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Heat capacities and volumes of dissociation of phosphoric acid (kt, 2nd, and 3rd),

bicarbonate ion, and bisulfate ion in aqueous solution

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Departtnent of Chemistry and Oil Satzds Research Laboratory, University of L e t l ~ b r i d ~Lethbridge,


e,
Alta., Canada T l K 3 M 4
Received January 18, 1982
KEVING. ZEEB,and LORENG. HEPLER.Can. J. Chem. 60,2141 (1982).
JOHNW. LARSON,
Measurements at 25'C with aflow calorimeter and aflow densimeter have led to heat capacities and densities of aqueous solutions
of H,PO,, NaH2P04,Na2HP04,Na,P04, NaHCO,, Na2C0,, H 2 S 0 4 ,and various buffer solutions. Results are presented in terms of
apparent molar heat capacities (4,) and apparent molar volumes (4,). Analysis of the experimental 4, values to obtain the desired
standard state 4,O values for single electrolytes requires that allowance be made for hydrolysis and dissociation reactions of certain
solutes, along with extrapolation to zero concentration. Analysis of 4, values requires similar considerations of hydrolysis and
dissociation reactions, allowance for enthalpy and equilibrium changes ("relaxation") during calorimetric measurements, and
extrapolation to zero concentration. Procedures for these calculations are presented. The
and 4,O values that result from all of
these measurements and calculations are used to obtain ACpOand AVO values for acid dissociation reactions, which are then related
to effects of temperature and pressure on other thermodynamic properties.
JOHNW. LARSON,KEVING. ZEEBet LORENG. HEPLER.Can. J. Chem. 60,2141 (1982).
Des mesures a 2SC, l'aide d'un calorimttre a Ccoulement et d'un densirnetre a 6coulement, ont conduit aux capacites
calorifiques et aux densites des solutions aqueuses de H3P04, NaH2P04, Na2HP04,Na,P04, NaHCO,, H2S0, et de plusieurs
solutions tampons. On prksente les resultats en termes de capacites calorifiques molaires apparentes, (I$,), et de volumes molaires
apparents, (4,). Lorsqu'on effectue une analyse des valeurs experimentales de I$,, en vue d'obtenir les valeurs 4,O de 1'Btat
standard d'electrolytes specifiques, on doit tenir compte des reactions d'hydrolyse et de dissociation de certains solutes en plus de
faire une extrapolation b dilution infinie. Pour faire une analyse des valeurs I$,, on doit aussi prendre en consideration les reactions
d'hydrolyse et de dissociation, on doit tenir compte des variations d'enthalpie et d'tquilibre ("relaxation") pendant les mesures
calorimCtriques et faire une extrapolation b concentration zero. On presente les marches b suivre pour ces calculs. On a utilise les
valeurs de
et de 4,O qui resultent de toutes ces mesures et de tous ces calculs, pour obtenir les valeurs de AC,,O et de A V0 pour les
reactions de dissociation des acides que l'on peut alors relier aux effets de temperature et de pression sur d'autres proprietes
thermodynamiques.
[Traduit par le journal]

Introduction
The thermodynamic properties of the aqueous
acids listed in the title are important in such fields as
boiler water chemistry, interaction of aqueous
solutions with minerals, biochemistry, marine
science, and analytical chemistry. The research to
be described in this paper was undertaken to
provide information about changes in heat capacity
(ACP0)and volume (AVO) accompanying dissociation of these acids and then to use these values in
calculations of the thermodynamics of dissociation
over ranges of temperature and pressure. Obtaining the desired standard state changes in volume
from measured densities of solutions requires
appropriate extrapolations to zero concentration
and also "corrections" for such chemical reactions
as hydrolysis and dissociation, for which we have
developed convenient methods. Evaluation of
standard state changes in heat capacities involves
similar "corrections" and extrapolations and also
requires that allowance be made for "relaxation"
'Visiting scientist from Department of Chemistry, Marshall
University, Huntington, W. VA. 25701, U.S.A.

effects that are associated with the changes in


equilibrium states that occur with changing
temperature during the course of calorimetric
measurements of heat capacities.
Experimental
Our heat capacity measurements have been made with a
Picker flow calorimeter of the type previously described (1). A
small systematic error in measurements with this calorimeter
has been detected and corrected on the basis of measurements
(2-4) on NaCl (aq) solutions. Densities of solutions were
measured with a flow densimeter (5). Results of all of these
measurements refer to (25.0 0.1)"C.
BDH AnalaR grade Na2C0, was dried at 270C. BDH reagent
grade NaH2P04and Na3P04 were recrystallized from waterethanol and dried at 150C. Fisher certified Na2HP04.7H20and
Baker reagent grade NaHCO, were used as received. The
Na2HP0,.7H20 was analyzed for water by heating to constant
weight at 150C.
All compounds mentioned above were titrated with
standardized HCI or NaOH and found to contain no appreciable
acid-base impurities 'ind had overall purities of not less than
99.7%.
Stock solutions of sulfuric acid and phosphoric acid were
prepared from ACS reagent grade concentrated acids and
distilled water, and were then analyzed by titration with
standardized NaOH solutions.
Buffer solutions of NaHCO,/Na,CO, and NaH2P04/Na2H-

