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

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: DOI: Reference:

S0040-6031(16)30004-1 http://dx.doi.org/doi:10.1016/j.tca.2016.01.009 TCA 77429

To appear in:

Thermochimica Acta

Received date: 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-1,2,3triazole-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 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Measurement and Correlation of the Solubility of (1Benzyl-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†* [email protected] †

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.

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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.

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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.

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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 rootmean-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-4yl)methanol Nomenclature List of symbols A

parameter in Eq.8

a

parameter in Eq.5,7

B

parameter in Eq.8

b

parameter in Eq.6,7

C

parameter in Eq.8

c

parameter in Eq.3,4,5,6

d

parameter in Eq.3,4,5,6 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

R

gas constant (J·mol-1·K-1)

T

temperature (K)

Tm

average melting point of BTZM (K)

x

mole fraction solubility of solute

xexp

the experimental mole fraction solubility of solute

xcal

the calculated mole fraction solubility of solute

Greek letters ΔHdo

standard dissolution enthalpy (J·mol-1)

ΔfusHo

standard fusion enthalpy (J·mol-1)

γ

activity coefficient

λ

parameter in Eq.9

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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 magnetic resonance (1H NMR and

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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

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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 (CDCl3, 400 MHz), δ(ppm): 7.50~7.46 (m, 2H), 7.45~7.39 (m, 5H), 4.39 (s, 2H).

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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

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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 The 1H NMR spectra and

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C 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

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BTZM was successfully obtained. The structure of BTZM was also characterized by 1H NMR (Figure 5), and

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C NMR (Figure 6). 1H NMR (CDCl3, 400 MHz), δ(ppm): 7.486 (brs, 1H),

7.393~7.268 (m, 5H), 5.511 (s, 2H), 4.763 (brs, 2H), 3.351 (brs, –OH).

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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

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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 solidliquid 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:

x

m1 M 1 m1 M 1  m2 M 2

(1)

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

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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.

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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

(3)

where c and d are the model parameters. We combine equation (2) with equation (3) obtaining the equation (4) ln ( x)   fus H o / RTm   c  ( fus H o / R  d ) / T

(4)

For the systems studied, the following substitutions for equation (4) was made a   fus H o / RTm   c

(5)

b   fus H o / R  d

(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 )  C ln(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:

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

ln1   1  x  x  h T K   Tm K  1

1



(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  x cal  x exp x exp 1 N ARD   x cal  x exp  x exp N i 1



(10) (11)



12

2 1 N RMSD    x cal  x exp x exp   N i 1 



(12)

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

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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]: H do  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 calculated values of ΔHdo were listed in Table 6. From the Table 6, it can be seen that all of the standard enthalpy values ΔHdo 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

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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.

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C.T. Zhang, B.Y. Liu, X. Wang, H.R. Wang, Measurement and Correlation of the Solubilities of L-Valine in Water, Ethanol, N,N-Dimethylformamide, Acetone, and Isopropyl Alcohol between (293.15 and 343.15) K, J. Chem. Eng. Data. 59 (2014) 2704−2708.

19

Figure Captions

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

20

(A) 3064

3032

Transmittance

700

(B) 3065

3032 2097

(C)

3030 3065 3262 1013

4000

3500

3000

2500

2000

1500

1000

-1

Wavenumbers (cm )

Figure 2. IR spectra of benzyl chloride (A), benzyl azide (B), and BTZM (C).

21

500

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 watercirculating 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

Figure 11. 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 modified Apelblat equation.

30

Tables Table 1.The Source and Purity of the Materials and the Purification Methods Material

Initial purity (mass fraction)

Purification method

Analysis method

Final purity (mass fraction)

Source

Benzyl chloride

0.990

Distillation

GCa

0.996

Sinopharm Chemical Co. Ltd.

Sodiumazide

0.990

-

-

-

Tianjin Kermel Chemical Co.

Propargyl alcohol

0.980

Distillation

GC

0.995

Zhengzhou Xinshun Plating Co.

