Solution Thermodynamics of Benzotriazole in Different Pure Solvents

Article pubs.acs.org/jced

Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Solution Thermodynamics of Benzotriazole in Different Pure Solvents Yanan Luan,†,‡ Jing Li,† Musika Kaliwanda,† Na Wang,† Kui Chen,† Xin Li,† Weiyi Su,§ and Hongxun Hao*,†,‡ †

National Engineering Research Center of Industrial Crystallization Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China ‡ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China § School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China S Supporting Information *

ABSTRACT: Solubility data of benzotriazole (BTA) in 14 solvents were measured by a static gravimetric method from 268.15 to 303.15 K. The results illustrated that the solubility of BTA in N,N-dimethylacetamide is the highest whereas that in 1,2-dichloroethane is the lowest in all the tested solvents. And the values of solubility increase with increasing of temperature. Additionally, the modified Apelblat equation, the λh equation, the NRTL model, and the Wilson model were employed to correlate the experimental solubility data. It was found that all the selected thermodynamic models could give satisfactory correlation results. Furthermore, the thermodynamic properties of BTA during the dissolving process, including the enthalpy, the Gibbs energy, and the entropy, were also calculated and analyzed.

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INTRODUCTION BTA (Figure 1, C6H5N3, CAS Registry No.95-14-7) is a heterocyclic compound containing three nitrogen atoms, which generally exists as white crystal and can be used in various fields.

of BTA in different solvents. From literature review, it was found that no solubility data of BTA in organic solvents have been published. Therefore, in this study, the solubilities of BTA in 14 pure organic solvents (including acetone, methanol, ethanol, isopropyl alcohol, sec-butanol, acetonitrile, ethyl acetate, dichloromethane, methyl acetate, ethyl formate, propyl acetate, 1,2-dichloroethane, N,N-dimethylformamide, N, N-dimethylacetamide) were measured by using a gravimetric method under atmosphere pressure (0.1 MPa) over the temperature range from 268.15 to 303.15 K. The experimental solubility data were correlated by four thermodynamic models, including the Apelblat equation, the λh equation, the NRTL model, and the Wilson model. In addition, the dissolution thermodynamic properties of BTA in the tested solvents, such as the Gibbs free energy, the enthalpy, and the entropy, were also derived through the experimental data and the NRTL model.4−7

Figure 1. Chemical structure (a) and three-dimensional structure (b) of BTA.

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It has been known that BTA is an effective corrosion inhibitor to prevent undesirable surface reactions for copper and its alloys under atmospheric and immersed conditions.1 It has also been used to protect archeological and historical relics.2 Additionally, BTA has already been applied as a restrainer in photographic emulsions and as a reagent for the analytical determination of silver. Furthermore, it can also be used as antifreezing agent in heating and cooling system.3 In the manufacture of BTA, crystallization technology is generally used to obtain the final product. To develop and design a crystallization process to produce BTA product with ideal properties, such as purity, morphology, and particle size distribution, it is essential to know its thermodynamic data, such as solubility © XXXX American Chemical Society

EXPERIMENTAL SECTION

Materials. BTA with a purity (mass fraction) of 0.990 was supplied by Shanghai Macklin Biochemical Co., Ltd. Isopropyl alcohol, ethyl acetate, dichloromethane, and ethyl formate were purchased from Tianjin Jiangtian Chemical Co., Ltd. sec-Butanol, acetonitrile, methyl acetate, propyl acetate, 1,2-dichloroethane, N,N-dimethylformamide, and N,N-dimethylacetamide were Received: December 14, 2017 Accepted: February 22, 2018

A

DOI: 10.1021/acs.jced.7b01085 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Sources and Mass Fraction Purities of Materials Used in This Paper

a

chemical name

CAS Registry No.a

source

mass purity

purification method

analysis method

BTA acetone methanol ethanol isopropyl alcohol sec-butanol acetonitrile ethyl acetate dichloromethane methyl acetate ethyl formate propyl acetate 1,2-dichloroethane N,N-dimethylformamide N,N-dimethylacetamide

95-14-7 67-64-1 67-56-1 64-17-5 67-63-0 78-92-2 75-05-8 141-78-6 75-09-2 79-20-9 109-94-4 109-60-4 107-06-2 68-12-2 127-19-5

Shanghai Macklin Biochemical Co.,Ltd. Chemical Reagent Six Factory, Tianjin, China Chemical Reagent Six Factory, Tianjin, China Chemical Reagent Six Factory, Tianjin, China Jiangtian Chemical Technology Co., Ltd., Tianjin, China Yuanli Chemical Technology Co., Ltd., Tianjin, China Yuanli Chemical Technology Co., Ltd., Tianjin, China Jiangtian Chemical Technology Co., Ltd., Tianjin, China Jiangtian Chemical Technology Co., Ltd., Tianjin, China Yuanli Chemical Technology Co., Ltd., Tianjin, China Jiangtian Chemical Technology Co., Ltd., Tianjin, China Yuanli Chemical Technology Co., Ltd., Tianjin, China Yuanli Chemical Technology Co., Ltd., Tianjin, China Yuanli Chemical Technology Co., Ltd., Tianjin, China Yuanli Chemical Technology Co., Ltd., Tianjin, China

