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Comments on Simultaneous Determination of K and AH

Analysis of Some Calorimetric Data Concerning the


Formation of Bisulfate Ion in Aqueous Solution
Sergio Cabani and Paolo Gianni
Istituto di Chimica Fisica, Unioersita’di Pisa, Via Risorgimento 35, 56100 Pisa, Italy

A critical analysis is conducted on some experiments thermodynamic study of reversible reactions which involve
relative to formation of the bisulfate ion. This i s given ion formation and take place in solutions with variable
as an example of the possibility of simultaneous de-
termination of K and A H from calorimetric measure- ionic strength.
ments. Interpretation of calorimetric data depends In particular the following points will be emphasized: the
upon the expressions used to specify the activity difficulties which are met with in the identification of the
coefficients or the existence of multiple equilibria. source of systematic errors even when their presence is reason-
ably suspect and the caution with which calorimetric data,
IN THE PAST FEW YEARS, various authors ( I ) have employed even of high precision, are to be considered when information
calorimetry as a self-consistent technique to obtain the stan- is simultaneously desired on the enthalpy change and the
dard free energy, enthalpy, and entropy of formation for rela- equilibrium state of relatively complicated reactions. A
tively low stability adducts. Analyses were also conducted comparison will be made finally between experiments con-
by us ( 2 ) and others (3) to ascertain the effect of error prop- ducted with the enthalpic titration procedure and experiments
agation on the values of K and AH for simple reactions of in which separate additions of one reagent are made to
the type (2): the calorimeter charged with the second reagent.
A+B*AB (1) EXAMINATION OF SOME CALORIMETRIC DATA ON
THE DISSOCIATION OF THE BISULFATE ION
or of the type (3):
Many papers have been published concerning the ioniza-
HA + B-*HB+ A- (2 ) tion equilibrium of HS04-, but there is some disagreement
with regard to the value to be attributed to its thermodynamic
when these values are calculated using only calorimetric data. equilibrium constant ( 4 ) . Essentially, this depends upon the
Our analysis ( 2 ) of the effect of random errors, which as- expression chosen for the product of the ionic activity coeffi-
sumed the reaction heat 4r to be the only quantity affected by cients I’ = Y=+ y ~ 0 ~ ~ - / y ~ 8Moreover,
0~-. it seems arbitrary
errors, provided revealing insights into: the magnitude of whether to consider (5), or not consider ( 4 , 6-8), the forma-
the adduct stability constant which is necessary to study the tion of ion pairs when ions like Na+, KC, Ag+, or Ca2+ are
formation process by solely calorimetric methods, the experi- present in solution. For convenience Table I presents a
mental conditions which must be satisfied in order t o mini- summary of the results obtained for both the thermodynamic
mize the errors effect, and the criterion which may be adopted equilibrium constant and the reaction enthalpy of the ioniza-
t o give proper weight to single experiments. tion of H S 0 4 - at 25 “C (see also References 4 , 9-12). Some
As far as systematic errors are concerned, they were ex- of those AH values have been calculated from pK determina-
pressed by a constant error on a generic molar dilution or tion at various temperatures (5,6,8,10,13), others from calori-
solution heat of the titrant (A). When increasing amounts of metric measurements (14-18).
A are added to a solution containing reagent B at the con- -
centration COB (enthalpic titration), surprisingly consistent (4) A. K. Covington, J. V. Dobson, and Lord Wynne Jones, Tram.
values of K and AH are computed for each of the different Faraday SOC.,61, 2057 (1965).
additions of A . This occurs even when the additional heat (5) C. W. Davies, H. W. Jones, and C. B. Monk, ibid., 48, 921
( 1952).
due to the systematic error is large with respect to the true (6) I. M. Klotz and C. R. Singleterry, Thesis, University of Chi-
reaction heat. However, the average values ( E or F H ) cago, 1940. For K and A H data, see Ref. l l . Values of param-
corresponding to titration curves with different COB vary eters A, iB, and C were deduced from: W. J. Hamer, “The
sensibly among each other and monotonically with COB (see Structure of Electrolytic Solutions,” John Wiley and Sons,
New York, N.Y., 1959, p 240.
Tables I and I1 of Reference 2). (7) M. Kerker, J. Amer. Chem. SOC.,79, 3664 (1957).
This analysis showed, therefore, that very different con- (8) W. L. Marshall and E. V. Jones, J . Phys. Chem., 70,4028 (1966).
centrations of both reagents are needed to obtain significant (9) J. J. Christensen, R. M. Izatt, L. D. Hansen, and J. A. Part-
values of K and AH. ridge, ihid , p 2003.
Unfortunately, even when the variation of the thermody- (10) H. S. Dunsmore and G. H. Nancollas, ibid., 68, 1579 (1964).
