J u t i t ~20, 1957 ACTIVITY COEFFICIENTS AND COMPLEX O F HG(I) SULFATE 30 13

[CONTRIBUTED FROM THER O S S CHEMISTRY LABORATORY,

The Activity Coefficients and Complex of Mercury(1) Sulfate in Sulfuric Acid Solutions
at 2S01
BY SHIRLEY
4 . BROWNAND JAMES E. LAND
RECEIVED 1, 1957
FEBRUARY

The solubility of mercury(1) sulfate in sulfuric acid solutions of various molalities was measured a t 25'. By eniployiiig
the values for the ratio of the concentration of hydrogen sulfate ions to the concentration of sulfate ions in these sulfuric acid
solutions as given from Raman spectra, the ionic strengths of the mercury(1) sulfate, sulfuric acid solutions were calculated.
From a plot of the reciprocal of the mean molality of the mercury(1) and sulfate ions as. t h e cube root of t h e ionic strength,
an extrapolation gave the theoretical solubility product constant for the mercury(1) sulfate in mater. This constant then
was used to compute the mean ionic activity coefficients of the mercury(1) sulfate in sulfuric acid solutions with concentra-
tions between 0.002 and 2 rn. A mechanism for the formation of t h e species H[Hgp(SOa) (HSOa)] was postulated and proof
of its existence in solution advanced.

The use of mercury(1) sulfate in the preparation mercury(1) sulfatesulfuric acid solutions could be
of standard e.m.f. cells has prompted many studies represented as a function of acid molarity by the
on its solubility in water and sulfuric acid solutions. equation
A most complete and conclusive article on this
topic is that of Craig, et a1.,2 who reported on the
d 0.9975 + 0.0624C(~~so,)-k 1.0918 x lo-3C(~2s0,)

solubility of mercury(1) sulfate in sulfuric acid The molalities of the dissolved mercury(1) sulfate
solutions from 0.002 to 3.5 c a t 0 and 28O, and also determined agreed within experimental error with
they showed that a linear interpolation of their re- those computed from the results of Craig, e t a1.,2
sults to 25' agreed very closely with those re- using the above density, concentration relationship.
ported by H ~ l e t t . ~ From a large scale plot of the molality of the
Our interest in the mean ionic activity coeffi- mercury(1) sulfate (using both our measured
cients of mercury(1) sulfate grew out of an at- values and those computed from reference 2)
tempt to overcome certain difficulties in the cal- against the log of the molality of the sulfuric acid,
culation of the Eo for the Hl, HzS04, solvent, TABLE
I
Hg2S04, Hg e.m.f. cell used in determining the
mean ionic activity coefficients of sulfuric acid a t THE SOLUBILITIES, THE RECIPROCAL OF THE M E A N IONIC
low molalities in mixed solvent^.^ MOLALITIES,AND THE MEANIONIC ACTIVITY COEFFICIENTS
Not being able to compute the practical ac- OF MERCURY(I) SULFATE AND THE MOLALITIES OF THE
tivity coefficients of mercury(1) sulfate in sulfuric SWLFATEIONA N D THE FACTOR FOR ITS DETERMINATION IN
acid solutions from the solubility results given in SULFURIC ACID SOLUTIONSOF VARIOUSMOLALITIES
the literature, since they were recorded in molarities m of m X lO40f m of
and density values were not reported, we per- His04 HgiSOi YR (so4)- l/m* ir Yt

formed enough solubility measurements over the 0.002 11.120 0.972 0.002 820.6 0,007 0.677
range of acid molalities reported to give a relation- ,003 10.158 ,956 ,002 679.8 ,009 ,561
ship between concentration and density a t 25". ,004 9.455 ,942 ,003 6 3 4 , 2 , 01 1 ,523
With such results and those in the literature the ,005 8.923 ,926 ,003 601.2 ,013 ,496
mean ionic activity coefficients of mercury(1) sul- .006 8.608 ,912 ,004 576.1 ,015 ,475
fate in sulfuric acid were calculated and also it was ,007 8.386 ,896 ,004 553 .O ,016 ,456
possible to postulate the presence of a soluble mer- ,008 8.262 ,882 ,004 5 3 6 . 8 ,018 ,443
cury complex. .009 8.141 ,866 ,005 516.7 ,020 ,426
Experimental ,010 8.068 ,852 .005 502.9 ,021 ,415
Solid mercury(1) sulfate, prepared by the method of .020 7.574 ,710 ,008 416.8 ,037 ,344
Hulett,6 was added in excess to the sulfuric acid solutions ,030 7.450 ,582 .010 362.8 ,052 ,299
contained in brown, ground glass stoppered bottles. The ,040 7.557 .474 ,013 320.3 ,066 .264
sealed bottles were agitated mechanically in a constant tem-
perature bath maintained at 25 3= 0.02" for 3-4 days. .After ,050 7.641 .380 ,016 284.2 ,082 .234
agitation the solutions were allowed to stand in the bath ,060 7.746 ,300 ,020 254.1 ,100 ,210
until clear, a sample removed by suction into a special pyc- ,070 7.854 ,250 ,024 231.8 ,117 .I91
nometer (previously describede) for the density determina- .080 7.968 ,215 ,027 214.4 ,135 ,177
tion, then analyzed for H g and sulfuric acid using techniques
described in reference 2. ,090 8.041 ,189 ,031 200.6 ,152 ,166
,100 8.119 ,170 ,034 189.2 ,169 ,156
Results and Discussion ,200 8.867 ,108 ,060 137.2 ,320 .113
Over the range of concentrations of sulfuric acid ,300 9.373 ,078 ,086 111.6 ,471 ,092
studied it was found that the density a t 25" of the ,400 9.783 ,054 ,120 9 2 . 4 ,640 ,076
( 1 ) Presented a t t h e Southwide Chemical Conference of T h e ,500 10.062 ,035 .l70 76.6 ,839 ,063
American Chemical Society, December 6-8, 1956. .600 10.291 ,032 ,198 70.0 .997 ,058
( 2 ) D. N. Craig, G. W. Vinal a n d F. E. Vinal, J. Researrh N a t l . Bur.
Slandards, 17, 709 (1036). This reference contains a bibliography a n d
,700 10.463 ,029 .216. 66.6 1.132 ,055
a critical evaluation of all articles published on this subject t o 193G. ,800 10.555 .027 ,240 6 2 . 9 1.279 ,052
(3) G. A . Hulett, Trans. A m . Electrochem. SOL.,6, 109 (1901). ,900 10.573 ,025 ,265 5 9 . 8 1.430 .049
(4) J. E. L a n d a n d H . D. Crockford, THIS J O U R N A I , 72, 1808
1.000 10.549 ,019 ,320 5 4 . 4 1.640 ,045
(1950).
( 5 ) G. A . Hulett, Phys. R e v , , 32, 257 (1911). 1.500 9.966 ,014 .467 46.4 2.434 ,038
(6) S. A. Brown a n d 5. E . L a n d , J . Chem. Edzcc., 33, 7 2 (19.56). 2.000 9.091 ,010 ,631 4 1 . 8 3.262 ,034
3016 SHIRLEY
A. BROWNAND JAMES E. LAND Vol. 79

