu. 

P(CH")« + C«H»I « P(CH«WC^»)I. 
Trtmethyl- lodlde'oftrinethyl- 

photphine. ethyl.phoipbonium. 

The phosphines treated with diatomic bromides (dibromide of ethylene, for example), 
yield, among other products, the monobromide of aphosphonium-molecule, in which the 
fourth atom of hycbogen is replaced by a brominated alcohol-radide ; thus triethyl- 
phosphine, treated wiUi dibromide of ethylene, yields the mcmobronade of bromUn^ 
triethyl-phoBphonium : 

T(C^Wy + CJ«H«Br« - P[(C^*Br)'.(C«H»)^Br. 
(See Akmonittx-basbs.) 

Alkalahides. 
I. Mpnalkalamldes or Allra lamfd— ■ 

1. Secondary Alkalamides, — ^They represent 1 vol. ammonia in which 2 atom 
of hydrogen are replaced, one by an acid, the other by a base radide. 

Mercurobenzamide , N.Hig.C*H*O.H. 

Argentosulphophenylamide , 
Etbylfbrmamide • • . 
Ethylacetamide .... 
Phenylbensamide (benzanilide) . 
Ethylcyanamide • 



N.Ag.C«ffSO«.H. 

N.(^».CHO.H. 

N.C«H»C«HK).H. 

N.C«H».(?HK).H. 

N.O«H».CN.H. 



Those which contain metals are formed by the action of primary amides on metallic 
oxides ;• they are decomposed bv most acids, which remove their metaL Those eon- 
taining silver are readily attacked by chlorides of acid-radicles, yielding seoondaiy 
amides and chloride of silver : 

N.Ag.(?HSO» H + (m^O.Cl » Aga + N.C«H«SO*.C'H»O.H. 

Argentoialphophe- Chloride of SuIpbopbeoylbensamMe. 

DylamiaAi bentoyL 



ATiKALAMIDES. 179 

Tbon eoDtaiiiiiig oi]gaiiie iMse-ndides, are formed by the same naetions as primaiy 
amides, a primaiy amine being substitated for ammonia : 

1. ij action of pcimazy amines on monobasio anhydrides (Gerhard t) : 

N.O"H».H« + ((m»0)«0 - Cra»O.H.O + N.C«H».CHK).H. 
neoflonine. Bcnsoicaa. Beoioie acid. Pheaylbensamlde. 

hjdrid*. 

2. By action of primaiy amines on chlorides of acid-radides (Q-e rhar dt) : 

K.CH«.H« + C«HH).a « HCl + K.CH».C*H«OJI 

MeUiyUmiii** Cblorid* of Methjlacetamida 

acfltyl. 

S. 3f action of primaiy amines on ethers : 

N.C»H».H« + C*H»O.C»H*.0 « C^».H.O + N.O"H».0*HK).H. 

EUqrlamine. Acetic «ther. Alcohol. EthyloeeUmtdc. 

4b By action of monohasie adds on cyanio etheis (W arts) : 

CHN.ILO + N.O«H».CO - CO.O + N.C*H».CHO.H. 
Fonnlcadd. pranateof CarboDie EUi/l-fbrnuunMo. 

ethyl. anhyd. 

They are czystalline, and generally do not combine with acids ; boiled with adds 
cr ilkalia, they take up HK), and regenerate their add and primaiy amine : 

N.CTH».C«HK):H + HK) « N.O^».H« + C»H«0.H.O. 

PheojiaeeUinide. Phcnylamina. Acetic acid. 

ThcM containing cyanogen act as weak allcalis, forming with concentrated adds com- 
poands vfaich are decomposed by water. B^ heat they are decompoeed in rather a 
peealiar nfanner, yielding a tertuiy alkalanude, and a kind of intermediate dialkala- 
mide, which oontaizis only monatomic radides : 

8(lir.C«H».CSr.H) - N.(C«H»)«.CN + N«.C«H».(CN)«.H« 
BOiylcyaaainido Dtothvlcyana* Ethyldlcyandianida. 

mida. 

Aoonrdine to G-erhardt (Ann. Ch. Phys. [3] liii. 307) secondary alkalamides are 
acted Tip^by pentadiloride of phosphorus in the same way as primaiy and secondaiy 
asiidcs: 

N.cw.(7iPo.H + pa» - if(crH»nc«ff»)ci + poa» + na 

PbtnyUbeiuaBiide* Chloride of pheoyl* 

beiumnuyl. 

2. Tertiary A iJkal amides. — They represent 1 molecule of ammonia in which all 
the hjdrosen is replaced ; (a) by 1 basic and 2 add monatomic radides ; (6) by 2 basic 
and 1 add monaftoniie radicles ; (e) by 1 basic monatomic, and 1 add diatomic radide. 

0. Warereplaeed by 1 borne and 2 add monatovdo radioUs : 

Ethyl-diacetamide K.C*H*.(C^K>)* 

Fhenyl^^benjEandde . . , • . N.C'KCC'H'O)' 

Thej are foamed : — 

1. 3j action of chlorides of add^radides on seoondazy alkalamides (Gerhardt 
aodChiosza): 

N.OfH».CrrEPO.H + C»H»0.C1 - HCa + N.CFH»^C»HK))». 
PiMBylbaiiaamidei Chloride of Fhanyldibeniamkla. 

benioiyl. 

% By ftefioii cf monobasic anhydrides on cyanic ethers (Wnrts): 

(C«H»0)«.0 + N.C»H».CO - 00,0 + N,(?H».(C«H»0)« 

Acetic anhy. Cyaoate of Ethyldiaoetamide* 

drldau ethyl. 

They sere neutral bodies, combining neither with adds nor with bases. 

k B*ar9 TtpiMtd by 2 bade and 1 add monatomic tadieU: 

Methyl-ethyl-cyanandde « , • . , N«CH".C'H*.CK 

Diethyl-cyanamide N.(C<H*)'.GN. 

The only membets of this group hitherto fonned, contain (^anc^n as the add- 

ndide. liiey are formed by Uie action of chloride <k cyanogen on secondaiy amines 

(Cahonrs and Cloes) : 

N.O»H» C^».H + CN.a - HCl + KC«H»,(>H».CN. 

BthylphcnylamtaM* Sthylpbenyk^a- 

namlde. 

They are Uqnid and TolatQe without decomposition. Heated with acids or alkalis, 

N 2 



180 AMIDES. 

they regenerate a seeondRi7 amine and cjanic acid, which latter is farther decom- 
posed into carbonic anhydride and ammonia : 

N.(C«H»)«.CN + HHO - ]Sr.(C«H»)*H + CN.H.O. 
Dlethyl-qrana- Dlethylamine. Cjaslc add. 

mlde. 

N.CO.H + H*0 - NH« + CO.O 

CTinIc acid. 9 

e. H* are replaced hy 1 monatomie baeie, and 1 diatonUo acid, radide, — Ab these 
compounds correspond to those seoondaiy amides which are commonly called imidei 
we will retain the same termination for them : 

Phenyl-snocinimide (snccinanile) • • • • N.l>M\^C*H*0*)* 
Ethyl-carbimide (cyanic ether) . « • « • N.G^'.^CO)" 

With the exception of cyanic ethers, the only members of this gronp that have been 
studied are those containing phenyl as their basic radicle; they are commonly called 
anUee. They are obtained by the action of phenyLunine on dibasic anhydrides or 
acids (probably also on the coiresponding chlorides) : 

N.C«H».H« + C»H"0«.0 - H»0 + N.C«H».C'*BP«0« 
Camphoric FheDylcamphorimide. 

anhydride. 

N.C«H».H« + CWH>«0«.H».0« « 2H«0 + lSr.C«H».C»«H»K)«. 

Camphoric add. 
Boiled with dilute ammoniai they form the ammomum-salt of an amie add : 



N.O»H*.C*H«0« + NH*.H.O = N.H.C«H».C*H*0«.NH*.0 

PhenyUttcciniinide. Phenylsaocinamate of 

ammoDlum. 

Fused with potash, they regenerate phenylamine and their add: 

N.C*H».C«H*0« + K*H*0* « C*H*0«.B?.0 + N.C^» H«. 

Succinate of 
potastiunu 

Afl cyanic acid may be regarded as carbimide, cyanic ethers may obTiooslj be 
regarded as alkalimides. With potash they exhibit the same reaction as the foregoing 

a,llra.MtTii MAB * 

N.C»H».CO + K*H«0« « CO.K».0» + n!C'H».H«. 
By the action of water or ammonia, they form Bialkalamides (compound ureas): 
N».(C«H*)«.(CO)» + H»0 « CO.O + N".CO.(C^»)«.H«. 

S mol. cyapic ether. Diethylcarbamide. 

N.OTP.CO + NH» - N*.CO.C*H».H«. 

EtbylcarbamMc 

n. BlalkaUunldM. 

There are no primary dialkalamides : but there exists a dass of compounds occupy- 
ing an intermediate place between primaiy and secondary dialkalamides. Thej re- 
present 2 mols. of ammonia, in which 8 atoms of hydroffen are replaced, 2 by a diatomic 
acid-radide, and 1 by a monatomic base-radide. With tbe exception of phenyl-ozamide^ 
N'.C^^GK)*.H^ the only members of this dass are the eompound urtae, representisg 
urea or carbamide in which 1 H is replaced by a base-radide : 

Ethyl-carbamide (ethyl-urea) .... N«.(CO)''.C«H».H» 
Phenyl-carbamide (phenyl-urea) . . . • N«.(CO)''.C^*.H', 

Tliey are formed by the action of a primary amine on cyanic add, or of ammonia on 

cyanic ethers : 

N.C«H»ja« + N.CO.H - N».CO.C«EP.H» 
NH« + N.OO.C«H» « N«.CO.C"H».H» 

Th^ are decomposed by potash, yielding carbonate^ a primary amine and ammonia: 
N«.CO.C«H».H» + H«.K«.0« » OO.K«.0« + N.C^*.BP + NH». 

2. Seeon dary Dialkalamides, — ^They represent 2 molecules of ammonia in which 
4 atoms of hydrogen are replaced by 2 monatomic base-radides and 1 diatomic acid 
radide: 

Dimethyloxamide m(CH«)« (CK)«)''JP 

Diphenylsucdnamide N*.(CW)*.(C«H<0*)..H* 

Diethylcari)amide (diethyl-urea) .... N*.(C"H»)«.(COy.BP 



ALEALAMIDES. 181 



Thejr in finmed: 

1. Bj beatiiig the nomial salts of oiganic alkalis r 

C«0\N.CH»JEP)« - 2H*0 « N«.(CH»)«.0»0*,H« 
OzAlato of nethy. DimethylozainJde. 



1 3j aetion of primaiy amines on etlien of dibasic acids : 

(K)».(C»H»)«.0» + N«.(CH«)*^* - (C^«.H».0» +m(CH«)«CK)«.H«. 
Outato of ethyl. S moL methyU S mol. alcohol. Dimcthyloumide. 

amioe. 

3. By action of prinuuy amines on chlozideB of acid-radicles : 

-sPAiyiPfjE^jEP + co.a* - ana + N«.(cm*)« co.h». 

S BKH. phanylamiiio. Chloride Diphenylculninlde. 

of cartHmyl. 

The oompoimd meaa (alkal-carbamides) belonging to this group are also formed by 
the aefcbacf water en cyanic ethers : 

2(N.00.C^«) + HH) « CO.O + N«.(C«H*)».CO.H» 
Cyanai« of DieChjlcarbamide. 

ethyL 

An tiiese seeondaiy dialkalamides are decomposed by potash, yielding a primazy 
uuDc^ and the normal potassinm-salt of their acid: 

N».(0«H«)».O»O«.H« + H«K»0» - K».(C*H»)«.H« + C«0».K«.0« 

Dlethyloxaiiiide. S molt, ethyl- Ozali^ 

amine. potass. 

Hofinann regards melanilinc^ C^EPIN* and a compoond, C*'H*^, which he has ob- 
taioed by^e aetion of dichloride of carbon on phenjoamine, as cyan-diphenyldiamide, 
1P.CN.(OT»)«JBP, and cyantriphenyldiamide, :^^.CN.(C•H»)^H^ respectively,—*, e, as 
diilkahmides containing only monatomic radicles. Considering the reaction by which 
the ktter at least of these oomponnds is formed, it may perhaps be preferable to regard 
it as deriving fiom 8 molecoles of ammonia, in which a portion of the hydrogen is 
icplaced by the tetratomic radicle, CT ra. ae N«.C.(C«H»)«.H«. 

Pebil has described the following compounds, intermediate between aeoondaiy and 
tertiaiy dialkalamides : 

Diphenyldtrimide N«.(C-H»)«.(C*H»0*r.H: 

Diphenylaconitimide N».(C^»)«.(C>H»0»r.H. 

They oorreqpond to the monadd phenylinm-salts of tribasic acids, less the elements 
ofSatomaofwater: 

8. Tertiary Dnalkalamides. — They represent 2 molecoles of ammonia in which 
all the hydrogen is replaced by base- and acid-radicles, one of which at least mnst be 
polyatomic. This process is represented by componnd-nreaa, in which all the hydro- 
Ken is replaced by baaic radides, — «.^. Tetrethylcarbamide or tetrethyl-nrea, 
1^.(C0)*'.(J^B[')^ iysobyBnflfssnlphocyamde of ethylene (ethvlene-disnlphocarbamide) 
N'.(GS)'.(C^*)*. obtained by boiling chloride of etnylene witii an alcoholic solution of 
snlphocfanate of potassium (Proc. Soy. Soc. viiL 188), and by Hofmann's diphenyl- 
eaitoxamide, K».rCO)''.(0K)«XC«H»)*', obtained by the action of dilute hydrochloric 
add on dicyanmeianiline. 

CP'H^'N* + 3HC1 + 3H«0 - 3NH*C1 + N».CO.CK>«.(C*H»)« 

More nkht probablT be obtained by the action of seoondazy amines on chlorides of 
tod radides, or on ewers of dibasic adds : 

2(N.(CH>)«.H) + C*H*0«.a* - 2Ha + N*.(CH»)^C<H*0«. 

TetramethjUnoci- 

2[NX0«H»)«jq + C<H*0« (C«H«)«.0* - 2(0«H»JLO) + N».(C*H»)*.C*H«0« 

Soodnate ofetDyL Tetrethykuodnamlde. 

1. Secondary Trialkal amides, — They correspond to 3 molecules of ammonia, in 
vhieh 6 atoms of hjdrq|;en are replaced by 1 triatomic add-radide and 8 monatomic 
b8ae.radides. Examples are Pebel's triphenyldtramide^ K'.(Cna*)*.(C^*0«)'*'.H', ob- 
tained by the aetion m dtric add on phenylamine : 

O^BPO*.H».0» + 8(N.C^.H«) - N».(C«B[»)«.(?H»0*.H» + 3H«0. 

It eonesponds to the normal dtrate of phenylium, less the dements of 8 atoms of 
vater. Also SchifTs triphenylphoephamide, N'.(CH»)'.PO.H', and trinaphtylphos- 

N 3 



182 AMMONIA. 

phamide^ N'.(C'*H')'.PO.H*, obtained by the aetion of pbenylamine and naphtjlamine 
respectiTelj on ozychloride of phofphonia (Ann. Ch. Pnann. eL 800) : 

POa« + 3(N.Cra*.H«) - N».(C»H»)«J>aH«. + 8Ha 

2. Tertiary Trialkalamides, — ^The c^annric ethen may be placed in this diii- 

Bion, e, g, cyannrate of etl^yl, N«.(60)»,(C*H»)».— F. T. C. 

and ASKOKWMJJKM^ See Ctavttbahic AjCIIM. 



EXOUnn. A red earthy mass from Chile, containing 86*5 antimony, 14*8 
tellurium, 12'2 copper, 32*2 mercnry, and 2'ff qnarti, besidsB oscygen; pvobtUy a 
mixture. (Bammeubtrg^t Mintralchemifi, p. 426.) 

AIIMOVXJL. NH*. (S^nymes, VolaiiU MaU, MkMu mr, Ammomaeal goi, 
Jmnumiajuet Ammoniak.) 

S^MtoTf, — The eariiesi mention of aqoeoos amwMwii% whioh was known long befen 
the gas itself^ is made by Raymond Lully, in the thirteenth oenturf : he prepared it 
from urine, and called it MtreuHut vd tpiritus ammaUt. Basil Valentine, in the 
fifteenth century, first pr^ared it from sal-anmioniac : he still retained the name spiritut 
urina. It was Bergman (1782) who first designated it bj^ the name ammonia, Am- 
moniacal gas was disooyered by Priestley, who describes it in 1774 by tho name of 
alkaline air ; he also observed its decomposition by the electric spariu 8<abeele» in 1777. 
ascertained that it contained nitrogen, regarding it as a compound of nitiiigen and 
phlogiston. Its true oomporition was first ascertained by BerthoUet ^1785) ; and it 
was finally aneJysed with still greater exactness, by his son Am. BertnoUet in ISOflw 

Katural Souroet, — Ammonia exists in the air as carbonate of ammoniwn : in rain- 
water, oBperially in that of thunder-showers, as nitrate. In sea-water, and in many 
mineral springs. In most kinds of clay and soils: in seequioxide of iron, and in the 
nugority of iron-ores. Sal-ammoniac and ammonium-alum are found as minerals, the 
former chiefly in Tolcanic regions, and in some specimens of rock-salt. Ab amiiMmiacal- 
salts, in animal fluids and excronents (especially in nrine), and in the juices of many 
plants. 

Fi>rmaii(m, — Ammonia cannot be formed by the direct combination of its elements 
in the free state. When 1 toL nitrogen and 3 vols, hydrogen are passed throng^ a 
red-hot tube, no ammonia is formed, not eren if spongy platinum be present. But it 
is formed with sreat readiness by the combination of its elements, wnen one or both 
of them is in uie naeeent state : tL f. at the moment of its Ubeiation from another 
compound : and in this manner ammonia may be formed from many snbstancesi dganie 
and inorganic. 

1. FrSm inorganic wbeianeei. — On igniting a mixture of oxygen, nitrogen, and 
excess of hydrogen, nitrate of ammonium is formed. (Th. Saussure.) 

a. Formation from nascent hydrogen and free nitrogen, — Water containing at- 
mospheric air yields nitric acid at the positive pole, and ammonia at the negative pole 
of a voltaic battery (Sir H. Davy). Moistened iron-filings, in contact with atmo- 
spheric air or nitrogen at the ordinaiy temperature, induce the formation of ammonia 
(Ghevallier, Berzelius). (Will states that no ammonia is thus formed.) This 
reaction accounts for the existence of ammonia in rust of iron, and iron ores generally. 
When liver of sulphur ia fused with an e^ual weight of iron-filings, and water dropped 
on the hot mass, ammonia is evolved (Hollunder). When oertain metals wluch 
combine readily with oxygen (potassium, arsenic, lead, iron. &c.) are heated with the 
hydrates of potassium, SMium, barium, or calcium, in contact with air, ammonia is 
formed. Faraday states that this formation of ammonia takes place even in an atmo- 
sphere of hydrogen : a fact explained by Bischof as arising from the difllcnlty of 
obtaining hydrogen free ftom atmospheric air. Beiset also points out that the hydrogen 
will contain nitric oxide, if the sulphuric acid employed for its generation contains 
nitric acid or nitric oxideu 

b. Formation from nasomt nitrogen and free hydrogen. — A mixture of 2 vols, nitric 
oxide and 6 vols, hydrogen passed over gently heated qwngy platinum, yields ammonia 
and water (Hare; Ville, Ann. Ch. Phya. [3] xlvi) The same gases when passed 
through a red-hot tube, only yield ammonia when some porous substance is present; 

Eumioe-stone, or feme oxide acts most energetically (Keiset). Nitrous oxide and 
ydrosen in excess yield ammonia when in contact with hot spongy pUtinum or plati- 
num-mack. Hydrogen saturated with nitric acid vapour acts in a similar manner. 

c ForTfuUion from nascent hydrogen and nascent nitrogen, — Moist nitric oxide 
passed over heated iron-filings yields ammonia. A mixture of nitric oxide and hydro- 
sulphuric acid, passed over heated soda-lime, yields ammonia (Ville^. Certain 
metals which decompose water at a high temperaturo (iron, zinc, &c.), wnen treated 
with dilute nitric acid, or the acjueouB solutions of certain nitrates, vidd ammonia. 
Ammonia is formed when nitric acid is added to one and sulphuric add in a hydrogen 



AMMONIA. 183 

maxaim^ alio liy tlie deeompodtioii of chloride, iodide, and phoBpliide of nitrogen, 
and of all bodies beknigin^ to the elaas, amides, by water. When a mixture of baryta 
and earbonaeeooa matter u heated in contact with air, cjanide of barium is formed, a 
eaa^KHUid which is deoompoaed by steam at ^00° G. into carbonate of barium and 
amaonia: Maigneritte and Sonideyal have lately proposed to employ this process for 
thepmaration of ammonia on the laige scale. (Bep. Chun. App. li 170.) 

2. From aryanic mib$Umcu. — Many mm^nitrogemma organic bodies form ammonia 
by nolongcd contact with air and water : «.^. in the process of putresCaction. Sugar, 
OTaiaf<p«, taitmtes, && yield ammonia when heated with alkaline or alkaline-earthj 
hydrates, in contact with air. Oxygen-compounds of nitrogen, heated with organic 
Hsdnring agents, &^. nitric oxide with aloohol-yapour, nitric acid with gum, form 
swmfwiTa Most ntiroffemsed organic compounds ^eld ammonia, either ^e or com- 
bined, in tlie processes of potrefustion or of diydisttUatibn : it is from this source tiiat 
the ammonia eodsting in nature is chiefly deriyed. 

Preparation, — ^Powdered sal-ammoniac is mixed with twice its weight of slaked lime, 
the miztnre ooyared with a layer of coarsely powdered quick lime, about equal in weight 
to tlie sal-ammomac used, and the whole heated gradually in a flask or retort : for the 
preparstioii of ammonia on a large scale, iron yessels are used. The gas is passed 
throo^ a two-necked bottle, in which aqueous yapour is condensed, and any solid 
paitiHea that may be earned oyer azeanested ; it is then dried by passing oyer solid 
potash or qvi^ lime — or better, a mixture of the anhydrous oxides of potassium and 
oqi^wk; obtained by heating nitrate of potassium with finely diyided copper reduced 
fimm the oxide by hydrogen (S t as), (chloride of calcium absorbs the gas)— ^d collected 
over meremy. If the gas is ^ure, it should be entirely absorbed by water. In order 
to obtain perfectly diy ammoma, Vogel recommends saturating a concentrated aqueous 
solalion of ammonia with solid chloride of calrium, heating gently, and passing the 
gaa orer solid potash. 

Ih 'c pe9iie $. — Colourless gas, of a pungent smell, and strong alkaline taste. Its 
^wofie gravity is (calculated) 0*5893; (H.Dayy) 0*6901; (Thomson) 0*5931; (Biot 
and Arago) 0*5967. 1 litre at 0^ C. and 760min. barometric pressure weighs 0*7752 
grm. (Biot and Arago). Its specific heat (water a 1) is 0*508 (Kegnault). Its 
le&actaTe power (air a 1) is 1*309 (Dulong). 

It does not support either combustion or respimtion : animals die when immersed 
in it. It is feebly combustible : when issuing m a thin stream into atmospheric air, 
it may be kindled, and bums with a pale fliune. It colours turmeric paper brown, 
and reddened litmus blue : the colours disappear on exposure to the air. 

It may be condensed by cold and pressure, and obtained both in the liquid and solid 
fann. Faraday prepares liquid ammonia as follows : Ammonio-chloriae of silver is 
introduced into a very strong glass tube, closed at one end, which is then bent at an 
aeate ang^e^ the chloride being in the loncer Hmb. The shorter limb is then sealed 
and immersed in ice, and the chloride gradually heated : it fuses at 38^ C, and be- 
tween 112^ and 119^ C. gives off all its ammonia, which condenses to a liquid by its 
own pfesBOze in the cool part of the tube. As the chloride of silver cools, the liquid 
ammfliiM. boils yiolentlv, and is reabsorbed by the chloride. Gnyton de Morveau and 
Bunsen have condensed ammonia without pressure by a mixture of chloride of calcium 
and ice, the fonner at ~ 52^ C, the latter at — 40^. Liquid ammonia is a colourless, very 
mobile liquid, refracting light more powerfully than water; specific gravity 0*76: 
boiling-point at 749min. braometic pressure, — 33*7^ C. (Bunsen.) Its tension at 
-17-78^ C. a 2*48 atmospheres: at 0° C. » 4*44 atm. : at 10-8^ C. » 6 atm.: at 
I9-44<' C. a 7-60 atm. : at 28*31° C. » 10 atm. 

Faraday has obtained solid ammonia by exposing the dry ^ to a pressure of 20 
atmoi^iheres and to a cold of — 75° C, produced by solid carbomc anhydride and ether. 
It is a white, transparent, crystalline body, which melts at —75° C, and has a higher 
specific gravity than liquid ammonia. 

DoeomooUiono. — I)iy ammonia is decomposed by a succession of electric sparks : 
the resoiting gas is double the volume of the original gas, and consists of 1 vol. nitrogen 
and 3 vDlsTnydrogen. Also by being passed tlm)ugh a red-hot porcelain tube contain- 
ing eopper or iron wire ; gold-, silver-, or platinum-wire acts similarly, but less ener- 
geticafiy. No change is produced in the gold and platinum-wire : the copper and iron 
wii« are rendered brittle, and sometimes increased in weight, owing to the formation 
of a nitride. — 2 vols, ammonia mixed with not less than 1, nor more than 6 vols. 
oxygen, are exploded by the electric spark : the products, if the oxygen be in excess, 
are water and nitrate of ammonium ; if the ammonia be in excess, water, nitrogen, 
and hydrogen. — Aqueous ammonia, in contact with finely divided copper or platinum, 
and oxjffftm, cft atmoopherie air, is converted into nitrite of ammonium, both its con- 
stitaeBts imdeigoing oxidation (Handwb.) — ^Ammonia is decomposed by several of the 
ooygen-eompoiinds of chlorine and nitrogen. Dry ammonia mixed with dry hj/po^ 

N 4 



184 AMMONIA. 

cklorctu anhydride explodes yiolently at the ordinaiT' temperature, -with sepantioo of 
chlorine. Aqueous ammonia added gradually to aqueous hypochhrmu aeid^ the 
mixture being kept cool, yields nitrogen, and chloride of nitrogen. Ammonia nuzed 
with proper proportions of nitroua or nitric oxide, explodes by the electric spark, yield' 
ing water and nitrogen. Ammonia is Tiolently decomposed at the ordinaiy temperatme 
by peroxide of nitrogen^ whether liquid or gaseous, with evolution of nitric oxide and 
nitrogen (Dulong). — In contact with chlorine in tiie cold, ammonia bums with a red 
and white flame, forming chloride of ammonium and free nitrogen (4NH* + C9,' ^ 
3NHK)1 4- N); when chlorine is passed into strong aqueous ammonia or a solution of an 
ammoniacal-salt» chloride of nitrogen is also formed. — Iodine does not deoompoee 
diy ammonia: in presence of water, iodide of ammonium. and an iodine-denT^ 
tive of ammonia are formed. — ^With bromine^ ammonia yields bromide of ammo- 
nium and free nitrogen. — ^Passed with vapour of phosphorius through a red-hot tube, 
ammonia yields phosphide of hydn^n and free nitrogen. — ^Passed over red-hot char- 
coal', ammonia yields cyanide of ammonium and free hydrogen. — ^With bistUphide of 
carbon, ammonia gives hydrosulphuric and sulphocyanic acidb (NH' + CS* i- B^ + 
CSH). — ^When potassium or sodium is heated in dry ammonia, hydrogen is evolved, 
its place being supplied by the metal, and nitride of potassium and hydrogen (potusap 
mine), NKH', is formed. — In contact with zinc-ethyl, ammonia gives zinc-amine KZnH' 
and hydride of ethyl, C^*. Mainy metaUie oxides decompose ammonia with the aid of 
heat : the products are sometimes water, nitrogen, reduced metal, and more or less of 
an oxygen-compound of nitrogen ; sometimes, water and a metallic nitride. — ^Ammonia 
reacts with anhydrous acids, chlorides of acid-radides, and many compound ethers, 
giving amic ados, or amides. In like manner, it gives with many derivatives of the 
alcohols, amic bases or amines. (See Aiao Acids, Amc Basbs, Ajcdbs, Amikbs.) 

We have seen that ammonia is decomposed by certain metals and metallic oxides, 
hydrogen being liberated, and compounds formed representing ammonia in which a 
part or the whole of the hydrogen is replaced by a metaL There are certain organic 
compounds {e. g. monobasic anhydrides, compound ethers, &&) which are capable of 
decomposing ammonia in a similar manner, with formation of compounds representing 
ammonia in which the hydrogen is wholly or partially replaced by an orsanic radide, 
acid or basic. The numerous and interesting class of compounds which are thus 
formed frY>m ammonia by the partial or total replacement of its hydrogen by other 
radicles, oreanic or inorganic, acid or basic, is known by the generic name of amides: 
under which name they ore fiilly described. 

Combinations. — 1. With Water {Solution of ammonia. Aqueous ammonia^ or 
simply Ammonia, Spirits of hartshorn, Salmiakgeist, Liquor ammonii). 

Both water and ice absorb ammonia with great avidi^, with considerable evolution 
of heat, and with great expansion. Davy found that 1 vol. water at 10° C. and 29*8 
inches barometric pressure absorbs 670 vols, ammonia, or nearly half its weight : the 
specific gravity of this solution is 0*875. According to Dalton, water at a lower tern* 
perature absorbs even more ammonia, and the specific gravity of the solution is 0*85. 
According to Osann, 100 pts. water at 249 C. absorb 8*41 pts. at 66^ C. 5*96 pts. am- 
monia. 1 voL water by absorbing 505 vols, ammonia, forms a solution occupring 
1*5 vols., and having specific gravity 0*9 : this, when mixed with an equal bulk of 
water, yields a liquid of specie gravity 0*9455 : whence it appears that aqueous 
Ammonia expands on dilution. (Tire.) 