(11) T. F. Young and D. E. Irish, Airn. Rec. Phys. Chem., 13, 448
namic parameters of the reaction under study leads one to sus- (1962).
pect the presence of a systematic error, it is not easy and some- (12) R. M. Izatt, D. Eatough, J. J. Christensen, and C . H. Bartholo-
times impossible to unequivocally localize its origin. mew, J. Chem. SOC.( A ) , 1969, 45.
I n this note some calorimetric measurements relative to the (13) M. H. Lietzke, R. W. Stoughton, and T. F. Young, J . Phys.
Chem., 65, 2247 (1961).
formation of H S 0 4 - ion will be examined. This is an example (14) J. M. Readnour and J. W. Cobble, Iiiorg. Chem., 8, 2174
of the possibilities offered by calorimetry for an accurate (1969).
(15) K. S. Pitzer, J . Amer. Chem. SOC.,59, 2365 (1937).
(1) F. Becker, Chem.-Ing.-Tech., 41, 1069 (1969). (16) E. Lange, J. Monheim, and A. L. Robinson, ibid., 55, 4733
(2) S. Cabani and P. Gianni, J . Chem. SOC.( A ) , 1968, 547. (1953).
(3) J. J. Christensen, D. P. Wrathall, J. 0. Oscarson, and R. M . (17) J. M. Austin and A. D. Mair, J . Phys. Chem., 66, 519 (1962).
Izatt, ANAL.CHEM., 40, 1713 (1968). (18) A. G. Zielen, J. Amer. Chem. SOC.,81, 5022 (1959).

ANALYTICAL CHEMISTRY, VOL. 44, NO. 2, FEBRUARY 1972 253


~~~

Table I. K and AH Values for the Ionization of HS04- at 25 “C


Parameters used for the -AH
calculation of log ra K X lo2 Kcal
Method A BB C moles K g l mole- 1 Ref.
emf: Hz,Pt/NaHS04,NazS04,NaCI/AgCI, Ag 0.5 1 0.2 1.02 ... (5Y
: Hz, Pt/HzS04, HCI/AgCl, Ag 0.5 1 0.2 1.03 5.20 (5)
: Hz, Pt/HzSO4, HCl/AgCl, Ag 0.5085 1 0.36 1.046 f 0.009 ... (10)
: Hz, Pt/HzS04, HCl/AgCl, Ag 0.5085 1.59 0 1.02 5.30 (10)
: Hz, Pt/NaHS04, NaZSO4/HgzSO4, Hg 0.5107 1.9 0 1.06 f 0.09 *.. (4)
Spectrophotometry 0.5085 1.9 0 1.015 5.19 (6)
Spectrophotometry 0.5085 (1.7) (-0.015) (1.02) ... (20)”
Solubility: AgzS04in HzS04 0.5085 ? 0 1.032 4.91 (13)
Solubility: CaS04in H2S04 0.5080 0.94 0 1.03 f 0.02 3.85 (8)
Conductivity ... ... ... 1.02 ... (5, 7)d
Conductivity ... ... ... 1.03 5.10 (13p
Calorimetry: NazS04dilution in HClO4 ( p = 1) ... ... ... ... 5.20 (15)
Calorimetry: dilution of aqueous HzS04 ... ... ... ... 5.30 (16)’
Calorimetry: HC104 dilution in ( p = 0.02) ... ... ... ... 5.74 (17)
Calorimetry: Na2S04dilution in HClO4 (p = 2) ... I . . ... ... 5.54 (18)
Calorimetry: Na2S04solution in HC1 ( p = 0.01-0.03) ... ... ... 1.03 4.12 (14Y
4
;
a log r = -4A
(1 aBd> - + ”)’
* Data from Hamer (19) revised by changing the expression for log r and taking into account the formation of NaS04- ions.
c The value of the ionization constant of HS04-, at p = 0, K = 1.02 X 10-2 given by Kerker (7) is used by these authors for calculating
the best value of iB and C with a least square treatment of their data.
d From a new analysis of the conductivity data of Sherrill and Noyes (21).
e From Equation 11 of this reference based on the experimental data of Sherrill and Noyes (21).
Calculated by Singleterry (6) as reported in Ref. 11, p 448.
0 The value 1.03 X suggested by Young and Irish (11), is used for the various experiments independently of the actual p value;
the AH value has been reported to p = 0.

Table 11. pK and AH values obtained by Christensen, Izatt, et a[. in a


Calorimetric Study of Proton Ionization from HS04-
Calculation Interaction
System PK -AH (Kcal mole-’) log r proceduree Na+. . .Sod2- Ref.
Na2S04-HC104 1.91 =t0.01 5 . 6 4 f 0.08 (a) SSE Neglected (9)
1.88 f 0.04 4.90 =t0.30 (b) VMM Neglected (12)
1.96 f 0.08 4.90 f 0.30 (b) VMM Considered (12)
(Pr4nN)2S04-HC104 2.20 f 0.1 4 . 1 f 0.5 (a) SSE ... (9)
1.99 ( ?) (b) VMM ... (12Y
(R4N)zS04-HC104 1.97 f 0.03 4.9 f 0.20 (b) VMM ... (12Y
(R = Pr“, Et, Me)
.-

-zZAl/ p
blog r =
+
1 BBdp
- C’z2p. +
See ref. (22); SSE stands for “simultaneous solution of equations” and VMM for “numerical variable metric method of minimization.”
