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~ is equivalent to an assumption that

the hydration of an ammonium salt, however, may one molecule of ammonia is coordinated with

be taken as illustrations of anionic solvation,* the ammonium ion, and that four molecules, or

since coordination through the ammonium ion is two diammonol molecules, with the trinitride ion.

improbable. Ammonation of ammonium salts, The formula of the pentammonate may on this

especially a t lower temperatures, occurs f a r more basis be written [NHgNH4]+ [N3*2(NH&]-.

frequently than hydration. Unless this am- Summary

monation can be attributed to a coordination of

simple or associated ammonia molecules through Pressure-temperature-concentration relation-

the ammonium ion, it seems inevitable that it ships of the system ammonium trinitride-am-

must be ascribed to solvation of the anion. monia have been investigated over ranges from

In the system ammonium trinitrideammonia 0 to 4000 mm., -90 to +30°, and 0 to 100% am-

the diammonate is believed to exhibit anionic monia. Two solvates, ammonium trinitride di-

solvation. Whether coordination takes place ammonate, NHdN3.2NH3,and nmmonium trinitride

through hydrogen or through nitrogen atoms, pentummonute, NH4Ng5NH2, both of which are

however, is a question to which the final answer white crystalline solids, have been obtained. The

cannot as yet be given. The pentammonate, on diammonate undergoes inversion into anammon-

the other hand, with its inversion temperature ous salt at -9 O ; the pentammonate undergoes

at - 71 O, probably does not show exclusively inversion into the diammonate at -71". The

anionic ammonation, but may rather be identical eutectic is located a t -87" and 76% ammonia.

(9) In all probability liquid ammonia, like water, is associated,

with the diammonate, except that each of the and contains such molecular species as NHs, ammonol, (NHr)t,

three ammonia molecules has undergone dimeriza- diammonol, and (NH3)3, iiiammonol, analogous to hydrol, dihydrol

and trihydrol.

(8) Sidgwick, "The Electronic Theory of Valency," Oxford

University Press, 1929, p. 194. ITHACA, N.Y. Aucus~13, 1934

RECEIVED

OF CHEMISTRY, COLUMBIA UNIVERSITY]

BY JOSEPH SHRAWDER,

JR., AND A. COWPERTHWAITE

IRVING

Galvanic cells involving sulfuric acid have been is well designed to provide the required measure-

studied by a number of investigators.2 With few ments in the dilute range. The solubility of lead

exceptions the investigations have been confined sulfate, 43.5 mg. per liter in pure water at 20°t4is

to the use of the mercury-mercurous sulfate elec- sufficiently low in dilute acid to obviate any large

trode. While this electrode is reversible to sul- correction from this source.

fate ion and functions nicely in relatively concen- Previous attempts to measure the potential of

trated solutions, the solubility of mercurous sul- the above cell have been made by Lewis and

fate is sucha as to prohibit its use in solutions more B r i g h t ~ n ,Vosburgh

~ and Craig,6 and Baum-

dilute than approximately 0.005 molal. For the stark.2e Of these, only Baumstark was able to

evaluation of E it is desirable that measurements secure reproducible results, the other workers re-

be obtained to a lower concentration, porting deviations of the order of 0.01 volt.

The cell In the present work the electromotive force of

Pb-Hg (2 phase), PbSO&), Hg%(m), HZ this cell has been measured from 0 to 50' over

(1) This paper is from a dissertation presented by Joseph Shrsw- the concentration range 0.02 to 0.001 m.

der, Jr., to the Faculty of Pure Saience of Columbia University in The methods which have been commonly em-

partial fultllment of the requirements for the degree of Doctor of

Philosophy. ployed for the extrapolation of electromotive force

(2) (a) Brdnsted, 2. physik. Chem., 68, 693 (1909); (h) Edgar, data to infinite dilution vary from simple graphical

Thesis, Massachusetts Institute of Technology, 1912; (c) Lewis

and Lacy, THISJOURNAL, 56, 804 (1914); (d) Randall and Cush- extrapolations, on the one hand, through a variety

man, ibid., 40, 393 (1918); (e) Baumstark, Dissertation, Catholic (4) Purdum and Rutherford, ibid., 88, 3221 (1983).

