Article

pubs.acs.org/jced

Measurement of Solubility of Thiamine Hydrochloride Hemihydrate

in Three Binary Solvents and Mixing Properties of Solutions
Xiaona Li,†,‡ Dandan Han,†,‡ Yan Wang,†,‡ Shichao Du,†,‡ Yumin Liu,†,‡ Jiaqi Zhang,† Bo Yu,†,‡
Baohong Hou,†,‡ and Junbo Gong*,†,‡
†
State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin
300072, People’s Republic of China
‡
The Collaborative Innovation Center of Chemical Science and Engineering of Tianjin, Tianjin University, Tianjin 300072,
People’s Republic of China
*
S Supporting Information

ABSTRACT: Data on (solid + liquid) equilibrium of thia-

mine hydrochloride hemihydrate (HH) in {water + (ethanol,
acetone, or 2-propanol)} solvents will provide essential sup-
port for industrial design and further theoretical studies. In this
study the solid−liquid equilibrium (SLE) was experimentally
measured over temperatures ranging from 278.15 to 313.15 K
under atmospheric pressure by a dynamic method. For the
temperature range investigated, the equilibrium solubility of
thiamine hydrochloride hemihydrate (HH) varies with tem-
perature and the composition of the solvents. The experimental solubility was regressed with different models including the
modified Apelblat equation, λh equation, as well as NRTL equation. All the models gave good agreements with the experimental
results. On the basis of the solubility data of HH, the thermodynamic properties of mixing process of HH with mixed solvents
were also discussed. The results indicate that the mixing process of HH is exothermic. Besides, the model outwardly like the
Arrhenius equation was employed to quantitatively exhibit the relationship between solubility and solvents mixtures polarity of
solvents mixtures.

1. INTRODUCTION Up to now, there exist five solid-state forms of thiamine hydro-

Crystallization is one of the most common operations used in
the separation and purification, especially in the cases of
pharmaceuticals, foods additives and biological macromolecular
foods.1 The solubility of pharmaceuticals in selected solvents is
critical for identification of drugs to develop more efficient active
pharmaceutical ingredients. The quality of the final product, such
as crystal size, crystal habit, yield, and purity, will be directly
determined by the level of design and control of crystallization
process.2
Thiamine hydrochloride (VB1, C12H18Cl2N4OS, CAS Regis-
try No. 67-03-08, Figure 1) plays an important role in digestive
Figure 1. Molecular structure of thiamine hydrochloride.
chloride reported in the literature.7−9 According to the literature,
thiamine hydrochloride hemihydrate (HH) is the most stable
form in contact with water. Once formed, the dehydration is
initiated only when heated to 120 °C.10,11
Because the crucial role of thiamine hydrochloride in the
industry, it is necessary to find a suitable solvent for its separation
and subsequent recrystallization to achieve the industrial scale
synthesis with high purity. However, despite the fact that people
have investigated much about the transformation among the five
forms of thiamine hydrochloride, only a few have attempted to
discuss its purification methods to obtain products with high
yield and high purity. Solution crystallization is used as the
separation and purification method in the manufacturing process
of thiamine hydrochloride. Therefore, detailed solubility data
and thermodynamic properties of thiamine hydrochloride
in different solvent systems are crucial to fully understand and
design a reliable crystallization process for its purification.
Data on (solid + liquid) equilibrium of thiamine hydrochloride
hemihydrate (HH) in {water + (ethanol, acetone, or 2-propanol)}
solvents will provide essential support for industrial design and
further theoretical studies. Thus, the aim of the present work is to

system, nerve conduction and normal heart activity.3−5 It is Received: July 10, 2016
mainly used in animal feed and nutrient supplements in feed Accepted: September 6, 2016
industries, medicines, cosmetics, other industries, and so on.6,7

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.6b00613

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

determine the solubility of the most stable form HH in the three
binary solvents at temperatures ranging from 278.15 to 313.15 K
by the gravimetric method. The Apelblat equation, λh equation
and NRTL equation were adopted to correlate the solubility
data. On the basis of the NRTL equation, the thermodynamic
properties of mixing process for the solutions of HH in binary
solvents were calculated, respectively. Finally, the form out-
wardly like the Arrhenius equation was applied to quantitatively
correlate the solubility of HH and the dielectric constant of the
binary solvents.
2. EXPERIMENTAL SECTION
2.1. Materials. All the organic solvents with analytical grade
(ethanol, 2-propanol, and acetone) were purchased from Tianjin
Kewei Reagents Co. Ltd. (Tianjin, China) and used without
further purification. The thiamine hydrochloride, with mass
fraction purity higher than 0.99, was purchased from Aladdin
Industrial Co. (Shanghai, China). It was characterized to be
nonstoichiometric hydrate thiamine hydrochloride (NSH) by
X-ray diffraction. According to the literature, HH powder was
obtained by suspending NSH in water for 12 h at 40 °C, then the
product was dried at 40 °C for 24 h.10 Ultrapure water (resistivity
= 18.2 MΩ cm) used throughout the measurement process was
prepared in our laboratory. The detailed information on the
chemicals used in the present work can be found in Table 1.
light intensity and concentration of particles in suspension. All
experiments were carried out in a 50 mL jacketed glass vessel
with a magnetic stirrer applied as dissolver. A mercury-in-glass
thermometer with uncertainty of ±0.1 K inside the vessel
displayed the real temperature. The circulating water bath
(CHY1015, Shanghai Shunyu Hengping Scientific Instrument
Co. Ltd., China) was introduced to the apparatus to control
temperature maintaining the setting temperature within the error
range of ±0.1 K. The transmitted laser (JD-3, Department of
Peking University, China) was employed to observe the
dissolution by the change of the intensity of the solution. The
solute and solvents were weighted by an electronic analytical
balance (AL204, Meteler Toledo, Switzerland) with an accuracy
of ±0.0001 g.
At a fixed temperature, predetermined masses of solvents
(50 mL) were added into the jacketed vessel. A condenser was
employed to prevent the evaporation of the solvents. A fixed
amount of HH was added into the vessel when the temperature
was stable. At first, the laser beam was blocked by the undissolved
particles in the solution, so the intensity of laser beam through
the vessel was low. The intensity increases gradually with the
dissolution of the solute. When the HH just disappeared, the
intensity reached the maximum. Then an additional solute of

Table 1. Sources and Mass Fraction Purity of Materialsa,b

mass
fraction purification analysis
chemical name purity source method method
thiamine ≥0.990 Aladdin Industrial Co., recrystallized HPLCa
hydrochloride China
ethanol >0.997 Tianjin Kewei none GCb
Chemical Co., China
2-propanol >0.997 Tianjin Kewei none GCb
Chemical Co., China
acetone >0.997 Tianjin Kewei none GCb
Chemical Co., China
a
High performance liquid chromatography. bGas chromatography.