From exuerimental data reuorted in Reference 9 .
From new experimental daia.

Recently Izatt and Christensen (9, 12) computed K and A H 0.1 and A H = -4.1 i 0.5 when the reagent was (Pr4”N)*sod.
for ionization of HS04- from enthalpic titrations in which Later on in Reference 12, the above data were re-analyzed by
aqueous solutions of HC1O4 were added t o aqueous solutions the same authors with the following alterations : assuming
of sodium or tetra-n-alkylammonium sulfates. In Reference that no association exists between akylammonium cations
9, these authors did not take into consideration the formation and Sod2- ions while this association is possible when the
of ion pairs and used for the activity coefficients product the cation is Naf ; using for the activity coefficients the equation:
equation :
2.0364;
2.0366~ log r = - (4)
log r = -
1 + 1.654; (3) 1 + 1 . 6 5 4-p+ I I
The results were: pK = 1.91 f 0.01 and A H = -5.64 f using in the calculations the numerical variable metric
0.08 Kcal mole-’ using Na2S04as the reagent; pK = 2.20 f method of minimization (VMM) instead of the simul-
taneous solution of equations (22). Moreover, values of
(19) W. J. Hamer, J. Amer. Chem. SOC.,56,860 (1934). the relative apparent molal enthalpy for HC104 dilution
(20) W. L. Reynolds and S. Fukushima, ltzorg. Chem., 2, 176
( 1963).
(21) M. S . Shrrril and A. A. Noyes, J . Amer. Chem. SOC.,48, (22) R. M. Izatt, D. Eatough, R. L. Snow, and J. J. Christensen,
1861 (1926). J . Phys. Chem., 72, 1208 (1968).

254 ANALYTICAL CHEMISTRY, VOL. 44, NO. 2, FEBRUARY 1972


Table 111. K and AH of Dissociation of H S 0 4 - Obtained from Calorimetric Data:
Results Derived Using Different Expressions for log r and Different Values for of HCI04
IC IId IIIe IVf
CNS~SO,~ x lozb -AH -AH -AH -AH
Run5 (moles L-l) pK (cal mole-’) pK (cal mole-’) pK (cal mole-’) pK (cal mole-’)
i 2.5090 1.93 5410 1.916 5425 1.896 5072 1.916 5420
k 1.2520 1.93 5450 1.929 5436 1.933 5110 1.929 5423
h 0.4990 1.90 5730 1.914 5549 1.938 5197 1.921 5474
i 0.2493 1.88 5890 1.907 5621 1.933 5287 1.928 5426
a Runs chosen from Table I, Reference 9: titrant was 0.9910F HC104.
Na2SOcconcentration before HC104 is added.
Data taken from Table I1 of Reference 9. Heats of dilution of HClOa (q$klOr) have been evaluated from $L values given by Vanderzee
and Swanson ( 2 4 ) (see Figure 1, curve a). Calculations were performed using the simultaneous solution of equations method.
Data obtained using the “trial and error” procedure described in Reference 2; all the data points were given the same weight, Modifi-
cations have been introduced to allow for the variation of ionic strength ( p ) : the expression log r = -2.036 d p / ( l + 1 . 6 5 4 ~has
) been
used. The heats of reaction were obtained by subtracting from the heats reported in Table I of Reference 9 &Alo, evaluated from +L
values given by Vanderzee (Figure 1, curve a). p values at each point of a run were calculated from pK values of column I; this approxirna-
tion is justified by the fact that rather large variations of pK determine changes in p values which do not alter appreciably the values of
dil.
qHCIO,.The sixth point of run i was discarded as obviousQ erroneous. -
+
e As in ( d ) except that the expression log r = - 2 . 0 3 6 4 ~ / ( 1 +
1 . 6 5 4 ~ ) p was used.
f As in ( d ) except that q$kIo4 were deduced from the dotted curve of Figure 1.

Table IV. Example of the Results Obtained by the Simultaneous


Calculation of K and AH of Dissociation of HS04- from Thermometric Titration Curves.
