Measurement and correlation of the solubility of (1-benzyl-1H-1,2,3-triazole-4-yl)methanol in water and alcohols at temperatures from 292.15 K to 310.15 K

Article abstract of DOI:10.1016/j.tca.2016.01.009

The solubilities of (1-benzyl-1H-1,2,3-triazole-4-yl)methanol (BTZM) in water, methanol, ethanol, n-propanol, isopropanol, and n-butanol were measured at temperatures ranging from 292.15 K to 310.15 K by a dynamic method under normal atmospheric pressure. The results showed that it increased with the increasing temperature and the order of solvents was: Order: Methanol > ethanol > n-propanol > n-butanol > isopropanol > water except three points. The solubility data were correlated with the Van't Hoff equation, modified Apelblat equation, and λh equation. The average relative deviations (ARD) were 1.87%, 1.53%, and 1.71%, and the root-mean-square-deviations (RMSD) were 2.37 × 10^-2, 1.51 × 10^-2, and 2.12 × 10^-2, respectively. It was found that the modified Apelblat equation gave the best correlation results. Furthermore, the dissolution enthalpy of BTZM was calculated by the modified Apelblat equation.

Full text of DOI:10.1016/j.tca.2016.01.009

Accepted Manuscript
Title: Measurement and correlation of the solubility of
(1-benzyl-1H-1,2,3-triazole-4-yl)methanol in water and
alcohols at temperatures from 292.15 K to 310.15 K
Author: Shuqin Liang Huiying Li Le Shen Huanxin Li
Zhendong Mao Huiping Li
PII:
S0040-6031(16)30004-1
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.tca.2016.01.009
TCA 77429
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Thermochimica Acta
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Revised date:
Accepted date:
12-9-2015
16-1-2016
26-1-2016
Please cite this article as: Shuqin Liang, Huiying Li, Le Shen, Huanxin Li, Zhendong
Mao, Huiping Li, Measurement and correlation of the solubility of (1-benzyl-1H-1,2,3-
triazole-4-yl)methanol in water and alcohols at temperatures from 292.15K to 310.15K,
Thermochimica Acta http://dx.doi.org/10.1016/j.tca.2016.01.009
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Measurement and Correlation of the Solubility of (1-
Benzyl-1H-1,2,3-triazole-4-yl)methanol in Water
and Alcohols at temperatures from 292.15K to
310.15K
Shuqin Liang†, Huiying Li‡, Le Shen†, Huanxin Li†, Zhendong Mao†, Huiping Li†*
huipingli@zzu.edu.cn
†School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou, Henan
450001, People's Republic of China
‡China Certification & Inspection (Group) Henan Co., Ltd., Zhengzhou, Henan 450000, People's
Republic of China
*Corresponding author: Tel.: +86 0371 67781807.
1

Graphical Abstract
251658240
The solubilities of BTZM in water, and different pure alcohols (methanol, ethanol, n-propanol,
isopropanol, and n-butanol) have been measured at temperatures ranging from 292.15K to
310.15K by the dynamic method under normal atmospheric pressure. The solubilities of BTZM
in the different solvents follow the order methanol > ethanol > n-propanol > n-butanol >
isopropanol > water except three points.
2

Highlights
1. The (1-Benzyl-1H-1,2,3-triazole-4-yl)methanol was successfully synthesized and
characterized by IR and NMR.
2. The solubilities of (1-Benzyl-1H-1,2,3-triazole-4-yl)methanol in water and alcohols were
measured.
3. The experimental solubility data were correlated with the Van’t Hoff equation, modified
Apelblat equation and λh equation model.
4. The dissolution enthalpy of (1-Benzyl-1H-1,2,3-triazole-4-yl)methanol was calculated by
using the modified Apelblat equation.
5. The solubility data, correlation models, and the thermodynamic parameters were discussed in
detail.
3