2.2. Apparatus and Procedure. 2.2.1. Characterization by Figure 2. Powder X-ray diffraction (PXRD) patterns for excess solid of
X-ray Diffraction. First, the prepared powder by suspending VB1 in different conditions: (a = purchased materials; b = prepared
method according to the literature was measured by X-ray materials; c, d, e = sediments in binary solvents water (xwater = 0.10, 0.50,
diffraction. To ensure there was no form transformation among 0.90) + ethanol at T = 313.15 K, respectively).
the five hydrates during our process of solubility measurement,
we put excess solid of HH into all experimental compositions
and temperatures, respectively. The suspension was sure to be
agitated for 24 h the time of which is enough for our measure-
ment at a certain temperature. Then the X-ray spectra of the
sediments were measured by Cu Kα radiation (1.54). The
condition was on 2θ = 2−50° with a step size of 0.02°. Then the
scanning rate was set at 1 step/s.8,11
2.2.2. Characterization by TGA/DSC. TGA/DSC (Model
TGA/DSC, Mettler-Toledo, Switzerland) was formed to get
thermal analysis of HH under the protection of nitrogen. The
measurements were carried out under the protection of nitrogen
with a heating rate of 10 K/min. The amount of sample used was
about 5−10 mg.
2.2.3. Solubility Determination. The laser monitoring tech-
nique was used to determine the solubility of HH. The apparatus
were similar to that had been described in the literatures.12,13 The
method is based on the Lambert−Beer Law, which correlates Figure 3. Thermal analysis (TGA/DSC) of HH.

B DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 2. Mole Fraction Solubility of HH in the Binary Ethanol + Water Solvent Mixtures at Different Temperatures from 278.15
to 313.15 K at p = 0.1 MPaa,b,c,d,e
x0B 103 xaexp x0B 103 xAexp 103 xAcal(Apelbat) 103 xAcal(λh) 103 xacal(NRTL)
T = 278.15 K
0.000 38.58 0.000 39.34 39.77 39.16 39.16
0.099 27.21 0.100 27.59 27.76 28.82 27.88
0.198 19.45 0.200 19.59 19.57 20.51 19.79
0.298 12.97 0.300 13.03 13.04 13.86 12.93
0.398 8.59 0.400 8.63 8.59 8.88 8.33
0.499 5.15 0.500 5.17 5.05 4.90 4.99
0.599 2.55 0.600 2.55 2.52 2.62 2.74
0.700 1.19 0.700 1.19 1.18 1.16 1.44
0.800 0.54 0.800 0.55 0.52 0.54 0.59
T = 283.15 K
0.000 40.97 0.000 41.83 41.75 41.62 40.87
0.098 31.13 0.100 31.62 31.22 31.54 31.31
0.198 22.57 0.200 22.82 22.71 23.04 22.84
0.298 15.28 0.300 15.54 15.57 15.89 15.27
0.398 10.02 0.400 10.07 10.20 10.32 9.74
0.499 5.63 0.500 5.65 5.88 5.81 5.55
0.599 2.98 0.600 2.99 3.01 3.05 3.13
0.700 1.37 0.700 1.37 1.38 1.38 1.61
0.800 0.60 0.800 0.60 0.62 0.62 0.65
T = 288.15 K
0.000 43.24 0.000 44.19 43.98 44.19 42.96
0.098 33.08 0.100 33.64 34.71 34.43 33.38
0.197 24.59 0.200 24.95 25.98 25.79 24.96
0.297 17.40 0.300 17.59 18.26 18.14 17.50
0.398 11.48 0.400 11.54 11.96 11.92 11.25
0.498 6.57 0.500 6.59 6.84 6.86 6.44
0.599 3.42 0.600 3.42 3.55 3.54 3.55
0.699 1.54 0.700 1.54 1.62 1.62 1.81
0.800 0.66 0.800 0.66 0.71 0.71 0.72
T = 293.15 K
0.000 46.20 0.000 47.30 46.46 46.87 45.11
0.098 38.23 0.100 38.97 38.17 37.50 37.53
0.197 29.92 0.200 30.00 29.32 28.77 29.60
0.297 21.43 0.300 21.60 21.07 20.61 21.35
0.397 14.14 0.400 14.24 13.87 13.72 13.81
0.498 8.24 0.500 8.27 7.97 8.05 7.90
0.599 4.16 0.600 4.17 4.15 4.09 4.16
0.699 1.92 0.700 1.92 1.89 1.89 2.08
0.800 0.82 0.800 0.82 0.82 0.81 0.82
T = 298.15 K
0.000 48.27 0.000 49.47 49.22 49.66 47.98
0.098 41.87 0.100 42.77 41.55 40.75 40.78
0.197 33.63 0.200 34.12 32.69 31.98 32.89
0.296 24.82 0.300 25.22 23.95 23.33 24.61
0.397 16.64 0.400 16.78 15.92 15.71 16.31
0.498 9.82 0.500 9.87 9.29 9.40 9.39
0.598 5.09 0.600 5.10 4.78 4.71 4.92
0.699 2.34 0.700 2.34 2.20 2.21 2.38
0.800 0.95 0.800 0.96 0.92 0.91 0.92
T = 303.15 K
0.000 50.43 0.000 51.74 52.28 52.58 51.18
0.098 42.92 0.100 43.86 44.79 44.20 42.95
0.196 34.55 0.200 35.15 36.01 35.46 34.58
0.296 25.76 0.300 26.05 26.83 26.31 26.10
0.396 17.51 0.400 17.66 18.10 17.91 17.58
0.497 10.33 0.500 10.39 10.82 10.92 10.20
0.598 5.27 0.600 5.29 5.45 5.39 5.34
0.699 2.48 0.700 2.48 2.55 2.56 2.63
0.800 1.02 0.800 1.02 1.04 1.03 1.02

C DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 2. continued
x0B 103 xaexp x0B 103 xAexp 103 xAcal(Apelbat) 103 xAcal(λh) 103 xacal(NRTL)
T = 308.15 K
0.000 52.79 0.000 54.22 55.67 55.63 54.70
0.098 45.82 0.100 46.89 47.85 47.85 46.28
0.196 37.38 0.200 38.18 39.24 39.19 37.58
0.296 28.52 0.300 28.68 29.64 29.57 29.04
0.396 19.42 0.400 19.61 20.38 20.35 19.78
0.497 12.24 0.500 12.31 12.60 12.63 12.09
0.598 5.99 0.600 6.01 6.16 6.15 6.09
0.699 2.86 0.700 2.87 2.95 2.95 2.99
0.800 1.17 0.800 1.17 1.15 1.15 1.15
T = 313.15 K
0.000 58.69 0.000 60.46 59.40 58.81 57.15
0.097 50.10 0.100 51.38 50.68 51.71 50.42
0.196 42.11 0.200 43.02 42.31 43.20 41.67
0.295 32.42 0.300 32.99 32.34 33.12 32.79
0.395 22.79 0.400 23.22 22.75 23.03 23.17
0.496 14.78 0.500 14.89 14.68 14.54 14.54
0.598 6.97 0.600 6.99 6.89 6.98 7.05
0.699 3.45 0.700 3.46 3.41 3.40 3.45
0.799 1.26 0.800 1.26 1.27 1.29 1.28
a 0
xBis the initial mole fraction of ethanol in the binary solvent mixture; ax0Bis the final mole fraction of ethanol in the binary solvent mixture;xexp
A is the
experimentally determined solubility based on thiamine hydrochloride in soultions; xexp A is the experimentally determined solubility based on HH in
A (Apelbat) and xA (λh) are the calculated solubility by Apelbat and λh based on xA , respectively. xA (NRTL) are the calculated
soultions; xcal cal exp cal
b c
solubility by NRTL equation based on xexp A . The standard uncertainty of temperature is uc(T) = 0.1 K. The relative standard uncertainty of the
solubility measurement is ur(x) = 0.02. dThe relative uncertainty of pressure is ur(P) = 0.05. eThe relative standard uncertainty in mole fraction of
ethanol (1) in the solvent mixtures is ur(x0B) = 0.005.