0008-4042/82/162141-10$01.00/0

0 1 9 8 2 National Research Council of Canada/Conseil national de recherches du Canada

CAN. J. CHEM. VOL. 60, 1982

TABLE1. Apparent molar heat capacities and volumes of aqueous NaH2P0,/Na2HP0,


buffers at 25.0C
1?1

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mol kg-'
0.0440
0.0820
0.1235
0.1558
0.2206
0.2394
0.3185
0.3951
0.4823
0.6921
0.8286
0.0366
0.0538
0.0641
0.1025
0.1030
0.1450
0.1681
0.2035
0.2410
0.2870
0.3504

4c

4v

4c

4v

J K-' mol-'

cm3mol-I

mol kg-'

J K-' mol-'

cm3 mol-'

27.95
28.28
28.78
28.50
28.76
29.63
29.35
30.48
30.10
30.99
32.34

0.0501
0.0719
0.1004
0.1177
0.1565
0.2028
0.2460
0.2792
0.3500
0.4189
0.493 1

F2 = 0.900
2.2
5.0
11.7
12.7
20.4
26.7
30.9
41.6
45.1
60.9
73.2
F2 = 0.100
-116.1
- 112.2
- 106.5
-93.1
-91.3
-76.6
-69.8
-58.0
-49.2
-35.9
-21.7

Experimental results and analyses of data


Results of measurements with the Picker flow
calorimeter are heat capacities per unit volume of
solution. Combination of these heat capacities with
the densities that we have also measured leads to
heat capacities per unit mass of solution. Further
combination of these latter heat capacities with the
already known (6) heat capacity of water
(4.1793 JK-I g-l) leads to apparent molar heat
capacities. Similarly, densities of solutions in
combination with the already known density of
water (0.997044 g ~ m - ~lead
) to apparent molar
volumes. These apparent molar properties are
defined according to
+Y

= Y(so1'n) - n lYlOI Cn,


i> 1

17.73
17.80
18.68
18.85
19.58
20.00
20.40
20.78
2 1.42
22.01
22.58

7.27
7.63
7.96
8.74
8.86
9.63
9.78
10.52
10.81
11.63
12.17

PO4 were prepared from known masses of the solids and


distilled water. These buffer solutions were made with mole
ratios equal to 911, 111, and 119. Solutions of N a 3 P 0 4 were
DreDared from known masses of solid and distilled water.
FuAher solutions were prepared by quantitative dilutions of
several of these solutions.

[I1

F2 = 0.500
-61.2
-53.1
-43.9
-37.9
-30.2
- 19.9
-12.1
2.5
6.8
15.9
26.9

apparent molar heat capacities and volumes, are


listed in ~
~ 1, 2,b and l3. ~ ~
~ ~of these ~
is described in the
paragraphs.
Our principal interest in this investigation has
been to obtain the +,O and +,O values for zero
concentration that are identical to the corresponding partial molar quantities that then lead to ACpO
and AVO values for various dissociation reactions.
Analysis of our apparent molar volumes for this
purpose requires that appropriate allowance be
made for hydrolysis and dissociation reactions of
certain solutes along with extrapolation to zero
concentration. Analysis of our apparent molar heat
capacities requires similar considerations of
hydrolysis and dissociation reactions, allowance
for enthalpy and equilibrium changes during
calorimetric measurements, along with extrapolations to zero concentration. Because of their
relative simplicity, we consider volumes first.
Apparent molar volumes of reasonably dilute
solutions of electrolytes are accurately represented
by equations of the form
Av(d1)11Z(o)31Z(m)
lIz
Bvom
[2] +, = +,O

in which Y is the extensive property (heat capacity


or volume) of a specified quantity of solution, n1 is
the number of moles of water in the specified
quantity of solution, Y10 is the molar property of in which AV and o come from the Debye-Hiickel
pure water, and ni for i > 1 represents the numbers theory and Bv is an adjustable parameter for each
of moles of solutes. Results of our measurements of solute. We have used
AV(dlO)llZ
= 1.865 cm3 molk3I2kg1I2
heat capacities and densities, expressed in terms of

LARSON ET AL

TABLE
2. Apparent molar heat capacities and volumes of aqueous NaHC031Na,C03 buffers
at 25.O"C
4c(4csp)

4v

mol kg-I

J K-I mol-I

cm3mol-I

mol kg-I

J K-' mol-I

cm3 mol-I

0.0660
0.0788
0.1418
0.1621
0.2435
0.2837
0.3887
0.4556
0.5127
0.6023
0.7080
0.8369

