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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.
0008-4042/82/162141-10$01.00/0
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
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
[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
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
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
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
TABLE
5. Standard state heat capacities and vol-
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
[9]
PO,'- (aq)
+,
= (1 - cr)+,(3Na+
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
BI,
cm3 mol-z kg
- 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
2145
LARSON ET AL.
Species
4c0
J K- mol-
H3P04(ad
H2P04-(aq)
HP042-(aq)
~0,3-(4
HC03-(aq)
C032-(aq)
HS0,-(aq)
Sod2-(ad
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
+,
+,
+,"
+,
+,
+,";
+,"
2146
Reaction
AC, O
AVO
J K-I mol-I
cm3 mol-l
2147
LARSON ET AL.
TABLE
8. Selected standard state thermodynamic properties for acid dissociation reactions in aqueous
solution at 298.15 K and 1 atm
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.
LARSON ET AL.
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)
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 200.161.223.66 on 04/03/14
For personal use only.
2149
+ (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.
2150
10. R. A. ROBINSON
and R. H. STOKES.Electrolyte solutions. 29.
2nd ed. revised. Butterworths, London. 1965.
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