M-1882

J. Chem. Thermodynamics 1986,18, 351-357

Enthalpy of solution of oxalic,

succinic, adipic, maleic, malic,
tartaric, and citric acids, oxalic
acid dihydrate, and citric acid
monohydrate in water at 298.15 K
ALEXANDER APELBLAT”
Department of Chemical Engineering, The University of Alberta,
Edmonton, Alberta, Canada T6G 2G6

(Received 28 Ma-v 1985; in revised form 8 Ju1.v 1985)

Enthalpies of solution of several organic acids in water at 298.15 K were measured in an LKB
calorimeter. The molar enthalpies of solution extrapolated to infinite dilution are for
anhydrous oxalic acid, A,,H,“(298.15 K) = (8853k99) J’mol-’ and for oxalic acid
dihydrate, A,,Hz(298.15 K) = (35225+72) J. mol-i. The molar enthalpies of solution for
finite molalities are: anhydrous citric acid, A,,H,(298.15 K, m = 0.0200 mol. kg-i) =
(18211&69) J’mol-‘; citric acid monohydrate, A,,H,(298.15 K, m = 0.0203 mol’kg-i) =
(29061+ 123) J mol- i; succinic acid, A,,, H,(298.15 K, m = 0.0334 mol. kg- ‘) = (28705 f 89)
J’molli; adipic acid, A,,H,(298.15 K, M = 0.0195 mol’kggi) = (32848&82) J’mol-‘:
maleic acid. A,,H,(298.15 K, m = 0.0256 mol. kg- i) = (21333 k 29) J. mol- i; malic acid,
A,,H,(298.15 K, m = 0.0318 mol.kg-i) = (21846k86) J.mol-i; and tartaric acid,
A,,,H,(298.15 K, m = 0.0310 mol.kg-i) = (15705+29) J.mol-‘. The molar enthalpies of
hydration are for oxalic acid, AhydrH,(298.15 K) = -(26.34&0.17) kJ.mol-‘: and for citric
acid, A hYdrH,(298.15 K) = -(10.85+0.19) kJ.mol-‘.

1. Introduction
In a continuation of the study of organic-acid-water interactions,“’ the enthalpies of
solution of oxalic, succinic, adipic, maleic, malic, tartaric, and citric acids in water at
298.15 K are reported. Knowledge about the thermochemical properties of aqueous
solutions of organic acids is rather limited. (2) Becker and Rothc3’ and Spedding and
Millerc4’ measured the enthalpy of dilution of oxalic acid at 298.15 K, while
Richards and Gucker”’ and Richards and MaiP determined it for tartaric acid and
citric acid at 289.15 and 293.15 K. The enthalpy of solution at 298.15 K was
measured for oxalic and citric acids(3*4,7) and the apparent molar heat capacity for
oxalic acid only.‘4’

2. Experimental
Oxalic acid dihydrate, (CO,H), .2H,O, (99.50 mass per cent); succinic acid.
HO,C(CH,),CO,H, (99.25 mass per cent); tartaric acid,
’ On sabbatical leave from Department of Chemical Engineering, Ben Gurion University of the Negev,
Beer-Sheva. Israel.

0021-9614/86/040351+07 $02.00/O Q 1986 Academic Press Inc. (London) Limited

352 A. APELBLAT

HO,CCH(OH)CH(OH)CO,H, (99.70 mass per cent), were supplied by Merck.