Preparation. — 1 part of sal-ammoniac in lumps is introduced into a glass flask, 
with 1} parts slaked lime, and from 1 to 1| parts water : and the flask is connected 
by bent tubes with three Woulfe*s bottles. The first bottle, which is intended to 
arrest any solid particles that may be carried over mechanically, and any empyrea- 
matic oil contained in the sal-ammoniac, as well as to condense aqueous vapour, con- 
tains a small quantity of water (Mohr prefers milk of lime). The second bottle con- 
tains the water to be saturated with ammonia: it should contain a quantity of water 
about equal in weight to the sal-ammoniac employed, and should not be more than 
three parts full, to allow for the expansion. These two bottles should be placed in cold 
water, and each provided with a safety tube. The third bottle contains a little water, 
to retain any ammonia that may pass through the second bottle. The fiask is then 
heated in a sand-bath, care being taken that its contents do not boil over : and the 
operation continued till about half the water in the flask has distilled over into the first 
bottle. The first bottle then contains a weak and impure solution of ammonia : the 
second a pure and strong solution (if a perfectly saturated solution be required, the 
quantity of water in this bottle should not exceed } the weight of the sal-ammoniac 
employed) : the solution in the third bottle is weak, but pure. 

The proportions of lime and water to be added to tlie sitil-ammoniac in order to pro- 
duce the largest yield of ammonia have been variously stated : those given above are 



AMMONIA. 



185 



WW most genenillj TfHxired. Accoidmg to the eqnatioxi, CaHO + NH*C1 » NH* + 
CftO + HK), the amount of slaked lime should be to that of sal-ammoniac as 
37 : 5Z'5, or 69 parts of the former to 100 parts of the latter. But in practice it is 
alwmjs focmd necessarj to employ a larger proportion of lime ; for not only is the lime 
of eommeice always impure, but also it is impossible to bring the whole of it into such 
eontact with the sal-anmioniae, as would ensure the completeness of their reaction. 
Hm object of adding water is to ensure the gradual solution of the sal-ammoniac, and 
eooeequently its more complete contact with the lime. There are also other disad- 
TBotagefl which attend the absence of water. If the lime and sal-ammoniac are mixed 
io a state of powder, a large quantity of ammonia is lost before the mixture is intro- 
duced into the flask ; and the heated mass expands on cooling so as invariably to 
break the flask. These inconyeniences are avoided by first placing the sal-ammoniac 
in lumps in the flask, and then oorering it with the powdered Hme : but in this case 
the heat required is sufficient to TolatiUse the sal-ammoniac, which is liable to stop 
up the deliveiT-tube and canse a dangerous explosion. Moreover a larger quantity 
of empyreumatic oil passes over with the ammonia : and the chloride of calcium formed 
in the flask obstinately retains a portion of the ammonia, which is consequently lost. 
On the other hand, the addition of too much water diminishes the product of am- 
monia, and hampers the operation in other ways. 

In the preparation of aqueous ammonia on a large scale, the gas is generated in 
cut-iron or copper vessels : earthenware vessels are generally fouad not to answer, 
owing to the porosity of their structure. 

The aqueous ammonia thus prepared may contain the following impurities, which 
ue easily detected : 

Carbcmate o/anuniOmum. — Oecnrs when the lime employed contains much carbonate, 
or when the solutioa has been exposed to the air. Causes turbidity when heated with 
chloride of barium. 

Cilorme. — Owin^g to chloride of ammonium having been sublimed, or carried over 
mechanically. The solution, saturated with nitric acid, gives a cloudiness with nitrate 
of sihrec 

Lime. — Gamed over mechanically. CKves a precipitate with oxalic add : left as a 
•olid Rsidne on evaporation. 

Copper at Lead. — ^Derived from the generating vessel. The former is detected by the 
ioktion becoming tinged with blue on evaporation ; the latter by hydrosulphuric acid. 

Empyrmmatio oil, — From the sal-ammoniac. The solution has a yellow colour 
and a pecoliar smell. 

FnpeirHeB. — Aqueous ammonia is a colourless transparent liquid, smelling of 
KinmAnU^ and having a sharp burning, urinous taste. Its specific gravity varies from 
1*000 to 0'8o, according to the amount of ammonia it contains: its boiling-point varies 
similarly (see D a 1 1 o n ' s table, ir^ra.) A perfectly saturated solution freezes between 
—38^ and —41^ C, forming shining flexible needles: at —49^ C. it solidifies to a 
grey geUtinous mass, almost without smell (Fourcroy and Yauquelin). It loses 
afanort an its anunonia at a temperature below 100^ C. The following tables have 
been constructed, showing the amount of real ammonia contained in aqueous ammonia 
of difierent densities : 



Dal-tom. 


H. Davt. 


Uri. 


S^edflc 


Pcremtacs 


Boiling 


Specific 


Percentage 


Specl6c 


Percentage 


Specific 


Percentage 


fnrttjr. 


AniiBOouu 


Point. 


grtiTii7. 


Ammonia. 


gravity. 


Ammonia. 


gravity. 


Ammonia. 


OH} 


3S-8 


-4« 


0^50 


82-8« 


0-8914 


97-940 


0-9868 


15-900 


e« 


3S6 


+3-5« 


0-8857 


99-25 


0*8937 


27-688 


0-9410 


14-575 


IW7 


»9 


ltf» 


0-9000 


se>oo 


0-8967 


37-038 


0*9455 


18*350 


OM 


17-t 


ir> 


0*9054 


25-37« 


0-8983 


26-751 


0-9510 


11-985 


•-» 


94*7 


sa» 


0*9166 


93 07 


0-9000 


96-500 


0-9564 


10-600 


MO 


SS-S 


wo 


0-9255 


19 54 


09045 


25-175 


0-9614 


9 275 


»9I 


19*8 


8r» 


0-9826 


17-52 


0*9090 


93-850 


0-9662 


7*950 


9n 


17'4 


44« 


0-93I85 


15*88 


0-9138 


29-525 


0-9716 


6-625 


»« 


lfr-1 


ifp 


0*9485 


14*53 


0-9177 


21-200 


0-9768 


5-500 


»M 


19-8 


47° 


0-9476 


18*46 


0-9227 


19-875 


0-9828 


3-975 


Mft 


10-5 


esp 


0*9518 


19-40 


0-9275 


18-550 


0-9887 


3-650 


»S6 


8-a 


w> 


0-9545 


11-56 


0-9320 


17*225 


9945 


1-338 


(W 


»S 


79" 


0-9578 


10-82 










o« 


4-1 


vr 


0-9S97 


10-17 










0« 


SD 


980 


0-9616 
0-9699 


9-60 
9 50* 










•Tl 


lesenimiben 


weredetf 


tnnined by 


experiment : 


the rest in 


Davy's table 


by calculat 


lou. 



186 



AMMONIA. 



J. Orra DetenniiLations made at 16^ C. 



Spedfle 


p0reeDta« 
AmmoDik. 


Specific 


PeroenUffe 


Specific 


PercoiUge 


gravtt/. 


gnwltj. 


AmmooU. 


graTicjr. 


AflUBooia. 


0*9617 


12K)00 


0-9607 


9-035 


09697 


7-9M 


0-9fi31 


11-876 


0-9613 


9-600 


0-9703 


7-135 


cwas 


11-780 


0W16 


9-376 


0-9707 


7-000 


0-9631 


ires5 


0-9631 


0-860 


0*9711 


6-876 


0*9696 


11-500 


0-96BI6 


9-135 


0-9716 


e750 


0-9640 


11-375 


0-9631 


9<XI0 


OiTTtl 


6'636 


0-9645 


1I-980 


O-OfOO 


8-875 


0-9736 


6500 


09660 


11-195 


0-9641 


8-750 


0-9730 


e«i 


0^666 


11-000 


0-9646 


8-635 


0-9735 


6-850 


0-9S66 


10-960 


0-9660 


8-600 


0-9740 


0-185 


00669 


10875 


0-9664 


8-376 


Oi»745 


6100 


0-9664 


10760 


0-96!» 


8-380 


0-9749 


6-875 


0-9609 


10-0S5 


0-9664 


8-196 


0^64 


5-750 


0-9674 


10-600 


0-9669 


8-000 


0-9760 


5-636 


01M78 


10-375 


0-9673 


7-875 


0-9764 


6-600 


0-9MS 


10-350 


0-9678 


7-760 


Oi)768 


5-876 


0^9588 


10-1S6 


0-9683 


7-685 


0-9773 


5-360 


0-9693 


10-000 


0-9688 


7-500 


0-9n8 


6136 


0-9697 


9-876 


0-9693 


7-375 


00783 


tixn 


O-960I 


9-760 




1 







Ifc Cajuus. (Ann. Gh. Phaim. xciz. 164.) DetenninatioDfB made at 14^ 0. 



Specific 


P.C. 


Spedflo 


P.C. 


Spedfle 


P.C. 


Spedfle 


P.C. 


Spedfle 


P.C. 


Spedfle 


p.a 


gravity. 


Amm. 


gravity. 


Amm. 


gravity. 


Amm. 


gravity. 


Amm. 


gravity. 




gravity. 


Awn. 


0-8M4 


86-0 


0-8976 


80-0 


0i)133 


34-0 


0-9814 


18-0 


0^630 


I8i) 


09749 


65 


0-8848 


86-8 


0-H981 


89-8 


0-9139 


33-8 


0-9321 


17-8 


Oi»637 


11-8 


0-97A7 


6-8 


0-8863 


36-6 


08986 


99-6 


0-9146 


33-6 


0^037 


17-6 


0-9684 


11-6 


0^66 


6-6 


0-8866 


35-4 


0-8991 


89-4 


0-9150 


83'4 


0-9833 


17 4 


0-9648 


11-4 


0i»73 


5-4 


0-8860 


353 


0-8996 


99-8 


0*9166 


332 


0-9940 


17-3 


0^649 


ll-S 


09781 


6-2 


0-8864 


36-0 


0-9001 


89-0 


0-9163 


83-0 


0-9347 


17-0 


0^566 


11-0 


O9990 


65 


08068 


34-8 


0-9006 


88-8 


0-9168 


22-8 


0-9368 


16-8 


0-9663 


10-8 


fr9999 


45 


0-8873 


346 


0-9011 


28-6 


0-9174 


22-6 


0-9360 


16-6 


0-9571 


10^ 


0^807 


45 


0-8877 


34-4 


0-9016 


88-4 


0-9180 


8-2-4 


0-9366 


16*4 


0-9578 


10-4 


0-9815 


4-4 


0-8881 


34-3 


0-9081 


38*3 


0-9186 


22*3 


0*9373 


16-9 


0-9686 


109 


0-9883 


45 


0-8886 


340 


0-9086 


88-0 


0^191 


33-0 


0-9380 


16-0 


0-9998 


10-0 


09831 


45 


0-8889 


33-8 


0*9031 


37*8 


0-9197 


31-8 


0-9386 


168 


0-9601 


9-8 


0-9839 


85 


0-8894 


836 


0-9036 


37-6 


0-9303 


81-6 


0-9393 


16-6 


09606 


9*6 


0^847 


35 


O-O'tOe 


33-4 


0-9041 


37*4 


0i»09 


91-4 


0-9400 


16-4 


0-9616 


9-4 


0-9866 


3-4 


0-89« 


38-3 


0-9047 


973 


0-9316 


81-3 


0*9407 


16-8 


0-9633 


9-3 


0-9863 


»8 


0-8907 


33-0 


0-9068 


27-0 


0-9281 


81 


0-9414 


16-0 


0-9681 


9-0 


0-9373 


35 


0-8911 


3S« 


0*9087 


36-8 


0*9287 


30*8 


0-9430 


14-8 


0-9639 


8*8 


09883 


35 


0-8916 


83-6 


0-9068 


86« 


09883 


30-6 


0*9427 


14-6 


0-9647 


86 


01890 


t< 


0-8930 


83*4 


0*9068 


36-4 


0-9239 


204 


0-9434 


14-4 


0-9664 


8-4 


0-9(199 


3-4 


0-89-i6 


833 


^9073 


86-3 


0*9346 


30-8 


0-9441 


14-8 


0^668 


8-2 


0*9907 


35 


0-8999 


88 


0-9078 


86-0 


0-9261 


30-0 


0-9449 


14-0 


0*9670 


8-0 


0^15 


35 


0-8884 


31-8 


0-9083 


36*8 


0«67 


19*9 


0-9466 


13*8 


0-9677 


7-8 


05984 


15 


0-8988 


31-6 


0-9089 


36*6 


0-9964 


196 


0-9463 


13-6 


0-9685 


7-6 


05932 


15 


08943 


31-4 


0-9094 


26-4 


0-9371 


19*4 


0-9470 


13-4 


0-9* 93 


7-4 


05941 


1-4 


0*8948 


81-3 


0-9100 


86-3 


09277 


19-2 


0-9477 


13*3 


0-97UI 


7-3 


05950 


1-8 


0-8963 


810 


0-9106 


36*0 


0-92KS 


190 


09484 


18-0 


0-9709 


70 


05959 


15 


0-8967 


30-8 


0*9111 


34-8 


1 0-9889 


16-8 


09491 


138 


0-9717 


6-8 


05967 


•5 


a8963 


30-6 


0-9116 


34-6 


1 0^296 


18-6 


0-9498 


18-6 


0-9736 


0-6 


05976 


06 


0-8967 


30-4 


0-9183 


84*4 


0-930-i 


18-4 


9605 


18-4 


0-9733 


6-4 


05968 


(^4 


0-8971 


30-8 


0-9187 


84-8 


, 0-9308 


18*2 


0-9612 


12-2 


0*9741 


6-3 


05991 


05 



By the aid of these tables, the strength of aqueous ammonia, like that of commeraal 
aleohol, may be approximately ascertained hv taking its specific gravity. (See also 
Qriflin's Table given in Ure^s Dictionary ojArts, ManufaciureSf and Mines^ vdL i. 
p. 132, and Chem. Soc. Qn. J. iii. 260.) 

Boscoe and Bittmar (Chem. Soc. Qu. J. idi. 147), have detenninedtheamonntof 
ammonia-^ absorbed by water at yarions pressures and temperatures. The results 
are given in the two following tables. 

Table A shows the weight of ammonia-gas in granmies G absorbed by 1 gramme 
of water at 0^ C. and various jpar^to/ pressures P.* 



* By partial presfure It meant the total preature under which the absorption oocurt, 
of aqueona vigour at 0° C 



the 



AMMONIA. 



187 









Table A 








p. 


G. 


F. 


O. 


P. 


0. 


P. 


O. 


ow 


IHM 


0*tt 


0*466 


086 


0-9S7 


1*46 


1*49 


0«1 


INM4 


ow 


0'61i 


000 


0-963 


1-ao 


1-SM 


MB 


»«M 


0-35 


0-661 


0^ 


1001 


1*66 


1-664 


0<B 


0>M0 


O-W 


0-607 


1-00 


1037 


1-60 


1-646 


Ml 


0-I4S 


oa 


0«46 


1-06 


r075 


1-66 


1-707 


• » 


0-176 


0*50 


O^BO 


MO 


1-H7 


1-70 


1-770 


••T* 


o^ns 


0-56 


0*731 


1-16 


1-161 


1-76 


1-836 


O-lOO 


O^ft 


aeo 


O-TW 


1*30 


1-903 


130 


1*906 


t^m 


04l» 


0« 


0-W4 


1-36 


1-363 


1-36 


1-076 


0-l« 


0-SSI 


0-70 


0-840 


1*30 


1-810 


1-M 


SHM6 


o-m 


0*381 


0-76 


0-379 


1-36 


l*30t 


1*96 


- 3-130 


tPSOO 


0-411 


om 


O906 


1-40 


1-416 


IHW 


3-196 



Fiom these nnmben it appears : (1) that the quantity of ammonia absorbed by 
vitcr at 0^ G. is fiff from beuff proportional to the pressure ; and (2) that for equal 
iaoements of pressiue np to about 1 metre of mercmy, the corresponding increments 
of absorbed ammonia continnaHy diminish, but that above this poin^the amount of 
disiohred gas inocases in a more rapid ratio than the pressure. 

Table B ahowB the weight in grammes of ammonia (column IL), absorbed by 
1 giamme of water under the pressure of 0*76". and at yarious temperatures (oohimn I). 

Tabu R 



1 ■• 


11. 


I. 


11. 


I. 


11. 


I. 


11. 


/ opa 


0«76 


le^c. 


0-668 


»2*»C. 


0-889 


48°a 


0-944 


/ ** 


0«8S 


18» 


0-654 


340 


0969 


60° 


0-999 


1 *• 


1^798 


80«» 


0-696 


36° 


0-343 


69° 


0-214 


«• 


0761 


88«» 


0-499 


38° 


0-394 


64° 


0-900 


8P» 


V7\t 


24* 


0-474 


40° 
49° 


0-807 


66° 


(M86 


1€^ 


0^79 


86» 


0-449 


0-eM 






l«» 


0646 


88" 


0-486 


44« 


0-975 






I4f» 


0^618 


30« 


0-403 


46° 


0-969 


- 





A^ufloas ammonia possesses the property of dissolying many salts which are insoluble 
wrmter. Thus it diasolTeB chromic and stannic oxides, the protoxides of tin, cadmium, 
4tcL, the oxides of copper and silrer. The compounds thus formed are decomposed 
^rj- beat, loau^ ammonia, sometimes with explosive violence. Many other salts are 
almo flolnhie in aqueous ammonia, e.ff. phosphate, chloride, bromide of silver, &cl : in 
the original salt can be recovered unchanged by evaporating off the awimnT iia ; 
intimate combination is effected. 



2. With alcokol. (liquor ammoniaci alcoholicus). 

Alcohol, like water, absorbs ammonia in great quantity, with eonsiderable expansion 

and evolntion of heaL The aleohoUe solution is prepared in precisely the same way as 

the aqoeons solution, akohol of B6 — 90 p. c being substitntra for water in the second 

Vko^tle. The proportion of alcohol to the sal-ammoniac employed should be somewhat 

less than in the ease of water. The specific gravity of the solution of course varies 

with the amount of alcohol and ammonia whid^ it contains. 

5. WUk metallie wUs. Ammonia forms solid compounds with oortain metallic 
ondes (of gold, silver, platinum, mercury, antimony, &c) which are decomposed l^ heat, 
freqnenUy with explosive violence. Cortain metidlic chlorides, bromides, and iodides 
(pi ailrer, nJrium, ^) absorb ainmonia, frequently with evolution of heat Some of 
these oompoonds lose their ammonia when exposed to the air ; others, but not all, when 
heated. Some dissolve in water without decomposition, forming solutions from which 
the whole of the ainmonia is not precipitated b^ dichloride of pktinum : the nugority 
are decon^KMed by water, which sometimes dissolves the orifi;inal salt and separates 
ammonia, sometimes precipitates the metal as hydrate. Simuarly, certain crystalline 
•atts, when freed from their water of crrstallisation, absorb ammonia abundantly and 
in atomic proportion, forming compounds which are decomposed hy heat or by water. 
/imwwwiiA also combines with metallic cyanides, with fluoride of silicon, and other bodies. 

4. Witi acidff forming ammomacal salts, (See Akmoniacal Salts.) 

6. WUk fU^fitanc Ofu^drides, forming the ammonium-salts of amic adds. (See 
Ave Acoml) F. T. C. 



188 AMMONIACAL SALTS. 

Ammonium-^altSf Sels ammoniacauXf Ammoniah' 



salze. 

Ammonia combines veiy readily with acids, which it neutntliseB completely, formiiig 
definite crystalline salts, known by the name of ammoniacal or ammonimn-ealts. 
These salts are isomorphons with those of potassinm, and are in their genefral properties 
so closely analogous to metallic salts, that they are nniversally regarded as bdonsiiig 
to this class of bodies. There is, however, a characteristic difference in tibeir mocteof 
formation. While other metallio salts are formed by the substitiition of a metal tar 
the hydrogen of an add, e,ff» chloride of zinc, ZnCl = HCl + Zn — H : ammoniacal 
salts are formed by the direct combination of ammonia with the add, without elimi- 
nation of hydrogen, — e.g. chloride of ammoninm, NHK))1 « NH' + HGL 

Among the various theories by which it has been proposed to represent the oonsti- 
tntion of these salts, that which most dearly m>resses their analogy with other 
metallic salts is unquestionably the Ammonium Theory of BeizeUus. According to 
this theory, ammoniacal salts contain a compound metaJ, ammomum^ NH\ analogous 
to potassium, sodium, and other metals, the salts of which, ammoniumrsdlU, are 
analogous to other metallic salts. Thus, chloride of ammonium, CINH^, is analogous 
to chloride of potassium, CIK ; sulphate of ammonium, SO\NH*)*, to sulphate of 
potassium, SO*K', &c This hypothetical metal has never been isolated. An amal- 
gam of mercury and ammonium is, however, known to exist, which affords strong 
corroborative evidence, not only of the existence of ammonium, but also of its metallic 
nature, metals bdng the only bodies which are capable of forming amalgams with 
mercury. This singular substance, discovered simultaneously in 1808, by Seebeck, at 
Jena, and by Berzehus and Pontin, at Stockholm, was originally prepared by Hie action 
of dectricity upon aqueous ammonia in contact with mercury. A strong solution of 
aqueous ammonia in which mercury is placed, is brought into the voltaic cirde, the 
negative pole dipping into the mercuiy, and the positive pole into the liquid. An- 
other method is to cup the negative wire into mercury, wnich is placed in a cavity 
hollowed out of a fra^ent of a solid ammoniumHsalt, carbonate, sulphate, phosphate, 
or chloride, the positive wire being inserted into the salt itself, or connected with a 
metallic plate on which the salt r^ts. Oxygen, or, if chloride of ammonium be em- 
ployed, chlorine, is evolved at the positive pole, but scarcdy any gas at the negatiTe 
pole ; while the mercury increases very largdy in volume, and assumes the consistence 
of butter. When completdy saturated with ammonium, the amalgam is lighter than 
water : obtained by the former method, it has frequently a ciystfSline structure It 
is a very unstable compoxmd, decomposing spontaneously as soon as it is removed from 
the voltoic circle, being resolved into liquid mercury, and a mixture of 2 vols, am- 
monia, NH*, and 1 vol. hydrogen, H. When cooled bdow 0° C, it solidifies and crys- 
tallises in cubes. At a very low temperature, it contracts, and becomes brittle; 
decomposition does not begin till the temperature rises to 29^ C. According to Sir H. 
Davy, it contains 1 atom NH^ to 753 atoms mercuiy. The amalgam may also be 
prepared without the intervention of electridty, by bringing potassium- or sodinm- 
amalgam — the latter is more energetic in its action — ^into contact with an anmioninm- 
salt, either solid and moistened with water, or as a concentrated aqueous solution. 
The amalgam thus prepared contains, according to Gay-Lussac and Th^nard, 1 part 
nitrogen and hydrogen to 1800 parts mercuiy. It contains a certain portion of potas- 
sium or sodium, and on this account is less unstable than the amalgam prepared by 
dther of the former methods : it may be preserved for a considerable time m anhy- 
drous rock-oil, or in an atmosphere of hydrogen. 

Formation. — Ammonium-ssJts are farmed by bringing ammonia or carbonate of am- 
monium directly into contact with acids. 

Properties. — Ammonium-salts are isomorphous with potassium-salts. They hare 
mostly a pungent, saline, somewhat urinous taste. They are all soluble in water, 
generally with facility : less soluble in alcohol or ether. Ainmonium-salts of colouriess 
acids are colourless. 

« 

Beactione of Ammonium^salts. Teats for Ammonia. — Ammonium-salts 
are variously affected by heat : all, however, are wholly or partially volatilised, with 
or without decomposition. The carbonate, and those which contain no oxygen (chloride, 
iodide, &c.), are volatilised undecomposed. All others lose their ammonia when heated. 
Some, e.g. the phosphate, and borate, evolve ammonia undecomposed, leaving the add. 
Others, e.g. sulphate, evolve nitrogen, the add being more or less completdy r«inced 
by the hydrogen of the ammonia : the nitrate is decomposed into nitrous oxide and 
water. Their aqueous solution, when exposed to the air (still more rapidly when 
evaporated), generally loses ammonia, an acid salt, or a normal salt mixed with, excess 
of acid, being formed ? hence, in cirstallising an ammonium-salt, ammonia must be 
occasionally added during evaporation. When treated with chlorifu^ tiieir aqueons 
solution yields hydrochloric add and nitrogen ; or, if tlie salt contains a powerful add, 



] 



AMMONIACAL SALTS. 189 

BjdrocUaric add And chloride of nitrogen (D nl on g). With a solution of hypochhrmu 
mi^ dry ammoniiim-aaltB yidd water, chloride of nitn^n, and nitrogen, while nitrogen 
and chlorine remain in solution (B al ar d). In solution theyare decomnosed bj pro- 
iuiitBt with liberation of ammonia ; not by sesc^uioxides. When heated, either solid 
cr in soliitioD, with a fixed alkali, baryta, lime, oxide of lead, &&, they erolve ammonia : 
mM^Mma. eroels only half the ammonia, forming a double salt. 

TbemctioB by which ammonium-salto are generally detected, is their decomposition 
vliCD heated wittt fixed aUkalis or alkaline earthe. If the ammonia erolred be in so minut« 
t q[untity that its characteristic smell cannot be perceiTod, it is easily reoo|;nised by 
iti prapertf of restoring the blue colour to reddened litmus-paper, and of forming dense 
vfaite fumes by contact with a p;lass rod moistened with culute hydrochloric add. If 
the erolTed •mmATiU be brought into contact with a strip of paper moistened with a dilute 
Mutel soiution of subnitrate of mercury, sulphate of copper, or sulphate of manganese^ 
in dw £ist case a black stain is produced on the paper, in the second a blue, in the 
third a brown. — A solution of mofybdate of sodium containing phosphoric acid (phos- 
phomolybdate of sodium), giTes with ammonium-salts, a yellow predpitate, soluble in 
aDolii and non-TolatOe organic adds, insoluble in mineral adds : in yezy dilute am- 
Bonivm solutions, the formation of the predpitate is gradual; it is accelerated by heat. 
When a solution containing an ammomum-ndt or free ammonia is mixed with potash, 
and a K^ution of iodide ojmerewry in iodide of potassiwn added, a brown raedpitate 
or oolraatioB is immediately produced (Nessler). (NH' + 4HgI » KHgTl + SHI). 
Tlik is hy &r the most delicate test for ammonia. —With diehloride of piatinum^ 
asuDoiuimi-salts giTo a jeQow crystalline predpitate of chloroplatinate of ammonium, 
Ftd'NH*, alight^ soluble in water, insoluble in alcohol or acids. When ignited, the 
predpitate is conrerted into pure metallic platinum, perfectly free from chlorine, 
mth odd tariraie of sodium (or tartaric actd), they give a wmte predpitate of add 
tartrate ot ammonium, filightiy soluble in cold water, readily soluble in aUudine solu- 
tione and in mineral acids. The carbonaceous residue left on igniting this predpitate 
has no alkaline reactioxi. — ^A not too dilute solution of an ammonium-salt gires with a 
eoooentnted solution of sulphate of aluminium^ a crystalline predpitate of ammonium- 
alooL— Only Tery concentrated solutions of ammonium-salts giye predpitates with 
pfreUofftff or fiuosilicic acid, — Subnitrate of mercury gives a hrown colour in solu- 
tions eontaining free ammonia. — ^A slightly alkaline solution of an ammonium-salt 
giTes a irbite predpitate with chloride qfmfrcury, — ^Alcoholic solutions of ammonium- 
salts burn with a blue or violet flame. 

Reactions very similar to those just described, e. g. with phorohomolybdate of sodium, 
iodomcrenrate of potasdum, di<mloride of platinum, chloride of mercuiy, &c., are 
likewise produced by the salts of methylamine, ethylamine, and other compound 
ammonias. These oi^ganic bases may, however, be distinguished with certainty from 
ammonia its^ by igniting the subeitanoe under examination with oxide of copper, 
and pasBsg the evolved gases into baiyta water, when, if carbon ^is present, a 
picdpftate of carb(mate of baryta will be produced. (See Analtsxs, Oboanic, p. 226.) 

Separation and Estimation of Ammonium. — ^Ammonium is separated from 
all other metals except the alkaline metals, by its non-predpitation by hydrosulphuric 
add, snlphide or carbonate of ammonium, or phosphate of sodium, in presence of chloride 
of ammoniuuL From sodium and lithium it is separated by dichloride of platinum 
and alcohol, which predpitates potassium and ammonium as chloroplatinates, while 
sodium and lithium remain in solution. The mixed chloroplatinates are converted by 
ignition into a mixture of metallic platinum and chloride of potassium, the latter of 
vfaidi is dissolved out by water, the solution evaporated to diyness, gently ignited, 
and weighed. The weight of platinum ooiresponding to the amount of potasdum 
thos obtained being deducted from the total weight of metallic platinum, the remaining 
platinum represents the ammonium present : 1 atom of platinum corresponds to 1 atom 
of ammoniuuL This method is applicable only when the metals are present as salts which 
axe soluble in alcohol, e,g, aa cnlorides. Sulphates are best converted into chlorides 
bf adding carbonate of barium, and saturating the filtrate with hydrochloric addL 

The bat method for the separation of ammonium from all other metds is to heat 
the compound under examination in a combustion-tube with excess of soda-lime, and 
to collect the ammonia evolved in a bulb-apparatus containing hydrochloric add. The 
chloride of ammonium thus obtained is mixed with excess of dichloride of platinum 
(pofeetljfree from nitric add), and evaporated to dryness on a water-bath. The 
nsidne is treated with alcohol, which dissolves excess of the dichloride : the chloro- 
platinate of ammonium is collected on a weighed filter, dried at 100^ C, and weighed ; 
or converted by ignition in a porcelain crucible into metallic platinum, from the weight 
of whieh the amount of ammonia is readily calculated. This method is not appliciu)le 
to the separation of ammonia from other volatile organic bases. 

