Oct., 1950
ENTROPIES OF ALKALIMETALAND TETRAALKYLAMMONIUM BROMIDES
4411
[CONTRIBUTION FROM TEE CHEMICAL. LABORATORY OF THE UNIVERSITY OF CALIFORNIA]
Applications of the Eastman Thermocell Equati0n.l I. Certain Absolute Ionic Entropies and Entropies of Transfer of Alkali Metal and Tetraalkylammonium Bromides and Hydroxides BY J. C. GOOD RICH,^^ FRANKM. GOY AN,^^ E. E. M O R S EROGER , ~ ~ G. P R E S T O AND N ~ ~M. B. YOUNG^^
It has been shown by Eastman3 that the e. m. f. of thermocells of the type exemplified by Ag, AgBr, KBr (0.01 M ) , AgBr, Ag Tz T2 TI Ti
may be treated by classical thermodynamic methods. For a differential temperature between the two electrodes, Eastman has shown that FdE/dT for such a thermocell in which the Soret effect is excluded is given by the equation F d E / d T = ASR
+ tcSc* - ~ASA*
(1)
where ASR is the entropy change in the electrode reaction occurring a t the higher temperature when one equivalent of positive electricity flows through the cell from the hot t o the cold electrode. The symbol, F, represents the faraday equivalent, dE/dT is the electromotive force of the cell divided by the temperature difference, tc and t A are are the the transference numbers and SC*and SA* entropies of transfer of cation and anion, respectively. Equation (1) is referred to in this paper as the Eastman thermocell equation. The term on the left-hand side of equation (1) is obtained by direct measurement of the small but reproducible e. m. f. produced by appreciable temperature gradients. Eastman3 explored the possibility of using this equation for numerical caiculations by the use of certain reasonable assumptions which lead to rough approximations of entropies of transfer of ions based upon fragmentary data then available. On the basis of his assumptions he calculated values of the entropy of transfer of certain positive ions, the values of which led to a tentative value for the absolute partial molal entropy of chloride ion. Eastman's original estimates of the values for entropies of transfer of ions have gone unchallenged up to the present time, as evidenced by the work of Bernhardt and C r ~ c k f o r dwho , ~ made use (1) Ermon Dwight Eastman, Professor of Chemistry at the University of California until his death in 1945 and beloved mentor of all of the authors of this paper, planned and directed the work leading to this publication. The war interrupted his plans for completing and publishing this work, and his untimely death deprived the present authors of his leadership in this undertaking. The data presented here are taken from the authors' doctorate theses deposited at the LibrarJ of the University of California. (2) (a) Deceased. (b) College of Pharmacy, University of California, Medical Center, San Francisco 22. (cJ The Brown Company, Berlin, New Hampshire. (d) Lieutenant, U. S. Navy, Bureau of Ships, Navy Department, Washington, D. C. (e) 726 Oak Avenue, Davis, California. (3) Eastman, THISJOURNAL, 60, 292 (1928). and microfilm EUPplement of contributions by L. D. Tuck, R. G. Preston and M. B. Young showing that the entropy of electrons may be neglected, and givins the complete derivation of equation (1) as presented by Pruiessor Bastrnan to his graduate students. (4) Brrnhnrdt aud Crockford, J . Phys. Chcnr., 46, 473 (1942).