Table 3. Mole Fraction Solubility of HH in the Binary 2-Propanol + Water Solvent Mixtures at Different Temperatures from
278.15 to 313.15 K at p = 0.1 MPaa,b,c,d,e
x0B 103 xaexp x0B 103 xAexp 103 xAcal(Apelbat) 103 xAcal(λh) 103 xacal(NRTL)
T = 278.15 K
0.000 38.58 0.000 39.34 39.77 39.16 39.16
0.099 25.04 0.100 25.36 25.72 26.18 23.60
0.198 16.42 0.200 16.56 16.24 16.20 16.76
0.299 9.57 0.300 9.60 9.63 9.61 10.28
0.399 5.14 0.400 5.17 5.01 4.68 5.35
0.499 2.19 0.500 2.20 2.20 2.35 2.29
0.600 0.78 0.600 0.78 0.80 0.76 0.79
0.700 0.29 0.700 0.29 0.28 0.26 0.21
T = 283.15 K
0.000 40.97 0.000 41.83 41.75 41.62 40.87
0.099 28.70 0.100 29.12 28.69 28.83 26.21
0.198 18.54 0.200 18.71 18.66 18.65 18.92
0.298 11.01 0.300 11.07 11.26 11.25 11.76
0.399 5.86 0.400 5.88 5.85 5.69 6.18
0.499 2.71 0.500 2.73 2.70 2.77 2.69
0.600 0.95 0.600 0.95 0.93 0.91 0.94
0.700 0.28 0.700 0.28 0.31 0.30 0.25
T = 288.15 K
0.000 43.24 0.000 44.19 43.98 44.19 42.96
0.098 31.51 0.100 32.02 31.79 31.67 29.34
0.198 20.85 0.200 21.07 21.36 21.37 21.37
0.298 13.21 0.300 13.31 13.10 13.11 13.45
0.399 6.75 0.400 6.78 6.88 6.88 7.15
0.499 3.19 0.500 3.20 3.25 3.24 3.15
0.600 1.07 0.600 1.07 1.08 1.08 1.11
0.700 0.34 0.700 0.34 0.35 0.35 0.31
T = 293.15 K
0.000 46.20 0.000 47.30 46.46 46.87 45.11
0.098 34.15 0.100 34.74 34.98 34.69 32.91

D DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 3. continued
x0B 103 xaexp x0B 103 xAexp 103 xAcal(Apelbat) 103 xAcal(λh) 103 xacal(NRTL)
T = 293.15 K
0.198 23.78 0.200 24.07 24.35 24.37 24.08
0.298 15.13 0.300 15.28 15.18 15.19 15.37
0.398 7.84 0.400 7.84 8.12 8.26 8.27
0.499 3.87 0.500 3.87 3.86 3.79 3.70
0.600 1.27 0.600 1.27 1.26 1.28 1.32
0.700 0.40 0.700 0.40 0.39 0.40 0.37
T = 298.15 K
0.000 48.27 0.000 49.47 49.22 49.66 47.98
0.098 37.56 0.100 38.28 38.26 37.91 36.71
0.197 26.60 0.200 26.96 27.65 27.67 27.14
0.297 17.38 0.300 17.56 17.50 17.52 17.55
0.398 9.19 0.400 9.27 9.63 9.85 9.57
0.499 4.50 0.500 4.51 4.50 4.40 4.33
0.600 1.48 0.600 1.48 1.47 1.50 1.57
0.700 0.47 0.700 0.47 0.44 0.45 0.45
T = 303.15 K
0.000 50.43 0.000 51.74 52.28 52.58 51.18
0.098 40.51 0.100 41.35 41.60 41.34 41.10
0.197 31.70 0.200 32.21 31.28 31.30 30.28
0.297 19.95 0.300 20.18 20.10 20.11 20.02
0.398 12.21 0.400 12.30 11.48 11.69 11.17
0.499 5.20 0.500 5.21 5.18 5.08 5.06
0.599 1.73 0.600 1.73 1.72 1.75 1.86
0.700 0.49 0.700 0.49 0.50 0.51 0.54
T = 308.15 K
0.000 52.79 0.000 54.22 55.67 55.63 54.70
0.098 44.15 0.100 45.14 44.99 44.98 45.79
0.196 35.06 0.200 35.69 35.26 35.26 34.04
0.297 22.33 0.300 22.54 22.99 22.99 22.81
0.397 13.35 0.400 13.51 13.72 13.80 12.87
0.499 5.81 0.500 5.82 5.87 5.85 5.90
0.599 1.98 0.600 1.98 2.03 2.03 2.20
0.700 0.55 0.700 0.55 0.58 0.58 0.66
T = 313.15 K
0.000 58.69 0.000 60.46 59.40 58.81 57.15
0.098 47.27 0.100 48.41 48.40 48.84 51.19
0.196 38.40 0.200 39.15 39.61 39.59 38.24
0.296 26.18 0.300 26.43 26.20 26.18 25.94
0.397 16.21 0.400 16.40 16.47 16.20 14.93
0.498 6.57 0.500 6.59 6.58 6.71 6.88
0.599 2.42 0.600 2.42 2.39 2.36 2.60
0.700 0.68 0.700 0.68 0.67 0.65 0.79
a 0
xBis the initial mole fraction of 2-propanol in the binary solvent mixture; ax0Bis the final mole fraction of ethanol in the binary solvent mixture; xexp
A is
the experimentally determined solubility based on thiamine hydrochloride in soultions; xexp A is the experimentally determined solubility based on HH
A (Apelbat) and xA (λh) are the calculated solubility by Apelbat and λh based on xA , respectively. xA (NRTL) are the calculated
in soultions; xcal cal exp cal
exp b c
solubility by NRTL equation based on xA . The standard uncertainty of temperature is uc(T) = 0.1 K. The relative standard uncertainty of the
solubility measurement is ur(x) = 0.03. dThe relative uncertainty of pressure is ur(P) = 0.05. eThe relative standard uncertainty in mole fraction of
2-propanol (1) in the solvent mixtures is ur(x0B) = 0.005.