Ammonium-salts may occasionally be estimated by loss. This is the case when the 



190 AMMONIACAL SALTS 

ammonimn-Balt is entirely Tolatile, and when no other TolatUe or deegmpoeiMe eom* 
pound IB preeent The snbetance under examination is heated in a water-hath until it 
ceases to loae weight : it is then moderately i^ted and weighed again, when the Iobb 
of weiffht repreeents the amount of ammomnmosalt present TUa is a convenient 
method for the estimation of chloride, nitante, or normal sulphate of ammaninin, in 
presence ot the oorresponding fixed alkaline salts. 

Ammonia may also oe estimated by distilling it into a known quantity of dilute acid, 
and determiiung Tolumetrically by a standard alkaline solution the excess of free acid. 

The following sie the principal ammonium-salts : 

1. AcBTATBs OF AiocoNiux. o, NomuU acetate, C'HKI'.KH^ — A white odouriess 
salt, obtained by saturating glacial acetic acid with diy ammonia. 

h. Acid acetate, C*H«0» NH* + OH*0« — Obtained as a white crystalline eabli- 
mate, when dry powdered chloride of ammonium is treated with an equal wei^t of 
acetate of potassium or calcium, ammonia being given off simultaneous^. (See Acas- 

TATBS, p. 12.) 

2. Casbonatbs or Ajcxomiux. — H. Bose (Pogg. Ann. xlriiL 362^ admits the 
existence of a considerable number of carbonates of ammonium, to which he «^«"g"f 
yezy various and complicated formuhe. But, according toH. Beville (Compt. rend. 
aExxiy. 880 ; Ann. Ch. Phys. [8] xL 87), there exist only two carbonates of ammonium 
of definite composition. 

a, Normal carbonate, CO^NH*y [or CO'.NH*0 - (70«^fl>.JGra].— This salt has 
nerer been isolated. The salt which crystallises from an alcoholic solution of aeequi- 
carbonate of ammonium saturated with ammonia, is simply sesquicarbonate. Kexther 
can it be obtained from a saturated solution of commercial sesquicarbonate in stzong 
aqueous ammonia. It may be obtained in aqueous or alcoholic solution, or, as sesqui- 
carbonate, in combination with the add carbonate (b), (Pelouze et Fremy, Traits 
de Chimie, ii 222.) 

b, Acid carbonate, CO«.NH*.H [or CC^.NB*0 + CO«.-arO.]— Obtained by satorating 
an aqueous solution of ammonia or sesquicarbonate of ammonium with carbonic an- 
hydride. Or by treating the commercial sesquicarbonate finely powdered, with alcohol 
of 90 per cent., which dissolves out normal carbonate, leaving a residue of acid car- 
bonate. Sesquicarbonate of ammonium is similarly decomposed by cold water ; bat 
in this case, a larger quantity of the acid carbonate is dissolved. All carbonates of 
ammonium, when left to themselves, are gradually converted into acid carbonate. It 
forms large crystals, belonging to the ri^ht prismatic or trimetric system. According 
to D e ville, it is dimorphous, but never isomorphous with acid carbonate of potasaimn. 
When exposed to the air, it volatilises slowly, without becoming opaque, ana gives off 
a slight ammoniacal odour. At the ordinary temperature, it is soluble in 8 parts 
of water ; if this solution be heated above 36^ C, it is decomposed, evolving carbonic 
anhvdride. Even at ordinary temperatures, the solntion, whether concentrated or dilute, 
gradually becomes ammoniacal on keeping (Gmelin). It is insoluble in alcohol; 
but when exposed to the air under alcohol, it dissolves as normal carbonate, evolving 
carbonic anhydride. 

' It has been found native in considerable quantity in the deposits of guano on the 
western coast of Patagonia, in the form of white crystalline masses, with a atrcmg 
ammoniacal smell. (Ulex. Ann. Cb. Pharm. IxvL 44.) 

c, Sesquicarbonate, C»0^*H» + 2H«0 [= ZC0'.2NH*0 + 8JTa]-.0btained by 
dissolving commercial carbonate of ammomum in strong aqueous ammonia, at aboat 
30° C, and crystallising the solution. It forms large transparent crjrstals, representing a 
right rectangular prism, with the &ces of the corresponding rhombic octahedron 
resting on the angles. These crystals decompose very rapidly in the air, losing water 
and ammonia, and being converted into di-aad carbonate. This salt may be resaxded 
as a mixture or compound of 1 atom of normal carbonate with 2 ot atoms acid caroonate 
rCO^. (NH«)« + 2(C6».NH*.H) = (?0»N*H>T : a view which is confirmed by its be- 
haviour with water and alcohol ; which, when added in quantitjr insufflcirat for the 
complete solution of the salt, dissolves out normal carbonate, leaving a residue of add 
carbonate: 100 pts. water at 13° G. dissolve 25 pts. sesquicarbonate, at 17°, 30 pts. ; at 
32°, 37 pts. ; at 41°, 40 pts.; at 49°, 60 pts. rBerselius): above this temperature, 
carbonic anhydride is evolved, and a solution of normal carbonate formed. 

Commerdal carbonate of ammonium {sal volatile, salt of hartshorn, &e.) oonaifltB 
of sesquicarbonate, more or less pure. It is prepared on a large scale by the dry dis> 
tillation of bones, hartshorn, ana other animal matter. The product thus obtained is 
contaminated with empyreumatic oil, finom which it is purified by subliming it once or 
twice with 1} times its weight of animal charcoal, in cast-iron vessels over which glass 
receivers are inverted. By repeated .sublimation, the salt is partially deconapoeed. 
Another method of preparing it is by heating to redness a mixture of 1 pt. chloride or 
'' ^^ sulphate of ammonium, and 2 pts. carbonate of caldum (chalk), or carbonatci of potaanimi. 



.«■«■ 



CARBONATES — CHLORIDE. 191 

in 1 Rtort to iriueh a reoeiTer is luted : ammonia and water are first disengaged, and 
then the seeqnicarbonate distils over and solidifies in the neck of the retort and the 
reeaTer. On a small scaler s^ass ressels are employed : on a laige scale, an earthenware 
or eist-iron retort, and an earthenware or leaden reoeiyer, which, when filled by 
Tcpeated dialallata'ons, is broken or cat in two : 10 pts. sal-ammoniac yield from 7 to 8 
piL sesqiiiearbonate. ^8ee DictUmaty of Arts, Mam^faeturea and Mine$j i. 136.) The 
alt thus mepared is hable to contain tiie following impuritiee : 

i^ipora^itfttifo of ammomum : when sulphate of ammonium, or chloride containing 
fnipbate, is employed in the preparation. The salt neutralised with acetic add gives 
a white preeipttate which turns black on addition of nitrate of silver. — Sulphate of 
am aon iu a i , from the same causes : detected by hydrochloric acid and chloride of barium. 
— Sd-cmmonute : detected by nitric add and nitrate of silver. — Lead, from the recdver : 
the salt has a grey colour, and when dissolved in dilute nitric add, gives the reactions 
of lead. — Lime and chloride of caieium, carried over mechanically : from these and 
other fijDsd imparities the salt is freed by re-sublimation. 

The sesqiiiearbonate obtained as above is a white, transparent, fibrous maas^ with 
a pangent caustic taste^ and a strong ammoniacal smelL Exposed to the air, it is 
gndnalhr converted into add carbonate. It is oompletdy volatile, though not without 
partial deoompodtion. Its aqueous solution is strongly alkaline : from a hot saturated 
aohttioitt, the add carbonate crystallises on oooling^ but not in the ordinary aystaUine 
kmxL (Deville.) 

The aqneous solution of this salt (epiritue eaUe antmoniact), is eztendvdy employed 
in medirine as a stimulant. It is also a very valuable reagent. The solid salt is 
c mptoj e d in the manufacture of other ammoniacal salts. 

3. CmoBiim of Amcoiouii, CINHl {HydrochloraU or muriate qf ammonia, Sal" 
ammomae, etdnavree Ammoniak, Bahniak, Chlorure cPammonium^ or Cklorure am^ 

Hydroehkrie add gas and ammonia combine volume fbr vxdume, with great evolu- 
taoD of hea£, fetming solid chloride of ammonium. This salt forms colourless feathery 
oystala, wluch, when examined by a lens, are found to consist of an aggregation of 
cubes or oelahedrons. It has no smeB, but a pungent taste ; its specific gravity is 1*5. 
It disBolveB in 2*72 pts. water at 18*75^ C, with great reduction of temperature ; and in 
about its own wdght of water at 100^. It is less soluble in alcohol When exposed 
to the air, it loses ammonia, and becomes add to test-paper. When heated, it vola- 
tOiaeB undeoomposed, without previous fudon. After sublimation, it forms white 
oystalline masses^ which are exceedingly tough and difficult to powder : to obtain it 
in a polvendent state^ a hot saturated solution is evaporated to dryness very rapidly, 
with eontimial agitation, when the salt is left as a crystalline powder. 

Chkride of ammonium is decomposed by several metals, potassium, iron, &c, a 
metallic chloride being formed, and ammonia and hydrogen separated. It is also 
decomposed by many salts ; by some, e, g. alkaline and alkaline-earthy hydrates, 
oompletelj^, ammonia being evolved; by otheiji, as by cupric and ferric salts, partially, 
double salts beinff formed. Some salts, e^g, platinic chloride, combine with it 
dizeetiy, fiarming <£mble salts (chloroplatinates). Some metallic hydrates are soluble 
in a solution of sal-ammoniac, e^dally those of dnc and maenesium. 

Sal-ammoniac is found native in many volcanic regions; auo in small quantities in 
sea-water. It is readily formed by heating nitrogenised animal matter containing 
chloride of sodium, or with which that salt has been mixed. Until the middle of the 
last centuzy, sal-ammoniac was obtained ahnost exdudvdy from £^ypt, where it was 
prepared i:n this manner, by subliming the soot obtained by the combustion of camd's 
dn^. It is now largdy manufactured in Europe, chieflv from the impure carbonate 
of anmxminm which is obtained in gas-works, or by toe dry distillation of animal 
matter, niiis carbonate is converted into chloride by the addition of hydrochloric 
add, or of the mother-liquor from salt-works, containing the chlorides of magnedum 
and caldum, and by evaporating the solution (ammonia beinff added from time to time^^ 
crystals of sal-ammoniac are obtained. These are contammated with empyreumatic 
od, which is destnnred by heating the crystals to a temperature ^ little below their 
subliming poinl Tney are then dusolved m water, the solution decolorised by boiling 
with animal ehaiooal, and again cr^staUised. The salt is finally purified by sublima- 
tion, whidi is performed at a brisk heat, in large glass or euthenware bottles, the 
DcdL of wiiidi must be carefully kept unobstructed, to avoid the risk of explodon : the 
bottles are then broken and the sal-ammoniac removed in cakes. Metallic receivers 
an soinetimes emploTed in the sublimation ; in this case, the outer surfiice of the sal- 
ammoniac IS daik-ooloured, owing to metallic impurities, and must be scraped off. 

In some manufactories, the carbonate of ammonium is first converted into sulphate, 
and sobfieonentlv into chloride. This is generally done by filtering the solution of 
cadmiate tmongjk a stratum of powdered gypsum (sulphate of cakium}, when insoluble 



192 AMMONIACAL SALTS. 

carbonate of calcium is formed, and a solution of sulphate of ammonium obtained. 
This solution is mixed with chloride of sodium, CYaporated to dryness, and the sal- 
ammftniac separated from the residue by sublimation. Or the solution of the two salts 
is eraporatcd at the boiling heat, when sulphate of sodium, being less soluble at a high 
than at a lower temperature, mostly crystidliBes out and is removed. The soluticMi is 
then cooled, when the sal-ammoniac dystaUises out, since its solubility diminishes 
rapidly with decrease of temperature. The crystals thus obtained are purified as 
aboTe described. ' Feirous sulphate may be employed instead of gypsum to couTert 
the carbonate of ammonium into sulphate ; this is a more expensive process, bat it 
possesses the advantage of removing the greater part of the empyreumatic oi!, irhich 
IS carried down by the precipitated iron-stidt. (Berzelius.) 

In the factory at BuxweUer, in Alsace, sal-ammoniac, phosphorus, and gelatin are 
prepared by tiie following ingenious process. Bones are digested in hydrochloric acid, 
which dissolves out the bone-earth, leaving the cartilage insoluble : tiie latter is em- 
ployed for the preparation of gelatin. The hydrochloric solution is mixed with crude 
carbonate of ammonium, when sal-ammoniac is formed, and phosphate of calcium preci- 
pitated in the finely-divided state in which it is best adapted for the preparation of 
phosphorus. [For ^rther details of the manu&cture of sal-ammoniac, see Dictionary 
of Arts, Manufacturea and Mines, i. 141.] 

Sal-ammoniac is employed in medicine. In the laboratoiy it serves for the pre- 
paration of ammonia^ and carbonate of ammonium, and for frigorific mixtures. It is 
employed in dyeing ; also in metal-works, as a deoxidising agent, especially for copper. 
A solution of chloride of silver in chloride of ammonium is employed for plating cop- 
per and brass. It enters into the composition of a cement used for fixing iron m 
stone : this cement is formed by moistening with a solution of sal-ammoniac, iron- 
filings mixed with 1 or 2 per cent, sulphur. Impure sal-ammoniac has recentlj been 
employed as manure. 

4. HTDRiLTB OF Ajofoiauic, KH^H.O. — This compound has never been isolated. 
The aqueous solution of ammonia behaves in many respects like a solution of hydrate 
of ammonium. 

5. NiTEATB OF Ammonithi, NO'.NH* [or NO^,NH^O t^ N0^J<IH*,HO\. {imrwm 
flammans.) — Obtained by crystallising a mixture of nitric acid with a slight excess of 
aqueous ammonia. It forms long flexible needles : if the ciystallisation be effiscted 
very slowly, it may be obtained in six-sided prisms. When the solution is evaporated to 
a very small bulk, the salt solidifies into a dense amoiphous mass. It has a pungent 
taste. It is soluble in about half its weight of water at 18^ C, and in still less at 100^: 
its saturated solution boils at 164^ C, and contains 47*8 per cent salt: when dissolved 
in water it produces great cold. It is soluble in alcohol. Exposed to the air, it ddi- 
quesces slightly, loses ammonia, and becomes acid. When heated, it foses perfectly 
at 108° C, and boils without decomposition at 180°. Between 230° and 260° it is de- 
composed into water and nitrous oxide, (NO'.NH* » K-0 + 2H'0). If it be heated 
too rapidly, ammonia^ nitric oxide, and nitrite of ammonium are also formed. (Ber- 
zelius). When thrown into a red-hot crucible, it bums with a slight noise, and a 
pale yellow flame. In presence of spongy platinum, it is decomposed at about 170° C. 
into nitrogen and nitric acid. (M i 1 1 o n and B e i se t.) 

Nitrate of ammonium is formed when a mixture of nitrogen, o^gen, and excess of 
hydrogen is submitted to the electric current; also when hydrosulphuric acid is passed 
into a dilute solution of nitric add. It is also formed by the action of nitric acid on 
several metals, especially tin. 

6. NrrmTB of Ammoniuk, NO^NH< [« ^O'.MP.fl'O].— Obtained by double decom- 
position of nitrite of lead and sulphate of ammonium, or of nitrite of silver and chloride 
of ammonium : the solution is evaporated in vacuo. Or by passing nitrous fumes into 
aqueous ammonia, and evaporating over lime (Mi 11 on). It forms an imperfectly 
crystallised mass. It is decomposed by heat into ninogen and water, (NO'.NK* » "S* 
+ 2H^0). Its aqueous solution is similarly decomposed, suddenly if acid, gradually 
if alkaline. 

7. Oxalates of Ammonium. — a. Normal oxalate, C0*(NH*)» + H*0. — Obtained 
by neutralising oxalic acid with ammonia, and crystallising. It forms long prisms 
united in tufts, belonging to the rhombic, right prismatic or trimetric system : soluble 
in 3 pts. cold water, insoluble in aloohoL It is veiy slightly Volatile at ordinaiy 
temperatures. When carefully heated to 220° 0. it is entirely decomposed into carbonic 
oxide and carbonate of ammonium ; when it is heated more strongly, some oxamide is 
formed. Its solution is employed as a reagent for precipitating oucium-salts. 

*. Acid oxalate, G*0*.NH*.H + HK). — Obtained in the crystalline form by adding 
bxalic, sulphuric, nitric, or hydrochloric acid to a solution of the normal salt. It crys- 
tallises in the trimetric system. It reddens litmuSi and is less soluble than the normal 



PHOSPHATE — SULPHIDE. 1 93 

nit It 18 decompoeed by heat, yieldiBg, among other products, oxamide, (?0^^*, 
and oxaBue acid, C'O'iNH^ 

c QmathxtxalaU, Hp^^er-aeid oxalate, C*0*.NH«.H + C«0*H« + 2HK). — Obtained 
hy djatallifling a solution of eqnal parts of acid oxalate and oxalic acid. The ciystals 
bdosg to the tzidinie or doubfy oblique prismatic system, and are isomorphous with 
the ooR«Q>ondisg potassium salt. They are very soluble in hot water. At 100^ C. 
tbey efikxreaee slightly, and lose their water of crystallisation. 

8. TsosnuLTss of Ajcmokiuk. — a. Normal phosphate, PO^(NH"*)* [or PG^,ZNH*0.^ 
— ^When a solution of monacid phosphate or ammonium is mixed with anmionia, 
tiiis salt separates as a aystalline magma: it cannot be dried without losing ammonia, 
being conver t ed into &. 

b. JHammorde phosphate, PO*.(NH*)«.H [or PO».2iVH«0.jyO]. (Ordinary phosphate 
of ammonium^ formeny called neutral phosphate,) — Obtained hy adding a slight excess 
of Mnmoma or carbonate of ammonium to acid phosphate of calcium (solution of bone- 
eaith in hydxt>chloric or dilute sulphuric acid) ; when phosphate of calcium is precipitated, 
and monacid phosphate of ammonium remains in solution. It forms large, colourless, 
transparent crystals, belonging to the monoclinic or oblique prismatic system. It has 
a cooling, saline taste, and an alkaline reaction. Exposed to the air, it effloresces 
d%htly, losing ammonia. It is soluble in 4 pts. cola, and in a smaller quantity of 
boiling water; insoluble in alcohoL By a red heat^ it is conyerted into metaphospborio 
add, PO*.(NH*)«.H = PO^ + 2NH» + H-0). 

e. MimamfHome phosphate, PO^(NH*).H« [or P0^.NH*0.2HOJ. (Formerly called 
aeid phosphate.) — Obtained by adding phosphoric acid to aqueous ammonia, till the 
sohition is strongly acid, and no longer precipitates chloride of barium ; or by boiling 
a dilute solution of b and evaporating it to dystaUisation. It crystallises in the dimetric 
or square prismatic i^stem. It is somewhat less soluble in wat^ than b, and is 
Bimilariy decomposed by heat. 

The {^ORiliates of ammonium are employed for the preparation of metaphoephorio 
add. As the residue of their ignition always retains ammonia, it must be moistened 
with nitric acid, and again calcined. Gay-l«ussac has proposed to preserve muslins 
and other inflammable textures from ignition by steeping them in a solution of these 
aslta ; the salt being decomposed by heat, the tissue is covered with a film of metaphos- 
phorie acid« which preserves it from contact with the air, and prevents its breaking 
nto flame. These salts cannot^ however, be applied to fabrics which have to be 
washed and ironed, because the heat of the iron would decompose them, expelling the 
ammonia. The same objection applies to sulphate of ammonium, which is otherwise 
cfficadoua in diminishing the inflammability of light tissues. From recent experiments 
by Yersmann and Oppenhein^Pharm. J. Trans. [2] i. 886), it appears that the 
only salt universally applicable for rendering such fabrics non-inflammable, is the 
neutral tongstate of souimi. (See Tuhgstates.) 

Some of the double phosphates of ammonium and other metals are of considerable 
bBportsDce. The phosphate of sodium, ammonium and hydrogen, PO^Na.KH*.H, com- 
monly called microoosmic salt, or phosphorus salt, is much used as a blow-pipe flux, 
being converted by heat into transparent metaphosphate of sodium, which (ussolves 
many metallic aalts with characteristic colours. 

9- SuLFBLa.TBS OF AxxGNifTV. — o. Nomtol Sulphate, SO*(KH*)« [or 80'.NH*0.] 
(fflauber'a Sd seeretum.) — Obtained by neutralising dilute sulphuric acid with 
ammnmit OT carbouate of ammonium. It forms crystals belonging to the trimetric or 
right prismatic syst^n, isomorphous with potassic sulphate. It is colourless, and has 
a very bitter taste ; it is soluble in twice its weight <k cold, and in its own weight of 
boihi^. water; insoluble in alcohol. It fuses at 140^ C: above 280°, it is decomposed, 
ammonia, nitrogen, and water being given ofi^, and acid sulphite of ammonium 
sablimed. 

It is found native as Mascoffnine. It is manufactured on a large scale (as already 
described nnder Sal-ammoniac) by neutralising with sulphuric add, or decomposing 
hj gypaum, the impure carbonate of ammonium obtained m gas-works, &c. and ctys- 
tafliaing the solution. The crystals are heated, to destroy animal matter, and purified 
by recrystaUisation. Sulphate of ammonium is employed in the manufacture of am- 
Booinm-alum : also as manure. 

Al Add sulphate, SO*.NH^H, [or 250».^S*0.^rO^.— Obtained by treating a solution 
of a with sulphuric add. It crystallises in thin rhombohedrons. It is soluble in ita 
own wdght of cold water, and in alcohoL It deliquesces slowly in the air. 

10. 8ui.FBXDBfl ov Ajocomiuic. — o. Sulphide, (KH^)^. — ^When a mixture of dry hy- 
drac^phnrie acid and ammonia, the latter in excess, is exposed to a temperature of 
— 180 C. 2 vols, ammonia combine with I vol. hydrosulphunc acid, and form sulphide 
of ammonium. The same compound is formed when sulphide of potassium is distilled 

Voi.1. O 



h 



184 AMMONIA. 

ehlorom anhydride explodes Tiolently at the ordinaxy temperature, with fleparation of 
chlorine. Aqueous ammonia added gradually to aqueous hypochlarvua acid, the 
mixture being kept cool, yields nitrogen, and chloride of nitrogen. Ammonia mixed 
with proper proportions of nitrous or rUtrie oxide^ explodes by the electzic spark, yield- 
ing water and mtrogen. Ammonia is violently decomposed at the ordinaiy temperature 
by peroxide of nitrogen^ whether liquid or gaseous, with evolution of nitric oxide and 
nitrogen (Dulong). — In contact with chlorine in the cold, ammonia bums with a red 
and white flame, forming chloride of ammonium and free nitrogen (4NH* •¥ CI' » 
3NHK!1 + K); when chlorine is passed into strong aqueous ammonia or a solution of an 
ammoniacal-saltk chloride of nitrogen is also formed. — Iodine does not decompose 
dry ammonia: in presence of water, iodide of ammonium and an iodine-deriva- 
tive of ammonia are formed. — ^With bromine^ ammonia yields bromide of ammo- 
nium and free nitrogen. — ^Passed with vapour of phoephorie through a red-hot tube, 
ammonia yields phosphide of hydrogen ana free mtrogen. — ^Passed over red-hot ehar^ 
coal, ammonia yields cyanide of ammonium and free hydrogen. — ^With bietdphide of 
carbon^ ammonia gives hydrosulphuric and sulphocyanic aci£ (NH* + GS* -■ H?S + 
GSH). — ^When potassium or sodium is heated in dry ammonia, hydrogen is evolved, 
its place being supplied by the metal, and nitride of potassium and hydrogen (potassa- 
mine), NKH*, is formed. — In contact with zinc-ethyl, ammonia gives rinc-amine NZnH' 
and hydride of ethyl, CH*. Many metallic oxides decompose ammonia with the aid of 
heat : the products are sometimes water, nitrogen, reduced metal, and more or less of 
an oxygen-compound of nitrogen ; sometimes, water and a metallic nitride. — ^Ammonia 
reacts with anhydrons adds, chlorides of acid-radicles, and many compound ethen, 
giving amio adds, or amides. In like manner, it gives with many derivatives of the 
alcohols, amic bases or aTnines. (See Amio Acros, Amio Bases, Aigcdbs, Aionbs.) 

We have seen that ammonia is decomposed by certain metals and metallic oxides, 
hydrogen being liberated, and compounds formed representing ammonia in which a 
part or the whole of the hydrogen is replaced by a metal. There are certain oiganic 
compounds {e. g, monobasic anhydrides, compound ethers, &&) which are capable of 
decomposing ammonia in a similar manner, with formation of compounds representiiig 
ammonia in which the hydrogen is wholly or partially replaced by an organic radide, 
acid or basic The numerous and interesting class of compounds wmch are thus 
formed from ammonia by the partial or total replacement of its hydrogen by other 
radides, orsanic or inorganic, acid or basic, is known by the generic name of oinddes: 
under which name they are fhUy described. 

Combinations, — 1. With Water {Sdtdion of ammonia^ Aqueous ammonia^ or 
simply Ammonia, Spirits of hartshorn, Salmiakgeist, Liquor ammonit). 

Both water and ice absorb ammonia with great avidity, with considerable evolution 
of heat, and with great expansion. Davy found that 1 vol. water at 10° C. and 29*8 
inches barometric pressure absorbs 670 vols, ammonia, or nearly half its weight : the 
specific gravity of this solution is 0*875. According to Dalton, water at a lower tem- 
perature absorbs even more ammonia, and the specific gravity of the solution is 0*8^. 
According to Osann, 100 pts. water at 24° C. absorb 8*41 pts. at 55° C. 5-96 pts. am- 
monia. 1 vol water by absorbing 505 vols, ammonia, forms a solution occnpjing 
1*5 vols., and havinff specific gravity 0*9 : this, when mixed with an equal bulk dt 
water, jields a liquid of specific gravity 0*9455: whence it appears that aqueous 
lunmoma expands on dilution. (Ure.) 

Preparation. — 1 part of sal-ammoniac in lumps is introduced into a glass flask, 
with 1 J parts slaked Ume, and from 1 to 1| parts water : and the flask is connected 
by bent tubes with three Woulfe*s bottles. The first bottle, which is intended to 
arrest any solid particles that may be carried over mechanically, and any empyrea- 
matic oil contained in the sal-ammoniac, as well as to condense aqueous vapour, con- 
tains a small quantity of water (Mohr prefers milk of lime). The second bottle con- 
tains the water to be saturated with ammonia : it should contain a quantity of water 
about equal in weight to the sal-ammoniac employed, and should not be more than 
three parts frill, to fdlow for the expansion. These two bottles should be placed in cold 
water, and each provided with a saiety tube. The third bottle contains a little water, 
to retain any ammonia that may pass through the second bottle. The flask is then 
heated in a sand-bath, care being taken that its contents do not boil over: and the 
operation continued till about half the water in the flask has distilled over into the fiist 
bottle. The first bottle then contains a weak and impure solution of ammonia : the 
second a pure and strong solution (if a perfectly saturated solution be required, the 
quantity of water in this bottle should not exceed } the weight of the sal-ammoniac 
employed) : the solution in the third bottle is weak, but pure. 

The proportions of lime and water to be added to the «d-ammoniac in order to pro- 
duce the largest yield of ammonia have been variously stated : those given above aro 



AMMONIA. 



185 



now most general]/ nn^eived. According to the equation, CaHO + NH^Cl — NH" + 
Old + HH), the amount of slaked lime should be to that of sal-ammoniac as 
37 : 63*5, or 69 parts of the former to 100 ports of the latter. But in practice it is 
ahrgjFB found neoeiKary to employ a larger proportion of lime ; for not only is the lime 
of oommerce alvays impure, but also it is impossible to brinff the whole of it into such 
contact with the sal-ammoniac, ajs would ensure the completeness of their reaction. 
The object of adding water is to ensure the gradual solution of the sal-ammoniac, and 
eoiseqiiently its more complete contact with the lime. There are also other disad- 
Tutages which attend the absence of water. If the lime and sal-ammoniac are mixed 
in a state of powder, a large quantity of ammonia is lost before the mixture is intro- 
duced into the flask ; and the heated mass expands on cooling so as inrariably to 
break the flask. These inconyeniences are avoided by first placing the sal-ammoniac 
in hunpe in the flask, and then oorering it with the powdered lime : but in this case 
the heat required ia sufficient to Tolatilise the sal-ammoniac, which is liable to stop 
up the deliveiy-tube and cause a dangeorous explosion. MoreoTer a larger quantity 
of empyreomatic oU passes OTer with the anmionia : and the chloride of calcium formed 
in the flask obstinately retains a portion of the ammonia, which is consequently lost. 
On the other hand, the addition of too much water diminishes the product of am- 
monia, and hampers the operation in other ways. 

In the preparation of aqueous ammonia on a large scale, the gas is generated in 
ctst-iron or copper vessels : earthenware vessels are generally found not to answer, 
oving to the porosity of their structure. 

The aqueous ammonia thus prepared may contain the following impurities, which 
are easily detected : 

Corixmaie of ammonium, — Occurs when the Ume employed contains much carbonate, 
or when tiie solution has been exposed to the air. Causes turbidity when heated with 
chloride of barium. 

Chlorine. — Owing to chloride of ammonium having been sublimed, or carried over 
mechamcally. The solution, saturated with nitric add, gives a cloudiness with nitrate 
ofnlvec 

Lime. — Carried over mechanically. Gives a precipitate with oxalic acid : left as a 
■olid residue on evaporation. 

Copper or Lead. — ^Derived from the generating vessel. The former is detected by the 
solution becoming tinged with blue on evaporation ; the latter by hydrosulphuric acid. 

