Solvent Solubility of thiamine in Pure and Mixed Solvents in Function

of Temperature.

Lorena Cristina Pres Borges; Arthur Henrique Rodrigues Rezende 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 91689167, e-mail: ricardo@icte.uftm.edu.br;

Data corresponding solid-liquid equilibrium (SLE) of thiamine in pure dimethyl

sulfoxide (DMSO), different aqueous solvent mixtures containing water + dimethyl
sulfoxide (DMSO) were measured with temperature range from 298.15K to 313.15K at
5.0K under atmospheric pressure by employing gravimetric method. The experimental
results indicated that the solubility of thiamine in aqueous solvent mixture increase with
increasing both temperature and mass fraction of water. The experimental data were
well-correlated with the rational models to account the non-ideality of the systems.

Introduction

Vitamin B1 (C12H67ClN4OS.HCl, Thiamine solubility data in water are

molecular weight = 337.33) also called
thiamine has great importance in the
food industry in general. The thiamine
is a vitamin belonging to the B
complex, and can be found in the cuticle
of rice, brewers yeast, grains, egg yolk,
liver, kidney, in pork, the fish in peanut,
Walnut, legumes, and green and leafy
vegetables. Acts in different parts of the
body and plays a major role in the
nervous, muscular and cardiovascular
system, in addition to assisting in
glucose metabolism. Thiamine
deficiency causes brain damage; in
some cases it may be irreversible.
Among the diseases caused by vitamin
B1 deficiencies are: beriberi,
Wernicke's encephalopathy and
Korsakoff's syndrome (HARPER,
1983). Thiamine is not stored in large
amounts in the body, by providing your
daily diet is necessary. It is unstable to
alkali and heat stable to heat at pH acid
compound.
widely found in literature. However,
these data solubility in other solvents
such as dimethylsulfoxide (DMSO) and
DMSO + water mixtures may be
important for studies of separation and
purification of the feedstock. On the
other hand, processes of crystallization
of thiamine require a large amount of
data solubility thereof with good
accuracy. Unfortunately, there are few
solubility data of this vitamin that show
the relation of dependence of this
solubility with temperature and with the
concentration of the initial solvent
mixture, as can be seen in studies of
NETO et. al.(2010). Thus, to obtain
solubility data of thiamine under known
conditions of temperature, pressure and
concentration of the initial mixture of
solvents is important in improving
manufacturing processes and
purification (crystallization) of this
vitamin.
Experimental
Materials

Vitamin B1 with a mass fraction of

higher 99.0% was obtained from Synth.
The organic solvent, DMSO was
obtained from Vetec with 99.9% of
purity. All chemicals were used
received without further purification.

Apparatus and procedure

In the essays, solubility data of

electrolyte, thiamine, was determined in
mixed solvents as a function of
temperature by gravimetric method
under atmospheric pressure in the
temperature range from 298.15K to
313.15K. In this article the experimental
apparatus for measured the solubility of
the vitamin B1 was a glass jacket with
35cm of total volume linked in series
by latex hose, the temperature was
regulated by a thermostatic bath and the
Cell temperature was measured by a
thermometer.
Saturated solutions of Vitamin were
prepared with different concentrations
of DMSO in bidistilled deionized water.
The solutions were prepared to achieve
equilibrium with excess electrolyte,
while they were subjected to a constant
temperature maintained by circulating
water coming from the thermostatic
bath. A magnetic stirrer was used to
promote the agitation of the solution
and ensure the establishment of
equilibrium. The stirring period
consisted in 162 minutes, followed by a
rest period of 180 minutes. Finally, the
sampling was made in triplicate samples
were withdrawn from a previously
thermostated syringe according to the
temperature of the solution. The Sample
analysis was made from the gravimetric
method. In Figure 1 we visualize the
layout of the experimental apparatus.
Figure 1. Experimental apparatus
representation: 1, 3 and 5 Jacketed
glass cell; 2, 4 and 6 Magnetic stirrer;
8, 9 and 10 Thermometer; 7 Latex
rose; 11 Thermostatic bath; 12
Temperature indicators; 13 Septa.
Results and discussion
Solubility data
The data of mole fraction solubility of
thiamine in mixed solvents as a
temperature function are listed in Table
1 and Figure 2. From Table 1 and
Figure 2, we can conclude that the
solubility of thiamine in all the mixed
solvents increases with increase of both
temperature and mass fraction of water
in DMSO solution.
The results suggest that an explanation
for the increased solubility of thiamine
with increasing mass fraction of water is
in fact thiamine be a molecule with big
polar structure. Thus, the water
molecule that is smaller and less volume
than the molecule of DMSO is easier to
cluster around the molecules of
thiamine.
Table 1. Thiamine solubility in
solventwater mixtures as a (3)
temperature function.
C1
T(K) 0.0000 2.0000 5.0000 10.0000 20.0000
1 (mol.kg-1) (4)
298.1500 0.0574 0.0655 0.0815 0.1007 0.1892
303.1500 0.0585 0.0659 0.0729 0.1037 0.1875
308.1500 0.0691 0.0696 0.0824 0.1175 0.2028 Experimental points were fitted by
313.1500 0.0762 0.0748 0.0871 0.1285 0.2375 nonlinear regression using the
Levenberg-Marquardt (MARQUARDT,
1963) method to obtain the
dimensionless parameters , , ,
, and , still solve the
optimization problem. The objective
function was used to minimize the sum
of squared residuals. In two fits the
parameters presented low standard
deviations. Both parameters have shown
low standard deviation. The average fit
of the experimental points for the two
Figure 2. Solubility of thiamine () in models was analyzed by means of the
function of de mass fraction of DMSO correlation coefficient (R). The average
in water (1) + DMSO (2) initial deviation of the experimental values
solution without thiamine at four and standards deriving the values
temperatures. calculated by the model were obtained
in both cases.