Maleic acid, HO,CCH: CHCO,H, (99.70 mass per cent) and citric acid
monohydrate, HOC(CH,CO,H),CO,H . H,O, (99.60 mass per cent), were from
B.D.H. dl-Malic acid, HO,CCH(OH)CH&O,H, (99.50 mass per cent), was from
Sigma Chemical and adipic acid, H0,C(CH,),C02H, (99.90 mass per cent), was
from Fluka.
The purities of solid samples were established by potentiometric titration with
0.1 mol. dme3 NaOH. The organic acids were used without further purification,
but were dried in an all-glass Biichi TO-50 vacuum oven at 353 K during 2 to 4 d.
Ampoules were filled in the air, immediately upon cooling of the sample after its
removal from the oven, and stoppered. With the exceptions of the hydrates of oxalic
and citric acids, no impurity corrections were introduced, because the absorption of
moisture by the solids is mainly responsible for lower than theoretical acidity of the
solid samples and the excess water was removed during the thermal-vacuum drying.
Oxalic acid dihydrate and citric acid monohydrate were introduced into the
ampoules directly from bottles when anhydrous oxalic and citric acids were
prepared by placing the hydrates into the vacuum oven for a few days at 343 to
373 K. The compositions of hydrates were determined by the difference in mass.
Since hydrates were undried before the calorimetric experiment, the actual acid
content of samples was taken into consideration by introducing the impurity factor.
The water content of oxalic acid dihydrate was 29.35 mass per cent while the
theoretical value is 28.58 mass per cent and of citric acid monohydrate was 8.50
mass per cent instead of 8.57 mass per cent.
The measurements were performed in an LKB-8700 Precision Calorimetry
System using the same procedure as described previously.‘**g’ The mass of water in
the reaction vessel of calorimeter was (99.53 f 0.02) g.
Since with exception of oxalic acid, (4) there are no heat capacities for the aqueous
solutions of organic acids, it was possible to adjust our results to 298.15 K only
approximately. Specific heat capacities were determined by the Grenthe, Hessler,
and Ots(“) method, though without desirable electrical modifications in the
calorimeter. The obtained heat capacities are not accurate enough to evaluate C,,,
values, especially for low molalities, nevertheless they can serve as a first
approximation; succinic acid, C,,,/(J . K-r mol- ‘) = 198 - 35{m/(mol. kg- ‘)} for
m < 0.6 mol. kg-‘; adipic acid, C’,,, = 201-60{m/(mol . kg-‘)} for m < 0.15
mol.kg-‘; maleic acid, C,, ,,, = 160+ 15(m/(mol. kg-‘)} for m < 1.4 mol.kg-‘;
malic acid, C,,, = 144+49{m/(mol.kg-‘)) for m < 1.4 mol. kg-‘; tartaric
acid, C,,, = 247-57{m/(mol. kg-‘)} for m < 1.0 mol. kg-‘; and citric acid,
c,* m = 175+9l{m/(mol.kg-‘)} for m < 1.5 mol.kg-‘. The molar heat capacities
of solid acids were taken from the literature or estimated: oxalic acid dihydrate,
C P.m = 191 J.K-‘.mol-‘; anhydrous oxalic acid, C,., = 107 J.K-‘.mol-‘;
succinic acid. C,,, = 152.93 J.K-‘.mol-‘;“” adipic acid, C,,, = 175
J.K-‘.mol-‘; maleic acid, C,,, = 150 J.K-‘.mol-‘; malic acid, C’,,, = 158
J K- ’ mol- ‘; tartaric acid, C,, m = 180 J . K- l . mol- ‘; citric acid monohydrate,
C = 267.30 J. K- 1 . mol- 1;(7.“I and anhydrous citric acid, C,,, = 225.66
J .‘ic”- 1 , mol - 1 (7)
 ENTHALPY OF SOLUTION OF ORGANIC ACIDS 353
The molar masses M and the densities p used throughout this study are oxalic
acid dihydrate, M = 126.667 g.mol-‘, p = 1.653 g.cmM3; succinic acid,
M = 118.089 g+mol-‘, p = 1.5724 g.cm-“; adipic acid, M = 146.143 g.moll’.
p = 1.360 g.cme3; maleic acid, M = 116.073 g. mol- ‘, p = 1.590 g. cmm3; malic
acid, M = 134.089 g.mol-‘, p = 1.601 g.cmP3; tartaric acid,
M = 150.088 g. mol-‘, p = 1.7598 g. cm-j; and citric acid monohydrate,
M = 210.140 g.moll’, p = 1.542 g+cmT3.