EmpynwnaUe oil. — From the sal-ammoniac The solution has a yellow colour 
and a peculiar smelL 

Prcpertia. — Aqueous anmionia is a colourless transparent liquid, smelling of 
»nimAni> and having a sharp burning, urinous taste. Its specific gravity varies from 
1*000 to 0*85, according to the amount of ammonia it contains: its boiling-point varies 
similaily (see D al to n 's table, if\fra.') A perfectly saturated solution freezes between 
—3^ and —41° C, forming shining flexible necnlles: at —49° C. it solidifies to a 
grey gelatinous mass, almost without smell (Fourcroy and Yauquelin). It loses 
almost an its ammonia at a temperature below 100° C. The following tables have 
been constructed, showing the amount of real ammonia contained in aqueous ammonia 
of diflerent densities : 



Daltov. 


H. Davy. 


Urb. 


aii«iflc 


Peremtasc 


Boiling 


Specific 


PerooDUigo 


Specific 


Percentage 


Specific 


Percentage 


(raruj. 


AfwniiHffTi 


Poiot. 


gravity. 


Ammoala. 


gravity. 


Ammonia. 


gravity. 


Ammonia. 


om 


S5-3 


-4*> 


0-S750 


82-3* 


0-8914 


87-940 


0-9368 


15-900 


OSS 


»6 


+3-4° 


0-8857 


39-25 


0-8937 


S7-6S3 


0-9410 


14-575 


0<7 


»9 


10» 


O'SfXm 


seoo 


0-8967 


87-038 


0-9455 


13-250 


MS 


S7-3 


ir» 


OD0S4 


28-87« 


0-8963 


86-751 


0-9510 


11-995 


0« 


«•? 


MO 


0-9166 


«t)7 


0-9000 


96-500 


0*9564 


10-600 


*«» 


St-9 


30° 


0-9355 


19 54 


09045 


25-175 


0-9614 


9 275 


Ml 


»8 


370 


0-9396 


17-52 


0-9090 


83-850 


0-9669 


7*950 


lr9l 


17-4 


440 


0*9885 


15-88 


0-9133 


29-626 


Oir716 


6-625 


m 


Ift-l 


50» 


0-9436 


14-53 


0-9177 


21-200 


0-9768 


5-500 


M4 


1»8 


««» 


0-9476 


18-46 


0-9227 


19-875 


0-9828 


3-975 


»M 


10-5 


63« 


0-9513 


18-40 


0-9278 


18 550 


0-9887 


9-660 


»9S 


t-s 


TdP 


0-9545 


11-56 


0-9320 


17'825 


9945 


1-39& 


^n 


« 


79» 


0-9573 


10-82 










frW 


4*1 


«r» 


0-9597 


10-17 










•« 


H) 


97P 

1 


0-9616 
0-9698 


9-60 
950* 










•Tl 


IM6 mmben 


weredet4 


Brmmed bj 


experiment : 


the rest in 


Davy'i table 


by calcutat 


lou. 



196 



AMMONIUM-BASES. 



quent decomposition of the iodide bo formed, by hydrate of silyer. The deeompoait i oti 
by heat of the hydrates of the ^^hosphontum-bauea, di£Eeis from that of the ooiresiMBiid- 
ing ammoninm-bases : e.ff. 



P(C»H»)*H.O 

Hydrate of 

tetrethyl- 

pboiphoDium. 



P(C«H*)«0 + C^».H. 

Oxide of Hydride of 

trletbTlphot- ethyL 

pbincb 



FoLTAicicoNiux-BASBS. — ^These oompotrnds bear to the monammoninm-l 
just described, the same relation that the diamines and triamines bear to the man- 
amines : they may be considered as representing two or more molecules of hydrate of 
ammonium in which the whole or part of the hydrogen is replaced by polyatomic 
radicles. As in the case of the monammoninm-bases, l£ere is a difference between the 
polyammoninm-bases in which only part of the hydrogen is replaced, and those in 
which it is all replaced : the former cannot be obtained in the isolated st«te ; the latter 
are stable compounds and possess strong alkaline properties. But both these classes 
of hydrates haye been less studied, and are therefore hitherto less important^ than the 
corresponding salts, which are for the most part equally stable, whether still containing 
replaceable hydrogen, or no. We shall therefore in this article treat of the polj- 
ammonium compounds generally, making no essential distinction between hydrates 
and other salts, or between those compounds in which the hydrogen of ammonium is 
wholly, and those in which it is partially replaced. Moreover, as the bodies of this 
class containing phosphorus and arsenic haye been at least as much studied as those 
containing nitrogen, it will be most conyenient to speak of the action of polyatomie 
compound on l£e basic deiiyatiyes of ammonia generally, taking as special examples 
of the yarious reactions hitherto known, compounds containing nitrogen, phoephoras 
or arsenic, as these or those happen to be best known. 

A Action ov Diatoxio Cslobzdbs, Bboxzdbs, ob Iodides : — 

1. On Ammonia, 

The experiments which haye been made in this direction are ahnost confined to 
the action of bromide of ethylene on ammonia. The products thus farmed axe ti&e 
following : 

Dibromide of ethylene-diammoniuum . . N'(Ofe*)H*Br* 



Dibromide of diethylene-diammonium 
Dibromide of triethylene-diammonium 



. N«(Cte*)*H«Bi» 

. N«(Cto<)»H*Br». 
These compounds, when distilled with potash, giye, lespectiyely, ethylenaminev 

K«(;C4[*)H*, diethylenamine, N*(C?H«)*H«, and triethylenamine, N«(C«i[«)», bodies 
which are likewise acted on by bromide of ethylene, the final product beinff asabstanee 
▼eiy analogous to bromide of tetrethylium, and which is probably ubiomide of 

tetrethylene-diammonium, K'(C*H*)*Bi'. 

2. On Prifnary derivatives of ammonia^ jmmary amines. 
Bromide of ethylene giyes with ethylaiome and phenylamine : 



Dibromide of ethylene-diethyl-diammonium 



NXOB*X(?H»)*H*Bt« 
N«(C?H*)«(C«H»)*H:»Bi». 



Dibromide of diethylene-diethyl-diammonium 
and similar phenyl-compounds. 

8. On Tertiary derivaMves of ammonia. 

Just as dibasic acids can combine with one or with two atoms of ammonia, so like- 
wise can diatomic ethers (such as chloride or bromide of ethylene, or iodide oi methy- 
lene) combine with one or with two atoms of the tertiaiy deriyatiyes of ammonia.* 
Thus triethylphosphine with bromide of ethylene giyes the compounds — 

( V^ / - * «• Bromide of bromethyl-triethylphosphonium " (Hofmann). 



(C»H»)«P \ 

(C«H«)"Br«> 
2[(C«H*)T] J 



« Bromide of ethylene-hexethyl-diphosphonium ** (H o f m ann). 



The condition of the bromine contained in these compounds is worth noticing. T^ 
addition of nitrate of silyer to a solution of the first compound piecipitates only half 
the bromine contained in it, but nitrate of silyer precipitates all the broidine contained 
in the second. This difference is explained by Hofinann, by supposing that 1 atom of 

* Bromide of ethylene iind lodfde of methylene combine directly with only 1 Atom of Che tertiary 
amines, but the compounds with two atoms can be obtained b/ the action of hjrdrObromlc, or hydrlodic 
ethers on ethjlenamine. 



AMMONIUM-BASES. 197 

&y>inine in the first eompoimd is contained in the form of bromeihylt G'H^r : his 
-fiev of the oonstitation of the two compounds is expressed in the names quoted 
ahoTBw It is not» however, difficult to account for the difference in the behayiour of 
the two bromides without making this supposition. When we remember that the 
bromine in bromide of ethyl is not precipitated by nitrate of silver, but that it 
becomes so immediately bromide of ethyl is combined with ammonia or an analogous 
body, it does not seem surprising that one of the two atoms of bromine in bromide of 
ethylene should become saline (or accessible to ordinary reagents) when that body is 
oombined with ona molecule of a representative of ammoma, and that both atoms 
should beeome saline when it is combmed with two molecules of an anunoniarderiva- 
fivBL In an compounds formed upon the model of the first compound, only 1 atom of 
die salt-ndide is preeipitable by nitrate of silver ; in all those formed upon the model 
(^tbe second, both atoms are preeipitable. 
The IbDowing are the most important transformations of the above or similar bodies. 



a. The compound /nzn*V*p( ^ decomposed by heat thus : 

C^^Br') _ TTO^ . C»H«Br 



Bromide of vioyl-trfo- 
thjdphofpboniam. 

5. When > dilute solution is treated with hydrate of silver, it loses all its bromine 
and gives /ni^xfp ' [t "vhich may be regarded as a compound of triethylphosphine 

with glyeoL Tnis subs(4mce is a strong base, but^ as in the bromine compound, only 
one half of the elements combined with the ethylene, are directly replaceable by acid 

zadieLes (s.^. hydrochloric add gives /QSH»\sp* [ ) • ^^ bromide of phosphoros, it 

regenerates the original bromine-compound. In a concentrated solution, hydrate of . 

silver gives (rvmim [,difirering£romthelast substance by the elements of an atom of 

wafter. This compound may be regarded as containing oxide of ethylene and triethyl- 
phosf^iine, and belongs to the same daas of bodies as the bases * which Wnrtz ob- 
tained by the action of ammonia on oxide of ethylene : — 

C»H».0 ) 2(C*H*.0)> 3(C«H*.0)) 

(C*H»)«PC H'NJ H»N J 

BUiTkne-trtetnyl- D!eChy1ene- Trlethylene- 

faydorpboqdiixM. dihydoramlne. trihydoramine. 

e. 'Die same compound is c onver t ed by acetate of silver at lOO^' 0. into acetate of 
Tinyl-triethylphosphonium, P(C*H»)"0«H».C«H»0«. This reaction probably has two 

(C«H»)»P ( ■*■ 2{C»H»AgO«) - (c«H»)>P J + ^^' 

(C«H»)*P J " {om*yF ^ + c^ o 

If this be so, the second stage of the reaction, is precisely similar to the decomposi- 
tion already mentioned of the bromine-compound by heat 

tL By nascent hydrogen it is converted into bromide of tetrethylphosphonium : — 






e. With derivatives of ammonia, it gives bodies of the type of the second compound. 
The fiallowing bodies have been so obtained. 



C*H«Br» ) C»H*Br« ) C»H*Br» ^ 



C«H«Bi« 
,(C«H»)»P 
{CB^yN ^ 



,(C«H»)«P 
(CH»)«P , 



C»H<Br* 
, (C^»)«P 
((yH»)«P^ 



C?H«Br» 

,(C«H»; 

(0»H 



Br« ) 

»)«AsJ 



It has already been stated that bodies of this dass part with all their bromine to 
eelts of silver. Hydrate of silver gives 2{((yR^YP'\ \ ^^ dmilar bodies. These 
ttze strong bases and give the corresponding salts by the action of adds. 2[Y^H*1^1 [ 
is decomposed by heat into ^QXQtvtpr* & compound already mentioned, and oxide of 

• Am nUoaial nunm for bodtot derlring from the mixed type 2,^o } namely amic bate» and amie 

Um terns kmbramine$ and kifdoramida (not to be confounded with hydramides) may be used* 
bcr, art. Nombnclatueb). 

O 3 



198 AMMONIUM-BASES. 

triethylphoephine, P(C»H»)«0.— ^C»H»)*P V ia decomposed by heat into /c^^f«ad 
triethylarsine, (C'H*)*As. 

B. AonoN OF Tblltokic Chlobides, Bbomzdbs, ob Iodxdbs : — 

1. On AmmonicL 

Tribromide of glyceryl, (C*H*)Br*, giyes -with ammonia a base containing NO^H'lJi*, 
and bromide of ammonium. The reaction probably takes {dace according to the 
following stages : — 

lo C«H*Br» « C*H*Bi« + HBr. 

^ 2(0»H<Br*) + NH» - NC«H»Br» + 2HBr, 

the hydrobroraic acid which is formed of course combining with ammonia. The first 
stage of the reaction is analogous to the conversion of bromide of ethylene into brom- 
ethylene by the action of alcoholic potash : the compound, C'H'Br* may be regarded 
as dibrom-propylene, or as bromide of brom-allyl, (C'H^r)'Br. In the latter case, 

((C«H*Br) 
the product of its action on ammonia becomes N. /nsH^^^' dibromrdiaUylamine. 

(Maxwell Simpson). 

2. On Primary derivativea of ammonia. 

Chloroform, (CH)Cl', reacts on phenylamine, forming the hydrochlorate of a monoaod 
base, containing, G^'H^'N', and which may be oonsid^ed as representing two moleciiles 

of phenylamine in which the radicle ((S!k) replaces H*; thus /q<h«^sh{^' 

3. On Tertiary derivatives of ammonia. 

Iodoform, (jCHk)!*, combines with three molecules of triethylphosphine^ giving 
sr^P^H'^vpi C * '^^ compound parts with all its iodine to silver-salts, which accords 

with what IS said above respecting the compounds of bromide of ethylene with trie- 
thylphosphine. Its solution treated with hydrate of silver does not give a correspond- 
ing hydrate, but hydrate of methyl-triethylphosphonium and oxide of triethylphos- 
phina. 

sS^yp] + ^^^^ - f^dyp] + 2[(<?H»)»p.o] + sAgi. 

C. Acnov OF Tbtbatoxig Chlobides, Bromides, qb Iodidbs on DsBiVATim 

OF AjOIONIl. 

It 

Bichloride of cazbon, (C)Cl^ reacts on phenylamine thus : — 

SCCfffN) + Ca* ^ 8HC1 + C»»H"N".HCL 
8 iDol. pheny- 
lamine. 

The product of this reaction may be regarded as the hydrochlorate of a base de- 
riving from three molecules of phenylamine by the substitution of (C) for H^: vi& 

It 

(C) ) 

ff j 

(Tor details, see various papers by Hofmann, Proc. Hoy. Soc vols. ix. and x, also 
the Articles PnosPHOBrs, Absenio, ANTDfomr.) 

Amicokiux-bases CONTAINING Mbtals. — ^A verv large number of compoonds 
have been obtained by treating different metallic salts with ammonia. Some of these 
compounds are apparently of similar constitution to the salts of the organic ammoninm- 
bases, or to easily conceivable derivatives of them. But it is impossible to reduce the 
greater number of them to any consistent system, before they have themselves b«en 
more thoroughly examined, ana we have more definite notions as to the atomidfy of 
the metals contained in them. The following are examples of some of these com- 
pounds which can be written as analogous to known or conceivable oiganie com- 
pounds. 



1 



N 

01 

I 



i&k*) (unknown.) 
(C»H*). 



AMMONIUM-BASES — AMORPHISM. 199 

litUOic Cmmpotmdt. Organic Analogvtet. 

N^«CuCl N.H».C?H*.C1 

NHXHg^Cl .... N.H»(C*H»)«C1. 

(or N«HXHS)*a«(?) .... N«H^(C«fi*)».CL* 

N(Hg)«Cl N(C«H»)«CL 

(or ]S^Hg)K31« (?) .... N*(C«ll7CL» 

NH>(Hg)Cl« .... N(CH«)«(C«rf)Br». 
rH» N 

(Hg) . . . . 0- 

(Hi) I 

KH»(P*t)a« P(C«H»)«(C«rf*)Bi«. 

N*H«(Pt)a« I*(C«H»)«(C*tf«)Br». 

%*Hg - 200 

The attempts which hare heen made by some chemista to make formnlffi for many 
other metallic deriTatires of the ammoninm-salta, by supposing ammonimn eapable of 
repladnff hydrogen in ammoninxn, or by awmTniTig the existence of such radicles at 
PtCl or^O, may be described in words used with reference to another subject, by 
the author of one such attempt^ as " unwissenschafUiche Spielereien, die hier keine 
Berik* hnVh tigung yerdienen." — G. C. F. 

■XQimi* (See Allaictoic and Amniotio Liquids.) 

A mineral allied to nickel-glance, and probably identical with it. 

(Gm. i 102.) — Solid bodies which do not exhibit any crystalline or 
regular structure, even in their minutest particles, are said to be amorp&oue (a, priTatire, 
ai^ ^apfH form). Such are opal and other forms of silica, also glass, obsidian, pumice 
■tone, bitumen, resins, coal, albuminous substances, and numerous precipitates. Such 
bodies hare a smooth eonchoidal firacture, never exhibitingagranulatedappearance on the 
broken surfifMe ; they have no particular planes of cleayage, such as are found in dystals^ 
but require the same amount of force to separate lihem in all directions : they also 
oondnct heat equally in all directions, and nexer exhibit double refraction, excepting 
wben pKBsed or otherwise brought into a forced state. In short, the essential character 
of an amoiphous body is perfect uniformity of structure in eyery direction, each particle 
being similarly related to all those which surround it, the character of a fluid without 
its mobility, whereas in crystallised or organised* bodies, the molecular fbrces act with 
greatest energy in certain lines or axes, thereby determining an arrangement of the 
particles According to fixed laws, and causing the body to exhibit different degrees of 
teuarity, elasticity, permeability, refracting power, and conducting power for heat and 
deetnciW^ in different directions. It must not be assumed that a Dody is amorphous 
became it does not exhibit a regular shape in the mass : marble and loaf-sugar haye 
BO definite external form ; but they consist of aggregates of minute crystals, and when 
broken, exhibit, not a eonchoidal, out a granular fracture. 

Hie amorphous state is by no means pecuUar to certain substances, a great number 
of bodies being capable of existing both in the amorphous and in the crystalline state. 
8n]{^nr, when it solidifies slowly from fusion or solution, forms regular crystals, but 
when poured in the melted'state into cold water, it solidifies in a soft^ plastic, yiscid 
mass, capable of being drawn out into threads, and exhibiting no trace whateyer 
of erystalline structure. Phosphorus also assumes a regular crystalline form when 
■bwly cooled from solution in bisulphide of carbon or from frision, but when cast into 
moulds and quidEiy cooled, it forms a waxy solid, haying a eonchoidal fracture ; and 
by other modes of treatment to be described hereafter, it may be reduced to a perfectly 
amorphoos red powder. Carbon is crystalline in the diamond and in graphite ; amor- 
phous in charcoal, lamp-black, and the yarious other forms which it assumes \7hen 



* Ite Urm mmarpkomi la gcnenllj used in eontradUtiDctlon to crifstaOttu alon« ; bat Iti proper aia 
b la cp p o rido o to rrgmtoTt whether cryttalHiie or organised : for organic itructuree exhibit many 
p io p e iUM of wbkb ■morphooa bodies, properij lo called, are destitute ; thus wood, according to the 
rweatchaa of Dr. T|ndali, exhiUU three distinct axes of dearage, permeability, elasticity, and.eooo. 

O i 



300 AMORPEnSM. 

separated from organic bodies by imperfect combustion. Boron and silicon exhibit 
similar varieties. Arsenions acid, as it collects in the chimneys of Aunaces in which 
arsenical ores are roasted, is a elassjr amorphous mass ; but b^ dissolying it in hot 
water or hydrochloric acid, and leaving the solution to cool, it is obtained in the cry- 
stalline form (see Absenio). Native sulphide of antimony, which is crystalline, may 
be rendered amorphous by melting it in a glass tube and plunging the tube into ioe- 
cold water : and by melting it again and cooling slowly, the crvetaUine structure may 
be restored. Similar tran^ormations may be effected with native sulphide of mejvuij, 
also with the minerals Yesuvian and Axinite, and certain varieties of garnet Glass^ 
which is perhaps the most characteristic of amorphous bodies, may be devitrified bj 
keeping it for some time in the soft state at a high temperature : it then acquires a 
ciystelline structure and becomes nearly opaque, fbrming the substance called Reau- 
mur's porcelain. Generally speaking, rapid cooling from fusion is favourable to the 
assumption of iAie amoiphous structure, while crystallisation is promoted by slow cool- 
ing, the particles then having time to arrange themselves in a definite manner. It is 
alro true to a great extent that bodies which pass at once from the perfectly fluid to 
the solid state, — water, for instance, — ciystaliise on solidifying, whereas those which 
pass through the viscous form, like glass, solidify in the amoiphous state ; to this, how- 
ever there are some striking exceptions : thus sugar, the solution of which is ex- 
tremely viscid when concentrated, solidifies by slow evaporation in crystals of great 
size and regularity. 

The passage from the amorphous to the crystalline state sometimefl takes place 
spontaneously, the body all the while remaining solid. Vitreous arsenious acid, wnich, 
when recently prepared, is perfectly transparent, becomes turbid when left to itself for 
a few months, and subsequently white and opaque. Sugar which has been melted in 
the form of barley-sugar is in the vitreous state, but after a while acquires a crystal- 
line structure and becomes opaque. These phenomena show that the molecules of 
bodies, even in the solid state, possess a certain freedom of motion. 

The change from the amorpnous to the crystalline condition, or the oontnury, is 
generally accompanied by an alteration of ether physical properties. Bodies are for 
the most part denser and less soluble in the crystalline than in the amoiphous state, 
and have less specific heat. Yesuvian, which ciystallises in square prisms of specific 
gravity about 3*4, and garnet, whidi occurs in rhombic dodecahedrons of specifie 
gravity 3*63, both form by fusion and subsequent cooling, transparent classes whose 
specific gravity is about 2*96, so that, in passing from the dystalline to the nmoiphons 
stete, garnet suffers an expansion of about J and yesuvian of ^. The glass also dis- 
solves readily in hydrochloric acid, whereas the ciystallised minenls are quite 
insoluble. Many other crystalline siliceous minerals not soluble in acids become so 
by fusion, probably from the same -eauses. Quarts, which is oystallised silica, is 
much harder and denser than opal, which is the same chemical compound in the 
amorphous stete. Quartz-powder dissolves but veiy slowly in boiling potash-ley and 
is qmte insoluble in that hquid when cold, whereas pulverised opal is gradually dis- 
solved at ordinary temperatures and in a few minutes at the boiling heat. A remark- 
able exception to the general rule is, however, presented by arsenious add, which is 
both less dense and more soluble in the ciyirt^Uline than in the vitreous state. 

Another difference first observed by Ghraham is, that bodies have greater specific 
heat in the amorphous than in the crystalline state. Ordinary phosphate of sodium 
(PO*Na%) solidifies fiH>m fusion in the vitreous state ; the corresponding arsenate in 
the crystalline form : now the former in solidifyinff gives out perceptibly less heat in 
a given time than the latter, a greater portion of the latent heat of nision appearing to 
be retained by it. Ck>nnected with this law is the remarkable phenomenon of incan- 
descence which many bodies exhibit when their temperature is gradually raised. 
Hydrated oxide of chromium if heated merely to the pomt at which it parts with its 
water, remains nearly as soluble in acids as before, but if the heat be raised nearly to 
redness, the oxide suddenly becomes incandescent, and is afterwards found to be much 
denser and nearly insoluble in acids. Similar phenomena are exhibited by alumina 
and zirconia. Gadolinite (silicate of yttrium) which in its natural stete exhibits a 
conchoidal fracture and obsidian-like appearance, becomes vividly incandescent wh^ 
moderately heated, and is afterwards found to dissolve but very imperfectly in hydro- 
chloric acid, although before ignition it is veiy easily soluble ; ito density mcreases at 
the some time, though ito absolute weight remains unaltered. Yitreous arsenious 
acid also sometimes exhibito incandescence in passing from the amoiphous to the crystal- 
line stete. When a solution of the vitreous acid in hot hydrocmoric acid is left to 
cool in the dark, the formation of every crystal is accompanied by a flash of li|;ht ; but a 
solution of the oystalline add, under the same circumstances, exhibito no light what- 
ever. 



AMPELIC ACID— AMYGDALIN. 201 



An acid iBomeric with salicylic acid, CHK)*, obtained in 
■nfl quantity by the action of atrong nitric acid upon those Bchiat-oila which boil 
between 80^ and 1 60^ C. Picric add and a floccolent matter are formed at the same time. 
AmpeKc add ia a white aubatanoe, without odoor, nearly inaolnble in cold water, but 
little aohible in boiline water. Its solution reddena litmua. Boiling alcohol and ether 
dinolTe it readily, and on cooling deposit it in the form of a powder, having a scarcely 
perecptible oystalline character. Saturatdd with ammonia, it exhibits the following 
naetUMML With chloride of caldum, a white predpitate, which does not form when 
hot; the mixture depodts dystalB on cooling. No precipitate with the chlorides of 
bariiim, stzontium, manganese, or mercuir. A green predpitate with acetate of 
nickel ; bine with acetate of copper ; and white with acetate and nitrate of lead. 
(Laurent, Ann. Ch. Phya. [2] Iziy. 825.) 

AMraUDT. A substance resembling creosote, obtained from that portion of 
adust-oQ which boils between 200^ and 280^ C. The oil ia shaken up seyeral times 
with strong solphuric add, then mixed with ^ or ^ of its bulk of aqueous potash, and 
the liquid is left at rest for a day. The lower wat^ layer of liquid ia tiien separated 
from tne upper oily layer, and shaken up with dilute sulphuric add, and the oil which 
rises to the sur&ee is remored with a pipette, and gently heated with 10 or 20 times 
its balk of vater, which dissolyes the ampelin, leayin^ a small quantity of oil. On 
separating this oil, and adding a few drops of sulphuric add to Ihe aqueous solution, 
the ampelin rises to the surfiice in the form of an oil, having a slight brownish tint 

Ampelin disaolres in 40 or 50 times its Tolume of water, and is separated from the 
■ohtiott by a few dropa of sulphuric or nitric add, eyen when yery dilute. Potash, soda, 
and their carbonates render the solution slightly turbid at the first instant, but it recovers 
its transparency when heated. Carbonate of ammonium renders it permanently turbid. 
Chloride of sodium or chloride of ammonium added to a sdution of ampelin in caustic 
potash or carbonate of potasdum separates the ampelin, which is then not redissolyed 
OB heatiug the Ikjuid. Ampelin dissolyes in alcohol, and in all proportions in ether. 
It does not solidify at — 20*^ C. It is decomposed by distillation, yidcung water, a light 
oil, and chaicoaL Boiling nitric add attadu it strongly, producing oulic add, and 
an losolnble yiscous substance. (Laurent, Ann. Ch. Fhys. [2] Ixiy. 321.) 

and AMVBZBOliZTa. (See Hobnblbndb.) 




A name applied by Beizelins to salts which, according to 
his views, are compounds of two oxides, sulphides, selenides, or tellurides, e, a, sulphate 
of copper, CuK).SO' ; sulpharsenate of potassium, SE^S.As'S* ; sulphantimonate of 
sodium, SNa^.Sb'S*, &c., — such salts containing three ultimate dements — in contra- 
distinction to the haloid-salts, namely, the chlorides, bromides, iodides, &c., which 
are binary compounds of the first order, containing only two elements, such as diloride 
of sodium, NaCl, iodide of silver, Agl, &c. It is eyident that the so-called amphid 
salts are those which bdong to the water-ttfpe^ e. g. nitrate of copper, CuK).N*0* » 

1^ Sulpharacnate of potasdum, 3K"S.As*S* = S» j^^^'", whereas the haloid- 
compoonda belong to the type HH or HG. 

See Lbucxtb. 

See DroniMm. — AXPKOSSIilTBa See ANORTHmi. 




, C**H*0". — ^Produced by the metamorphods of amyedalin 
under the infinenoe of alkalis. Amygdalin dissolves in cold baiyta-water without 
deeompodtion, but on boiling the mixture, ammonia is disengaged. The ebullition is 
continued until the liberation of ammonia ceases altogether; a current of carbonic 
add is then passed through the liquid, to predpitate the excess of baryta; and the 
aeid is finally liberated from the barium-salt by cautious predpitation vrith sulphuric 
add. It is a slightly add liquid, which dries up to a gummy mass, — insoluble in 
absofaite alcohol, cold or boilmg, and insolubte in ether. Boiled with a mixture of 
peroxide of manganese and sulphuric add, it yidds formic and carbonic acids and hydride 
of benxoyL Its salts are not well defined ; they are more or less soluble in water. 
(Liebig and Wohler, Ann. Ch. Pharm., Ixiy. 185.) 

AmygdaiaU of ethyl is obtained, accordins to Wohler, by dropping a mixture of 
alcohol and amygdalin into hydrochloric add gas. (Wohler, Ann. Ch. Pharm. Ixyi. 
MO.) 



r, C»H«^0" + SH^O.— A crystalline prindple existing in bitter- 
> fa»ondi , the leaves of the Cerasus lauro-ceriuus, and many other plants, which by 
distillation yield hydrocyanic add. The bitter-almond oil and hydrocyanic add do 
not exisf roidy formed in these plants, but are the result of the decomposition of 
amygdalin under the influence of emulsin, a nitrogenised fermentable princi^e axisting 
with it in the plant 



^ 



202 AMYL. 

To prepare amygdalin, — the oil is expreBs<^ from the paste of bitter-ahnonds, and 
the reaidual mass extracted with boiling alcohol. This alcoholic solution is rendend 
tnrbid by the presence of globules of oil, whichore allowed to collect and separated hj 
decantation; it is then evaporated to half its original volome, and the amjgdaHn 
separated by the addition of ether, in which it is insoluble. The precmitated tmyg- 
diuin is pressed between folds of bibulous paper, washed with ether, and finally oys- 
tallised from concentrated boiling alcohol. (L i ebig and Wo hi er.) 

Amygdalin ciyBtallises in white scales haying a pearly lustre, insoluble in ether, bat 
yeiy soluble in water, from which it crystallises in thin transparent prisms contaizuBg 
3 atoms of water of crystallisation. Its aqueous solution has a slightly bitter tast& 
It deflects the plane of polarisation of a ray of light to the -left : [a] » ZS'Sl. The 
change which amygdalin undergoes by the action of emulsin (and other albomiDOU 
vegetable principles), is expressed by the following equation : 

C»H«^0» + 2H»0 « (rH«0 + CNH + 2C«H'«0« 
Amygdalta« Hydride Hydro- Gluoow. 

ofbenioyl. cyanic 
acid. 

By distillation with nitric acid, or other oxidising agents, it is resolved into am- 
monia^ hydride of benzovl, benzoic, formic, and carbonic acids. Caustic alkalia con- 
vert it into amyedalic acid. 

It is a neutral body, forming compounds neither with acids nor with alkalis. 

