Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Determination of Solubility and Thermodynamic Properties of Benzophenone in Different Pure Solvents Jinbo Ouyang,*,†,‡ Bing Na,†,‡ Guoxuan Xiong,‡ Li Xu,‡ and Tianxiang Jin†,‡ †
Jiangxi Province Key Laboratory of Polymer Micro/Nano Manufacturing and Devices, East China University of Technology, Nanchang 330013, P. R. China ‡ School of Chemistry, Biology, and Materials Science, East China University of Technology, Nanchang 330013, P. R. China ABSTRACT: The solubility of benzophenone in various pure solvents, including water, ethanol, 1-propanol, isopropanol, methanol, 1-butanol, isobutanol, 1-octanol, acetonitrile, acetone, ethyl acetate, and methyl acetate, has been measured at temperatures between 278.15 and 318.15 K by a gravimetric method under atmospheric pressure. The solubility obtained in the selected pure solvents increases with the increasing temperature. Several thermodynamic models, including the modified Apelblat model, NRTL model, and Wilson model, were applied to correlate the measured solubility. It was found that the correlated results of the three models were in good agreement with the experimental results. In addition, the dissolution thermodynamic properties of benzophenone in the pure solvents were determined.
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INTRODUCTION The crystallization process is an important chemical purification method, with which one can separate the target component from the solution and obtain a high purity for it. This method is widely used to prepare a variety of products, including pharmaceuticals, spices, fine chemicals, etc.1 Solubility and dissolution thermodynamics are both important parameters for the design and operation of crystallization. In order to obtain the product with a high purity and high production, it is necessary to determine the solubility and dissolution thermodynamics properties.2−6 As an important organic intermediate, benzophenone (C13H10O, 182.2 g/mol, CAS: 119-61-9, Figure 1) is widely used in the
isobutanol, 1-octanol, acetonitrile, acetone, ethyl acetate, and methyl acetate has been measured at temperatures between 278.15 and 318.15 K by a gravimetric method under atmospheric pressure.10 The experimental data in pure solvents were correlated with the modified Apelblat equation11 and two local composition models (Wilson12 and NRTL models13). Differential scanning calorimetry (DSC) was used to determine the melting point and the enthalpy of fusion of benzophenone. In addition, X-ray powder diffraction (XRPD) was applied to characterize the benzophenone samples in all of the experiments and to make sure that the sample polymorph of benzophenone was used. Dissolution Gibbs energy, dissolution enthalpy, and dissolution entropy were determined to understand the dissolution behavior of benzophenone in pure solvents.
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EXPERIMENTAL SECTION Chemicals. Benzophenone with a mass fraction purity higher than 0.99 was purchased from Aladdin (China). All of the solvents of the analytic reagent used in the experiments, including methanol, ethanol, 1-propanol, acetone, isopropanol, 1-butanol isobutanol, 1-octanol, acetonitrile, ethyl acetate, and methyl acetate, were purchased from Tianjin Kewei Chemical Reagent Co. Ltd. of China. The distilled−deionized water with conductivities acetonitrile > ethyl acetate > methyl acetate > 1-octanol > isobutanol > 1-butanol > 1-propanol > isopropanol > ethanol > methanol > water. Therefore, acetone was used as a good solvent during the crystallization of benzophenone, while water was used as the antisolvent. Thermodynamic Modeling. The modified Apelblat equation, the Wilson model, and NRTL model were applied to correlate the experimental solubility of benzophenone in different pure solvents to extend the application of the measured solubility, and the correlated results are given in Table 2. The average absolute deviation (AAD) was applied to evaluate the correlation results, and the AAD is defined as follows.4
were applied to correlate the measured solubility. It was found that the correlated results of the three models were in good agreement with the experimental results. Furthermore, the dissolution enthalpy, dissolution Gibbs energy, and dissolution entropy of benzophenone in pure solvents were calculated, and the results revealed that the dissolution of the benzophenone in the selected pure solvents was endothermic and spontaneous.
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Corresponding Author
*Tel: +86-0791-83896550; E-mail:
[email protected]. ORCID
Jinbo Ouyang: 0000-0002-8139-3648 Funding
The authors are grateful for the financial support from the National Natural Science Foundation of China (21706028), Natural Science Foundation of Jiangxi Province 20171BAB213016), Science and Technology Research Project of Jiangxi Provincial Education Department (GJJ160578), and Doctoral Initial Funding of East China University of Technology (DHBK2016111). Notes
The authors declare no competing financial interest.
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N
AAD =
x − x cal 1 ∑ i i N i=1 xi
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REFERENCES
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where N is the number of experimental points in each solvent, and xi and xcal i stand for the measured solubility and the calculated solubility, respectively. The results of AAD are given in Table 3. The AAD data listed in Table 3 show that their values calculated by different models are lower than 10%, which means that the correlated results of the modified Apelblat equation, Wilson model, and NRTL model have a good agreement with these measured solubilities. For pictorial comparison, the experimental solubility data in the pure solvents and the correlated solubility data by the modified Apelblat equation are depicted in Figure 4. Dissolution Thermodynamics. The Wilson model was applied to calculate the dissolution enthalpy △disH, dissolution Gibbs energy △disG, and dissolution entropy △disS, and the calculated values are shown in Table 4. According to the negative values of △disG, it can be concluded that the dissolution process is spontaneous. Furthermore, the absolute values of △disG increase with the increasing temperature, which shows that the dissolution process is temperature favorable. Meanwhile, the values of △disH are all positive, which reveals that the dissolution of benzophenone in the selected pure solvents is endothermic. This phenomenon can be explained by the temperature-dependent solubility of benzophenone. Furthermore, the values of △disS are all positive, which illustrates the dissolution process of benzophenone in these solvent systems is entropydriven.
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CONCLUSIONS The solubility of benzophenone in 12 pure solvents at temperature between 278.15 and 318.15 K was successfully measured by a gravimetric method. The results indicate that the solubility of benzophenone increases with increasing temperature. The modified Apelblat model, NRTL model, and Wilson model G
DOI: 10.1021/acs.jced.8b00196 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.jced.8b00196 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
