You are on page 1of 4

J. Chem.

Thermodynamics 36 (2004) 4144


www.elsevier.com/locate/jct

The molar enthalpies of solution and solubilities of


ammonium, sodium and potassium oxalates in water
Batella Menczel, Alexander Apelblat *, Eli Korin
Department of Chemical Engineering, Ben Gurion University of the Negev P.O. Box 653, 84105 Beer Sheva, Israel
Received 19 June 2003; accepted 17 September 2003

Abstract
The molar enthalpies of solution of sodium oxalate Dsol Hm (Na2 C2 O4 ; T 296:57 K, m 0:00768 mol  kg1 ) (16.59  1.32)
kJ  mol1 and potassium oxalate monohydrate Dsol Hm (K2 C2 O4  H2 O; T 299:01 K, m 0:0274 mol  kg1 ) (29.31  0.98)
kJ  mol1 were calorimetrically determined. The case of ammonium oxalate monohydrate, Dsol Hm ((NH4 )2 C2 O4  H2 O; T 296:99
K; m 0:03401 mol  kg1 ) (35.0  4.9) kJ  mol1 was previously considered in [11]. Solubilities of ammonium oxalate, sodium
oxalate and potassium oxalate in water were measured in the (273 to 333) K temperature range. Presented data are compared with
the literature results.
2004 Elsevier Ltd. All rights reserved.
Keywords: Ammonium; Sodium; Potassium oxalates; Solubilities; Molar enthalpies of solution

1. Introduction
In many industrial, geological and biological systems
oxalate ions are of considerable importance due to their
capacity to form stable complexes with various metal
ions. Considering only technological applications, ammonium oxalate is used as an ingredient in the manufacturing of explosives and metal polishing compounds,
sodium oxalate serves in metal cleaning preparations, in
textile, leather and tanning industries and potassium
oxalate in cleaning natural bers, in photography and
all of them in analytical and solvent extraction chemistry (sodium oxalate as primary volumetric standard for
manganometry and acidimetry) [1]. Determination of
dynamic and thermodynamic properties of aqueous solutions of oxalic acid and various oxalates is connected
with continuous interest in these applications, but also
with the plant nutrition and disease control.
Solubility measurements with ammonium, sodium
and potassium oxalates started early ([26]) but mostly
as the determination of the liquid-solid diagrams at one
or two temperatures. These investigations were mainly
*

Corresponding author. Tel.: +972-8-6461487; fax: +972-8-6472916.


E-mail address: apelblat@bgumail.bgu.ac.il (A. Apelblat).

0021-9614/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2003.09.012

directed to establish the formation of double salts of


various oxalates. However, more systematic determinations of solubility as a function of temperature were also
performed and they are tabulated by Seidell [7] and
Stephen and Stephen [8]. Unfortunately, the thermal
properties of aqueous solutions of oxalates are very
scarce. Only the molar enthalpy of solution of potassium oxalate monohydrate in the (291 to 293) K temperature range reported by Perreu [9] and the molar
enthalpy of dilution [10] are known. Recently, we measured the molar enthalpy of solution of ammonium
oxalate monohydrate in water [11].
In this work, the solubility of oxalates in water, in the
(273 to 333) K temperature range is presented and
compared with the literature data. Besides, calorimetric
measurements with sodium oxalate and potassium oxalate monohydrate are also reported.
2. Experimental
Ammonium oxalate monohydrate, (NH4 )2 C2 O4 
H2 O; sodium oxalate, Na2 C2 O4 and potassium oxalate
monohydrate, K2 C2 O4  H2 O, all reagents of mass fraction 0.995 to 1.01 were purchased from Merck and used
without further purication.

42

B. Menczel et al. / J. Chem. Thermodynamics 36 (2004) 4144

Suspended in an excess solid oxalates were dissolved


in distilled water by stirring for 0.5 h in double wall
tubes. The change of temperature, in both directions,
was obtained by circulating water from an external
thermostat. The stirring was followed by a gravitational
settling of about 30 min. These times were established in
the preliminary experiments. Weighted samples of saturated solutions, in duplicate, were titrated with 0.1 mol/
kg solutions of potassium permanganate which was
standardized with the solid sodium oxalate (99.95%).
The mean values of the solubilities are reported. Estimated error in the solubilities experiments is less than
one per cent.
The enthalpies of solution were determined in a Parr
1455 Solution Calorimeter. The mass of water in the
reaction vessel of the calorimeter was 100 g. The energy
equivalent e 525:7  9:8 J  K1 , was established
using the dissolution of potassium chloride in water. The
results of calorimetric measurements were not adjusted
for temperature and dilution eects because heat capacities and enthalpies of dilution are unknown. The
enthalpies of solutions are presented for the mean molality and temperature of all calorimetric experiments
for a given oxalate.