-AHL
(cal
Runb 103mac~ol” 103m~a:s0,d ffe qobsd’ (call q7Qfcal) 6qh (cal) 102 K I O ~ K L mole-’)
k 0.5081 1.252 0.1275 0.9209 0.8665 +0.0013 1,181 1.178 5436
1.0162 0.2303 1.6801 1.5707 -0.0033 1.174
1.5243 0.3128 2.2916 2.1262 +O. 0030 1,181
2.0323 0.3794 2.8038 2.5815 +O. 0006 1.179
2.5404 0.4335 3.2326 2.9524 -0.0017 1.177
3.0485 0.4781 3,5909 3.2519 +o. 0021 1,180
3.5566 0.5152 3.9033 3.5050 +0.0017 1.179
4.0647 0.5465 4.1733 3.7160 +O. 0037 1,181
4,5278 0.5732 4.2220 3.9048 -0.0033 1.176
5.0809 0.5963 4.6401 4.0634 -0.0052 1.174
j 0.5081 0.2493 0.1940 0.3220 0.2758 -0,0040 1.216 1.239 5621
1.0162 0.3146 0.5381 0.4411 -0.0002 1.239
1.5243 0.3971 0.7051 0.5543 $0.0022 1.248
2.0323 0.4572 0.8453 0.6392 $0.0016 1.245
2,5404 0.5033 0.9658 0.7034 +o ,0020 1.247
3.0485 0.5399 1.0764 0.7557 +o. 0010 1.243
3.5566 0.5698 1.1783 0.7985 +o. 0001 1.240
4.0647 0.5947 1.2735 0.8353 -0.0018 1.233
4.5278 0.6159 1.3647 0.8635 -0,0003 1.238
5.0809 0.6342 1 ,4498 0.8868 + O , 0019 1.247
a Calculation performed as in section 11, Table 111.
Data taken from Table I, Reference 9. Initial volume of Na2S04solution: 100 cc. Titrant: 0.9910F HC1O4.
Moles of HCIOa added.
Moles of Na2S04in the solution.
; H S O ~are the moles of HSO4- at equilibrium.
e a = M H S O , / ~ N ~ ~ S O ,M
f Heats reported in Table I, Reference 9.

qv = qobsd - q2kIo,. For the evaluation of q&o, see Table 111, note d.
6q = qtcalcd - qr. Values of q,calcd have been calculated using the Z a n d AH values reported in the last two columns of the Table.
Values of the thermodynamic dissociation constants calculated at the single point of titration curve with the AH values reported in the last
column of the Table.
Values of K and AH which produce for each run the minimum of 2(6q)2.

given by Parker (23) were employed instead of those of Van- agreement with that suggested by Young and Irish (11) in
derzee (24) used previously. Under these conditions the their review on the ionization reaction of the H S 0 4 - ion. The
discrepancies mentioned above disappear, as can be noticed A H value, instead, is slightly lower in module than that pro-
from the values of K and A H reported in lines 3 and 6 of posed by the latter authors ( A H = -5.22). This treatment
Table 11. does not seem, however, very convincing, especially when one
Of the values proposed by them as the more reliable (pK = compares Equation 4 with the analogous equation with two
1.96 =t0.08 and A H = -4.9 i 0.3), the pKvalue is in fair adjustable parameters reported in Table I: the 0.5 value for
parameter C used by Izatt and Christensen in fact results in
abnormally high activity coefficients. In addition, the agree-
(23) V. B. Parker, Thermal Properties of Aqueous Uni-Univalent ment between K and AH values relative to experiments in
Electrolytes, NSRDS-NBS2, U S . Government Printins Office, which sodium or tetralkylammonium sulfates were used,
Washington D.C., 1965.
(24) C. E. Vanderzee and J. A. Swanson, J . Phys. Clzem., 61, 285 respectively, is not, in our opinion, a sufficient proof of the
(1963). real formation of NaS04- pairs.

ANALYTICAL CHEMISTRY, VOL. 44, NO. 2, FEBRUARY 1972 255


These criticisms were suggested by the examination of some assumed; an additional value of A H = +0.49 Kcal mole-'
of the data reported in Reference 9. That note also reported was also tested owing t o the ambiguities of the data reported
a body of data relative to the titration of Na2S04solutions of in the literature for this quantity (see Table V).
widely varying concentration, with HC104. We noticed The choice should be between the values AH" = -0.49
there that K and A H values exhibited a regular variation with and AH" = +1.1 Kcal mole-', both obtained calorimetri-
C'N~~SO, (see Table I I I ~ s e c t i o nI), although point t o point cally. However, the thermodynamic inconsistency of the
agreement of K values at a given concentration was good (see second set of data reported in Table V cannot immediately be
the examples reported in Table IV). attributed to a misprint. In fact in both References 12 and
A few tests allowed us to rule out that the observed trend 25 the following set is reported for the ion pair KS04-: log
is due to the calculation procedure or to the differences be- K = 0.75 & 0.1; AH" = 1.01 f 0.05 Kcal mole-'; AS" =
tween Equations 3 or 4 for computation of activity coefficients 0.0 + 0.2. Again the condition AS" = (AH" - A F o ) / T is
(see sections I1 and I11 of Table 111). The formation of not satisfied if all the thermodynamic functions are attributed
N a S 0 4 - species or possible errors in the kalues employed for to the formation process of the ionic pair.
the relative apparent molal enthalpy of HC104 ( ~ ~ L ~ ~ were I O ' ) The results obtained with all the different combinations of
then taken into consideration. Calculations were repeated q5LHC104, log I' equations and AHfN,so,values reported above,
assuming the validity of the dilution curves reported in the are summarized in Table VI.
