M-2008

J. Chem. Thermodynamics 1987, 19, 317-320

Solubility
of oxalic,
malonic,
succinic,
adipic,
maleic, malic, citric,
and tartaric
acids in water from 278.15 to 338.15 K
ALEXANDER

APELBLAT

and EMANUEL

Department of Chemical Engineering,

Beer Sheva, Israel
(Received II March

Ben Gurion

MANZUROLA
University of the Negev,

1986; in jinal form 1 July 1986)

Solubilities of several dicarboxylic acids (oxalic, malonic, succinic, adipic, and maleic) and
hydroxycarboxylic acids (malic, citric, and tartaric) in water were determined in the 278.15 to
338.15 K temperature range.

1. Introduction
The present work follows our earlier studies on organic acid-water interactions
where the apparent molar volumes(l) and the molar enthalpies of solution(2) of
several organic acids in water were determined. Systematic measurements of
solubility of eight organic acids in water were performed at 5 K intervals from
278.15 and 338.15 K. The reported results are compared with the solubilities in the
literature.3-5) With the exception of citric acid(6-9) only a few new measurements of
solubility had been reported for the acids under consideration.(O-ll)

2. Experimental
Solid samples of organic acids used in this work are described elsewherec2 with the
exception
of malonic acid, HO,CCH,CO,H
(99 mass per cent), which was from
Merck. Suspended in an excess, solid acids were dissolved in distilled water by
stirring for 10 h in double-wall tubes thermostatted
by circulating
water.
Fluctuation of temperature was less than fO.O1 K. The stirring was followed by a
gravitational
settling overnight. Weighed samples of saturated solutions were
titrated with solutions of NaOH (Merck), standardized with potassium hydrogen
phthalate (Merck). Phenolphthalein
served as an indicator. Excellent reproducibility
of results was observed. The molar masses A4 used throughout this work are: oxalic
acid, M = 90.636 g. mol-l;
malonic acid, A4 = 104.062 g. mol-;
succinic acid,
M = 118.089 g.mol-;
adipic
acid, M = 146.143 g.mol-;
maleic
acid,
M = 116.073 gemol-;
malic
acid,
M = 134.089 g.mol-;
citric
acid,
M = 192.125 g.mol-;
tartaric
acid,
M = 150.088 g.mol-I;
water,
M = 18.0153 g.mol-l.
a To whom correspondence should be addressed.
0021-9614/87/030317 +04 %02.00/O

0 1987 Academic Press Inc. (London) Limited

318

A. APELBLAT

AND

E. MANZUROLA

3. Results and discussion

The solubility of a solid in a liquid as a function of temperature T can be expressed
at constant pressure, by the relation:12)
{a in m/~(l/T)}(l
+a In y/a In m) = -A&&/R,
(1)
where Aso,Hm is the molar enthalpy of solution, R is the gas constant, and m and y
are the molality of the solute and its activity coefficient. For ideal-dilute solutions
when compositions are expressed in mole fractions x, equation (1) reduces to the
SchrGder equation. (r3) For solutes forming a hydrate having h molecules of water,
equation (1) takes the form: 2,

{a In m/a(lp-)j(i +a In y/a In WI) = -A,,,N,/{R(i

-hmM,)},

(2)

where M, is the molar mass of H,O. For ideal-dilute solutions straight lines are
expected by plotting ln(m/m) against l/T or In x against l/T (m = 1.0 mol. kg-).
From an analysis of experimental results it is evident that this is only partially true
and more or less curved lines are observed. Departure from the straight-line
behavior results from the temperature dependence of the enthalpy of solution, nonideality of solutions, and from the change of composition of the solid phase in
equilibrium with the saturated solution (breaks in solubility curves are attributed to
transitions between different hydrate forms of the solute).r4
Davies and Griffithso ) showed that the effect of dissociation of dicarboxylic acids
in water on the solubility is negligible and that they can therefore be treated as
unionized solutes.
Solubilities of oxalic acid and other dicarboxylic acids in water, expressed as mole
fractions, over the studied temperature range are presented in table 1. There is a
reasonable agreement up to about 303 K with literature values but at higher
temperatures there is a distinct difference between our values and those of Koppel
and Cahn from 1908. quoted by Seidell. (3) Since the compositions of solid phases in
equilibrium
with the saturated solutions were not determined in this work, the
observed curvature of solubility lines is not related to the existence of transition
temperatures. Using equation (2) for oxalic acid dihydrate and neglecting the
activity coefficient term, the apparent enthalpy of solution at 298.15 K is
AsolN, = 26.5 kJ. mol-I. This value is about 40 per cent lower than that based on
the calorimetric values from the molar enthalpy of solution at infinite dilution(2) and
new enthalpies of dilution of oxalic acid. (15) From the difference in both values we
can only predict that for solutions near the saturation point a In y/a In m > 0.
There is satisfactory agreement between our values and older ones from before
1899 cited by Seidellt3) for malonic acid. From equation (1) the molar enthalpy of
solution at 298.15 K is Aso,H, = 11.8 kJ.mol-.
Results of solubility determinations
for succinic acid were compared with the
values over the 1874 to 1919 period compiled by Seidell.(3 New measurements of
solubility performed by Davies and Griffithso in 1953 for succinic acid and adipic
acid are expressed as concentrations and without knowledge of the densities of
saturated solutions cannot be used for comparison. However, from estimated values
it is clear that they are in a good agreement with those presented here. The apparent