ABEVX, 0»H", or C"H« (Gm. xi. pp. 1—83; Gerh, ii. pp. 675— 708). -The 
fifth term of the series of alcohol-radicles, G'H^'*'^ The alcohol in an impure state 
(potato-fusel oil), appears to have been first noticed by Scheele ; and has been invee- 
tigated, together with its derivatives, by Pellet an (J. Chim. med. i. 76, also Ann. 



Ch. Phys. [2] xxx. 200), Dumas (Ann. Ch. Phys. [2] Ivi. 314 ; Dumas and Stas, 
Ann. Ch. Phys. [2] Ixxiii 128) ; Cahours (Ann. Ch. Phys. [2] Ixx. 81, kv. IM); 
and Balard, Ann. Ch. Phys. [3] xii. 294). The radicle itself was isolated byFnuok- 
land in 1849. (Chem. 8oc Qu. J. iii. 307 ; Ann. Ch. Pharm. Ixxiv. 41.) 

Amyl in the free state, C»H« = C»H".C»H", is prepared by the action of OM- 
amalgam upon iodide of amyl, the reaction being completed by the addition of potas- 
sium (Frankland). — 2. By the action of sodium upon iodide of amyl (Wurtz).— 
3. By the electrolysis of caproate of potassium (Brazier and Gossleth). — 4. By the 
destructive distillation of certain kinds of coal (Greville Williams). 

(1.) Pasty zinc-amalgam is brought into the copper cylinder used in the preparation 
of zinc-ethyl (see Ethyl) : the cylinder is then half filled with granulated zinc and 
iodide of amyl is added. After genUy warbling to expel the air, the cylinder is closed 
and heated for several hours at about 170° C. After cooling, it is opened and potassitm 
is added (about ^th by weight of the iodide of amyl employed). The cylinder is 
again closed and neated for an hour at the same temperature. To obtain the amjl, 
the cylinder is heated in a water-bath at 80° C, whereupon amvlene and hydride of 
amyl pass over. On applying the heat of a naked flame, amyl distils over, and msf 
be purifled by one rectification. (Frankland.) 

(2.) Iodide of amyl is warmed with sodiuni, and distilled; the product again dis- 
tilled from sodium and rectified, the portion which passes over at 158° C. being collected 
apart. (Wurtz, Ann. Ch. Phys. [3] xliv, 276.) 

(3.) A concentrated solution of caproate of potassium is submitted to the electrolytie 
action of six zinc-carbon elements, the platinum poles being separated by a porous 
diaphragm. Amyl collects upon the surface of tne liquid surrounding the negative 
pole : it is distilled from alcoholic caustic potash and washed with water. (Brasier 
and Gossleth, Chem. Soc. Qu. J. iii. 221.) 

(4.) Bog-head naphtha is submitted to fractional rectification, the portion boiling be- 
tween 164° — 169° C. being collected apart, and the product thus obtained is submitted 
to the action of fuming nitric acid, the action of the acid being checked by cold. The 
mixture on standing separates into two layers, the upper of which is again shaken 
with nitric acid. The product which has remained unacted upon is washed with 
caustic soda and water successively, dried with solid caustic potash, and distilled over 
sodium. The resulting liquid is again rectified at 167°— 160° 0. (C. Oreyille 
Williams, Phil. Trans. 1867, 447.) 

Amyl is a transparent colourless liquid, of agreeable smell and burning taste. 
Specific gravitv, 0*77 at 1 1° C— Boiling-point 166°— 169° C. Vapour-density 4-90. It 
is miscible with alcohol, immiscible with water. Amyl is not acted upon bv faming sol* 
phuric acid ; it is slowlv attacked b^ nitric and nitro-sulphuric acids, ana decomposed 
after long digestion with pentachlonde of phosphorus. 

Beouidb of Ahti.. — Prepared by the action of bromine and phosphorus upon 
amylic alcohol (Cab ours, Ann. Ql Phys. [2] Ixx 98). In three flasks are placed reflpe^ 



AaiYL. * £03 

tireir 15 pts. of amjlic alooliol, 2| pts. of bromine, and 1 pt. of phoaphonus. A little 
of the bromine is added to ihe amjlic alcohol, and the latter is ponred upon and 
digested with the phosphorus to decoloration. It is then poiored into its own flask, 
wad a little more bromine is added. The process is repeated, and the final product is 
washed with water, dried, and rectified. 

Bromide of amjl is a transparent colourless liqpd, heavier than water. It has an 
ifliaceoai odoor and sharp taiste. It is soluble in alcohol, insolable in water. De- 
eompoaes bj boiling with aleohoUc caustic potash« 

CHLoaxsB or AxTL, G*H"GL — Obtained by the action of strong hydrochloric acid 
upon amjlic alcohol (Balard, Ann. Oh. Fhj& [sf zil 294) ; also bj the action of penta- 
ehloride of phosphoms npon amjlic aloohoL (Cahours.) 

PrtparatioH. — 1. Amyiic alcohol is heated in a retort to 110^ C, a rapid current of 
hjdrochlorie add being passed through the tubulus into the amjlic alcohol; the 
blonde of amjl as it is formed distils oyer. When the retort is nearlj empfj the 
distiOate is poured back, and the same process repeated (^Guthrie). The product is 
theo shaken with strong hjdrochlorie acid, in which amjhc alcohol is soluble, chloride 
of amjl insohible, — ^then with water. 

2. Amjlic alcohol is distilled with its own weight of pentachlortde of phosphorus, 
wtthed, dried, and rectified. 

GUoride of amjl is a 4»lourless, transparent, neutral liquid, of agreeable odour. It 
hoils at 101^ C. Vaponr-densitj, 3'8. Bums with a luminous flame bordered with 
green. 

Chkmne acts upon chloride of amjl, giying rise to substitution-products, which go 
as&ri8C*H>Cl«Ci 

Ctaxidb 07 Akti.. See CrAiaDEa 

Htdbatb of AKTL,orAMTL-Ai.coHOL,C*H«0 « ^^" 1 [or C^'iT'O* « 

C^ff^OMO]. — Afnylate of Hydrogen. Hydrate of Amyl. Hydrate of Pentyl. Hy* 
drgttd Oxide of AmyL Fusel-oil. — ^This alcohol seems inyariablj to accompanj ethjHc 
akohol(8ee AiicoHOLS, p. 97) when the latter is formed bj fermentation. The conditions 
of its fonnation are unknown; it seems, howeyer, to occur in largest quantitj in those 
Bqiiids which remain most alkaline during fermentation. In the disollation of yege- 
table juices which haye been fermented, the latter portions of the distillate contain 
witer, ethjlic, propjlic (?) butjlic and amjlic alcohols, besides the acids and aldeh jdes 
of ^ese aIcoh(U8 and ptrobablj higher fattj acids and aldehjdes. To 'obtain the pure 
amvlic aloohol from the crude product, it is shaken seyeral times with hot milk of Ume, 
decuited, dried oyer chloride of calcium, and rectified at 132^0. 

Amjlic akohol is a transpar^t colourless liquid haying a peculiar odour (the peatj 
smell ciwiuskj is duo to its presence in small quantities), which causes coughing, and 
buniiig taste. It bums with a white smokj flame. Solidifies at about — 22^ C. 
%)eciflc gravitj 0-811 at 19^0. Boiling-^int 132^0. Vapour-densitj 3147. 
Soluble in oommoB alcohol and ether, nearlj insoluble in water. It dissolyes small 
quantities of sulphur and phosphorus. 

Aeoording to Pasteur (Compt. rend. zli. 296), ordinarj amjlic alcohol is a mixture 
of two amjlic alcohols identical in chemical composition and yapour-densitj, but 
difieiiDg in their optical properties, one of them turning the plane of polarisation of a 
T»j of light to the left, while the other is opticiall j inactive. A difference of solubilitj in 
raneof the salts obtained from tiie mixed alcohols, famishes the means of their separa- 
tion ; the actiye amjl-sulphate of barium is 2| times more soluble in water than the 
corre^nding inactive s^t. The optical rotatozj power of amjlic alcohol varies, on 
aeooust of its being a variable mixture of these two modifications. This difierenee in 
the two amvlic alcohols is said to be traceable in some other of their derivatives, e, g. 
^coic add prepared frrom active cjanide of amjl, rotates the plane of polarisation. 
O^^ttrta.) 

Jkoompositions of Amyl-alcohol. — 1. ^j heat The vapour of amjl-alcohol passed 
throng a glass tube heated to dull redness, is resolvea into tritjlene (propjlene) 
luanh-gas and other hjdrocarbons. (B ej n o Id s .) 

2. Bj oxidation. — Amjl-alcohol is difficult to set on fire, and bums with a white 
BDokj flame. In contact with the air at ordinarj temperatures, it iis veij slowlj 
oxidised and acquires a slight acid reaction. The oxidation is greatlj accelerated bj 
the presence of platinum-black, the amjl-alcohol being then converted into valeric 
aeid: 

G»H»0 + 0« = C*ff»0« + H'O. 

AiQyl.aIoohol distilled withji mixture of sulphuric acid and peroxide of manganese or 
bichromate of potassium, jields valeric aldehjde, valeric acid, and valerate of amjl. 
The same products, together with nitrite of amjl and hjdrocjanic acid, are formed- 
I7 the action of nitric add. Amjl-alcohol is also converted into valeric add bj heat<- 



^ 



201 AMYL. 

ing it to 220^ C. with a xnixtnre of lime and hydrate of potassium, hydrogen gas being 

evolved : 

C*H«0 + KHO « C«H«0* + 4H. 

Amyl- Valente of 

alcohol. potatsium. 

3. By stdphurie acid. — ^Amyl-alcohol mixes readily witVstrongsnlphniicacid, forming 
a red liqnicC which contains amylsnlphnric acid, SO^O^H'^H, as well as free solf^iirie 
acid. On <^i«rf-inmg the mixture, the amyl-alcohol is del^drated, and amylene, OH** 
passes over, together with the polymeric compounds, C"H* and C"H**, and perhaps 
also amylic ether, (C*H"VO ; at the same time, however, a portion of the alcohd is 
oxidised and converted mto valeric aldehyde and valeric acijd, sulphurous acid beiiig 
evolved and a black pitchy mass remaining in the retort 

4. With |?Ao«pAorK?a^, amyl-alcohol ^elds amyl-phosphoric add, PO*.C*H".H".— 
Distilled with phosphoric anhydride, it is converted into amylene and its multiples. 

6, Trichloride of phosphorus converts amyl-alcohol into phosphite of amyl, amjl- 
phosphorous acid, chloride of amyl, and hydrochloric acid : 

3(C»H".H.O) + PC1» « PO«.(C»H")'.H + C»H"a + 2HC5L 

Fhosphlte of amyl. 

and 8(C*H".H.O) + Pa» = PO«.C«BP'.H« + 2C»H»»a + BUL 

Amylphotphorotti '' 

add. 

6. With pentachloride of phosphorus^ amyl-alcohol forms chloride of amyl, hydro- 
chloric acid, and chlorophosphoric acid, or, wken the amyl-alcohol is in excess, diamjl- 
phosphoric acid : 

C*H".H.O + PC1» = C»H"a + Ha + P0C1« 

Chlorophos- 
phoric 
add. 

and 9(C»H".H.O) + 2PC1» = SOff^a + 6HC1 + 2rP0^(C»H»»)*.H] + WO. 

ulamylphospboric 
add. 

7. Chlorine^as is absorbed in larse quantify by amyl-alcohol and forms chloramylal, 
a compoimd homologous with chloral. — 8. Amyl-alcohol absorbs hydrochloric add gas 
and mixes with the concentrated aqueous acid ; on heating the mixture chloride of amjl 
is formed. — 9. It dissolves, with the aid of heat, in a concentrated aqueous solutioii of 
chloride of /pine, forming a liquid which boils at 130^0., and yields a distillate of amylene 
and its multiples. — 10. Distilled with phosphorus and Sromine or iodine, it yields 
bromide or iodide of amyl. — 11. Distilled with fluoride of boron, at fluoride of siUam, 
it yields amvlene and its multiples, but little or no oxide of amyl. — 11. Phosgene gas 
is abundantly absorbed by amyi-alcohol, forming chloroformate of amyl, and the liquid 
when distiUed yields carbonate of amyl (Medio ck) [vnth evolution of phosgene (?)] 

c»H".H.o + coa« » cao«.c»H»» + Hca. 

Phot- Chlorofonnate 
gena. of amyl. 

and 2(CaO«.C*H") - CO«.(C*H»*)' + COa« [?] 

Carbonate of 
amyl. 

Carbonate of amyl is also obtained by adding water to the solution of phosgene in 
amyl-alcohol (M e d 1 o c k) : 

2(CC10«.C*H«') + H»0 « 00».(C*H»>)« + 2Ha + C0«. 

21. Disulphide of carbon, in presence of potash, oonvertB amyl-alcohol into amylsal- 
phocarbonic or amylxanthic acid (p. 2Q6). — 13. Chloride of cyanogen is rapidlr 
absorbed by amyl-idcohol, and forms products similar to those which it yields wim 
ethyl-alcohoL 

C*H"0 + CNa + H»0 « C«ff «N0« + HCL 

Amyl- Amjl-ure" 

alcohol. thane. 




Amyl-alcohol combines with a few metallic chlorides in the same manner as ethyl- 
alcohol. With chloride of calcium and dicMoride of tin, it forms aystalline com- 
pounds which are decomposed by water. It dissolves in caustic potash and soda. 

Htdbidb op Amyl, C*H".H. — Iodide of amyl is heated with sine and its own 
volume of water for a few hours to 142° 0. in a copper cyKnder (see zinc-ethyl), and 
the contents are distilled from a water bath at 60*^. The distillate consists prindpeJly 
of amylene and hydride of amyl. The mixture is left for 24 hours in contact wid 






AMYL. 205 

erastie potesh, and again rectified from a water-bath at 36^. The distillate is 
iniiMned in a freezing mixture and treated vith a mixtore of anhydrous and filming 
waifbuic add, which retains the amylene. Lastly, the hydride of amyl is distilled 
from a water-hath (Frankland, Ann. Ch. Pharm. IxxiT. 41). Colourless transparent 
hqiiid, luTiog a pleasant odour. Specific grayity 0*638, at 14^ C. Boiling-point 
30° GL YapoDr-density 2*382. 

lonini or AmtLi C*H"L — ^Prepared by the action of iodine and phosphoms upon 
amylie akohd (C a hours, Ann. Ghl Phys. [2] Ixz. 81). Ponr parts of iodine are 
placed in one flas][, and excess of phosphoms in another. Seven parts of moist amylie 
aleohol are poured npon the iodine, the liquid shaken tlQ opacity is produced, then 
poured upon the phosphonis and dieted till the colour is removed — again poured 
jtfGa the iodine, and so on, till all the iodine is exhausted. The nearly colourless 
product bo obtained, ib washed with slightly alkaline water, dried over chloride of 
eakinm and rectified. The latter portions are the purest. 

Iodide of amyl is a colourless transparent liquid of &int odour and pungent taste. 
Specific gravity 1*611 at 11® C. Boiling-point 146<>. Vapour-density 6-676. It turns 
iKDwn on exposure to light. 

OxiDB OP AxTi., C"H*=0 = (C*H")«0 For C^^IPWl — Amylie ether, AmylaU 
of AstyL — Prepared by the action of sulphuric acid on amyl-alcohoL Strong 
nlphmic acid is heated to 150° C. in a retort, and amyl-alcohol allowed to enter 
dovly throngh the tubnlus ; the distillate is then shaken with carbonate of sodium, 
washed and rectified. — ^2. By the action of amylate of potassium on iodide of amyl. 
Amjiate of potassium is digested in a retort, connected with an inverted con- 
dooer, with an equivalent quantity of iodide of amyl, and the product is distilled and 
leetified — 3. By the dry distillation of amylsulphate of calcium (K^kul^). Oxide 
of smyl boils at about 180® C. It is colourless and of agreeable odour. 

Oxide of Amyl and £Myl, C'H»«0«<?H».OH".0. Amylate of Ethyl, Ethylaie 
9f Am^ Etkylamylic Ether. Prepared by the action of amylate of potassium upon 
iodide of ethyl, or of iodide of amyl upon etbylate of potassium. (W illiamson, Chem. 
Soc. Qq. J. XV. 103, 234.) — (1.) A known weight of potassium is dissolved in absolute 
alcohol in a tubulated retort ; iodide of amyl is added in sufficient quantity for there 
to be rather less than 1 at. of iodine for every at. of potassium in the ethylate of 
potaannm; the retort is connected with an inverted condenser; and the contents 
are digested for some time. After distillation, water is added, and the liquid which 
separates out is dried and rectified. — (2.) Iodide of ethyl is added to a hot solution 
of potash in amylie alcohol, digested &c, asinl (Guthrie). Amylate of ethvl is 
a ookorlesB transparent Hquia of agreeable odour, similar to that of sage. It is 
bg^ter than water. Boiling-point 112*^0. Vapour-density 4*04. 

AmylaU of Methyl^ or MethylaU of Amyl, C«H"0 - C*H"0, is prepared in the same 
manner as (1) amylate of ethyl (Williamson). Boils at 92^ C. Vapour-density 
374. 

Amylate of Potassium, C*H"KO. — On bringing freshly cut potassium into diy 
amrlic alcohol, the potassium is dissolved and hydrogen is evolved. To obtain this 
body in a state of purity, the action is aided by heat until the mass becomes viscid. 
Any gloVoks of metal which have remained unacted upon are removed, and the pro- 
duct is poured upon a cold slab, and allowed to solidify. It is then strongly pressed 
between many fmds of bibulous paper to remove the unaltered amylie aloohoL 

Aoiylate of potassium is a Grystalline white body, soapy to the touch, and alkaline 
to the taste. It is soluble in the alcohols. By water it is instantly converted into amylie 
aleobol and hydrate of potassium. 

Aii^flate of sodium, CH"NaO. Closely resembles amylate of potassium. 

StriPHinns of Ahtx. IProto sulphide of Amyl. (0»H")"S or C"H«S.— 
Equivalent quantities of amylsulphate and monosulphide of potassium are intimately 
Bnzed in a retort (by solution and evaporation) and distilled (Balard, Ann. Ch. Phys. 
[3] xiL 248). Colourless liquid of offensive odour. Boiling-point 216^ C. Vapour- 
aeiisity 6-3. 

Dieulphide of Amyly CHIT'S. — Obtained by distilling together amylsulphate and 
disalphide of potassium (O. Henry, Ann. Ch. Phys. [3] xxv. 246). Amber-coloured 
hqail Boiling at about 260^. Specific gravity >9 18 at 18^ 0. 

ga/j»Atigg of Amyl and Hydroyen: Amyl-mercaptan, C»H".H.S [or (^•W^S.ffS.] 
Aoared by saturating caustic potash with sulphuretted hydrogen, adding the 
|»oanct to crude amylsnlj^hate of potassium (prepared by mixing equal weights of 
amylie alcohol and sulphuric add, neutralising with carbonate of potassium and filter- 
nig) and distilling from a capacious retort in a chloride of calcium bath. The oily 
drops in the distillate are washed, dried, and rectified (Kreutzsch, J. pr. Chem. 
'^'* 1). Coloorkfls Hquid of intolerable odour. It is soluble in alcohol and ether. 



206 AMTL. 

but insolnble in water. Specific gravity 0845 at 09 C. Boilin^point about 120^ C. 
Vapoar-density 3*631. It combines wiUi metallic oxides. 

Amylmercaptide of mercury is obtained as a colourless liquid on brin^;ing amyl- 
mercaptan in contact with mercuric oxide. The mixture solidifies to a solid maas on 
cooling. The compound is insoluble in water, but soluble in boiling aloohoL Tlie 
other amylntercaptides are not distinctly known. 

Sulphide of Car bony It Amy I, and Hydrogen, AmyUulpkoearbome aad, 

Amylxanthie acid, CH'^H) » c*H" h[ "^ — ^^^ ^^ ^^ ^ prepared from the 

potassium-salt by treating the aqueous solution of the latter with dilute hydrochlorie 
acid (Balard, Ann. Ch. Phys. [3] xii. 307). light yellow oily liquid, of penetrating 
odour, heavier than water, acid to testpaper. It is quickly decomposed bv wnter. 

AmyUcanthate of potaesivm^ C*H".K.S*0. — A cold saturated solution of hydrate of 
potassium in amylic alcohol, is treated with bisulphide of carbon until the alkalini* 
reaction has disappeared, and the yeUow ciystals of the potassium-salt which a^Mrate 
out on cooling, are washed with ether, and dried between blotting paper. 

The ethyl and methvl salts of amylxanthie acid, are formed by digesting eqniTalent 
quantities of ethylsulpnate or methylsulphate of potassium, with amylsul^ocarbonate 
of potassium, lliey are oily liquids lighter than water. (Johnson, Chem. See Qn. J. 
V. 142.) 

Dioxysulphocarbonate of Amyly CH^S^O.— The compound so-called, which contains 
1 at. hydro^n less than amybcanthic add, is produced by the action of iodine 
on amylxanthate of potassium. It is an oily liquid which boils at 187^ C, iindergoing 
decomposition at the same time, and yielding among other products amylxanthate of 
amyl, GS^.(OS?*)*. Digested with aqueous ammonia, it yields amylxanihaU of 

ammonium, and aanthamylamide or ^phocarbamate of amyl, ^ nsH" ( O 

2C«a"S«0 + 2NH» - CS«O.C»H"jna[« + C«ff«NSO + S. 

•- ^ -^ *- 

Dioxyralpho. Arajlxanthato of Xanthamy- 

caibonato of amnonium. lamide. 

amyl. 

The last mentioned compound, xanthamylamide, is a yellow neutral oil, which boils 
at 184° C. but not without decomposition, being resolved by distillation into amyl- ■ 
mercaptan and cyanuric acid : 

3C«H'»NS0 - 3C»H»2S + C«N»H»0«. 

Heated on platinum foil, it bums with a vellow luminous flame, eiving oflT white 
vapours. Boiled with hydrate of barium, it is resolved into amyl-alcohol and anlpho* 
cyanide of barium : 

(>H»«NSO + BaHO « C»H»«0 + CNSBa + H*0; 

similarlv with potash. It is decomposed by chlorine and by nitric acid. 

Xantnamvlamide is insoluble in water, but dissolves readily in alcohol and ethec 
It imites with chloride of mercury, forming the compound (^'*NS0.4Hi^^ which 
crystallises in white featheiy crystals. With dichloride of platinum duBolved in 
water, it forms a vellow precipitate. (M. W. Johnson, Chem Soc. Qu. J. r. 142.) 

AmystUphocarbafmc acid, C*H"NS^ (see next page). 

Tellubidb of Amtl, or Tbli.ubahtl, (C*H'*^*.Ta. has been obtained in 
an impure state by diBtilling telluride of potassium with amylsulphate of «^l<nTim 
It is a liquid having a strong disagreeable odotir, and boiling at about 198^ C. but 
decomposing at the same time, aod depositing tellurium in small shining pfrisma. By 
exposure to the air it is converted into a white mass. The nitrate of teUoramyl 
is a colourless heavy oil, obtained by heating telluramyl with moderately strong ni^e 
acid. Treated with the bromide, chloride, or iodide of hydrogen or sodium, it yields 
the ' corresponding compounds of telluramyl in the form of viscid heavy oils. The 
chloride treated with oxide of silver, yields oxide of telluramyl in the form of an oily 
liquid soluble in water, and so strongly alkaline that it separates anunonia from sal- 
ammoniac. It forms a crystalline salt with sulphuric acid. (Wohler and Bean, Ann. 
Ch. Pharm. xcvii. 1.)— F. O. 




I 

Amtlahinb, C*H:"N « C*H".H>.N. Amylammonia, AmyUa.'-'rbjB oiganic base 
is formed: H.) By heating cyanate orcyanurate of amyl with caustic potash (Wurts, 
Ann. Ch. Phy«. [3] xxx. 447) : 

CNO.C»H» + 2KH0 « C»H>«N + CO«K« 



Cyanate of Hydrate Amyla- Carbonate 

amyl. ofpotas- mine* ofj 

ilun 



lum. aium 



AMTLAMINES. 207 

(2.) In the de alructive distUUtion of animal substances (Ander8on).^3.) By heat' 
b^ amylralphate a£ potassium with alcoholic ammonia to 250^ C. (Berthelot). — (4.) 
By the dry distillation of leucine, carbonic anhydride being at the same time eyolyea 
(Sehwanert* Ann Ch. Pharm. cii. 221): 

C^»»NO« = C*ff »N + CO* 



Leucine. Amyla- 

mtne. 



Also bj carefbllY distillinff a solution of horn in strong caustic potash, leucine being 
then formed and afterwards decomposed as above (S c h wan er t). — (6.) By the action 
of esostic potash on flannel, tetiyhunine being also found among the products. (Gr. 
Williams, Chem. Gaz. 1858, 310.) 

PrnaraHon. — Cyanate or cjanumte of amy! (obtained by <^i«*:i'lling cyanate of 
potaasinm with amylsulphate of potassium) is distilled with strong caustic potash ; 
the distillate is neutralised with hydrochloric add, evaporated and reciystallised ; 
and the faydrochlorate of amylamine decomposed by distillation firomlime and rectified 
over hydrate of barium. Colourless liquid! Specific gravity 0*75 at 18^ C. Boiling- 
point 94^ C. Amylamine precipitates most metallic oxides which are predpitable 
by ammonia ; it redissolves alumina. 

Carbonate of amyinmine is formed as a crystalline solid, when its base is exposed to 
the carbonie add (rfthe air. — Hydrobromate of amylamine^ OH'^N.HBr, or bramide 
of itmyHutiL, C^H"NBr, is formed by adding hydrobromie add to the base. — Hydro- 
cktoraU of an^lamine, C»H>«N.Ha or chl^mde of amylium, C*H»«NC1, forms* with 
diefakffide of platinum a double salt, OH^'NCLPtQ*, which is soluble in boiling water. 

Am^s^phocarhanuiUofAmyUum,C^m^^^ N(H»;0»'h>^" | S ' is P«xl^»^ 
by the union of 2 molecules of amylamine with 1 molecule of bisulpnide of carbon : 
(C^'H^NS* « 2C*H"N + CS«). The mixture of the two substances becomes warm, 
and on cooling deposits the compound in whito shining scales, insoluble in water and 
in ether, bnt easily soluble in alcohoL At 100^ C. it decomposes after a while, giving 
off nUphuretted hydrogen. Treated with hydrochloric add, it yields chloride of 

amylium, and amylsulphocarbamie add ^ H ( q ' "^^ich. is an oily body, 

soluble in ether, ammonia and potash; mixed with amylamine, it reproduces the 
^ saUa. (A. W. Hofmann, Chem. Soc. Qu. J. xiii. 60.) 



DiAMTtAMiNB, (C»H")«HN.— When amylamine is heated to lOO^^C. with bromide 
of amyl, direct combination occurs, and the solid hydrobromate of diamylamine is formed. 
The base is obtained by distillation of the bromide with caustic potash (Hofmann, 
PhiL Trans. 1851, p. 357). Slightly soluble in water. Boiling-point about 170^. 
The salts of diamylamine are difficidtly soluble in cold water, more readily in hot 



TBrAXTLAMiNB, (C*H")'N, is obtained by heating diamylamine with bromide of 
ly], and distilling the so-formed bromide of triamylium with caustic potash (Hof- 
mann). Its propertiee and those of its salts are similar to those of diamylamine. It 
boils at about 257^ C. 

TsTBAXTLiux, N(C^")*. Tetramylammontum. — ^Ammonium in which the whole 
of the hydroeen is replaced hj amyl. Not known in the separate state, but obtained 
as an iodide by the action of iodide of amyl on triamylamine, the mixture solidifying, 
after three or four days' boiling, into an unctuous o^stalline mass. The iodide of 
tetmmylium is also produced, but very slowly, by heating iodide of amyl in a sealed 
tube with strong aqueous ammonia. This salt, N(C^H").I, dissolves sparingly in 
water, f<Hining an extremely bitter liquid, from which it is precipitated in the crystal- 
line £arm by alkalis. Boiled with oxide of silver, it yields a very bitter alkaline solu- 
tion of the kydraie of tetramylium : 

N(C»H")M + AgHO = Agl + ^^^*^"^|o. 

On mixing the liquid with potash, or concentrating it strongly by evaporation, the 
hydrate of tetramylium rises to the sur&ce in the form of an oily layer, which 
pindnaBy ■olidifie& A moderately concentrated solution of the base left to evaporate 
in an atmosphere free from carbonic add, deposits the hydrate in definite crystals 
sometimes an inch long, and containing several atoms of water of ciystallisation. 
These aystals when heated, melt in their water of crystallisation, and ultimately 
leaTB the pure hydrate in the form of a semi-solid transparent mass. At higher 
tempentiires, the hydrate is completely decomposed, giving off water, triamylamine, 
snd a hydrocarbon, which is probably amylene : 




208 AMFLENE. 

N(0»H'«)*H.O « H«0 + N(C»H»»)« + C»H» 

Hydrate of Triamy- Amylene. 

tetramylium. lamine. 

Hydrate of tetram jlinm dissolyes readily in acids, fbrnung eolntions vUch yiold 
crystalline salts by evaporation. The sulpnate cryBtallises in long^ capiUuy tfarads : 
the nitrate in needles, the oxalate in large deliquescent J^tes, the chloride in Umins 
with palm-like ramifications; the chloroplatinate, (049")*NGLPtCl*, in bentiM 
orange-yellow needles. (Hofmann, Chem. Soc Qn. J. ir. 316.) — ^F. G. 

(For the Amyl^hoaphinea^ Arsines, and Stibines, see FHOsPHO&xrs, Anfflnm^ ud 
Amtdcont.) 