>0.990 >0.995 >0.999 >0.997 >0.997 >0.99 >0.995 >0.995 >0.995 >0.980 >0.98 >0.98 >0.99 0.995 0.99

none none none none none none none none none none none none none none none

HPLCb GCc GCc GCc GCc GCc GCc GCc GCc GCc GCc GCc GCc GCc GCc

CAS Registry Numbers are supplied by the author. bHigh-performance liquid chromatography. cGas chromatography.

syringes and organic membranes are preheated or precooled to be consistent with the solution temperature. Finally, the glass vial containing the filtrate was immediately weighed by using an electronic analytic balance (Mettler Toledo ML204) with accuracy of ±0.0001 g and was then placed into a vacuum oven (Taisite Tianjin DZ-2BC) at 323.15 K. The weight of the glass vial was measured every 4 h until the difference among three measurements was less than 0.0010 g. Each process was repeated three times, and the average value was used to calculate the solubility data. The mole fraction solubility (x1) of BTA in different solvents can be calculated by the following equation.9

purchased from Tianjin Yuanli Chemical Co., Ltd. All other solvents like acetone, methanol, and ethanol were purchased from Tianjin Sixth Chemical Reagent Factory. All of the selected organic solvents and BTA were used without further purification. Purities and sources of all the materials used in this study are listed in Table 1. X-ray Powder Diffraction. X-ray powder diffraction (XRPD) was performed to identify and characterize the crystal form of BTA before and after each experiment. The XRPD spectra were obtained by using a D/max-2500 (Rigaku) diffractometer (Cu Kα radiation, λKα1 = 1.5406 Å) over diffraction angle (2θ) from 2° to 50° with a scanning rate of 0.067° s−1 at 100 mA and 40 kV. Differential Scanning Calorimetry (DSC) Measurements. DSC (DSC 1/500, Mettler-Toledo) was used to characterize the melting temperature and the enthalpy of fusion of the samples. It was calibrated by using indium (Tm = 429.75 K; ΔfusH = 3267 J/mol−1)8 and zinc (Tm = 692.68 K; ΔfusH = 7320 J/mol−1)8 before starting all experiments. In this study, 5−10 mg BTA samples were weighed by an analytical balance (Mettler Toledo AB204-N) with an accuracy of ±0.0001 g and placed into an aluminum pan. Under protection of a nitrogen atmosphere, the samples were heated at a heating rate of 10 K/min from 303.15 to 453.15 K by using an empty pot as reference. Every DSC experiment was repeated three times. The standard uncertainty of the melting temperature Tm is 0.5 K and the relative standard uncertainty of the enthalpy of fusion ΔfusH is 0.02. Solubility Measurements. The solubility data of BTA in different pure solvents were determined by the gravimetric method. The reliability and accuracy of this method have been verified in our previously published paper.4 The process can be described as follows. A known amount of pure solvent and an excess amount of BTA were added into a 100 mL jacketed glass vessel. The temperature of the glass vessel was controlled by a thermostat (CF41, Julabo) with an accuracy of ±0.01 K. A magnetic stirrer was used to mix the suspension in all experiments. The solid−liquid mixture in the glass vessel was continuously stirred for 10 h to ensure the solid−liquid equilibrium at a given temperature. Afterward, the suspension was kept static for 3 h at the same temperature. Thereafter, 2 mL of supernatant was rapidly withdrawn by using a syringe and filtered into a preweighted glass vial through an organic membrane (0.2 μm PTFE filter, Tianjin Legg Technology Co. Ltd.). In addition, all

x1 =

m1/M1 m1/M + m2 /M 2

(1)

where m1 and m2 are the mass of BTA and solvent, respectively, and M1 and M2 represent the molar mass of BTA and solvent, respectively.

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THERMODYNAMIC MODELS Modified Apelblat Equation. The semiempirical Apelblat equation was deduced from the Clausius−Clapeyron equation, and it can correlate the solid−liquid equilibrium experimental data. The equation can be expressed as follows:10 ln x1 = A +

B + C ln T T

(2)

where x1 is the mole fraction solubility of solute, T is the absolute temperature, and A, B, and C are empirical parameters. Generally, the values of A and B are related to the changes in the activity coefficient in the solution. C represents the effect of temperature on the enthalpy of fusion. λh Equation. Buchowski et al. proposed the λh semiempirical equation, which has then been used to correlate the liquid−solid equilibrium of many systems. The λh equation can be expressed as11 ⎡ ⎛1 ⎛ 1 − x1 ⎞⎤ 1 ⎞ ln⎢1 + λ⎜ ⎟ ⎟⎥ = λ h ⎜ − ⎢⎣ Tm ⎠ ⎝T ⎝ x1 ⎠⎥⎦

(3)

where x1 is the mole fraction of solute in saturated solution, T is the absolute temperature, Tm is the melting temperature of the solid solute, λ and h are two model parameters in the equation, B



Article

Table 2. Molar Volumes and Densities of BTA and Solvents Used in This Study density (g/cm3)a

substance BTA acetone methanol ethanol isopropyl alcohol sec-butanol acetonitrile ethyl acetate a