literature for HC104 (see Figure 1); Equations 3 and 4 were The previously indicated monotonic dependence on
both used for the activity coefficients. As far as K and A H is clearly seen to disappear in more than one case (compare
of formation of the hypothetical species NaS04- are concerned, sections IA and IIIB of Table VI). In terms of the best fit,
the values log K = 0.65 and A H = -0.49 Kcal mole-' were however, the best solution (see section IV of Table 111) appears
to be that obtained by: ignoring the formation of ion pairs,
Table V. Thermodynamic Data Reported using Equation 3 for the activity coefficients, and using for
for N a S 0 4 - Formation at 25 "C HC104 dilution an arbitrary curve intermediate between those
AH' AS O
reported in the literature (dotted curve of Figure 1). There-
log K T (Kcal mole-') (e.u.) Ref.
0.65 f 0 . 1 -0.49 i 0.05 +1.3 i 0 . 3 (12) (25) R. M. Izatt, D. Eatough, J. J. Christensen, and C. H. Bar-
0.65 f 0 . 1 -0.49 i 0.05 - 1 . 3 i 0.3 (25) tholomew, J. Chem. SOC.( A ) , 1969, 47.
0.72 +1.1 ... ~ 6 ~ 1 7 ) (26) I. L. Jenkins and C. B. Monk, J. Amer. Chem. SOC.,72, 2695
(1950).

Table VI. K and A H of Dissociation of HS04- Calculated Taking into Account the Presence of NaS04- Ionsa,*
A B
AHLsso4 c,.; x loz -AH -AH
Section (cal mole-') ,Yo' Run (moles l.-l) pK (cal mole-') pK (cal mole-')
i 2.5090 1.911 5550 1.922 5072
I -490 k 1.2520 1.911 5536 1.924 5160
h 0.4990 1.918 5524 1.938 5201
i 0.2493 1.911 5598 1.937 5266
Vanderzee
i 2.5090 1.986 5299 1.957 5042
I1 +490 k 1.2520 1.987 5335 1.987 5064
h 0.4990 1.936 5516 1.956 5198
i 0.2493 1.920 5596 1.947 5267
i 2.5090 1.986 5291 1.962 5013
111 +490 k 1.2520 1.991 5293 1.991 5025
h 0.4990 1.947 5404 1.965 5111
i 0.2493 1.947 5356 1.971 5060
Parker
i 2.5090 1.911 5541 1.922 5065
IV -490 k 1.2520 1.915 5489 1.924 5 144
h 0.4990 1.925 5438 1.947 5112
i 0.2493 1.937 5355 1.962 5057
a For the calculation of the thermodynamic constant, K&,,, and of the enthalpy change, AHHBo,,of dissociation of HSOa-, each run was
analyzed separately in the following way: (1) values of qr were calculated by subtracting from the q values taken from Table I of Ref. (9)
qfIikio,either calculated from the data of Vanderzee (24) (sections I and 11), or from those of Parker (23) (sections 111 and IV). The p
values necessary for the evaluation of q$&or were calculated as indicated in note d and e, Table 111. (2) A series of values are tentatively
assigned to KEs0, while the thermodynamic dissociation constant of NaS04- is attributed the constant value KGm, = 0.22 ( 1 2 ) . Each
K&,, value produces n values of the concentration quotient K;iso, ( n = number of the experimental points of the run) as well as IZ values
of Khaso4through an iterative procedtre which, for each poin:, ends when constant p is reached. (3) The heat contribution of the ion pairs
is evaluated as qNSso,= (mNas0, - mNaso,) where mNaS04are the moles of NaS04- in the solution before HClOl is added, and
mNuSO, the moles in the equilibrium mixture. The sign of AHLaS0,,the formation enthalpy of NaSOa-, is given following the usual thermo-
dynamic convention. (4) Values of qr' = qr - qsas0,are then calculated assigning a positive sign to q. values although they correspond to
1
absorbed heat. (5) For each set of the n values of K;,,,, a value JAHHso,I= ;Zqr'/mHsO,is calculated and then the term 2(6q)2 being
bq = qr' - /AHHso,l'mHso4; mHSO,are the moles of HSOa in the equilibrium mixture. (6) The "best pair" K&,,, A H H S O , is identified
as that which produces the minimum of the function 2(bq)2 = f(ds0,).
* In section indicated with A , log r was evaluated through: log I' = A
1
-'+
0364i
-
1.65di'
In section indicated with B , theequation log r =

-2.0364/11/(1 + 1.654;) + p was used.

