Molecular dynamics simulation and mechanism study on thermal conductivity of alcohols

LIU Wanqiang; YANG Fan; YUAN Hua; ZHANG Yuanda; YI Pinggui; ZHOU Hu

doi:10.11949/0438-1157.20200252

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Molecular dynamics simulation and mechanism study on thermal conductivity of alcohols

Fluid dynamics and transport phenomena | 更新时间：2026-07-24

- Molecular dynamics simulation and mechanism study on thermal conductivity of alcohols
- CIESC Journal Vol. 71, Issue 11, Pages: 5159-5168(2020)
- 作者机构：
  
  湖南科技大学化学化工学院，理论有机化学与功能分子教育部重点实验室，湖南省高校QSAR/QSPR重点实验室，功能膜材料湖南省工程研究中心，湖南湘潭 411201
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200252
  CLC： O 639
- Received：12 March 2020，
  
  Revised：2020-06-08，
  
  Online First：03 November 2020，
  
  Published：05 November 2020
- 稿件说明：
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刘万强, 杨帆, 袁华, 张远达, 易平贵, 周虎. 醇类有机物热传导的分子动力学模拟及微观机理研究[J]. 化工学报, 2020, 71(11): 5159-5168

LIU Wanqiang, YANG Fan, YUAN Hua, ZHANG Yuanda, YI Pinggui, ZHOU Hu. Molecular dynamics simulation and mechanism study on thermal conductivity of alcohols[J]. CIESC Journal, 2020, 71(11): 5159-5168
刘万强, 杨帆, 袁华, 张远达, 易平贵, 周虎. 醇类有机物热传导的分子动力学模拟及微观机理研究[J]. 化工学报, 2020, 71(11): 5159-5168 DOI： 10.11949/0438-1157.20200252.

LIU Wanqiang, YANG Fan, YUAN Hua, ZHANG Yuanda, YI Pinggui, ZHOU Hu. Molecular dynamics simulation and mechanism study on thermal conductivity of alcohols[J]. CIESC Journal, 2020, 71(11): 5159-5168 DOI： 10.11949/0438-1157.20200252.

摘要

传热是化工生产的基本问题之一，热导率是化工产品生产工艺设计中一类重要的热力学数据。通过非平衡分子动力学方法模拟了8种液态醇类有机物在不同温度下的导热过程。热导率计算值与实验值的平均相对偏差为3.77%。通过对热流的分解发现，分子动能、分子间库仑相互作用和分子内的二面角对醇类有机物的热传导影响较大。同时随着分子链增长，通过分子内相互作用进行的热传导逐渐占主导作用，表明醇类有机物的热能传输机理与分子结构有显著关系。此外，随着温度的升高，通过分子的动能、分子间库仑作用和分子内键角、键伸缩作用项传输的热流增大，表明温度对液态醇类有机物的热传导也有一定影响。本工作从微观分子间和分子内作用分析了液态醇类有机物结构和温度对热导率的影响，为液态有机物的热传导研究提供了微观依据。

Abstract

Heat transfer is one of the basic issues in chemical production

and thermal conductivity is an important thermodynamic data in the design of chemical product production processes. In this paper

nonequilibrium molecular dynamics methods are used to simulate the heat transfer of liquid alcohols at four different temperatures

and the thermal conductivity of the corresponding conditions is obtained. The average relative deviation between the calculated value and the experimental value was 3.77%. Through the decomposition of heat flux

it was found that molecular kinetic energy

Coulomb interaction and intramolecular dihedral angle contribute the most to the heat conduction of alcohols. At the same time

as the molecular volume increases

the thermal conduction pathway of the intramolecular interaction term gradually dominates

indicating that the thermal conduction mechanism of alcohols has a significant relationship with the molecular structure. In addition

as the temperature elevates

the heat flux transmitted through the molecular kinetic energy

intermolecular Coulomb interaction

and the intramolecular angle bending and bond stretching term increases

while the heat flux transmitted through the molecular potential energy decreases significantly. This work provides a microscopic explanation for the effects of the structure and temperature of liquid alcohols on thermal conductivity

and provides a micro foundation for the study of heat conduction of liquid alcohols.

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Keywords

references

Vargaftik N B . Handbook of Thermal Conductivity of Liquids and Gases [M ] . Boca Raton FL : CRC press , 1994 .

Algaer E A , Müller-Plathe F . Molecular dynamics calculations of the thermal conductivity of molecular liquids, polymers, and carbon nanotubes [J ] . Soft Materials , 2012 , 10 ( 1/2/3 ): 42 - 80 .

Bao H , Chen J , Gu X , et al . A review of simulation methods in micro/nanoscale heat conduction [J ] . ES Energy & Environment , 2018 , 1 : 16 - 55 .

Assael M J , Antoniadis K D , Wakeham W A . Historical evolution of the transient hot-wire technique [J ] . International Journal of Thermophysics , 2010 , 31 ( 6 ): 1051 - 1072 .

Nagvekar M , Daubert T E . A group contribution method for liquid thermal conductivity [J ] . Industrial & Engineering Chemistry Research , 1987 , 26 ( 7 ): 1362 - 1365 .

Rodenbush C M , Viswanath D S , Hsieh F . A group contribution method for the prediction of thermal conductivity of liquids and its application to the prandtl number for vegetable oils [J ] . Industrial & Engineering Chemistry Research , 1999 , 38 ( 11 ): 4513 - 4519 .

Tsotsas E , Schluender E U . Numerical calculation of the thermal conductivity of two regular bidispersed beds of spherical particles [J ] . Computers & Chemical Engineering , 1990 , 14 ( 9 ): 1031 - 1038 .