known mass (0.1−0.3 mg) was added into the vessel, along m/M
xA =
with which the intensity of the laser decreased immedi- (m /M ) + (mB /MB) + (mW /MW ) (1)
ately. The intensity of laser increased gradually along with
the dissolution of the particles of HH and reached the where m, mB, mW are the masses of HH, corresponding organic
former constant. This process was repeated until the solid solvent, and water, respectively. M, MB, MW represent the molecular
could not dissolve and the laser intensity kept constant. mass of HH, corresponding organic solvent, and water, respectively.
The mixture was considered as reaching phase equilibrium. The initial mole fraction x0B of ethanol, 2-propanol or acetone
Then the total consumption of the solute was recorded. Each in the binary solvents can be obtained from eq 2
measuring point was repeated at least three times. The mB /MB
saturated mole fraction solubility of HH (xA) was calculated xB0 =
from eq 1 (mB /MB) + (mW /MW ) (2)

E DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 4. Mole Fraction Solubility of HH in the Binary Acetone + Water Solvent Mixtures at Different Temperatures from
278.15 to 313.15 K at p = 0.1 MPaa,b,c,d,e
x0B 103 xaexp x0B 103 xAexp 103 xAcal(Apelbat) 103 xAcal(λh) 103 xacal(NRTL)
T = 278.15 K
0.000 38.58 0.000 39.34 39.77 39.16 39.16
0.099 23.03 0.100 23.30 23.30 23.21 22.67
0.199 14.69 0.200 14.80 14.86 14.11 14.56
0.299 7.97 0.300 8.03 7.95 7.90 8.01
0.399 3.59 0.400 3.60 3.46 3.46 3.69
0.500 1.41 0.500 1.42 1.43 1.54 1.39
0.600 0.42 0.600 0.42 0.42 0.40 0.40
T = 283.15 K
0.000 40.97 0.000 41.83 41.75 41.62 40.87
0.099 25.80 0.100 26.14 26.12 26.09 25.38
0.198 16.54 0.200 16.68 16.56 16.27 16.46
0.299 9.17 0.300 9.07 9.14 9.12 9.12
0.399 3.97 0.400 4.02 4.09 4.09 4.20
0.500 1.78 0.500 1.78 1.73 1.77 1.60
0.600 0.45 0.600 0.46 0.46 0.45 0.46
T = 288.15 K
0.000 43.24 0.000 44.19 43.98 44.19 42.96
0.099 28.87 0.100 29.30 29.20 29.22 28.38
0.198 18.63 0.200 18.81 18.58 18.69 18.60
0.298 10.73 0.300 10.73 10.48 10.48 10.42
0.399 4.67 0.400 4.73 4.80 4.80 4.81
0.499 2.01 0.500 2.01 2.04 2.02 1.84
0.600 0.50 0.600 0.50 0.51 0.51 0.53
T = 293.15 K
0.000 46.20 0.000 47.30 46.46 46.87 45.11
0.098 32.10 0.100 32.62 32.56 32.61 31.73
0.198 20.25 0.200 20.46 20.96 21.36 21.00
0.298 11.31 0.300 11.35 11.97 12.00 11.80
0.399 5.45 0.400 5.45 5.61 5.61 5.52
0.499 2.32 0.500 2.32 2.36 2.30 2.13
0.600 0.58 0.600 0.58 0.56 0.57 0.62
T = 298.15 K
0.000 48.27 0.000 49.47 49.22 49.66 47.98
0.098 34.93 0.100 35.56 36.21 36.27 35.50
0.198 23.78 0.200 24.06 23.77 24.30 23.74
0.298 12.59 0.300 13.93 13.64 13.68 13.44
0.399 6.55 0.400 6.59 6.53 6.53 6.36
0.499 2.72 0.500 2.73 2.69 2.61 2.44
0.600 0.63 0.600 0.63 0.63 0.64 0.72
T = 303.15 K
0.000 50.43 0.000 51.74 52.28 52.58 51.18
0.098 39.79 0.100 40.60 40.18 40.23 39.43
0.197 26.23 0.200 26.58 27.09 27.55 26.79
0.298 15.43 0.300 15.63 15.49 15.53 15.43
0.398 7.74 0.400 7.72 7.56 7.56 7.33
0.499 3.01 0.500 3.02 3.02 2.95 2.80
0.600 0.69 0.600 0.69 0.70 0.71 0.83
T = 308.15 K
0.000 52.79 0.000 54.22 55.67 55.63 54.70
0.098 43.72 0.100 44.69 44.47 44.47 43.91
0.197 31.22 0.200 31.71 31.02 31.11 30.19
0.297 17.43 0.300 17.53 17.56 17.56 17.59
0.398 8.48 0.400 8.70 8.71 8.71 8.37
0.499 3.35 0.500 3.36 3.34 3.32 3.22
0.600 0.78 0.600 0.78 0.79 0.79 0.97
T = 313.15 K
0.000 58.69 0.000 60.46 59.40 58.81 57.15
0.097 47.76 0.100 48.93 49.11 49.03 48.86
0.196 34.79 0.200 35.40 35.67 34.99 33.96

F DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 4. continued
x0B 103 xaexp x0B 103 xAexp 103 xAcal(Apelbat) 103 xAcal(λh) 103 xacal(NRTL)
T = 313.15 K
0.297 19.70 0.300 19.80 19.85 19.80 20.04
0.398 9.79 0.400 9.95 10.00 10.00 9.63
0.499 3.61 0.500 3.62 3.63 3.73 3.70
0.600 0.90 0.600 0.90 0.89 0.88 1.12
a 0
xBis the initial mole fraction of acetone in the binary solvent mixture; x0Bis the final mole fraction of ethanol in the binary solvent mixture; xexp
A is the
experimentally determined solubility based on thiamine hydrochloride in soultions; xexp A is the experimentally determined solubility based on HH in
A (Apelbat) and xA (λh) are the calculated solubility by Apelbat and λh based on xA , respectively. xA (NRTL) are the calculated
soultions; xcal cal exp cal
b c
solubility by NRTL equation based on xexp A . The standard uncertainty of temperature is uc(T) = 0.1 K. The relative standard uncertainty of the
solubility measurement is ur(x) = 0.03. dThe relative uncertainty of pressure is ur(P) = 0.05. eThe relative standard uncertainty in mole fraction of
acetone (1) in the solvent mixtures is ur(x0B) = 0.005.

Figure 4. Mole fraction solubility (xA) of HH versus mole fractions of ethanol (x0B) in water (W) + ethanol (B) binary solvent mixtures at different
temperatures.