V (cm3/mol)b

1.310 0.785025 0.792027 0.790029 0.785031 0.804933 0.790035 0.900037

density (g/cm3)a

substance

90.93 73.99 40.45 58.32 76.56 92.07 51.96 97.90

V (cm3/mol)b

24

dichloromethane methyl acetate ethyl formate propyl acetate 1,2-dichloroethane N,N-dimethylformamide N,N-dimethylacetamide

1.320 0.933026 0.918028 0.885030 1.26032 0.948034 0.937036

64.34 79.40 80.70 119.4 78.54 77.10 93.02

The density of BTA and solvents were found from the literature.24−37 bThe molar volumes of BTA and solvents were calculated by eq 12.

and λ represents the irrationality of the solution system while h represents the excess enthalpy of the solution.12 NRTL Model. The NRTL model based on the local composition concept has been widely used to describe the solid− liquid equilibrium. It can be used to calculate the activity coefficients of solutes in real solutions. The NRTL model can be described as eqs 4−8:13

reported by literature.16 The density of the solvents can also be found from literature. The molar volumes and densities of BTA and solvents used in this study are shown in Table 2. Dissolution Thermodynamics. In the nonideal state, the BTA dissolution process can be broken down into four energy steps: heating process, melting process, cooling process, and mixing process. The processes can be expressed as follows:17

⎡ τ G 2 ⎤ τ12G12 21 21 ⎥ ln γ1 = x 2 ⎢ + 2 2 (x 2 + G12x1) ⎦ ⎣ (x1 + G21x 2)

(4)

⎯⎯⎯⎯⎯→ solute(liquid) at Tm

G12 = exp( −ατ12)

(5)

⎯⎯⎯⎯⎯⎯→ solute(liquid) at T

G21 = exp( −ατ21)

(6)

⎯⎯⎯⎯⎯→ solute(solution) at T

heating

solute(solid) at T ⎯⎯⎯⎯⎯⎯→ solute(solid) at Tm

2

τ12 =

τ21 =

g12 − g22 RT

g21 − g11 RT

=

Δg12

=

Δg21

fusion

cooling mixing

On the basis of the assumptions above, the entire dissolution thermodynamic can be expressed as

(7)

RT

ΔdisM = x(Δheat M + ΔfusM + Δcool M ) + Δmix

where M can be replaced by Gibbs energy (ΔdisG), enthalpy (ΔdisH), and entropy (ΔdisS) and x refers to the mole fraction solubility of BTA in different solvents. ΔheatM of heating process and ΔcoolM of the cooling process can be calculated by the following equations:

(8)

RT

where Δg12 and Δg21 are model parameters related to the interaction energy, α represents the nonrandomness of the mixture and the value of α varies from 0.2 to 0.47,14 R represents the gas constant at a value of 8.314 J·mol−1·K−1, and T represents the temperature. In this study, α = 0.2 was chosen for the correlation of experimental solubility data of BTA in different pure solvents. Wilson Model. The Wilson equation can also be used to calculate the activity coefficients of solutes. It can be expressed as follows.15 ⎞ ⎛ Λ12 Λ 21 ln γ1 = −ln(x1 + Λ12x 2) + x 2⎜ − ⎟ x 2 + Λ 21x1 ⎠ ⎝ x1 + Λ12x 2 ⎡ Δλ ⎤ ⎡ λ − λ11 ⎤ V2 V2 exp⎢ − 12 exp⎢ − 12 ⎥ ⎥⎦ = ⎣ RT ⎦ ⎣ V1 RT V1

Λ 21 =

⎡ Δλ ⎤ ⎡ λ − λ 22 ⎤ V1 V1 exp⎢ − 21 exp⎢ − 21 ⎥ ⎥⎦ = ⎣ RT ⎦ ⎣ V2 RT V2

(10)

(14)

Δcool H = Cp(l)(T − Tm)

(15)

Δheat S = Cp(s) ln

Tm T

(16)

Δcool S = Cp(l) ln

T Tm

(17)

Δheat G = Δheat H − T Δheat S

(18)

Δcool G = Δcool H − T Δcool S

(19)

where Cp(l) and Cp(s) refer to the heat capacity of liquid and solid, respectively. Generally, the value of Cp(l) is very close to the value of Cp(s) because the volume of BTA is almost constant during the heating and cooling processes. Therefore, the values of ΔheatH + ΔcoolH, ΔheatS + ΔcoolS, and ΔheatG + ΔcoolG will be very close to zero.18 The value of ΔfusH can be measured by DSC, and the value of ΔfusG can be considered as zero due to the equilibrium of the system. Thus, the value of ΔfusS can be obtained as follows:19

(11)

V = M/ρ

Δheat H = Cp(s)(Tm − T )

̀

(9)

Λ12 =

(13)

(12) −1

where R is the gas constant with value of 8.314 J·mol ·K−1, Δλ12 and λ21 are two model parameters whose values can be calculated by fitting the experimental data, T represents the temperature, V1 and V2 represent the molar volume of the solute and the solvent, respectively, and V1 and V2 can be determined by the molar mass and density by eq 12, where M represents the molar mass and ρ is the density. The density of BTA is

ΔfusS = C

ΔfusH Tm

(20) DOI: 10.1021/acs.jced.7b01085 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


