Vapor-liquid equilibrium simulation for crotonaldehyde and its mixture with ethanal

doi:10.11949/j.issn.0438-1157.20141624

Abstract

Abstract: Gibbs ensemble Monte Carlo method with TraPPE-UA force field was used to study the vapor-liquid phase equilibrium of systems containing crotonaldehyde. To lay the foundation for the vapor-liquid phase equilibrium simulation, quantum chemistry calculations with B3LYP 6-311G (d, p) and MP2 6-31G (d, p) basis sets were firstly performed to obtain the lacking bond parameters and torsional parameters for crotonaldehyde molecular. Based on these parameters, a new TraPPE-UA force field was developed. Vapor-liquid phase equilibrium data of pure crotonaldehyde and its mixture with ethanal were calculated using the new force field and compared with experiment data. The saturated liquid densities of pure crotonaldehyde predicted by the new force field were in close agreement with experimental results, with deviations from 0.28% to 1.23%. This demonstrated that the new TraPPE-UA force field manifested high simulation precision for crotonaldehyde. For the binary system consisting of crotonaldehyde and ethanal, the deviation between simulations and experiments increased with rising temperature, and the minimum and maximum values were 0.13% and 7.44%, respectively.

Key words: crotonaldehyde, Gibbs ensemble Monte Carlo, phase equilibria, force field, computer simulation, statistical thermodynamics

摘要： 采用Gibbs系综Monte Carlo方法,对TraPPE-UA力场中缺失的烯醛类力场参数进行了补充和验证,为模拟含烯醛体系汽液相平衡奠定基础。分别使用B3LYP 6-311G (d, p)和MP2 6-31G (d, p)方法计算了丁烯醛分子中缺失的键参数、二面角扭转项参数。采用构建的丁烯醛分子的TraPPE-UA力场参数,分别计算了丁烯醛纯组分、丁烯醛与乙醛二元体系的汽液相平衡数据,并将模拟结果与实验值进行比较。丁烯醛纯物质模拟结果与实验数据相比液相密度偏差为0.28%～1.23%,模拟结果表明构建的TraPPE-UA力场对丁烯醛分子具有较高的模拟精度。丁烯醛与乙醛二元体系的模拟结果与实验数据相比最小误差为0.13%,但随着温度上升有增大趋势,最大误差为7.44%。

关键词: 丁烯醛, Gibbs系综Monte Carlo, 相平衡, 力场, 计算机模拟, 统计热力学

CLC Number:

O642.4⁺2

YANG Huaming, ZHANG Minhua, MA Jing. Vapor-liquid equilibrium simulation for crotonaldehyde and its mixture with ethanal[J]. CIESC Journal, 2015, 66(5): 1627-1632.

杨华明, 张敏华, 马静. 丁烯醛及丁烯醛-乙醛二元体系汽液相平衡模拟[J]. 化工学报, 2015, 66(5): 1627-1632.

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