3. THERMODYNAMIC MODELS ΔfusH ⎛ 1 1⎞

ln xi = ⎜ − ⎟ − ln γi
3.1. Modified Apelbat Equation. The modified Apelblat R ⎝ Tmelt T⎠ (5)
equation14,15 was used to show the relationship between the
mole fraction of HH and temperature where ΔfusH and Tmelt stand for the enthalpy of fusion and
melting temperature of solute. γi is the activity coefficient of
B solute in the saturated solution, which can be calculated by
ln xA = A + + C ln(T /K)
T /K (3) NRTL model

where xA is the mole fraction solubility, T is the absolute tem- (Gjixj + Gkixk)(τjiGjixj + τkiGkixk)
ln γi =
perature, A, B, and C are the empirical constants. The value of C (xi + xjGji + xkGki)2
denotes the effect of temperature on the fusion enthalpy. The
values of A and B refer to the variations in the solution activity [τijGijxj 2 + GijGkjxjxk(τij − τkj)]
coefficient. +
3.2. λh Model. The λh model equation which was originally xj + xiGij + xkGkj 2
developed by Buchowski et al.16 expressed the nonideality and
[τijGik xk 2 + Gik Gjk xjxk(τik − τjk)]
the enthalpy of solution. The equation has two parameters λ and +
h. It can be shown as eq 4 (xk + xiGik + xjGjk )2 (6)
⎛ 1 − x⎞ ⎛1 1 ⎞ where Gij, Gik, Gji, Gjk, Gki, Gkj, τij, τik, τji, τjk, τki, and τkj are
ln⎜1 + λ ⎟ = λh⎜ − ⎟ parameters of this model. The definition of these terms can be
⎝ xA ⎠ ⎝T Tm ⎠ (4) expressed as
where xA is the mole fraction solubility of the solute in the Gij = exp( −αijτij) (7)
solution. Tm is the melting temperature of the solute. T stands
for the absolute temperature. The parameters of λ and h are (gij − gjj) Δgij
determined by correlation of the solubility data. τij = =
RT RT (8)
3.3. NRTL Model. According to the solid−liquid phase
equilibrium theory and the solute−solvent interactions, the local where Δgij represents the Gibbs energy of intermolecular
composition equation17 can be simplified and expressed by eq 5 interaction, which are independent of the composition and
G DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Figure 5. Mole fraction solubility (xA) of HH versus mole fractions of 2-propanol (x0B) in water (W) + 2-propanol (B) binary solvent mixtures at
different temperatures.

Figure 6. Mole fraction solubility (xA) of HH versus mole fractions of acetone (x0B) in water (W) + acetone (B) binary solvent mixtures at different
temperatures.

temperature. αij is an adjustable empirical constant between
0 and 1. It is a criterion of the nonrandomness of the solution.
In order to evaluate the applicability and correlate accuracy of
the three models above, the average relative deviation (ARD %)
was also shown to assess the accuracy of different models.18 They
were calculated according to eq 9
100
N2
xA, i exp − xA, i cal
ARD% = ∑
N i=1
xA, i exp
exp cal
where xA,i and xA,i represent the experimental and calculated
solubility data, respectively, and N is the number of experimental
points.
4. RESULTS AND DISCUSSION
4.1. Identification and Characterization of HH. 4.1.1. X-ray
Powder Diffraction. The purchased material as well as the
prepared powder was tested by the X-ray powder diffraction
(PXRD) pattern and the results were turn out to be HH (Figure 2).
We also characterized the excess solid in different solvents,
the ratios of which were (water + 2-propanol/ethanol/acetone
(xwater = 0.1, 0.5, 0.9)) at fixed temperature (T = (278.15, 298.15,
313.15) K) after a 24 h of stirring. As shown in Figure 2, we take
the PXRD pattern of the sediments in different ratios of binary
solvents (water + ethanol) at temperature T = 313.15 K as an
example. All the PXRD pattern of HH samples have the same
characteristic peaks of HH, comparing with the PXRD pattern of
HH from the literature.10 Therefore, it can be confirmed that the
solute used in this study is thiamine hydrochloride hemihydrate
(9)
(HH) and there is no crystal phase transformation during the
process of solubility determination in the solution.
4.1.2. TGA/DSC. In order to ensure the form further, we also
use the TGA/DSC to characterize the solid of HH. The results
showed that the curves were the same and we take one as
example. As shown in Figure 3 (T = 313.15 K, xwater = 0.1), there
was negligible weight loss up to 120 °C. In the temperature range
of 120−200 °C, the observed weight loss of ∼1% is substantially
lower than the stoichiometric water content of 2.6% (w/w) in the
HH. The shoulder on the edge of the DSC endotherm indicated
that there were overlapping thermal events. This showed that the
dehydration and decomposition occurred at the same time at
higher temperatures (T > 120 °C). All these were consistent with
H DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 5. Relative Dielectric Constant, εr, of HH at p = 0.1 MPa and the Relative Parameters in Different Solvent Mixtures
εr
T/K x0B k Ex kJ·mol−1
278.15 0.099 0.198 0.298 0.398 0.499 0.599 0.700 0.800 0.81 2.18
77.98 70.64 63.73 57.27 51.26 45.67 40.52 35.77
283.15 0.098 0.198 0.298 0.398 0.499 0.599 0.700 0.800 0.89 2.12
76.25 69.06 62.30 55.97 50.06 44.60 39.55 34.90
288.15 0.098 0.197 0.297 0.398 0.498 0.599 0.699 0.800 0.93 2.04
74.55 67.51 60.90 54.70 48.91 43.55 38.61 34.06
293.15 0.098 0.197 0.297 0.397 0.498 0.599 0.699 0.800 1.00 1.94
72.89 66.02 59.55 53.47 47.81 42.55 37.71 33.26
298.15 0.098 0.197 0.296 0.397 0.498 0.598 0.699 0.800 1.00 1.85
71.27 64.56 58.23 52.29 46.74 41.59 36.85 32.49
303.15 0.098 0.197 0.296 0.397 0.498 0.598 0.699 0.800 1.02 1.79
69.67 63.12 56.93 51.12 45.68 40.65 36.01 31.75
308.15 0.098 0.196 0.296 0.396 0.497 0.598 0.699 0.800 1.02 1.70
68.11 61.72 55.67 49.99 44.68 39.75 35.21 31.04
313.15 0.097 0.196 0.295 0.395 0.496 0.598 0.699 0.799 1.15 1.65
66.60 60.36 54.47 48.92 43.72 38.88 34.44 30.36
2-Propanol + Water
278.15 0.099 0.198 0.299 0.399 0.499 0.600 0.700 1.39 2.55
76.97 68.72 61.05 53.96 47.43 41.46 36.03
283.15 0.099 0.198 0.298 0.399 0.499 0.600 0.700 1.47 2.44
75.19 67.06 59.50 52.51 46.08 40.21 34.88
288.15 0.098 0.198 0.298 0.399 0.499 0.600 0.700 1.49 2.33
73.44 65.43 57.98 51.08 44.76 38.99 33.75
293.15 0.098 0.198 0.298 0.398 0.499 0.600 0.700 1.43 2.19
71.73 63.84 56.49 49.69 43.47 37.79 32.65
298.15 0.098 0.197 0.297 0.398 0.499 0.600 0.700 1.38 2.06
70.06 62.28 55.04 48.34 42.21 36.62 31.57
303.15 0.098 0.197 0.297 0.398 0.499 0.599 0.700 1.47 1.98
68.42 60.77 53.62 47.03 40.97 35.48 30.52
308.15 0.098 0.196 0.297 0.397 0.499 0.599 0.700 1.43 1.87
66.81 59.27 52.22 45.73 39.76 34.36 29.49
313.15 0.098 0.196 0.296 0.397 0.498 0.599 0.700 1.36 1.95
65.24 57.81 50.88 44.47 38.58 33.27 28.49
Acetone + Water
278.15 0.099 0.199 0.299 0.399 0.500 0.600 2.78 3.02
77.01 68.81 61.18 54.11 47.62 41.68
283.15 0.099 0.198 0.299 0.399 0.500 0.600 2.85 2.90
75.29 67.25 59.76 52.83 46.48 40.65
288.15 0.099 0.198 0.298 0.399 0.499 0.600 3.02 2.81
73.60 65.73 58.39 51.59 45.36 39.65
293.15 0.098 0.198 0.298 0.399 0.499 0.600 2.94 2.68
71.95 64.23 57.03 50.37 44.27 38.67
298.15 0.098 0.198 0.298 0.399 0.499 0.600 3.04 2.58
70.33 62.78 55.73 49.19 43.20 37.73
303.15 0.098 0.197 0.298 0.398 0.499 0.600 3.30 2.50
68.75 61.35 54.44 48.04 42.17 36.80
308.15 0.098 0.197 0.297 0.398 0.499 0.600 3.46 2.42
67.20 59.98 53.19 46.92 41.16 35.91
313.15 0.097 0.196 0.297 0.398 0.499 0.600 3.70 2.34
65.69 58.62 51.98 45.83 40.18 35.04