F, = 0.900
-25.2(-25.7)
- 15.9(- 16.9)
- 12.3(- 12.5)
-7.3(-7.5)
-2.4(-2.5)
3.6(3.5)
9.7(9.6)
15.7(15.6)
17.7(17.7)
25.5(25.5)
32.6(32.6)
39.2(39.2)

20.85
2 1.60
2 1.44
21.93
21.96
22.50
22.53
22.86
22.96
23.37
23.54
24.03

0.0568
0.0844
0.1021
0.1518
0.1847
0.2376
0.2903
0.3172
0.3872
0.4265
0.5227

F, = 0.500
-82.7(-87.7)
-82.2(-85.3)
-74.8(-77.3)
-68.5(-70.1)
-61.2(-62.5)
-57.1(-58.1)
-45.5(-46.3)
-43.2(-44.0)
-31.9(-32.5)
-27.5(-28.0)
- 16.5(- 17.0)

10.30
9.95
10.39
10.72
11.14
11.39
11.95
12.04
12.56
12.69
13.3 1

0.0326
0.0584
0.0815
0.0958
0.1293
0.1526
0.2063
0.2150
0.2904
0.3048
0.4148

F2 = 0.100
- 121.0(171.1)
- 127.5(- 158.1)
-123.1(-145.6)
- 123.6(- 142.8)
-116.6(- 131.1)
- 115.9(- 128.2)
- 101.9(- 111.1)
-99.5(- 108.4)
-83.2(-90.0)
-81.7(-88.2)
-60.6(-65.7)

-2.60
- 1.44
- 1.01
-0.60
-0.19
0.24
0.79
1.06
1.79
2.02
2.96

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171

4v

4c(4cW)

TABLE
3. Apparent molar heat capacities and volumes of aqueous acids and salts at
25.O"C
m

mol kg-I

4v

4c(4cSP)

J K-I mol-'

~ m ~ m o l - ~ mol kg-'

H3PO4
70.4(61.4)
80.1(74.2)
84.5(79.8)
89.3(85.3)
90.0(86.4)
93.8(90.6)

43.78
45.32
45.89
46.18
46.39
46.50

H2S04

47.6(-53.5)
51.9(-14.9)
55.3(-3.2)
52.9(0.4)
55.5(9.7)
53.q12.6)
56.q19.1)
55.5(22.3)
56.3(28.9)

29.73
32.81
33.15
33.97
33.93
34.50
34.39
34.92
35.21

4v

4c(4cW)

0.0203
0.0405
0.0617
0.0825
0.1028
0.1295
0.1746

J K-I mol-I

cm3 mol-'

Na3P0,
-3.3(-341.7)
-39.q-301.8)
-56.6(-270.8)
-65.1(-249.5)
-70.4(-235.1)
-70.3(-217.2)
-66.7(- 195.2)

- 18.19
- 17.22
-16.29
-15.42
- 14.68
- 13.88
- 12.84

Na3P04 in 0.020171 NaOH


0.0150
0.0234
0.0499
0.0766
0.1035
0.1310
0.1671

35.5(-315.5)
-7.4(-309.0)
-42.q-260.9)
-55.3(-234.3)
-61.7(-217.3)
-60.5(-200.8)
-56.q- 183.9)

-16.73
- 18.27
- 15.96
- 14.82
- 13.90
-13.03
-12.02

from Millero (7) and the "valence factor" o as molality. For non-electrolytes and undissociated
weak electrolytes such as H,PO,(aq) we have
commonly defined (8) is
[2'] instead of [2]:
[3] o = Z/m = (0.5 Evizi2mi)/m
in which Z is the mold ionic strength. m; is the [2'1 4 v = 4v0 + Bvm
molality of a particular solute, and
is the total
Many of our measurements have been made on

>

2144

CAN. J. CHEM. VOL. 60, 1982

TABLE
5. Standard state heat capacities and vol-

buffer solutions that are described as containing


component solutes in ratios equal to 911, 111, and
119. We now define solute mole fractions F2and F3
according to

umes of aqueous solutes at 25.O"C

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and

41.O

Solute

4c0
J K-I mol-I

cm3mol-I

H3P04(aq,undiss.)
NaH2P04(aq)
Na,HPO,(aq)
Na3P04(aq)
NaHC03(aq)
Na2C03(aq)
H+(aq) HS0,-(aq)

