NOTES 1579

ethylene. It appears that propylene is not formed from

Table 11: YieldB of Ethane-CI4 and Ethylene-Cl' from
the Radiolysis of Methane-Cld a t 100 mm. Pressure
ethylene during the radiolysis.
in the Presence of Added Ethylene Acknowledgment. The author wishes to express his
appreciation to Dr. Richard Holroyd for helpful dis-
Aboorbed cussions on this study.
dose (e.v./g. C?(C'4eHs),
% CaH, of CHI) molecules/ C""I4/ C'4sH4 (cor.)/
added X 10-19 100 e.v. C"sHa C14rHs (17) If a value of 2 is assumed for the yield of ethane in methane
radiolysis and if, as is suggested by the methane-ethylene-Cl4
0.17 2 0.66 0.98 0.98 results, one third of the ethane observed is produced from ethylene
then the initial yield of ethylene calculated from its relative yield is
0.06 4 1.7 0.57 0.84 1.3 molecules/100 e.v. which is in agreement with values (G = 1.4
0.05 2 0.83 0.85 0.85 and 1.5)suggested previously10 in studies of the irradiation of methane
0.04 9 1.2 0.71 0.99 in the presence of added propylene and acetylene, respectively.
0 . 04a 43 1.9 0.07 1.16
0.03 2 1.1 0.91 0.91
0.03 2 1.7 0.76 0.93
0.02 2 1.5 0.66 0.86
0.02 2 0.85 0.73 1.14 Dissociation of the Bisulfate Ion1
a The 1 mc./mmole sa,mple of methane-c" was used in thiei

experiment. Other experiments listed here employed the 2; by H. S. Dunsmore

mc./mmole sample.
Chemistry Department, The University, Glasgow W . 8, Scotland

ane-C14 radiolysis (G = 1.5). However, it is not un-
reasonable since, as demonstrated by the results of
the methane-eth~1ene-C'~radiolysis, some ethane is pro-
duced from ethylene. (The yield of unlabeled ethane
produced from unlabeled ethylene was not measured
in the ethylene-methane-C14 radiolysis.) Using the
value of 1.2 for the yield of ethane-CI4, the initial
yield of ethylene is then 1.1 molecules/100 e.v.17
Other labeled products obtained in the radiolysis of
methane-C14 in the presence of unlabeled ethylene
included acetylene, propane, propylene, and isobutene.
If propane is considered to be singly labeled as suggested
by the results of the methane-eth~1ene-C~~ experiment,
then an enhanced relative yield, (CHgCHZC14H3/
C142H6) = 1.6, is obtained. Assuming complete
labeling, the yields of unsaturates also appear to be
enhanced: L e . , (G1'12H~/C142H6)= 0.1 ; (C1'&&/
C1d2H6)= 0.2; and (i-C144H8/C14zHB) = 0.08. (These
yields are approximate and could be in error by more
than SO%.) The yields of propane and unsaturates
are expected to be high, however, due to the relatively
large quantities of added ethylene present during the
radiolysis.
The present study clearly demonstrates that both
ethylene and propylene are important products in
methane radiolysis. Ethylene appears to be a primary
nlolecular product with an initial yield of approxi-
mately 1.1 molecules/lOO e.v.; however, a significant
fraction of the ethylene produced is converted during
the radiolysis to ethane and propane. Propylene
was produced in the Of pure methane and
in radiolysis of methane ln the presence of added
and G. H. Nancollas
Chemistry Department, Brookhaven National Laboratory,
Upton, New York (Received November 8 , 1963)
The second dissociation constant of sulfuric acid,
K z , has been the subject of extensive study and dis-
cussion. The bisulfate ion is relatively highly dis-
sociated and in calculating the therniodynainic equi-
librium constant, which may be approxirnated by
(1)
much depends upon the choice of parameters, B
and C, in the activity coefficient e x p r e s s i ~ n . ~I n~ ~eq.
1, I is the ionic strength, and A and B are the usual
Debye-Huckel constants.
Some of the earliest work on sulfuric acid was that
of Sherrill and i?rTogre~,~who combined transference
number and conductance data and obtained a value
K z = 0.0115 mole 1.-I a t 25'. Assuming the first
hydrogen to be completely ionized, they expressed the
degree of dissociation, a,by the equation
(1) Research performed in part under the auspices of the u. S. Atomic
Enerm-" Commission.
(2) V. 8. K. Kair and G . H . Nancollas, J . Chem. Soc., 4144 (1958).
(3) w. J. Hamer in "The Structure of Electrolyte Solutions," w. J.
Hamer, Ed., John Wiley and Sons, Inc., New York N. Y . , 1959, p.
236.
(4) M. S. Sherrill and A. A. Noyes, J . Am. Chem. Soc., 48, 1861
(1926).