Article

The mixed thermodynamic properties ΔmixM can be determined by Δmix M = ME + Δmix M id

The DSC results for BTA are shown in Figure 3. It can be seen from the figure that the endothermic peak of the melting

(21)

where M represents the excess properties and ΔmixMid represents the mixing thermodynamic properties of the ideal solution. The ΔmixGid, ΔmixHid, and ΔmixSid can be expressed as follows:20 E

Δmix Gid = RT (x1 ln x1 + x 2 ln x 2)

(22)

Δmix H id = 0

(23)

Δmix S id = −R(x1 ln x1 + x 2 ln x 2)

(24)

where x1 and x2 represent the mole fraction of BTA and solvent in the binary mixed solution and therefore x1 + x2 = 1. The GE, HE, and SE can be expressed as follows:21 GE = RT (x1 ln γ1 + x 2 ln γ2)

(25)

Figure 3. DSC plot of BTA.

⎡ ⎛ ⎡ ∂(GE /T ) ⎤ ⎛ ∂ ln γ2 ⎞ ⎤ ∂ ln γ1 ⎞ H E = − T 2⎢ ⎥ = − RT 2⎢x1⎜ ⎟ + x 2⎜ ⎟ ⎥ ⎢ ⎝ ∂T ⎠ ⎝ ∂T ⎠ p , x ⎥⎦ ⎣ ∂T ⎦ ⎣ p,x

process is at 369.26 K, which is consistent with the reported data (Tm = 369.15−370.15 K).22 The enthalpy of fusion of BTA is 15.225 kJ mol−1. Solubility Data of BTA in Pure Solvents. The experimental solubility data of BTA in 14 pure solvents at various temperatures are shown in Table 3 and are graphically shown in Figures 4 and 5. It can be seen that the solubility data of BTA in all selected solvents increase with the increasing of temperature. The solubility of BTA in various solvents can be classified as N,N-dimethylformamide > N,N-dimethylacetamide > sec-butanol > isopropyl alcohol > ethanol > acetone> methyl acetate > propyl acetate > ethyl formate > acetonitrile > 1,2-dichloroethane except for methanol, dichloromethane, and ethyl acetate. It is worth noting that the solubility of BTA does not strictly follow the principle of “like dissolves like”. The reason is probably related to the fact that dissolution is a complex process and the polarity is not the only influencing factor. It can also be influenced by other factors, such as the ability to form hydrogen bonds, the size of molecules, and the interaction between the solvent and the solute. In this work, four thermodynamic models, including the Apelblat equation, the λh equation, the NRTL model and the Wilson model, were used to correlate the experimental solubility data. The correlated results are also shown in Table 3. The parameters of these models are given in Tables S1−S4. The root-mean-square deviation (RMSD) and absolute relative deviation (ARD%) were used to evaluate the correlation results.23

(26)

HE − GE (27) T In this study, the activity coefficient was calculated by the NRTL model, where γ1 and γ2 refer to the activity coefficient of solute and solvent, respectively. SE =

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RESULTS AND DISCUSSION XRPD/DSC Analysis. The XRPD patterns of the raw material and solid phases after the solubility experiments are shown in Figure 2. It can be found that raw material and solid

ARD% =

100 N

⎡1 RMSD = ⎢ ⎢⎣ N

Figure 2. XRPD patterns of the raw material and the solid samples after solubility. The XRPD patterns from the bottom to the top are raw material and solid samples after solubility measuring experiments in acetone, methanol, ethanol, isopropyl alcohol, sec-butanol, acetonitrile, ethyl acetate, dichloromethane, methyl acetate, ethyl formate, propyl acetate, 1,2-dichloroethane, N,N-dimethylformamide, and N,N-dimethylacetamide, respectively.

N

∑ i=1

xiexp − xical xiexp ⎤1/2

N

∑ i=1

(xiexp

(28)

−

xical)2 ⎥ ⎥⎦

(29)

where N represents the number of the experimental points and exp xcal i and xi represent the calculated solubility data and the experimental solubility data, respectively. The values of ARD% and RMSD are shown in Table 3 as well. It can be clearly seen from Table 3 that the solubility data of BTA can be well correlated by the four models. The values of ARD% from the Apelblat equation are the minimum compared to results from other models, which suggests that the Apelblat model can give better correlation results.

phases of BTA after the solubility experiments have the same XRPD pattern, indicating that the crystal form of BTA remained unchanged during the experiments. D



Article

Table 3. Experimental and Calculated Mole Fraction Solubility of BTA in 14 Pure Solvents from 268.15 to 303.15 K under p = 101.3 kPaa,b T/K

102x1exp

102x1Apel

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

18.55 20.35 22.74 24.40 27.41 29.31 32.72 35.71

18.56 20.42 22.45 24.67 27.08 29.71 32.57 35.67 0.7425 2.377 × 10−3

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

24.77 26.80 28.37 30.93 33.29 35.86 38.69 42.29

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

22.44 24.15 25.94 28.29 30.90 33.80 36.79 39.15

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

24.04 25.93 27.52 29.72 31.78 35.28 36.84 39.98

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

26.03 27.57 28.96 30.79 32.85 35.66 37.36 40.61

268.15 273.15 278.15 283.15

3.212 3.813 4.701 5.568

24.84 26.62 28.60 30.79 33.22 35.91 38.88 42.15 0.4200 1.461 × 10−3 22.32 24.17 26.20 28.42 30.85 33.51 36.41 39.58 0.6585 2.546 × 10−3 24.04 25.79 27.71 29.78 32.04 34.49 37.15 40.03 0.6836 3.251 × 10−3 26.05 27.46 29.07 30.88 32.91 35.18 37.72 40.54 0.4710 2.231 × 10−3 3.220 3.850 4.615 5.542