256 ANALYTICAL CHEMISTRY, VOL. 44, NO. 2, FEBRUARY 1972


c.l/mol.
a t 25'C

50-

40-

+
0.05
0.05 os mHCe04

Figure 1. Relative apparent molal enthalpies for HC104 at 25 "C


a) Data reported by C. E. Vanderzee and J. A. Swanson (24)
b) Data reported by V. B. Parker (23)
c) Curve drawn arbitrarily

Table VII. Comparison between Some "Good Solutions" Obtained


for K and A H of Ionization of the HS04- Ion Considering a Group of Thermometric Titrations (9)4
AHL.,~,
- AR (cal
K x 102 (cal mole-1) log r mole-') ,Y'"' Notes
1.222 f 0.005 5552 f 16 -2.03642(1 + 1,6542 -490 Vanderzee (24) Section IA, Table VI
1.066 k 0.016 5052 It 22 -2.0364p:(l +1 . 6 d Z+p $490 Parker (23) Section IIIB, Table VI
1.193 f 0.009 5436 f 13 -2.03642(1 + 1.6543 ... Dotted curve, Section IV, Table 111
Figure 1
a In this group of experiments Na2SOaconcentration was varied from 2.5 X down to 0.25 X lo-* moles 1.-l. For convenience the
expression for log r, the values of AH',,,,, and the source of &"'"' values used for the calculation are reported. Each pair K-AB here
reported is the average of the values obtained as specified in the last column. AH values refer to ionic strengths in the range 0.01 < p <
0.1. K values are true thermodynamic values.

fore, if one agrees t o the criterion of the fitting between calcu- surements since this author did not report enough experi-
lated and experimental data being a sufficient support of the mental details.
hypotheses made, the HC104-Na2S04 system could be Very recently, however, Readnour and Cobble (14) reported
satisfactorily described in more than one way. These are, for the results of numerous calorimetric experiments in which
convenience, summarized in Table VII. solid N a 2 S 0 4 was added to aqueous HC1 solutions. The
In order to eliminate this ambiguity, there is evident need moles of H S 0 4 - formed were calculated by them using the
for more information which could even be obtained by simply Young value KTEso,= 1.03 X lo-? mole 1.-' and assuming
inverting the addition order of the reagents or by operating log r = 0 throughout all the experiments. Observed heat
in solutions with a high Na+ ion content. A few measure- effects were corrected for N a 2 S 0 4solution using data which
ments in such conditions have been reported by Pitzer (15) are, at 25 "C, in excellent agreement with those reported by
and by Zielen (18). When the data from Zielen are analyzed Rossini e t al. (27). Corrected heat effects, reported to 1 mole of
assuming that NaS04- species are present, A H values sensibly HSOd-, produced thevalue A H o = -4.12 f 0.11 Kcalmole-1
higher than both those proposed by Christensen and those for H S 0 4 - dissociation enthalpy at 25 "C and at p = 0. The
reported in Table I are calculated for H S 0 4 - formation (see extrapolation at p = 0 was made using a linear equation of the
the last column of Table VIII). These differences are suffi-
ciently marked to raise doubts about the existence of species type p = AH" + dp
- p where p has been obtained as a sum of
dP
such as NaS04,- or at least about the values of K and A H
(27) F. D. Rossini et a/., "Selected Values of Chemical Thermo-
reported for them (5, 12, 17). Unfortunately, we could not dynamic Properties," Nut. Bur. Stand. Circ. 500, U S . Govern-
perform analogous calculations on Pitzer's calorimetric mea- ment Printing Office, Washington D.C. 1952.

ANALYTICAL CHEMISTRY, VOL. 44, NO. 2, FEBRUARY 1972 257


Table VIII. Reexamination of Zielen's (I8) Calorimetric Measurements
on Formation Reaction of HS04- in the Hypothesis of the Formation of NaS04- Species
Stoichiometrk concentrations Moles at equilibrium"
after mixing (moles 1.-1) Qb mkaso4 m&,so4 mho4 Q*ImHSO,d
Runa cia2S04 ciC,04 c;aCl04 (calories) x 103 x 103 X 103 (Kcal mole-')
A 0.01 ... 1.98 -0.226 1 .OO 1.045 ... ...
B 0.010045 0.2007 1 ,7827 -7.773 ... 1.408 -5.52
0,010045 0,2007 1.7827 -7.773 1.00 0:458 1.090 -6.86
0.010045 0.2007 1.7827 -7.773 1.00 0.458 1.090 -7.39
a The experiments were carried out by mixing the following solutions:
Bulb Dewar
+
A : 5 cc. (0.4M NapS04 1.2M NaC104); 195 cc. 2M NaC104
+
B: 5 cc. (0.4M Na2S04 1.2M NaC104); +
195 cc. 10.2M HC104 1.8M NaC104)
Experimentally observed heat; the value Q = -7.773 has already been corrected for dilution.
rnbaso4 are the moles of NaS04- in the bulb; mLas0, and mLso4 are the moles at equilibrium, after mixing, of NaS04- and HS04-,
respectively. In the hypothesis that the ionization constants K of HS04- and NaS04- have the same ionic strength dependence, the equi-
librium concentration of these species has been calculated using K values obtained by the equation proposed by Reynolds (20). An iterative
procedure was followed which ends when constant values of p and of the species concentration are reached. The thermodynamic ionization
pK's were assigned the values +1.991 (20) and +0.65 ( 1 2 ) for HSOa- and NaS04-, respectively.