the literature.10 Besides, this phenomenon showed that HH did proved with relatively high accuracy by estimating the normal
not have a real melting point and the melting temperature Tm of melting points of 1215 organic compounds. The equation of this
HH could not be obtained by this conventional calorimetric method can be expressed as follows
method. It has been known that the melting point of compounds ΔHm
can be estimated by using group contribution method according Tm =
ΔSm (10)
to the literatures.19,20 Then a combined method of additive
group contribution and nonadditive molecular parameters21
was used to estimate the melting points of HH. The method was
ΔHm = ∑ nimi (11)

I DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Figure 7. Correlation of ln x versus εmix in water (W) + ethanol (B)
binary solvent mixtures at different temperatures: ■, T = 278.15 K; red
●, T = 283.15 K; blue ▲, T = 288.15 K; aqua ▼, T = 293.15 K; navy ◆,
T = 298.15 K; fuschia ◀, T = 303.15 K; green ▶, T = 308.15 K; brown
⬟, T = 313.15 K.
Figure 8. Correlation of ln x versus εmix in water (W) + 2-propanol (B)
binary solvent mixtures at different temperatures: ■, T = 278.15 K; red
●, T = 283.15 K; blue ▲, T = 288.15 K; aqua ▼, T = 293.15 K; navy ◆,
T = 298.15 K; fuschia ◀, T = 303.15 K; green ▶, T = 308.15 K; brown
⬟, T = 313.15 K.
ΔSm = C − R ln σ + RnΦ (12)
where nimi is the contribution of group i to the enthalpy of
melting. σ represents the number of positions into which a
molecule can be rotated that are identical with a reference
position and Φ indicates the molecular flexibility. The melting
point of HH and the fusion enthalpy ΔfusH calculated from the
above multilevel scheme were 518.15 K and 30.13 kJ·mol−1,
respectively.
4.2. Experimental Solubility. Experimental mole fraction
solubility data of HH in binary (ethanol + water, 2-propanol +
water, and acetone + water) solvent mixtures are listed in
Tables 2, 3, and 4. The average relative deviation (ARD%) were
also shown in Tables S1−3 to assess the accuracy of different
models, which all gave satisfactory correlation results. Besides, to
show the experimental values clearly, the plots of the solubility
data of HH in these binary solvents at the temperature range of
J DOI: 10.1021/acs.jced.6b00613
Article
Figure 9. Correlation of ln x versus εmix in water (W) + acetone (B)
binary solvent mixtures at different temperatures: ■, T = 278.15 K; red
●, T = 283.15 K; blue ▲, T = 288.15 K; aqua ▼, T = 293.15 K; navy ◆,
T = 298.15 K; fuschia ◀, T = 303.15 K; green ▶, T = 308.15 K; brown
⬟, T = 313.15 K.
(278.15−313.15) K were drawn in Figures 4−6. From
Figures 4−6, it can be clearly seen that the solubility of HH is
a function of temperature and increases with increasing
temperature in all studied binary solvent mixtures at constant
solvent compositions. Besides, at a certain constant temperature,
the solubility of HH decreased apparently with the increasing of
the initial mole fraction of the organic solvents (ethanol/
acetone/2-propanol). It can also be concluded that the solubility
of HH in mixed solvents followed the order of (ethanol + water)
> (2-propanol + water) > (acetone + water), which indicated
that the solubility increased with an increase of the polarity of
the mixture solvents. This result shows that the three organic
solvents + water mixture is the suitable cosolvents for the
recrystallization of HH.
These phenomena may be due to the polarity of the different
solvents, hydrogen bonding interaction, ionization of the solute,
and so on.22
4.3. Correlation of the Solubility Data of HH versus
Dielectric Constant. Referring to the molecular structure of
thiamine hydrochloride (Figure 1) and the physicochemical
properties of different solvents, the polarity was thought to
be one factor to determine the solubility order, which was in
according with the empirical rule of “like dissolves like”. If the
solvent molecules and the solute molecules have the similar
polarity, it needs smaller energy barrier for the solute molecules
to combine with solvent molecules. The order of solvents’
polarity was as follows: water > ethanol >2-propanol > acetone.
From above, we can only get the qualitative conclusion that the
solubility of HH rises as the polarity of the binary solvents
increasing. The empirical polarities (ENT ), dipole moments (μ),
and dielectric constants (ε) of the solubility behavior of solute in
the selected solvents are usually used as the criterions of solvent
polarity. The relative dielectric constant (εr) is a good index of
polarity among them. We used a modified form of Arrhenius
equation to quantitatively show the relationship between the
solubility and the dielectric constant of the binary solvents in this
work. According to the literature,23 the dielectric constants of
mixture solvents on composition of solvents were calculated by
the sum law of square roots
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 6. Mixing Thermodynamic Properties of HH in the Binary Ethanol + Water Solvent Mixtures from 278.15 to 313.15 K at
p = 0.1 MPaa
x0B ΔmixG kJ·mol−1 ΔmixS J·mol−1·K−1 ΔmixH kJ·mol−1 x0B ΔmixG kJ·mol−1 ΔmixS J·mol−1·K−1 ΔmixH kJ·mol−1
T = 278.15 K T = 298.15 K
0.099 −1.092 0.137 −1.054 0.098 −1.335 0.051 −1.319
0.198 −1.222 1.190 −0.891 0.197 −1.456 0.371 −1.345
0.298 −1.262 2.048 −0.692 0.296 −1.473 1.254 −1.099
0.398 −1.236 2.496 −0.542 0.397 −1.395 1.892 −0.831
0.499 −1.143 2.659 −0.403 0.498 −1.252 2.263 −0.577
0.599 −0.989 2.588 −0.269 0.598 −1.064 2.355 −0.361
0.700 −0.790 2.313 −0.147 0.699 −0.839 2.222 −0.176
0.800 −0.548 1.758 −0.059 0.800 −0.582 1.682 −0.080
T = 283.15 K T = 303.15 K
0.098 −1.135 0.106 −1.105 0.098 −1.362 0.038 −1.351
0.198 −1.277 0.990 −0.997 0.196 −1.468 0.336 −1.366
0.298 −1.306 1.876 −0.775 0.296 −1.489 1.197 −1.127
0.398 −1.268 2.373 −0.596 0.396 −1.414 1.823 −0.861
0.499 −1.160 2.596 −0.425 0.497 −1.267 2.211 −0.597
0.599 −1.005 2.538 −0.286 0.598 −1.074 2.327 −0.369
0.700 −0.800 2.294 −0.151 0.699 −0.848 2.209 −0.179
0.800 −0.555 1.732 −0.065 0.800 −0.590 1.673 −0.083
T = 288.15 K T = 308.15 K
0.098 −1.180 0.090 −1.154 0.098 −1.413 0.023 −1.406
0.197 −1.312 0.870 −1.061 0.196 −1.508 0.207 −1.444
0.297 −1.347 1.723 −0.850 0.296 −1.533 1.041 −1.212
0.398 −1.300 2.252 −0.651 0.396 −1.448 1.698 −0.925
0.498 −1.184 2.508 −0.461 0.497 −1.303 2.083 −0.661
0.599 −1.020 2.490 −0.303 0.598 −1.093 2.271 −0.393
0.699 −0.811 2.275 −0.155 0.699 −0.862 2.186 −0.189
0.800 −0.563 1.724 −0.066 0.800 −0.600 1.677 −0.083
T = 293.15 K T = 313.15 K
0.098 −1.272 0.077 −1.249 0.097 −1.477 0.012 −1.473
0.197 −1.399 0.564 −1.233 0.196 −1.594 0.057 −1.577
0.297 −1.416 1.464 −0.987 0.295 −1.591 0.833 −1.331
0.397 −1.350 2.064 −0.745 0.395 −1.503 1.499 −1.033
0.498 −1.219 2.381 −0.521 0.496 −1.348 1.924 −0.745
0.599 −1.040 2.426 −0.329 0.598 −1.116 2.205 −0.425
0.699 −0.825 2.248 −0.165 0.699 −0.879 2.154 −0.205
0.800 −0.573 1.710 −0.071 0.799 −0.608 1.667 −0.086
a
The combined expanded uncertainties are uc(ΔmixS) = 0.065ΔmixS, uc(ΔmixG) = 0.044ΔmixG (0.95 level of confidence).