FIGURE 1. Solubility of ammonium oxalate in water as a function of


temperature. r, reference 3; d, reference 4; N, reference 5; , this
work.

3. Results and discussion


The solubilities of ammonium and alkali metal oxalates in water, determined in this work are presented in
table 1 and compared with the literature values in gures
1 to 3. As can be observed, there is a good agreement
between dierent works in the case of ammonium oxalate and sodium oxalate. However, our values for potassium oxalate are systematically lower than the old
results of Koppel and Cahn [2] and Rivett and OConnor [3] and the reason for this discrepancy is not clear.

FIGURE 2. Solubility of sodium oxalate in water as a function of


temperature. r, reference 3; N, reference 4; d, reference 7; , this
work.

TABLE 1
Solubilities m of ammonium, sodium and potassium oxalates as a
function of temperature T
T /K

273.15
278.15
283.15
288.15
293.15
298.15
303.15
308.15
313.15
318.15
323.15
328.15
333.15

m/(mol  kg1 )
(NH4 )2 C2 O4

Na2 C2 O4

K2 C2 O4

0.201

0.210
0.219

1.483
1.598
1.739
1.811
1.957
2.06
2.17
2.30
2.39
2.51
2.62
2.73
2.89

0.259
0.361
0.422
0.496
0.577
0.653
0.777
0.880
1.004
1.164

0.243
0.263
0.270
0.284
0.301
0.316
0.326
0.345
0.355
0.367

FIGURE 3. Solubility of potassium oxalate in water as a function of


temperature. N, reference 2; r, reference 3; N, , this work.

The solubility of salt hydrates having h molecules of


water as a function of temperature is given by [12]


o ln m
Dsol Hm T
o ln c

; f 1
;
o1=T
mR1  0:001hM1 mf
o ln m T
1

B. Menczel et al. / J. Chem. Thermodynamics 36 (2004) 4144

where Dsol Hm (T ) is the molar enthalpy of solution; m is


the total number of moles of ions given by one mole of
electrolyte; c is the activity coecient, M1 is the molecular mass of water and R is the gas constant. Since in
our case the change of activity coecients with molality
m near the saturation point is unknown, the factor f was
replaced by unity and the enthalpy of solution becomes
the apparent molar enthalpy of solution.
If the solubility of oxalates is formally represented by
B
ln m A C ln T ;
2
T
where A, B and C are adjustable constants, then introducing in our case h 0 and h 1 and m 3, the apparent molar enthalpy of solution at the saturation
point is
Dm Hsol T 3R1  0:001M1 hmCT  B:

In equation (3) it was assumed, basing on the electrical


conductance measurements [13], that alkali metal oxalates are strong electrolytes. Ammonium oxalate behaves dierently, there is a possibility of formation of
undissociated molecules of ammonia and some timedependent hydrolysis products [13]. It seems that 1 <
m < 2 is more appreciable value for concentrated ammonium oxalate solutions. The apparent enthalpy of
solution is comparable with results of calorimetric determinations because
Dsol Hm T Dsol Hm1 T  Ddil Hm T ; m ! 0;

where the rst term is the molar enthalpy of solution at


innite dilution and the second term (usually much
smaller then the rst one) represents the molar enthalpy
of dilution of saturated solution. As can be expected, the
apparent enthalpy of solution obtained from the solubility experiments and Dsol Hm (T ) from the calorimetric
experiments have only similar values considering that
the enthalpy of solution is measured at the nite concentration and the enthalpy of dilution is usually
unknown.
Solubilities of the oxalate salts can be expressed by
lnfm;NH4 2 C2 O4 g 82:003 1346:7K=T
13:449 lnT =K;
R2 0:9992;

Dsol Hm fNH4 2 C2 O4 g 33:0 kJ  mol1 ;

Dsol Hm Na2 C2 O4 21:8 kJ  mol1 ;

Dsol Hm fK2 C2 O4 g 24:0 kJ  mol1 ;

10

where for ammonium oxalate, m 1:5 was introduced


into equation (3).
The results of the calorimetric measurements with of
sodium oxalate and potassium oxalate monohydrate are
presented in table 2 (for ammonium oxalate monohydrate see [11]). DH T denotes the enthalpy change of
the dissolution process at temperature hT i, which is the
average of the initial and nal temperatures of the calorimetric experiment and mf is the molality of the nal
solution. In the absence of heat capacities and the enthalpies of dilution at temperatures of calorimetric experiments, the molar enthalpies of solution are only
given for an average value of molality m and temperature T and they are: Dsol Hm (T 296:57 K, m 0:00768
mol  kg1 ) (16.59  1.32) kJ  mol1 for sodium oxalate, Dsol Hm (T 299:01 K; m 0:0274 mol  kg1 )
(29.31  0.98) kJ  mol1 for potassium oxalate monohydrate and Dsol Hm (T 296:99 K; m 0:03401 mol 
kg1 ) 35.0  4.9 kJ  mol1 for ammonium oxalate
monohydrate [11].