Volume 68, Number 6 June, 1964

1580
a (A + AT - AH)/(AH + Aso,)
AHSO, = (A - AT - a h s o , ) / ( l - a )
where T is the stoichionietric transference number,
and for the sulfuric acid solution, A is the observed
conductance and AH, Aso,, and AHSO,are the equiv-
alent conductances of H+, Sod2-, and HS04- ions,
respectively. The dissociation quotient K,’ ( = [H+].
[Sod2-]/[HSOd-]) was calculated at each ionic strength,
and Kz was obtained by extrapolation on a plot of log
Kz’ against Ill’. Kerker5 has extended the calcula-
tions to other temperatures and to ionic strengths as
high as 4.43 M . The method, however, is open to
serious objection since it is impossible to correct for
ion pairing in such concentrated sulfate solutions with
any certainty. In addition it was assumed that the
equivalent conductances of H + and s04-’ ions could be
obtained from HCI and KzSOd data at the same ionic
strength as that prevailing in the sulfuric acid solution
under consideration. Using a high-speed DEUCE elec-
tronic computer we have recalculated the conductance
and transference number data for concentrations below
0.05 m. The Kz’ values are in close agreement with
those obtained by Kerkerj6 although the calculated
AH SO^. given in Table I, show marked differences. AH
and Aso4 a t each concentration were interpolated from
ionic strength plots of HC1 and K2S04 conductance
data. The steepness of these curves made estimation
difficult at I < 0.01 M and, taking this into considera-
tion, the best extrapolated K z = 0.0104 mole kg.-’;
Kerkerj obtained 0.0102 mole kg.-I.
Table I : The Dissociation Constant and Equivalent
Conductance of HSOa- a t 25”
MH28Oax loa 5.00 6.25 12.50 2 5 . 0 0 50.00
102Kz’(this work) 1.67 1.75 2.06 2.55 3.36
A ~ ~ ~ ~ ( t h i s w o r k4)1 . 7 41.6 40.2 39.0
102Kz’(Kerker) 1.69 , , , 2.09 2.53
AH604 (Kerker) 46.8 .., 45.3 39.8
A number of electromotive force studies have been
made in cells without liquid junction of the type
Hz, PtlHC1, XI AgCl, Ag. Hanier,G using X = Na2SO4,
obtained K, = 0.0120 mole kg.-I which was in poor
agreement with 0.0104 from ~pectrophotonietry.~
Moreover, the temperature coefficient led to a heat of
ionization, AH” = -2.2 kcal. mole-I, very different
from the calorimetric value, -5.2 kcal. mole-’, of
Pitzer.8 Davies, Jones, and NonkQhave recalculated
Kamer’s e.ii1.f. data with allowance for the forniation
of KaS04- ion pairs and obtained K z = 0.0102 mole
The Journal of Physical Chemistry
NOTES
kg.-I. Mixed acid cells in which X = HzS04 do not
suffer from the disadvantage of secondary-ion associa-
tion and two such studies have been made.2r‘0 The
derived K Zvalue is markedly dependent upon the choice
of parameters in eq. I ; assuming B& = 1, all the data
have been recalculated using the computer programmed
to yield the C value for zero slope of Kz us. I plots, a
least-squares procedure being used. The results are
summarized in Table 11. Although Monklo had sug-
gested that, using C = 0.2, there was a definite change
with ionic strength in the Kz values obtained by Yair
and Nancollas, it is quite clear that a common C = 0.36
yields self-consistent K z values for all the available
e.m.f. data. The use of C = 0.3 in the Davies equation
Table I1 : The Dissociation Constant of HS0,- a t 25”
Davies, Jones, and
Monka Nair and Nancollas
Best C value 0.36 0.36
Mean K2 X l o 2 1.020 i 0 . 0 1 3 1 . 0 4 6 f 0.009
a See ref. IO. * See ref. 2.
for activity coefficients has already been proposed by
DavieslI in the light of recent activity data. When
X = HzS04,plots of Kz against I for different C values
give a series of converging curves with the best C
showing zero slope. For the sake of comparison, the
computer program was then altered to set C = 0 and
vary B&. Another series of convergent curves of K Zus.
I was obtained, with B& = 1.59 giving zero slope and
K z = 0.0102, again by a least-squares procedure. This
leads to a value of 4.8 for & and extrapolated Kz values
ranging from 0.0109 for B& = 1 to 0.0092 for B& = 2.5.
This is shown in Fig. 1. Hamer observed nonconver-
38.0 gency of log K z us. I plots of his data (X = YazS04) when
3.38 various & values were inserted in the activity coefficient