SOLUBILITIES
TABLE

1. Solubilities

OF ORGANIC
of dicarboxylic

CO,H

CO,H

co2

CH,

(%),

&J,

CO,H

bO,H

CO,H

CO,H

CO,H
CHCO,H
II
CHCO,H

319

IN WATER

and hydroxycarboxylic

T/K
____
278.15
283.15
288.15
293.15
298.15
303.15
308.15
313.15
318.15
323.15
328.15
333.15
338.15

ACIDS

acids in water
CO,H
I
CHOH
I
CH,
COzH

CH,CO,H
HOCCO,H
&H,c~,H

CO,H
I
CHOH
CHOH
I
CO,H

x
0.00924
0.01124
0.01479
0.01863
0.02301
0.02690
0.03421
0.04133
0.04934
0.05887
0.06956
0.07813
0.09830

0.1686
0.1791
0.1903
0.2038
0.2176
0.2309
0.2455
0.2633
0.2767
0.2911
0.3120
0.3335
0.3532

0.00539
OOO680
0.00859
0.01092
0.01337
0.01591
0.01928
0.02384
0.02961
0.03550
0.04237
0.04862
0.06023

0.00123
oOO143
0.00194
0.00239
0.00307
0.00381
0.00476
0.00619
0.00843
0.01080
0.01518
0.02135
0.02437

0.06729
0.07786
0.08688
0.09686
0.1109
0.1237
0.1419
0.1545
0.1745
0.1842
0.1990
0.2177
0.2323

0.1123
0.1214
0.1318
0.1454
0.1578
0.1681
0.1810
0.1976
0.2094
0.2313
0.2482
0.2691
0.2939

0.09084
0.09975
0.1100
0.1195
0.1321
0.1496
0.1617
0.1687
0.1823
0.1904
0.1991
0.2103
0.2239

0.1211
0.1273
0.1326
0.1370
0.1435
0.1503
0.1583
0.1638
0.1720
0.1826
0.1924
0.1989
0.2088

at 298.15 K is
molar
enthalpy
of solution
for m = 0.752 mol. kg-
Aso,Hm = 28.2 kJ-mol-.
This value is very close to A,,,H,(298.15
K,
calorimetrically.(2)
m = 0.0334 mol. kg- ) = 28.7 kJ . mol- as determined
However, it is not clear whether this agreement results from a small enthalpy of
dilution or from compensation for the activity coefficient term in equation (1).
Our results for adipic acid are slightly higher than those of Attane and
Doumanil
but with increasing temperature, both sets approach the same
solubility curve. The apparent molar enthalpy of solution at 298.15 K and for
m = 0.171 mol. kg-l,
Aso,Hm = 34.7 kJ . mol-l
can be compared
with the
calorimetric result: As,,H,(298.15 K, m = 0.0195 mol. kg-) = 32.8 kJ.mol-1.(2)
There is very satisfactory agreement between our values and those reported by
Seidell(3 for maleic acid, over the entire temperature range. The apparent molar
enthalpy
of solution
at 298.15 K and for m = 6.921 mol.kg-
is
Aso,Hm = 20.3 kJ. mol-
and the calorimetric
result is relatively
close:
A,,,H,(298.15 K, m = 0.0256 mol.kg-l)
= 21.3 kJ.mol-.2)
Solubilities of malic acid in water are in very good agreement with the values
compiled by Seidell. (3) The apparent molar enthalpy of solution at 298.15 K for
m = 10.4 mol. kg-
is AsolH, = 12.7 kJ. mol-.
This value is far from the
calorimetric result obtained for dilute solutions of malic acid: A\,,, H,(298'.15 K,
m = 0.0318 mol.kg-)
= 21.8 kJ-mol-.
Probably, the enthalpy of dilution will
play an important role here.
As a result of its industrial importance, the solubility of citric acid in water had
been repeatedly measured and with few exceptions there is satisfactory agreement
between the published values and ours. There are two distinct branches of the
solubility curve with the transition temperature estimated by Dalman(14) to be near

320

A. APELBLAT

AND

E. MANZUROLA

309 K. Since the osmotic coefficient 4 of citric acid is known at 298.15 K,(17) as a
function of molality it is convenient to transform equation (2) to the form:(12)
wwmvm
+ wiam)d
= -A,,,~LI~
- hmkfd.
(3)
The osmotic coefficient of the saturated solution is 4 = 1.629 and from Levien
we have, A4/Am = 0.0598 kg. mol- l. Introducing these values into (3), and putting
h = 1, m = 8.448 mol. kg-l, and Am/A(l/T) = - 14625 mol. kg-l. K, the molar
enthalpy of solution is Aso,Hm = 26.0 kJ. mol-.
This value is in an excellent
agreement with the calorimetric result 26.3 kJ . mol-
obtained from the molar
enthalpy of solution at infinite dilution of citric acid monohydrate
and the molar
enthalpy of dilution of citric acid.(15) Levien, 7, on the basis of the Dalman
solubilities, estimated that ALsolHm= 29.8 kJ . mol-. This is higher than ours, but
still satisfactory considering that the evaluation of Am/A(l/7) for this system is
difficult because the slope varies considerably with temperature.
Seidellc3) presents two sets of solubility measurements for tartaric acid in water
but remarks that . . . determination by Dalman (14) 1937, differing somewhat from
the results of Leidief18, 1882. Probably, this difference can be explained by
incorrect reading or presentation of temperature. If in ail Leidie measurements
temperature is shifted by 5 K, then both sets (including our results) are in very
satisfactory agreement. The apparent enthalpy of solution at 298.15 K for
m = 9.300 mol. kg- i is A,,iH, = 8.0 kJ.mol-l.
This value is far from the
calorimetric enthalpy of solution determined for dilute aqueous solutions of tartaric
acid: A,,,H,(298.15
K, m = 0.0310 mol.kgg)
= 15.7 kJ.mol-.2
The authors acknowledge the technical assistance of Miss Rachela Croitorie.
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