3. Results and discussion

The results of calorimetric measurements with succinic, adipic, maleic, malic, and
tartaric acids are presented in table 1. ASo,H denotes the enthalpy change at (T)
which is the average of the initial and final temperatures of the solution experiment.
The results were corrected for the enthalpy of vaporization of water into the air
space in the ampoule at 298.15 K. (9) The adjustment of the molar enthalpy of
solution to A,,,H,(298.15 K) was performed using C,,, and C,,, values, already
mentioned above. In the absence of enthalpies of dilution, only the enthalpy of
solution for an average molality is available. The molar enthalpies of solution as
determined in this study are:
succinic acid, AS,,,H,(298.15 K, m = 0.0334 mol. kg- ‘) = (28705 &- 89) J . mol- ‘:
adipic acid, A,,, H,(298.15 K, m = 0.0195 mol. kg-‘) = (32848 + 82) J. mol- ‘;
maleic acid, A,,,H,(298.15 K, m = 0.0256 mol.kg-‘) = (21333+29) J.mol-‘:
malic acid, A,,,H,(298.15 K, m = 0.0318 mol.kg-‘) = (21846$86) J-mol-‘;
tartaric acid, A,,,H,(298.15 K, m = 0.0310 molskg-‘) = (15705+29) J-mol-‘.
The uncertainty is in each case twice the standard deviation of the mean.

TABLE 1. Calorimetric molar enthalpies of solution of succinic, adipic, maleic, malic, and tartaric acids

w in -A,e,H _(T) A,,H,(298.15 K)

w m Ad (T) &,,&(298.15 K)
ii -J K J.mol-’ i mol.kg-’ J K J.mol-’

Succinic acid HO,C(CH,)aCO,H

0.39325 0.03346 95.167 298.14 28567 0.45022 0.03831 109.08 298.15 28600
0.42355 0.03604 103.30 298.13 28792 0.48388 0.04117 118.25 298.16 28849
0.44104 0.03752 107.34 298.14 28732 0.51637 0.04393 125.48 298.16 28688
Adipic acid HO,C(CH,),CO,H
0.25078 0.01724 56.561 298.12 32937 0.28620 0.01968 64.278 298.13 32801
0.26155 0.01978 59.276 298.11 33098 0.30019 0.02064 67.478 298.13 32830
0.26259 0.01805 58.999 298.11 32812 0.31967 0.02198 71.547 298.13 32691
0.27040 0.01859 60.973 298.12 32932 0.32106 0.02207 71.984 298.13 32749
0.28173 0.01937 63.239 298.13 32783
Maleic acid HO,CCH : CHCO,H
0.25083 0.02171 46.078 298.14 21302 0.29891 0.02587 54.919 298.16 21310
0.27109 0.02347 49.978 298.14 21380 0.31793 0.02752 58.532 298.16 21354
0.29387 0.02544 53.949 298.15 21292 0.33988 0.02942 62.581 298.15 21357
 354 A. APELBLAT

No enthalpies of solution have been reported for any of these organic acids in
water, but an indirect comparison is possible with the enthalpy of solution of
succinic acid in 0.1 mol. dm-’ HCl. It has been determined by Gunn:(i3’
A,,,H,(298.15 K, 0.16 mol.dme3) = (28723521) J.mol-’ and by Vanderzee:(14’
A,,,H,(298.15 K, 0.0268 mol. dme3) = (28702533) J. mol- ‘. These values are
very close to the reported enthalpy of solution of succinic acid in water.
In table 2 are presented results of calorimetric measurements with anhydrous
citric acid and citric acid monohydrate. Since the water composition of the hydrate,
8.50 mass per cent, is very close to the theoretical value, 8.57 mass per cent, no
additional adjustment was performed, but the enthalpy of solution for the average
molalities was multiplied by the impurity factor, f = 1.004, of this sample. The
determined enthalpy of solution of anhydrous citric acid is A,,,H,(298.15 K,
m = 0.0200 mol. kg- ‘) = (18211 f 69) J . mol- ’ and of citric acid monohydrate is
A,,,H,(298.15 K, m = 0.0203 mol. kg-‘) = (29061+ 123) J*moll’. These values
can be compared with results obtained by de Kruif et ~1.~~) for the anhydrous
acid: A,,,H,(298.15 K, m < 0.11 mol.kg-‘) = (18.47f0.09) kJ.mol-’ and for the

TABLE 2. Calorimetric molar enthalpies of solution of anhydrous citric acid and citric acid monohydrate