the values recorded in the accompanying table gested that between 0 and 0.15 c sulfuric acid a
were taken. basic, normal and acid species of Hg2S04 existed.
To calculate the mean ionic molality of the mer- Craig, et aL12postulated the formation of the com-
cury(1) sulfate, the needed molality of the sulfate pound HgHS04 to account for the increased solu-
ion was computed from the mass law equation for bility of the mercury(1) sulfate. Kendall and
the dissociation of the HS04- ion Davidson'" reported the formation of the unstable
acid salt Kg,S04.H2SO4 from the analysis of the
solid plase in contact with solutions of mercury(1)
sulfate in 100% sulfuric acid.
Values for the factor YR listed in the accompanying Since the increase in solubility of the mercury(1)
table were taken from a large scale plot of the sulfate coincides with the increase in the HS04-
values reported by Smith.' ion concentration, i t was reasoned that such an
The concentration of the HS04- ion can be taken equilibrium as this is possible
as the difference between the molality of the sul-
furic acid and the Sod- ion since Smith's work Hg804 + n(HS04-) [Hg,(S04) (HS04)nI"-
demonstrated no undissociated sulfuric acid to be Taking the logarithm of both sides of the mass law
present in the range reported here. The value equation for this equilibrium and rearranging gives
used for KHSO,- was 0.0120.8
The mean ionic activity coefficients listed in the
1% U[Hg,(80d(HSOc)n]"- = log aEIS0,- log k' +
accompanying table were determined from the thereby indicating that a plot of the log u [ H ~ ~ -
equation y* = (l/m*)K*'z, where m=t is the (SO,)(HSO,)n]n- VS. log CLHSO,- should produce a
mean ionic molality and K is the hypothetical ther- straight line of slope n and intercept equal to log K ,
modynamic solubility product constant for the if such an equilibrium is the case.
mercury(1) sulfate. K'/* was determined by The concentration of the soluble mercury com-
plotting l/m* vs. the cube root of the ionic strength plex was taken as the difference between the
and extrapolating to zero ionic strength. The molality of the mercury(1) sulfate a t all values
value found for K was 6.81 X of ??zH,SO, between 0.06 and 0.4 and that a t m H , s o ,
= 0.03, since the mercury(1) sulfate concentration
The behavior of -y& with changing ionic strength
is illustrated in Fig. 1. a t this latter molality may be considered to be the
maximum possible concentration of the Hg2S04
species in sulfuric acid solutions more concen-
trated than 0.03 m. A plot of --log m [ H g z ( S 0 4 ) -
( H S 0 1 ) ~ l n -VS. -log ~ H S O , - , shown in Fig. 2," gave

4.5

' ,
L!
0 0.61
W
o
_J t
S L O P E = 0 95
I
,
-
/
_
I_
L
__
I
0.4 0 .a 1.2 1.6
-LOG M H S O ~
Fig. 2 ,
Fig. 1.
a series of points that fall close to a straight line
The shape of the solubility curve of mercury(1) with a slope of 0.95, thereby indicating the prob-
sulfate in sulfuric acid solution indicated the
formation of a soluble complex. Eppleye sug-
able complex ion to be [Hg2(S04)(HS04) I-.
AUBURN,ALA.
( 7 ) H . M. Smith, P h . D . thesis, University of Chicago, 1949. -___
(8) H. S. Harned a n d B . B. Owen, "The Physical Chemistry of Elec- (IO) J. Kendall and A. W. Davidson, T H I S J O U R N A L , 43, 979 (1921).
trolytic Solutions," Reinhold Publ. Corp., New York, N. Y., 1943, p ( 1 1 ) For a n explanation of t h e use of concentration r a t h e r t h a n
430. activity t e r m i , c j A. B. G a r r e t t , h l . V. Noble a n d S. Miller, J . Chem
(9) h l . Eppley, Trans. A m . Eiecluoche?,r. Soc., 6 3 , 172 (1928). E d u c . . 19, 486 (1942).