'•i, '4f $ Committee on Publication Barton W. Evermann Chairman and Editor C. Hart Merriam David White A. D. Hopkins Lyman J. Briggs PROCEEDINGS OF THE Washington Academy of Sciences Vol. IX 1907 WASHINGTON JUIvY, I907-FEBRUARY, 1908 AFFILIATED SOCIETIES. Anthropological Society of Washington. Biological Society of Washington. Botanical Society of Washington. Chemical Society of Washington. Columbia Historical Society. Entomological Society of Washington. Geological Society of Washington. Medical Society of the District of Columbia. National Geographic Society. plhlosophical society of washington. Society of American Foresters. Washington Society of the Arch^ological Institute OF America. Washington Society of Engineers. ?^77 Pbess of The New era printing company Lancaster. Pa. CONTENTS. The Experimental Data of the Qiiantitative Measurements of Electrolytic Migration ; by James W. McBain Distribution of the Subcutaneous Vessels in the Head Region of the Ganoids, Polyodon and Lepisosteus ; by Wm. F. Allen Origin and Evolution of Angiosperms through Apospory ; by 0 F. Cook Heredity and Mendel's Law ; by Charles B. Davenport Mendelism and other Methods of Descent ; by 0. F. Cook Linnaean Memorial Address ; by Edward L. Greene . Linnaeus as a Zoologist ; by Dr. William H. Dall A Review of the American Components of the Tenebrionid Sub family Tentyriinae; by Thomas L. Casey Contents, Organization, Membership and Index 79 179 189 241 272 275 523 ILLUSTRATIONS PLATES FACING PAGE I. Dissection of Yiesid oi Polyodon spat/mla 126 II. Principal Trunks of Polyodo7i spathula 12S III. Portions of Lymphatic Trunks of Polyodon 130 IV. Deeper Dissection of Portions of Lymphatic Trunks of Polyodon 132 V. Dissections of Portions of Lepisosteus tristoechus and Lepisosteus osseus 1 34 VI. The same continued 136 VII. Dissection of Portion of Lepisosteus tristoechus 138 VIII. Dissection of Portion of Lepisosteus osseus 140 IX. Transverse Sections of Portions of Lepisostejis osseus and Branchial Arch of 7^(c/yc>(/c« 142 X. Dissections of Portions of /'io/yi?fl?o?z 144 XI. The same continued 146 XII. The same continued 148 XIII. Transverse Sections of Portions of Polyodon 150 XIV. The same continued , 152 XV. The same continued 1 54 PROCEEDINQS OF THK WASHINGTON ACADEMY OF SCIENCES Vol. IX, pp. 1-78. July 31, 1907. THE EXPERIMENTAL DATA OF THE QUANTITA- TIVE MEASUREMENTS OF ELECTROLYTIC MIGRATION. to the end of the year i9o5. Collected and Arranged by James W. McBain. CONTENTS. Introduction Plan of the bibliography 2 Experimental methods 3 Accuracy of the determinations 3 Errors introduced by the use of diaphragms 4 Errors introduced by the method of calculation 5 Interpretation of the results 7 Hydrated ions 7 Movement of undissociated electrolyte 8 Complex ions, hydrolysis S Anomalous results ii Qualitative experiments 12 Arrangement of the abstracts, abbreviations, etc 12 Chronological abstract of the literature 14 Index of chemicals 7° Index of authors' names ^ 76 Index to experiments with solvents other than water 78 INTRODUCTION. The following compilation is a result of a search through the literature of the subject in connection with my experimental work in 1904 at the University of Toronto on the transference numbers of the weak acids. So much time was required to find and collect the scattered papers in this field, that at the sugges- Proc. Wash. Acad. Sci., July, 1907. I 2 McBAIN tion of Professor W. Lash Miller I decided to compile a syste- matic summary of the existing data. I take this occasion of expressing to him my sincerest thanks for this suggestion, and for his valuable advice as to the arrangement of the results ; and I desire also to acknowledge my indebtedness to the Carnegie Institution of Washington for the grant under which I was working. The compilation was far advanced before I left Toronto, and the whole has been revised and brought up to date in Leipsic and Heidelberg. My thanks are due to Professor Luther for the interest he has displayed in the work, and to Professor Jahn for his kindness in furnishing me with out-of-print dissertations from his laboratory. To make this collection has cost me many months of labor extended over the past three years ; but any doubt of its useful- ness is removed by the frequency with which I still chance on memoirs whose titles give no indication that they contain experi- ments on electrolytic migration. PLAN OF THE BIBLIOGRAPHY. My object is to present the results in tabular form, with enough of the experimental details to enable the reader to esti- mate the intrinsic value of the measurements. Hence in addi- tion to the author, title, year, volume and page of the periodical in which the papers appeared, I have given in each case a full list of the chemicals experimented with, the concentrations of the solutions, the composition of the solvent, the nature of the electrodes, the amount of electrolysis (voltameter readings), the temperature, the change in the middle (supposedly unaltered) portions, the diaphragms employed if any, the number of experi- ments, and the final results ; also some information as to the form and size of the apparatus, and occasional critical remarks. The material is arranged chronologically'; an alphabetical index of authors, an index of chemicals, and an index to ex- periments made in solvents other than water, are provided. In the majority of cases, however, I have not stated the method of analysis employed, nor given the duration of the experiments (chance for diffusion). 'Alphabetically within the year. MEASUREMENTS OF ELECTROLYTIC MIGRATION 3 EXPERIMENTAL METHODS. The experimental methods of determining migration values are five in number : the analytical or Ilittorf method (pre- viously used by Faraday and by Daniell and Miller), the direct or meniscus-velocity method, the method based on measurement of concentration cells with and without diffusion, the method based on measurements of the limiting current density at which normal products occur at the electrodes, and the method of Nernst and Riesenfeld for two immiscible solvents with a linear distribution ratio (Verteilungscoetlicient). Of these only the first two as yet yield accurate and reliable results. The results of all five methods have been abstracted in the present bibliography. The literature for the fourth method, mainly theoretical, is : H. W. Weber, Wied. Ann., 7, 469 and 536 (1879). A. Witkowsky, ibid., //, 759 (1880). C. L. Weber, Zeit. phys. Chem., ^, 182 (1889). Sheldon and Downing, Phys. Rev., /, 51 (1893). B. Klossing, Beibl., 18^ 220 (1894). Th. des Coudres, Wied. Ann., 57, 232 (1896). E. Salomon, Zeit. phys. Chem., 2^, 55 (1897) ; ^j, 336 (1898). C. Ullmann, Zeit. f. Elektrochem., j, 516 (1897). H. J. Sand, Phil. Mag. (6), /, 45 (1901) ; Zeit. phys. Chem., ?5, 641 (1901). C. Christiansen, Drudes Ann., ^, 787 (1902). P. Straneo, Ace. dei Lincei (5), // (I), 58, 171 (1902). F. G. Cottrell, Zeit. phys. Chem., ^^, 385 (1903). U. Grassi, ibid., ^^, 360 (1903). E. Brunner, ibid., ^7, 56 (1904). ACCURACY OF THE DETERMINATIONS. The accuracy of transport determinations is usually much overrated. For the better experiments of such workers as Bein, Kiimmell, Loeb, and Nernst, and the best experiments of Hit- torf, the results seem to be reliable to one or two units in the second decimal place ; the work of Steele and Denison is more accurate. Very accurate measurements ^ have been made with ^Probably Tower's measurements of sulphuric acid fall in this class ; the ex- perimental details are inaccessible in Heidelberg. 4 Mc BAIN four substances by Noyes and by Noyes and Sammet, and a long series has appeared from Jahn's laboratory, which are espe- cially interesting as they are all made according to the same method ; the analytical work is wonderful. Noyes has more confidence in the absolute value of his results than Jahn has in his, although the experiments of Noyes and Sammet hardly surpass the best work of Jahn's pupils. However I have copied the results of Noyes to four decimal places, while Jahn calculates his to three. Luther ^ estimates the reliability of the best measurements as amounting to one or two units in the third decimal place; and E. Wolff, ^ one of Jahn's pupils, speaks of the " hitherto accepted limit of accuracy of one per cent." It seems much easier to obtain constant results than absolutely reliable values ; the dif- ference between the final values of two investigators is often several times as great as the maximum difference between the individual results of either. ERRORS INTRODUCED BY THE USE OF DIAPHRAGMS. Even in the earliest experiments the difficulty of preventing the mixing of the solutions through convection currents was met by the use of diaphragms. Faraday used a porous asbestos wick, Daniell and Miller porous earthenware, while Hittorf employed intestinal membrane in most of his measurements. Recently Bein^ and then Hittorf * investigated the influence of various membranes upon the migration values, and found that while some of them, such as earthenware, had no influence apart from cataphoresis, others changed the migration values of many substances very greatly. Nernst attempted ° to deal with these cases by his theory of the phenomenon at the meniscus between two immiscible solvents during electrolysis, and Hit- torf' replied; it seems to me that the objections raised by the ^ Winkelmann's Ilandbuch der Phjsik, 2 Aufl., 1905, Bd. IV, S68. This ex- cellent review of the subject contains also a selection of the most accurate work up to 1903, including experimental details. * Dissertation, Berlin, 1903. 'Zeit. phjs. Chcm., 2S, 439 (1S99). *Arch. neer. (3), 6, 671 (1901); Zeit. phjs. Chem.,j9. 613 (1902); 4J, 239 (1903) ; Zeit. f. Elcktrochcm., S, 4S1 (1902). *Drude's Ann., S, 600, 609 (1902) ; Zeit. f. Elektrochem., 7, 644 (1902). ^Drude's Ann., 9, 243 (1902). MEASUREMENTS OF ELECTROLYTIC MIGRATION 5 latter might be removed b}' assuming tlie existence of hydrated ions. In general it is possible to obtain good results without casting suspicion upon them by the use of membranes, as is shown by the accurate measurements of Noyes and Sammet, Jahn's pupils and others. For measuring very weak electrolytes such as acetic acid, the use of some sort of diaphragm is almost indis- pensable ; I used bundles of glass tubes of small bore, which is cumbersome, but is otherwise free from criticism. The dia- phragms which are least open to objection are cloth, cotton batting, earthenware, and agar-agar. It is unfortunate that it is just in the case of weak electrolytes where diaphragms would be most useful that cataphoresis (electric endosmosis) is most prominent. Solidified gelatine, intestinal membrane, fish- bladder, gold-beaters' skin, membrane of an egg, and parch- ment, are the diaphragms which exert the greatest influence upon the migration ; the influence varies with the nature of the electrolyte and its concentration. ERRORS INTRODUCED BY THE METHOD OF CALCULATION. There are several methods of calculation in use, although only one of them is correct. Hittorf described this with the greatest clearness in his classical researches ; yet of only six- teen authors besides Jahn's pupils can I say with certainty that their results were correctly calculated. In many cases the data given in the papers are not sufficient to warrant a definite ex- pression of opinion ; but it is safe to assert that of the authors who used the analytical method, not more than half calculated their results correctly. In measuring migration we are measuring the movement of the electrolyte through the solv^ent ; hence the calculation must be based upon a constant amount of solvent. If for example we find that before electrolysis the vt grams of water in an electrode compartment contains a certain amount of electrolyte, we must determine the amount of electrolyte contained in w grams of water after electrolysis. The favorite among the other methods is to determine the amount of electrolyte in a constant volume of solution before and after electrolysis ; it is evident that only 6 McBAIN in special cases will equal volumes of solutions of different con- centrations contain the same amount of solvent. Hittorf^ picked out particular cases measured by Wiedemann and showed that the error thus introduced amounted to as much as 20 percent of the migration value ; in other cases it was neg- ligible. In very dilute solutions this error vanishes. Another method bases the calculation upon constant weight of solution ; as is evident, this is always wrong. Here, again, the error is worst in concentrated solutions, and becomes negligible when the solutions are very dilute. In general, I have had to leave it to the reader to calculate whether the error introduced by wrong methods of calculation is large or not ; in a few cases, however, I have made the calculation myself, and when the error was vanishingly small, I have stated that the results were correctly calculated. Possibly the following consideration of the effect on the