order in peroxide in agreement with the cxpcri- which is formed in the rate-dcterinining step, is rap-

mental data. The experimentally determined rate
constants k1 and k - 1 are related to the constants
given in eq. 7 and 8 by the equations
kl = kR2K3KJ4/K,K~'
k- 1 = kK4Kj/K?k'?X'
which show that log kl should be proportional to 4
log X and that k-1 should be proportional to 2 log
1/X. The value of (HSOd-)/(H$3O,), which we
designate by X, has been related t o the Hammett
acidity function, Ho, by the equation3
ZIo = - S 30 + log (HSOI-)/(IIZSO,)
Values of 4 log X and Z log l/X as a function of c/o
sulfuric acid were calculated from Brand's data and
are shown in Fig. 2. The slopes of these lines are
-0.55 and +0.23 while the slopes of the log k l os. yo
sulfuric acid and log k-1 DS. yo sulfuric acid are
-0.59 and +0.24.
The good agreement is further evidence for the
idly oxidized to NOzf by a persulfate ion. Since
potassium nitrite yields the nitrosonium ion in sul-
furic acid, it is just as efiective a catalyst as potas-
(9) sium nitrate or nitric acid.
The temperature dependence of hl and k-1 is
(10)
shown in Fig. 3 , the former being determined in
%.870 sulfuric acid and the latter in 88 9y0acid.
From thc slopes of these lines the activation energy
of kl is 13.3 kcal. per mole, and of k-1 15.3. Since
k'a and X have negative temperature coefficients
and since thesc appear in the numerator in the
equation for kl and in the denominator for k-1, the
tsmperature dependence and hence the activation
energy of kl would be expected to be lower than that
of k-1.
The rate-determining step shown above is prob-
ably a sequence of steps which may be formulated as
SOL+ + so,YO,- --+ OzY--O o-sO*-oso~
02x- O-o-so~-oso~---f xi03 + + so,-- + KO? +

proposed mechanism. The nitrosonium ion, NO +, SO3+ --+ so++ 02

(3) J C D Brand, J Chcm S o c , 1002 (19;O) IRERDCEU PROPI\GGROIJUD.
RLn

[CONTRIBUTIOV F R O X TIIE DEPARThfEST O F CHEMISTRY, CLARKSOU COLLEGE O F TECHNOLOG\

]

The Ionization of Sulfuric Acid'

BY MILTOX
RERKER
8. 1956
RECEIVEDOCTOBER

The method of Sherrill and Soyes, based on conductance and transference number, has been used to calculate the ioniza-
tion of sulfuric acid at 18 and 50" from data in the literature and to extend the results a t 25' to higher concentrations. T h e
results have been compared with those obtained by other methods. The effect of the nature of the counterion on the equiva-
lent conductance of sulfate and hydrogen ion has been examined. The equivalent conductance of bisulfate ion has been
calculated a t 18, 25 and 50".