Abstract
The solubilities of (1-Benzyl-1H-1,2,3-triazole-4-yl)methanol (BTZM) in water, methanol,
ethanol, n-propanol, isopropanol, and n-butanol were measured at temperatures ranging from
292.15K to 310.15K by a dynamic method under normal atmospheric pressure. The results
showed that it increased with the increasing temperature and the order of solvents was: order:
methanol > ethanol > n-propanol > n-butanol > isopropanol > water except three points. The
solubility data were correlated with the Van’t Hoff equation, modified Apelblat equation, and λh
equation. The average relative deviations (ARD) were 1.87%, 1.53%, and 1.71%, and the root-
mean-square-deviations (RMSD) were 2.37×10-2, 1.51×10-2, and 2.12×10-2, respectively. It was
found that the modified Apelblat equation gave the best correlation results. Furthermore, the
dissolution enthalpy of BTZM was calculated by the modified Apelblat equation.
Keywords: Solubility; Correlation; Thermodynamic property; (1-Benzyl-1H-1,2,3-triazole-4-
yl)methanol
Nomenclature
List of symbols
A
a
B
b
C
c
parameter in Eq.8
parameter in Eq.5,7
parameter in Eq.8
parameter in Eq.6,7
parameter in Eq.8
parameter in Eq.3,4,5,6
parameter in Eq.3,4,5,6
d
4

h
parameter in Eq.9
M1
molar mass of solute
M2
molar mass of solvent
m1
mass of solute
m2
mass of solute
N
total number of experimental points
gas constant (J·mol-1·K-1)
temperature (K)
R
T
Tm
average melting point of BTZM (K)
mole fraction solubility of solute
the experimental mole fraction solubility of solute
the calculated mole fraction solubility of solute
x
xexp
xcal
Greek letters
o
ΔHd
standard dissolution enthalpy (J·mol-1)
standard fusion enthalpy (J·mol-1)
activity coefficient
ΔfusHo
γ
λ
parameter in Eq.9
5

1. Introduction
1,2,3-triazole and its derivatives, five-membered nitrogen heterocyclic compounds, have been
widely used in modern chemistry, agricultural, drug discovery, polymer materials,
macromolecules, and functional materials [1,-4]. (1-Benzyl-1H-1,2,3-triazole-4-yl)methanol
(BTZM, C10H11N3O, CAS RN 28798-81-4) is an important chemical intermediate and applied to
synthesize triazole ethers [5], polynuclear azoles [6,-8], and ligands [9,10] through replacing the
alcoholic hydroxyl group with halogens and other nucleophilic reagents. Proton exchange
membranes based on the 1H-1,2,3-triazole functional group showed good protogenic
conductivity and thermal stability. Besides, the biological properties of BTZM have been
attracted more attentions [11,,12]. BTZM can be synthesized using benzyl halide, sodium azide,
and propargyl alcohol as the raw materials. The solution crystallization is a key step in the
manufacturing processes of BTZM. The accurate equilibrium solubility data of BTZM varying
with temperature and solvent is overwhelming important to optimize crystallization processes
and operation conditions. Many studies have focused on the synthesis of BTZM [13,,14], but no
report on the purification methods to get high purity product was found.
In this work, BTZM was synthesized and its structure was characterized by IR, and nuclear
13
magnetic resonance (1H NMR and C NMR). Its solubilities in water, methanol, ethanol, n-
propanol, isopropanol, and n-butanol have been measured at temperatures ranging from 292.15K
to 310.15K under normal atmospheric pressure using a dynamic method by a laser monitoring
observation technique. The experimental solubility data were correlated with the Van’t Hoff
equation, modified Apelblat equation, and λh equation. Moreover, the dissolution enthalpy of
BTZM in the above mentioned solvents was obtained by using the modified Apelblat equation.
2. Experimental sections
6