AMTlXSn. G^H>*, or C^W\ — ^This hydrocarbon, a homologae of ethyleDeor 
olefiant gas, and the fifth term of the series, C"H^, is produced dy the dehydntion 
of amyUc alcohol by sulphuric acid, phosphoric anhydride^ or chloride of sine, also bj 
the dry distillation of amyl-solphate of calcinm (^eknl^). To prepara it^aooft- 
centrated aqneons solution of chloride of zinc is heated to 130^ 0., with an equal ToliUDe 
of amylic alcohol : and the product is distilled from, a water-ba^ over caustic potash, 
and repeatedly rectified (Balard, Ann. Ch. Phys. [3] xiL 320). It is a transparent 
colourless, Teiy thin Uquid, having a fEunt but onensiye odour. Boils at 39° C. 
(Balard); at86*(Frankland); at420(E^kuU). Vapour-density, 2*68 (Balard), 
2*386 (Frankland), 2*43 ^E^kuU); (by calculation, for 2 yoL -^ 2-4266). The 
yapour is rapidly and completely absorbed by sulphuric anhydride and pentacfalabde 
of antimony (Frankland). It possesses anaesthetic properties, and has been tried 
as a substitute for chloroform, but has been found to be yezy dangeroos, having in 
more than one instance led to fatal results. 

Amylene is diatomic, like ethylene, uniting with 2 at. Br, NO', HO, &&, and vith 
1 at 0, S, &c. 

AcBTATB or AicTLHMS, CEL^K)^ a (CE^OY \ ^'' ^ producod by heating the bo* 
mide CH^'Br*, with a mixture of acetate of silyer mixed with glacial acetic arid: 

C»H»Br« + 2(C«H«O.Ag.O) = 2AgBp + /ctslo)*! <>*• 

It is a colourless neutral liquid, insoluble in water, boiling above 200^ C. and euily 
decomposed by alkalis into acetic acid and amylene-glycoL (Wurts, Ann. Ch. JPhTi. 
[3] Iv. 468.) 

Bbomidb of Ahylhnb, CH^'Br*, is produced by passing bromine-vapour into unj- 
lene. Heated in a sealed tube with alcoholic ammonia^ it forma bromide of amnio- 
nium, and bromamylene^ C^H'Br. — By treating amylene with a larger quantihr of 
bromine, another compound is formed, containing OH^r*, probably dutromuu «/ 
broTnamylenCf C^H'Br.Br'. This compoimd, treated with alcoholic potash, yields di- 
hromamylene^ C^H'Br*. (Cahours, Ann. Ch. Phys. [3] xxxviii 90.) 

HTDSA.TB OF Amtlsmb, OP Aktlknb-Gltool, C*BPH)* =■ m '(0*. — Prepared 

by distilling acetate of amylene tidth dry pulverised hydrate of potassium, and poxifiad 
by a seoond distillation in the same manner, and subsequent rectification jwr m: 

(C^?l°* + 2KH0 - 2(C*h«b:o«) + ^'^*jo«. 

It is a colourless, very syrupy liquid, having a bitter taste with aromatic afte^taft& 
When cooled with a mixture of solid carbonic acid and ether, it solidifies into a hiid 
transparent mass. It does not affect polarised light. Its specific gravity is 0*987 at 
0^ C. It boils at 177^, and distils without alteration. When pure it dissolves in yater 
in aU proportions. The aqueous solution turns acid when exposed to the air in contset 
with platinum-black, yielding chiefly carbonic acid, with only a small quantity of a 
fixed acid, apparently butylactic acid. When gently heated with nitric arid, it is 
rapidly oxidised, the chief product of the action being butylactic acid, CH^» 
(Wurtz, loc, cit) 

Amylene-glycol, treated with hydrochloric acid, either gaseous or aqueous, is oon- 
yertecC slowly at ordinary, more quickly at higher temperatures, into the eUorhgdm 
of amylene-glyeol^ C*H**.H0.C1. This compound cannot be isolated by remains dis- 
solvecl in the excess of acid and is decomposed by distillation. The acid sedation 
treated with potash yields oxide of amylene. 

NiTHTLiDB OF AuTLBKB, C»H»^NO*)« NUroxtde o/ Jiiivfon^.— Obtained by 
passing peroxide of nitrogen (nitryl, NO', prepared by heating anhydrous nitrate of lead) 
into a fiask containing amylene, and surroui^ed by a fbaezing mixture. The gas ii io- 



AMTLENE. 209 

rtntlr absorbed, and the amylene is gradnaHy oonyerted into a pasty mass of minntd 
aysfaa^ which may be purified by Tmshinff with oold alcoho], reciystallisation from 
bdling ether and drying in racno over suphnric acid. It gave by analysis, 37*26 
per cent. G» 6*61 H, and 17*66 N ; the fbrmnla requiring 3709 C, 618 H, and 17*28 K. 

The eompoimd ma^ also be obtained, though less advantageously, by passing vapour 
of amylene mixed with air into foming nitric acid. It is remarimble as affording the 
first examine of the direct combination of nitzyl, (NO'), with an organic radicle. 

Heated br itself in a dry tube, it decomposes at about 95^ C, giving off nitrous an- 
hjrdride^ IPO', and nitrons acid, HKO', and leaving a heavy liquid apparently containing 
niiMte of amyL Heated with quick lime, it gives off an aromatic body, probably con- 
sating of oxide of amylene. (Guthrie, Ghem. Soc Qu. J. xiii, 45, 129.) 

Oxnn OF AsncLBNB, (CH*')''.0, a volatQe liquid, isomeric with valeric aldehyde, 
It boils at 9SP C. Has a pleasant ethereal odour, and a rough taste. Specific gravity 
in the Uqnid state, 0*8244 at 0° 0. Vapour-density by experiment 2*982, by odcula- 
tioo (^2 voL) a 2*806. It bums easOy, with a yellow flame. It is insoluble in water, 
and is not converted into amylene-glycol whei^ heated with water in a sealed tube. 
It disBolreB in alcohol, in ether, and in a mixture of the two. It mixes with acids. It 
unites with asihfdraus or crystalUsahU nitric acid at a higher temperature, but the 
oraabiiiatioii is attended with partial decomposition. (A. Bauer, Compt. rend. 
litfOO.) 

AxszjDOi mTH SuLFRUB AKD Chlobdib : 

L Dieklorogulphide of Amylene, C^«SC1«, or C^JI»»i8»CZ*.— Protochloride of sul- 
phur (8CP) is brought into a flask surroxmded with ice and an excess of amylene 
added Xfacj gradually. The excess of amylene is evaporated o% — ^the residue digested 
and washed with water, dissolved in ether, filtered, and evaporated. It is a non- volatile 
liquid, having a pungent odour, insoluble in water, soluble in ether and alcohoL 
^peciilc gravity, 1*149 at 12^ C. Distilled with excess of alcoholic caustic potash, it 
yieldB amylene, dindpkide o/fiuyl (C^B*8), and other products. 

2. JDisulpkochloride of Amylene, 0*H>*SG1, or C^»IP*£Pa,— On treating disulphide 
of ddoirine (SCI), with excess of amylene, and evaporating the latter, a transparent 
yellow, non-volatale liquid, of faint and nauseous odour is obtained, having the above 
composition. It is obtained pure by digestion with water, solution in ether, filtration, 
and evaporalion. Specific gravity, 1*149 at 12^ C. Soluble in ether, absolute alcohol, 
and snlnhide of carbon. (Guthrie, Chem. Soc* Qu. J. xiL 112.) 

BiBii^ihochlaride of amylene treated with chlorine, gives off hydrochloric acid, and 
is eomreitedinto a non-volatile liquid, of specific gravi^ 1*406 at 16^ C, miscible with 
ether, iiisolnilde in water, but soluble in hot alcohoL This liquid gave by analysis 
nmnbera agredng approximately with the formula, C^*WCl*8, which may be that of 
cUoromdpSde o/triciloranwlene, C^IPO^XSa, or that of sulphide of tetrachloramyl, 
C^B'Cfiya, (Gmthrie, Ohem. Soc Qo. J. xiii 43.) 

Ainxfisni wtee Bvlpsur asd Oxygbn : 

Ditfdjphoxide of Amylene, C^^IP^SPO, — ^Prepared by digesting the disulphochloride in 
akohobc solution with protoxide of lead, till all the chlorine is combined, dissolving in 
ether, filtering and evaporating. Specific gravity, 1*064 at 13^ G. Non-volatile, yeUow, 
or almost colourless. Soluble in ether and alcohol, insoluble in water. 

Hydrate of Disulphoxide of Amylene, Q^B^S'O.HO, — ^Disulphochloride of amylene is 
heated in alcoholic solution for some hours, in a current of ammonia ; the liquid is then 
poured off fiom the chloride of ammonitim formed, and heated for some hours in a 
sealed tube to 100^ C. with alcoholic ammonia ; the excess of alcohol is driven off 
in a water-bath ; the residue treated with water ; and the oil which is thereby pre- 
eipitated is washed with water. Yellow liquid of meaty odour. Somewhat soluble 
in hot water, soluble in alcohel and ether. Kon-volatile. Specific grarity 1*049 at 
8P. (Gnthrie, Chem. Soc Qti J, x* 120.)— F. O. and H. W. 



if C**H^O». or C»*J2«0'.— This add is contained, together 
with eardol, io the pericarps of the cashew nut (Anacardium oocidentale). The pericarps 
aie extraeted with ether, which dissolves out both the anacardic add and the eardol ; 
the ether is distiUed of^ and the residue, after being washed wilh water to free it from 
tanniii. Is dissolved in 16 or 20 times its weight of alcohol. This alcoholic solution is 
digfsted with recently predpitated oxide of lead, which Amoves the anacardic add in 
the tbni of an insoluble lead-salt The lead-salt is suspended in water, and decom- 
posed by sulphide of ammonium, and from the solution of anacardato of ammonium, 
obtained after the removal of the sulphide of lead by flltration, the anacardic add is 
liberated by the addition of sulphuric add. After repeated purification by solution in 
alooliol, eoDversion into a lead-salt, and decompodtion of this salt by hydrosul- 
pfaaxic add, the add is obtained as a white crystalline mass, which malts at 26^ C. It 
VOL.L P 



^ 



210 ANACARDIC ACID — ANALYSIS- 

luui no smell, bat its flATonr is aromatic and bnrning. When heated to 200^ 0. it u 
decomposed, producing a colourless yery fluid oiL It bums with a smol^ flame, stains 
paper, and liquefies by prolonged contact with air, emitting an odour smiilar to that 
of rancid fat Alconol and ether dissolve it readily, and these sdutboB reddea 
litmus. 

Some of its salts are crystalline, others amorphous. The silver-salt is a polTenleDt 
white precipitate, soluble in alcohol, in presence of a free add. It contaba tvo 
atoms of metal, C**H*'AgK)'. The lead-salt> obtained by mixing a boiling alcoholic 
solution of anaoffdic acia with an alcoholic solution of acetiite of lead, is aaid to ooa-' 
tain O^H*«Pb^O' or C*^JS^Flf'0' ; if this formula be correct^ the add is tetnbasie 
[or dibasic, if the smaller atomic weights of carbon and o^gen are used]. The sahs 
of ammonium, potassium, barium, calcium and iron, have been described, but they ik 
not very definite, and their formulae have not been fixed. (Stadeler, Aim. GL 
Fharm. Ixiii. 137.) 

JLVA&CXMBt ^**UsiO» + BPO - Na«O.SiO« + Al«0«.3SiO* + H«0 or 

SNaO.SiO* + S{JJPO*,2SiO^ 4- 2 HO.—A mineral belonging to the seolite fianilj 
containing, according to H. Boee's analysis, 65*7 per cent, of silica, 13*5 soda, 23'0 
alumina, and 8*3 water, which agrees very nearly with the preceding formda. It 
belongs to the regular system. Primary form a cube ; it occurs also m lendte-octi- 
hedrons, and in cubes with the fistces of the leudte-octahedron r6pladn|r the solid 
angles. Cleavage indistinct, parallel to the faces of the cube. Specific gravity from 2-1 
to 2*2. Softer than felspar. In its purest form, it is colourless and transparait^ bat 
sometimes white indining to grey or fiesh-colour. According to Brewster, it pdanM 
light in a peculiar manner, indicating a grouping of the molecules vety different from 
t^t which is usually found in the re^:alar system. Before the blowpipe, it loses viter 
and becomes milk-white ; but when the heat is increased, it becomes dear again, and 
then melts quickly to a transparent glass. It is readily decomposed by h^drodilone 
add, with separation of visdd silica ; after ignition, however, the decompositioii is \m 
easy. Analcime occurs frequently in defts and geodes in granite, trap-rocks and lara. 
It is found on the Calton HOI, Edinburgh, at Talisker in the Isle of Sky, in Bmnbarton- 
shire, in theFerroe Islands, in the Hans, and in Bohemia. 



rA&T8zs— orosaAvio. 

The object of chemical analysis is to ascertain the composition of any Bahstaooe 
whatever. The distinction usually made between organic and inorganic eompouids, 
has led to a corresponding division into organic and inorganic analysis: the latter 
being confined to the investigation of inorganic or mineral compounds. The metfaodf 
employed in this branch of analysis, are far more numerous and varied than thoN 
hitherto devised for the analysis of organic compounds. Inorganic analysis is divided 
into qualitative and quantitative analysis. The former teaches qb how to ascertain the 
elements of a substance with regard to their quality only, and how to separate them ooe 
from another : the latter establishes the methods of proceeding, by whidi we detennine 
the relations of weight or volume, which these dements bear to one another. It is 
obvious that, before we can proceed to estimate the quantities of each dement con- 
tained in a compound, we must know what are the elements that it oontaixis : benee 
qualitative must always precede quantitative analysis. 

^ Analvsis is one of the most recent of the various branches of chemical sdence. Cob- 
siderable progress had already been made in synthetical chemistiy, in the prepanticn 
of chemical compounds, &c. at a time when the foundations of uialyticau ehemis^ 
(in the sense at present attached to the term) had not even been laid. Leas than a 
centuiy ago, when the properties and compounds of many dements were dther entirely 
unknown or but imperfectly established, few problems were more difiScult than that w 
inorganic analvsis: the analyst had need of both penetration and caution in the highest 
degree, in order to discriminate between known and tmknown substances. It ia qdIj 
within a comparatively recent period, that the discovery of many new demeats, and 
the more complete investigation of the reactions of those already known, have enaUd 
us to construct a systematic conrse of analysis, drcumscribed within definite and vdl 
established rules. 

Analytical chemistry, as we have already observed, aims at two objects, each oloady 
connected with the other : — 1. To ascertain what are the dements contained in sob* 
stances whose composition is unknown : — 2. To determine the rdative proDOitions of 
those dements whose existence has previously been qualitatively asoertainecL In the 
earliest analvtical researches, both these objects were pursued simultaneoudy. Henoe^ 
in the very brief sketch of the history of analytical chemistry, which it is sov oar 
purpose to eive, it is not possible to trace the progress of eadi of these branehes (£ 
analysis independently of the other, for this purpose it is more convenient to tdopt 



AN ALYSIS— INORGANIC. 2 1 1 

the dntinetuw of Analysis in ike wet and tn the dry v>ay (vide infra) : for these two 
bnadia of uuljaia aimed onginallj at different objects, and tiie progress of each 
w in gKtt messore independent of that of the other. 

The earliest analytical methods of which we hare any information were in the dry 
WIT. Tlie7 were directed ezdnslTely to the separation of noble from, ignoble metals; 
aid thejr were generally conducted qnantitatiTely, the object being to determine the 
eoounerdal valve of alloys, &&, by extracting the amount of the most precions metal 
eoDtainedin them. Aa early as the second centory B.a, Agatharchides of Unidos (quoted 
hj Dioionu Sieahis) gives an account of a method employed by the Egyptians for the 
otnctioa and piirificati<Mi of gold, which closely resembles the process of cupellation, 
at pneent so eoctensiTely employed for the separation of silver from lead. Strabo 
(about the Christian era) describes the extraction of silTer from its ores by fusion with 
kad; and all the analytical methods which we meet with in the course of several 
sneeenTe eentories are but modifications of the same process. We find a description 
oftheproeeasgiTen by Geber in the latter half of the eighth century, which corre- 
^onda TtTj clteely with that at present employed. 

8taetly apeaking; the employment of anialysis in the dry way for qualitative pur- 
poaea, ia of much later date, commencing from the observation of the behaviour of 
difftrait metallic compounds when exposed to a high temperature in contact with 
certain reagents, commonly called fluxes. It is to Pott, Profeasor of Chemistry at 
betliBy arc 1750, that we owe the first distinct record of these observations ; he 
pointed out that it was possible, by the addition of certain fiuxes, to fiise many 
anhatsiifm which were infusible alone ; and that the colour of the fused mass afforded 
infonnation as to the nature of the original substance. This method of experimenting, 
vhiehwia eonducted by him in crucibles and fumades, on a comparatively large 
Male, reeeived an immense extension by the introduction of the blowpipe, by means 
of whidi £ir more accurate indications were obtained with a much smaller quantity of 
the anginal sabstaneew The first mention of this implement occurs about 1660, in the 
MoDoia of Uie Academia del Gimento, at Florence, when it ia noticed as being em- 
piojred by ghsa-blowexs ; and the first indication of its use for chemical purposes, is 
mnd in Konkel's Ar9 vitraria expertmentaHs, 1678. Cramer, a German chemist, in 
hi BemaUa JfHs doeinuutiom (1780), ^ves the earliest instructions for its use as 
an implement of analysia. The fiirther mvestigation of the results to be attained by 
nieana of this invaluable instrument} was effected mainly by a succession of Swedish 
GhemiatB, of whom Cronstedt and Bergman were perhaps the most remarkable ; and it is 
to Beadiiis that the establishment of the existmg system of blowpipe analysis was 
finalbf ovin^ 

Aeooiding to the present oonrae of analysis, the method by the dry way is usually 
employed onfy in the psdiminaiy examination : the cases are very rare in which its 
resolts can be relied upon fot complete information as to all the constituents of a 
a nhat a nc a For this purpose^ reeouise is now invariably had to analysis in the wet way. 
The early hiatoiy of this method of analysis is vexy obscure, amounting in fact to 
nothing bat the enumeration of a few random reactions, in the employment of which 
ooayatem was obsesvedL It was originally employed solely for the quahtative detection 
of adnltentions in drugs, &c. It was next directed to the examination of mineral 
vaten, to which purpose it was mainly confined until the latter half of the seventeenth 
eenta^, at which penod the first true perception of the problem -involved in analytical 
ehoaiatiy was obtained b^ Boyle, who gave to this branch of the science the name by 
vhieh it is at pcesent designated. He was tilie first to establish clearly the idea of a 
^emittl dement, and to seek for methods of ascertaining what elements or known 
eDBBSoonds are contained in any substance of unknown composition. Although these 
methods e(Mnprise many reactions which were known before his time, still he has the 
credit of being the first to generalise these scattered fiicts, and to collect them into a 
ohaKntaystan. Among the new reactions introduced in his time, we may mention 
the precipitation of calcium-salts by sulphuric add, as serving for the detection of 
eithv eaieium or sulphuric add ; of silver^salts by hydrochloric acid, as a test for 
both silver and ehozine ; that of iron with tincture of galla ; the blue colour of copper- 
■ihs vith excess of ammonia^ dec. Since the time of Boyle, analytical chemistry, in 
the hands of Harggzaf| Scheele, Bergman, Klajnoth, H. ^iose, &c. has made continual 
advueas, the enumeration of which cannot be attempted in a blief historical summary 
Kke the present ; ontil by degrees it has assumed the systematic form of which wo 
•hall presoitly {ooceed to give an outline. 

The establishment of quantitative analysis, as a distinct branch of chemical sdence, 
ii of eoBBpantmly recent date. For a long time it was almost entirely neglected, 
little if any importance being attached to the relative proportions in which elements 
ematin a compoand. Until the latter half of the last centory, it was confined to the 
pnzposa of aanying, or of determining approximately the value of ores ; and it was not 

F 2 



^ 



212 ANALYSIS-INORGANIC. 



until Layoiflier, with sacli triumphant success, employed the balance as a means of 
refuting old errors and of establisning new traljis, that inquiries into the quantitttiTO 
composition of bodies came to be r^arded as the only sure test and foundatioii for 
chemical theory. Almost all the quantitatiye analyses by which any reUable know- 
ledge of the constitution of substances has been obtained, are included in tiiis penod, 
and date within the last 60^ or 70 yean. The empirical results thus obtaineo, hxn 
led to the discoveiy of the most important theoretical truths, e. g, the theory of atoms 
and equiTalents, the law of multiple proportions, &&, which in turn have been of in- 
estimable yalue in controlling the results of analysis, and ensuring to them a degne of 
aocunUT which could neyer hare been attained by merely empirical determinatioDs. 

Until a comparatively recent period, the only method of quantitatiTe analysis was 
that by vmaht. By this method, the substance to be estimated is either vd^ied 
directly, or m the form of some compound of known composition, from whose w^gfat 
that of the substance to be estimated is readily calculated, the reagent by whidi the 
substance is separated being always employed in excess. More recently, another method 
has been introduced, which depends upon the employment of only the exact qnantitj 
of the reagent which is necessary to produce the reaction desired ; and upon the dfr- 
termination of this quantity, not by weight, but by measure. This method, knovn as 
the Volumetrie method of analysis (see Akaxtsis toluxbtbio), is only applicable 
in cases where the point at which the reaction is complete can be deteimined aeea- 
lately by means of some distinctly visible phenomenon occurring in the solution to be 
analysed. The first introduction of this method is due to Descroizilles, who, at tbe 
dose of the last century, applied it to the valuation of bleaching powder by means of 
indigo-solution : since whicn time it has been gradually extended until it has grovn 
into a distinct and most important branch of anuysis, which, in most cases, is at least 
equal in accuracy to the method by weighty while it is greatly eupeiior in ^eed aad 
facility of execution. 

The methods of qualitative analysis oonsiat in brin^g the sobstanee nnder ex- 
amination into contact with other bodies of known properties, and observing the 
phenomena which ensue. These phenomena consist in alterations, either in state of 
aggregation, form, or colour, depending upon some chemical change. AUbodiea^bidi 
we employ for this purpose, we call by the general name of reagents, the ensaing phe- 
nomena are called reaetions. Acids, bases, salts, and simple bodies (elements) an 
alike used as reagents. 

By means of reagents, the ehemiat puts questions to the substance under exanisir 
tion, enquiring whether it contains this or that group of chemically similar elements, 
or only this or that member of such group. If the question be put correctly— i& if 
all the conditions under which the reaction expected can be produced by the leagait 
employed be carefully observed, the answer is decisive as to the presence or absence of 
the element, or group of elements, sought: if, on the other hand, these conditions' 
a. e. the properties and chemical relations of the bodies formed by the chemical ehiDga 
which constitute the reaction, have been wholly or partially neglected, the ansver, if 
not certainly erroneous, is at least of doubtful accuracy. 

Keagents may be employed either in the tost way or m the dry way. In the wetvsT, 
the reagent in solution, i. e, in the liquid form, is brought into contact with the sub- 
stance to be examined, which is also in the liquid form. In the dry way, the tvo 
bodies are brought together in the solid state, and subjected to a high tempeiatiiT& 
Of the utmost importuice in analysis by the latter method, is the knowledge of the 
use of the blowpipe, and of the behaviour of bodies in the djifferent flames which es& 
be produced by it. (See Blowfifb.) 

Many reagents exhibit the same, or a similar behaviour, with a certain fixed nnmbff. 
i. e. with a group, of elements, and with most of the compounds of these elementa ; and 
can therefore, be employed for the division of the elements into groups. Soch reagents 
are termed ^«nera/ reagents. Others serve for the further distinction of the seversl 
members o/^such groups : their selection depends upon the knowledge of the spedsl 
characteristic behaviour to such reagents of each single dement^ or of each of its 
several compounds. Such reagents are called special or oharaeteristio ree^etUs, Their 
number is much greater than that of the general reagents, l^eir natore being as varioos 
as that of the substances which can come under examination : their selection deq^ds 
upon the solubility or insolubility, colour, or other physical or chemical properties of 
the new compounds to which they give rise. They may frequently be employed re- 
ciprocally : thus, starch is a characteristic test for iodine, and ledproeaUy, iodine is a 
characteristic test for starch. 

The analyst has not only to establish that this or that body is present in aoompoond, 
but he has also to prove that no other body is present besides those which ns has 
actually found. Hence it is evident that he must not treat the substance nndff ex- 
amination with any reagent induMrimiaately. He must follow a certain fixed order, 



ANALYSIS— INORGANIC. 213 

I metlHMfiflil fljatem, in the application of reagents, which will be the same for all 
inoigiiiie sahetanees whateyer, let their elements be what thej may. This systematic 
method, vhich cannot be departed from or abbreviated wiUiont danger, except in 
certain cases bj the experienced chemist^ consists in the employment of general reagents 
iat the successxTe eUmmation of gron^ of elements possessing certain conmion chemical 
^KfottkB; and finally, in the recognition of each member of soch groups by the em- 
pbymeat of characteriaric reagents. If the object be n5t a complete and accurate 
uaijais, but merely to establish the presence or absence of some particnlar body, the 
chsnetmstic reagent may in many cases be employed at onee, without preyions 
nooQiM to generw reagents. 

The fint thing to be done in the qnalitatiTe analysis of a solid body, is to subject 
it to a pRliminaiy eTamination in the dry way, by which means important information 
18 to its composition may fireqnently be obtained : after which it is dissolved, and ita 
eoBstitnenti aseeortainfid by framinajaon in the wet way. The oounM of qnalitativB 
a]nlylil^ therafine, consists of 3 parts : 

I JMxminaiy examination in the dry way. 
IL Sdution, or oonversion into the liquid form. 
HL AoaljBis of tiie solution in the wet way. 

We ahsll now proceed to trost soceessively of each of these operations. 

L Prdminary ExanUnaiion. 

Tbaa consists partly in an aocuiate observation of the physical properties of tbe 
nbatanee (its form, colour, hardness, speciflc gravity, &c) : but chiefly in observing 
its behaviour at a Jdgh temperature, either alone, in contact with air, or with some 
ckemiol compound which produces either decomposition or simple solution. 

1. The tubkanee ia heated alone in a dry test-tube, on charcoal, or on platinuinrfoU, 
~ Water, sulphur and its adds, ammonium-, arsenic^, and mercoiy-compounds are 
eooplelely volatilised. Carbon burns when heated in the air. If water is evolyed, 
obeore whether it is add or alkaline to litmus. If gases are cYolyed, observe whether 
they are oonbiistible : and if so, whether their combustion is sustained or intermittent, 
(hganifi oompounds are decomposed by heat^ generally with evolution of inflammable 
gas aad sepsntion of carbon : when heated with strong sulphuric acid and bichromate 
of potMiinm, they erpolye carbonic anhydride, which gives a white predpitate with 
hale- or bazyta-water. Bodies which are very rich in oxygen, nitrates, chlorates, per- 
ch k r a tea, bramates, iodates, deflagrate when heated on charcoal. Host alkaline, and 
some alkaline-earthy salts, melt without Tolatilising or changing colour ; after strong 
ignitioD, the residue is alkaline to test-paper. Many silioites (espedaJly seolites) 
melt whan a thin fragment of them is exposed in platinum-tongs to the blowpipe flame. 
Borates and almn swell up: other salts, e. g. chloride of sodium, decrepitate. Of 
metals: antimony, lead, tin, bismuth, cadmium, zinc, tellurium, fuse readily before 
the blowpipe, giving an incrustation of oxide; gold, silyer, and copper, fdse with 
difteolty, and giye no incrostation ; iron, nickel, cobalt, molybdenum, wolfram, and 
piatiaom metals are inftasible. The oxides and salts of the earthy and alkaline-earthy 
metals are infusible, or difllcnltiy fhsible ; they become yividlj incandescent, with a 
vhite light, but do not change colour; the earths, after ienition, are not alkaline to 
test-paper. The oxides and salts of some metals assume a darker colour when heated : 
those of zin^ tin, titanium, columbium (niobium), and antimony, become yellow: those 
of lead, bismuth, mercury (and chromates), become dark-brown. 




silieatea |;ive a blue infutiUe nuua : zinc-oxide and titanic luhydride become yeUotoish- 
$rten: bmoxide of tin, bhaeh-green: antimonic andcolumbic anhydrides, dirty-green: 
nagnesia and tantalic anby&des, fieelnred: baryta, brown or brick-red: ^ucina^ 
Hme^ and atrontia, gr^- 

1 7%e eubstance is heated on platinum-tnr$ (if a metallic salt, on charcoal) in the 
i^ner blowpipe flame, and the cohur of the outer flame observed, — A, yellow colour in- 
dicatea aodium : a f^det, potassium : a carmine^^, lithium or strontium. The yellow 
eoloar imparted by sodium, completely oyerpowers those of the other alkaline metals: 
bat, if the flame be observed throujg[h dark blue slass, the yellow rays are cut ofl; and 
the edoars of potassium and lithium are plainly visible, even in presence of a large 
ezcesi of aodium. A reddish^yeUow colour indicates calcium ; a yeUow-green, barium or 
Bolybdennm ; a green, cupric oxide, phosphoric, boric, or tellurous add ; a Uue, arsenic, 
SBtimouy, lead, selenium, or cupric chloride. In many cases, the colour is rendered 
^"^^ ^ipazent if the substance be previously moistened with hydrochloric add, or a 

p 3 



1 



214 ANALYSIS— mORGANia 

little chloride of fiilver added: phosphates and borates should he moistefied vitli 
sulphuric acid. 

The delicacy and sharpness of these chxomatie indications are greatly inereased hj 
a method of obserration lately introdnced by Bnnsen and Kirehho£ It oooaiti 
mainly in igniting a metallic salt on platinum wirs, in a feebly Imninons and neailj 
monochromatic &me, such as that of a Bonsen's gas-bnmer, and obseniog the 
flame through a prism. Very characteristic spectra are thai prodooed, edntaiui^ 
luminous coloured bands coincident in position with certain of f^unhofei'B lino. 
Sodium gives a spectrum reduced to a single bright nanow band; Utkiim, a fanght 
red and a fainter yellow band ; poiassiumf a spectrum nearly resembling the ordinvj 
solar q)ectrum in the middle, but characterised by a bright line near the red ex- 
tremity, and a fainter line near the violet end of the spectrum. The stnmam 
spectrum consists of a broad brisht orange band, with some fiunter red hands; tlie 
(foleium spectrum, of a broad brignt green band, a somewhat narrower bright oru^ 
band, and some fainter yellow bands; and that of bariufn, of several bngfat grwo, 
yellow and orange with two faint red bands. The sodium reaction is extremdj 
delicate, sufficing for the detection of a quantity of sodium as small as jg^m^ 
a milligramme ; distinct indications are likewise obtained with ^^^A^^ of a milli- 
gramme of lithium, j^ milligramme of potassium and barium, y^^os isHligniniDd 
of strontium, 16566666 nuUignmme of calciunL (For details see the artide Laaa ; abo 
Pogg. Ann. ex. 161 ; Chem. Soc. Qu. J. ziii. 270.) 