The ionization of sulfuric acid has been studied i n solving the above equation, Sherrill and Noycs
by electromotive force,* ~ o l o r i m e t r y , ~kinetics,6
.~ used values of AH and Aso4obtained from the con-
Rarnan spectra6-8 and a combination of con- cluctance and transference number of hydrochloric
ductance and transference n ~ m b e r . ~Sherrill and acid and potassium sulfate a t the ionic strength
Xoyes employed transference number as well as prevailing in the sulfuric acid solution under con-
conductance data because of the unavailability of sideration. However, they did recognize that this
the equivalent conductance of the bisulfate ion. "ionic strength principle" could not be justified
Xssuming the first hydrogen is completely ionized, theoretically. Since the ionic strength in the sul-
they developed the equations furic acid is given by m ( l 2 a ) , eq. 1 had to be +
01 = ( A +
AT - AH)/)(AR Aso,) (1)+solved by a series of successive approximations.
The results of Sherrill and Noyes are confined to
A~aso, = ( A - k,T - aAqo,)/(l - ct) (2) 23' because of the limited data for T available a t
where that time.1° I n this paper we extend their calcula-
CY fraction of HSO4- dissociated tions to 18 and 50' using data which have since ap-
.\ equivalent conductance of HtSO4 peared in the literature. We have also carried the
equivalent conductance of H + in the I I S O , 25' calculations to higher concentrations.
, \ R o ~ equivalent conductance of SOr- in the II2Si), The stoichiometric transference number, T ,
.iFrao, equivalent conductance of HSOI- in tho I i ~ S 0 l n hich appcars in the above equations is related to
T 5toichiometric transference number the individudl ionic transference number, l 1 t , by
(1, Tiiis work has been supported b y t h e Atomic Iinergy Coinriiir- = fii - LHSOi (3)
sion, C o n t r a c t No. A T (30-1)-1801.
(2) (a) W. J . Hamer, THISJ O U R N A L , 56, 800 (1931); ( h ) C . TV. 1%liere
Davies, 11. W.Jones and C. B. Monk. T r a n s . F n r n d n y SOC.. 48, 927
. ~~,
11952). t,, = (,jlIT/C\ (1)
(3) I. M , Klolz, Thesis University of Chicago. 1940 /1!w1~ = rnso,Aiwo4/r.\ (5)
(4) C R . Singleterry. Thesis, 7Tniwrsity of Chicago, 1910
[,i) w. C B r a y and H. A. 1.iebhafiky. THIS JOURNAL, 57, 5 1 (193:). and are the norlnalities o f 11 .+,
CH, C ~ ~ S Oarid
, G
16) S.K Rao, I n d r n n .I. P h y s . , 14, 143 (1940).
( 7 ) €I 11, S m i t h , Thesis. University of Chkaso. 1040.
€GO4- and HzSOr, respectively. I n the Hittorf
(a) I,. Ti A I P r a n v i l l e , T h r r i c I'nirPrsity < ? f Ch;cago. 1049. (10) 0. F T i r r e r . ibid.. 26, 1039 (1901).
('1) 11.S. Shrriill a n d A . h. Noyr.; Trirs J O I ~ R N A I , 48, , 18'il f!92l'i). (11) 1I Spiro, J . C h e w Edtrc., 33, 40.1 11950).
July 20, 3'337 IOPI'IZATION
OF SULFLXIC
ACID 3665