Methanol

0.995

-

GC

-

Tianjin Kermel Chemical Co.

Ethanol

0.997

-

GC

-

Tianjin Kermel Chemical Co.

n-Propanol

0.998

-

GC

-

Tianjin Kermel Chemical Co.

Isopropanol

0.990

-

GC

-

Tianjin Kermel Chemical Co.

n-Butanol

0.995

-

GC

-

Tianjin Kermel Chemical Co.

BTZM

0.960

Recystallization

HPLCb

0.990

Synthesis

a

b

Gas chromatograph. High performance liquid chromatography.

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Table 2. The Experimental and Calculated Solubility of BTZM in Different Alcohol Solvents and Water at Temperature T = (292.15 to 310.15) K and Pressure p = 0.1 MPaa 102 RDVf 102 xcal,Aple 102 RDAple 102 xcal,λh 102 RDλh Methanol 292.15 12.23 12.52 2.37 12.56 2.70 12.36 1.06 295.15 14.62 14.59 -0.21 14.6 -0.14 14.52 -0.68 298.15 17.15 16.95 -1.17 16.93 -1.28 16.98 -0.99 301.15 20.02 19.63 -1.95 19.6 -2.10 19.73 -1.45 304.15 22.21 22.67 2.07 22.64 1.945 22.79 2.61 307.15 26.22 26.11 -0.42 26.09 -0.50 26.17 -0.19 310.15 29.96 29.98 0.07 30.02 0.20 29.88 -0.27 Ethanol 292.15 5.663 5.382 -4.96 5.471 -3.39 5.434 -4.04 295.15 6.810 6.748 -0.91 6.788 -0.32 6.834 0.35 298.15 8.330 8.422 1.10 8.412 0.98 8.535 2.46 301.15 10.34 10.47 1.26 10.42 0.77 10.58 2.33 304.15 12.85 12.95 0.78 12.88 0.23 13.02 1.32 307.15 15.83 15.95 0.76 15.92 0.57 15.89 0.38 310.15 19.75 19.58 -0.86 19.65 -0.51 19.23 -2.63 n-Propanol 292.15 4.217 3.951 -6.31 4.009 -4.93 4.047 -4.03 295.15 5.021 4.926 -1.89 4.951 -1.39 5.023 0.04 298.15 6.071 6.114 0.71 6.107 0.59 6.202 2.16 301.15 7.423 7.556 1.79 7.523 1.35 7.618 2.63 304.15 9.089 9.299 2.31 9.257 1.85 9.308 2.41 307.15 11.31 11.40 0.80 11.38 0.62 11.31 0.00 310.15 14.11 13.92 -1.35 13.96 -1.06 13.67 -3.12 n-Butanol 292.15 3.416 3.322 -2.75 3.356 -1.76 3.368 -1.41 295.15 4.075 4.026 -1.20 4.038 -0.91 4.061 -0.341 298.15 4.809 4.859 1.04 4.852 0.89 4.880 1.48 301.15 5.794 5.843 0.85 5.822 0.48 5.847 0.91 304.15 6.946 7.000 0.78 6.976 0.43 6.985 0.56 307.15 8.315 8.358 0.52 8.346 0.37 8.323 0.10 310.15 10.02 9.944 -0.76 9.971 -0.49 9.892 -1.28 Isopropanol 292.15 3.221 3.017 -6.33 3.057 -5.09 3.107 -3.54 295.15 3.897 3.784 -2.90 3.802 -2.44 3.871 -0.67 298.15 4.700 4.726 0.55 4.722 0.47 4.800 2.13 301.15 5.764 5.876 1.94 5.853 1.54 5.921 2.72 304.15 7.075 7.274 2.81 7.244 2.39 7.271 2.77 307.15 8.890 8.967 0.87 8.951 0.69 8.889 -0.01 310.15 11.18 11.01 -1.52 11.04 -1.25 10.82 -3.22 Water 292.15 0.1470 0.1358 -7.62 0.1370 -6.80 0.1411 -4.01 295.15 0.1705 0.1661 -2.58 0.1665 -2.35 0.1698 -0.41 298.15 0.1974 0.2022 2.43 0.2020 2.33 0.2041 3.39 301.15 0.2375 0.2452 3.24 0.2445 2.95 0.2450 3.16 304.15 0.2901 0.2962 2.10 0.2954 1.83 0.2939 1.31 307.15 0.3562 0.3565 0.08 0.3561 -0.03 0.3526 -1.01 310.15 0.4333 0.4275 -1.34 0.4284 -1.13 0.4231 -2.35 a x, mole fraction; xexp is the experimental mole fraction solubilities; xcal,Vf, xcal,Aple, and xcal,λh represent the calculated solubility data by the Van’t Hoff equation, modified Apelblat equation, and the λh equation. Standard uncertainties u are u(T) = 0.1K, ur(p)=0.05, and relative standard uncertainties for solubility in different alcohols is ur(x) = 0.01, and ur(x) = 0.02 in water. T/K