-w A&f _(T) A,,H,(298.15 K) -w m A,,,H _(T)

m A.,,H,(298.15 K)
__ __
g mol,kg-’ J K J.mol-’ g mol,kg-r J K J,mol-’

Citric acid HOC (CH,CO,H),CO,H

0.21490 0.01438 26.211 298.13 18298 0.44264 0.02315 41.162 298.13 18109
0.30627 0.01602 28.988 298.11 18156 0.48596 0.02541 46.215 298.17 18258
0.40385 0.02112 38.372 298.14 18235 18211+69”~*
Citric acid monohydrate HOC(CH,CO,H)&O,H H,O
0.31500 0.01506 43.817 298.16 29200 0.43158 0.02063 59.140 298.15 28177
0.32798 0.01568 45.063 298.16 28847 0.43802 0.02093 60.118 298.16 28824
0.39725 0.01899 55.527 298.21 29357 0.45008 0.02151 61.559 298.15 28724
0.41458 0.01981 57.526 298.14 29142 0.46091 0.02203 63.874 298.21 29110
0.41612 0.01989 57.143 298.14 28841 0.46128 0.02205 63.392 298.11 28871
0.42409 0.02027 59.066 298.14 29252 0.48885 0.02336 66.731 298.15 28670
0.42444 0.02029 58.181 298.14 28786 0.49185 0.02351 66.649 298.16 28590
0.42889 0.02050 59.610 298.14 29188 29061& 123 a.’
Malic acid HO$CH(OH)CH,CO,H
0.39387 0.02951 64.564 298.15 21966 0.43928 0.03292 71.204 298.16 21723
0.41389 0.03101 67.619 298.15 21894 0.45346 0.03398 73.686 298.16 21779
0.42080 0.03153 68.665 298.14 21868
Tartaric acid HO,CCH(OH)CH(OH)CO,H
0.44787 0.02998 47.016 298.09 15747 0.47637 0.03189 49.845 298.10 15694
0.44844 0.03002 47.026 298.15 15732 0.49325 0.03302 51.549 298.10 15677
0.44951 0.03012 46.976 298.06 15677

’ Twice the standard deviation of the mean.

b For the average molality: m = 0.0200 mol. kg-‘.
’ Multiplied by the impurity factor, f= 1.004; for the average molality: m = 0.0203 mol. kg- ‘.
 ENTHALPY OF SOLUTION OF ORGANIC ACIDS 355
hydrate: A,,,H,(298.15 K, m < 0.11 molekg-‘) = (29.25f0.20) kJ.mol-‘. There
is satisfactory agreement between both sets of results. It is interesting to note that
Levian”” derived from solubilities and osmotic coefficients, the enthalpy of solution
of citric acid monohydrate in saturated solution: A,,,H,(298.15 K, 8.487 mol. dmP3)
= 29.79 kJ .mol-‘, using the Williamson equation”@ for a monohydrated non-
electrolyte.
Since the enthalpy of solution of the hydrate and anhydrous citric acid were
measured for almost the same average molality, it is possible to evaluate the
enthalpy of hydration of citric acid. From
H&,0,(s) + 2775H,O(l) = H,C,O,(aq, m = 0.02 mol. kg- ‘), (1)
H&,0, . H,O(s) +2774H,O(l) = H,C,O,(aq, m = 0.02 mol. kg- ‘), (2)
it follows that
H&,0,(s) + H,O(l) = H,C60, . H,O(s), (3)
yielding the molar enthalpy of hydration: A,,,,H,(298.15 K) = - (10.85 +O. 19)
kJ . mol-’ in nice agreement with de Kruif et aI.‘&‘) result: A,,,,H,(298.15 K) =
-(10.78&0.29) kJ.mol-‘.
The results of solution experiments with anhydrous oxalic acid and oxalic acid
dihydrate are presented in table 3. For the dihydrate, they were corrected for the
excess water over the theoretical value, by assuming that the excess water is present

TABLE 3. Calorimetric molar enthalpies of solution of anhydrous oxalic acid and oxalic acid dihydrate