102x1λh Acetone 18.43 20.39 22.50 24.76 27.19 29.79 32.57 35.54 0.8456 2.594 × Methanol 24.46 26.53 28.73 31.06 33.51 36.11 38.85 41.74 0.8759 3.069 × Ethanol 22.08 24.12 26.28 28.59 31.04 33.64 36.40 39.32 0.8209 2.672 × Isopropyl Alcohol 23.86 25.76 27.78 29.91 32.18 34.59 37.14 39.86 0.9133 3.370 × sec-Butanol 25.68 27.39 29.21 31.14 33.19 35.37 37.69 40.17 0.9795 3.261 × Acetonitrile 3.061 3.768 4.608 5.601 E

102x1NRTL

102x1Wilson

10−3

17.89 19.98 22.22 24.67 27.24 30.07 33.00 36.17 1.764 4.756 × 10−3

17.88 19.99 22.23 24.70 27.26 30.10 33.01 36.18 1.790 4.859 × 10−3

10−3

24.34 26.45 28.90 31.13 33.60 36.18 38.85 41.45 1.232 4.445 × 10−3

24.27 26.42 28.93 31.15 33.64 36.21 38.86 41.40 1.334 4.762 × 10−3

10−3

21.92 24.04 26.30 28.62 31.07 33.65 36.40 39.48 1.029 3.231 × 10−3

22.08 24.16 26.40 28.66 31.03 33.53 36.21 39.27 0.9826 3.394 × 10−3

10−3

23.25 25.29 27.59 29.88 32.40 34.69 37.73 40.53 1.745 6.010 × 10−3

23.80 25.64 27.80 29.91 32.27 34.36 37.32 40.00 1.162 4.448 × 10−3

10−3

24.25 26.38 28.73 31.09 33.55 35.95 38.92 41.57 2.801 1.040 × 10−3

24.98 26.88 29.05 31.18 33.42 35.55 38.39 40.86 1.691 6.321 × 10−3

3.195 3.836 4.635 5.550

3.207 3.842 4.638 5.548 DOI: 10.1021/acs.jced.7b01085 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


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Table 3. continued T/K

102x1exp

102x1Apel

288.15 293.15 298.15 303.15 ARD%c RMSDc

6.717 7.823 9.672 11.82

6.666 8.030 9.686 11.70 1.019 9.453 × 10−4

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

6.600 8.550 10.13 11.71 13.30 16.25 19.17 23.63

6.850 8.190 9.773 11.64 13.84 16.42 19.45 23.00 2.675 3.750 × 10−3

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

4.167 4.658 6.201 8.986 12.17 15.28 19.78 25.22

3.830 5.028 6.605 8.682 11.41 15.01 19.74 25.94 4.624 4.568 × 10−3

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

10.97 11.94 13.25 14.55 16.18 17.72 19.69 22.27

10.97 12.00 13.19 14.54 16.08 17.84 19.84 22.13 0.4840 9.858 × 10−4

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

6.411 7.172 8.094 8.959 9.892 10.70 12.30 13.49

6.440 7.184 8.002 8.902 9.889 10.97 12.15 13.45 0.8094 1.183 × 10−3

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c

8.234 9.370 10.34 11.63 13.13 14.61 16.69 18.54

8.273 9.267 10.39 11.66 13.10 14.71 16.54 18.60 0.5529

102x1λh Acetonitrile 6.769 8.136 9.733 11.59 1.975 15.34 × 10−4 Ethyl Acetate 6.572 8.040 9.755 11.74 14.03 16.63 19.57 22.88 2.931 4.753 × 10−3 Dichloromethane 3.445 4.818 6.626 8.962 11.91 15.55 19.92 25.02 4.151 3.395 × 10−3 Methyl Acetate 10.76 11.94 13.24 14.67 16.23 17.95 19.84 21.94 0.8431 1.780 × 10−3 Ethyl Formate 6.487 7.203 7.995 8.872 9.847 10.93 12.15 13.52 1.004 1.161 × 10−3 Propyl Acetate 8.187 9.244 10.42 11.71 13.16 14.76 16.54 18.53 0.6906 F