trans- port number caused by neglecting the loss of gases at the elec- trodes may be of use. During the passage of 96,540 coulombs 8 grams of oxygen escape, hence the amount of the constituents of the solvent at the anode appears to be 8 grams less than really was, and so the apparent migration value of the anion is increased by the number of g-mols of electrolyte contained in 8 grams of water. This holds for all electrolytes where oxygen is evolved at the anode. Similarly, the migration value of the cation obtained at the cathode where hydrogen is escaping is increased by the number of g-mols of electrolyte in one gram of water; this is generally negligible. The correction to be sub- tracted from the migration value of the anion found b}- analysis at the anode is therefore 0.008 for normal solutions and 0.0008 for decinormal solutions ; similarly for the cathode analysis, one eighth as much has to be added to the migration number of the anion. These corrections are mostly negligible, but the calcu- lation is useful as showing the absolute value of the errors intro- duced by the chemical processes at the electrodes. It is easy to extend it to other cases ; for instance, the correction at the cathode where a metal is precipitated and not weighed, is equal to its gram-equivalent weight multiplied by the correction de- iPog. Ann., 103, 8 (185S). MEASUREMENTS OF ELECTROLYTIC MIGRATION 7 duced above for hj'drogen. For a metal dissolving at the anode, where the electrode is not weighed, the correction is equal to the correction for oxygen (but taken with opposite sign) multi- plied by one-eighth the gram-equivalent weight. ^ INTERPRETATION OF THE RESULTS. The transport number of any component of a solution is the number of gram-equivalents of that component which enters or leaves one of the electrode compartments during the passage of 96,540 coulombs of electricity. Hittorf has shown how in certain cases (double cyanides, stannic chloride, cadmium iodide, for instance) these transport numbers may suggest definite views as to the constitution of the electrolyte. In the following paragraphs I shall briefly discuss the bearing of transport measurements on the hypothesis of hydrated ions, and on that of the possible movement of undis- sociated molecules of the electrolyte ; and I shall explain the methods of calculating the concentrations and mobilities of the complex ions or products of hydrolysis that may be assumed to exist in the solutions of certain salts. A few measurements which are not easily reconcilable with the prevalent theory of solutions are collected under the heading " anomalous results." Hydrated Ions. In a solution of sodium chloride (to take a concrete example) it is customary to assume the ions Na' and CF together with water and undissociated molecules of NaCl. It is, however, possible to assume the existence of hydrated ions : (Na-fxHgO)' , and (CI -f yH20)', or of complex ions, or even that the undis- sociated NaCl moves towards one of the electrodes, under the influence of a fall of potential, as colloids do. If hydrated ions be assumed, it is evident that in calculating the transport numbers from the experimental data, allowance must be made for the water carried by them into the electrode compartments and set free at the electrodes. I have shown elsewhere ^ that this correction may be expressed by the formula (-^y ^xjC, in which 1^ and 1^ represent the mobilities of ^Zeit. f. Elektrochemie, //, 216 (1905). 8 McBAIN the cation and anion respectively, x and y the number of g-mols of water combined with one equivalent of each ion, A the equivalent conductivity, and C the total concentration of the electrolyte expressed as the number of g-equivs solute in one g-mol water. Thus it is evident that if the transport num- bers of the hydrated ions are to be very different from those of Na" and CI', either the ions must differ widely in mobility and have a large amount of combined water, or the difference in hydration of the ions must be great. The numerical example given in the paper quoted shows that in general the change in the transport number caused by assuming that the ions are hy- drated, is small. In very concentrated solutions, however, the difference would be greater : and the h3^pothesis might be checked by measuring the transport of some non-electrolyte added to the solution, choosing one which will not react with the electrolyte in question.^ Movement of Undissociaied Electrolyte. The fact that transport numbers for simple electrolytes are independent of the concentration discredits the hypothesis. The movement of non-electrolytes measured by Nernst, Garrard and Opperman^ and by Morgan and Kanolt '' corresponds to a transport number of the order of magnitude of o.oi. This is however a negligible quantity, being within the experimental error of most measurements ; and the alternative assumption of hydrated ions is from other considerations very plausible.* Complex Ions, Hydrolysis. Three methods have been worked out for dealing with elec- trolytic solutions which are assumed to contain complex ions in equilibrium with simpler ions and undissociated molecules ; the first was developed and applied by Burgess and Chapman, the other two by myself. The first and second methods are appli- cable to special cases only ; the third is general, and may also be employed in dealing with hydrolysis. (i) The method of Burgess and Chapman^ is based on the ' Ibid., II, 961 (1905). ^Nachr. Gott. Akad., 1900, 68. *Zeit. phjs. Chem., 4S, 365 (1904). *See Baur, Ahren's Saminhing, S (1903). *Joiir. Clicm. Soc, 8^, 1305 (1904). MEASUREMENTS OF ELECTROLYTIC MIGRATION 9 results of the careful study that has been devoted to solutions of iodine in potassium iodide solutions. Jakowkin and others have shown by means of several physico-chemical methods that KI3 and KI are electrolytes of equal degree of dissociation ; the dissociation constant for the reaction F^ ;=i I^ -(- 1 is also known, from these data and a transport determination in solutions con- taining iodine and potassium iodide the mobility of the tri-iodion was calculated, and found to agree with that calculated from conductivity measurements assuming that the dissociation of potassium tri-iodide is the same as that of potassium iodide. (ii) In solutions of the haloid salts of cadmium and zinc the transport of the halogen increases rapidly with the concentra- tion, and finally approaches a maximum. This may be in- terpreted by assuming that, when the maximum is reached, the concentration of the simple ions is negligibly small ; by making suitable assumptions as to the formula of the complex its trans- port number may be calculated, and from the experimental numbers for intermediate concentrations the relative amounts of simple and complex ion may be obtained. In the case of cadmium iodide ^ the numbers so arrived at are in accord with freezing point, and conductivity, and with the requirements of the mass law. The applicability of the method is restricted by the condition that, if the results are to be reliable, the maximum must be reached before the solution becomes too concentrated. (iii) The third method is based on the assumption that in solutions containing a number of ions the migration of each is given by the product of its concentration into its migration velocity. This view was advanced by Hittorf in 1857 ; it has been tested and confirmed by numerous experimenters with known mixtures of two simple salts having a common ion ; and it has been used in the mathematical developments of Kohlrausch." Let ?/, V, 2Vy ►v, represent the mobilities of the ions K*, Cd", 'R. Schrader, Zeit. f. Elektrochem., 3, 498 (1897). E. v. Stackelberg, Zeit. phys. Chem., 23, 493 (1897). K. Hopfgartner., Zeit. phjs. Chem., 2j, 115 (1898). H. Jahn, Zeit. phys. Chem., 27, 354 (1898). H. Hotfmeister, Zeit. phys. Chem., 27, 345 (1898). E. Berliner, Dissertation, Berlin, 1902 — to appear this Winter with other work from Jahn's laboratory in the Zeit. phys. Chem. *Wied. Ann., 6^, 209 (1897). 10 McBAIN I', and Cdig' respectively, in a solution of potassium cadmium iodide ; and «, b, c, d, their concentrations expressed as gram- equivalents per cubic centimeter. Three of the mobilities, viz. : M, V, zif, may be taken as known ; and among the four concen- trations there must exist the relation a + d = c -\- d so that four of the eight symbols, u, Vy w, x, a, d, c, d, repre- sent unknowns. Four experiments giving four independent relations involving these four are therefore necessary in order to determine the concentration of each of the ions, and the mobility of Cdl/. Such, for example, are the following : 1. The specific conductivity x may be determined ; by Kohl- rausch's law au -}- dv -}- cw -\- dx =^ X. 2. The quantity of potassium which enters the cathode com- partment during the passage of one faraday through the solu- tion may be determined ; it is aujx equivalents. 3. Similarly, the net gain of cadmium in the anode compart- ment per faraday, is {idx — bv)lx equivalents. 4. And the gain of iodine at the anode per faraday r [c2v -\- 2^x)/x equivalents. These are not the only experiments, however, that might be employed. By means of E.M.F. measurements, for instance, the concentrations b or c might be determined ; t-he freezing point gives a -\- }^b -i- c -{- d, etc. The experiments thus furnish more equations than unknowns, and the surplus may be used to check the theory. This has been done in my paper ' in which the concentrations were calculated from transport measurements and one E.M.F. determination; the results so obtained are in accordance with the conductivity and freezing points. It may be remarked that when the number of analytical com- ponents among the ions of a solution is represented by «, the migration of the ii-ih may be calculated from those of the remaining « — i by means of the stoechiometrical relations. Hence agreement between the directly measured migration of the «-th component and the calculated value is the best proof that unsuspected ions (due to hydrolysis, for example) have not been overlooked. ' Zeit. f. Elektrochem., //, 961 (1905). MEASUREMENTS OF ELECTROLYTIC MIGRATION II Anovialous Results. Of remarkable results there are many. Highly interesting are the researches of Daniell and Miller in 1844. These well known and capable experimenters, fully alive to the significance of the results they were obtaining, found that in many cases components now recognized as cations did not move at all. Later measurements agree in showing that in these very solutions the cation moves about as fast as the anion. Hittorf and others have suggested explanations for Daniell and Miller's results, but unfortunately the explanations suggested only make things worse. Chassy, in 1890, made a number of measurements with mixtures of two and more electrolytes. His results are sum- marized by Ponsot ' and are quite at variance with the pre- dictions of the present theory ; his is the only experimental work in this field. Bein, in 1898, found for ammonium hydroxide a transport number widely different from that predicted by Kohlrausch's law of the independent migration of the ions. In 1904 I obtained a similar result for acetic and propionic acids. These are the only measurements that have been made with very weak electro- lytes, and all three obey Ostwald's law ; these results should not be so difBcult to believe when Jahn and Nernst hold that the mobility of an ion varies greatly with the concentration, without any more evidence than that the conductivity and freezing points which agree so well with one another both refuse to obey Ostwald's law, although the latter does not take into account the possible displacement of the equilibrium by the electrical forces. The accurate measurements of Noyes and Sammet in 1902 gave a result for hydrochloric acid differing by four percent from that calculated from the careful conductivity measurements of Goodwin and Haskell ;^ the transference measurements have been confirmed in Jahn's laboratory by Joachim, and the diver- gence has to be regarded as real. Divergences equally great even amongst the most carefully measured electrolytes are so ' Comptes rendus, 13S, 192. ^Phjs. Review, ig, 369 (1904). 