University of America, 1932. (5) Lewis and Brighton, ibid., SQ, 1906 (1917).

(3) Hsrned and Sturgis, THISJOUENAL, 47, 945 (18251. (6) Vosburgh and Craig, ibid., 61, 2009 (1928).

Nov., 1934 THEACTIVITY OF SULFURIC

COEFFICIENTS ACID 234 1

of empirical methods, to the functional methods trodes were used in each cell, the average deviation being

based on the Ilebye-Hiickel theory. The com- of the order of 0.02 mv. The hydrogen electrodes were

freshly plated for each cell.

plete solution of the Debye-Hiickel equation Apparatus.-The type K potentiometer, Eppley stand-

through the third approximation for the case of ard cell, and thermometers were calibrated and frequently

unsymmetrical valence type electrolytes has been checked during the course of the investigation. Water

made available by means of tables communi- thermostats were used with temperature control main-

cated by La Mer, Gronwall and Greiff.' How- tained t o r0.02'.

Lead Nitrate.-Baker Analyzed salt was recrystallized

ever, the validity of extensions of the Debye- four times, filtered by suction and dried a t 110'.

Hiickel theory to the cases of unsymmetrical val- Sulfuric Acid.-C. P. sulfuric acid was redistilled three

ence type electrolytes and of electrolytes giving times in a Pyrex still a t atmospheric pressure. The final

ions of unequal size has been brought into question distillate was then diluted with sufficient distilled water

by Halperna8 In addition, the incomplete dis- to make nine liters of approximately half molar solution.

This stock solution, from which all the solutions subse-

sociation of the bisulfate ion contributes to Ihe quently studied were made by weight dilution, was stored

uncertainty involved in any application of the in a large Pyrex bottle and was carefully analyzed a t

Debye-Hiickel theory to sulfuric acid solutions. intervals of two months by precipitation as barium sulfate,

The work of Hamere in measuring the dissocia- and by titration against acid potassium phthalate using

tion constant of the bisulfate ion over a wide range carbonate-free sodium hydroxide solution as an inter-

mediate. Weight burets were employed in this titration.

of temperatures has offered the possibility of ap- The concentration of the stock solution was known to one

plying this parameter in an effort to obtain EQ part in four thousand.

without recourse to postulates other than the Lead Sulfate.-This was prepared by adding a 0.5

limiting law of Debye. This is desirable since molar solution of sulfuric acid to a 10% solution of purified

the conclusions of Halpern confirm the functional lead nitrate. The product was washed by decantation

for two weeks, after which it was filtered and dried at 110'.

nature of the limiting law (i. e., the square root Mercury and hydrogen were purified in accordance with

dependence, if not the constant). standard procedure.

Experimental Methods Lead Amalgam.-The amalgams were prepared elec-

trolytically following the directions of La Mer and Parks,""

Since the electrodes employed require oxygen-free con- and were stored in reservoirs of the type described by

ditions, a cell similar to that employed by Cowperthwaite, Cowperthwaite and La Mer."b Attempts to obtain satis-

La Mer and BarksdalelO has been used. With the exctp- factory amalgams from stick lead and purified mercury

tion of a hydrogen inlet tube added to the base of the were uniformly unsuccessful, due to the difficulty encoun-

central compartment, the cell employed here differs only tered in obtaining lead of sufficient purity.

in dimensions from that used by the above authors. The

technique employed with this type of cell has been pre- Theoretical

sented elsewhere.1° The cell upon which measurements have been

One unique feature of the manipulation consists in the

made may be represented as

use of dried lead sulfate in the lead amalgam-lead sulfate

electrode. Previous workers" have followed the procedure Pb-Hg (2 phase), PbSOl(s), HzSOa(m), HZ (1)

of storing the lead sulfate under water. In the present for which the corresponding cell reaction is

work the lead sulfate was dried, powdered and added to Pb (2 phase amalgam) + HzSOa(rn) =

the amalgam limbs immediately after the amalgam was

introduced. The addition of sufficient solid lead sulfate

PbSOd(s) + Ha (2)

The conventions employed here and in what fol-

to leave a thin film over the surface of the amalgam has

given excellent results. Electrodes prepared in this man- lows are those established by Lewis and Randall,

ner checked among themselves to better than 0.1 mv. whose nomenclature will be followed throughout.