4. l%e substance is heated on charcoal in tie reducing flame with eorhonaU of 
sodium^ or toith carbonate of sodium and cyanide of potassium. — Most aZBenic eom* 
pounds give a smell of garlic All sulphur-, selenium-, and tellurinm-oompomids, gire 
an allumne sulphide, selenide, or telluride, which, when moistened, leaves a buck 
stain on a clean silver plate. Tin-, silver-, copper-, and gold-compounds givemaUeaUe 
shining scales : compounds of nickel, cobalt, iron, molybdenum, wolftam, and thr 
platinum-metals are reduced to a grey infusible powder: no incrustation is fanned in 
any of these cases. Antimony-compounds give a brittle metallic globule, and a iriiite 
incrustation: bismuth, a brittle globule and a brown-yellow incrustation: lead, a 
malleable globule, and a yellow incrustation. Zinc and cadmium are not reduced to 
the metallic state, but give, the former a white incrustation, not volatile in the outer 
flame, the latter, a brown-red incrustation. 

5. ITie substance is heated in a ^lass tube, open at both ends, held ohU^f,—'^ 
following substances yield gases having a peculiar smell : sulphides, of bunung emlphor; 
selenides, of horseradish ; arsenides, of garlic ; many ammonium-salts, of ammonia; 
fluorides (especially on addition of microcosmic mlt), of hydrofluoric acid. A metallie 
sublimate indicates arsenic- or mercury-compounds : a white sublimate is given "bj 
arsenides (crystalline), by antimonides and tellurides, (fbsible), and by many ammonip- 
salts. A fused sublimate is given by the higher sulphides (brown-yellow), by selenidfs 
and selenium (blackish-red), and by sulphide of arsenic (yellow). All h^^ted salts 
or substances containing hygroscopic water yield drops of water, the acid or alkaline 
reaction of which should be ascertained. 

6. Ihe substance is heated in contact with metallic ginc and dilute hydroMrie or 
sulphuric add. —Many metallic acids are reduced to lower oxides by this treatmeDt, 
a change of colour being produced. Titanic acid gives a violet colour : tungstic add, 
and the chlorides of tantalum and cohimbium, a blus : molybdie acid, blue, changing to 
green and dark-brown : oolumbous acid, Hue, changing to dark brown: chromic add, 
ffreen, iodic add, brown, or if starch be added, blue. 

n. Solution of Solid Bodies. 

After having ascertained by the preliminary examination in the dry way, to vliat 
class of bodies the substance under examination belongs, the next step is to bring it 
into the liquid form, in other words, to dissolve it. In o^er to effect this, it is generally 
necessary, when the nature of the substance allows it, to reduce it to a fine powder by 
pounding in a mortar, and, if necessary; by subsequent levigation with water. This 
IS indispensable in the case of minerals, especially of silicates, and of all other difficnlUy 
soluble, insoluble, or difficultly decomposible compoimds. If the substance contains 
oxganio matter, this should be removed before proceeding further, as its presence 
materially interferes with the reactions of many minenJ compounds. This may gene- 
rally be effected by heating the substance strongly for some time in contact viui air 
(more speedily with oxygen), until the whole of the carbon is converted into carbonic 
anhydride. In many cases, the oxidation of the carbon is. facilitated by dropping nitric 
acid on the heated substance. 

The solvents which are usually employed in the analysis of inorganic bodies a« 
water, hydrochloric and nitric adds, and aqua-regia. The finely-powered snbstance 
is first boiled with from 12 to 20 times its weight of distilled water, in order to ascertain 



J 



ANALYSIS— INORGANIC. 215 

Hb eooplete or partial Boliil>ility gp inflolubili^ thereiiL If it be not completdj dis- 
nhed, the aohitioii is fQtcred off from the residue, and a drop or two of it eraporated 
to diyness on platinnm-fi)!], when, if the sabstanoe is partially soluble in water, a dis- 
timet residiie is left ; if the snbstance is completely insoluble, there is no reetdoe after 
w poa m ti o n. In the former ease, the solution is tested with Utmns papor to see whether 
it has a neutral, add, or alkaline reaction, and set aside for further examination. 
The pootion insobiblft in water is then treated suoeessiyelj with dilute 9nd> concentrated 
kjfdneUorie acid, particular attention beinff paid to the nature of the gases, if any, 
iha^Tf erolvvd, and to the separation of aoud products of de<x>mposition. Carbonates 
evnlve carbonie anhydride^ with effervescenoe ; peroxides, duromates, and chlorates 
STohe dilonne; ^anides, hydrocyanic acid; many sulphides, hydrosulphuric add; 
solpfaitea and hyposulphites, sulphurous anhydride, with separation of eulphur in the 
latter cases. Host metals (iron, dnc, tin, &c) evolTo hydr^en ; or, if arsenic or an- 
timony be present^ arsenide or antimonide of hydrogen. If hydrochloric acid does not 
eompletely dissolTe the substance, it generally effects the complete separation of one 
or more elements ; for which reason the solution should be separated from the residue, 
end esamined uart. The residue may consist of compounds undeoomposible by 
hydiochlozic adi^ which existed in the original substance ; or of insoluble compounds 
fonned l^ the decompodtion of the original substance by hydrochloric add. Thus 
solpbiir IS separated from pdysulphides, pulverulent or gdatinous silica from many 
wlicatei, tmi^itic add from tungstates, &c. ; or if lead, suver, or subsalts of mercury 
be preeent; insoluble chlorides of these metals will be formed. 

n the sabatsnee is not completdy soluble in hydzodilorio add, the insoluble reddue 
is treated snceesuYdy with nitrie acid and amta regia. In many cases («. g, with 
phosphates, arsenates, silicates, tungstates, &c), these compounds act merely as sdyents; 
on many other bodies they exert an on'dimng action. Thus, most sulphides, when 
treated with nitric add, separate sulphur, whi(£, by prolonged disestion with the add, 
collects into jeSiow globnles which swim on the su^hoe of the liquid, or disappears 
altogether, being oxidised into sulphuric add, which may be detected in the solution, 
unless it forms an insoluble salt with the dissolved metal Sulphide of lead is con- 
voted \fj nitric acid into snlphate of lead : sulphides of antimony and tin into white 
oxides: protoenlphide of mercury is insoluble in nitric add, readily soluble in aqua regia. 
Most metals are completdy soluble in nitric add : the only metals not attacked by it 
are gold, platinum, and the rarer metals found in platinum-ores (with the exception 
of pelladiiim, whidi is slowly soluble in nitric add). Gold and platinum are soluble 
in aqua regia. Tin and antimonv are not dissolved by nitric acid, but are converted 
into white oxides, insoluble in the acid ; thej are readily soluble in aqua regia (or 
hjdrodikrie add and chlorate of potasdum\ if excess of nitric acid be avoide£ 

When a findy powdered substance is neitner dissolved by suocesdve treatment with 
the above solvents, nor so decomposed or attacked by tiiem as to give an idea of its 
natnrc^ it most be rtndcred solubis, in order that its constituents may be determined 
in the wet way. The method of doing this frequently depends upon the results of 
the pdiminaiy examination. The following are the prindpal insoluble (or difficoltly 
Bohilkle) substuoes. 

1. Adpiaieg (of barium, strontium, cslcium, and lead). When heated on charcoal 
with carbonate of sodium, they give an alkaline sulphide : sulphate of lead gives also 
a maTleahle metallic globule; it is blackened by sulphide of ammonium, and soluble 
in basie tartrate of ammonium. They are rendered soluble by fusion with 3 — 4 pts. 
alkaline carbonate: after treating the fused mass with water, the solution contains 
the add as alkaline sulphate, and the residue the base, as carbonate, which is now 
sduble in hydrochloric add. In this and in all the following cases, the substance 
most be powdered as findy as possible before fVision. The smphates of strontium, 
caldnm, and lead are decomposed (the first not completdy), by cugestion with a solu- 
tion of sodic carbonate : su lpha te of caldum is somewhat soluble in water. 

2. Siliea and tHieates, — ^When heated before the blowpipe with microcosmic salt, 
they swim undissolved in the fused bead. They are rendered soluble by fosion with 
S— h( ptsL alkaline carbonate (or hydrate of barium), treatment with hydrochloric add, 
and evaooration with frwe add, when the silica remains insoluble ; or by treatment 
with faydiofluaric and sulphuric adds. 

3. Fluorides (fluorspar, &c)— When gently heated with concentrated sulphurio 
add, they evolve hvdrofluoric add, which corrodes glass : if silica be present, fluoride 
of silidum is evolved, which gives a predpitate on contact with water. They are 
denoimposed by fridon with 4 pto. alkaline carbonate, with addition of dlica if neces- 



4. Mumma or Muamnatea.^Thej sive a blue infiisible mass when heated with 
eobalt-eolution. They are rendered sduble by fudon with 3 — 4 pts. add sulphate of 



p 4 



216 ANALYSIS-QUALITATIVE. 

6, Chromie oxide (cbrome-iion-ore). — ^It giyes a green l>6ad in both flamei vHh 
borax or microcosmic Bait Chrome-iron-^re in deoompoeed b^ snoceMiTO tuion viih 
acid sulphate of potassiiun, and with alkaline carbonate and nitre. 

6. Binoxide of tin, and AnHmonie anhydride, — Thej are colonred yeDov bj nl- 
phide of ammonium, and dissolved by digestion in excess of the reagent : when bested 
on charcoal with sodie carbonate, they yield, the first a malleable, the second a Irittlfl, 
metallic globule. They are rendered soluble in adds by fiision with 3— 4 pts. alUiiM 
carbonate. 

7. Tantalic, tungetie, iHaniCt and oolwnbous anhydrides. — ^They give with inim- 
oosmie salt a blue, violet, or (in presence of iron) a blood-red, bead : with one and 
hydrochloric acid, a coloured solution. They are r^idered solubU by fbsion vith 6 pti. 
acid sulphate of potassium. 

8. Chloride, bromide, iodide, ofeilver ; JSulphidee of molybdenum, lead, ^— CUonde, 
bromide, and iodide of silver, are soluble in cyanide of potassium : when heated on ebtf* 
ooal with sodic carbonate, they yield metallic silver. Insoluble sn^hides prs off 
sulphurous anhydride when heated : sulphide of molybdenum gives a yeIlDwiu*gnai 
bead with microsmic salt, and is converted by roasting into mo^bdie anhydride^ which 
gives a blue colour with sine and hydrochloric acid. 

9. Metals (osmide of iridium, or residues of platinxmi-ores). — ^The insoluble nb- 
stance has metallic lustre, or is a black powder, not affected by ignition. It is rendarad 
soluble by mixture with, chloride of calcium and ignition in a stream of chlorine; or 
by fbsion with potash and chlorate of potassium. 

10. Carbon, — ^The insoluble substance is black (as diamond, colourless) : it du- 
appears when strongly ignited in an open platinum crucible, or before the bbw^oe. 
It detonates when fioisea with nitre, forming carbonate of potassium; and julds 
carbonic anhydride when i^ited with oxide of copper. 

If the preliminaiy examination furnishes no distinct idea as to the natiiie of tbe 
insoluble substance, it must be ftised with four times its weisht of carbonates of po(i»- 
slum and sodium, the fiised mass exhausted with water, and tiie residue treated vith 
hydrochloric acid. If the substance contains any easily reducible metal (azMni^ 
antimony, tin, lead, bismuth, &c) it must not be fosed in a platinum cnidUe. 

III. QualiiaHvs Analysis of Solutions. 

The first stens to be taken in the qualitative analysis of solutions axe to asBertvD 
whether the solution is neutral, acid, or alkaline to test paper ; and whether it oontuDi 
any non-volatile constituents. For the latter purpose^ a small portion of it is cue' 
fully evaporated on platinum-foil : when, if non-volatile compounds are present • 
residue is left which does not disappear when strongly heated, and should besaboiitted 
to the preliminary examination alx>ve described. 

These precautions are of course unneoessair when the solution has been vuidol^ 
the analyst Inmselfl as described in Section IL : but they should never be neglected 
when the substance to be examined is already in the liquid form, since, if careAi% 
performed, they may enable him to conclude at once as to the presence or absence of 
whole groups of bodies. Thus it is evident that a solution whi(A, after earefid enfo- 
ration, leaves no fixed residue, cannot contain any non-volatile metallic salts. A 
solution neutral to test-paper can generally contain only salts of the alkaline or alkaliBe- 
earthy metals, since the salts of most other metals have an add reacKon. An olhAsi 
solution (in which no non-volatile organic compounds are present), cannot contain vm 
metals wnose salts are insoluble in alkaline liquids : if the alkaline reaction be eaitfod 
by the presence of an alkaline carbonate, the presence of ihe alkaline-earthy m^ 
is impossible. Jf, however, non-volatile oiganic compounds are present, an aBoliiif 
solution may contain salts of copper or sesquisalts of iron, as well as sach oxidtfi 
cyanides, sulphides, &c., as are soluble in cyanide of potassium or alkaline solpbi^ 
The presence of ceortain acids implies the absence of certain metals, and viee verw: 
thus the same add solution cannot contain sulphuric add and barium, hydrocklon^ 
add uid silver, &c Silver need not be looked for in an alloy soluble in hydioehlooe 
add, nor gold, antimony, tin. Sec in one soluble in nitric add. 

It is advisable, when possible, to examine for adds and metals in separate portioBi 
of the solution. 

a. Examination for Metals, 

The systematic course of examination for metals which is now almost ezelofiTeif 
employed, depends upon the behaviour of metallic salts in solution towards the foUo** 
ing general reacents : hydrochloric acid, hydrosulphurio acid, sulphide of ammonisii^ 
and carbonate of ammonium. It will be observed that all these reagents are rolatue'' 
so that in their application no substance is introduced into a solution which cano^ 



ANALYSIS— INORGANIC. 217 

W ranored hj simple eleTation of temperature. Their application depends npon 
tlie different solability of metallic chlorides and snlphides, and of the carbonates of 
the alkaline-earthj and aftaline metals. By means of these general reagents, as 
ve hsTe alieadj observed, the metals are diyided into certain groups, which aro 
meeaanb^ eliminated from the solution nnder examination; bj which proceeding 
tlie detection of each indiTidoal member of each group is considerably ndlitated. 
The foDovibg are the groups into which the metallic elements are thus divided : 

«. Metils whose ehloridet are insoluble, or difScnlUy soluble in water or dilute acids. 
Tlieae are lead, silyer, and mercuiy (the last as sub-salts). These metals are not gene- 
nDy daased in a group bj themaelyes, but are included in the group next following, 
to ^ueh thej also oelong^ 

A Group 1. — Metals whose ttdphides are insoluble in water or in dilute acids. 
TIm^ ire all precipitated from their slightlj acid solution hj hydros ulphuric 
aeid. They are ftother diyided into two subdiyisioos according to the bdiayiour of 
thdr ndphides to sulpbide of ammonium. 

BubdiimonJ. — ^Metals whose sulphides possets add properties. Their sulphides 
aie sohUe in aftaline sulphides (sulphides of ammonium, potassium, or sodium), 
fanioff therewith soluble sulpho-salts, which are generally analogous to the oxygen 
nlti of tiie same metals, oxygen being replaced by sulphur. They are arsenic, anti- 
mony, tin, gold, platanum, iridium, selenium, teUuzium, molybdenum, wolfram, 

8»ibdHimon B.— Metals whose sulphides do not possess acid properties, not com- 
hinmg with alkaline sulphides, and so bein^ insoluble therein. Aey are lead, silver, 
mcRoxy, bismuth, copper, cadmium, palladium, rhodium, osmium, ruthenium. (Sul- 
phide of mereuiT is soluble in sulphide of potassium or sodium : sulphide of copper is 
Bomevbat aoluble in sulphide of ammonium.) 

7. Qtoa^ 2. — Metals which are not precipitated by hydrosulphurie add, but which 
are peeipitated by sulphide of ammonium, m>m acid solutions. This group 
ilso » fiirther subtuvided. 

AfUtewoM jL — Metals which are predpitated as sulphides. They are nickel, 
eolaH, mimganese, iron, uranium, zinc Th&x sulphides are insoluble in water, but 
adable in dilute adds, with evolution of hydrosulphurie add: hence they are not 
pnopitited at all hy hydrosulphurie add m>m acid solutions, and not completely 
from nsDtnl solutiona. They are however completely predpitated from an acid solu- 
tion bj sulphide of amimonium, the add being neutralised by the ammonia contained 
in it 

StAdimskm B. — ^Metals which are predpitated as hydraUs, They are aluminium, 
ghidnum or beryUiuzn, zirconium, thorium, yttrium, erbium, terbium, cerium, lan- 
thanum, did^mium : titanium, tantalum, columbium, chromium. (The first ten metals 
in this sabdiTision ar<e known as meials of the earths^ or earthy metals). They do not 
eomfaiie with sulphur in the wet way, and so are not predpitated by hydrosulphuzio 
icid under any drennostances. Their hydrates, however, bemg insoluble in water, are 
pncipitated from thfur neutral or add solutions by sulphide of ammonium, the add 
DTviiidi they were held in solution being neutraUseid by the ammonia of the reagent, 
voile hydrosolphuric add escapes. 

Oertain eompounda of the earthy and alkaline-earthy metals with non-volatile adds 
(pbosphates, iwUt^Mi^ borates, &c.), beina soluble in dilute adds and insoluble in 
vater, are similariy piedpitated hj sulphi& of ammonium. 

S. Otoi^ 3.— Mietals whose sviphides and hydraUs are soluble in water ; which, 
tiurefoie, are not predpitated by hydrosulpuhric add or sulphide of ammonium from 
uj lofaition. This group induces the alluUine-earthy and atkaUne metals. They are 
wther subdivided acooraing to their behaviour to carbonate of ammonium in presence 

of ddoride of Mwmnni-nnn 

Subdinsum JL — Metals which are piedpitated by carbonate of ammonium, 
lliej are barium, strontium, caldum. Their normal carbonates are insoluble in water 

or Uk chloride of ftmyn nniii Tn. 

Suhdtmsum B, — ^Metals which are not precipitated by carbonate of ammonium. 
^Rieyaremagnedum, potasdum, sodium, lithium, ammonium. Carbonate of magne- 
nnn is insoluble in water, soluble in chloride of ammonium : the carbonates of the other 
fmr metals (alkaline metals), are soluUe in water. The different solubility of their 
plMphiteB affords a means for the forther detection of the metals of this suodividon. 

In the usual dassification, the alkaline-earthy metals rbarium, strontium, caldum, 
■■gMsium) constitute Group 8 : and Group 4 comprises tne alkaline metals. 

The following table exhibits in a compendious form the behaviour of all tha 
nttali to the guieral reagents aboye enumerated. 



ANALYSIS — DTOEGANIC. 



Behaviour of Metallic Solutions with Hydrochloric Acid, 



HydrosulphtiTio Acid. 



M«Uli which ITS pn- 
eipiutad u eiioriJeM 
from thair usntnJ at 
uid uUlioiit b; ^jl' 

dneUorie aeid.* 



Uetali which uv pnci^tatud u cnlphidca from thdr 
hjdnchloric add loliilian bj ^fJretBfyitirie add. 



MeliltvliaMnlk 

dueediaiatai 
•olntioa I^ If' 



Lead (putnlly), whiles 
ciyitilliiie, lolable in 
hot water, predpiUtBd 
these* hf inlphDiii! 

BUvn, whila, curdy, 
•olnbls in Mnmotiu, 
precipitated thence by 

Hxtrnxj u nbtalt, 

whits, fiuelf-diiided, 
biackeoed br am- 



&AtU« im tulpkidt of 



Ararale (jellow). 
Antincn^ (orange), 
nn* (bnwn or jellow). 
0«ld \fbi^ 

[««»))"'""■ 

XolfbduilUB+ (brown). 
[Btknllllll] (red-jellow). 

[T«Unriaiii] (bluk). 



Imolubh 



jCbUd:). 



SOvar 

LMdf 

Capptr 

Oadmisn (jellew). 
Kmath (hrown). 
[Palladlnm] % \ 
[Oamlnm] I (hiack- 

[ShodiuB] I brown). 
[KntlianlaBi] ) 




viA KlTv K wfdte wvAa, 
nuM-] lolnbla lu niter. 

hrdr^kiriii (or nlbtiO llS^ 



■n MlaHeTgndS^ ef 






* Vennr u DrotoHlt ie 
PtedD. whUa Iff a BUU hj- 
Soin^ hU( Uluk br »- 

SrtMJsris.'s 

aCHtJOMttOU. 

int oiiiiUdM or in tu 



mntr to we — el 



Tin netala cndowd thai [ ] oia tctj lare, n 



AMYLENR 209 

Bfantljr absorbed, and the amylene is gradnany converted into a pasty mass of minute 
oyrtals, which may be pnrifLed by washing with cold alcohol, reciystaLlisation &om 
boiling ether and drying in Tacno over smphuric add. It gare byanalysis, 37 '26 
per cent C, 6-61 H, and 17*66 N ; the £»nnula requiring 37*09 0, 618 H, and 17*28 N. 

The oompoand may also be obtained, though less advantageoosly, by passing yaponr 
of amylene mixed with air into fnming nitric add. It is remarkable as affording the 
first esample of the direct combination of nitryl, (NO'), with an or^mic radicle. 

Heated Vr itself in a dry tube, it decomposes at about 96^ C, giving off nitrons an- 
hydride, N*U', and nitrons add, HNO', and lea'nng a heavy liqnid apparently containing 
niteate of amyl. Heated with quick lime, it gives off an aromatic body, probably con- 
sisting of oxide of amylene. (Guthrie^ Ghem. Soc Qo. J. xiii 46, 129.) 

OxmJi or AmumB, (C^H**)''.0, a volatile liqnid, isomeric with valeric aldehyde. 
It boils at 95^ C Has a pleasant ethereal odour, and a rough taste. Specific gravity 
in tbe liquid state, 0*8244 at 0^ 0. Yapour-density by experiment 2*982, by (^cula- 
tion (2 voL) ■■ 2*806. It bums easily, with a yellow flame. It is insoluble in water, 
and is not converted into amylene-glycol when heated with water in a sealed tube. 
It dissolves in alcohol, in ether, and in a mixture of the two. It mixes with aeids. It 
unites with an^ydrotu or crystaUisahU fiitrie acid at a higher temperature, but the 
combination is attended with partial decompodtion, (A. Bauer. Compt; rend, 
li.600.) r- r N 

Axxxsmi WITH BunPBXjR iJXD Chlobikb : 

1. Diehhroeulpkide of Amylene, 0^»«SC1«, or C^5>»5*CP.— Protochloride of sul- 
phur (SCI') is Drought into a flask surrounded with ice and an excess of amylene 
added very gradually. The excess of amylene is evaporated off, — ^the residue digested 
and washed with water, dissolved in ether, filtered, and evaporated. It is a non-volatile 
liquid, having a pungent odour, insoluble in water, soluble in ether and alcohoL 
Specific gravity, 1*149 at 12^ C. Distilled with excess of alcoholic caustic potash, it 
yields amylene, disulphide o/fusyl (en's), and other products. 

2. IHsulpkoehhride of Amylene, CH^'SCl, or C^^H^S^CL—On treating disulphide 
€i chlorine (SCI), with excess of amylene, and evaporating the latter, a transparent 
yellow, non-Tolatile liquid, of faint and nauseous odour is obtained, having the above 
compodtion. It is obtained pure by digestion with water, solution in ether, filtration, 
and evaporation. Specific gravity, 1*149 at 12° C. Soluble in ether, absolute alcohol, 
and snmbide of carbon. (Guthrie, Chem. Soc. Qu. J. xii. 112.) 

Djaoiphochloride of amylene treated with chlorine, gives off hydrochloric add, and 
is converted into a non-volatile liquid, of specific gravify 1*406 at 16° C, miscible with 
ether, insoluble in water, but soluble in hot alcohol. This liquid gave bv analysis 
mnnbezs agreeing approximatdy with the formula, 0*WCl*8, which may be that of 
Mtromdpkide ofirichloranwlene, C^\IPC^),SCS, or tha^t of sulphide of tetrachloramyl, 
a\B?Cf)8. (Gathrie^ Chem. Soc. Qa. J. xiii. 43.) 

AXTUERB WITH SOLFHUB AND OxTOEN: 

Disuljphoxide of Amylene, O*B}*^0. — ^Prepared by digesting the disulphochloride in 
alcohohc solution with protoxide of lead, till all the chlorine is combined, dissolving in 
ether, filtering and evi^porating. Specific gravity, 1*054 at 13° C. Non-volatile, yellow, 
or almost colourless. Soluble in ether and alcohol, insoluble in water. 

Bydrate of Ditulphoxide of Amylene, Q^B^S'O.ffO, — ^Disulphochloride of amylene is 
heated in alcoholic solution for some hours, in a current of ammonia ; the liquid is then 
poured off from the chloride of ammonium formed, and heated for some hours in a 
sealed tube to 100° C. with alcoholic ammonia ; the excess of alcohol is driven off 
is a water-bath ; the residue treated with water ; and the oil which Is thereby pre- 
cipitated is washed with water. Yellow liquid of meaty odour. Somewhat soluble 
in hot water, soluble in alcohol and ether. Non-volatUe. Specific griavity 1*049 at 
8®. (Guthrie, Chem. Soc Qtt J. x* 120.)— F. G. and H. W. 



U C^H^O*. or C»*J2"0'.— This add is contained, together 
trith eardol, in the pericarps of the cashew nut (Anacardiwn ocoidentale). The pericarps 
are extracted with ether, wluch dissolves out both the anacardic add and the caidoi ; 
the ether is distilled ofi^ and the reddue, after being washed wilh water to firee it &om 
tannin, is dissolved in 15 of 20 times its weight of alcohol* This alcoholic solution is 
digested with reeentiy predpitated oxide of kad, which removes the anacardic add in 
the form of an insoluble lead-salt The lead-salt is suspended in water, and decom- 
posed by sulphide of ammonium, and from the solution of anacardate of ammonium, 
obtained after the removal of the sulphide of load by filtration, the anacardic add is 
h*berated by the addition of sulphuric add. After repeated purification by solution in 
alcohol, oonvernon into a leacUsalt, and decompodtion of this salt by hydrosul- 
phuric add, the add is obtained as a white crystalline mass, which mdts at 26° C. It 
Vol. L P 



220 ANALYSIS — INORGANIC. 

If we suppose the case of a solution oontaiuiug all the metals, it is ohvions that, hj 
the successiye application of each of these general reagents, we shall sepaiate, fint) W 
hydrochloric acid, those metals whose chlorides are insoluble ; secondly, by hydrosBl- 
phuric acid, those metals whose sulphides are insoluble in dilute acids : thirdly, hj 
sulphide of ammonium, those remaiaing metals whose sulphides or hydrates tn 
insoluble in neutral or alkaline liquids ; and lastly, by carbonate of ammoniun, those 
metals whose carbonates are insoluble : so that at last we haye only the alkaline 
metals left in solution. In order, however, to effect the complete sepuation of each 
group, the general reagents must be employed in the order aboTe stated: for solpbide 
of ammonium would precipitate those metals whose sulphides are insoluble in ailnte 
acids, as well as those whose sulphides are only insoluble in neutral or alkaline Hqnids; 
and carbonate of ammonium, if employed before the other reagents, would pzedpitite 
most of the metab*of Groups 1 and 2, their carbonates beinjg auo insoluUe. 

The following rules, the importance of which will be obrious on the least zefleetion, 
must also be strictly observed. 

1. The mineral add employed to acidify the original solution (when it is not ilietdy 
sufficiently acid), is either hydrochloric or nitric acid. Both are employed dilute, and 
not in sufficient quantity to interfere with the formation of the sulphides of Gronp L 
Hydrochloric is generally preferable to nitric add : for it serves as a general reag^t, 
separating at once those metals which form insoluble chlorides. If nitric add be em- 
ployed, these metals will be found in the predpitate by hydrosulphuric add. 

2. The precipitation by each general reagent must be complete. To ensore thii^ 
the reagent must be added gradu^y, allowing the predpitate to subdde between eadi 
addition, until no ftirther predpitate is produced. In the case of hydrosulphuric aod, 
the predpitation is complete inien the solution, after agitation, still smells stronglj of 
the gas. Gentle heat facilitates the separation of predpitates in almost every caML 
Arsenic (as arsenic add), gold, platinum, iridium, rhodium, and molybdenum, are 
predpitated very slowly by hydrosulphuric add. Tungsten and vananinm are not' 
precipitated by hydrosulphuric add i^m an add solution : they are, however, iodnded 
m Group 1, because their sulphides ^obtained by adding sulphide of ammoniim and 
then hydrochloric add), are insoluble in adds, but soluble in sulphide of ammoninm. 