εm1/3 = ∑ φεi i1/3 ⎛ Ex ⎞

i ⎝ Rεmix (T ) ⎠
Akerlof has already reported that the logarithm of dielectric
constant is a linear function of the absolute temperature. The
dependence of relative dielectric constant on temperature can be
reflected by eq 1424
εr(T ) = a + bT + cT 2 + dT 3
where εi is the relative dielectric constant of pure compo-
nent i and φi represents the volume fraction of component
i in the solvent mixtures in absence of solute. The parameter a,
b, c, and d available from the literature are empirical coef-
ficients.
The dielectric constants of the binary solvent mixtures
could be calculated through the eq 13−14 and the results
were listed in Table 5. The plots of ln xA with −1/εmix were
drawn in Figures 7−9. According to the Figures, the lin-
ear fitting of ln xA versus −1/εmix was good for HH, which
could be described by a model outwardly like the Arrhenius
eq eq 15
(13) xA = k exp⎜ − ⎟
(15)
where xA is the solubility of solute, and R is the gas constant.
εmix(T), a function of temperature and composition of sol-
vents, stands for the dielectric constants of binary solvents at a
certain temperature. Ex represents the dissolution energy
(14) barrier. When the value of M is greater, it is more difficult for
the solids to dissolve in binary solvents. The values of Ex and k
can be calculated from the slope and the interception of the
plot, which are listed in Table 5. The results indicated that this
model could well describe the relationship of the solubility and
dielectric constant. The solubility increased with increasing
dielectric constant and the content of water in binary solvents,
which was in accordance with the rule of “like dissolving like”.
4.4. Solution Mixing Thermodynamics. For real
solutions, it is necessary to study the mixing thermodynamic
properties of the solute in different binary solvent mixtures.
When the activity coefficients are taken into consideration,
the thermodynamic properties such as the mixing enthalpy
(ΔmixH), the mixing Gibbs energy (ΔmixG) and the mixing
K DOI: 10.1021/acs.jced.6b00613
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Journal of Chemical & Engineering Data Article

Table 7. Mixing Thermodynamic Properties of HH in the Binary 2-Propanol + Water Solvent Mixtures from 278.15 to
313.15 K, p = 0.1 MPaa
x0B ΔmixG kJ·mol−1 ΔmixS J·mol−1·K−1 ΔmixH kJ·mol−1 x0B ΔmixG kJ·mol−1 ΔmixS J·mol−1·K−1 ΔmixH kJ·mol−1
T = 278.15 K T = 298.15 K
0.099 −1.373 2.039 −0.806 0.098 −1.609 2.324 −0.916
0.198 −1.724 2.370 −1.065 0.197 −1.935 2.623 −1.153
0.298 −1.974 2.460 −1.289 0.297 −2.144 2.706 −1.337
0.399 −2.144 2.408 −1.474 0.398 −2.254 2.690 −1.451
0.499 −2.230 2.234 −1.608 0.499 −2.305 2.573 −1.537
0.600 −2.222 1.909 −1.691 0.600 −2.261 2.323 −1.568
0.700 −2.087 1.399 −1.698 0.700 −2.104 1.875 −1.545
T = 283.15 K T = 303.15 K
0.099 −1.442 2.112 −0.844 0.098 −1.663 2.397 −0.936
0.198 −1.775 2.430 −1.087 0.197 −2.022 2.697 −1.205
0.298 −2.009 2.521 −1.295 0.297 −2.194 2.770 −1.355
0.399 −2.167 2.481 −1.464 0.398 −2.309 2.747 −1.477
0.499 −2.247 2.322 −1.590 0.499 −2.326 2.652 −1.522
0.600 −2.231 2.018 −1.659 0.599 −2.273 2.417 −1.540
0.700 −2.089 1.526 −1.657 0.700 −2.110 1.982 −1.509
T = 288.15 K T = 308.15 K
0.098 −1.496 2.180 −0.868 0.098 −1.727 2.475 −0.964
0.198 −1.823 2.492 −1.105 0.196 −2.083 2.770 −1.229
0.298 −2.055 2.580 −1.312 0.297 −2.241 2.836 −1.367
0.399 −2.192 2.553 −1.457 0.397 −2.338 2.819 −1.470
0.499 −2.264 2.408 −1.570 0.499 −2.346 2.732 −1.504
0.600 −2.239 2.124 −1.627 0.599 −2.286 2.508 −1.513
0.700 −2.093 1.649 −1.618 0.700 −2.116 2.084 −1.474
T = 293.15 K T = 313.15 K
0.098 −1.546 2.249 −0.887 0.098 −1.782 2.550 −0.984
0.198 −1.880 2.557 −1.131 0.196 −2.142 2.842 −1.252
0.298 −2.098 2.643 −1.323 0.296 −2.308 2.901 −1.399
0.398 −2.221 2.622 −1.453 0.397 −2.390 2.879 −1.489
0.499 −2.284 2.491 −1.554 0.498 −2.369 2.809 −1.489
0.600 −2.249 2.225 −1.597 0.599 −2.302 2.595 −1.489
0.700 −2.098 1.765 −1.581 0.700 −2.125 2.181 −1.442
a
The combined expanded uncertainties are uc(ΔmixS) = 0.065ΔmixS, uc(ΔmixG) = 0.044ΔmixG (0.95 level of confidence).

