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AT 298~15°K


Chemistry Department, The University. ShcWcld, S3 7HF, England

(Receiwd 20 August 1974)

Abstract-Earlier emf data on cells using the PbSO,/Pb(Hg) electrode have hern used. in COnJUnCtlOn with
a recent determination of the standard potential of this electrode, to calculate stoichiometric activity coeC-
ticicnts of H,SO, in water at 298,lSK.

Numerous investigations are reported in the literature too large and more recent determinations by both
of the stoichiometric activity coefficients of sulphuric LY#I~[ lo] and spectrophotometric methods[ I I] indi-
acid in aqueous solutions. Cell emf’measurements have catc a value for this in the region of (0.0104 f 00M4)
been the most frequent method of evaluation, but mole kg- ‘. It is also apparent from inspection of Fig.
freezing temperature and vapour pressure methods 3 of ref. [7] that contrary to the authors’ statement, the
have also been used[ 11. extrapolation procedure used to deduce the standard
The range of values obtained is up to 20 per cent at cell potential, is not reconcilable with the Debye-
a molality of 0.02 mole kg- 1which is unfortunate since Hiickel limiting law for the appropriate activity coefli-
aqueous sulphuric acid solutions are often used as a cients. Consequently the quoted standard cell potential
primary standard in osmotic coefficient detcrmina- (- 350.52 mV) is incorrect. Baumstark[8] used an un-
tions using the isopiestic method. For many years the refined extrapolation method to obtain the standard
accepted values were those of Harned and Hamer [Z, 31 cell potential and whilst the procedurejs open to many
based on the cells criticisms, neglect of both association of NC and
SOzJm ions. and deviations from the Debye-Hiickel
Pt,H,IH,SO,IPbSO,(PbO,,Pt limiting law. coincidentally resulted in him obtaining
and a value (-352.17 mV) which is close to that we con-
sider correct. The experimental results obtained do,
Pt,H,IH,S041Hg,SO,IHg. (2) however. show more scatter than those obtained by
Hamer’s[4] value for the dissociation constant of the Shrawdcr and Cowpcrthwaite[7].
bisulphate ion was used in the necessary extrapola- We have recently[ 121 determined the standard elec-
tions. Covington et a&5] concluded that the results trode potential of the PbSOJPb(Hg) electrode at
obtained earlier[2,3] were in error, particularly at low 298.15”K from cell5 using a calcium-ion-exchange
molalities of sulphuric acid. Covington[S] found con- membrane electrode. That this latter electrode behaves
sistent results for the above two cells and his results are in a Nernstian manner has also been shown[ 131. The
considered the most reliable, notwithstanding the fact value we obtained for the standard electrode potential
that some uncertainty ( f 0.4 mV) is associated with the was -(3526 k 0.4)mV. The error limits given arc
standard potentials of cells 1 and 2 because of the in- maximum possible errors and arise principally from
herent ambiguity[6] in the bisulphate ion dissociation extrapolation problems[ 141. Using this result we can
constant. The results of Shrawder and Cowperth- use the earlier[7, S] experimental data to obtain stol-
waite[7] and of Baumstark[X] obtained using cells of cliometric activity coefficients of H,SO, in aqueous
the type solutions which arc independent of the bisulphate ion
dissociation constant.
Pt,H,lH,SO,IPbSO,IPh(Hg) (3) As was mentioned above, the experimental data on
have been largely &regarded by recent authors, poss- ccl1 ejn/ of Baumstark[X] arc apparently of lower preci-
ibly because of the disparity between the quoted acti- sion than those of Shrawder and Cowperthwaite[7]
vity coefficients for sulphuric acid but also because of although the results obtamed do scatter about these
the advcrsc opinion on the reliability of the lead sul- latter‘s results. Accordingly we have treated only the
phate-lead amalgam electrode in acidic solutions, results of Shrawder and Cowperthwaite[‘i]. The stoi-
expressed by Harned and Hamer[9]. chiometric mean molal activity coefficients (7) of
in evaluating the standard potential of cell 3, HZSO, were calculated from
Shrawder and Cowperthwaite[7] used Hamer’s[4]
E = E’/PhSO,/Ph(Hg) - (3R T/2F) In 7
estimate of the dissociation constant for the bisulphate _ R T/28’) In 4m’(nr + Z)
ion (0.0120 mole kg ’ I. This value is almost certainly
where E is Ihe observed emf of cell 3, E”/PbSOJ
Pb(Hg) is the standard electrode potential of the lead
*Present address: The Steetley (3ompany, Carlton Road, sulphate-lead amalgam electrode, 111is the stoichio-
Worksop, England. metricmolalityofsulphuricacid,Zisthemolal solubibty
258 Stoichiometric activity coefficients

Table 1. Stolchiometric activity coefficients of H,SO, in aqueous solutions at 298,15”K

Stoichiometric activity coefficients

Schrawder and Cowperthwaite[ 171
Original Present Harned and Covington*
m/mole kg- ’ analysis analysis Hamerr t’t nl[S]

0~001 o-837 o-796 + ONI 0.830

0.002 O-767 O-730f 0.005 o-757
0005 O-646 0.614 * 0,004 0.639
0.010 0543 0516 f 0.003 0.544 O-516
0020 O-444 0.422 + PO03 0.453 O-420

* The lowest molality investigated by CovingtonLS] was approximately 7.2 x lo3 mole kg- I. The given activity coeffi-
cients were calculated at rounded molalities using the parameters quoted in ref. [S].

of PbSO, in the sulphuric acid solution under investi- 2. H. S. Harned and W. J. Hamer, J. Am. them sm. 57,
gation and the other symbols have their usual mean- 27 (1935).
ings. 3. W. J. Hamer, J. Am. chew. Sot. S7, 9 (1935).
4. W. J. Hamer, J. Am. them. Sot. 56,860 (1934).
The results obtained are given in Table 1. Included 5. A. K. Covington, J. V. Dobson and Lord Wynne-Jones,
in Table I are the results of the original erroneous Trans. Fnradoy Sot. 61,205O (1965).
analysis of Shrawder and Cowperthwaite[II] and those 6. A. K. Covington, J. G. Freeman and T. H. Lilley, J.
of Harned and Hamer[2,3] and Covington et al[SJ, It phys. Chem. 74,3773 (1970).
is apparent that the present analysis gives results which 7. J. Shrawder and I. A. Cowperthwaite, J. Am. &em. Sot.
agree, within experimental error, with those obtained 54.2340 (1934).
by Covington[S]. We consequently confirm his 8. G. Baumstark, Dissertation, Catholic Universitv of
opinion that the often used[l5] activity and osmotic America, Washington D.C. (1932).
coefficient data on sulphuric acid solutions are in 9. H. S. Harned and W. J. Hamcr, J. Am. chrm. SW. 57,
33 (1935).
10. A. K. Covington, J. V. Dobson and Lord Wynnc-Jones,
Acknowledgement--One of us (C.C.B.) thanks the S.R.C. for 7rans. Faraday Sot. 61, 2057 (1965).
a Research Studentship and the Steetley Company for finan- 1I. Ref. [l] page 385.
cial support. 12. C. C. Briggsand T. H. Lilley, submitted for publication.
13. C. C. Briggs and T. H. Lilley, J. Chr~. Thermodynamics,
6. 599 (1974).
REFERENCES 14. T. H. Lilley and C. C. briggs, Elrctrochim. dcm. 20, 253
1. For a discussion see R. A. Robinson and R. H. Stokes. (1975).
Electrolyte Solutions, Butterworths, London, 1965. 15. See ref. [l] Appendixes 8.4 and 8.9.