M’’ ~ mf A,,H
__ Asd’
- -(T) A,,H,(298.15 K) A,,,H,“(298.15 K)
i mol.kg-’ J J K J.mol-’ J.molli

Oxalic acid (CO,H),

0.23246 0.02594 25.575 298.11 9896 8762
0.25121 0.02803 28.264 298.10 10122 8943
0.30248 0.0337s 34.566 298.12 10282 8989
0.31458 0.03510 36.428 298.21 10401 9082
0.32231 0.03597 36.486 298.11 10187 8852
0.35204 0.03928 40.131 298.12 10258 8863
0.38130 0.04255 43.104 298.19 10160 8708
0.39837 0.04445 45.042 298.14 10170 8686
8853 i 99 u
Oxalic acid dihydrate (CO,H), 2H,O
0.40161 0.39660 0.03163 114.535 114.541 298.19 36390 35164
0.43211 0.42737 0.03408 123.367 123.374 298.20 36373 35074
0.47137 0.46548 0.03711 134.462 134.479 298.21 36390 35034
0.48022 0.47422 0.03780 137.012 137.019 298.22 36404 35035
0.50563 0.49932 0.03981 144.035 144.042 298.22 36346 34942
35’15
A- +_ 77”.”
L

* Twice the standard deviation of the mean.

’ Multiplied by the impurity factor,/= 1.005.
356 A. APELBLAT

in the form of a saturated solution of oxalic acid. The mass w’, of C,H,O, .2H,O
presented in ampoules, was calculated from
wr = flW. (4)
where w is the mass of sample inside of each ampoule and
fi = WW-W,~2H,O)C(nU -P)IM(C,H,O,))-P/M(H,O)I/(~-~), (5)
where p = 0.2935 is the mass fraction of water in the sample, Mi are the molar
masses, and the mole ratio of H,O to C,H,O, in the saturated solution is
n = 45.95.“”
The enthalpy change adjusted to reflect only the enthalpy of solution of the
dihydrate Aso,H’, is given by
Aso,H’ = Aso,H -f2 WA,,, H,(sat. sln. + m,)/M(C,H,O,), (6)
where Aso,H is the experimentally measured change in enthalpy and
fi = (1-P-~~M(C,H,O,)IM(C,H,O,.~H,O)). (7)
The final molality of oxalic acid after breaking the ampoule is

m, = 41 -PWWJW,)(~, +PW% (8)

where wi = 99.53 g is the mass of water in the reaction vessel of the calorimeter. In
the approximation to the infinite-dilution conditions the enthalpies of dilution of
oxalic acid”*’ were used and the final result was multiplied by the impurity factor,
f = 1.005, of this sample.
The determined molar enthalpy of solution, extrapolated to infinite dilution is for
anhydrous oxalic acid: A,,, Hg(298.15 K) = (8853 + 99) J. mol- ’ and for oxalic acid
dihydrate: A,,,H,“(298.15 K) = (35225+72) J. mol-‘. This value can be compared
with the re-calculated Spedding and Miller’4*18’ result for the dihydrate:
Aso,HE(298.15 K) = (35648 f 193) J. mol- ‘. The agreement is satisfactory.
From the changes in state determined in this study,
C,H,O,(s) + coH,O(l) = C,H204. coH,O, (9)
C,H,O, .2H,O(s) + coH,O(l) = C,H,O, . coH,O, (10)
the change occurring in the reaction:
C,H,O,(s) + 2H,O(l) = C,H,O, .2H,O(s). (11)
which represents the hydration of oxalic acid, can be evaluated. The molar enthalpy
of hydration is AhydrH,(298.15 K) = -(26.34+0.17) kJ.mol-‘. There is nice
agreement with Jorissen’s result, published in 1910: A,,,,H,(298.15 K) =
-26.61 kJ. mol- ‘.(19) For a lower temperature, Becker and Rotht3’ obtained
A,,,,drH,(293.25 K) = -(27.57f0.21) kJ.mol-‘.

The author is indebted to Mrs Luna Wajsbrot for her fine technical assistance and
to Dr Celina Dobrogowska for many helpful discussions.
 ENTHALPY OF SOLUTION OF ORGANIC ACIDS 357
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