Solubility of succinic acid in pure solvents and in mixed solvents as a

function of temperature.

Arthur Henrique Rodrigues Rezende; Lorena Cristina Pres Borges and Ricardo
Francisco Pires

Chemical Engineering Department, Federal University of Tringulo Mineiro.

Av. Doutor Randolfo Borges Jnior, 1250, 38064-200, Univerdecidade, Uberaba-MG;
tel. +55 34 91759249, e-mail: ricardo@icte.uftm.edu.br;

Data corresponding solid-liquid equilibrium (SLE) of succinic acid in pure water,

different aqueous solvent mixtures containing water + dimethylformamide (DMF) and
pure DMF were measured with temperature range from 303.15K to 323.15K under
atmospheric pressure by employing gravimetric method. The experimental results
indicated that the solubility of succinic acid in aqueous solvent mixture increase with
increasing both temperature and mass fraction of organic solvents. The experimental
data were well-correlated with the rational models to accounted the nonideality of the
systems

Introduction
Succinic acid, also called butanedioic
acid or amber acid, is a dicarboxylic
acid of molecular formula is C4H6O4
that is an important industrial chemical.
The succinic acid is widely distributed
in almost all plant and animal tissues
and that plays a significant role in
intermediary metabolism. In addition,
succinic acid has larger applications in
the medicine, pesticides, sensitive
material, spices and food additives.
As know, aqueous solubility is an
important parameter in the separation
and crystallization process of
electrolytes. However, the purification
process of succinic requires a large
number of accurate solubility data. This
work is mainly aimed to measure the
solubility of succinic acid in mixed
solvents as a function of temperature
and test the capability of the solubility
correlation models (HEIDMAN et. al.,
1985; YAWS et. al., 1993) to correlated
the experimental data.
Solubility data of acid compounds have
a broad application and importance in
the pharmaceutical industry. 2,4 A variety
of pure solvents, including water and
solvent mixtures, can usually be
employed in a particular crystallization
process during the manufacturing of
pharmaceuticals.3,4 Measurements of
acid solubilities in water and aqueous
solutions have been receiving a growing
interest. Although there are some
experimental phase equilibrium data in
aqueous solutions of acid compounds, 1-4
very little are available for those with
no aqueous media.
In this work solubility of succinic acid
was measured in pure water, pure
dimethylformamide (DMF) and in
binary mixtures containing water and
DMF. The experiments were performed
in a temperature range of 303.15K to
323.15K ranging from 5K to 5K and
carried out an a atmospheric pressure by
the gravimetric method. The
experimental data were correlated using
Heidman and Yaws modified models.
Experimental
Materials
Succinic acid with a mass fraction of
higher 99.0% was obtained from
ISOFAR. The organic solvent, DMF
was obtained from Vetec with 99.8% of
purity. More details about purity of
solvents are listed in Table 1.
Table 1. Specifications of the
reactants.
Acid-saturated solutions were prepared
with varying mass fractions of DMF in
bidistilled deionized water. These
solutions were allowed to reach
equilibrium with excess acid while in
the jacketed glass cell where the
temperature was controlled by
circulating thermostated water. In order
to reach solution equilibrium
conditions, the magnetic stirrer carryed
out stirring for 162 minutes and
decanted for 180 minutes at constant
temperature. After that, samples around
4 cm of solution were withdraw in
triplicate using a thermostatized syringe
with temperature monitored. The
samples were analyzed by gravimetric
method. . In the Figure 1 we can see the
representation of the experimental
apparatus.

Compounds Producer Purity (%)

Succinic
ISOFAR 99%
acid
DMF Vetec 99.8%

All chemicals were used

received without further purification.