method T is equal to the nuniber of equivalents of, The equilibrium quotient Kz' for the second ioni-
sulfuric acid transferred from anode to cathode zation of sulfuric acid extrapolates to the ionization
region per faraday of electricity passed when elec- constant IC2, at infinite dilution. The values of the
trodes reversible to sulfate ion (e+, Ag, Ag,SO?; ionization constant a t 18 and SOo, as calculated
Hg, I-IglSO4) are used. With the galvanic cell from conductance and transference number data,
method T is obtained from are reported here for the first time and are com-
T = dE~/tlE (6) pared with the results of other methods in Table
IV.
E is the electromotive force of the sulfuric acid con-
centration cell without transference in which the I
TABLE
anode is reversible to hydrogen ion and the cathodc ~ O X I Z A T I O NO F A N D EQUIVALENT CONDUCTANCE OF
to sulfate ion. ET is the electromotive force of ZISod- AT 18'
the sulfuric acid concentration cell with trans- Quotient
ference in which both electrodes are reversible to of Eqiiiv.
Molality Fraciion activity con-
sulfate ion. of HSOI- Ionic Equilibriiim coef- ductance
HzSO, ionized strength quotient ficients of HSOl -
HamerI2 has determined T for sulfuric acid over
a wide range of concentration and temperature by 0 0.0124 1 43.6
the galvanic cell method. He found that T re- 0.0005 0.936 0.00144 .0141 0.851
mained constant in the range from 0.05 to 0.2 m. .0010 ,888 .00273 ,0150 ,800
and then dropped rapidly with increasing concen- .0025 ,790 .00645 .0168 .714
tration, falling to about 0.5 in concentrated sulfuric .0050 ,696 ,01196 ,0194 ,619 40.1
acid. Using the Onsager equation, he calculated .0100 .600 ,0220 .0240 .500 38.7
the variation of t H with concentration in the infi- .0250 ,461 ,0481 .0312 ,385 85 4
nitely dilute range where the sulfuric acid is com- .0500 ,333 .0835 .0333 .360 32.0
pletely ionized. Since in this range T would be .lo00 .317 .1634 .0614 ,195
expected to increase with concentration he sug- ,2500 .298 .309 ,1377 .OS71
gested that the constancy of T in his dilute solu- ,5000 ,295 ,795 .271 ,0443
tions was actually a manifestation of a flat maxi- 1.133 .403 2.05 1.U83 ,0111
mum and that a t concentrations lower than 0.05 TABLEI1
tn, T would decrease. H a n d s work is discussed OF HySOI A N D EQUIVALEXT
IONIZATION CONDUCTANCE
OF
by Harned and Owen.13 Ranning and Waltz14 HS0,- AT 25"
extended the work of Hamer to solutions of sul- Equiv.
furic acid in anhydrous methanol a t 25'. Fergu- Fraction
HSOa- Ionic
Equi- Quotient of con-
Molality librinm activity ductance
son and Frnnce'j had made an earlier study of the of H&Ol ionized strength quotient coefficients of HSOd-
same cell as Hamer a t 25' for one pair oi concen- 0 0.0102 1 51.2
trations. 0.00023 0.959 0.0007295 ,0118 0.864
We have used Hamer's extensive values of T to ,0010 ,874 ,002618 ,0130 .785
calculate the dissociation of sulfuric acid a t 18 and ,0050 ,667 ,01167 . o m ,604 46 8
50" by the method of Sherrill and Noyes and to .0125 ,523 .G2558 .0209 .488 45.3
extend their results a t 23' to higher concentrations. ,0250 .417 .0156S ,0253 ,403 39 8
The equivalent conductance of H S O I - also has been ,0500 ,326 ,08357 ,0335 ,302 38 7
calculated. ,1000 ,266 ,1532 ,0459 ,222
Values of A H were obtained froni the equivaleiit ,250 ,267 ,3811 ,1185 ,0861
~ o n d u c t a n c e ~ and
~ , ~ ' transference nuniber18*19of ,526 ,311 ,853 ,311 ,0328
HCl. For ilso, we used the equivalent conduct- ,933 ,362 1.608 .722 ,0141
ance2oe21 and transference number22p22of K2SO4. 1.13 .436 2.16 1.23 .00707
For the equivalent conductance of H2S04 we used 1 .so .73 4 . 4 3 8.31 .on123
the data of Noyes,2n Kolilrausch,21 Campbell,24
and Roughton.25 TABLE111
Our results are presented i n Tables I, I1 and 111. IONIZATION
OF H2S04 AND EQUIVALEXT
COSD~JCTANCE
OF
(12) W J . Hamer. THISJ O I T R E A L . 67, 662 (1935). HS0,- AT 50'
(13) H. S. Harned and B. B. Owen "Physical C h e m i s h y o f Elec- QuotiPnt
trolytic Sol'itions," 2nd E d , Reinhold Publ. Corp.. New Y < , r k .N Y.. of Eqniv.
Fraction Equi- activity con-
1Q50, pp. 442-443 Molality HS.0,- Ionic librium coef- durtance
( 1 4 ) E. W. Kanning. and J. Waltz. THISJ O U R N ~ L 63, 3i7R (1941). of HISO, ionized strength quotient ficients of H S O l -
(15) A. L. Fergnson and W G France, ihid. 43 2150 (1921).
(16) T Shedlovsky i b r d . . 5 4 , 1111 (1932).
0 0.0053 1 73.3
(171 B B. Owen and P. H Sweeton, i f d . 63 3511 r1911). 0.00100 0.764 0.00253 .0057 0.93
(18) H S Harned and E . C Drehy, i b i d . 61. 3113 (1939). .00500 .493 ,00993 .0073 .73 66.5
(In) I . . G . Longsworth. ibid , 5 4 , 2741 (19:32). .00625 .456 .Ill195 .0076 .70 65.4
(20) A. A. Noyes, "The Electrical Condurtivity of Arcueous Solu- .02506 .259 .0376 .0110 .48 59.4
tions," Carnegie Institution ofWa=b!ngton, Washinkton. D C. I907
(21) F. Kohlrausch and L. Holborn, " D a s Leitvermogen der Flek- ,04016 .214 ,0573 .0183 .40 57 5
trolytc," B. G. T e u h n e r , Leiprig and Berlin, 1916. .05025 .200 ,0704 .0151 .35 55.8
(22) L G. I n n g s w o r t h , THISJ o U R N A l . , 67, 1185 (1935); 60, 3070
(19381 Harned and Owenz6have pointed out the neces-
(23) A. A. Noyes and K . G . Falk, i h i d . , 33, 1436 (1911). sity for re-examining the methods of computing
(24) A. S. Campbcll. E. M. X a r t i n i a r k , D. Bisset a n d M. E. ionization constants from electromotive forces for
Bcdnis, Can. J. Chem., 31, 303 (19.53).
( 2 5 ) J E . Renghton. J A p P l C'h?in (I,oitdunI, 1. S > l p p l Tssuc No. 2, acids as strong as HS04-. They give no weight to
S-141 (1951). (26) Ref. 13, p. 430.
366G LIILTON KERKEK Vol. 79