94.5
8.6
- 168.1
-367
-11.6
-215.5
21.7

48.1
30.1
2.8
-22.4
23.6
-6.8
35.2

in which subscript 2 refers to a 1:1 electrolyte and


subscript 3 refers to a 2: 1 electrolyte. For F2values
+
of 0.9, 0.5, and 0.1 we have o values equal to 1.2,
2.0, and 2.8, respectively. As shown in Tables 1
and 2, we have made measurements on solutions dissociated (cr) from K6 and the Davies equation for
having three different F2values at several different activity coefficients (y):
total molalities.
[7] log y = ( - A Z ~ I " ~ ) / ( ~Ill2) + 0.1z21
For our NaH2P04/Na2HP04 and NaHC031
Na2C03 buffer solutions we find that hydrolysis The apparent molar volumes of solutions of
and dissociation corrections are negligible. We phosphoric acid are expressed as
have therefore obtained values of +v5 and Bv by [81 +V = (1 - cr)+v(H3PO,) + @+V(H++ H2P04-)
(o)312(m)112
least-squares fitting of 4, - Av(d10)112
against o m , as suggested by eq. [Z], with results Substitution of the appropriate version of eq. [2]
that are given in Table 4. Further linear least- and [Z'] in [8] leads us to obtain the desired
squares fits of +,O values for buffers against apparent molar volume of undissociated phosphoric acid, +,0(H3P04), by extrapolating
corresponding F2 values lead to +,,,O
and +,,,O
values for single electrolyte components of the
bv - crbvO(H+ H2P04-) - (u)312Av(d10)112(tn)1
buffers, as reported in Table 5. Using
(1 - a )
to zero concentration. Our value for +,0(H3P04) is
from Millero (7), based on the useful convention listed in Table 6.
that
The hydrolysis of solutions of sodium phosphate
is represented by

we then obtain the conventional ionic volumes


for H2P04-(aq), HP0,2-(aq), HC03-(aq), and
C032-(aq)that are listed in Table 6.
For solutions of phosphoric acid we need
consider only the first dissociation as in
for which we have the equilibrium constant K6
from a recent review (9). We calculate the fraction

[9]

PO,'- (aq)

+ H,O(liq) = HPO,,~-(aq)+ OH-(aq)

We have calculated cr (fraction hydrolyzed) values


from the equilibrium constant (9) and activity
coefficients (10). The apparent molar volumes of
solutions of sodium phosphate are then expressed
as
[lo]

+,

= (1 - cr)+,(3Na+

+ ~ + ~ ( 2 N +a +HP042-) + c+(Na+ + OH-)


- cr V0(H20)

TABLE
4. Parameters for eqs. [2] and [16] for aqueous NaH,PO,/
Na,HPO, and NaHC031Na,C03 buffers at 25.O"C
4c0
F2

Bc

4v0

J K-' mol-I J K-I m01-~kg cm3 mol-I

BI,
cm3 mol-z kg

Substitution of appropriate versions of eq. [2] in


[lo] and rearrangement of the resulting complicated expression has led us to extrapolate
[+V- ~t+~O(2Na+
+ HP042-)

- E + ~ O ( N+
~ +OH-) + cr V0(H20)
- (6 - 2~t)A~(d,~)~~~(Z)'~~]
- a)
0.900
0.500
0.100

-32.7
-112.1
-195.8

NaHC0,1Na2C03
39.1
20.5
35.9
8.4
38.7
-3.8

1.2
1.1
1.2

to zero ionic strength to obtain the desired


+,O(3Na+
that is listed in Table 5 and
thence the conventional +v0(P043-)that is listed in
Table 6.

2145

LARSON ET AL.

experimental apparent molar heat capacity is from


the thermal effects associated with changes in
chemical equilibrium ("relaxation") and is designated
We therefore have

TABLE6. Standard state heat capacities


and volumes for aqueous species at 25.O"C,
based on cbYo(H+)
= 0 for ions

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Species

4c0
J K- mol-

The contribution of "relaxation" to the apparent


molar heat capacity is given (1 1, 12) by

H3P04(ad
H2P04-(aq)
HP042-(aq)
~0,3-(4
HC03-(aq)
C032-(aq)
HS0,-(aq)
Sod2-(ad

Thus the desired contributions due to the aqueous


solute species can be obtained as

"From ref. 19.


bFrom ref. 7.

Procedures for calculating (daldr) from equilibrium constants, enthalpies, and activity coeffiSulfuric acid in our solutions is completely cients for systems of various charge types follow
dissociated into H+(aq) and HS0,-(aq) and some of those previously described (11, 12) and recently
extended (13). The required equilibrium constants
the bisulfate ions are further dissociated as in
and enthalpies have been taken from a recent
review (9).
The "relaxation" effects on heat capacities of
We have calculated a (fraction of HSO,- disNaH2P04/Na2HP04buffer systems are very
the
sociated) values from the equilibrium constant
(9) and the Davies equation (10). The apparent small compared with the experimental uncertain= +cSP for these
molar volumes of sulfuric acid solutions are ties. We have therefore taken
solutions and used the
values in Table 1 for our
expressed as
subsequent calculations for this system. For all
other systems we have calculated
values by
way of experimental
values and eq. [15], which
has involved calculation of AH(da/dT) as deSubstitution of the appropriate forms of eq. [2] scribed in detail elsewhere (11-13), with results
in [12] and rearrangement lead us to obtain presented in parentheses in Tables 2 and 3.
+vO(H+ HS0,-) by extrapolation of
The next step has been to analyse the +cSP values
in Tables 2 and 3 and the
( = +,")
values in
Table 1 on the basis of the equation