12 McBAIN common, that Luther has come to the conclusion that it is not worth while discussing whether Kohlrausch's Law is strictly quantitative or not until the experimental data are more reliable. QUALITATIVE EXPERIMENTS. Qualitative or semi-quantitative experiments are sufficient to show whether a given component of a solution moves toward the anode or toward the cathode during electrolysis. In order that the results may be decisive as to the constitution of the solution, however, further experiments must be made to find whether or no the component in question is present in colloidal form ; this has been done in recent papers from the Leipsic laboratory. If the experiment is carried out by electrolysing the solution between two other " electrode solutions," the presence of one of the components of the intermediate solution in the cathode compartment may justly be regarded as evidence that the com- ponent in question formed a constituent of some cation ; the converse, however, is not necessarily true. It is possible that the component which in the intermediate solution formed part of a cation might have acted as anion in the cathode solution, and that it was consequently, in large part at least, driven out as soon as it entered. The experiments of Richards and Bonnet in 1904, and of Lind in 1903, offer a case in point; the authors are however doubtless justified in the conclusions which they draw, for the rate of transformation of the various modifications of chromic sulphate into each other is notoriously slow. ARRANGEMENT OF THE ABSTRACTS, ABBREVIATIONS USED. In the following abstracts general information is given in a paragraph which does not require further explanation. In the tables, the first column gives the chemical measured ; the sec- ond the concentration (m denotes mols, that is gram-formula- weights) ; the third the temperature ; the fourth the number of grams of silver or copper deposited in the voltameter, indicated by the abbreviation " g Ag," *' g Cu," etc. ; the fifth the per- cent change in the composition of the middle (supposedly unal- tered) portions, calculated by myself; the sixth, the number of experiments (" ex ") ; the next indicates which electrode solution MEASUREMENTS OF ELECTROLYTIC MIGRATION 13 was analyzed, " a" denoting the anode compartment, " c" the cathode compartment, and " ac" meaning that both were analyzed and used in computing the transport number; next comes the transport number of the anion, here the cipher before the decimal point is always omitted, and the number is filled out to three decimal places by dashes when the experiments were less ac- curate ; attached to the transport number is given half the maximum divergence (multiplied by i,ooo) between the indi- vidual results, preceded by the sign ±. Thus " 23 ex a .170 ±4" means that 23 experiments were performed, the analyses at the anode compartment were used to compute the transport, the transport number found for the anion was 0.170, the maximum divergence between the indi- vidual results was 0.008. Very inaccurate experiments would be given as follows : " 5 ex ac .51 — ± 67 " meaning that the transport number found is 0.51, and the difference between the two extreme results was 0.134. Noyes' results are given thus : ** ac .1657 d= 2.3 " meaning 0.1657 with a maximum difference between the results of 0.0046. I am convinced that this maxi- mum divergence does not in most cases give an exaggerated impression of the inaccuracy of the experiments. The arrangement just described is followed as far as possi- ble ; often, however, a column is left out when the data are lacking, or when they have been given in the paragraph at the top. Extra columns, special arrangements of the data, etc., are explained in each special case. In deciding what experiments it was fair to average together, in almosf all cases I have been much more tender with the results than the authors themselves ; many authors show what they think of their own results by averaging together all their values, even when obtained under different conditions of tem- perature and concentration. When only one experiment was performed under each set of experimental conditions, I did not feel justified in averaging the results even where their accuracy seemed questionable. Thus I have tried to give the experi- ments the benefit of the doubt ; the reader should take this into account when trying to decide in any particular case whether the transport numbers really vary with the temperature, etc., or not. 14 McBAIN [iSi4Porrett ABSTRACT OF THE LITERATURE OF ELECTROLYTIC MIGRATION. 1 814. R. Porrett. Abstracts Phil. Trans., /, 510, from Phil. Trans., p. 519. On the Nature of the Salts termed Triple Prussiates, and on Acids formed by the Union of certain Bodies with the Elements of Prussic Acid. The author observed the movement of Fe and of K in the electrolysis of ferrocyanic acid solution. 1833. M. Faraday. Experimental Researches in Electricity, fifth series, III, Theory of Electro- chemical Decomposition. Phil. Trans., 123, 6S2, 525-530. Ostwald's Klas- siker, 86, 85. Pogg. Ann., 32, 436. Two pieces of apparatus, each consisting of two electrode cups connected by a strip of asbestos, were set up in series. One was filled with sulphuric acid of specific gravity 1.02 12, the other with a chemically equivalent solution of sodium sul- phate. Pt electrodes were used and the contents of the four cups were weighed and titrated before and after the electrolysis. The change in acidity in each cup of the sodium sulphate ap- paratus was 24^-3 times as great as in the sulphuric acid appa- ratus. The sulphuric acid contained a small percentage of inorganic sulphates. (From these experiments it would follow that in sulphuric acid w for SO^ lies between .4 and .33.) 1839. J. F. Daniell. On the Electrolysis of Secondary Compounds. In a letter addressed to M. Faraday. Phil. Trans., i2g, 97. Apparatus : A vertical U-tube with two diaphragms of bladder in the bend ; tubes were attached to collect the gases from each of the electrodes separately. The current was measured by a water voltameter. In seven electrolyses with i-io percent solutions of sulphuric acid the migration value of the SO^ was found to be n = |. In one of these experiments a Zn anode was employed, in the others Pt electrodes were used. As a result of futher electrolyses, the author concluded that the cur- rent was carried solely by the electrolyte, and adopted Davy's formulas for the oxy-acids and their salts, and those of Berzelius for the ammonium salts. 1844 Daniell] ABSTRACT 1 5 X840. J. F. Daniell. Second letter on the Electrolysis of Secondary Compounds. Addressed to M. Faraday. Phil. Trans., ijo, 209. The author electrolyzed various solutions in an apparatus consisting of two electrode compartments connected to a third cell by a siphon with partitions of membrane. The total elec- trolysis was determined by measuring the gases evolved. The solutions in each of the three cells were analyzed. In the ex- periments with caustic alkalis the membranes were replaced by porous earthenware. HjSO, specific gravity 1.076 n = \ H,PO, 6-1 1 percent « = i KOH » = i Ba(OH), specific gravity 1.0085 « = l Sr(OH), specific gravity 1.007 « = ! KjSO, n = \ 1844. J. F. Daniell and W. A. Miller. Additional Researches on the Electrolysis of Secondary Compounds. Phil. Trans., 134, i ; Pogg. Ann., 64, 18. Apparatus : a horizontal cylinder divided into three compart- ments by vertical partitions of bladder. The Pt electrodes were placed in the end compartments which were provided with tubes for collecting the gases evolved. A water voltameter was placed in the circuit. Experiments with copper sulphate, zinc sulphate, and ammo- nium chloride showed that the cation was not moved by the current. For potassium sulphate, barium nitrate, and calcium sulphate, the migration values were respectively w = |, « = |, n = \\. Semi-quantitative experiments showed that both ions were moved in the cases of sodium tungstate, potassium chro- mate, potassium arsenite, and sodium carbonate ; in the case of sodium chloride the chlorine was moved in greater amount than the sodium. Further experiments were carried out with copper sulphate, aluminium sulphate, ferric sulphate, magnesium potassium sul- phate, potassium aluminium alum, potassium copper sulphate, potassium sulphocyanide, potassium cyanide, potassium ferro- cyanide, potassium ferricyanide, potassium sulphate, ammonium oxalate, potassium arsenite, potassium arseniate, sodium sul- phite, sodium hyposulphite, and the phosphates of sodium. i6 McBAIN [1845 Pouillet 1845. M. Pouillet. Note 6ur I'electrochimie. Comptes rendus, 2o, i sem., 1544. Apparatus : a U-tube ; capacity lO c.c. ; Pt electrodes ; no diaphragms ; no middle portion ; a water voltameter. The author found no transport of gold in solutions of gold chloride; for the chlorides of iron, manganese, and cobalt n = .66 — ; for other chlorides 11 lay between .7 — and .8 — . The author deduced that the action of the electrodes is unequal owing to the positive and negative constituents of an electrolyte having electric charges opposite in sign but unequal in amount. 1853. w. Hittorf. Ueber die Wanderungen der Jonen wahrend der Elektroljse. Fogg. Ann., 8g, 177, Ostwald's Klassiker, 21. Apparatus : (i) a short wide glass cylinder of which the two parts could be isolated by sliding the upper half sideways ; capacity 44 c.c. ; the anode consisted of the metal corresponding to the electrolyte ; the cathode was of Ag. No middle portion ; no diaphragms. In the second column are given the number of grams of water in which one gram of salt was dissolved. CuSO« 6.35 5° igAg lex C.724 9-56 5° 1 1 3 C.712 18.1 4° 0.9 I C.675 40-148 4° 0-5 3 C.644 9-56 20° 1.4 I C.7I3 AgNOa 2.48 11° 1.2gAg lex C.468 2-73 19° 1.9 t I C.478 5.18 1 8° I.l 1 c-495 10.4 19° 05 I C.51 — 14-247 19° 0.2 5 C.526 AgjSO, 123 17° o.igAg 1 3ex c-554 AgC,Il30, 127 15° o.2g Ag 3ex c-373 AgNOj 309 4° o.2gAg 1 2ex C.573 in ethyl alcohol 1856. W. Hittorf. Ueber die Wanderungen der Jonen wahrend der Elektroljse. Pogg. Ann., g8, 1, Ostwald's Klassiker, 2/. Apparatus : (ii) Cathode cylinder fitted into neck of anode cylinder; capacity about 80 c.c. ; Ag cathode ; no middle por- tion ; no diaphragms, (iii) Horizontal cylinder divided by two partitions of porous earthenware into three compartments, (iv) Four superposed glasses, with diaphragm of intestinal mem- brane (Darmhaut) ; the upper (cathode) vessel contained free 1856 Wiedemann] ABSTRACT I7 acid; the middle portion was tested for acid and cadmium. This apparatus (iv) was made in four sizes for solutions of dif- ferent concentrations; the smallest anode vessel contained 12 C.C., the largest 238 c.c. ; Pt cathode, Cd anode. In the second column are given the number of g water in which one g of salt are dissolved. CuSO, 9-56 o.8g Ag 11.6 2.0 KCl 4-85 12° i-ig Ag 6.61 4° 0.7 18.4 7° 0.8 39-4 9° 0.7 254 50° 0.6 449 90° 0.4 KBr 2.36 !2° o.7g Ag 117 7° 0.7 Kl 2.7-8.5 1-12° o.Sg Ag 170.3 3° 0.4 KjSO, 12 4-12° o.9g Ag 413 7° 0.3 KNO3 5-8 9° o.4g Ag KCjHsO, 1.4-48 H° o.7g Ag NH.Cl 5.28 12° i-ig Ag 12.2 10° 1-5 28.0 10° 0.9 175 7° 0.7 lex a. 716 Cu anode. 2 a.704 " " lex a. 516 2 a.516 I a.514 2 a-5iS 2 a-.Si5 I a. 503 2ex a.528 2 a-5i3 3ex a.511 I a. 492 2ex 2 a.500 a. 498 2CX a.450 2ex a.33S lex a-5i7 I a.514 I I a.514 a.508 1856. G. Wiedemann. Ueber die Bevvegung der Flussigkeiten im Kreise der geschlossenen galvan- ischen Saule und ihre Beziehungen zur Elektroljse. Pogg. Ann., 99, 177. Apparatus: two glass jars connected by a wavy siphon, capacity 200 c.c. ; Pt electrodes; no diaphragms ; no middle portion. Blank experiments showed the existence of an un- changed middle portion in the cases of sodium sulphate and potassium iodide. Hittorf, Pogg. Ann., 103^ 8, shows that the results are incor- rectly calculated. In the electrolyses of the copper salts between Pt electrodes, the acid formed at the anode reached the cathode portion, and Wiedemann points out that the current was partly carried by free acid. A further series of determinations were made using porous earthenware diaphragms, repeating the experiments with sul- Proc. Wash. Acad. Sci., June, 1907. i8 McBAIN [1856 Wiedemann phuric acid, nitric acid, copper sulphate, copper nitrate and silver nitrate. The results when corrected for cataphoresis corresponded with the numbers obtained with the apparatus described above in which diaphragms were avoided. The concentrations are indicated in the second column in grams of SO^, NO,, etc., per 100 c.c. HjSO^ 2-14 SO4 i.3-2.4gCu 3ex ac.i8o±:6 1 HNO3 7.7 NO3 4.2 NO, 2.0g Cu 2.0 lex I a.148 a. 142 KOH 2.23 K o.6g Cu lex ac.245 2.09 K 0.6 I ac.215 NaOH 3.13 Na i.igCu lex ac.i6i 2.63 Na I.I I ac.r53 CuSO^ 3.67 Cu 1.52 Cu i.4gCu 0.7 lex I ac.i8i ac.iS6 3.17 Cu 0.5 I ac.360 Copper anode. 2.54 Cu 1.78 Cu 0-5 0.3 I I ac.355 ac.321 11 (1 t( it 1.52 Cu 0-3 I ac.339 " " Cu(NO,), 1.66 Cu 2.72 Cu o.gg Cu 0.9 lex I ac.241 ac.368 Copper anode. AgNO, 1.92 Ag 2.96 Ag 2.66 Ag i-3g Ag 1.6 I.O lex I I ac.236 ac.535 ac.521 Silver anode. NaCl 1.94 Na o.6g Cu lex ac.378 1857. A. Weiske. Die Ueberfuhrung des Chlors bei der Elektrolyse seiner Verbindungen mit den Metallen der Alkalien und alkalischen Erden. Pogg. Ann., loj, 466, Habili- tations Dissert. Apparatus : two flasks connected by a straight tube with a glass cap ; capacity 100 c.c. ; no diaphragms ; no middle portion. The calculation is based (incorrectly) upon constant volume of solution. The author discusses the prevalent theories of electrolysis. KCl I-IO percent o-4g Ag loex C.516 i: 9 NaCl 9.21 percent 0-4g Ag 4ex C.686 ±: 8 2.86 " 0.4 4 c.685 ±g 0.844 " 0.2 I C.680 CaClj 1-9 percent 0-3g Ag 9ex C.690 zb8 BaCl, 0.5-8 percent o-3g Ag Sex C-53I ± 9 SrCl, 1.07 percent o-3g Ag 4ex C.648 ± 8 0.757 " 0-3 3 C.650 ± 9 0.146 '« 0.2 I c-655 5-2-5-6 i.og Ag iv 6ex a-Si3 98 I.Og iv 8 a. 509 3-8-S-5 0-5 V 2 C.501 4.62 12° o.6g Ag V lex C.479 9-63 11° 0.8 V I C.487 31-5 7° 0.4 V I C.494 94.1 8° 0.7 V I C.497 1859 Ilittorf] ABSTRACT I9 1858. W. Hittorf. Pogg. Ann., loj, i ; Ostwald's Klassiker, 21. Apparatus : (iv) see Hittorf, 1856. In these experiments a Zn anode was used and the cathode was surrounded by a solution of potassium chloride ; (v) four superposed glasses of which the uppermost contained the anode and the lowest the cathode. The cathode was bent into the form of a U-tube to permit the escape of hydrogen. Earthenware and bladder diaphragms. In the second column are given the number of grams of water in which one gram of salt was dissolved. KCi KNO, KC2H3O, 1.3-94 14° o.8gAg V 3ex c.331 In addition experiments are detailed showing that in solutions containing potassium iodide and potassium chloride both I and CI are transported by the current. 