The parameter values obtained for the

Data correlation
modified models of Heidman and Yaws,
identified by H and Y, respectively, are
The relationship between the solubility
shown in Table 2.
measured by the molality, and the
temperature was proposed by
mathematical models for Heidman Table 2. Data fitting using the
(1985) and Yaws (1993), represented by Statistic 7.0.
Equations 1 and 2, respectively.

B Estimate Standard error

ln m = A + + C ln T (1)
T 2.50 0.47
Ah
Bh -1612.24 146.61
B' C ' H
log m = A '+ + (2) Ch 1.04 0.032
T T2 R 2
R =0.978
Ay 3.50 0.53
Models Heidman and Yaws, this article By -1909.70 164.23
have been changed in order to obtain Y
Cy 573160.20 19554,31
better results. These modified models R2= 0.978
R
are represented by Equations 3 and 4,
respectively, similar to that performed
The means of the relative deviations to
in PIRES et.al (2012).
fitted data for the system thiamine +
water + DMSO were 0,054% and
4,261% for adjustments Heidman and
Yaws, respectively.
The deviations for the data of solubility
of thiamine in mixtures of solvents
(DMSO + water) are showing in Figure
3.
Figure 3. The deviations for the data
of solubility of thiamine in mixtures
of solvents (DMSO + water).
From the Figure 3 it is possible to
observe that the fitting of both models
showed no biased characteristics. Both
low molalities as to higher values, the
models deviations were small in
magnitude being lower than 3%. This,
can to indicate a good fitting for both
the Yaws model as for Heidman model.
It is noted in this case an average of the
relative deviations smaller than 5%,
which shows little variation between the
results correlated by the model and
those obtained experimentally. In turn,
the correlation coefficients for both
models showed that 97.0% higher
settings. Given the above, it can be seen
that both models are also suitable for
the correlation / prediction of the
experimental data obtained in the
laboratory under specified conditions.
Conclusion
The solubility data of thiamine in the
solvent mixture (water + DMSO)
depict, in an isothermal system, the
solubility of the vitamin is very high in
water (highly hygroscopic solution); it
has an increased before increasing the
concentration of water as a cosolvent in
combination with DMSO. Common
behavior among vitamins as observed in
OLIVEIRA et.al. (2013). Added to this,
it is observed that increasing
temperature the thiamine solubility
increases too, in according to observed
by KISLNIKOV et.al (1981), GRANT
et. al (1990) and LIANG et.al (2012).
We also observed a good relationship
between the experimental results and
the results described by the fitting
models. Finally, it observed that models
satisfactorily accounted the variability
of experimental data obtained.
Nomenclature
: Molality of thiamine
C1: Water concentration (mass%)
C2: Concentration of DMSO (mass%)
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