TABLE
1V fate differs from that obtained from thallium sulfate
DISSOCIATION CONSTAXT 01' IIsoi-' x 10' in the direction t h a t would be expected from the
From Prom greater ion association in the latter.
conductance F r o m electromotive force spectro-
and Hamer photometry,
Temp., transference recalcd. Klotza and VI
TABLE
"C. no. Hamergb by Daviesz5 Davies25 Singleterry' OF S U L F AAT
I < Q ~ I ~ . ~ LCOSDUCTANCE
ENT ~ E25' FROM CON-
16 1.24 1.30 1.14 1.26 1.26 ~LICTAYCE AND TRANSFERENCE NUMBER OF VARIOUS
25 1.02 I ,20 1,02 1. o : j 1.02 SALTS~U
-23,1.7--30
50 0.53 0.79 0.G9 0.50 0.48 Ionic strength SagSOp KzS04 TltSOa ZnSOd CdSOd
0.002 76.1 76.0 76.0 76.1 76.0
Hamer's electromotive force results, citing instead
,010 71.2 71.3 70.1) 71.1 70.4
those of Klotz3 and SingIeterry4 obtained by a
colorimetric method. The temperature depend- ,050 63.4 63.4 69.7 .. 63.8
ence of their ionization constants leads to heats of .lo0 58.9 59.0 53.4 .. 61.2
ionization which are in accord with the accepted Although the equivalent conductance of the sul-
values, while those of Hamer are in gross disagree- fate ion does depend to some extent upon the
ment. Klotz and Singleterry report that the error nature of the cation, the agreement among the re-
in their results is probably less than 2%. Davies, sults is quite good, especially in view of the uncer-
Jones and Monk2 have recalculated Hamer's data, tainties involved in the ion association of t h e solu-
introducing correct values of activity coefficients tions. Even a t 0.1 ionic strength, the fraction
and bringing them into slightly better agreement with ionized would differ by only 1.5% if the equivalent
the colorimetric work. They have, furthermore, conductance of 53.4 derived from the thallium sul-
carried out electromotive force measurements in a fate data had been used instead of 59.0 derived
cell which minimizes the ion association, obtaining from the potassium sulfate data.
results in good agreement with Klotz and Single- The fraction ionized ci is not very sensitive to
terry. The ionization coilstants calculated from the equivalent conductance of sulfate ion since in
the data of Sherrill and Noyes a t 25' and by us a t cq. 1 it is added to the much larger equivalent con-
1s and 50' are also in agreement with the colori- ductance of the hydrogen ion. This simply trans-
metric work. fers the onus of the method to the determination of
Although Sherrill arid Noyes recognized that the equivalent conductance of the hydrogen ion.
ionic conductivities are not determined by ionic In Table VI1 we have compared the values of
strength, they formally used an ionic strength prin- '113 obtained froin several monobasic acids a t com-
ciple in estimating the equivalent conductance of parable ionic strengths. I t is apparent that thr:
the sulfate and hydrogen ions in sulfuric acid, and anion effect is small. We should like to call attcn-
we have followed their heuristic procedure. tion to the agreement between the hydrochloric and
\Ne have used the data for potassium sulfate in iodic acid results where the available conductance
estimating the equivalent conductance of sulfate and transference number data are quite accurate.
ion because they are available over a wide range of What is especially striking about the agreemeat is
conditions. In Tables V and V I there is compiled that iodic acid is only partially dissociated so t h a t
the equivalent conductance of sulfate ion a t several the equilibrium data have also entered into the cal-
ionic strengths at 18 and 25' as obtained from a culation much as in the case for the bi-bivalent
number of other salts. For the bi-bivalent salts, salts treated a h o w .
where ion association is appreciable, the equivalent
conductance of the sulfate ion is calculated from TABLE
VI1
the product of the anion transference number and ~!:QLJlVALh':N1' C u X D U C I A S C E O F I - I Y ~ R O G E
I ONN A T 25' l ~ R O M
the equivalent conductance of the salt, divided by CONDUCTANCE A N D TRANSFERENCE P\rTI'IIIBER O F \:ARIOUS
the degree of dissociation. The correctioll for ioii ACIDS
association is not so easily made for the uni-bi- Ionic strength HCl'~-lQ HNOr21t?7 HI27 HI 0 3 2 1 .
valent salts but even a rough approxiination in- 0. 0 1 339.9 340 .. 339.3
dicates it is small enough to be neglected. The .05 330.9 830 331 330.0
equivalent conductance of sulfate a t 0.1 ionic . 113 325.5 325 326 ...
strength obtained from sodium and potassium sul- .2!? 320.4 .. 316
'rAB1.E The quotielit of activity coefficients 71%is de-
EQUIVALENT CONDUCTASCE 4 T 18" FROM
O F SCLFATE fined by
COSI)UCTANCL; A N D TRASSPERENCE SUMBER OF I'ARIOUS ?il = (ia)(.iSoa-)/YH?904- (7 I
SALTS" -"
Ionic strength XarSOa &SO4 CdSOr CuSOa MgSOh
aI1d
0.002 63.0 63.4 64.7 66.0 63.5 k'z k-2'yR (Xi
. nio 59.0 59.6 60.0 60.j 58.2 where Kz and ICz' are the ionization cullstant and
, (I50 3 . 8 54.2 5-1,1 , . .. equilibrium quotient, respectively, and 711+, ?so4
.IOU 50~1 SI..? 51,s .. .. and y11s0,- are ionic activity coefficients. Young
~