38.7 expression, but he omitted using the same parameter in
the calculation of H + activity as he used in the calcula-
tion of SO4+ activity. Recalculation of Hamer’s data
~ ~~
(5) M. Kerker, J . Am. Chem. Soc., 79, 3664 (1957).
(6) W. J. Hamer, ibid.,5 6 , 860 (1934).
(7) I. M. Klotz and C . R. Singleterry, Theses, University of Chicago,
1940; quoted by R. A. Robinson and R. H. Stokes, “Electrolyte
Solutions,” Butterworth and Co., Ltd., London, 1959.
(8) K. S. Pitzer, J . Am. Chem. Soc., 59, 2365 (1937).
(9) C. W. Davies, H. W. H . Jones, and C. B. Monk, Trans. Faraday
Soc., 48, 921 (1952).
(10) C. B. Monk, “Electrolytic Dissociation,” Academic Press,
London, 1961.
(11) C. mi. Davies, “Ion Association,” Butterworth and Co., Ltd..
London. 1962.
NOTES
-- Bd
1.0
- Bd
0 1.0 2.0
I x 102.
Figure 1. Variation of Kz with I when various Bd values
are used in the activity coefficient expression.
using consistent parameters and a,lso allowing for
SaS04- still shows that for this cell there is no
convergency. The data of Nair and Nancollas2 at
0' were also recalculated varying Be, and zero slope
was obtained with Bd = 1.6. This value was used
to obtain Kz a t all the other temperatures. A least-
squares method then gave AH = -5.3 kcal. mole-'
and A S = -27.0 cal. deg.-' mole-', which may be
compared with the uncorrected values, -5.6 kcal.
mole-' and -27.7 cal. deg. -l mole-', respectively.
The agreement with Pitzer's values,* AH = -5.2
kcal. mole-' and A S = -26.3 cal. deg.-' mole-', is
very good, but is not so satisfactor,y with those of
Austin and Mair.I2
Recently, Reynolds and F u k ~ s h i i n a 'have
~ redeter-
mined K2 a t various ionic strengths using a spectro-
photometric method. Their data, when plotted accord-
ing to eq. I, show an appreciable curvature with an
extrapolated Kz = 9.4 X IOp3 mole l.-'. These au-
thors, however, assumed K2 = 0.0102 and expressed
its variation with ionic strength by the equation
10gKz' = -1.991 + 2.041"2/(1 + 1.7OI"') + 0.03141
Experimental and calculated values are compared in
Table 111, and it is seen that deviations are appreciable
at the lower ionic strengths.
1581
-
Table 111: T h e Dissociation of HSOd- a t Higher
Ionic Strengths
I 0,100 0.250 0.750 1.53
102K2'(ref. 12) 2.57 3.62 5.64 7.36
1O2K2'(eq.2) 2.70 3.70 5.60 7.41
= 1.5
It is clear from the above calculations that the best
value of K z is 0.0103 f 0.0001 mole kg.-'. Conducto-
= 1.59
metric, spectrophotometric, and potentiometric values
all fall within this range showing very good agreement
for such a highly dissociated ion.
Lietzke, Stoughton, and Young14 have calculated the
dissocjation constant of the bisulfate ion from solubility
determinations of silver sulfate in sulfuric acid a t tem-
peratures between 25 and 225'. Although the method
is least precise near room temperature when the dis-
sociation is greatest, they give the same value, K 2
= 0.0103 mole kg.-' as the best average at 25'.
Acknowledgment. We wish to thank Dr. R. W. Dod-
son for valuable discussions.
(12) J. .M.Austin and A. D. -Mair, J . P h y s . Chem., 6 6 , 519 (1962).
(13) W. L. Reynolds and S. Fukushima, Inorg. Chem., 2 , 176 (1963)
(14) M. H. Lietrke, R. W. Stoughton, and T. F. Young, J . Phus.
Chem., 6 5 , 2247 (1961).
The Conductance of Tetra-n-butplammonium
Picrate in Chlorobenzene at 25'
by J. B. Ezell and W. R. Gilkerson
Department of Chemistry, University of South Carolina,
Columbia, South Carolina (Received Sovember 18, 1565)
The limiting equivalent conductance, ito, of a salt
may be much smaller due to the "FUOSS" effect' in
solvents of low dielectric constant (less than 7, gener-
ally) than one would estimate assuming the Walden
product for the salt, AOVO,where 7 0 is the solvent vis-
cosity, to be independent of solvent. If so, this would
greatly affect values of the ion pair dissociation con-
stant of the salt, K , reported in the literature. h
report2 from this laboratory indicated low values of A.
(as much as 50% below the estimate based on the
(2) Walden product) for tetra-n-butylammonium picrate
(1) R. M . Fuoss, Proc. 'L'atl. Acad. Sei. U . S . , 45, 8 0 i (1959).
( 2 ) W. R. Gilkerson and I?. E. Stnmm. J . A m . Chem. S o c . , 8 2 , 5295
(1960).
Volume 88, -\-umber 6 J u n e , 1,964