The hydrogen electrodes employed were of two types. With the reactions written in the direction indi-

For the higher concentrations the standard black elec- cated, the cell potential is positive in sign, and

trodes were found to be satisfactory. For the concentra- the substance of variable activity occurs to the

tion 0.002 m and below, better results were obtained using

bright platinum electrodes. These were prepared follow- left of the equality sign. The equation for the

ing the directions given by Lorch.lZ Four hydrogen elec- cell potential becomes, therefore

nF In 4% m + -

+ 3RT 3RT

(7) La Mer, Gronwall and Greiff, J . Phys. Chem., 36, 2245 (193L). E = EO - nF

In f (3)

(8) Halpern, J . Che.w. Phys., 9, 85 (1934).

(9) Hamer, THIS JOURNAL, 16, 860 (1934). as may be verified by reference to the free energy

(10) Cowpertbwaite, La Mer and Barksdale, ibid., 66, 544

(1934). equation and the definition of mi. The function

(11) (a) La Mer and Parks, ibid., 69, 2040 (1931); (b) Cowper-

thwaite and La Mer, ihid., 19, 4333 (1931); (c) Bray, ibid., 49, 2372

Eo' may then be defined as

(1927) EO' = E - 3R- T In 4I/1m

(4)

(12) Lorch, Dissertation, Columbia University, 1932, 12 F

2342 JOSEPH SHRAWDER,

JR., AND A. COWPERTHWAITE

IRVING Vol. 56

ers extend over the entire range of acid concentra-

tions studied in this work. The desired solubility

In the equations used thus far, no recognition data were obtained by plotting the available data

has been given the fact of incomplete dissociation on a large scale followed by interpolation to the

of the bisulfate ion. If, instead of the total acid required concentrations and extrapolation to the

concentration, the stoichiometric concentration required temperatures.

of ions is employed in equation (4), a new function Table I records the calculated solubilities in

is thereby defined. This will be denoted by the millimoles per liter in sulfuric acid of the indi-

symbol E*. cated molalities.

The quantity Eo* for an incompletely dissoci-

TABLE I

ated electrolyte is thus the analog of the quantity

CALCULATED

SOLUBILITY

OF LEADSULFATEIN SULFURIC

Eo' for the completely ionized electrolytes. For ACIDOF MOLALITY

m (MILLIMOLES

PER LITER)

the case of sulfuric acid, it can be shown that m 00 12.5O 25' 37.59 50'

0.02 0.0099 0.0124 0.0152 0.0183 0.0220

.Ol .0107 .0134 .0166 .0199 ,0238

.005 .0122 .0153 .OB9 .0227 .0273

.002 .0170 ,0213 .0262 .0314 .0377

(7) .001 ,0238 .0299 .0372 ,0448 .0541

Calculation of CY

In the calculation of Eo*, values for CY, the de-

gree of ionization of bisulfate ion, are required.

The data given by Hamerg along with the calcu-

Equations ( 5 ) and (8) may be used to compute lated solubilities of lead sulfate may be em-

activity coefficients for sulfuric acid at each of the ployed in this computation. The expression for

temperatures and concentrations studied. The the second dissociation constant of sulfuric acid is

activity coefficients presented in this paper have

f H + mE*fBOP mP04' =

been computed on the basis of equation (5). f H 8 O r mE8Or-

K2 (11)

These have been called by BrOn~ted'~ "stoichio-

We may assume that the activity coefficients of

metrical activity coefficients."

the hydrogen and bisulfate ions will cancel,

Experimental Data and Calculations since they are activity coefficients of univalent