1859. W. Hittorf. Pogg. Ann., 106, 337, 513. Ostwald's Klassiker, 2j. Apparatus : (ii) See Hittorf, 1856. (iv) See Hittorf, 1856, for the experiments with potassium cyanide the membranes were replaced by porous earthenware ; in the experiments with the alkaloid hydrochlorides the cathode was surrounded by hy- drochloric acid, (v) See Hittorf, 1858. (vi) Five superposed glasses with membranes. Anode of Cd in the lowest vessel, Pt cathode in the uppermost. The anode was surrounded with a protecting solution : potassium acetate in the experiments with potassium oxalate, potassium chloride in those with potassium chromate, sodium chloride in those with sodium mono- and di- sodium phosphates, sodium nitrate in those with sodium phos- phate and pyrophosphate and also with iodic acid ; (vii) an anode vessel closed at the bottom with membranes was fitted to the top of the cathode U-tube ; Pt electrodes. In the experi- 20 McBAlN [iS59Hittorf ments with potassium cyanide, sodium platinichloride, and potas- sium gold chloride, the silver anode was placed at the top and surrounded with the solution of potassium cyanide. In the second column are given the number of grams of water in which one gram of salt was dissolved. In the sixth column are recorded the weights of the anode portions (includ- ing protecting solutions if any). KjC^O^ 4.18 i-ig Ag vi 26g I ex a' .441 KCrO, 9-54 i-4g Ag vi 23g I ex a .512 KjCrjO, 14.6 0-4g Ag iv 8g lex a .502 KCIO^ 119 o-3g Ag iv 220g I ex a •463 KCIO3 26.6 o-4g Ag IV 6og lex a •445 115 0.4 iv 220g I a .462 KCN 7.66 o.4g Ag iv I2g lex a •457 105 0.15 iv 5ig I a •47- NaCl 3-47 13° I .og Ag iv "g lex a .64S 5-54 9° 0.9 iv "g 2 a .647 20.7 16° I.I iv 33g I a •634 105 17° 0.4 iv 33g I a .628 315 6° 0-5 iv 2IOg 4 a .620 Nal 22.1 o.4g Ag iv 3ig lex a .626 NjLjSO^ 11.8 9° o.9g Ag iv 34g lex a .641 50-7 9° 0.6 iv 32g I a •634 NaNOj 2.07 I.2g Ag iv i5g lex a .588 2.99 9° 0.8 iv iig 1 a .600 34-128 12° 0.4 iv 55-2 I og 4 a .614 NaCjIl302 2.81 8° i.og Ag iv log lex a •415 7.18 13° 0.5 iv log a .421 41-3 6° 1.2 iv 2IOg a .424 84.6 11° 0.6 iv 2 log a •443 BaClj 3.2-3.8 6-14^ ig Ag iv 12g 4ex a .662 8.39 19° 1-7 iv 35g a .642 79.6 20° 0.4 iv 6og a .616 126 10° 0.4 iv 2IIg a .614 Ba(N03), 16.2 8° o.2g Ag iv .'i9g lex a .641 56.5 H° 0.14 iv 59g a .620 134 11° 0.6 iv 2IIg a .602 CaClj 1.70 20° o.7g Ag iv I2g lex a .780 2.07 12° o.S iv I2g a .771 2.36 3° 0.7 iv 12g a •765 2.74 10° 1.4 iv 12g a •749. 3-95 21° I.O iv 12g a .727 21-229 20° 03 iv 32-58 2 a •683 138 9° 1.2 iv 2I5g I a •673 1859 Ilittorf] ABSTRACT Cal, 1-3^ o.Sg Ag iv i6g lex a .732 Ca(NO,), 1.^2 7° o.7g Ag iv I2g lex a .718 3-96 1 1-7 iv 12g I a .652 112 / 0.9 iv 2I5g I a .613 MgCl, 2.48 6° o.4g Ag iv iig lex a .806 3-7 15° 1.2 iv 11-37 2 a .778 22.2 14° 0.8 iv 32g I a .706 128-241 6- 15° 0.4 iv 58-213 2 a .677 Mg I, 0.796 i-ig Ag iv i6g lex a .777 MgSO, 5.28 4° i-4g Ag iv log lex a .762 209 5° 0-5 iv 2I2g 1 a .656 MnClj 331 7° i-4g Ag iv iig lex a .758 190 9° 05 iv 2I3g I a .682 ZnSO^ 2.52 o.7g Ag iv i6g I ex a .778 4-05 I.O iv I4g I a .760 267 0-3 iv 220g I a .636 Feci, 2.07 i-3g Ag vii i4g lex "c .746 25.2 0.2 vii 20g 1 c .600 AICI3 22.7 o.4g Ag iv i2g lex a .714 UO2CI2 10.4 o.4g Ag iv 26g lex a .868 Morphine H.Cl 54-9 o-3g Ag iv 92g lex a .815 Strychnine H.Cl 55.7 o-5g Ag iv 93g lex a .861 HCl 2.91 i-3gAg iv i3g lex a .319 9.86 7° 1-3 iv 9g I a 193 36.2 8° 0.4 iv 9g I a .168 82.3 8° 0-5 iv 56g I a .161 141 1.4 iv 220g I a .171 321 8° 0-3 iv 2I2g I a .216 2126 6° 03 iv 2I4g I a .210 SnCV 13-5 o.4g Ag vii i2g lex c .180 HBr 8.65 o.7g Ag iv log lex a .178 HI 4.82 o-7g Ag iv i3g lex a .201 117 0.4 iv 88g I a .258 HjSO^ 0.557 i-7g Ag y i9g lex a .40c Ft anode 1.438 2.6 v I5g I a .2S8 " " 5-42 1-3 iv log. I a .174 Cd " 233 0.9 iv 58g I a .177 " " 98 0.6 iv I72g 1 a .212 " " 161 0.4 iv i74g I a .206 " " HIO» 13-3 0.2g Ag vi 25g lex a .102 Ag " Na.PjO, 35-6 o-4g Ag vi 22g lex a .645 " " NaaPO, 26-19 0.4-0.6 vi 23g 2ex a 2 " " Na.PO., 10.6 o-5g Ag iv I3g lex a -573 ' Regarded b} Hittorf as I part HCl in 24.3 parts water. * Current carried mostly by . ilkali resulting from hjdrolysis. 21 22 McBAIN [1859 Hittorf K,.Fe(CN)e 5-30 o.6g Ag vii 23g lex a .482 K.Ag(CN), 7.71 o.5g Ag vii 2Ig lex c .406 Naj.PtCls 1.87 o.6g Ag vii Hg lex c .562 I3-I 0.4 vii 22g I c .519 KCI.AUCI3 6.08 o-3g Ag vii I2g lex c 35-9 0.2 vii 2Ig 1 c KCl.HgClj 7-37 o-5g Ag vii 24g lex c KC1.2HgClj 8.19 o-3g Ag vii 23g lex c KC1.4HgCl3 9-59 o.2g Ag vii 23g lex c K.Cdlj 0.327 i.og Ag vii 2.?g lex c -43- KCd.I, 2.30 0.6 ii I2g lex a .79-1 58.7 0.3 ii 87g 1 a .560 K.(C,H5)SO, 6.55 o.3g Ag iv 9g lex a .302 Naj.HPO^ 20-31 o.6g Ag vi 22g lex a .516 K.H2PO, 7-59 i.og Ag vi 25g lex a .377 10.3 0.7 vi 25g I a .266 Na.HjPO, 5-71 o-9g Ag vi 26g lex a .383 Cdlj 1.83 o-3g Ag ii i8g lex ai.25S 3-04 11" 0.7 ii i6g I ai.192 4. 28 12° 0.7 ii i6g I ai.14- 18.1 11° 0.4 ii Hg I a .931 69.6 0.2 ii 222g I a .642 167 10° 0-3 ii 220g 1 a .613 Znlj 0.664 2.og Ag ii 23g lex ai.157 Zn anode 2.457 2.1 ii i6g I a .727 " 112. 9 0.4 ii 220g 1 a .675 " ZnCl, 2.77 i.8g Ag ii I6g lex ai.o8— " " 333 0.4 ii 21 9g I a .700 " " CdCl, 1.27 7-11° o.8gAg ii i7g 3ex ax. 015 1.98 7° 1-7 ii HS I a .873 2.76 10° I.I ii i7g I a .779 3-36 10° 0-5 ii i3g I a .772 5-76 I.O ii I2g 1 a .744 98.7 8° 0.6 ii 220g I a .725 192 11° 0.5 ii 222g I a .70S Cdl, 1.107 o.2g Ag ii l6g lex a2.i02 Ethvl alcohol 1-394 0-3 ii l.^g I a2.ooi " '• 1.695 0.4 ii I4g I ai.909 " " 2.190 0.4 ii 25g I ai.848 2.466 03 ii 32g I ai.S27 2.466 03 ii 33g I ai.819 " " S-375 0-3 ii iig I ai.552 " " 37-23 0.1 ii 29g I ai.3iS ' For interpretation and recalculation of these results see J. W. McBain — Zeit- f. Elektrochem., //, 215. 1905. 1870 Bourgoin] ABSTRACT 23 Znl, 0.520 o-7g Ag U? 2Ig lex a2.i6iZn an.Ethjl ale 0.707 0.9 ii.? i9g ai.ooS " " '•533 0.8 u? i5g ai.711 " " 1-534 0.6 ii.? i5g ai.705 " 4-933 0.2 ii.' •ig ai.254 " 16.14 0.2 ii.' 30g a .747 " ZnCl, 1-74 o-9g Ag u? i3g lex ai.998 " " 6.79 0.5 u? log ai.538 " Cdl, 3-179 O.Ig Ag u? "g lex a2.3 — Aiuyl alcohol 1868. E. Bourgoin. Du role de I'eau dans I'electroljse. Ann. Chim. Phjs. (4), ij, 47. Apparatus : capacity 40 c.c. I have deduced the following migration values from the ex- perimental data afforded by the work of the author ; the calcu- lation is based (incorrectly) upon the change in constant volume of solution, not upon a constant weight of solvent. KOH 1. 68m lex ac.746 1. 14 lex ac.749 HjSO^ o.2-o.5m 3ex ac.i68 HNOj 1. 66m lex a .126 1868. E. Bourgoin, De I'electroljse des acides organiques et de leurs sels. Ann. Chim. Phjs- (4). ^^' 157- In this extended investigation carried out from another stand- point, in no case are sufficient data afforded to permit of the deduction of migration values, unless possibly in the case of succinic acid (n .6 — or .3 — ?). 1870. E. Bourgoin. Memoire sur I'inegalite des pertes d'acide et de sel dans le voisinage des p61es> Ann. phys. Chim. (4), 2/, 264. The author rejects Hittorf's explanation of the changes of concentration during electrolysis in favor of "^that of d'Almeida ; and classifies the acids according as the acidity at the anode increases or decreases by electrolj'sis. The details of two experiments with oxalic acid are given. In the first, the loss of acid at the cathode was one third of that corresponding to the hydrogen collected from that electrode. In the second, the loss of acid was three times as great at the cathode as at the anode. 24 McBAIN [ 1878 Kirmis 1878. M. Kirmis. Zur Wanderung der lonen. Wied. Ann., 4, 503. For apparatus see Wiedemann, 1856; capacity no c.c. ; no diaphragms. The siphon became considerably heated. No middle portion ; anode Cu, and cathode Pt. The calculation is incorrect (based on constant volume of so- lution, not constant amount of water). CUSO4 5.06 percent 1^° 4-5g Ag 3ex C.723 4-S3 40 2.7 3ex C.713 3-52 22° 5-9 3ex C.702 3-17 13° 4.8 3ex C.690 2.20 24° 2.0 3ex C.686 1-75 23° 2.1 3ex C.685 1.04 (1 ^-,0 3-5 3ex c-655 0.497 90 1-5 3ex C.641 1-5 0-8° 4ex C.7S0 Pt anode 1 881. J. Kuschel. Die Bestimmung der Ueberf uhrungszahlen der lonen f iir Lithium- und Kohlen- saureverbindungen. Wied. Ann., /j, 289; Dissert. Breslau. Apparatus : (i) superposed glasses ; diaphragms of gold- beaters' skin. The Pt cathode was surrounded by free acid, the anode was of Cd ; the middle portion was tested for free acid and for Cd. (ii) a U-shaped cathode tube with three superposed glasses ; capacity 25-60 c.c. ; Pt electrodes. In the experiments with the carbonates the middle portion was tested for neutrality by litmus after precipitation by barium chloride. For the experiments with the caustic alkalis, porous earthen- ware was substituted for the diaphragms of gold-beaters' skin. The method of calculation is correct. KCl 13-0.23% — g Ag 1 4ex .518 LiCl 6.89 m 18° o-4g Ag lex a. 773 3.21 21° 0-5 i 2 a.753 ± 2 1.78 19° 0.4 2 a. 738 zb 9 0.809 17° 0.4 4 a. 739 ± 7 0-235 iq° 0.2 2 a.7i8±8 0.118 14° 0-5 a. 694 0.103 13° 0.4 a.705 0.046 i6° 0.4 a. 670 0.039 17° 0.3 a.679 Lil 3.12m 17° 0.2 lex a.719 1.41 20° 0.2 2 3.712 ±4 i882 Lenz] ABSTRACT 0.67 17° 0.2 i 2 a.727± 17 0.66 i9» 02 i I a. 700 0.33 19° 0.2 i 2 a. 706 ± 1 0.074 16° 0.2 ' 3 a.692 lb 9 0.037 H° 0.14 • 3 a.702 ± 9 0.014 '4° O.I i 2 a. 682 ifc 2 K,CO, 8.112m 26° o-5g Ag i i 2ex C.341 ±0 3-15 23° 0.8 i i 2 C.404 db I 1.61 22° 0.5 i i 2 C.416 dr 0 0.764 22° 0.3 i i 2 c-437 ± 7 0.441 24° 0.2 i i I c-434 0.151 21° 0.2 i i 2 c-377 ± 3 0.074 24° 0.14 1 i 2 C.372 ± 4 0.029 24° 0.07 i i 2 C.302 ± 7 Na,CO, 2.84m 23° o.4g Ag i i 2ex C.530 zb I 0.985 23° 0.4 i i 2 C.548 ±: 0 0.189 24° 0.2 i i 2 c.5i9±o 0.093 24° O.I ' i i 2 C.474 zb 7 LijCOj 0.232m 25° o.2g Ag i i 2ex C.582 dz 5 0.136 21° 0.2 i i 2 c-593 ± 9 LijSOi 0.159m 23° o.2gAg i i 2ex C.649 rb 4 0.090 22° O.I i i 2 c-595 ± 3 KOH 0.804m 23° o.6g Ag i i 2ex c.739zb8 0.190 27° 0.3 i i 2 C.730 db 0 0.103 22° 0.2 1 i 2 C.742 d= 10 NaOH 1 .084m 25° o.6g Ag 1 i 2ex C.827 zb 4 0.285 230 0.3 1 i 2 C.800 zb 5 0.108 21° 0.1 1 i 2 C.843 ± 4 LiOH 1.495m 25° o.4g Ag i i lex C.890 0.402 21° 0.4 i 2 C.863 ± 3 0.201 21° 0.4 i i 2 C.848 ± 9 25 1882. R. Lenz. Ueber das galvanische Leitungsvermogen alkoholischer Losungen. Bei- blatter, 7, 399, from M^m. de St. Pdtersb. (7), Jo, 64. The transference of the iodine in aqueous and alcoholic solu- tions of Cdlj and of KI was determined in an apparatus con- sisting of an H-tube fitting on top of an anode vessel. The contents of the latter were analyzed, The following table con- tains the values of n for iodine obtained by the author by inter- polation from his experiments. The percent of alcohol in the solutions is given at the head of the column, the concentration of the Cdl2 in the first column. The method of calculation is based (wrongly) on constant volume of solution. 26 McBAIN [1882 Lenz o 5 10 ^5 20 25 30 {m I-I35 l.IIO 1.089 1-073 1.072 1.077 1.088 ^m 1.044 1.021 1.017 1.022 1.032 1.044 1-057 im 0.929 0.914 0.915 0.922 0-934 0.952 0.974 Jm 0.808 0.818 0.831 0.851 0.876 0.899 0.928 3S 40 45 50 55 60 (>5 im 1.108 1. 130 1.160 1-193 1.226 1.262 1.300 ^m 1.070 1.088 1.120 1-159 1.192 1.229 1.265 im 1.000 1.028 1.058 1.089 1.121 1.160 1.19S im 0-959 0.989 1.019 1.052 1.088 1.127 1.170 70 75 80 85 90 95 Im 1-338 1-378 1.417 1.460 1-502 1-549 2"! 1-305 1-3^4 1.384 1.427 1-471 1-515 im 1.239 1.282 1.329 1-375 1.421 1.470 im 1.212 1.262 1.306 1-357 1.404 1.45S With solutions of potassium iodide the values « = .5ii to n = .520 were found independent of the concentration and of the amount of alcohol present. The experiments with potassium chromate were carried out in a slightly modified apparatus, in which a Pt cathode sur- rounded by potassium carbonate solution, and a Mg anode were employed ; n = .46 — to w = .51 — independent of the concen- tration and of the percent of alcohol. The paper further contains a number of measurements of conductivity and diffusion. 1885. J. Moser. Elektrische und thermische Eigenschaften von Salzlosungcn. Wien. Sit- zungsber., g2, Abth. II, 652. The author calculated the migration values by means of the formulae of Helmholtz from the E.M.F. of concentration cells with and without diffusion. ZnClj + 100 H2O and ZnCl^ + 750 HjO lex .71— ZnSO^ + 100 HjO and ZnSO^ -f 800 H^O lex .64— 1886. 