2.1. Materials
Benzyl chloride and propargyl alcohol were commercially available from Sinopharm Chemical
Reagent Co. Ltd (Shanghai, China) and Zhengzhou Xinshun Plating Co. (China), respectively.
All of the solvents and sodium azide with analytical grade, purchased from Kermel Tianjin
Chemical Co., were used to measure the solubility without further purification. The water used in
the experiment was double-distilled water (conductivity < 4 μS·cm−1). Detailed information of
the materials used in the work was listed in Table 1.
2.2. Synthesis of BTZM
The synthesis mechanism of BTZM was shown in Figure 1 and the specific synthetic method
was described as follows:
First, benzyl chloride (42 mmol) was dissolved in the mixture of water (5 mL) and ethanol (40
mL), then NaN3 (52 mmol) was added in three-necked flask with strong magnetic stirring. The
formed solution was heated and refluxed for 8h. After completion of the reaction, the reaction
mixture was cooled. Afterwards water (100 mL) was added and extracted with diethyl ether
(2×50 mL) three times, and the combined ether layer was dried over anhydrous sodium sulfate,
filtered and evaporated under reduced pressure. The colorless liquid benzyl azide (5.14 g, 92.1%)
was obtained. The structure of benzyl chloride was characterized by IR (Figure 2A) and benzyl
azide was confirmed by IR (Figure 2B), 1H NMR (Figure 3), and 13C NMR (Figure 4). 1H NMR
13
(CDCl3, 400 MHz), δ(ppm): 7.50~7.46 (m, 2H), 7.45~7.39 (m, 5H), 4.39 (s, 2H). C NMR
(CDCl3, 100 MHz), δ(ppm): 54.83, 128.31, 128.38, 128.92, 135.50. Then, a solution of benzyl
azide (25 mmol) and propargyl alcohol (30 mmol) in 30 mL tetrahydrofuran and a mixture of
sodium ascorbate (2.5 mmol) and copper(II) sulfate pentahydrate (0.5 mmol) in 10 mL water
were added in a 100 mL three-necked flask. The reaction mixture was heated and stirred at the
7

reflux temperature for 20 h. After completion of the reaction, the reaction mixture was cooled to
room temperature, then 100 mL water was added and extracted with dichloromethane three times,
and the combined organic layer was dried with anhydrous sodium sulfate and desolventized. The
yellowish green needles crystal BTZM (4.46 g, 96.0% purity by HPLC) was obtained and then
recrystallized from ethanol three times to obtain the white needles crystal (more than 99.0%
purity by HPLC).
2.3. Characterization of BTZM
1
The H NMR spectra and 13C NMR spectra were collected by a Bruker DPX-400 NMR
spectrometer. IR spectra were recorded on the IR-200 spectrometer (Thermo Nicolet Corporation,
America). The mass fraction purity of BTZM was identified by an Agilent-1100 high
performance liquid chromatography (HPLC). The purity of solvents and raw materials used in
this work were checked by the gas chromatograph (GC-7900. Techcomp(China) Ltd). The
melting point was determined by a WRS-1B digital melting point apparatus (Shanghai precision
& scientific instrument Co., Ltd). Figure 2 presents the IR spectra of benzyl chloride (A), benzyl
azide (B), and BTZM (C). For all the samples, the absorption band at approximately 3065 and
3032 cm-1 can be attributed to the stretching vibrations of =C–H on the benzene ring. The
absorption bands appearing at 700 cm-1 in Figure 2A is related to the stretching vibrations of C–
Cl. Compared with Figure 2A (benzyl chloride), the new absorption band appearing at
approximately 2097 cm-1 (Figure 2B) is assigned to the stretching vibrations of –N=N+=N-.
These results confirm that benzyl azide was successfully synthesized. Compared with Figure 2B,
new peaks corresponding to BTZM are observed at 3262 and 1013 cm-1 in Figure 2C. The peak
at 3262 cm-1 is characteristic peak of hydroxyl groups, and the absorption band appearing at
1013 cm-1 is assigned to the characteristic peak of triazole group. These results indicate that
8