Apparatus and procedure

In the experiments, solubility data of

electrolyte, succinic acid, was measured
in mixed solvents as a function of
temperature by gravimetric method
under atmospheric pressure in the Figure 1. Experimental apparatus
temperature range from 303.15K to representation: 1, 3 and 5 Jacketed
323.15K. In this paper the experimental glass cell; 2, 4 and 6 Magnetic stirrer;
apparatus for measured the solubility 8, 9 and 10 Thermometer; 7 Latex
acid was a glass jacket with total rose; 11 Thermostatic bath; 12
volume around 35cm connected in Temperature indicators; 13 Septa.
series by latex hose and the temperature
was controlled by a thermostatic bath.
Cell temperature was monitored with a
thermometer.
 Results and discussion
Solubility data

The data of mole fraction solubility of

succinic acid in mixed solvents as a
temperature function are listed in Table
2 and in Figure 2. From Table 2 and
Figure 2, we can conclude that the
solubility of succinic acid in all the
mixed solvents increases with increase
of both temperature and mas fraction of
DMF in aqueous solution.
The results are showing that the
Figure 2. Solubility of succinic acid in
solubility of succinic acid increases
function of de mass fraction of DMF
with rising the mass fraction of DMF.
in water (1) + DMF (2) initial solution
This phenomenon could be explained
without succinic acid at six
based on the molecular structure of the
temperatures.
solvent and solute molecules in the
system. The ionization of succinic acid
produces anions with a nonpolar part. Data correlation
Thus, molecules of DMF are attracted
by these anions because owing a similar The relationship between mole fraction
structure to the succinic acid anions. of the solubility and temperature was
modeled by Heidman and Yaws models,
Equations 1 and 2, respectively.
Table 2. Solubility succinic acid in B
mixed solvents as a temperature ln m = A + + C ln T (1)
T
function.
DMF B' C '
T(K) 0.000 5.0534 10.042 25.038 100.000 log m = A '+ + (2)
1 (mol.kg-1) T T2
298.15 0.712 0.821 0.939 1.559 4.991
303.15 0.877 1.020 1.141 1.660 5.721
In this paper the models, Heidman and
Yaws, was modified for best results.
308.15 1.066 1.233 1.432 2.047 6.165
This modified models are Equations 3
313.15 1.299 1.492 1.694 2.446 6.105 and 4, respectively.
318.15 1.556 1.794 2.026 2.787 6.373
(3)
323.15 1.852 2.173 2.562 3.140 7.202

(4)

To solve the optimization problem and

calculate the dimensionless parameters
, , , , and , the
experimental points were fitted by
nonlinear regression using Levenberg
Marquardt method. Also, the objective
function minimized was the sum of
residual squares. In two fits the
parameters presented low standard
deviations. The average fit of
experimental points to both models by
taking into account correlation
coefficient (R). In all cases the average
relative deviations were obtained
between the experimental values and
calculated by the model using.

The correlation obtained for Heidman

and Yaws modified models, designated
by H and Y respectively, are presented Figure 3: The deviations for the data
in Table 3. of solubility of succinic acid in
mixtures of solvents (DMF + water).
Table 3. Data fitting using the
From Figure 3 it is possible to observe
Statistic 7.0.
that the experimental data and the
results of the model Heidman and Yaws
Estimate Standard error shows that the deviations are low in the
lowest solubility and larger deviations
Ah 10.240 0.917 that occurring during the greater
Bh -3091.960 282.622 solubility.
H
Ch 0.003 1.000.10-4
R 0,962
Ay 11.230 0.751
Conclusion
By -3400.100 232.630
Y
Cy 1505.230 52.241 The experimentally data obtained for
R 0.975 the solubility of succinic acid in
mixtures of solvents (DMF + water)
The mean of the relative deviations to using gravimetric method report that in
fitting data for the system acid succinic an isothermal system, the solubility of
+ water + DMF were 1.067% and the electrolyte in question increases
0.858% for adjustments Heidman and with increasing concentration in the
Yaws, respectively. mixture solution. Furthermore, the data
indicate an increase in the solubility of
The deviations for the data of solubility the acid as the temperature is raised, but
of succinic acid in mixtures of solvents the increments with temperature varied
(DMF + water) are show in Figure 3. for different solution. Finally, it is
concluded that solubility and
experimental parameters calculated by
the model HEIDMAN et al. (1985) and
YAWS et al. (1993) this study can be
used in the industry for purification of
the succinic acid mixtures of solvents
(DMF + water). The experiments
carried out with satisfactory results
compared to the results obtained in
(Xinmin et. Al., 2012).
 measurement and thermodynamic
modeling. Fluid Phase Equilibria, 2012.

Nomenclature [8] PRAUSNITZ, J. M.;

1: Molality of succinic acid
C1: Concentration of water (mass%)
C2: Concentration of DMF (mass%)
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