('27) "International Critical l'ables," hlcGrdw -13111Rouk Co., Inc., and B l a t have
~ ~ ~compared the values of Y R at 215"
New Y o r k , R'. Y , , 1923. obtained in dilute solutiolis by the conductance arid
( 2 8 ) n . n o w e t l an,^ I < . L V ( ; l L r r ~ ~mils , , I ,:3o7i
, y , J ~ , U ~ ~ 60, transference iiuinber method of Slicrrill m ( 1 N o ) ~ s
(1938).
(20) R . E. L a n g a n d C. V K i n g , ibi& 76, 4716 (1921). (31) h l . Spire, J . Phvs. C h r j n , , 60, !Ji'l, (195fi)
(30) C . W. Davis, J . Chcm. Soc., 140, 2093 (1938). (:<?I rr I' Y W I I ~~ I U II. .z UiiatL. i i
July 20, 1957 OF SULFURIC
IONIZATION ACID 3667

and the kinetic method of Bray and Liebhafsky with

those obtained in more concentrated solutions by
Rao6 using Raman spectra. Later, Smith7 and
Maranvilles obtained more accurate Raman spec-
tral data. Since we have extended the values of
YR a t 25' to the concentration range used in the
kinetic and Raman spectral studies, it is of interest
to compare results again, especially in the over-
lapping region. Figure 1 is a curve of YR a t 25'
versus the square root of the ionic strength. The
agreement among the three methods is excellent
up to an ionic strength somewhat greater than 1.
'This agreement is remarkable, especially a t the
higher ionic strengths. Our only justification for
extending the 25' calculations to these high con-
centrations has been this unexpected agreement
among the three methods.
A comment on the work of Bray and Liebhafsky
is in order. There was considerable scatter in their
results. I n plotting a function of YR against the
0.1 0.2 0.3
1.0 (Ionic strength)'/2.
Fig. 2.-Equivalent conductance of HSOh-. Circles are
0 SHERRILL AND NOYES computed from conductance and transference number data.
0 THlSlrJORK Lines are drawn with slope from limiting Onsager law.
R A Y AND LIEBHAFSKY
ACTUAL RESULTS) square root of the ionic strength, they drew a
W BRAY AND LIEBHAFSKY smooth curve which they presumed was an extrapo-
(SMOOTHEDRESULTS) lation of Sherrill and Noyes conductance and trans-
0.1 + SMITH ference number results but which obviously was
not the best representation of their own data.
Previous worker^^^^^^^ have used these smoothed
data but we find, despite the scatter, that the ac-
G2
2- \ tual data of Bray and Liebhafsky give better agree-
ment with both our calculations and the Raman
spectral results. I n Fig. 1, points representing both
their actual and smoothed results are shown.
0.01 The conductance data a t 50" do not extend to
sufficiently high concentrations to compare YR
with those from Raman spectra a t that tempera-
ture.
I n Tables I, I1 and I11 is also found the equiva-
lent conductance of the bisulfate ion as calculated
0 by eq. 2. I n Fig. 2, the equivalent conductance of
bisulfate ion is extrapolated to infinite dilution us-
0.001 ing the limiting Onsager slope for a uni-univalent
0 1 2 3 electrolyte. Since the slope itself is dependent on
(Ionic strength).'/l the intercept, it had to be determined by a series
Fig. 1.-Effect of ionic strength on the quotient of activity of successive approximations.
coefficients, YR, of HSOd- a t 25". POTSDAM, N. Y.