+,

+,

+,"

+,

+,

to zero ionic strength to obtain the +vO(H+


HS0,-) that is listed in Table 5. The conventional
+,O(HSO,-) is listed in Table 6.
Analysis of experimental apparent molar heat
capacities for reactive systems to obtain the
desired +,O
values of specified solute species
requires that we allow for the temperature
dependent state of equilibrium and related thermal
effects. These "relaxation" effects have been
considered previously for other systems by
Woolley and Hepler (11) and by Jolicoeur,
Lemelin, and Lapalme (12). As these earlier
investigations have shown, experimental apparent
molar heat capacities (+,) can be regarded as a sum
of two kinds of contributions. One contribution is
from the solute species present in the solution
of interest and is designated
it is this
contribution that we will relate to the desired
standard state heat capacities of various solute
species. The other contribution to the total

+,";

in which Ac is derived from the Debye-Hiickel


theory and Bc is an adjustable parameter. We have
used
from Desnoyers (14,15). In this connection we note
that there is recent evidence (16, 17) for a slightly
larger value of AC(dl0)li2,but the difference is not
enough to be significant for our present purposes.
results with eq. [16] in
We have used our
carrying out calculations and extrapolations to zero
concentration in ways that are equivalent to those
already described in detail for our +, values. The
resulting +cO values are listed in Tables 4 and 5.
These +cO values have been combined with the
conventional +cO(H+)= 0 and +,O(Na+) = 43 J K-I
mol-I and +C0(S042-)= -278 J K-I mol-I from
earlier work (18, 19) to obtain the conventional +,O
values listed in Table 6.

+,"

2146

CAN. J . CHEM. VOL. 60. 1982

TABLE7. Standard state changes in heat capacity and


volume for acid dissociation reactions at 25.0C, from
values in Table 6
+,O
and

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Reaction

AC, O

AVO

J K-I mol-I

cm3 mol-l

We have used the conventional standard state


heat capacities and volumes listed in Table 6 for
calculation of ACpO and AVO for the acid
dissociation reactions listed in Table 7. It should be
emphasized that the arbitrariness in setting
(PyO(H+)=0 to obtain the conventional values in
Table 6 cancels out of the calculations leading to
Table 7 so that the reported ACpOand AVO values
are independent of the conventional values chosen
for +,O(H+).
We estimate that uncertainties in most of our +,O
and 4 , O values are about f0.6cm3 mol-I and about
f 4 J K-I mol-I, respectively; exceptions are
Na3P04(aq), P043-(aq), and HS0,-(aq) for which
uncertainties are larger than for the other solutes.
Our further estimates for uncertainties in 4,O are
about f 3 cm3 mol-I for Na3P04(aq)and P043-(aq)
and about f 0.8 cm3 mol-I for HS0,-(aq). We also
estimate that uncertainties in
are about
f 20 J K-I mol-I for Na3P04(aq)and P043-(aq) and
about f 8 J K-I mol-I for HS0,-(ad. As shown in
the next section, results of several earlier
investigations provide evidence that most of our
4,O values (Tables 5 and 6) and related AVO values
(Table7) are reliable to within the estimated
uncertainties; the only exceptions are Na3P04(aq)
and P043-(aq) and the related AVO for dissociation
of HP042-(aq), for which the true uncertainties
may be larger than our estimates above. Uncertainties in most earlier ACpO values are so large that
they provide little evidence for or against our ACpO
values and our estimates of their uncertainties.
Comparisons of results
There have been many investigations of partial
molar volumes and also dissociation constants at
various pressures that have yielded volumes to be
compared with our values in Tables 6 and 7. Nearly
all such results obtained before 1973 have been
cited and summarized in Hamann's excellent
review (20). Now we also have some useful results
from more recent investigations.
Hamann (20) has listed AVO = - 16.6 and