1
BTZM was successfully obtained. The structure of BTZM was also characterized by H NMR
13
1
(Figure 5), and C NMR (Figure 6). H NMR (CDCl3, 400 MHz), δ(ppm): 7.486 (brs, 1H),
13
7.393~7.268 (m, 5H), 5.511 (s, 2H), 4.763 (brs, 2H), 3.351 (brs, –OH). C NMR (CDCl3, 100
MHz), δ(ppm): 54.19, 56.15, 122.00, 128.12, 128.76, 129.11, 134.53, 148.50. Melting point:
351.75K–351.95K (Lit. 349.15K–351.15K and Lit. 349.15K–350.15K) [Error! Bookmark not
defined.15].
2.4. Experimental apparatus and procedure
The solubilities of BTZM in the selected solvents were measured by a dynamic method similar
to those described in the literatures [16,- [18]. The experimental apparatus were illustrated in
Figure 7. Its core is a 100 mL jacket glass vessel with an electro-magnetic stirrer. The desired
temperature was controlled by the circulating water which was provided by a thermostated bath.
A mercury-in-glass thermometer with an uncertainty of ± 0.1K was used to detect the
temperature of the system. Condenser was used to prevent the volatilization of solvents. The
dissolution of the solute was monitored by a laser beam system, which included a laser
generator, a photoelectric converter, and a light intensity display instrument. At the beginning of
the experiment, a certain number of solute and solvent was loaded into the dissolution kettle. At
the early stage, the light intensity penetrating through the solution would reached the maximum
value because of the complete dissolution of the solute, then a certain amount of solute was
added to the vessel, the light intensity penetrating through the solution would reduce to the
minimum value. If the solute was completely dissolved in the solvent, another amount of solute
(5-15 mg) was added until the last addition would not be dissolved. The total mass of the added
solute was recorded. The mass of solute and solvent was weighted by a precision electronic
analytical balance (Mettler Toledo AB204-N, Switzerland) with an accuracy of 0.0001 g. All the
9

data points were measured at least three times, and then the arithmetic average was taken.
Moreover, to test and verify the reliability of the experimental apparatus for measuring the solid-
liquid equilibrium data, the solubility of potassium chlorate in water was measured using this
apparatus and compared with the data in literature [19] (see Figure 8), it can be clearly seen that
the experimental data were consistent with the literature values, the average relative error was
less than 2%, so the experimental apparatus and the experimental method were reliable.
The experimental mole fraction solubility of the solute (x) in different pure solvents can be
obtained from the following equation:
m1 M1
x 
(1)
m1 M1  m2 M2
where m1 and m2 are the mass of BTZM and solvent, respectively. M1 and M2 are the molar mass
of BTZM and solvent, respectively.
3. Results and discussion
3.1. Solubility data of BTZM and correlation models
The mole fraction solubilities of BTZM in different pure solvents measured at a temperature
range from 292.15K to 310.15K under normal atmospheric pressure were presented in Table 2
and Figure 9. It can be concluded that the solubility of BTZM in all of the studied systems was
the function of temperature and it increased nonlinearly as the temperature increased. At the
given temperature range, the solubility of BTZM in the various solvents was in the order of
methanol > ethanol > n-propanol > n-butanol > isopropanol > water except three points.
From the molecular structure of BTZM shown in Figure 1, it has a benzene ring, a nitrogen
heterocyclic ring, and a hydroxyl. The solubility of organics depends on its functional groups in
a certain extent. The molecular of BTZM contain the hydrophobic phenyl and hydrophilic
hydroxyl. However, the role of hydrophobic phenyl was stronger than hydrophilic hydroxyl, so
10