of these entropies of transfer in calculating a new value for the absolute partial molal entropy of chloride ion. Fully aware of the tentative nature of his assumptions and the lack of satisfactory data, Eastman sponsored an extensive series of studies of all types of simple thermocells designed to yield data applicable to the solution of equation (1). The present paper is a record of a part of this work. Theoretical implications discussed in connection with a study of the Soret effects led to the speculation that large symmetrical ions would have low entropies of transfer, approaching zero with increasing size of the ion. A series of symmetrical quaternary ammonium ions should, according to speculation, satisfy these requirements. Extensive studies of thermocells involving dilute solutions of these ions led to confirmation of these implications and to entirely new values for the entropies of transfer of ions, This paper is the first of a series designed to present the essential data and techniques evolved in Professor Eastman's Laboratory. No chronological order is attempted; instead, the following series of measurements were selected on the basis of their contribution to an orderly development of ideas leading to the new values of the entropies of transfer and of the absolute partial molal entropies of certain ions : (a) tetraalkylammoniuni, lithium, sodium and potassium hydroxides with mercury-mercuric oxide electrodes ; (b) tetraalkylanimonium, lithium, sodium, potassium and ammonium bromides with silver-silver bromide electrodes. The reduction of the data from these two series of salts leads to values for the entropies of transfer of the positive and the negative ions involved and to the absolute partial molal entropies of hydroxide and bromide ions, Selection of the Temperature Gradient and the Concentration Best Suited for Comparative Studies lie thermocells selected for investigation corConsidrespond to Eastman's Type I1 erable exploratory work was done to determine suitable cell design and optimum concentrations and temperature differences. It was found that the lowest concentration that could be investigated with ease was, 0.001 m for a temperature difference of 10' (average temperature 25'). An appreciable quantity of data was obtained for concentrations of 0.1, 0.01 and 0,001 m. A study of the measured e. m. f. of the thermocells as a ( 5 ) Eastman, T H IJ O ~ U H N k L , 60, 283 (192% (6) Eastman, rbrd , 48, 1482 (1926)
1 . C. GOODRICH, F. 11.Gouxx, E. E.MORSE. K.( i . PRESTON AND 11. B. YOUNG
4412
Vol. 7 2
iunctioii of the log of the molality of the electro- eorporated in the thermocds. Only those methlyte showed only slight deviations from ideal be- ods which were found to produce stable and reprohavior at a concentration of 0.01 m. Therefore, ducible electrodes are described in this paper. It the standard concentration used throughout this was established beyond question that the %ret research was 0.01 V L , 'The standard temperature effeat did not influence the results reported. difference of LO" was similarly checked by measur- Siuch longer periods of time than the three- to ing several thermocells h t 5" intervals for an aver- five-hour observation periods necessary for this age temperature 01' %>". Most of this preliminary work are required to produce a measurable Soret work was done using the calomel electrode with gradient in the svstenis described. the alkali metal chlorides and hydrochloric ac*icl. Experimental ,md it was shown that the irieclsured e . 111. i pcrPurification of the Salts. --Several of the comtnercially degree C. was the s a m ~For both the .i :md IU" ill- available quatclrnnrp ammonium salts were purificd by terv'ils (average teinperaturc 23" I iable 1 sets recrystallization from water or organic solvents. Those iortli the data up01I \vhicli this conclusion W:IS compounds not readily available were synthesized using based. The effect 02 coI1eentraholl FWS 4he sub- standard methods. Iodides were sometimes converted to Ivct ot continiiniis in\ tifi~tirmh v all coiitril~iitcir~ bromides through the hydraXide, using silver oxide followed by hydrobromic acid. All of the salts were obI O t h i s worL t i n e d in the solid state by crystallization. The sodiuni ,md potassium bromides used i n this work were obtainet 1 from reliable sources and were twice recrystallized from c 41 O \ l E L 1IiLII;?.1OChl I. I conductivity mater and carefully dried before use. The lithium bromide was dried in a vacuum desiccator over Kl, I N I E R V A I , phosphorus pentoxide after it was prepared from e. P 1: m f , ntilli\wlt/degrec hydrobromic acid and P. lithium carbonate. A record AT = 100 AT = 5,,LO 0-30 0') ( 2 2 5-27 i ' ~r)f the methods of preparation atid the significant properI i t s ot some of the halts are iiiclucicd in Table 11.
1,\b1.3 I (I1
1 I
PI,RAII
e.
Liectroijrc
;LIolaltt)
HCI IiCL SaCl XaCI
0 (ilC10.5 t w9
~r,4€31,E 11
0963 li
S'tll
I911i
I n the early stages of tlie investigatioii i t nab discovered that apparent discrepancies in thc e. ni. 1'. nieasureinents for identical silver-silver bromide cells were eliminated by reversing the cells in the temperature gradient. By reversal, two equilibrium e. ni. f. values were obtained foi each thermocell, the averages of which were found to be closely reproducible. Permanent differences in the silver- silver bromide electrodes, of the order of magnitude reported by Smith and 'raywere thus cancelled. It was found that these differences did not occur with the mercury-mercuric oxide electrodes ; therefore, reversal was omitted from the procedure for these electrodes. Aiost of the later and more accurate ineasurenients with the silver-silver bromide electrodes were made by the method of reversal which is referred to as the "reversal technique. " Another approach not involving the reversal of the thennocells in the temperature gradient is referred to as tlie "transfer technique because pairs of electrodes were transferred s w cessively from one theruioerll to the next of a bc rirs maintained in the temperature gradient. 'rhr differences in e. 111. E. produced by several differelit electrolytes were found to be the same by both inethods within the experimental errors, and certain slightly Iar'ger deviations were attributed to failure to remove oxygen of the air in the applica tion of the transfer technique. Rdiminary studies ihcluded several methods for preparing the different types of electrodes in S m i t h and T i ~ l o i
.'
I < r * r , i r I I '>,.(I
I I
1,1111
,1111
1,/
,I/
az
ri;
/