0. Lodge. On the Migration of Ions and an Experimental Determination of Absolute Ionic Velocity. Brit. Assoc. Rep., 1886, 389. In the following series of experiments, two cups were con- nected by a horizontal siphon. When the current was passed through, the ions from the cups moved through the siphon, their progress being followed by a color change or by the formation of a precipitate. l88S Loeb] Cups. BaClj. NajSO^ 10% BaCl.,, Na^SO, 5% BaCl^, Na^SO^ 5 7o BaClj, NaCl BaClj, KI BaClj, KBr 10% SrCl,, NaCl 10% SrClj, KBr 10% SrCI,, KI 10% CuSO,, H.SO^ CUSO4, CuSO^ CuSO,, NaOH (NHJ,SO„- ABSTRACT S if /ton. 6% IICI, litmus 23ex 6% HCl, litmus i4ex CjH^Oj, agar agar gex C,n^Oa, IL^SO^, AgNOj, agar agar 4ex CjH^Oj, I IjSO^, AgNOj, agar agar sex CjlliOj, HjSO^.AgNO;,, agar agar 3ex CjH^Oj, H2SO4, AgNOj, agar agar 2ex C^H.Oj, lI,SO^,AgNO„ agar agar 2ex C3II4O2, HjSOijAgNOj, agar agar 2ex NaCl, BaCl^, NaOH, phenol phthalein 3ex NaCl, K.FeCje lex NaCl, phenol phthalein lex NaCl, Nessler solution lex 27 = i Ba/SO, Ba/SO« Ba/SO^ Ba/Cl Ba/I Ba/Br Sr/Cl Sr/Br Sr/I HVSO,= 1888. M. Loeb and W. Nemst. Zur Kinetik der in Losung befindlichen Kdrper. Zeit. phys. Chem.,^, 948. Apparatus similar to Gay-Lussac's burette, with side tube at top for cathode ; anode at bottom ; capacity 60 c.c. ; Ag elec- trodes. In preliminary experiments with silver nitrate the loss in the whole apparatus was 0.06 percent, the loss in the middle portions was 0.5-0.7 percent; no diaphragms ; method of cal- culation correct. The paper further contains a number of conductivity meas- urements in confirmation of Kohlrausch's law. AgNOs AgClOa AgClO, 0.1043 m 0.0521 0.025 0.025 0.0105 o 0245 m 0.0247m Ag(C2H5)S04 0.0243m 0.0061 CioH,.S03.Ag CeH,.S03.Ag CjHjOjAg Ag^SiFle AgjSjOj 0.0129m 0.0250 0.0250m 0.0097m 0.0282m 0.0246m 0.0246 ' Absolute velocity of H ion = 2" OH nearly as quick as H." 20° 26° 26° 0° 26° 25° 25° 25° 25° 29° 25° 25° 25° 22° 25° o« 0.0027. o.o8g Ag 0.08 0.05 0.05 0.03 0-05g Ag o.o4g Ag o-05g Ag 0.02 oo3g Ag 0.04 o.04g Ag 0.02g Ag o.05g Ag o.04g Ag 0.05 lex I I I 2 2ex 2ex 2ex I lex I 2ex 2ex 2ex 3ex 2 ac.528 ac.524 ac.522 ac.538 ac.522 ± 2 ac.501 ± 2 ac.513 ±2 ac.387 zb 2 ac.384 ac.390 ac.386 ac.347 ± 4 ac.376 ± I ac.465 ± 2 ac.605 dz I ac.604 d: I 28 McBAIN [188S Loeb CgH.i.SOj.Ag 0.0238m 0.0222 0.0222 24° o.o6g Ag 29° 0 04 0° 0.04 lex I 2 ac.293 ac.295 ac.273 zh 0 1889. C. L. Weber. Ueber absolute Geschwindigkeit der lonen. Zeit. phys. Chem., 4, 182. The author deduced the following migration values from measurements of the limiting current density at which normal products appear at the electrodes and above which secondary reactions occur. The third column below gives the velocities in mm. per second. CuSO^ I of So.i6g Cu per litre 0.017 \ of 8o.i6g Cu per litre 0.023 \ of 8o.i6g Cu per litre 0.024 y'j of 8o.i6g Cu per litre 0.028 jJtj of 8o.i6g Cu per litre 0.021 ,j\ of 8o.i6g Cu per litre 0.022 jI^^ of 8o.i6g Cu per litre 0.033 ^^^ of 8o.i6g Cu per litre 0.042 CdSO^ 0.1 m 0.023 0.04 0.029 0.02 0.026 o.oi 01036 0.005 0.045 0.0025 0-051 Zn(N03)2 0.2 m 0.091 0.1 0.1 1 1 0.04 0.095 0.02 0.077 0.01 0.084 0.005 0.051 0.0025 0.052 0.0012 0.051 i8go. A. Chassy. Nouveau Transport Electrique. Ann. chim. phys. (6), 21, 241. The author determined the movement of one component of mixtures of salts in aqueous solution. Misled by assuming that the decomposition products at the electrodes indicated the salt that had carried the current, he had to explain the observed movement of the other salts present by the assumption of the movement of non-dissociated molecules. In the following list the first salt was in each case the only one measured. Many cases are omitted in which only one component of the mixture was indicated. For summary see Ponsot — Comptes rendus, 138, 192. 1892 Bein] ABSTRACT 29 Sulphates of Zn, Cu. " Zn, Cd. " " Zn, Ag. " Zn, Na, Mg, Cu. " Zn, Cu, Ni, K. Nitrates " Ba, Ag. " Ba, Cu. " Ba, Ni. " Ba, Zn. " Ba, K, Cu. " " Ba, K, Cu, Na, Zn, Mg, Co, Ag. " Pb, Ba, Zn, K. " Cu, Ba, Ag, K. Chlorides " K, Zn. " " Ca, Na, Zn, Cu. " Zn, Ba, Mg, K. Sulphates " K, Cd, Cu, with acetate of Zn. K.^SO„Zn(C2Hj02)j. Zn(C2H30.Jj, K^SO,, Na^SO,, NaCjHjOj. 1890. W. Kistiakowsky. Die wasserigen Losungen von Doppelsalzen. Zeit. phys. Chem., 6, 97. Apparatus a knee-shaped burette; capacity lOO c.c. ; Ag electrodes; no diaphragms ; middle portion unchanged. The concentrations are expressed in mols per looog solution. AgNOj 0.0189 15' o-04g Ag lex ac.531 AgsCr(CjOJ3 0.022 14° o.osgAg 3ex ac.57- ± 18 1892. W. Bein. Beitriige zur experimentellen Bestimmung von Ueberfiihrungszahlen in Salz- losungen. Wied. Ann., 4b, 29. Apparatus of three types, capacity 55-90g, viz. ; (i) super- posed glasses with diaphragms of fish bladder (B), or usually of porous earthenware (E) ; (ii) a winding spiral and U-tube, no diaphragms ; (iii) a knee-shaped burette. In experiments with CuSO^, CdClg, CaCU, and CdL the volt- age was varied from 20-100 volts without affecting the results » In the fifth column below are given the concentration changes in the middle portions; the values in the last column given in ( ) are those obtained by Bein in 1899 by a recalculation. The method of calculation is correct ; the accuracy of the better experiments is estimated to be one or two units in the second decimal place. 30 McBAIN [1892 Bei CuSO, o.73%Cu 20-30° o.o6g Cu 0.6-0.06% E 6ex a.647 zb 24 0.73 16-19° 0.05 0.5-0.1 ii 2 ac.638 zh 2 0.76 16-24° 0.06 0.4-0.03 B 8 a.79-±i7 0.76 74° 0.05 1-5 ii I ac.622 KCl o.4i%Cl 18-19° o.o6g CI 0.1% B 2ex a.496 zfc 3 (.530) 0.6 74-75° 0.03 0.3 ii 2 ac.509 zh 9 AgNOj i-85%Ag 13-15° o.o6g Ag 0.5-0.05% iii 3ex ac.525 ± 3 0.6 75-96° 0.06 2-0.4 iii 6 ac.512 =h6 NaCl o.92%Cl 7-8° o.o6g CI o-3% ii 2ex ac.6o8 zh 3 0.92 95° 0.05 0.8-0.1 ii 3 ac.551 =h2 BaClj, 0.84% CI 12° o.o7g CI 1-0.3% ii 2ex ac.580 zb 2 0.84 89° 0.07 0.5 ii I ac.565 0.58 74° 0.05 0.6 ii I ac.580 Cdlj 0.68% I 20° O.Igl 1-0.4% i, ii E 3ex ac.65- zb 25 (•652) 0.68 76° 0.06 1-5 ii 2ex ac.6oozb 13 CdClj 0.9% CI 8° o.o5g CI 0.7% ii 2ex ac.567zb 2 0.6 21° 0.6 0.6-0.01 i E 4 a. 546 ^z 20 (•557) 0.87 96-97° 0.07 0.8-0.5 ii 2 ac.570zb5 CaCl, o.8%Cl 9° o.o5g CI 1-0.1% ii 2ex ac.6o2 zb 2 0.45 i6° 0.08 0.3-0.04 i B 6 a. 610 zfc 16 (•638) 0.85 94° 0.04 0.2 ii I ac.549 1892. W. C. D. Whetham. Ionic Velocities. Proc. Roy. Soc, ji", 284. Zeit. phys. Cliem., //, 220. Phil. Trans., 184, A, 337. The author measured the velocity of the meniscus between pairs of solutions of electrolytes, first with direct, and then with reversed current. The apparatus consisted of two vertical tubes joined by a third much narrower tube bent parallel to the others for the greater part of its length. Two solutions of equal spe- cific resistance were placed in the apparatus, the specifically heavier below the other. The surface of contact lay in the narrow vertical tube, where the fall of potential per cm. could be determined. In the following table, the salts experimented with are named in the first column, and in the succeeding columns in order are given the concentrations, the solvent (W = water, Am = aqueous ammonia, Al = '* alcohol of 0.05 strength "), the ion to which the rate of the meniscus movement was ascribed, the number of experiments, the observed velocity in cm. per second per unit 1S93 Sheldon] ABSTRACT 31 potential fall, and the velocity calculated from Kohlrausch's conductivity measurements and Hittorf's migration determina- tions. In the case of the alcoholic solutions, for lack of migra- tion determinations, the sum of the observed ionic velocities is compared with that calculated from the conductivity. CuClj and NH^Cl CuCIj and NH^Cl KCl and KMnO^ KCl and KMnO^ KjCrjO, and K.,CO;, KjCr^O, and KCl CoCNOs), and CoClj CoClj and CaCl^ Co(N03)j and CaCNOj), 1893. S. Lussana. Einfluss der Temperatur auf die elektromotorische Kraft der Concentrations- elemente und die Wanderung der lonen. Beibliitter, //, 218, from Atti del R. 1st. Venet., Ser. VII, j, iiii (1892). Apparatus : Horizontal tube bent into five parallel portions, with vertical tubes sealed on at the ends and at the middle ; 3 (?) middle portions. The author found the migration of the cation (i-«) propor- tional to the absolute temperature {T). In the second column below is given the weight of salt in lOOg water ; in the third the value found for io''{i-n)/T; and in the last the transport of the anion at o° C. o.iSm Am Cu lex 0.00026 0.00031 o.i Am CI lex 0.000309 0.00031 0.0046m W CI lex 0.00057 0.00053 0.046 W CI lex 0.00059 0.00053 o.im w Cr,0, 3ex 0.00047 0.00047 0.1 w CrjO; lex 0.00044 0.00047 0.05m 0.05m Al Al CI f Co 2ex 2ex 0.000026 0.000022 • 0.000060 Al Co lex 0.000035 0.000044 } 0.000079 ZnS047H20 57.694-2.319 26632-25244 .27-.31 CuSO,5H50 5.008-0.712 24627-22076 •33--40 Pb(N03), 26.512-4. 618 I 8955- I 5982 .48-53 1893. S. Sheldon and G. M. Downing. Die kritische Stromdichtigkeit fiir Kupferniederschlage und die absolute Geschwindigkeit der Wanderung der lonen. Beibliitter, /^, 1090, from Phjs. Rev., /, 51. The author deduced the migration values from measurements of the limiting current density at which normal products appear at the electrodes, and above which secondary reactions occur. The velocity is presumably in cm. per second for unit potential fall. CUSO4 0.1- 1. 89m 0.00020-0.000445 32 McBAIN [1894 Campetti 1894. A. Campetti. Ueber den Einfluss des Losungsmittels auf die Geschwindigkeit der lonen. Beiblatter, j8, 942 (from Nuov. Cim. (3), JJ, 225). LiCl water ac.705 ethjl alcohol ac.71- methyl alcohol ac.64- AgNOj water ac.518 ethjl alcohol ac.51- methyl alcohol ac.47- 1894. S. Lussana. Einfluss von Magnetismus und Warme auf die Wanderung der lonen. Beiblatter, 18, 364; (from Atti R. 1st. Veneto (7), 4, 13 pp., 1893, Sepab.). An extension of the author's work of the year before, with the same apparatus. In solutions of NiSO^, NaCl, KCl, and CuCl, the relative velocity of the cation (i-«) is proportional to the absolute temperature. In order to ascertain whether magnetism exerts any notice- able influence on the transport, measurements were made of the rate of motion of the meniscus between acidified solutions of ferrous and cupric sulphates in and out of the magnetic field. The author finds that magnetism probably slightly reduces the rate of the ferrous ion ; the resistance of ferrous sulphate solu- tion is not noticeably affected by a magnetic field whose lines of force are perpendicular to the direction of the current. 1894. W. C. D. Whetham. On the Velocities of the Ions and the Relative lonization-power of Solvents. Phil. Mag., j5, 392. For apparatus, method and explanation of the following table, see Whetham, 1892. In these experiments the solutions were solidified with agar agar jelly. In the experiment with sodium acetate one half of the solution was colored red by caustic soda, the other half "decolorized by means of a few drops of dilute acetic acid." A measurement was made of the rate of motion of the red color at the boundary between solutions of ferric chloride and ferric acetate (containing ferric chloride) ; in order to explain his results the author ascribed the color to colloidal ferric hydrate, and adduced a number of conductivity measure- ments and experiments with dialyzed iron, in support of this view. 1896 DesCoudres] _ ABSTRACT 33 KjCrjO, and K.^COj o.i in W Cr,0, lex 0.00044 0.00047 NaCjHjO, 0.07m W II lex 0.000065 0.00030 1895. W. C. D. Whetham. On the Velocities of the Ions. Phil. Trans., 1S6, A, 507. An extension of the author's work in 1892 and 1894. The same apparatus was employed. The solutions were solidified by the use of agar agar. The rate of extension of the precipi- tate formed at the surface of contact was measured ; the cur- rent being passed in one direction only. The experiments were carried out at from 8-17° and corrected for 18°. The solutions were o.i m. BaCl^ ; and NaCl + " a little " NajSO^ CaClj ; and NaCl + " considerable " Na^COj AgNOj-, and NaNOj + " a little " NaCl Na.,SOi; and NaCl + BaClj 1896. C. Cattaneo. Ueber den Einfluss des Ldsungsmittels auf die Geschwindigkeit der lonen. Beibliitter, ^/, 749 (from Rendic. R. Ace. del Lincei (5), J, 2 Sem. 207; 6, I Sem. 279. Nuovo Cim. (4), 6, 140.) With sodium chloride and ammonium chloride a Pt cathode and a Zn or Cd anode was used ; with hydrochloric acid the anode was of Au or Cu. NaCl NH.Cl HCl Ba 2ex 0.000389 0.000366 Ca lex 0.000349 0.000290 Ag lex 0.0004S8 0.000462 SO4 2ex 0.000447 0.000492 water .66- glycerine .64- ■water •51- glycerine •57- water .224 ethyl alcohol .205 methyl alcohol .236 amyl alcohol .240 glycerine • •237 ethyl alcohol with chloroform * .209 ethyl alcohol with chloroform and ethyl ether .218 1896. Th. DesCoudres. Messungen der elektromotorischen Kraft Colley' schen Gravitationselemente. Wied. Ann., j7, 232. From measurements of the E.M.F. of gravitation cells with electrodes of Hg/HgjClg the author deduced the following values for n. Proc. Wash. Acad. Sci., June, 1907. 