102x1NRTL

102x1Wilson

6.678 7.954 9.679 11.78 0.6890 5.677 × 10−4

6.674 7.949 9.678 11.78 0.6562 5.531 × 10−4

6.752 8.246 9.837 11.63 13.64 16.38 19.42 23.37 1.903 2.420 × 10−3

6.709 8.232 9.846 11.66 13.68 16.42 19.43 23.29 1.919 2.630 × 10−3

4.176 4.964 6.398 8.795 11.83 15.21 19.86 25.34 2.026 1.963 × 10−3

3.839 4.687 6.329 8.999 12.17 15.55 19.92 24.86 1.834 2.086 × 10−3

10.68 11.91 13.24 14.69 16.27 17.98 19.85 21.91 1.068 2.080 × 10−3

10.49 11.77 13.15 14.65 16.29 18.04 19.96 22.06 1.520 2.552 × 10−3

6.411 7.173 8.006 8.913 9.902 10.97 12.17 13.45 0.7101 1.159 × 10−3

5.950 6.785 7.716 8.733 9.853 11.06 12.48 13.96 3.569 3.448 × 10−3

8.158 9.234 10.41 11.72 13.17 14.76 16.56 18.51 0.7723

8.022 9.138 10.36 11.70 13.19 14.81 16.63 18.58 1.032 DOI: 10.1021/acs.jced.7b01085 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


Article


102x1exp

8.085 × 10−4

RMSDc 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

1.589 2.040 2.635 3.051 4.094 5.229 6.384 7.793

102x1λh

102x1Apel

1.595 2.024 2.561 3.228 4.056 5.080 6.342 7.894 1.945 9.568 × 10−4

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

48.92 50.06 51.40 52.68 54.09 55.43 57.09 58.92

48.95 50.09 51.32 52.64 54.06 55.56 57.15 58.83 0.1103 6.957 × 10−4

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 ARD%c RMSDc

55.02 56.15 57.09 58.24 59.41 60.58 61.86 62.90

55.03 56.08 57.16 58.27 59.41 60.57 61.76 62.97 0.07942 5.826 × 10−4

Propyl Acetate 9.665 × 10−4 1,2-Dichloroethane 1.564 2.014 2.572 3.258 4.096 5.117 6.351 7.838 1.915 8.953 × 10−4 N,N-Dimethylformamide 48.94 50.10 51.33 52.65 54.05 55.54 57.14 58.85 0.1008 6.234 × 10−4 N,N-Dimethylacetamide 55.22 56.12 57.08 58.13 59.25 60.47 61.78 63.20 0.2106 1.534 × 10−3

102x1NRTL

102x1Wilson

1.004 × 10−3

1.387 × 10−3

1.708 2.107 2.615 3.149 4.008 5.065 6.316 7.920 2.843 10.26 × 10−3

1.667 2.077 2.600 3.150 4.026 5.091 6.336 7.904 2.223 8.432 × 10−4

47.25 49.30 50.86 52.81 54.54 56.71 58.21 59.59 1.563 9.527 × 10−3

44.74 47.43 49.82 52.46 54.95 57.72 59.97 62.06 4.175 2.529 × 10−3

50.92 52.92 55.68 57.89 60.14 62.56 64.78 67.88 4.175 2.897 × 10−2

48.32 51.10 54.38 57.33 60.31 63.39 66.32 69.88 6.491 4.415 × 10−2

a

Standard uncertainties are u(T) = 0.05 K and u(p) = 0.3 kPa. Relative standard uncertainty is ur(x1) = 0.05. bxexp represents experimental solubility data, and xApel, xλh, xNRTL, and xWilson represent the calculated solubility of BTA by the modified Apelblat equation, λh equation, NRTL model, and Wilson model, respectively. cARD% and RMSD are the average relative deviation and root-mean-square deviations, respectively, they are calculated by eqs 28 and 29.

Figure 4. Solubility data of BTA in seven pure solvents: (▶) N,Ndimethylacetamide; (●) methanol; (△) isopropyl alcohol; (■) acetone; (⬡) dichloromethane; (◀) methyl acetate; (▽) acetonitrile. The curves are the correlation results based on the modified Apelblat equation.

Figure 5. Solubility data of BTA in seven pure solvents: (□) N,Ndimethylformamide; (★) sec-butanol; (⬢) ethanol; (⬟) ethyl acetate; (◁) propyl acetate; (☆) ethyl formate; (○) 1,2-dichloroethane. The curves are the correlation results based on the modified Apelblat equation. G



Article

Table 4. continued

Dissolution Thermodynamic Properties. The dissolution thermodynamic data of BTA were calculated by using experimental solubility data and the NRTL model. The results are given in Table 4. It can be seen that the values of the

T/K 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

Table 4. Dissolution Thermodynamic Properties of BTA in 14 Pure Solventsa,b T/K 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

ΔdisG (kJ/mol)

ΔdisH (kJ/mol)

Acetone 3.088 3.373 3.750 4.009 4.481 4.774 5.305 5.764 Methanol −0.5893 4.308 −0.6453 4.632 −0.7092 4.878 −0.7667 5.280 −0.8291 5.647 −0.8916 6.044 −0.9522 6.477 −1.001 7.025 Ethanol −0.4760 4.116 −0.5260 4.390 −0.5791 4.675 −0.6316 5.048 −0.6852 5.460 −0.7386 5.913 −0.7930 6.374 −0.8585 6.729 Isopropyl Alcohol −0.5332 4.464 −0.5831 4.765 −0.6392 5.013 −0.6937 5.359 −0.7529 5.678 −0.7986 6.223 −0.8712 6.453 −0.9257 6.930 sec-Butanol −0.5718 4.957 −0.6246 5.195 −0.6825 5.406 −0.7400 5.688 −0.7984 6.004 −0.8512 6.438 −0.9210 6.687 −0.9726 7.178 Acetonitrile −0.06381 0.3757 −0.07669 0.4479 −0.09180 0.5553 −0.1094 0.6614 −0.1299 0.8034 −0.1538 0.9419 −0.1805 1.177 −0.2115 1.456 −0.3684 −0.4151 −0.4627 −0.5192 −0.5704 −0.6343 −0.6892 −0.7509