Q* = Q - (0.458 - 1.045) X ( a negative Q value indicates absorbed heat; AH&,so4 is the formation enthalpy of NaS04-.
This quantity was arbitrarily assigned the value of + 0.49 Kcal mole-', respectively: second and third values of this column.
~~ ~~ ~~

Table IX. Reexamination of Readnour and Cobble's Calorimetric Measurements Relative to HSOd- Ionization a t 25 "e
2.0364; 2.0364;
-log r 0 1 + 1.65di 1 + 1.654; -P
-AH -AH -AH
c",,,x 103 C~,,so4x 103 cHSo4
x 103 cal mole-' cHso4 x 103 cal mole-' CMSo4x 103 cal mole-'
7.866 1.939 0.7898 4038 0.6046 5275 0,6256 5098
7.866 2.281 0.9188 4039 0.6990 5311 0.7136 5202
7.866 2.720 1 ,0805 3993 0.8157 5294 0.8336 5180
7.866 3.196 1,2500 4024 0.9363 5379 0.9580 5257
7.866 4.416 1.6607 3794 1,2214 5164 1.2574 5017
11.826 2.140 1 ,0924 4152 0.8419 5392 0.8605 5275
11.826 1.914 0.9819 4203 0.7593 5439 0.7756 5325
11.826 4.084 1.9950 4004 1.4975 5340 1,5409 5189
11.826 4.329 2.1024 3997 1,5742 5345 1 6207 5192
11.826 5.588 2.6357 3857 1 ,9353 5260 2.0000 5090
19.747 3.240 2.0483 4118 1.5942 5297 1.6409 5146
19.747 2.320 1,4838 4077 1.1648 5202 1.1968 5063
19.747 5.465 3,3571 4038 2.5602 5304 2.6508 5123
19.747 5.604 3.4357 4006 2.6165 5270 2.7110 5087
4024 i 28 5305 + 19 5160 f 23
a The experiments were conducted by adding solid Na2S04to the calorimeter charged with HCl solutions. CiC1and C~-,,s~, are the
stoichiometric molarities of the reagents in the various runs. ' CHso4,the concentration of HS04- at equilibrium, was calculated using HSOa-
ionization constant values given by log K , = - 1.987 - log r. The equations for log r are reported in the Table. An iterative procedure
was adopted which ends when constant p is reached. The formation of ion pairs is not taken into account.

the dissociation enthalpy of HS04- a t the ionic strength p and The enthalpy values were considered independent of the
a Debye-Huckel term. ionic strength. The results are reported in Table X.
These data have been reexamined by us again using KT=so4= It may be noticed that use of Equation 3 for log r leads
1.03 X mole 1.-' but assuming log r # 0. A H values indeed to K and A H values satisfactorily in agreement with
were not extrapolated t o p = 0 but a n average value was those proposed by Young and Irish (11). N o conclusion can,
taken: thus AT = -5305 and T H = 5160 cal mole-' were however, be made concerning the presence of ion pairs owing
obtained when log r was calculated through Equation 3 or t o the small incidence they would have, if present, in these
Equation 4, respectively, (see Table IX). Inclusion of a p experimental conditions.
dependence of the A H values shown, in the relevant p range,
results in negligible variations of these quantities with respect CONCLUSIONS
t o the experimental errors. When Cobble's procedure is The example reported above, although based on a limited
employed, A H values at p = 0 of -5441 (Equation 3 for log number of experimental data, seems to suggest: first, the
r)and - 5357 (Equation 4 for log I?) cal mole-' were obtained. need for other experimental information to correctly
Cobble's data have also been used by us for the simulta- characterize the equilibrium states in acidic solutions of SO-
neous determination of K and A H . Equations 3 and 4 were dium sulfates, particularly to establish whether the ion pair
used for log r for sake of comparison with Christensen's NaS04- is formed; second, the values pK = 1.988 and A H =
data. The possible formation of ion pairs was also taken -5.2 Kcal mole-' proposed by Young and Irish remain, in
into account and, for comparison, the values log K T X B ~ = o4 view of the above recent calorimetric measurements, the most
+0.65 and AHs.sor = -0.49 Kcal mole-' were assumed; reliable data. In effect the procedure of simultaneous cal-
a value AHX,soa = f0.49 Kcal mole-' was also tested. culation of K and A H applied t o Cobble's data yields, when

258 ANALYTICAL CHEMISTRY, VOL. 44, NO. 2, FEBRUARY 1972


Table X. Simultaneous Calculation of K and AH for the Ionization
Reaction of HS04-, at 25 “C, from Calorimetric Data of Different Authors.