BTZM is dissolved slightly in water. According to the rule of “like dissolves like”, polar protic
solutes are generally found to have very high solubility in such polar protic solvents because can
form the hydrogen bonds between the molecules to ensure solute dissolution. The substances
which contain the same functional groups can be miscible. Therefore, BTZM can be dissolved in
alcohols.
According to the theory of Bronsted–Lowry acid and alkali, which can provide protons are
exactly acid substances, which means, the acid strength is consistent with solubility data [20].
This theory is applicable as the consequence in this paper. Based on the organic chemistry
knowledge, the ability to provide the hydrogen atom rank as: methanol > ethanol > n-propanol >
isopropanol > n-butanol. This theoretical explanation is consistent with the rule “like dissolves
like”.
In conclusion, the solubilities of BTZM in the solvents follow the order of methanol >
ethanol > n-propanol > isopropanol > n-butanol > water, and they are increased with the
increasing temperature. However, due to the stronger space steric of isopropanol, the solubility
of BTZM in isopropanol is smaller than that in n-butanol at high temperature.
The experimental data were correlated with different models which included the Van’t Hoff
equation, modified Apelblat equation, and λh equation.
In terms of thermodynamics, the solubility of a solute in a solvent was calculated using the
equation (2) [21,,22]:
1
ln(x)  (fus H o / R)(Tm T 1)
(2)
where x is the mole fraction solubility of BTZM at the corresponding absolutely temperature T,
ΔfusH is the enthalpy of fusion of BTZM, R is the gas constant, Tm is the average melting point of
BTZM of which the standard uncertainty is 0.5K, and γ is the activity coefficient of BTZM.
11

Prausnitz point out that the activity coefficients of components in real solution show a weak
dependence on temperature when the temperature was far from the critical region and given as
[23]:
ln()  c  d /T
where c and d are the model parameters.
(3)
(4)
We combine equation (2) with equation (3) obtaining the equation (4)
ln(x)  fusH o / c (fus H o / R  d)/T

RTm

For the systems studied, the following substitutions for equation (4) was made
a  fus H o /
b  fusHo / R  d

RTm

 c
(5)
(6)
Thus, Van’t Hoff equation reveals the relationship between the mole fraction of the solute and
temperature based on the assumption of the solution is ideal solution and is given as:
ln x  a  b

T K

(7)
where x is the mole fraction solubility of BTZM at the corresponding absolutely temperature T. a
and b are the model parameters. The modified Apelblat equation was a semi-empirical model,
and it considered that the solubility of BTZM depended linearly on temperature, which was
widely used by Apelblat [24,,25] can be expressed by equation (8).
ln x  A B (T K) Cln(T K)
(8)
where x is the mole fraction solubility of BTZM at the corresponding absolutely temperature T.
A, B, and C are the semi-empirical constants.
The λh equation was first developed by Buchowski et al [26], which can be used to describe
the solution behavior. The equation is given as followed:
12

1

ln
1 

1 x

x

 h


T K

1 

Tm K

(9)
where λ and h are the model parameters.
The relative deviation (RD), average relative deviation (ARD), and root-mean-square-deviation
(RMSD) between experimental and calculated mole fraction solubility of BTZM were calculated
by eqs 10 to 12:
RD 

xcal  xexp

xexp
(10)
(11)
N
1
ARD 

xcal  xexp

xexp
xexp
N 
i1
1 2
N
2
 1



RMSD 

xcal  xexp


(12)
N 

i1

where xexp and xcal are the experimental and calculated solubilities of BTZM, respectively. N is
the total number of the experimental points. Moreover, xcal,Vf, xcal,Apel, and xcal,λh are the
calculation values of the Van’t Hoff equation, modified Apelblat equation, and λh equation. The
RD, xcal,Vf, xcal,Apel, and xcal,λh for different pure solvents were listed in Table 2, the parameters a, b,
A, B, C, λ, and h together with R2, ARD, RMSD were listed in Table 3, 4, and 5, respectively.
Solubility curves calculated from the Van’t Hoff equation and the modified Apelblat equation
for different alcohol solvents and water were shown in Figure 10 and Figure 11, respectively. It
can be clearly seen from the Table 2, Figure 10 and 11, the values of the correlated solubility are
in good match with the experimental values, and in a certain temperature, the solubility order is
methanol > ethanol > n-propanol > n-butanol > isopropanol > water except for three points, it
indicated that the solubility of BTZM in different alcohol solvents depends on the polarity of
solvents. The ARD and RMSD of the three models are 1.87%, 2.37×10-2 (Van’t Hoff), 1.53%,
1.51×10-2 (Apelblat) and 1.71%, 2.12×10-2 (λh), respectively. These results indicate that the
solubility data of BTZM in different alcohol solvents and water can be well correlated by these
13