34 McBAIN [i896DesCoudres McBAIN NaCl 19.9 percent .66- BaCl^ 17.0 " .64- LiCl 17-3 " •77- KCl 16.8 " .50- HCl 3-56 " .150 CdClj 30.1 " I.02-I.I0 i8g6. A. Rosenheim. (Experiments by W. Bein.) Ueber die Einwirkung anorganischer Metall- sauren auf organische Sauren. Zeit. anorg. Chem., //, 175, 225. Apparatus : two U-tubes connected by a siphon ; capacity io8g ; Pt electrodes ; no diaphragms ; no middle portion. The object of the investigation was to determine the constitution of these complex compounds. Concentration 1-2 percent ; one experiment each ; 18° C. In the last column is given the com- ponent analyzed. CjO^, Mo, W, and V moved in all cases toward the anode. (NHJ,0.2M0, o.3g Ag f .530 MO3 1 -539 NH, M03.C203.3H,0 o.o8g Ag f -47- C,0, '^'^ 1 .48- MO3 r .306 C,0, K2O.WO3.C2O3.HjO o.2g Ag ac j .327 WO3 ( .540 K (NH,)20.2Cj03.2M03.3H,0 o.3g Ag f .40- C,03 ' 1 .40- MO, (NH,),0.2M0,.C.A 0.2g Ag ac .33- C.,0, 3(NHJ20.V,05.4C,03.4H.,0 0.02g Ag ( .36- c,o, 1 .36- Vfi, " o.ig Ag ac .39- CjO, 3KjO.Al203.6C203.5H,0 o.4g Ag ac .50- CjO, 3K,O.Cr,03.6C,03.6HjO o.6g Ag ac .33- CjO, K,O.Alj03.4C203.7JH20 o.3g Ag ac .39- C,0, 1897. V. Gordon. Ueber die Abhiingigkeit der Ueberfiihrungszahlen des Kadmium in wasserigen Losungen von der Temperatur. .Zeit phvs. Chem., 2j, 469. Apparatus : N-tube fitting into the top of an Erlenmeyer flask ; capacity 100 c.c. ; anode Cd, cathode Hg ; no diaphragms ; method of calculation correct. CuSO^ CdSO, 9-10 percent o.6g Ag 0.07 percent 2ex a .720 ±6 I1.4 9^ I-2g Ag 0.1 " 3ex a .672 ± 10 II.4 40° 1-2 0.1-0.2 " 2 a .717^5 12 " 81° 1.9 0.5 2 a .719^4 34-5 9" 1-9 0.2-0.5 2 a .8o3±o 1897 Nernst] CdBr, CdL 34 34 29-5 29.4 29.4 35 35-5 percent ABSTRACT 40' 3 0.1 69^ 3 0.2-0.6 f I gAg 0.2-0.01 39^ 1-5 0.5-0.00 75° 2-3 1-0.4 40° i-7g Ag 0.1-0.2 74° 2.0 0.17 35 percent. 2 a .8iOrfc6 2 a .797 ±15 3ex a .894 ±5 3 al.040rb34 3 a .970^25 2ex ai.232 ±8 2 ar.23iii 17 1 897. F. W. Kiister. Ueber lonenreaktionen und ihre Bedeutung fiir die Elektrochemie. Zeit. f. Elektrochem., 4, 10$. When a current is passed through a U-tube whose lower half is filled with cupric sulphate solution, while both arms are filled with sodium sulphate solution into which the electrodes are dipped, then the blue layer moves toward the cathode ; when the lower solution is Fehling's solution, and the upper Seignette salt, the blue color moves toward the anode, as the copper is contained for the most part in complex anions. 1897. W. J. Mather. A New Apparatus for Determining the Relative Velocities of Ions ; with some Results for Silver Ions. Johns Hopkins Univ. Cir., /6, No. 130, 45 (1897), Am. Chem. Jour., 26 (1901), 473. Apparatus : an M-shaped tube provided in the middle with a glass tap of large bore ; capacity 90 c.c ; Ag electrodes ; no diaphragms ; no middle portion ; calculation based (incorrectly) on constant volume of solution. AgNOj 0.1 m 0° 0.1 g Ag 3ex ac.541 dr 0 0.1 29" 0.05 I ac.532 0.1 48° 0.15 3 ac.528± I 0.025 0° 0.07 I ac.538 0.025 45° 0.08 I ac.525 0.1 24° 0.15 2 ac.532 zb I 49 percent alcohol 0.108 20° 0.05 3 ac.594 ±1 2 absolute alcohol . AgC.HsO 2 0.025m 0° o.o5g Ag 2ex ac.373 ± I 0.025 28° 0.03 I ac.382 0.025 46° 0.08 3 ac.389 ± I 1897. w. Nernst. Zwei einfache elektrochemische Vorlesungsversuche. Zeit. f. Elektrochem. J, 308. A 0.003m solution of potassium nitrate is placed in the arms of a U-tube over a solution of potassium permanganate of the 36 McBAIN [iS97Nernst same specific conductivity, weighted with urea. During the passage of the current the red layer moves toward the anode with a velocity within a few percent of that calculated from the conductivity of potassium permanganate. 1897. A. Schrader. Zur Elektrolyse von Gemischen. Zeit. f. Elektrochem., j", 498. Auszug aus Berliner Inaug. Dissert. Apparatus: an c/3-tube ; capacity 150 c.c ; no diaphragms. The paper is mainly devoted to the determination of the transport in aqueous solutions containing a pair of electrolytes, viz. : KCl and KI ; HjSO^ andCuSO^. In addition the follow- in(j results of measurements with acetic acid between Ag elec- trodes are given without experimental details. "The rate of transport of acetic acid seems to become constant only at dilu- tions where the error of analysis is nearly as great as the quantity measured." 0.79m .362; 0.74m .307; 0.59m .241 ; 0.48m .212; 0.36m .182: 0.25m .169. 1898. W. Bein. Zur Bestimmung der Ueberf iilirung bei der Elektrolyse verdiinnter wasseriger Salzlosungen. Zeit. phjs. Chem., 27, i. Apparatus of various forms, complete, and somewhat compli- cated ; no diaphragms ; Pt cathode, Cd anode ; method of calcu- lation correct. The capacities of the apparatus are given in hektograms in the sixth column below, the percent changes in the middle por- tion in the fifth column. HCl NaCl Percent Percent. 0.02-0.05 CI 9° 0.02g CI O.I 1-5 2ex aC.167 ±L I 0-035 50° 0.03 5 2 aC.199 ± 0 0.035 96° 0.03 5 3 ac.252 rfc 10 0.2-0.5 i6» 0.03 0.2-2 I 8 ac.i7o±3 0.2-0.5 77° 0.04 0 1 3 ac.219 ± 12 '3-9 97° O.I 1 .-1 I a^-393 0.02-0.05 CI 10° 0.02g CI 0.0-0.3 7 sex ac.615 ± 12 0.040 51° 0.03 5 2 ac.583 ± 5 0.040 97° 0.03 1-5 2 ac.547 ±: 4 0.25 76° 0.03 I I ac.586 0.2-0.9 12° 0.03 0.3-5 I II ac.613 ± 20 0.50 76° 0.03 0 1 2 ac.570 ±1 5 1S98 Bein] ABSTRACT 37 0.2-0.9 95° 0.05 I 4 ac.557±4 12. 1 21° 0-3 1 ■2 I ac.677 14.2 970 0.14 I 2 I ac.567 KCl 0.04-0.5 CI 11° 0.02g CI 0.04-4 1-7 5ex ac.503 ± 20 0.30 76° 0.6 I 3 ac.5iorb2 NII.Cl 0.2 CI 20° 0.02g CI 0.6 I 2ex ac.507 db 6 RbCI 0.19 CI 22° 0.02g CI I icx ac.515 CsCl o.iS CI 20° 0.02g CI I lex ac.508 TlCl 0.04 CI 21° 0.02g CI 5 lex ac.516 LiCl 0.036 CI 20° o.o3g CI 5 2ex ac.624 zfc 4 0.035 970 0.02 5 2 ac.6i7zfc6 0.2-0.5 20° 0.03 I 6 ac.672 ± 9 0.20 96° 0.03 I 2 ac.6io db 9 CaCl, 0.039 CI 22° o.o3g CI I lex ac.553 0.039 49° 0.03 5 I ac.555 0.0391 97° 0.03 5 I ac.530 0.204 97° 0.03 I I ac.554 0.425 97° 0.04 I I ac.574 0.20 25° 0.03 I 3 ac.567 ±40 0.42 24° 0.04 I I ac.595 0.99 21° 0.05 I I ac.6io 14. 1 25° 0.26 h I ac.718 14. 1 97° 0.13 h I ac.79- BaClj 0.040 CI 10° o.o3g CI 7 2ex ac.559± i 0.041 50° 0.03 5 I ac.525 0.041 97° 0.03 5 I ac.515 0.30 10° 0.04 I 2 ac.570 dr 2 0.6-1.0 12° 0.06 I 3 ac.585zbii 0.77 96° 0.03 I I ac.543 0.301 76° 0.03 I 2 ac.553 ±3 0.202 78° 0.02 I I ac.518 CdCl, 0.036 CI 20° 0.02 5 lex ac.557 0.20 24° 0.02 I 2 ac.568 ± 3 0.20 96° 0.03 I 2 ac.475 d= 2 0.50 17° 0.03 I 2 ac.567 ± II 13.8 97° 0.12 h 2 ac.963 ± 3 13-8 24° 0.19 > h I ac.657 AgCjHgO, 0-43 Ag 24° o.oSg Ag lex ac.4i3Pt elec. 0-43 24° 0.07 I a.385' c.4i4Ag/Pt 0.43 49° 0.07 I c.4i2Ag/Pt 043 96° 2 C.438 ± 4 AgNO, 0-54 Ag 76° o.o4g Ag 0.2 I lex ac.517 0.40 96° 0.07 I ac.482 H,SO, 0.24 112804 11° o.o5g SO4 3ex ac.i75d=3 0.24 23° 0.05 I C.200 0.24 96° 0.05 2 ac.304 dz I 'Sui jeroxide formed at an ode- 3» McBAIN [iSgSBt CuSO^ 0.032CU 1° o-03g Cu 6 lex ac.615 0.032 15° 0.02 ( 5 I ac.633 0.30 0° 0.03 r I ac.6ii 0.30 50° 0.04 [ I ac.607 0.73 15° 0.05 I I ac.632 0.76 74° 0.05 [ I ac.622 0.30 97° t 5 ac.2i- to .47 SrClj 0.04 CI 21° o.03g CI 5 lex ac.560 0.20 20° o-o3g [ I ac.575 MgCl, 0.17 CI 21° 0.02g CI [ lex ac.615 MnCl, 0.20 CI 18° o.o3g CI 1.5 I lex ac.613 CuCl^ 0.18 CI 23° o.o3g CI [ lex ac.595 CoCl, 0.20 CI 18° o.o3g CI I ] [ lex C.596 9.8 26° 0.16 , k 2 ac.736 it 0 9.8 97° 0.13 h 2 ac.77- rh 2- NaBr 0.39 Br 22° o.osg Br ] [ lex ac.625 KI 0.63 I 25° 0.1 g I ] [ lex ac.505 HNO3 0.32 HNO3 25° o.o6g NO3 ] [ lex ac.172 NaNOs 0.33 NO3 19° 0.02g NO3 [ lex ac.629 TljSO^ 0.25 SO, 23° o.o3g SO, ] [ lex ac.528 MgSO, 0.24 SO« 24° o.o5g SO, J I ex ac.541 Na^COa 0.16 CO3 22° o.oi4g COj ] 2ex ac.590 ± 10 K,C03 0.13 COs 23° o.oi4g CO3 ] lex ac.435 Pt/Pt. NaOH 0.16 NaOH 25° o.o3g NaOH 1 lex ac.799 " NH^OH o.i8NH,OH 21° o.oi4g NH,OH 1 lex ac.562 " Ca(OH)2 o.ii Ca(OH), 24° o.o3gCa(OH), ] lex ac.786 " KMnO, 0.85 KMnO, 23° o.igKMnO, 1 lex ac.559 " HjCjO, 0.25 H,C,0, 26° o.o4g HjCjO, I lex C.214 " Succinic Acid 0.59 S.Ac. 23° o.o4g S.Ac. ] lex C.239 " i8g8. H. Hoffmeister. Ueber Stromleilung in gemischten Losungen. Zeit. phys. Chetn., 2y, 345. Mixtures of from 1-9 parts of a solution of silver nitrate with 1-9 parts of a solution of nitric acid, and of 1-9 parts of sodium acetate with 1-9 parts of acetic acid, all four stock solutions being normal, were electrolyzed. The concentration changes for the cations of the nitrates were in accordance with that de- duced by means of Rudolphi's dilution formula ; for the sodium in the acetate mixture in accordance with Ostwald's dilution formula, while the acetic acid moved if at all toward the anode. 1898 Kiimmell] ABSTRACT 39 i8g8. K. Hopfgartner. Ueber Stromleitung in gemischten Ldsungen von Elektrolyten. Zeit. phjs. Chem., 2j, 115. For apparatus see Gordon, 1897 ; capacity 250 c.c. The Hg cathode was surrounded by a concentrated solution of ZnClj ; for the electrolyses of sodium, hydrogen, and barium chlorides the anode was of Cd, for those with magnesium and cupric sul- phates Cu was used. No diaphragms. The changes in the middle portions are listed in the fourth column below; ig Ag in voltameter ; method of calculation correct. The paper also contains determinations of the transference in solutions of NaCl and HCl, BaCl^ and HCl, MgSO, and CuSO^, in widely different proportions, the concentrations vary- ing from o.i-i.om per liter. The results are in accordance with those calculated from the conductivities of the salts taken separately, using Rudolphi's dilution formula. NaCl o.im 16-17° 0.2-0.5 percent 3ex a.617 zb 14 0.2 13-19° 0.2-0.5 2 a.622 zfc I 0.5 9-23° 0.2-0.5 3 a.623 zb 3 0.8 13-19° 0.2-0.5 3 a.635 ± 2 0.9 13-20° 0.2-0.5 3 a.635 ± 4 HCl o.im 15-18° 0.1-0.7 " sex a. 167 zfc 20 0.2 17-19° 0.0-0.5 4 a.i64zfc3 05 13-26° 0.1-0.4 " 9 a.167 ± 18 0.8 14-20° 0.1-0.3 6 a.i57zh 10 0.9 13-20° 0.1 " 3 a. 159 rb 10 BaClj o.im 14-18° 0.4-0.2 " 4ex a.580 d= 13 0.2 15° 0.4-0.2 " 2 a. 592 ± I 0.5 11-15° 0.4-0.2 " 5 a.6ii zb 16 0.8 12-20° 0.4-0.2 " 5 a.617 ±: 21 MgSO, l.om 10-15° 0.4-0.2 " 3ex a. 749 ± 5 1-3 10-13° 0.4-0.2 " I a. 747 CuSOi i.om 6-11° 0.1 " 3ex a.696zb6 0.7 8-15° 0.1 " 2 a.684 zb 7 i8g8. G. Kiimmell. Die Ueberfiihrungszahlen von Zn- und Cd-Salzen in sehr verdiinnten Losungen. Wied. Ann., 64, 655. (i) The cathode vessel is attached to the top of the anode vessel by means of a side tube packed with cotton wool ; capacity 175 c.c; no change could be detected in the middle portion; Pt cathode ; for Zn salts Zn anode, for Cd salts Cd anode ; ap- 4© McBAIN [1898 Kummell parently the incorrect method of calculation based on constant volume of solution was used. ZnCI, o.oi-o.oo3m 0.030 Zn 4ex ac.603 dt 19 ZnBr, 0.01-0.003111 o.o2g Zn 3ex ac.6oo zh 12 Znl, 0.01-0.0031x1 o.02g Zn 3ex ac.589 =b 12 CdClj 0.01-0.00301 o.05g Cd 3ex ac.576 ± 8 CdBr, 0.01-0.003111 o.o5g Cd 3ex ac.584 =b 9 Cdlj 0.01-0.003111 o.o4g Cd 4ex ac.552 ± 9 ZnSO^ o.oi-o.oo3m o.03g Zn 4ex ac.664 d= 7 CdSO, 0.01-0.00301 o.o4g Cd 4ex ac.619 ±: 15 (ii) By means of Helmholtz's formulae, from the E.M.F. of concentration cells. ZnCl., o.i-o.ooim 4ex .585 i 3 CdCl, o.i-o.ooim 4ex •574 ± 10 ZnSO^ 0.025-0.001 m 2ex .587 ± 2 CdSO, 0.025-0. ooim 2ex .627 ±: 2 i8g8. D. Mcintosh. The Transference Number of Hydrogen. Jour. Phys. Chem., 2, 273. The transference number was obtained from the ratio of the E.M.F.'s of concentration cells with and without diffusion, making use of the formulae of Helmholtz. (i) Electrodes of hydrogen (platinised platinum), and mercury plus mercurous salt. HCl i.o-o.ooim 6ex •159 ±3 HBr " 6ex .158 ±6 HI " 6ex .161 ±1 18 H,SO, " 6ex .174 ±18 H,C,0, " 6ex .163 ±: 16 (ii) Electrodes of hydrogen and chlorine (platinised platinum). HCl i.o-o.i m lex .126 i.o-o.oi lex .297 o.i-o.oi lex .404 i8g8. 0. Masaon. Ueber lonengeschwindigkeiten. Zeit. phys. Chem., 2g, 501. Phil. Trans., 1899, /g2, 331. Apparatus : two electrode chambers (flasks) connected by a narrow tube containing the gelatinized solution to be measured. *' Indicators " were placed in the flasks (cupric sulphate or chlor- ide at the anode, and potassium chromate at the cathode), and 1899 Bein] ABSTRACT 41 the current passed until blue met yellow. Electrodes : Cu anode, Pt cathode; i8° C. 18° NH.CI I .oin KCl 0.5m ,.io 3 NaCl 0.5111 I 2 LiCl 0.5111 I K,SO, 0.5-im NajSO^ i-o.5m LijSO, 2-o.5m MgSO, 2-0. 5m 898. R. Peters. lex ac.490 lex ac.495 lex ac.490 lex ac.483 lex ac.598 lex ac.595 lex ac.587 lex ac.687 I ex ac.68o 2ex ac.467 ± 0 2ex ac.567 ±z 0 3ex ac.658 ±6 3ex ac.693 ± 9 Ueber Oxydations unci Reduktionsketten und den Einfluss komplexer Jonen auf ihre elektromotorische Kraft. Zeit. phjs. Chem., 26, 229. Apparatus — a U-tube into both arms of which were dipped tubes closed at the lower end with parchment forming the anode and cathode compartments respectively, in the U-tube were plugs of cotton batting; Pt. electrodes; no middle portion. The results are only qualitative, and show that in a solution of FeFl3.3NaFl + iHjO containing 0.8 mg iron in i c.c. the iron moves toward the anode, presumably in the form of FeFlg"'. In the case of an equivalent solution of Fe2(SOj3 under the same conditions the difference in titration value of a constant weight of solution before and after electrolysis was three times as great ; here the iron moved towards the cathode. i8gg. W. Bein. Einige Versuche iiber die Abhangigkeit der Ueberfiifirungen von Salzen von der Beschaftenheit dei- Membranen, vvelche die Elektroden-Losungen voneinander trennen. Ein Beitrag zu dem Verhalten von Membranen gegen Salzlosungen. Ze'*^. phjs. Chem., 28, 439. Apparatus : superposed glasses with diaphragms, viz. ; earth- enware (earth), fish bladder (fish b), parchment (parch), gold- beater's skin (gold). Capacity 200g ; Pt electrodes in the ex- periments with CdCl. 20-22° C. On page 447 of the paper is given a comparative table of Proc. Wash. Acad. Sci., June, 1907. 