entropy (ΔmixS) were calculated by the following equations25 Then, the mixing enthalpy (ΔmixH), the mixing Gibbs energy
based on the NRTL model (ΔmixG), and the mixing entropy (ΔmixS) can be calculated by the
following equations:26
Δmix G = GE + Δmix Gid (16)
n
Δmix H = HE + Δmix H id (17) GE = RT ∑ xi ln γi
i (22)
Δmix S = S E + Δmix S id (18)
where G , S , and H stand for the excess properties and ΔmixGid,
E E E n ⎛ ∂lnγi ⎞
HE = −RT 2 ∑ xi⎜ ⎟
ΔmixSid, and ΔmixHid are the mixing properties of ideal systems. ⎝ ∂T ⎠ p , x
The mixing thermodynamic properties of the ideal solution i (23)
can be obtained by the following equations:25
n HE − GE
Δmix Gid = RT ∑ xi ln xi SE =
T (24)
i (19)
where xi and γi represent the mole fraction and activity coefficient
Δmix H id = 0 (20) of component i in real solution, respectively. n = 2 means binary
n solution and n = 3 means ternary solution.
Δmix S id = −R ∑ xi ln xi The calculated mixing thermodynamic properties of HH were
i (21) given in Tables 6 to 8. As shown in these tables, it can conclude
where xi and γi stand for the mole fraction and activity coeffi- that the values of ΔmixG are all negative, which indicate that
cient of component i in real solution, respectively. For the solu- the mixing of HH in all studied solvents is a spontaneous and
tion with pure solvents, n = 2. For the solution with binary favorable process. The negative values of ΔmixH reflect that the
solvents, n = 3. mixing process is exothermic.
L DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 8. Mixing Thermodynamic Properties of HH in the 5. CONCLUSION

Binary Acetone + Water Solvent Mixtures from 278.15 to The solubility of HH in water + ethanol/2-propanol/acetone
313.15 K, p = 0.1 MPaa binary solvent mixtures was experimentally determined at tem-
x0B ΔmixG kJ·mol−1 ΔmixS J·mol−1·K−1 ΔmixH kJ·mol−1 peratures ranging from 278.15 to 313.15 K under atmospheric
T = 278.15 K pressure by a laser monitoring observation method. It was
0.099 −1.124 1.715 −0.647 obvious that the solubility of HH in all examined binary solvents
0.199 −1.273 2.001 −0.716 increased with the rising of temperature and decreased with the
0.299 −1.310 2.067 −0.735 addition of organic solvents (ethanol, acetone, 2-propanol).
0.399 −1.285 2.039 −0.718 Besides, the solubility was in the order of (ethanol + water) >
0.500 −1.212 1.966 −0.665 (2-propanol + water) > (acetone + water). The modified Apelblat
0.600 −1.086 1.886 −0.561 equation, the λh equation, and NRTL equation were used to
T = 283.15 K correlate the solubility in binary solvents system to correlate
0.099 −1.177 1.764 −0.678 the measured solubility data respectively, all of which could
0.198 −1.313 2.043 −0.734 give satisfactory correlation results. On the basis of the NRTL
0.299 −1.340 2.112 −0.742 equation, thermodynamic parameters including the mixing
0.399 −1.301 2.101 −0.706 enthalpy, entropy, and Gibbs energy were obtained. It was
0.500 −1.227 2.038 −0.650 found that the mixing process of HH was exothermic and
0.600 −1.094 1.976 −0.535 spontaneous. On the other hand, the phenomenon that solubility
T = 288.15 K of HH increased with the polarity of the binary solvents was
0.099 −1.235 1.816 −0.712 quantitatively explained by the function outwardly Arrhenius
0.198 −1.356 2.087 −0.755 equation. In general, the experimental results and the resulting
0.298 −1.375 2.155 −0.754 parameters can be used to optimize the purification process of
0.399 −1.322 2.158 −0.700 thiamine hydrochloride.
0.499
0.600
−1.240
−1.104
2.112
2.064
T = 293.15 K
−0.631
−0.509 ■
*
ASSOCIATED CONTENT
S Supporting Information
0.098 −1.294 1.871 −0.746
The Supporting Information is available free of charge on the
0.198 −1.391 2.136 −0.765
ACS Publications website at DOI: 10.1021/acs.jced.6b00613.
0.298 −1.395 2.210 −0.747
0.399 −1.345 2.213 −0.696 Calculated parameters for different models. (PDF)

■
0.499 −1.258 2.180 −0.618
0.600 −1.114 2.149 −0.484
AUTHOR INFORMATION
T = 298.15 K
0.098 −1.347 1.929 −0.772 Corresponding Author
0.198 −1.456 2.179 −0.807 *E-mail: junbo_gong@tju.edu.cn. Tel.: 86-22-27405754. Fax:
0.298 −1.425 2.260 −0.751 +86-22-27374971.
0.399 −1.373 2.266 −0.697 Funding
0.499 −1.271 2.253 −0.599
We are grateful for the financial support of the National Natural
0.600 −1.125 2.231 −0.459
Science Foundation of China (No. NNSFC 21176173), and the
T = 303.15 K
Major National Scientific Instrument Development Project
0.098 −1.430 1.989 −0.827
(No.21527812).
0.197 −1.504 2.230 −0.828
0.298 −1.480 2.298 −0.783 Notes
0.398 −1.402 2.318 −0.699 The authors declare no competing financial interest.
0.499
0.600
−1.286
−1.136
2.323
2.311
T = 308.15 K
−0.582
−0.435
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N DOI: 10.1021/acs.jced.6b00613
J. Chem. Eng. Data XXXX, XXX, XXX−XXX