The correction for the solubility of lead sulfate ions in a solution of low ionic strength. Then if

in the calculation of EO' and Eo* was made by the concentration of bisulfate ion is denoted by

separating the In 'm terms in equations (4) and (7) x, the expression becomes

into two parts, one for the sulfate ion and one for

the hydrogen-ion concentration. Then equations

(4) and (7) become, respectively where ml and m2 have the significance previously

indicated. The activity coefficient of the sulfate

ion has been assumed to be equal to f, for a typi-

Eo* = E + 2RT

3 In mla'/3 + cal bi-bivalent sulfate and has been computed by

use of the extended theory of Gronwall, La Mer

and Sandved employing an ion size of 3.64 A.

where ml is the gross molality of the acid and The choice of this value for "a" was prompted by

m2 = ml + the molal solubility of lead sulfate in the agreement obtained by La Mer and Parks*la

sulfuric acid of molality m. The solubility of and Cowperthwaite and La Mer using this

lead sulfate i s the various dilute solutions of ion size in applying the extended theory to cad-

sulfuric acid has been calculated from the meas- mium sulfate and zinc sulfate, respectively.

urements of Purdum and Rutherford4 at 20", Since equation (12) contains the two mutually

Pleissner14at 18* and Huybrechts and Ramelot16 dependent unknowns fso,- and x, it has been

(13) Brensted, TRISJOURNAL, 42, 761 (1920). necessary to employ a series of approximations

(14) Pleissner, AT^. Kaiser. Ges. A m f .,. 26.. 419 (1907).

. , in its solution. From the calculated values of x,

(15) Huybrechts and Ramelot, Bull. SOC. chim. Belg., 36, 239

(1927). the corresponding values of CY may be obtained

Nov., 1934 THEACTIVITY

COEFFICIENTS

OF SULFURIC

ACID 2343

calculated, along with the dissociation constants t , "C. 0 12.5 25.0 37.5 50.0

from which they are derived. EO 0.32810 0.33919 0.35052 0.36192 0.37376

TABLEI1

been obtained by the introduction of the appropri-

OF HS04-

THEDEGREEOF IONIZATION

12.5O ate values for Eo and Eo' into equation ( 5 ) .

,n 00

&

... 25' 37.6' 50'

TABLE V

0.0148 0.0137 0.0120 0.0102 0.00794 STOICHIOMETRIC OF SULFURIC

ACTIVITYCOEFFICIENTS

0 ACID

0.02 0.5509 0.5375 0.5090 0.4799 0.4174 m 00 12.5' 2S0 37.60 50'

.01 .6620 .6487 ,6245 .5944 .5353 0.02 0.516 0.478 0.444 0.416 0.386

.005 .7586 .7470 .7257 .6993 .6469 .01 .609 .574 .543 .515 .485

.002 .8597 .8512 .8355 .8152 .77G8 ,005 .700 .674 .646 .623 .596

.001 .9124 .9062 ,8949 .8799 .8515 .002 .7Y8 .782 .767 .752 .725

.001 .853 ,846 ,837 .828 .807

EO' and Eo* may now be calculated on the basis

Discussion of Results

of equations (9j and (10). Table I11 gives the

observed values of the electromotive force cor- Despite any theoretical objections to the use of

rected to one atmosphere partial pressure of hydro- the La Mer, Gronwall and Greiff extension of the

gen, along with the corresponding values of Eo'

and Eo*.

TABLE

I11

VALUESOF E( OBS.), EO' AND Eo*

m 0' 12.5' 25' 37.5' 50' 0.320

E(obs.) 0.09536 0.09555 0.09589 0,09625 0.09651

0.001 BQ' .32251 .33302 ,34366 .35432 .36483

EO' .32463 .33541 .34648 .35768 .36922

E(obs.) .11725 .11799 .I1895 .I1985 .I2050

0.340

,002 EO' .32012 .33012 .34032 ,35048 .36036

EO' .32361 .33400 .34484 .35581 .36717

E(obs.) .14487 .I4622 .14745 .14890 .I5037

.005 Eo'

EO*

.31549 .32463 .33366 .34291 .35217

,32175 ,33154 .34156 ,35205 .36365

E(obs.) .I6443 .I6588 .I6744 .I6909 .17067

0.360

[k

.01 Eo' .31060 .31873 ,32698 .33532 .34358

EO' .31981 .32881 .33836 ,34834 .35963

E(obs.) .I8301 .18467 .18637 .18828 .19004

.02 EO' .30473 ,31196 .31922 .32671 .33404

EQ* .31772 .32606 .33513 .34458 .35577

m+.