ΔdisS ( J·K−1·mol−1) 12.89 13.87 15.15 15.99 17.53 18.45 20.11 21.49

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

18.26 19.32 20.09 21.36 22.48 23.66 24.92 26.47

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

17.13 18.00 18.89 20.06 21.33 22.69 24.04 25.03

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

18.64 19.58 20.32 21.38 22.32 23.95 24.57 25.91

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

20.62 21.31 21.89 22.70 23.61 24.86 25.52 26.89

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

1.639 1.921 2.327 2.722 3.239 3.738 4.553 5.499

268.15 273.15 278.15 283.15 288.15 293.15 H

ΔdisG (kJ/mol)

ΔdisH (kJ/mol)

Ethyl Acetate 0.9201 1.199 1.427 1.656 1.887 2.322 2.758 3.432 Dichloromethane −0.07062 0.5917 −0.0853 0.6610 −0.1030 0.8919 −0.1229 1.324 −0.1468 1.831 −0.1782 2.337 −0.2152 3.081 −0.2583 3.991 Methyl Acetate −0.2288 1.881 −0.2584 2.036 −0.2900 2.245 −0.3245 2.451 −0.3609 2.708 −0.4011 2.947 −0.4425 3.252 −0.4834 3.650 Ethyl Formate −0.1387 1.090 −0.1571 1.212 −0.1771 1.359 −0.1994 1.496 −0.2236 1.641 −0.2505 1.764 −0.2777 2.015 −0.3085 2.193 Propyl Acetate −0.1727 1.312 −0.1969 1.486 −0.2245 1.632 −0.2544 1.827 −0.2867 2.050 −0.3224 2.271 −0.3593 2.580 −0.4008 2.852 1,2-Dichloroethane −0.03397 0.1781 −0.04156 0.2303 −0.05020 0.3000 −0.06067 0.3489 −0.07305 0.4758 −0.08765 0.6176 −0.1054 0.7650 −0.1274 0.9496 N,N-Dimethylformamide −5.846 15.65 −5.811 15.61 −5.755 15.57 −5.710 15.54 −5.650 15.50 −5.603 15.47 −0.1266 −0.1487 −0.1752 −0.2062 −0.2421 −0.2799 −0.3233 −0.3662

ΔdisS ( J·K−1·mol−1) 3.903 4.935 5.760 6.576 7.389 8.874 10.33 12.53 2.470 2.732 3.577 5.109 6.865 8.580 11.06 14.02 7.867 8.399 9.114 9.801 10.65 11.42 12.39 13.63 4.581 5.012 5.524 5.987 6.471 6.872 7.688 8.253 5.537 6.160 6.674 7.350 8.111 8.848 9.858 10.73 0.7908 0.9954 1.259 1.446 1.905 2.406 2.920 3.553 80.18 78.43 76.67 75.03 73.41 71.89



Article


ORCID

ΔdisG (kJ/mol)

298.15 303.15

−5.515 −5.407

268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

−5.047 −5.034 −5.047 −5.036 −5.024 −5.013 −4.989 −4.996

ΔdisH (kJ/mol)

N,N-Dimethylformamide 15.44 15.42 N,N-Dimethylacetamide 15.47 15.47 15.47 15.48 15.48 15.49 15.50 15.51

−1

Hongxun Hao: 0000-0001-6445-7737

−1

ΔdisS ( J·K ·mol )

Notes

The authors declare no competing financial interest.

70.30 68.69

Funding

This research is financially supported by National Natural Science Foundation of China (No. 21406049) and Major National Scientific Instrument Development Project (No.21527812).