TABLE 2
Calorimetric molar enthalpies of solution of sodium oxalate and
potassium oxalate monohydrate
DH/J

mf

ln fm; K2 C2 O4 g 29:690  2138:3=T  3:8257 ln T ;


R2 0:9988;

where the parameters of these equations were determined by an unweighted multivariate least-square
method and R2 denotes the squared correction coecient of the regression. From these equations the apparent molar enthalpy of solution at T 298:15 K are

hT i/K

1

Dsol Hm
(J  mol1 )

(mol  kg )
0.00747
0.00748
0.00752
0.00759
0.00759
0.00761
0.00761
0.00768
0.00769
0.00769
0.00775
0.00779
0.00797
0.00803

11.99
12.09
12.62
11.83
13.14
12.41
14.62
12.09
12.72
11.04
13.08
14.95
13.30
12.49

Na2 C2 O4
296.79
297.56
296.73
297.11
296.63
296.85
297.72
296.54
297.82
295.98
295.56
295.52
295.60
295.56

16 030
16 130
16 770
15 580
17 320
16 300
19 240
15 740
16 550
14 350
16 880
19 170
16 690
15 530

0.02721
0.02730
0.02732
0.02734
0.02736
0.02737
0.02741
0.02744
0.02746
0.02749
0.02766

73.60
79.38
79.91
83.06
78.86
83.06
82.01
80.44
83.06
78.33
81.49

K2 C2 O4  H2 O
301.31
300.98
301.03
295.91
300.93
296.41
300.93
296.84
296.32
297.06
301.35

27 050
29 080
29 250
30 380
28 830
30 350
29 920
29 320
30 250
28 500
29 460

ln fm; Na2 C2 O4 g 3:9203  974:85=T  0:3424 ln T ;


R2 0:9976;

43

44

B. Menczel et al. / J. Chem. Thermodynamics 36 (2004) 4144

Since the molar enthalpies of dilution of saturated solutions are unknown, it is impossible to compare the molar
enthalpies of solution coming from the calorimetric and
solubility experiments. However, considering that Ddil Hm
is usually a small fraction of Dsol Hm , the observed values
coming from two types of experiments are reasonable
similar. In the case of potassium oxalate monohydrate,
Perreu [9] reported the molar enthalpy of solution at innite dilution Dsol Hm (m ! 0, T 291 K to 293 K) 26.19
kJ  mol1 which is in a good agreement with our result.
References
[1] S. Budavari (Ed.), The Merck Index. An Encyclopedia of
Chemicals, Drugs and Biologicals, 11th ed., Merck Co. Inc,
Rahway, NJ, 1989.

[2] J. Koppel, M. Cahn, Z. Anorg. Chem. 60 (1903) 53.


[3] A.C.D. Rivett, E.A. OConnor, J. Chem. Soc. 115 (1919)
1346.
[4] F. Fl
ottmann, Z. Anal. Chem. 73 (1928) 1.
[5] E. Hill, E.F. Distler, J. Am. Chem. Soc. 53 (1931) 4316.
[6] H.T.S. Britton, M.E.D. Jarett, J. Chem. Soc. (1936) 1489.
[7] A. Seidell, Solubilities of Inorganic and Metal Organic Compounds, third ed., Van Nostrand, New York, 1953.
[8] H. Stephen, T. Stephen, Solubilities of Inorganic and Organic
Compounds, Pergamon Press, Oxford, 1963.
[9] J. Perreu, C.R. Acad. Sci. Paris 211 (1940) 182.
[10] E. Plake, Z. Phys. Chem. (A) 162 (1932) 257.
[11] A. Apelblat, E. Korin, J. Chem. Thermodyn. 35 (2003)
699.
[12] A.T. Williamson, Trans. Faraday. Soc. 40 (1944) 421.
[13] M. Bester-Rogac, M. Tomsic, J. Barthel, R. Neueder, A. Apelblat,
J. Solution Chem. 31 (2002) 1.

JCT 03/082