In Fig. 1, EO' has been plotted against ml/'

Fig. 1.

while Fig. 2 gives the function Eo* plotted in a

similar manner. The Debye limiting slopes for Debye-Hiickel theory, it is of interest to inquire as

the various temperatures have been included on to whether or not the extended theory will fit the

both plots. It will be observed that the function data and be of service as a method of extrapola-

Eo* approaches the limiting slope as the concentra- tion. We have therefore carried out the calcula-

tion is decreased. Eohas been evaluated at each tions necessary to compare the theory with the

temperature by taking the values of Eo*which fall experimental data at 25". In this computation

on the limiting slope and adding to them appro- an ion size of 1.75 A. has been employed. The

priate values of 3RTInF In f computed with the results are indicated graphically on Fig. 3 with

aid of the limiting law. The mean of the several circles denoting experimental points and the solid

values for Eo thus obtained has been taken as the line A representing the extended theory. Crosses

E o for that temperature. Values for Eo at five have been added to represent the values for Eo'

temperatures are given in Table IV. obtained by BaumstarkZeat 25". The value for

2344 JOSEPH SHRAWDER, A. COWPERTHWAITE

JR., AND IRVING Vol. 56

Eo used is that obtained using the extrapolation The values for E o thus obtained are probably

of the function Eo* as previously explained, so accurate to 0.1 millivolt. The value for EO at

that the curve drawn represents the best approach 25’ differs from that obtained by Baumstark

0.300

by 1.65 millivolts, which difference may be as-

signed to the difference in methods of extrapola-

0.320

tion since Baumstark extrapolated the Ea’

curve linearly.

0.340

2’

irl

0.306

0.380

?nlla.

Fig. 2.

to the experimental data obtainable by adjust-

ment of the ion size parameter. While the agree- 0.350

ment is unsatisfactory, it should be pointed out

that the theory does not provide convergent I

values for In f when only three terms are em- 0.02 0.06 0.10 0.14

ployed in the case of such a small ion size. In ml/z.

its present form, the third term of the series is of Fig. 3.-At 25’.

the same order of magnitude as the first. It is of interest to compare the activity coef-

In addition to the experiment points for EO’ and ficients obtained in this work with those obtained

the extended theory curve, A, Fig. 3 also contains by other methods. Table VI lists the coefficients

the limiting slope, B, and the experimental points calculated from equation (6) (column 1) with those

corresponding to the function Eo*. Through the given by Lewis and Randall, Randall and Scott’6

latter points has been passed a smooth curve, C, from the freezing point measurements, and

which fuses with the limiting slope. While the Baumstark.2e

point of fusion appears to vary somewhat with TABLEVI

temperature (Fig. 2), still the adherence is such as ACTIVITYCOEFFICIENTS

STOICHIOMETRICAL OF SULFURIC

to warrant the use of the limiting law in the ACID

extrapolation for EO. While the function EO’ must m

I XI

Baumstark

111

I.. & R.

IV

R . & S.

also extrapolate to Eo,the extrapolation is compli- 0.02 0.444 0.519 0.553

cated by the nature of the curve. If the Eo’ func- .Ol .543 ,617 .648

tion is to fuse with the limiting law, at low con- .005 .646 0.615 ,696 .734

centrations, it must exhibit a reversal of curvature .002 ,767 .735 .782 .825

at some point. The complete solution of the ,001 ,837 .804 .831 ,876

Debye-Huckel theory predicts just such a form The values obtained for the activity coefficients

of curvature in very dilute solution, but, as poixted are smaller than those given by Randall and Scott

out, it is not possible to obtain a quantitative and are larger than those of Baumstark. The

evaluation of the theory in the case of sulfuric latter difference arises from the difference in E o

acid. It has seemed expedient therefore to use values used. The values obtained by the freezing

the function Eo* and rely upon the limiting law, (16) Randall and Scott, THIS

JOURNAL,49, 647 (1927).