42 McBAIN [1899 Bein the results of Hittorf, Kuschel, Kirmis, and of the author, for the experiments in which diaphragms were used. HCl 0.207 percent CI 0.4 g CI earth lex a. 167 0.207 " " 0.4 parch I a. 1 76 0.297 " " 0.4 fish b I a.29- 0.208 " " 0.4 gold I c.29- NaCl 0.20 " " 0.2 g CI 0.05 percent earth 2ex ac.6oi zb I 0.2-0.3 " " 0.3 2-3 fish 6 ac.7i8zb27 LiCl 0.27 " o.05g CI 2-6 percent gold 3ex c.739±i7 CaCl^ 0.22 " " o.o3g CI earth lex a.582 0.22 " " 0.03 fish 4 a-733±i9 0.22 " " 0.03 gold 2 a. 805 ±: 0 CdClj 0.20 " " o.o4g CI 4 percent fish lex ac.763 0.68 " 0.06 earth I C.53S i8gg. W. Dittenberger und R. Dietz. Ueber das elektrolytische Verhalten des Platin- und Zinnchlorids. Ann., 68, 853. Wied. Apparatus : (i) anode and cathode cylinders connected at the bottom by a tube of 0.5 mm. diameter bent seven times ; (ii) and (iii) a similar tube bent three times (W-shaped). Capacity of (i) and (ii) 25-30g, of (iii) 300g ; Pt electrodes ; no diaphragms ; no middle portion. The weight of Ag given below is calculated from the ampere-minutes. The solutions were analyzed only for Pt and Sn. The method of calculation is incorrect (con- stant volume of solution instead of constant amount of water). Although the conductivity greatly increases, the migration num- ber is unaffected by setting the solution of H2.PtC1^0 in sunlight for 14 da3^s. Hj.PtCl.O 0.50 m 0.002 g Ag 0.44 0.002 0.41 0.003 0.36 0.003 O.IO 0.0006 O.OI 0.0006 0.005 0.0003 llj.PtCle 0.22 m 0.002 g Ag 0.007 0.0008 SnCI^ 6.6in 0.005 g Ag 1.2 0.002 lex ■p is the pressure in atmospheres. xgoi. H. Jahn's Schiller. Ueber die Wanderungsgeschwindigkeit der lonen in verdiinnten Ldsungen. Zeit. phys. Chein., J7, 673 ; 3S, 127. Apparatus : N-shaped tube fitting on top of the Erlenmeyer- flask-like anode compartment ; capacity of the anode vessel 300-700 c.c. ; no diaphragms ; Hg cathode surrounded by a concentrated solution of copper nitrate or cadmium sulphate ; i8°-i9° ; calculation correct. In the fourth column I have calculated the percent change in the middle portion. Bogdan. Percent. HCl o.o3i-o.(X)9im o.4g Ag o.i i7ex a .I74±6 Zn anode Bukschnewski. HNO3 0.25-0. 0066m o.2-4g Ag O.I-O.OI 23ex a .170 ±4 Ag (( Bogdan. KCl 0.03-0. 008m o.4g Ag O.I iiex a •503 ± 2 Zn " NaCl 0.03-0.008111 o.4g Ag 0.03-0.1 I2ex a .604 zfc 2 " " KBr 0.03-0.01 m o-4g Ag 0.03 gex a .504 ± 2 " " 0.069-0.034 0.5 O.I 6 a .500 ± 2 " <■<■ 1 o.oi 7-0.01 1 0.2 0.13 4 a •495 ± 3 " •., Na.CuPO,) is deduced from the movement of the heavy- metal toward the anode. The movement toward the anode of the green solution of chromic hydroxide in strong alkali demonstrates the existence of chromites ; the chromic hydroxide is not merely dissolved as colloid, for it can diffuse through parchment into alkaline solu- tion. Similarly the zinc in potassium zincate becomes more concentrated at the anode. 1903. S. C Lind. The Constitution of Potassium Ruthenium Nitroso-chloride in Aqueous Solution. Jour.j^m. Chem. Soc, 2j, 928. A 0.025 m solution was connected by siphons containing 0.05 m potassium chloride solution solidified by agar agar with anode and cathode compartments containing Pt electrodes sur- rounded by hydrochloric acid and potassium hy^drate respec- tively. A pink color moved toward the anode while no color change occurred in the cathode siphon. This shows that ru- thenium is contained in an anion, presumably RuCl^NO" ; the author further concluded that it proved that no cation contains ruthenium. 1903- J- W. McBain, Electrolytic Migration in Solutions of the Weak Acids. This paper has not been published in full; abstracts have appeared in Trans. Roy. Soc. Canada, May, 1903, and 1904, and in Trans. Am. Electrochem. Soc, 4, 184. (1903). Apparatus : many forms, mostly pairs of U tubes ; capacity 40-350 c.c. ; Pt. electrodes ; o.04g Ag ; diaphragms of cloth or bundles of small tubes ; 2-5 middle portions, the real one un- changed within 0.00 to 0.05 c.c. of decinormal alkali. The author eliminated the irregular and uncontrollable reac- tions occurring at the electrodes during the electrolysis of acetic and propionic acids, which would otherwise have discredited the results, by surrounding the electrodes with long columns of solutions of sodium sulphate, sulphuric acid, hydrochloric acid, etc. This made the apparatus complicated and the manipula- tion difficult. The electrode solutions were carefully tested for in the middle portions, but were usually altogether absent, and in no case present in quantity sufficient to cause an error of 20 percent in the result. An experiment with hydrochloric acid, H.C.HgO, 0.02-i.om 30° I7ex H.C3H50, o.im 30° I HCl 0.018m 30° I 62 McBAlN [1903 McBain using the same apparatus and protecting solutions gave a normal result. " " " ac.31- ac.34- ac. 19- 1903. P. Straneo. Zeit. phvs. Chem., 44, 640, from Rendic. Accad. Lincei, 1902, /, 58, 171. The author measured the E.M.F. between two electrodes placed in a solution of zinc sulphate just after a momentary current had been passed through ; the migration value calculated from the concentration changes thus indicated agreed with that obtained by the usual analytical method. 1903. F, Vogel. Untersuchungen liber Nitrite. Zeit. anorg. Chem., 3J, 410. Apparatus like Jahn's ; capacity of anode compartment 187 c.c. ; Cd anode ; middle portion unchanged. The barium was determined as BaSO^. The results are calculated incorrectly (based on constant weight of solution instead of constant amount of water). Ba(NOs)2 0.025-0. 032m 0.3-0. 6g Ag 2ex a.5SS =b 6 1904. F. Aletter. Die Jonenkonzentrationen ternarer Elektrolvte. Dissert. Rostock, results quoted by Kiimmel, Zeit. f. Elektrochem., //, 98, 1905. Pt electrodes ; no middle portion ; capacity of cathode com- partment 100 c.c. ; method of calculation incorrect (based on constant volume of solution instead of on constant amount of solvent). Further I think the number given below as the migra- tion of the C^O/' ion is really that of the cation K". In the case of lithium sulphate Aletter's calculation contains, in addition to the two systematic errors I have already mentioned, the further assumption that SO/' is monovalent. In the last column I have eliminated all but the first error. Aletter. McBain, K,C,0, i.o m 16° 0.2 g Ag C.24- .76- 0.5 16° 0.17 C.262 •738 LijSO^ 1.0 m 16° o.27g Ag a. 65 2 .696 0.5 16° 028 a.63- •74- « 0.25 16° 0.17 a.6(>- .80- 1904. J. S. Bridges. The Transference Numbers of Copper Chloride in Concentrated Solution. Thesis presented for degree of B.Sc Mass. Inst, of Tech., Boston. Inaccessible in Heidelberg. 1904 Franklin] ABSTRACT 63 1904. C. H. Burgess and D. L. Chapman. The Nature of a Solution ot Iodine in Aqueous Potassium Iodide. Jour. Chem. Soc. Sj, 1305. The authors deduce from the resuUs of the comprehensive study of sohitions of iodine in potassium iodide by previous inves- tigators that KI and KI., are equally " strong " (t. *) .■.■:: -^^^ PEr.S. Ci. .-IJWM\ PrEc.--- " ME'finv^iV L.LI mm. Intm.LV." ••■■ Rg.ll. D,Br.L.T(i,6.- D.BrL.T.^,0. D.Br.LTwQ A'^ Ptr.S. Car.V. LLI PLATE VII. Fig. 13. Ventral view of the same Lepisosteus trista:chus as Figs. 8 and 11. Shows the termination of tlie ventral lymphatic trunk in the pericardial sinuses and the union of the latter in a dorsal pericardial sinus, which lies directly above the bulbus arteriosus and communicates with the inferior jugular above. X !• Proc. Wash. Acad. Scl, Vol. IX. Plate VII. Add. M Pep. 5. (/) D.Pep.S. PEr.S.O. B.Aht. L.V.L.T. c c Pep. 5. L.l/. L.T. V. L.T. PLATE VIII. Fig. 14. Represents a dissection of a lo-pound Lepisosteus osseus in the region of the heart as seen from the ventral side. Ventral walls of the lym- phatic sinuses and the right inferior jugular removed to show the union of the ventral lymphatic trunk with the right pericardial sinns, the orifice of the latter which communicates with the dorsal pericardial sinus, and the termination of the two anterior branchial lymphatic trunks (nutrient branchial veins.'*) in the right fork of the inferior jugular. X !• Fig. 15. Is a deeper dissection of the same specimen as 14. Heart, ventral aorta, most of the efferent branchial vessels, and the ventral walls of the lym- phatic sinuses and inferior jugular removed to show the points of termination of the branchial lymphatic trunks (nutrient branchial veins.'*) in the inferior jugu- lar, the pericardial sinuses in the dorsal pericardial sinus, its connections with the inferior jugular above, and finally the discharging of the inferior jugular in the sinus venosus. X f- 140 Proc. Wash. Acad. Sci., Vol. IX V. Br.LT,) 0.. RIJ.V. V. Br. L.T. a) 0 Plate VIM SUv. V. A.Br.A.(0 E.Br. A. (I) L.I.J. V. Cor. A. A. (a.) Ver. FiO. If V Br.LTioO. R.l.X^/. V. Bn L.Tc^O. R I.J.V.O... D.Pep.S D. pErS.V. D.pEr.S.V. PEhS.O. W^^: PEr.S. S.l/En.O 5. Veh PEr.S ^t£r. V A. Br. A. (I) V. Ao. A.Br.A.a) • -A. &p.A.(3)*m. I.J.V. h.G. 16 PLATE IX. Fig. i6. Transverse section through a rather small Lepisosfeus osseus taken 33 mm. behind the opercle as seen from the rear. Shows the main longitudinal lymphatic trunks in section. Natural size. Fig. i6«. Transverse through the ventral h'mphatic trunk region 20 mm. caudad of Fig. 16 as seen from the rear. Natural size. Fig. 16b. Transverse section through the ventral lymphatic trunk region 20 mm. cephalad of 16 as seen from the rear. Note the trunk is curving off to the right preparatory to emptying into the right pericardial sinus. Natural size. Fig. 17. Represents the inner or posterior surface of the first branchial arch of a 70-pound Polyodon. Except at the two extremities the gill rakers are cut at their bases so as to best display the branching of the lymphatics (veins.') over the surface of the arch. At one place a few of the inner branchial filaments are removed to show the position of the branchial lymphatic trunk (nutrient branchial vein.?) in relation to the afferent and efferent branchial trunks. Pre- ceding this gap the filament lymphatic network (nutrient venous network?) is indicated on the outer surface of several of the filaments. X \- 142 Proc. Wash. Acad. Sci., Vol. IX. Car.V. CEn Muo Plate IX. D. LT. D.Ao. L.L.T. H Ep. V. Fig. 16 V.A vv. V LT, Fi G . 16 a. v.v V A V V VLT. =--^ M ■V.A. •V'L.T. Rg. I 6 Jo. PErC. FilLT. A r.LA. A,Br/\<„ EF.LA. ; BrLT,,, BrA L N NB>-.A^„ ' "■'■'"" : '''^l-r G ft.LN. G R N. : E BrA, Fig 17 PLATE X. Fig. iS. Microscopic preparation of an injected branchial filament of a 70- pound Polyodon as seen from above. The respiratory filament vessels are stippled and the lymphatic network (nutrient filament veins?), which are shown only in part, are drawn in outline. X 5°- Reduced i. Fig. i8a. A portion of the filament respiratory network. X450- Reduced i. Fig. 19. Dorsal view of the lymphatic (nutrient venous.') network of a 70- pound Polvodon. This network is superficial to the septa that contains the res- piratory network, and for the most part the transverse vessels run parallel to the spaces separating the respiratory septa. Its meshes are more irregular and very much coarser (compare with Fig. 18). A longitudinal filament lymphatic trunk (nutrient filament vein.') receives the network from the two opposite fila- ments. X 5°- Reduced f , 144 Tr F L V PLATE XL Fig. 20. A portion of the outer surface of a branchial arch of a 70-pound Polyodon at the base of two filaments. The main efferent branchial artery, which lies directly below the efferent filament arteries is not figured. The efferent filament and the nutrient arteries are stippled ; while the branchial and filament lymphatics (nutrient veins .^) are drawn in outline. X 5°- Reduced \. Fig. 21. Like Fig. 19, a dorsal view of the same filament taken nearer the basal end of the filament. Introduced to show the character of the so-called lymphatic network on the outer edge of the filament. X 5°- Reduced \. 146 Proc. Wash. Acad. Sci . Vol. IX. PlATE XI. F.G. 20. N.FlIA. E.FclA. ^VL-^- RI.L. FiG. 21. PLATE XII. Fig. 22. Portion of a longitudinal section through the so-called cephalic lym- phatic trunk of a 15-inch Polyodon. Note the papilla and the relative propor- tion of white corpuscles to red. X 450- Reduced f. Fig. 23. Transverse section through the jugular vein of a 15-inch Polyodon. Note papilla here also and that the red corpuscles predominate. Outline sur- rounding some of the corpuscles denotes plasma boundary. X 45o- Reduced \. 