I* IIC
AH&e.S04 -AHEso~ -AHHS04
log r log d e 3 0 4 (cal mole-’) PKLO~ (cal mole-’) PKHTso~ (cal mole-’)
-2.036& ... ... 1.994 5253 f 28 1.942 5316 f 37
1 +1.65di 0.65
0.65
-490
+490
1.998
1.990
5242 f 28
5363 f 28
1.911
1.929
5530 f 35
5568 f 37
-2 . 0 3 6 d i ... ... 2.027 4903 f 30 2.025 4656 =t42
1 + 1.654; + 0.65
0.65
-490
$490
2.027
2.018
4919 f 30
5034 f 29
1.993
2.016
4819 f 40
4838 f 42
pK and AH values were determined following the procedure of simultaneous calculation of these quantities outlined in Reference 2 .
When ion pairs NaS04- were assumed present, the procedure indicated in the footnotes of Table VI and in point b of this table were followed:
KNTaso,and values reported in the Table were assigned to their formation process. Reaction enthalpies were assumed independent
of the ionic strength in the p range considered.
b Results obtained by utilizing experimental data of Readnour and Cobble (see Table IX or Reference 14). In the 14 experiments reported,
p varies from -0.01 to -0.03. Thermal data (qJ introduced in the calculations were evaluated by subtracting from the experimentally
observed heats (see column 4 of Table 11 of Reference 14) the solution heat of sodium sulfate. Values of NasS04solution enthalpies at the
p values realized in the various experiments were obtained by the information in Reference 14. When ion pairs NaSOa- were postulated,
heat valuesq,’ = q I - qNnso4 wereemployed. qNBsor= -AHkas0, (rn:8so, - rnNnSO,)where rnNaSO,are the moles of NaS04- in the mixture
at equilibrium; rn&so4 represents the number of moles of NaSOa- present in a hypothetical solution at the same p as the actual equilibrium
mixture but containing only NalS04 at the same stoichiometric concentration C~.,so4 of the experiment. The sign of AH&,sodis given
following the usual thermodynamic convention. qr values were assigned a positive sign though they correspond to absorbed heat.
39 data points corresponding to the 4 titration curves of Christensen and Izatt (9) examined in this paper were introduced in the calcula-
tions. HCIOa dilution heat data were taken from Parker (23). p varies in the range 0.01 < p < 0.1.

log I’ is evaluated through Equation 3, the values: pK = the data calculated at the various p’s. Obviously this in-
1.994 and A H = -5.25 Kcal mole-’ which are in fairly good volves a great deal of experimental work.
agreement with the above mentioned data. A fair agreement However, contrary t o an interpretation recently gjven (28)
is also found on the other hand, with Christensen’s data: to our first paper (2), and to the impression which might result
pK = 1.942 and A H = -5.32 Kcal mole-’; third, the pro- from the example reported above, we are of the opinion that
cedure of performing several separate experiments seems to the simultaneous determination of K and A H can be a useful
us superior to the enthalpic titration technique, the former and powerful tool when properly used. To this purpose, in
being less affected by errors. In any case it is not correct t o both our analysis ( 2 ) and Christensen’s (3, 29), concerning the
assume that: ‘Thermometric titration calorimetry is par- error propagation, it has been emphasized that, depending on
ticularly well suited for the determination of AG, A H , and the system under investigation, proper concentrations of the
A S from a single titration (entropy titration) since, in a single reagents have t o be chosen and the observed heat effect must
run, one obtains the equivalent of a large number of determi- be of several orders of magnitude higher than the apparatus
nations by conventional calorimetry” (9). I t is, in fact, sensitivity. Large variation of the concentration of both
necessary t o sensibly change the concentration of both re- reagents, and inversion of their addition order is then im-
agents since, from a single titration curve, one can easily ob- portant t o ascertain the presence of some possible systematic
tain spurious values of K and A H in spite of their excellent error.
internal agreement; fourth, owing t o the still not well known I n all cases, especially precise and accurate data are needed
dependence of the formation constant and of the enthalpy and the technique of such a simultaneous determination is
change of reaction on the ionic strength of the medium, the advisable only for the study of very simple reactions.
use of experiments performed in different p conditions in-
volves the introduction of a larger number of adjustable param- RECEIVED
for review January 25, 1971. Accepted September
eters in the calculations. Uncertainties may therefore arise 9,1971.
in the choice of the correct K-AH pair even if the experiments
were carried out in proper concentrations of the reagents.
(28) J. J. Christensen, J. R. Rytting, and R. M. Izatt, J . Cliern.
It seems, therefore, more correct to determine pK and A H at SOC.( A ) , 1969, 861.
constant p. More reliable thermodynamic values of these (29) J. J. Christensen, D. P. Wrathall, and R. M. Izatt, ANAL.
quantities can be subsequently obtained by extrapolation of CHEM., 40, 175 (1968).

ANALYTICAL CHEMISTRY, VOL. 44, NO. 2, FEBRUARY 1972 259