Nov., 1934 PARTIAL MOLALHEAT OF DILUTION

OF SULFURIC ACID 2345

point method are subject to difficulties associated 0.002 and 0.001 m at each of the temperatures,

with extrapolation which axe fully as severe as 0, 12.5, 25, 37.5 and 50'.

with the electromotive force method, and are 2. A new method has been devised for ex-

particularly aggravated in this case of an im- trapolating to infinite dilution, taking into account

completely dissociated unsymmetrical valence the incomplete dissociation of the bisulfate ion,

type electrolyte. by means of which Eohas been obtained for each

temperature.

Summary

3. The activity coefficient of sulfuric acid has

1. The electromotive force of the cell Pb-EIg been evaluated a t each temperature for the five

(2 phase), PbS04(6), HeSO*(m),H:, has been meas- concentrations studied.

ured for the concentrations 0.02, 0.01, 0.005, NEWYORKCITY AUGUST15, 1934

RECEIVED

The Partial Molal Heat of Dilution of Sulfuric Acid from Electromotive Force

Measurements

A. COWPERTHWAITE A N D JOSEPH

BY IRVING SHRAWDER, JR.

In a previous electromotive force meets- tions studied, in which EO' is expressed in the

urements at concentrations from 0.001-0.02 rn and following manner

extrapolated values for Eo were given for the cell EO' = A + Bt + Ct4 + Dta (4)

Pb-Hg, PbSOi(s), H&h(M), HI (1) The constants for these equations have been

at 12.5' intervals from 0-50'. The reaction for determined by the method of least squares. This

this cell is method was selected in order to obtain a smooth-

+

Pb (satd. with Hg) H2S04(na)-+ ing of the experimental data with a view to se-

PbS0&) 4-Ef2 (1 atm.) (2) curing reliable derivatives. Equations of the

As the sulfuric acid is the only reactant of vari- quadratic type have been found to fit the experi-

able activity, these data used in connection with mental points almost as well as the cubic type

the Gibbs-Helmholtz equation permit the compu- used; however, the improvement secured by use

tation of the partial molal heat of dilution of sul- of the cubic equations appeared to be sufficient

furic acid. It has been shown by La Mer and to warrant the use of the four constant equations.

as~ociates,~that the introduction of the function The values for the constants of equation (4) for

EO' = E - ( v R T / n F ) In m into the Gibbs- the various concentrations are given in Table I.

Helmholtz equation gives the convenient form

TABLEI

CONSTANTS EO' = A

FOR THE EQUATION: + Bt + Ct* + Dta

m A B x 104 c x io' D x 100

This form of the equation is particularly useful in 0.000 0.32810 8.8717 1.029 8.294

that it may be used in the evaluation of - AHo .001 .32251 8.3111 9.015 -11.905

since EO' extrapolates smoothly to Eo at infinite .002 ,32012 7.8564 14.059 -20.454

dilution. .006 .31549 7.2306 2.068 0.116

In order to obtain the temperature coefficients .01 ,31060 6.4117 7.918 - 8.447

,02 .30473 5.6728 7.683 - 7.729

required in the above equation, an analytical

function has been set up for each of the concentra- By use of the above coefficients,the first deriva-

(1) This paper is from a dissertation submitted by Joseph Shraiv-

der, Jr., to the Faculty of Pure Science of Columbia University in

tive of EO' with respect to the temperature has

partial fulfilment of the requirements for the degree of Doctor of been evaluated at 25' for each of the values for

Philosophy. m. The calculation of - A H and of is then

(2) Shrawder and Cowperthwaite, Tars JOURNAL.66, 2340

(1934). readily carried oGt. The important quantities

(3) La Mer and Parks, ibid., 63,2040 (1931); La Mer and Cow- used in the thermal calculations have been sum-

p e r t h d t c , {bid., MI, 1004 (1933); Cowperthwaite, La Mer and

Barksdsle, ibid., 66, 644 (lea4). marized in Table 11.

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