-16.2cm3 mol-I for the first dissociation of


phosphoric acid. More recently, Lo Surdo, Bernstrom, Jonsson, and Millero (21) have reported
AVO = - 16.26cm3 mol-' for this dissociation. All
of these results are in good agreement with our AVO
= - 16.8cm3 mol-I.
Hamann (20) has listed AVO = -24.0 and
-24.1 cm3 mol-' for the second dissociation of
phosphoric acid, for which Lo Surdo et al. (21)
have recently reported AVO = -25.85 cm3 mol-I.
Our AVO = -26.1 cm3 mol-I for this dissociation
provides support for the value from Lo Surdo et al.
(21) in preference to the earlier values.
Lo Surdo et al. (21) have also reported AVO =
-35.96cm3 mol-' for the third dissociation of
phosphoric acid, for which we found AVO =
-24.0 cm3 mol-I. There is no obvious explanation
for the difference in these values.
We also note that the cPVO values reported by Lo
Surdo et al. (21) for H3P04(aq),NaH2P04(aq),and
Na2HP04(aq) are all in good agreement with our
corresponding values in Table 5. On the other
hand, their 4,O for Na3P04(aq)is in poor agreement
with our value.
Previous reviews by Millero (7) and by Hamann
(20) have led to a choice of AVO = -27.7 cm3 mol-I
for dissociation of HC03-(aq). The more recently
reported partial molar volumes of Perron, Desnoyers, and Millero (8) lead to AVO = -28.4cm3
mol-I. As shown in Table 7, our measurements
lead to AVO = -29.2cm3 mol-I for this dissociation. We suggest that both of the latter two values
are more accurate than the first value quoted
above.
Both Millero (7) and Hamann (20) chose AVO =
-21.7 cm3 mol-I for dissociation of HS0,-(aq).
More recent volumetric measurements by Rohwer,
Brink, and Cruywagen (22) lead to AVO =
-20.0 f 1.0 cm3 mol-I. These earlier values are in
good agreement with our AVO = -21.2cm3 mol-I
for this dissociation.
We now turn to some comparisons of our heat
capacities with earlier results.
Bates (23) has evaluated the first dissociation
constant of H3P04(aq) at 5" intervals from 0 to
60C. An equation of type log K = f(T) has been
fitted to the results; two differentiations with
respect to T have led to a reported ACpO =
- 154 f 5 J K-I mol-I at 25C. More recently, Mesmer and Baes (24) have investigated the first
dissociation of H3P04(aq)at 25" intervals from 0 to
300C. Their results have led to ACiO =
34 f 29 J K-I mol-I for the neutralization reaction

2147

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LARSON ET AL.

Combination of this result with ACpO= -215 J K-I


mol-1 for dissociation of water from a recent
review (9) leads to ACpO= - 186 f 30 J K-' mol-'
for the first dissociation of H,PO,(aq). Because of
the well-known magnification of uncertainties and
errors associated with double differentiation and
also because of the difficulties in evaluating accurately the relatively small pK of H3P04(aq) as
reviewed recently by Pitzer and Silvester (23, we
believe that our ACpO= - 128J K-I mol-I is the
best available for the first dissociation of
H,PO,(aq) For the second dissociation of phosphoric acid
we have four separate values of ACpOto compare
with our value. Bates and Acree (26) have determined this dissociation constant at 5" intervals from
0 to 60C; two differentiations of the derived log K
= f(T) have led to ACpO= -226 J K-I mole'. Bates
and Acree (26) also calculated ACpO= - 189J K-I
mol-I from the earlier dissociation constants of
Nims (27), determined over the temperature range
20 to 50C. Grzybowski (28) has determined dissociation constants at 5C intervals from 5 to 50C and
has similarly calculated ACpO= -200 f 9.5 J K-I
mol-I for the second dissociation. Finally, Mesmer
and Baes (23) have determined equilibrium constants for
at 25" intervals from 0 to 300C and have calculated
ACP0= 32 25 J K-I mol-I for this neutralization
reaction. Combination of this result with ACpOfor
dissociation of water (9) leads to ACpO =
- 183 f 26 J K-I mol-I for the second dissociation
of phosphoric acid. We suggest that our ACpO=
-220 J K-' mol-I is the best available value.
Although we are generally skeptical of ACpOvalues
based on double differentiation of log K = f(T), we
note that the equilibrium constants of Bates and
Acree (26) and Grzybowski (28) appear to have
been determined with considerable skill and accuracy; it is therefore gratifying to note that their (26,
28) ACpOvalues are in good agreement with our
value.
We do not know of any earlier results that permit
calculation of the heat capacity change for the third
dissociation of phosphoric acid to compare with
our ACpO= -242 J K-I mol-I.
For the dissociation of HC0,-(aq) we have
several ACpOvalues to compare with our value.
Harned and Scholes (29) have determined the
equilibrium constant at 5" intervals from 0 to 50C
and by double differentiation of the resulting equation of type log K = f(T) have obtained ACpO=
-276 JK-I mol-I. Nakayama (30) has treated the

experimental results of Harned and Scholes (29)