102 xexp

102 xcal,Vf

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Table 3. Parameters of the Van’t Hoff Equation for BTZM in Selected Solvents Solvent Methanol Ethanol n-Propanol n-Butanol Isopropanol Water

a 12.98 19.33 18.46 15.48 18.81 13.15

R2 0.9975 0.9988 0.9970 0.9991 0.9965 0.9946

b -4397.88 -6499.93 -6338.20 -5518.55 -6517.36 -5771.33

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102 ARD 1.18 1.52 2.17 1.13 2.42 2.77

102 RMSD 1.48 2.08 2.80 1.32 3.01 3.53

Table 4. Parameters of Modified Apelblat Equation for BTZM in Selected Solvents Solvent Methanol Ethanol n-Propanol n-Butanol Isopropanol Water

A -44.59 -199.79 -177.40 -131.20 -158.04 -102.50

B -1805.03 3387.49 2498.82 1094.86 1463.03 -555.71

C 8.58 32.64 29.17 21.85 26.34 17.23

34

R2 0.9966 0.9993 0.9978 0.9995 0.9971 0.9945

102 ARD 1.27 0.97 1.68 0.76 1.98 2.49

102 RMSD 1.58 1.40 2.18 0.89 1.41 1.57

Table 5. Parameters of λh Equation for BTZM in Selected Solvents Solvent Methanol Ethanol n-Propanol n-Butanol Isopropanol Water

λ 2.51 3.05 1.61 0.72 1.26 0.02

R2 0.9977 0.9965 0.9955 0.9991 0.9957 0.9941

h 2011.29 2252.09 3916.30 7337.25 5062.20 203216.40

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102 ARD 1.04 1.93 2.06 0.87 2.15 2.23

102 RMSD 1.29 2.29 2.49 1.01 2.46 3.17

Table 6. Thermodynamic Properties Related to Dissolution Process of BTZM in Different Pure Solvents at Temperature T = (292.15 to 310.15) K

T/K

a

ΔHdo/(kJ·mol-1) Methanol

a

Ethanol

b

n-Propanolc

n-Butanold

Isopropanole

Waterf

292.15

35.85

51.12

50.08

43.97

51.81

46.47

295.15

36.06

51.93

50.80

44.51

52.47

46.90

298.15

36.28

52.75

51.53

45.06

53.13

47.33

301.15

36.49

53.56

52.26

45.60

53.79

47.76

304.15

36.70

54.37

52.99

46.15

54.44

48.19

307.15

36.92

55.19

53.71

46.69

55.10

48.62

310.15

37.13

56.00

54.44

47.24

55.76

o

b

o

49.05 c

Relative standard uncertainties are ur(ΔHd )=0.02; Relative standard uncertainties are ur(ΔHd )=0.02; Relative standard uncertainties are ur(ΔHdo)=0.03; d Relative standard uncertainties are ur(ΔHdo)=0.02; e Relative standard uncertainties are ur(ΔHdo)=0.03; f Relative standard uncertainties are ur(ΔHdo)=0.04.

36