14S Proc. Wash. Acad. Sci., Vol. IX. ^CT W.C Plate XII. H. M. Fig. 22. F.C.T. Fig. 23. S M. F. P • M. PLATE XIII. Fig. 24. Transverse section through the so-called hyo-opercularis lymphatic trunk of a 15-inch Polyodon. The section is taken through a papilla near its surface. In this trunk the white corpuscles, although very scarce, greatly pre- dominate over the red. X 450- Reduced S. Fig. 25. Similar section to 24 through the hyo-opercularis artery. X 450- ^Reduced f . Proc. Wash. Acad. Sci., Vol. IX. Plate XIII. Fig. 24. Was <5S> PLATE XIV. Fig. 26. Similar section to 24 through the hvo-opercularis vein. Structure is very similar to the lymphatic trunk, but the red corpuscles greatly predom- inate. X 450- Reduced |. Fig. 27. A diagrammatic transverse section through three pairs of branchial filaments of Polyodon. Proc. Wash. Acad. Sci., Vol. IX. Plate XIV. Fig. 26. Fig. 27. 0 o n E.Fi!./l. Fil. A. Fil. A. XI Ini iQ -Fil.L.T. Fil. PLATE XV. Fig. 28. Is a transverse section through the branchial lymphatic trunk (nutri- ent branchial vein ?) of a 15-inch Polyodon. Note the predominance of red cor- puscles. In another portion of the section the wall is much thinner. X 45°. Reduced ^V- Proc. Wash. Acad. Sci.. Vol. IX. Fig. 28. Plate XV F. C.T. DISTRIBUTION OF SUBCUTANEOUS VESSELS IN GANOIDS I55 Vl. LIST OF ABBREVIATIONS USED IN THE FIGURES. A or I' prefixed to an abbreviation signifies anterior or posterior; R or L, right or left ; a series is numbered from cephalad to caudad. a. In Fig. i point where injections were made with PoJyodori. A.Bl. Air-bladder. A.Br.A.{i)-{^). Afferent branchial arteries i to 4. Add.M. Adductor mandibulae muscles. A.Fil.A. Afferent filament arteries. A.P.Tr.A. Afferent filament transverse arteries. A.T. Adipose tissue in brain cavity. Alt. Auricle. B.Art. Bulbus arteriosus. Br.A.(^i)-{j[). Branchial arches i to 4. Br.A.A. Branchial arch artery. Br.A.A.{i). Branchial arch artery for outer surface of arch. Br. A. L.N. Branchial arch lymphatic (venous?) network. Br.A.L. T. Branchial arch lymphatic trunk, (nutrient branchial vein?) . Br.F. Branchial filaments. ^/-.Z-. 7'.(i)-(4). Branchial lymphatic trunks (nutrient branchial veins?) 1-4. Br.L.T.{'^) and (4). Combined trunk formed by the union of the third and fourth branchial lymphatic vessels. Br.L.T.{i'). Ventral fork of the first branchial lymphatic trunk. Br.L.T.{\"). Dorsal fork of the first branchial lymphatic trunk. Br.L.T.{2'). Ventral fork of the second branchial lymphatic trunk. B>-.L.T.{i)0. Opening of branchial lymphatic trunk (i) into the hyo- opercularis sinus, Polyodoti. Br.L.T.{i)V.O. Opening of the first ventral branchial trunk in the in- ferior jugular. Br.S. Branchial sinus, Lefisosteus. Br.S.O. Branchial sinus opening into the pericardial sinus. c. Communications between the 2 forks of the ventral trunk. Car.V. Cardinal vein. Cen. Centrum. Ceph.L.T. Cephalic lymphatic \.x\xn)Ly Polyodon. Ceph. S. Cephalic sinus. Cer. Cerebrum. CI. Clavicle. C.L.T.O. Cephalic trunk opening into hyo-opercularis sinus in Polyodoti. Cor. A. Coronary artery. Cr. Cranial wall. Crb. Cerebellum. C.T. Connective tissue. d. In Fig. 20 capillary from nutrient branchial artery. D.Ao. Dorsal aorta. 156 ALLE>; D.Br.L.T.{i)-{^). Dorsal branchial lymphatic trunks (nutrient branchial veins ?) I to 4, Lepiso^teus. D.Br.L.T.{i)-[^)0. Dorsal branchial trunk openings into the branchial and occipital sinuses, Lepisosteiis. D.L. T. Dorsal Ij'mphatic trunk. D.Per.S. Dorsal pericardial sinus, Lepisosteus. D.Per.S.V. Semilunar valves of the dorsal pericardial sinus of Lepi- sosteus opening into the inferior jugular. E.Br.A\\')-^\). Efferent branchial arteries i to 4. E.Fil.A. Efferent filament arteries. E.F. Tr.A. Efferent filament transverse arteries. Enc.A. Encephalic artery. E?ic. V. Encephalic vein. End. Endothelium. Ex. Tunica externa (adventitia). Exos. Exoskeleton. F.A. Facialis artery. Fac.M. V. Facialis-mandibularis vein. F.C.T. Fibrous connective tissue. Fil. Filament. Fil.L.N. Filament lymphatic (nutrient venous.^) network. Fil.L.T. Filament lymphatic trunk (nutrient filament vein.'). F.L.T. Facial lymphatic trunk. F.L.T.{i). Anterior facial lymphatic trunk. F.L.T. O. Facial lymphatic trunk opening into the hyo-opercularis sinus. F. V. Facialis vein. Gh.M. Glossohaly muscle. G.R. Gill rakers. G. R.L.N. Gill raker lymphatic (venous.') network. G.R.N. Gill raker arterial network. Hep.V. Hepatic vein. Hyo.A. Hyoidean artery. Hyom. Hyomandibular. Hyo.O.A. Hyo-opercularis artery. Hyo.O.A.i^x"). Superficial branch of the hyo-opercularis artery. Hyo.O.L.T. Hyo-opercularis lymphatic trunk. Hyo.O.L.T.{i). Dorsal branch of the hyo-opercularis lympliatic trunk. Hyo.O.S. Hyo-opercularis sinus, Lepisosteus. Hyo.O. V. Hyo-opercularis vein. Hyo.O.V.{l). Superficial branch of the hyo-opercularis vein. I.J. V. Inferior jugular vein. Int. Tunica intima. Intin.L. V. Intermuscular or transverse l}Tiiphatic vessels. I. Per. Visceral or inner layer of the pericardium. J. V. Jugular vein. Kid. Kidney. L. Liver. I.,.Bt'.{i)-[^). I3ranchial levator muscles I to 4. L.Br. V. Branchial levator muscle veins. DISTRIBUTION OF SUBCUTANEOUS VESSELS IN GANOIDS I57 L.I.J. V. Left fork of the inferior juyiilar vein. L..L.T. Lateral lymphatic trunk. Z..iV.(i). Lymphatic network on surface of the thymus gland and adjacent region, Polyodon. L.JV.{2). Lymphatic network overlying the facialis blood vessels, Poh'odo>i. Z,.iV.(3). Lymphatic network in hyo-opercularis region of Polyodon. L. V.L. T. Left fork of the ventral lymphatic trunk. ^I. Dorsal sinus emptying into the inferior jugular, Polyodon. Man. Mandible. J\fcd. Tunica media. M.O. Orifice of the dorsal sinus opening into the inferior jugu- lar, Polyodon. My. Myelon. Myo. Myotomes. N. Posterior sacs of Polyodon that terminate in the inferior jugular. N.Br. A. Nutrient branchial arteries. N.Fil.A. Nutrient filament arteries. N.M. Nucleus smooth muscle. N.S. Nasal sac. 0. In Fig. 15 orifice of pericardial sinus leading into the dorsal pericardial sinus. Oc.S. Occipital sinus, Lepisosteus. Oc.S.O. Occipital sinus opening into the pericardial sinus. CEs.. OEsophagus. O.L. Optic lobes. O.Per.S. Parietal or outer layer of the pericardium. Op.M. M. Opercularis. O.V.M.{^\)-{\). Obliqui ventrales muscles 1 to 4. P. Papilla. Pec. A. Pectoral arch. Per. C. Pericardial cavity. Per.L.T. Pericardial lymphatic trunk, Polyodon. Per.S. Pericardial sinus, Lepisosteus. Per.S.{ i). Anterior continuation of the pericardial sinus. Per.S. O. Communications of the pericardial sinuses with the dorsal pericardial sinus. P.P. Pectoral fin. P. P. Add. Pectoral profundus adductor muscle* Prec. Precava. Prem. Premaxilla. P. S. Pectoral sinus. P.S.O. Pectoral sinus emptying into the occipital sinus. Pt. Post-temporal. P.C. Red corpuscle. Pes.N. Respiratory network. R.Hyom. Retractor hyo-mandibularis muscle. P.I.J. V. Right fork of the inferior jugular vein. R.I.J.V.O. Right fork of the inferior jugular opening into the in- ferior jugular. 150 ALLEN R.ImI.X. Ramus lateralis vagi. 5'. A sinus in Polyodoii, which lies above the ventral aorta and opens into the inferior jugular above. S.Cl. Supra-clavicle. S.AI.F. Smooth muscle fiber. S.P.Abd. Superficial pectoral abductor muscle. Spt'r. Spiracle. S.T. Communicating trunk from sinus 5" to inferior jugular. Ster.T. Sterno-hvoideus tendon. Stcr. V. Sterno-hjoideus vein. Sub. A. Subclavian artery. S. Veii. Sinus venosus. 5. Ven.O. Orifice of sinus venosus leading into the auricle. Tr.F.L,.V. Transverse filament lymphatic vessels (nutrient veins?). V. Point where cephalic sinus joins jugular vein. V.A. Ventral artery. V.Ao. Ventral aorta. V.Br.L.T.[i)-[j^). Ventral branchial lymphatic trunks (nutrient veins?) I to 4, LepisostcHS. V.Br.L. T.{i )-(4)(9. Ventral branchial trunks opening into the inferior jugular. Vefi. Ventricle. V.L.T. Ventral hmphatic trunk. V.L.T.O. Ventral lymphatic trunk opening into the pericardial sinus. V.V. Ventral vein. V. Vas. Vasa vasorum. W. C. White corpuscle or leucocyte. X. Combined trunk formed by the union of the third and fourth dorsal branchial trunks with the dorsal fork'of the second branchial trunk. z. Point of union of the third branchia trunk with the fourth. /. Olfactory nerve. //. Optic nerve. F.(2). Truncus buccalis maxillo-mandibularis. V and VII. Trigemino-facial complex. VIII. Auditory nerve. IX. Glossopharyngeal nerve. X. Vagus nerve. PROCEEDINGS OF THE WASHINGTON ACADEMY OF SCIENCES Vol. IX, pp. 159-17S. July 31, 1907. ORIGIN AND EVOLUTION OF ANGIOSPERMS THROUGH APOSPORY. By O. F. Cook. The phylogeny of the coniferous plants or gymnosperms has been traced through the ferns and the Cycadofilices, an extinct intermediate group. Evidence of this alliance of the gymno- sperms has increased rapidly in recent years, but has not been accompanied by any equally convincing indications that the angiosperms or true seed-bearing plants shared the same pteri- dophytic ancestry. Morphologists may be willing, therefore, to consider an alternative possibility, that the origin of the angiosperms should be sought more directly in some such prim- itive condition as the thallose liverworts, without the need of following back through the stages of development represented by the ferns and other " vascular cryptogams." This briefer course of evolution would be opened if we were to consider the female reproductive apparatus of the angiosperms as analogous to the fern-prothallia which are sometimes pro- duced directly from the parent plant, without the intervention of spores, that is, by aposporous growth from cells of the parent fronds. In this method of development the aposporous prothallus serves as means of attachment for the young plant during its embryonic stages, and can supply it with food- materials drawn from the parent. A reason why this rather obvious analogy has failed to receive adequate consideration in the past may be found in the fact that apospory is usually associated with apogamy or other absence of normal fertilization, and is commonly thought of as a method Proc. Wash. Acad. Sci., July, 1907. 159 l60 COOK of asexual propagation. It can be shown, however, that this implication is not necessary, and that apospory need not inter- fere with the formation of sex-cells, nor with the continua- tion of truly sexual methods of reproduction. The elimination of the spores does not require that the fusion of chromatin (mitapsis) which must precede the formation of new sex-cells, shall also be omitted ; it may be merely deferred and passed along to later generations of cells. If instead of occurring in the body of the parent plant, mitapsis were carried over into an aposporous female prothallus and thus approximated in time to the formation of the sex-cells we would have a condition similar in all important respects to the reproductive system of the angiosperms. The whole group of the archegoniate plants affords a con- spicuous instance of such deferment of mitapsis into later and later cell-generations, instead of taking place in the fertilized egg-cell as in the lower algae. Unless mitapsis had been de- ferred the larger " sporophytes " and increasingly abundant sporogenous tissues which characterize the various families of archegoniates could not have developed. A still further post- ponement of mitapsis, combined with apospory, is therefore entirely in accord with the general course of evolution already followed by the group from which the primitive angiosperms are now commonly believed to have arisen. THE VEGETATIVE CAPSULE OF ANTHOCEROS. Anthoceros is a thallose liverwort which has been accepted by some as representing a primitive ancestor of the ferns, but which may be used with greater propriety to illustrate a stage in the development of the angiosperms. Until fruiting begins, a plant of Anthoceros consists merely of a thallus, or plate of slightly differentiated cells, lying flat on the surface of moist soil. The fruiting part of the plant is an upright, cylindrical, two-valved capsule. The outer walls of the capsule consist of flesh}^, green tissues, like those of the thallus, and similarly endowed with the power of vegetative growth. This vegetative capsule is even provided with special- ized breathing-pores, though the thallus is without stomata. EVOLUTION OF ANGIOSPERMS THROUGH APOSPORY l6l Finally, the growth of the capsule is persistent and indetermi- nate. New tissue continues to form at the base and to push up from below long after the terminal portion has ripened its spores and shriveled away. A first step toward the derivation of angiosperms from An- thoceros would be taken if the two-valved vegetative capsule should acquire the power to pass through a resting stage and re- new its growth, after the death of the parent thallus. Some of the species of Anthoccros are perennial, even in very dry re- gions, either by the survival of the tip of the thallus, or by specialized tubers. The capsule continues to grow as long as the thallus lives, and, as Campbell well says: '