3. JSach group, when precipitated, must be thoroughly freed by washing with water 
from all members of the subsequent groups, which ma^r be contained in thesofaitioD. 
This washine; is effected, according to circumstances, either on a filter, or by decan- 
tation. If the predpitate contains any easily oxidable sulphides, a little hjdnaol- 
phuric add must be added to the wash-water ^if the sulphide is insoluble in dQatd 
adds, e. g, sulphide of copper), or a little sulphide of ammonium (if the sulphide is 
soluble in dilute adds, e, g. sumhides of iron and manganese), in order to prevent the 
partial oxidation of the sulphide by exposure to the air during the wasning of llie 
precipitate. After the precipitation of each group, it is advisable to ascertain tb 
presence or absence of any members of the succeeding groups, by carefully evaporating 
on platinum-foil a moderate quantity of the filtrate; i^ after ignition, there is no 
distinctly visible reddue, non-volatile substances need not be looked for fbrther. It 
is obvious that, if these two precautions (complete precipitation and thorough washing) 
be neglected, metals belonging to one group are liable to be found among those of 
another group ; and consequently, as the analysis proceeds, reactions will be obtuned 
which will be the source of ^;reat perplexity to the unpractised analjrst 

Eadi group of metals having been separated by the application of general reagents, 
the presence or absence of each member of each group is ascertained by means of 
special or diaracteristic reagents. It seldom happens that the number of elements 
contained in any inorganic compound exceeds ten or twelve : and in most cases some 
distinct idea of the nature of its principal constituents is afforded by the results of the 
prdiminaiy examination. In metallic minerals and alloys, the heavy metals an 
chiefly to be looked for : in silicates, the earthy, alkaline-earthy, and alkaline metal^ 
iron, and manganese. It frequently happens that important information may be 
derived from t£e colour of a precipitate or of a solution. Thus solutions of aiqpnf^ 
chromic, molybdic, and vanadic salts, are blue or green ; those of nickd-salts, green; 
those of ferrous-salts, light bluish-green ; those of chromates, gold-salts, ferric- and 
platinic-salts, yellow, wiui a red or brown tinge ; those of cobalt-salts, red, &c. Tfaesft 
colours are not perceptible when the amount of metal present is very small, or when 
they are masked by the presence of other metals, the colour of whose solutioDS ib 
complementary to them. 

In order to show the systematic method by which the memben of each group are 
detected in presence of each other, we wiU now briefly go through the most important 
groups mentioned in the table. 

1. Precipitate produced hy hydrochlorie acid. — Chloride of lead is soluble in a la^ 
quantity of water, especially on boiling; chloride of silver, in ammonia; subdilorioe 



1 



ANALYSIS — INORGANIC. 



221 



cimeecarj is llackened hy ammonia. (The addition of either hydxoohloric or nitrio 
acid may produce a precipitate in presence of such adds, hydrates, <granide8, sulphides 
^tc^ as ai« soluble in a&aline liquids, but insoluble in water; or a precipitate of 
solpbur, in presence of a polysalpmde or hyposulphite, or a white predpitate^ readily 
sohiUe in more water, in a saturated solution of a barium>salt.) 

2. PreeipttaU protktced by kydro9ulphurie acid, 

a. Portion mdubU in aUkaiine tulpmdea. — Sulphide of arsenic is soluble in acid sul- 
phite of potassium or in sesquicarbonate of ammonium, the salphides of antimony and 
tin are soIl When the three sulphides are dissolTed in aqua-regia, and the solution is 
introdueed into a Marsh's apparatus, antimony and arsenic are detected by the behaTiour 
of their gaseous hydrogen-oompounds ; tin, aiter its separation by zinc, by its solubility 
in hydrochloric add, and by the reaction of its solution with chloride of mercury. 

& Bortiim iruolMein alkaline ndpkidet. — The predpitate is treated with nitric 
acid : sulphide of mercoiy and sulphate of lead may remain undissoWed. In the 
solution, lead is detected by sulphuric add; silrer, by hydrochloric add; bismuth by 
its precipitation b^ ammonia, or hy water if no excess of add is present ; copper, by 
the blue colour of its anmioniacal solution, or by fenocyanide of potasdum ; cadmium, 
by the predpitation of its ammoniacal solution by hydrosulphuric add, after the addi- 
tion of cyanide of potasdum. 

3. PrteipUate produced by stdvhide ofammoniwn, — ^The predpitate is digested with 
ezoees of caustic potash in the cold : chromium, zinc, aluminium, and gludnum are found 
in the solution. Of the metals contained in the residue : cobalt, nickel, and manganese 
form soluble double salts with ammonia, and so are not predpitated by it : iron, uranium, 
the rarer earthy metals, and alkaline-earthy phosphates, oxalates, &c, are predpitated 
by ammonia, eren in presence of chloride of ammonium. The hydrates of uranium and 
the rarer earthy metals are readily soluble in carbonate of ammonium : ferric hydrate 
is less sohibles,.and the alkaline-earthy salts are insoluble. Ferric salts are detected 
by snlphocyanate or fenocyanide of potasdum ; the alkaline-earthy salts by appro- 
prijite characteristic reagentSL 

4. PrteipitaU produced by carbonate of ammonium* — The metals which compose 
this group rbarium, strontium, caldum) are diHtingnished by the different solubiHty 
of their sulphates, oxalates, chromates, &c. : and by the colours which they com- 
mnnicate to the blowpipe flame, or to that of burning alcohoL 

5. The solution, after the successiye application of the above general reagents, 
cmo only contain magnedum and the alkaHne metals. Magnesium is detected by its 
precipitation by phosphate of ammonium ; the alkaline metals by the colour which 
thej impart to the blowpipe or alcohol flame, and by the different solubility of their 

or diloroplatinates. Ammonium is always sought for in a separate portion of 



the (Hig^nal solution : it ii detected by the evolution of ammonia when any of its salts 

Edi 



heated with a fixed alkali or alkaline earth. 

Aypoaulpkite of sodium is decomposed by the salts of most of those metals which 
precipitated by hydrosnlphuric add nom an acid solution, a metallic sulphide being 
predpitated, it has been proposed to employ^ this compound as a general reagent 
instead of hydrosulphuric add, and so to avoid the unpleasant smeu of the latter. 
This sobstitution, however, has not as yet been generally adopted. 

Carbonate of barium may also be employed as a general reagent When a solution 
containing metallic salts is shaken up with excess of this salt, m the cold : 



Are predphated. 
Tin. 
Gold. 
Iridium. 
Bhodiunu 
PalladiunL 
Platinum. 



Ooppeor. 

Bismuth. 

Gadmium. 

-Altfu i'iiiilim j 

Manganese \ 

Iron ^ las sesquisalts. 

Uranium j 

Chromium, as sescjuisalt, or as chromic 

Titaninm,as titanic add. 



Are DOC predpitated. 
Silver. 
Lead. 
Iron 
Nickel 
Cobalt 
Manganese , 
Zinc. 
Cerium. 
Yttrium. 
Gludnum. 
Magnedunu 
Caldum. 
Barium. 
Strontium, 
acid. Ammonium. 
Lithium. 
Sodium. 
Potassiom. 



as protoealta. 



222 ANALYSIS — INORGANIC. 

' Mercniy, plAtmiun, pAUadinm, rhodium, iridiuxn, and gold set precipitated by* 
carbonate of barinm only when they are present as oxygennmltfl, not when preient as 
chloridefl, &C Anauc, antimonic, phosphoric, aelenic, and aulphnrie acxda ar^ BOft 
precipitated "bj carbonate of barinm nntil the aolntiona of their salts have beea 
addtuated with nitric or hydrochloric acid. Carbonate of barinm is not mnch wed m 
a general reagent ; it is however emplored with advantage for the s^Muataon of the 
metals which are precipitated by sulphide of anmioninm, since it precipitatee com- 
pletely those which are present as sest^uisalts, while the protosalts remain in SQlntion. 
When, in the course of a systematic qualitative analysis, one or more membea of 
the different groups have been recognised as constituents of the subetanee under ex- 
amination, by means of the reactions above enumerated, the results must be oonfinned 
by certain special reactions, which will be detailed at length in the articles devoted to 
the several elements, 

b. ExaminalionforJjsids. 

The qualitative detection of acids, ii, on the whole, more difficult than that of metds ; 
still, with due care, it may be accomplished with great precision. In most cases, the 
preliminaiy examination, as well as the nature of tiie metals already found* give iiif<^ 
mation as to what acids should especially be looked for. The knowlet&e of the 
solubility of different salts, and of the reactions of their aqueous solutions with 
vegetable colours, is of the greatest importanoe in this examination. By heatang the 
substance either alone or with concentnted sulphuric acid, the presence or absence of 
organUs and ifoUUile inorgamo acids is at once ascertained, these acids either vdati* 
lising undecomposed, or vielding volatile products of decomposition. For this pur- 
pose, a small portion of the dry substance is heated in a test>tube (not to boiline) with 
8 to 4 times its volume of concentrated sulphuric acid; when, in the case of afl adda 
which are either volatile without decomposition, or are decomposed by sulphuric acid 
at a high temperature, gases or va^uis are evolved, (he properties of whirh, in most 
cases, indicate the nature of the acids present 

1. Non-'VoUitiU acide : whose compounds evolve no vapours when heated with sul- 
phuric add, the mixture not being blackened — Silidc, Boric^ Phosphoric, Sulpfaioie, 
iodic, Arsenic, Sdenic, Tungstic, Molybdic, Titanic acids. 

2. Acid9 which evolve a eUowred gae^ the mixture not being blackened — Hydriodic, 
Hydrobromic, Bromic, Chloric, HypochlorouS| Nitrous adds. 

3. Aoide which evolve a colourlese aae, generaUg possesses an irritaUng smell 
and an acid reaction^ the mixture not beine blackened — a. Volatile witi^out decoxa- 
position: Hydrosulphuric^ Hydrochloric, Nitric, Acetic, Benzoic, Soccinic, Hydro- 
floric adds. The gas evolved is not inflammable, except in the case of hydro- 
sulphuric add — b. Decomposed — Cjranic, Chromic (evolves oxygen). Carbonic, 
Sulphurous, Hyposolphurous, Polythiomc, Oxalic, Formic, Hydrocyanic, Sulphocyanic^ 
ados, Ferro- and Ferri-cyanides. In most of these cases, tne gas evolved is inflam- 
mable. 

4. NonrVolatUe organic acids: Tartaric, Bacemic, Citric, Halic, Tannic, Gallic, 
Uric acids. The mixture is blackened, and carbonic and sulphurous anhydrides and 
carbonic oxide are evolved. 

The behaviour of a mixture of salts, when heated alone or with sulphuric acid, is 
often different from, that of each individual salt under the same circumstances. Thus 
a mixture of a nitrate or chlorate with a salt of an organic add, does not bladcen when 
ignited, but commonly detonates : a chloride, in presence of a nitrate, when heated 
with sulphuric add, evolves dilorine and red nitrous fumes ; in presence of a chromate, 
red fiunes of chlorochromic add ; in a mixture of a sulphite and a nitrate, ddorate, 
chromate, &c., the sulphurous add is converted into sulphuric add ; in a mixture of 
a sulphide and a sulphite, the two adds decompose each other, sulphur being sepa- 
rated, and the characteristic smell of each destroyed. Chloride and subchloride of 
mercury, and chloride of tin are decomposed with difficulty, if at all, by sulphuric 
acid. 

From a solution containing volatile and non-volatile adds, the former maybe 
separated by distillation with dilute sulphuric add. 

The general iMgents usually employed in the examination for adds in the wet way, 
are chloride or nitrate of barium ; chloride of caldum ; a mixture of sulphate of mag- 
nesium, ammonia, and chloride of ammonium ; seequichloride of iron ; nitrate of silver; 
and indigo-solution. By these reagents, the most important adds are divided into the 
following groupsL 

1. Acids which are precipitated by chloride of barium : — 

a. from a solution addtuated with nitric or hydrochloric add — Sulphuric, Selenie, 
Floosilidc adds. 



ANALYSIS — INORGANIC. 22S 

. &. Ram a nentnl aobdifm (the precipitate beiiig soluble in acids) ^- SiiIpliiuoiiB» 
PlK]i|)hiorie, Carbonic, SiUcie, Hydroflnoric, Oxalic, Chromic, Boric, Tartaric, Citric, 
AiMoion^ Anenie adds. The last five acids are not precipitated in presence of 



1 Adds vhich are preeipitsted by chloride of calcium : — 

a f^mm a neutral station only (the precipitate being soluble in acetic add) — Phos- 
phflric^ Anenie, Boric^ Carbonic, Snlpbnroos, Tartaric, Citric adds, and Femx^anides. 
k "Fnm a neutral ok acetic add soIittion---Siilphnric^ Hydxoflnonc^ Oxalic, Kacemic 



5. Aodfl irhieh are pzedpitated by aulpJkats of magnenum^ in jfre»enee of ammonia 
MdcUoridi ofammomum — Pbospbonc^ Arsenic^ Tartaric adds. 

4. Adds vhieh are detected by Hsquiddofide of iron : — 

a Are predpitated — Ferrocyanides (from a solution containing firee bydrodiloric 
add): Phosphoric^ Arsenic, Tannic adds (from a neutral or acetic aad solution) : Boric, 
Bencoc, Soodnic adds (iScom neutral solutions ouIt). 

b^ An coloured — In presence of free hydrochloric add ; Ferricyanides (brown), Sul- 
phocyinic add (red). In neutral solutions only : Acetic^ Formic, Sulphurous, Meconic 
idda (rod): Gallic add (black). 

6, Adds whieh axe predpitated by niiraU oftilver .* — 

f. Fran neutral solutions only (predpitate being soluble in dilute nitric add) — > 
Pliosphozie, P^^ro- and Meta-pbosphoiic, Arsenic, Arsenious, Chromic, Oxalic, Boric^ 
Taitaiic^ GitDC^ SaJphnrous, formic adds: Silide and Acetic adds from concentrated 
Nhitioos. 

& From add Mentions also (the predpitate being insoluble in dDnte nitric acid). 
Hjdzoehlorie^ Hydxobromie^ Hydriodio, Hydrocyanic, Sulpho^yanie, Iodic, Hydro- 
Bdpfannc adds, and Ferro- and f erri-cyanideSi 

6. hH^o^wHion is decolorised, without the addition of an add, by free chlorine 
and broimne ; by all the 03^gen-adds of dilbrine, when free, and by metallic hypo- 
ehloriteB ; l^^ free nitric add, if not too dilute, b^ alkaline scdphides, and by caustic 
alkilia On addition of sulphmnc add, and heatmg, by chlorates, bromates, iodates, 
and nitrates. On addition of bydrodiloric add, and beating (chlorine being erolred),. 
Vf an the foregoing compounds ; also Inr diromates, sdenates, tellurates, ranadi^es, 
TnanganatcB, permanganates, ferrates, ana all peroxides. 

In inrestigatinff the adds contained in a soluble compound, the first step is to as- 
certain the behaTiour of the solution to vegetable colours. Wben, as is frequently the 
caae^ a neutral solution is required, the solution, if add, is neutralised by ammonia : 
if alkaline, \fy nitric add, or, if nitrate of silver be not employed as a reagent, by 
hydrodiloric add. But, as manj of the heavy metals, as weU as some alkaline-earthy 
salts, are pfedpitated when their solution is neutralised by ammonia, it is generally 
necessaiy to remove from the solution all metals except the alkaline metals, before 
pioeeeding to test lor adds ; in whidi process, the presence or* absence of metallic adds, 
and of alkaUne-earthy phosphates, oxalates, &e. will be ascertained. When this is 
not done, it is frequentfy necessaiy to substitute for the general reagents mentioned 
abore^ the nitrate of the same base, since nitric add forms no insoluble salts : thus 
mtnte, instead of chloride, of barium, must be emploved in solutions oontaininff lead, 
dlTcr, or snbsalta of mercury. We have already mentioned cases in which the addition 
of nitric or favdrochloric add to an alkaline solution will produce a predpitate. The 
fitUowing adds are also predpitated by the mere addulation of their <Jkaline solutions : 
Tungstie, Molybdic, Antunonic, Benzoic, tJric adds ; Boric and Silidc adds from con- 
ccotnted solutions. Under the same circumstances, a predpitate of sulphur is produced 
in pnaence of hyposulpburous add or polysulphides : of iooine, in a solution containing 
an iodide and an iodate : of add tartrate of potasdum or ammonium, in a solution 
containing the normal tartrates of these metals. The nature of the metals found in 
a Bofaitjon win often imply the absence of one or more adds : generally speaking, a 
neotial or add sohition containing one of the metals whose salts are used as general 
nagenli for adds, need not be examined for any of those adds which are predpitated 
Ij that metal. Tfans^ sulpburic or bydrodiloric acid need not be sought for in soluble 
eoflBponnds omtaining barium or silver respectively. In order not to overlook Ibe 
presenoe ef uncombined volatile organic acids, the add solution is neutralised with 
csibonate of sodiimi, evaporated to diyness, and ignited : when the organic add, whidi, if 
free, wodd have been volatilised nndeoompos^ is decomposed, with separation of 
eaiboo. 

Sahstaaces whidi are insoluble in water or adds are rendered soluble by one of the 
methods already described, and the solution is examined for acids in the wet way. In- 
sobUe compounds of the heavy metals are mostly decomposed by digestion with 



224 ANALYSIS — INORGANIC. 

Bulphide of ammonimn ; Bulphates of stiontiiim and ealcimn by digestion with cajbonate 
of sodium : in both cases, the filtrate contains the acid, together with an eau^ess of the 
decomposing agents while the metal is found in the residue. Insoluble salts of arganie 
acids are decomposed hj boiling with an alkaline carbonate ; ferric salts of Tolatile 
oiganic acids by digestion with ammonia ; in both cases, the filtrate contains an alkaHne 
salt of the adoL eiulphides and all salts of the lower oxygen-acids of solphur, yield 
sulphuric acid when digested with nitric acid, or any other oxidising agenL 

The application of confirmatory tests is as necessary in the case of acida as in that 
of metals.— F.T.O. 

The methods of guantitativB inoraamo analysis cannot be included in one article. 
The processes for the separation and quantitatiTe estimation of each element are de- 
scribed in the article deyoted to that element. The analysis of ashes, soila, mineral- 
waters, &c and Tolumettic analysis, are also described in separate artidea. We may 
here howerer describe a method, of general application, which is found useful in many 
cases, -viz.: 

7%elndire€f method of Quantitative Analysis, — The usual method of de- 
termining the quantities of the several constituents of a compound or mixture, is to 
separate each of them in the form of a definite compound, whidi can be collected and 
weighed, e, a. silver as chloride, barium as sulphate, &c, and calculate the weight of 
the required constituent from the known com|>08ition of this compound. It aometiincs 
happens however, that the complete separation of certain subetonces is -very diiBcQ]^ 
or even impossible, and in that case, recourse is had to a method of determinatiaa, 
which depends on the general principle that any number of unknown quantities duj 
be determined simultimeously, if we can find between them a numMr of relatiaDB 
equal to that of the quantities themselves ; in other words, n unknown quantities may 
be determined by means of n equations* 

Suppose for example, we have a mixtnre, either solid or liquid, containing potassiDBi 
and sodium, in the form of hydrates or carbonates. Take two equal portions of the 
mixture (it is not necessary to know the weight of these portions), convert one poctioD 
into chlorides, the other into sulphates, and weigh the two products. Let the som of 
the weights of the chlorides be a, and that of the sulphates b : the unknown weigjbt 
of potassium «, and that of sodium y; then from the known atomic weights of the 
metals, their chlorides and sulphates, we have: 



74-5 






68-5 








89 


a 


+ 


23 


y 


~ 


a 


87 






71 








39 


X 


+ 


23 


y 


■" 


b 



whence the quantities x and y may be determined. 

Another form in which .the indirect method may be applied to the detenninatioo of 
two substances, is to bring them both together into a form in whidi they can be 
weiffhed, «.^. as chlorides or sulphates, and determine the^uantity of chlorine or of 
sulptiuric acid in the mixture ; thus, suppose a mixture of potash and soda to be eon- 
verted into chlorides : let the sum of the weights of these chlorides be «, and let the 
amount of chlorine in this mixture, determined as chloride of silver, be c ; then if « be 
the quantity of potassium and y the quantity of sodium, we have the two equations: 

Ka NaCl CI ^ CI ^^ 

k"* kt^"'' 2* •" ra^ -'^ 
^' 3"9-' + 2r^-'' 89~* + 2ry -*^ 

whence x and y may be found. 

If three substances are to be determined, e. g. barium, strontium} and calcium, we 
should of course require three equations, which, in the case supposed, might be obtained 
bv weighing the three substances, first as carbonates, then as oxalates, then as sul- 
phates. It is seldom, however, that the indirect method is applied to the determinatioa 
of more than two substances. 

A case in which this indirect method of anal^rsis is often applied, is to the d^er- 
mination of a small quantity of bromine or iodine in presence of chlorine, as in the 
analysis of mineral waters. The chlorine and bromine are precipitated by a solution 
of silver, and the mixed chloride and bromide of silver is weigheoL It is tiien i^ted 
in a stream of chlorine till all the bromine is expelled, and the resulting chloride ie 
again weighed: let the diflference of the two weights be d' then, since chlorine and 



ANALYSIS (ORGANIC> 225 

bramiiie repbice one another in the proportion of their atomic weights, viz. as 
Sd-dtoSO^vehaTe: 

«'-«- "'■ m- Ik 

whence Br — - Bt = d; g^— Br » </. 

and Aerefore Br ^ 1*797 d. 

The indirect method of analysis can only Be employed with advantage to ascertain 
die lebtiTe quantities of subetances whose atomic weights differ considerably : with a 
mixture of bodies of the same atomic weighty it cannot giro any definite result ; in 
&et the two equations which it inTolyee become in that case identicaL 



(OIBdAirac)* — ^The analysis of oiganic substances divides itself 
like that of inoiganic bodieSf into qualitatiTe and quantitative. A further division is 
tlso oonvenient, viz. into Elemewtary or Ultimate Analysis and Prosifnate analysis, 
aooording as the object of the inquiry is to determine the ultimate elements, carbon, 
hjdrogen, &c., of which Hie body is composed, or the proximate principles, such as 
fogar, Etaich, fibrin, &c, in which those elements are grouped. 

I. Elbksktabt OB Ultimatb Oboanio Analysis. 

Oiganic bodies are composed of carbon, hydrogen, and oxygen, with or without 
mtrogen, sometimes also associated with sulphur and phosphorus : these are all the 
ekmeots that occur in natural organic compounds ; those which are artificially prepared 
may contain any elements whatever. 

The detection and estimation of these elements dc^nds essentially on the process 
of GoKBUsnoiv. Wlien an organic compound is heated to redness in contact with free 
oxjgen, or with a substance which gives up that element with fiEunlity, it is com- 
pletely decomposed, its elements being separated either in the free state or in new 
iuma of oombination. 

Q^ultlattve Analjnrifc Chrbon and Hydrogen are detected by burning the 
eompoond in a gUss tube in contact with oxide of copper or chromate of lead. The 
eubon is then converted into carbonic add*, which if passed into baryta-water, forms 
1 white precipitate of carbon of barium, and the hydrogen into water, which collects 
in drope in a small cooled receiver attached to the combustion-tube, or, if in very small 
quantity, may be rendered visible by causing the vapour to pass through a narrow 
^an tobe lined with phorohoric anhydride, which if water is present, will be con- 
verted into phosphoric add and dissolved. Carbon may also, in nearly all cases, be 
detected by the black reddue which remains when the organic substance is burned in 
the air, or ignited in a close vessel, or heated with strong sulphuric add ; very few 
oiganic bodies contain suffident oxygen to bom away the carbon completely, even in 
contact with the air. The black residue of carbonaceous matter may b« distinguished 
from black substances of inorganic ori^, by burning slowly away when heated to 
redaeea, and by its property of deflagrating with nitre and chlorate of potassium. 

nitrogen in organic bodies is for the most part given off in the fr«e state when the 
eompoand is burned with oxide of copper, but a surer mode of detecting it, especially 
when in. small quantity, is to heat the substance in a test-tube with a considerable 
excess of hydrate of potasdum or sodium. The carbon is then converted into car- 
home add by the oxygen of the alkaline hydrate, while the whole or the greater 
put of the hydrogen unites with the nitrogen to form ammonia, which may be detected 
oy its odour, by its action on litmus paper, and by the white fumes which it produces 
when a glass rod dipped in dilute hydrochloric acid is hdd over the mouth of the 
tabe (see AmioifiA). A still more delicate test for nitrogen is the following, given by 
I^osBugne. A portion of the organic compound is fused in a test-tube with a smaJl 
piece Sl potasdum ; the mass is treated with water when cold ; and the liquid boiled 
with protosnlphate of iron partially oxidised by contact with the air. If it be then 
npertatorated with hydrochloric add, the presence of nitrogen will be indicated by 
the fcmnation of a predpitate of Prussian blue, or in case of very minute quantities, by 
ft bhiiah green colour being communicated to the solution. 

ddorine in organic bodies is detected by igniting the compound with quick lime, 
whetehj it is completely destroyed, the chlorine uniting with the calcium, in which 
state ox combination it may be dissolved out by water, and the chlorine precipitated 
by nitrate of silver. In some organic compounds which contain hydrochloric add 
ready formed, viz. the hydrochlorates of the organic bases, the chlorine may be imme« 
diatdy detected by nitrate of silver without this preliminary treatments 

* Throogboat thU article, the term earbonie aa'd is used for CO*, in accordance with eatabllihed 
w^e, liMti^ of the mora correct appdlaUoo carbonic tmkjfdride* 



226 ANALYSIS (ORGANIC) 

Bromine and Iodine may be detected hy similar treatment ; Fluorine in the same 
manner as in inorcanic bodies. 

Sulphur^ Phosphoruet and Arsenic, are detected by igniting the organic compomd 
with a mixture of hydrate of potassium^ and nitre or chlorate of potassinm, vhereby 
those elements are conTerted into sulphuric, phosphoric, and arsenic addi, the 
presence of which may be demonstrated by reactions appropriate to each. 

Metale occurring in oi^anic compounds, remain for tiie most in the form of oxides, 
or in the metallic state when the organic matter is burnt. Mercuiy may be detected 
m the ordinary way, by distillation with lime. 

QuantitatlTe Analysts* The first quantitative analyses of organic bodies were 
made by Gay-Lussac and Th^nard. The substance to be analysed was mixed with a 
known weight of chlorate of potaeatUTn, and made up into small pellets, whidi were 
dropped one by one through a stopcock of peculiar construction, into an iqvight ^bss 
tube heated to redness, the gas thereby produced escaping by a lateral tube and bang 
collected over mercury. The volume of gas was exactly measured, and the carbonic 
acid absorbed by caustic potash. The remaining gas consisted either of pure oxygen, 
or (in the case of azotised bodies) of a mixture of oxygen and nitrogen, the propo^ 
tions of which were determined eudiometrically (see Air ai^ysis of Gases). Knoving 
then the weight of the substance burned, the weight of the chlorate of potaasium used, 
and consequently the quantity of oxygen evolved, also the quantitv of carbonic add 
produced, and of the oxygen remaining after its absorption, sufficient data were obtained 
for calculating the amount of carbon, hydrogen, and oxygen in the substance analTsed: 
for, the difference between the total quantity of oxyeen which had disappeared, and 
that which was consumed in burning the carbon (this latter quantity bemg e^ual in 
volume to the carbonic acid produced), gave the quantity which had unitea with the 
hydrogen to form water, and thence the amount of hydrogen was calculated. 

This process was a great step in chemical science, and yielded many important 
results ; but it was difficult of execution, requiring great skill on the part of tlie 
operator ; it was also inexact in the case of nitrogenous bodies, and totally inapplicable 
to liquid or volatile compounds. Berzelius simplified it by mixing the chlorate of 
potassium with common salt, thereby causing the combustion to go on gradually, and 
rendering it possible to introduce the whole of the material at once. He also coueeted 
and weighed the water produced, and thus greatly simplified the calculation. 

Saussure and Prout burned the organic substance in an atmosphere of oj^gen. 
Front's apparatus was so contrived that the substance was burnt in a measured vofome 
of oxygen, and the volume of the gas remaining after combustion was compared with 
the original volume. Now, since the volume of carbonic add produced by the com- 
bustion of carbon is equal to that of the oxygen consumed, while that which unites 
with the hydrosen to form water disappears lUtogether, it follows that if the oigank 
substance contains oxygen and hydrogen exactly in the proportion to form water (as 
in acetic acid, sugar, &c.), the volume of gas remaining after combustion will be equal 
to that of the original oxygen : whereas if the proportion of hydrogen is greater (as in 
alcohol and ether), the volume of gas will be diminished by the combustion ; and if 
the proportion of hydrogen is less (as in oxalic acid), the volume of gas will be in- 
creased. Hence, by absorbing the carbonic acid with potash and measuring the 
residual gas, sufficient data were obtained for Aftlpulafing the quantities of carbon, 
hydrogen, and oxygen. 

The method now universally adopted for the estimation of carbon and hydrogen in 
organic compounds, consists in burning the compound with a large excess of oxide of 
copper or chromate of lead, and determining the quantities of carbonic acid and water 
produced by the combustion, not by measure but by weight, the water being absorbed 
by chloride of calcium, and the carbonic acid by potash. The use of oxide of copper 
was first introduced by Gay-Lussac and afterwards adopted by Ure ; but it is to Liebig 
that we are indebted for those modifications of the process which have brought it to 
its present state of simplicity and exactness. 

The process, as now performed, requires the following materials and apparatus. 

OxuU of Copper, — ^I^pared by dissolving copper in nitric acid, evaporating to dzy- 
ness, and calcining the residual nitrate in a crucible at a low red heat. As thus 
prepared, it is a dense, soft black powder, which rapidly absorbs water £nom the air 
even before it is quite oold. If, however, it be very strongly heated, it aggregates 
into dense hard lumps, which, when broken into small pieces and sifted from tiie finer 
powder, yield an oxide well adapted for the combustion of volatile liquids. Oxide of 
copper may also be prepared by igniting copper turnings in a muffle. The oxide thus 
obtained is much harder and less hygroscopic than that prepared from the nitrate, 
but it is not so easily mixed with an organic substance in the state of fine powder. 
Oxide of copper must always be heated to low redness immediately before use. 

Chromate of LeacU — ^Prepared by precipitating a solution of acetate of lead with hi- 



ELEMENTARY OR ULTIMATE. 227 

dtronute of potasdnm, fusing the washed and dried precipitate in a crucible, and 
pahensing it in an iron mortar ; it is then obtained in the form of a yell