76.51 75.08 73.77 72.45 71.17 69.95 68.73 67.63

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(1) Al-Hinai, A. T.; Osseo-Asare, K. Corrosion of Copper in BTA Solutions-Effects of Passive Film Removal. Electrochem. Solid-State Lett. 2003, 6, B23−B24. (2) Oddy, W. A.; et al. Corrosion and Metal Artifacts: A Dialogue between Conservators and Archaeologists and Corrosion Scientists by B. Floyd Brown. Stud. Conserv. 1978, 23, 187. (3) Sease, C. Benzotriazole: A Review for Conservators. Stud. Conserv. 1978, 23, 76−85. (4) Xu, R. L.; Hou, B. H.; Wang, N.; Lou, Y. J.; Li, Y.; Huang, J. J.; Hao, H. H. Thermodynamic Properties of Disodium Sebacate in Different Binary Solvent Mixtures. J. Mol. Liq. 2018, 252, 194−202. (5) Huang, X.; Wang, J. K.; Hao, H. X.; Ouyang, J. B.; Gao, Y.; Bao, Y.; Wang, Y. L.; Yin, Q. X. Determination and Correlation of Solubility and Solution Thermodynamics of Coumarin in Different Pure Solvents. Fluid Phase Equilib. 2015, 394, 148−155. (6) Guo, Y. M.; Hao, Y. H.; Zhou, Y. N.; Han, Z. Y.; Xie, C.; Su, W. Y.; Hao, H. X. Solubility and Thermodynamic Properties of Vanillyl Alcohol in Some Pure Solvents. J. Chem. Thermodyn. 2017, 106, 276− 284. (7) Wu, H.; Wang, J. K.; Zhou, Y. N.; Guo, N. N.; Liu, Q.; Zong, S. Y.; Bao, Y.; Hao, H. X. Solid−Liquid Phase Equilibrium and Dissolution Properties of Ethyl Vanillin in Pure Solvents. J. Chem. Thermodyn. 2017, 105, 345−351. (8) Mahé, N.; Nicolaï, B.; Barrio, M.; Perrin, M. A.; Do, B.; Tamarit, J. L.; Céolin, R.; Rietveld, I. B. Solid-State Properties and Dehydration Behavior of the Active Pharmaceutical Ingredient Potassium Guaiacol4-sulfonate. Cryst. Growth Des. 2013, 13, 3028−3035. (9) Gonçalves, E. M.; da Piedade, M. E. M.; et al. Solubility of Nicotinic Acid in Water, Ethanol, Acetone, Diethyl Ether, Acetonitrile, and Dimethyl Sulfoxide. J. Chem. Thermodyn. 2012, 47, 362−371. (10) Apelblat, A.; Manzurola, E. Solubilities of O-Acetylsalicylic, 4Aminosalicylic, 3, 5-Dinitrosalicylic, and P-Toluic Acid, and Magnesium-DL-Aspartate in Water from T = (278 to 348) K. J. Chem. Thermodyn. 1999, 31, 85−91. (11) Buchowski, H.; Ksiazczak, A.; Pietrzyk, S. Solvent Activity along A Saturation Line and Solubility of Hydrogen-Bonding Solids. J. Phys. Chem. 1980, 84, 975−979. (12) Chen, J.; Zeng, Z. X.; Xue, W. L.; Wang, D.; Huang, Y. Determination and Correlation of Solubility of Decahydropyrazino[2, 3-b]pyrazine in Methanol, Ethanol, and 2-Propanol. Ind. Eng. Chem. Res. 2011, 50, 11755−11762. (13) Renon, H.; Prausnitz, J. M. Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures. AIChE J. 1968, 14, 135−144. (14) Wei, D.; Pei, Y. Measurement and Correlation of Solubility of Diphenyl Carbonate in Alkanols. Ind. Eng. Chem. Res. 2008, 47, 8953− 8956. (15) Wilson, G. M. Vapor-Lliquid Equilibrium. XI. A New Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc. 1964, 86, 127−130. (16) Jiménez, P.; Roux, M. V.; Turrión, C. Thermochemical Properties of N-Heterocyclic Compounds II. Enthalpies of Combustion, Vapour Pressures, Enthalpies of Sublimation, and Enthalpies of Formation of 1, 2, 4-Triazole and Benzotriazole. J. Chem. Thermodyn. 1989, 21, 759−764.

The values ofΔdisG, ΔdisH, and ΔdisS are calculated by eqs 13−28. The combined expanded uncertainties U are Uc(ΔHd) = 0.060ΔHd, Uc(ΔSd) = 0.065ΔSd, and Uc(ΔGd) = 0.065ΔGd (0.95 level of confidence). a b

dissolution Gibbs energy (ΔdisG) of BTA in 14 solvents are all negative, which indicates that the dissolution of BTA in all selected solvents is spontaneous. The values of the dissolution enthalpy (ΔdisH) are all positive, which shows that the dissolution process is endothermic. In addition, the values of ΔdisH increase with increasing temperature, which is consistent with the solubility upward trend shown in Figures 4 and 5. Because the values of the dissolution entropy (ΔdisS) are all positive as displayed in Table 4, the dissolution process of BTA should be entropy driven in all selected solvents.

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CONCLUSIONS The solubility data of BTA in 14 pure solvents were determined from T = 268.15 to 303.15 K by using a static gravimetric method. The solubility data of BTA increase with increasing temperature in all selected solvents. The solubility data of BTA in different solvents are in the order N,N-dimethylformamide > N,N-dimethylacetamide > sec-butanol > isopropyl alcohol > ethanol > acetone > methyl acetate > propyl acetate > ethyl formate > acetonitrile > 1,2-dichloroethane. Moreover, the solubility of BTA in dichloromethane increases faster with temperature than in other solvents. The Apelblat equation, λh equation, NRTL model, and Wilson model were used to correlate the solubility data. The values of ARD% and RMSD show that the four models can give good correlation results for all selected solvents. Finally, the dissolution Gibbs energy, enthalpy, and entropy in the selected solvents were determined by using experimental solubility data and the NRTL model. The results show that the dissolution process of BTA in the selected solvents is spontaneous, endothermic, and entropy driven.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.7b01085. Parameters and deviations of the Apelblat equation, the λh equation, the NRTL model, and the Wilson model (PDF)

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REFERENCES

AUTHOR INFORMATION

Corresponding Author

*H. Hao. E-mail: [email protected]. I



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