In this paper, the solubility of 2,4,6-trinitro-3-bromoanisole (TNBA) in methanol, ethanol, n-propanol, n-butanol, dichloroethane, cyclohexane, ethyl acetate, acetonitrile, acetone, benzene, methylbenzene and water over the temperature range of 283.15–323.15 K has been determined for the first time by gravimetric method. In the experimental temperature range, the order of average solubility of TNBA in twelve pure solvents is as follows: acetone (23.1736 × 10–2) > benzene (16.3735 × 10–2) > acetonitrile (16.3586 × 10–2) > ethyl acetate (16.0661 × 10–2) > methylbenzene (14.4027 × 10–2) > dichloroethane (11.1222 × 10–2) > methanol (0.8543 × 10–2) > ethanol (0.6077 × 10–2) > n-propanol (0.4664 × 10–2) > n-butanol (0.4646 × 10–2) > cyclohexane (0.0693 × 10–2) > water (0.0186 × 10–2). The solubility of TNBA in twelve pure solvents was correlated using the modified Apelblat equation, λh equation, van't Hoff model and Jouyban–Acree model, and the predictive accuracy of the four groups of models was evaluated by the R2, ARD, and RMSD criteria, and the comparison revealed that Jouyban–Acree model had a better match with the experimental data with the highest accuracy. Additionally, the thermodynamic parameters of TNBA solubility in twelve pure solvents were calculated. The enthalpy of dissolution <InlineEquation ID="IEq1"> <EquationSource Format="TEX">$(\Delta{H}^\circ_\text{sol})$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mo stretchy="false">(</mo> <mi mathvariant="normal">Δ</mi> <msubsup> <mrow> <mi>H</mi> </mrow> <mtext>sol</mtext> <mo>∘</mo> </msubsup> <mo stretchy="false">)</mo> </mrow> </math></EquationSource> </InlineEquation>, entropy of dissolution <InlineEquation ID="IEq2"> <EquationSource Format="TEX">$(\Delta{S}^\circ_\text{sol})$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mo stretchy="false">(</mo> <mi mathvariant="normal">Δ</mi> <msubsup> <mrow> <mi>S</mi> </mrow> <mtext>sol</mtext> <mo>∘</mo> </msubsup> <mo stretchy="false">)</mo> </mrow> </math></EquationSource> </InlineEquation>, and Gibbs free energy of dissolution <InlineEquation ID="IEq3"> <EquationSource Format="TEX">$(\Delta{G}^\circ_\text{sol})$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mo stretchy="false">(</mo> <mi mathvariant="normal">Δ</mi> <msubsup> <mrow> <mi>G</mi> </mrow> <mtext>sol</mtext> <mo>∘</mo> </msubsup> <mo stretchy="false">)</mo> </mrow> </math></EquationSource> </InlineEquation> at mean temperature in different pure solvents reached 17.14–77.98 kJ·mol−1, − 12.51 to − 78.27 J·mol⁻1·K⁻1 and 20.93–101.66 kJ·mol⁻1, respectively. The results demonstrate that the dissolution behavior of TNBA in the selected solvents is an endothermic and non-spontaneous process.

Solid–Liquid Equilibrium Solubility and Thermodynamic Properties of 2,4,6-Trinitro-3-Bromoanisole in Different Pure Solvents

期刊论文
发表日期：

2025年10月6日

查看全文

Yongzheng Liu,
Yuqi Wu,
Zhike Tong,
Congying Li,
Xinyue Hu,
Xiaolan Song,
Fanfan Shen,
Duanlin Cao,
Linxiu Zhao

摘要

In this paper, the solubility of 2,4,6-trinitro-3-bromoanisole (TNBA) in methanol, ethanol, n-propanol, n-butanol, dichloroethane, cyclohexane, ethyl acetate, acetonitrile, acetone, benzene, methylbenzene and water over the temperature range of 283.15–323.15 K has been determined for the first time by gravimetric method. In the experimental temperature range, the order of average solubility of TNBA in twelve pure solvents is as follows: acetone (23.1736 × 10^–2) > benzene (16.3735 × 10^–2) > acetonitrile (16.3586 × 10^–2) > ethyl acetate (16.0661 × 10^–2) > methylbenzene (14.4027 × 10^–2) > dichloroethane (11.1222 × 10^–2) > methanol (0.8543 × 10^–2) > ethanol (0.6077 × 10^–2) > n-propanol (0.4664 × 10^–2) > n-butanol (0.4646 × 10^–2) > cyclohexane (0.0693 × 10^–2) > water (0.0186 × 10^–2). The solubility of TNBA in twelve pure solvents was correlated using the modified Apelblat equation, λh equation, van't Hoff model and Jouyban–Acree model, and the predictive accuracy of the four groups of models was evaluated by the R², ARD, and RMSD criteria, and the comparison revealed that Jouyban–Acree model had a better match with the experimental data with the highest accuracy. Additionally, the thermodynamic parameters of TNBA solubility in twelve pure solvents were calculated. The enthalpy of dissolution $(\Delta{H}^\circ_\text{sol})$ $(Δ H_{sol}^{\circ})$ , entropy of dissolution $(\Delta{S}^\circ_\text{sol})$ $(Δ S_{sol}^{\circ})$ , and Gibbs free energy of dissolution $(\Delta{G}^\circ_\text{sol})$ $(Δ G_{sol}^{\circ})$ at mean temperature in different pure solvents reached 17.14–77.98 kJ·mol⁻¹, − 12.51 to − 78.27 J·mol⁻¹·K⁻¹ and 20.93–101.66 kJ·mol⁻¹, respectively. The results demonstrate that the dissolution behavior of TNBA in the selected solvents is an endothermic and non-spontaneous process.