three models and the modified Apelblat equation with three-parameter provides a more accurate
prediction than the Van’t Hoff equation and λh equation with two-parameter.
3.2. Prediction of dissolution enthalpy in pure solvents
According to the literature, the standard dissolution enthalpy ΔHd of BTZM in pure solvents
can be described by the following equation [27,,28]:
Hdo  RT (lnx lnT)  R(B CT)
(13)
where R is the gas constant, B, and C are the Apelblat parameter obtained from the Table 2. The
o
calculated values of ΔHd were listed in Table 6.
o
From the Table 6, it can be seen that all of the standard enthalpy values ΔHd of BTZM in each
solvent are positive within the experimental temperature range, indicating dissolution is
endothermic, which can explain the increasing solubility of BTZM with increasing temperature.
Dissolution is an endothermic process because the interactions between the BTZM molecules
and the solvent molecules are more powerful than those among the solvent molecules themselves.
4. Conclusions
In the present study, BTZM was synthesized successfully, and its solubility in water, pure
alcohols (methanol, ethanol, n-propanol, isopropanol, and n-butanol) were determined at
temperatures from 292.15K to 310.15K using a dynamic method by a laser monitoring
technique. The mole solubilities of BTZM in those selected solvents were found to be a function
of temperature and increased nonlinearly with the increasing of temperature. The solubilities of
BTZM in the different solvents follows the order methanol > ethanol > n-propanol > n-butanol >
isopropanol > water except three points. The experimental data were correlated by the Van’t
Hoff equation, modified Apelblat equation, and λh equation. The calculation results show that in
the selected pure solvents, the modified Apelblat equation provides the best fitting results than
14

the Van’t Hoff equation and λh equation. Finally, the dissolution enthalpy of BTZM was
calculated on the basis of the modified Apelblat equation. The results show that the dissolving
process of BTZM is endothermic. The experimental solubility data and the correlation models
can be used for the purification of BTZM.
Funding Sources
This work was supported by International Cooperation Project of Henan Province
(104300510009).
Notes
The authors declare no competing financial interest.
15

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Figure Captions
Figure 1. Synthesis scheme of (1-Benzyl-1H-1,2,3-triazole-4-yl)methanol (BTZM).
20

(A)
3064
3065
3032
3032
700
(B)
(C)
2097
3030
3065
3262
1013
1000
4000
3500
3000
2500
2000
1500
500
Wavenumbers (cm-1)
Figure 2. IR spectra of benzyl chloride (A), benzyl azide (B), and BTZM (C).
21

Figure 3. 1H NMR spectra of benzyl azide.
22

Figure 4. 13C NMR spectra of benzyl azide.
23

Figure 5. 1H NMR spectra of BTZM.
24

Figure 6. 13C NMR spectra of BTZM.
25

Figure 7. Schematic diagram of the experiment apparatus:(1) laser generator; (2) magnetic
stirrer; (3) condensator; (4) precise thermometer; (5) dissolution kettle; (6) thermostatic water-
circulating bath; (7) photoelectric transformer; (8) numeral indicator.
26

Figure 8. Solubility of potassium chlorate in water. ■. literature values; ●. experimental values.
27

Figure 9. Mole fraction solubility (x) of BTZM against temperature in different pure solvents: ○,
water; ■, methanol; ●, ethanol; ▲, n-propanol; ▼, n-butanol; □, isopropanol.
28

Figure 10. Plot of mole fraction solubility (x) of BTZM against temperature in different pure
solvents: ○, water; ■, methanol; ●, ethanol; ▲, n-propanol; ▼, n-butanol; □, isopropanol. The
solid lines are correlated values by the Van’t Hoff equation.
29