slightly differently to obtain ACpO= -282JK-I
mol-I for this dissociation. More recently, Plummer and Busenberg (3 1) have analyzed equilibrium
data over a wider range of temperature; double
differentiation of their log K = f(T) now leads us to
ACpO= -291 JK-I mol-I at 298.15K. Plummer
(31) has also found that different selection and
treatment of the equilibrium constants leads to less
negative ACpOvalues. Perron, Desnoyers, and
Millero (8) have measured heat capacities of aqueous solutions of NaHCO, and Na2C03. We have
used their reported c$cO values in calculating ACpO
= -214 J K-I mol-I for the dissociation of HC0,-(aq). We know, however, that their reported c$,O
values for these salts and this calculated ACpOvalue
are incorrect because of neglect of the chemical
relaxation effect ( 1 1-13), which had not yet been
recognized (1 1) at the time Perron, Desnoyers, and
Millero (8) wrote their paper. We have therefore
made use of eqs. [13]-[15] with their experimental
results to obtain a corrected ACpO= -249 JK-I
mol-I for the dissociation of HC0,-(aq). We also
note that Peiper and Pitzer (32) have independently
and by a slightly different procedure (also using
slightly different auxiliary data) made "relaxation
corrections" to the results of Perron. Desnovers.
and Millero (8) to obtain ACpO= -260 J K-1 mol-I
for the dissociation of HC0,-(aq). These "corrected" ACpOvalues from the measurements of
Perron, Desnoyers, and Millero (8) are in good
agreement with our ACpO= -247 J K-I mol-I for
this dissociation.
For dissociation of HS0,-(aq) we have several
values for ACpOas follows. Lietzke, Stoughton, and
Young (33) have determined equilibrium constants
at temperatures from 25 to 225C and have obtained
an equation of type In K = f(T) from which we now
calculate ACpO= -209 J K-I mol-I for the dissociation of HS0,-(aq) at 298.15 K. Marshall and Jones
(34) have determined equilibrium constants from 25
to 350C and have calculated ACpO= -238 J K-I
mol-I. Young, Singleterry, and Klotz (35) have
reported results of their determinations of equilibrium constants at 10" intervals from 5 to 55C and
have calculated two values for the heat capacity
change associated with dissociation of HS0,-(aq):
ACpO= - 192 and -238 J K-I mol-'. Readnour and
Cobble (36) have measured enthalpies of solution
of Na2S04(c) in water and in dilute hydrochloric
acid at several temperatures and have calculated
ACpO = -356 J K-I mol-I for dissociation of
HS0,-(aq) at 25C. More recently, Criss (37) has
used the experimental results of Readnour and
Cobble (36) in some improved calculations and has
d

CAN. I. CHEM. VOL. 60. 1982

TABLE
8. Selected standard state thermodynamic properties for acid dissociation reactions in aqueous
solution at 298.15 K and 1 atm

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Reaction

Ka

L W O

AS0

ACP0

AVO

J mol-I

J K-I mol-I

J K-I mol-I

cm3 mol-I

"All K values here are based on compositions of solutions expressed in terms of molalities (mol kg-') of solutes and the hypothetical
one molal standard slate so that activity coefficients approach unit)1 as m approaches zero.

obtained ACpO= -280 J K-I mol-' for dissociation


of HS0,-(aq) at 25C. We believe that our ACpO=
-300 J K-I mol-I, supported by the value from
Criss (37), is the best value available for the
dissociation of HS0,-(aq) at 25C.
Thermodynamic calculations
A principal purpose of this research has been to
obtain AVO and especially ACpOvalues for acid
dissociation reactions with a view toward using
these values in calculating the dependences of
other thermodynamic properties on pressure and
temperature. For these calculations we want the
"best7' available values for the equilibrium constant K, AH0, AS0, ACpO,and AVO for dissociation
reactions at 298.15 K and 1atm. Our selected
values for these quantities are given in Table 8;
sources of these values are as follows.
Equilibrium constants for the first and second
dissociations of phosphoric acid have already been
cited (23-28). For the third dissociation we select
the K value from Quist and Vanderzee (38). Enthalpies for these dissociations have been selected
from values calculated with dln K/dT = AH0/RT2
(23, 24, 26-28) and from results of calorimetric
measurements (39-43). The selected ACpOvalues
are all based on our calorimetric results as reported
in this paper. Selected AVO values are based on our
results and on other values already cited (20, 21).
We take the equilibrium constant at 298.15 K for
dissociation of HC0,-(aq) from Harned and
Scholes (29) and the enthalpy of dissociation from
Berg and Vanderzee (44). Our selected ACpOis
based on the present calorimetric results and the
"corrected" results from Perron, Desnoyers, and
Millero (8). The selected AVO is a weighted average
of the values cited earlier in this paper.
For the dissociation of HS0,-(aq) we have
equilibrium constants from investigations already
cited (33-35) and many others, especially including
Covington, Dobson, and Srinivasan (45) and Pitzer, Roy, and Silvester (46). We select the K,,,.,,
value in Table 8 from this last investigation (46).

Pitzer, Roy, and Silvester (46) have also calculated


a AH2,,.,,O value for dissociation of HS0,-(aq),
which we have considered along with values
derived from investigations already cited (33-35)
and from several calorimetric investigations (47).
Our selected value is given in Table 8. We have also
selected ACpOfrom our results, in good agreement
with the recalculated ACpOfrom Criss, Readnour,
and Cobble (36, 37). The selected AVO is based on
our results and those cited earlier (7, 20,22).
Afirst approximation to the effect of temperature
on thermodynamic properties associated with
chemical reactions is to take ACpO= 0. In this
approximation both AH0 and AS0 are independent
of temperature and the effect of temperature on the
equilibrium constant is expressed as follows:

The ACpOvalues in Table 8 show that ACpO= 0 is a


poor approximation for the reactions of interest in
this paper; hence eqs. [19]-[21] can be regarded as
useful only when T is very close to 298.15K. We
therefore go on to the next approximation, a
non-zero ACpOthat is considered to be independent
of temperature.
Integration of (dAHO/dT) = ACpO with ACpO
taken to be independent of temperature leads to
and similar integration of (dASO/dT)= ACpO/Tleads
to

Combinations of eqs. [22] and [23] with

LARSON ET AL.

Effects of pressure on enthalpies and entropies


of reaction can be calculated with

or integration of
dln KIdT = AH01RT2
with [22] leads to the following:
[24] In KT= In K2,,,15 (AH2,,,,,0/298.15RT)
x (T - 298.15) - (ACP0/RT)(T -298.15)
+ (~c-01~) ln (T/298.15)
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For personal use only.

2149

[28] (dAHO/dP), = AVTO- T(dAVO/dT)p


and

[29] (dASO/dP), = -(dAVO/dT),


Of more immediate use to us in relation to the data
that we have available (AVO, but not usually
[251 I ~ K =
T (298.151T) lnK298.,5+ (AS298.1s0/RT) dAVO/dT) is
(T - 298.15) - (ACpO/RT)(T - 298.1')
[30] (d ln K/dPlT= - AVO/RT
ACpO/R)In (Tl298.15)
Integration of eq. [30] taking AVO to be independent
[261 In KT = -(AH298.,s0IRT) + ( A S Z ~ ~ . I ~ O / R )of pressure leads to
- (ACpO/RT)(T - 298.15)

+ (ACpO/R)In (Tl298.15)
Calculations with eqs. [24]-[26] and comparisons with experimental K values for several reactions show (48) that these equations yield very
accurate K values over the temperature range
0- 100C (273-373 K) and yield moderately accurate
K values at temperatures to 200C (473 K) or even
higher.
According to eqs. [19]-[21], In K should be a
linear function of 1IT.
. , with no minimum or maximum. It is, however, known that In K is not
generally a linear function of 1/T and that In K
versus 1/T or T often passes through a minimum or
maximum. Equations [24]-[26] are substantial
improvements over eqs. [19]-[21] in that the equations containing ACpOallow for non-linearity of
plots of In K versus 1IT and also permit a minimum
or maximum. Consideration of
shows that In K will go through a minimum or
maximum at the temperature where AH0 = 0. We
therefore set AHT0 = 0 in eq. [22] and solve to
obtain
[271 Tm= 298.15 - (AH,, ,,,,O/ACp0)
in which we have used Tmto represent the temperature corresponding a
Or
in
In K (or K). No minima nor maxima have been
observed for In K values for dissociation of
~ , p o , ( ~ q and
)
~ s o , - ( ~ q ) ,in accord with the
Tm<273 K values that we calculate using AH,,,,,,O
and ACD0values from Table 8. For dissociation of
H,Po,'(~~) and HC0,-(aq) we calculate Tm =
3 14 K and 357 K, respectively. Both these values
are in
accord with
(24, 26-28, 31). For dissociation of HP0,-(aq) we
calculate Tm = 369 K , but have no high temperature
experimental results to compare with this value.

in which K, represents the equilibrium constant at


1atm and P is the pressure of interest expressed in
atm. Use of K and AVO values from Table 8 in eq.
[311 leads to calculated Kp values that are in good
agreement with experimental results (20) over
moderate ranges of pressure. Better accuracy over
wide ranges of pressure can be obtained by considering AVO to be dependent on pressure (non-zero
partial molar compressibility changes) as summarized elsewhere (7, 20, 21).
Acknowledgments
We are grateful to the Alberta Oil Sands Technology and Research Authority and the Natural
Sciences and Engineering Research Council of
Canada for support of this research. We also thank
Dr. Gregory Allred for his helpful advice. Finally,
we thank Dr. K. S. Pitzer and Dr. L. N. Plummer
for sending us manuscript copies of their papers
(31, 32) and Dr. C. M. Criss for sending us the
results of his recent calculations.
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