Liu W , Lu H , Cao C , et al . An improved quantitative structure property relationship model for predicting thermal conductivity of liquid aliphatic alcohols [J ] . Journal of Chemical and Engineering Data , 2018 , 63 ( 12 ): 4735 - 4740 .

Lu H , Yang F , Liu W , et al . A robust model for estimating thermal conductivity of liquid alkyl halides [J ] . SAR and QSAR in Environmental Research , 2020 , 31 ( 2 ): 73 - 85 .

Ohara T . Contribution of intermolecular energy transfer to heat conduction in a simple liquid [J ] . Journal of Chemical Physics , 1999 , 111 ( 21 ): 9667 - 9672 .

Ohara T . Intermolecular energy transfer in liquid water and its contribution to heat conduction: a molecular dynamics study [J ] . Journal of Chemical Physics , 1999 , 111 ( 14 ): 6492 - 6500 .

Zhang M , Lussetti E , de Souza L E S , et al . Thermal conductivities of molecular liquids by reverse nonequilibrium molecular dynamics [J ] . Journal of Physical Chemistry B , 2005 , 109 ( 31 ): 15060 - 15067 .

李嘉辰 , 俞斌 , 王琦 , 等 . 分子模拟研究壳聚糖-氮化硼纳米管封装及输运阿霉素 [J ] . 化工学报 , 2020 , 71 ( 1 ): 354 - 360 .

Li J C , Yu B , Wang Q , et al . Molecular simulation on doxorubicin encapsulation and transport by chitosan-boron nitride nanotubes [J ] . CIESC Journal , 2020 , 71 ( 1 ): 354 - 360 .

王韬 , 刘向阳 , 何茂刚 . 离子液体 [bmim ] [Tf 2 N ]的分子动力学模拟 [J ] . 化工学报 , 2019 , 70 : 258 - 264 .

Wang T , Liu X Y , He M G . Molecular dynamics simulation of ionic liquid [bmim ] [Tf 2 N ] [J ] . CIESC Journal , 2019 , 70 : 258 - 264 .

杨慧芳 , 关海莲 , 李平 , 等 . 煤颗粒燃烧过程氧化机理及有机氮转化的分子模拟: 以宁东红石湾煤为例 [J ] . 化工学报 , 2020 , 71 ( 2 ): 799 - 810 .

Yang H F , Guan H L , Li P , et al . Molecular modeling of oxidation mechanism and organic nitrogen conversion in coal particle combustion: a case study on HSW coal of Ningdong [J ] . CIESC Journal , 2020 , 71 ( 2 ): 799 - 810 .

张博 , 何依然 , 刘迎春 , 等 . 异喹啉类生物碱和G-四链体结合的分子动力学研究 [J ] . 化工学报 , 2020 , 71 ( 1 ): 344 - 353 .

Zhang B , He Y R , Liu Y C , et al . Molecular dynamics study of binding of isoquinoline alkaloids to G-quadruplex [J ] . CIESC Journal , 2020 , 71 ( 1 ): 344 - 353 .

邹瀚影 , 冯妍卉 , 邱琳 , 等 . 十八烷酸热传导机制的尺度效应研究 [J ] . 化工学报 , 2019 , 70 : 155 - 160 .

Zou H Y , Feng Y H , Qiu L , et al . Size effect of heat conduction mechanism on stearic acid [J ] . CIESC Journal , 2019 , 70 : 155 - 160 .

Matsubara H , Kikugawa G , Bessho T , et al . Understanding the chain length dependence of thermal conductivity of liquid alcohols at 298 K on the basis of molecular-scale energy transfer [J ] . Fluid Phase Equilibria , 2017 , 441 : 24 - 32 .

Guevara-Carrion G , Nieto-Draghi C , Vrabec J , et al . Prediction of transport properties by molecular simulation: methanol and ethanol and their mixture [J ] . Journal of Physical Chemistry B , 2008 , 112 ( 51 ): 16664 - 16674 .

Petravic J . Thermal conductivity of ethanol [J ] . Journal of Chemical Physics , 2005 , 123 : 174503 .

Lin Y , Hsiao P , Chieng C . Constructing a force interaction model for thermal conductivity computation using molecular dynamics simulation: ethylene glycol as an example [J ] . Journal of Chemical Physics , 2011 , 134 ( 15 ): 154509 .

Fan Z , Pereira L F C , Wang H , et al . Force and heat current formulas for many-body potentials in molecular dynamics simulations with applications to thermal conductivity calculations [J ] . Physical Review B , 2015 , 92 ( 9 ): 94301 .

Torii D , Nakano T , Ohara T . Contribution of inter- and intramolecular energy transfers to heat conduction in liquids [J ] . Journal of Chemical Physics , 2008 , 128 ( 4 ): 44504 .

Matsubara H , Kikugawa G , Bessho T , et al . Effects of molecular structure on microscopic heat transport in chain polymer liquids [J ] . Journal of Chemical Physics , 2015 , 142 ( 16 ): 164509 .

Lv W , Henry A . Direct calculation of modal contributions to thermal conductivity via Green-Kubo modal analysis [J ] . New Journal of Physics , 2016 , 18 ( 1 ): 13028 .

Sun H , Mumby S J , Maple J R , et al . An ab initio CFF93 all-atom force field for polycarbonates [J ] . Journal of the American Chemical Society , 1994 , 116 ( 7 ): 2978 - 2987 .

Zhu W , Wang X , Xiao J , et al . Molecular dynamics simulations of AP/HMX composite with a modified force field [J ] . Journal of Hazardous Materials , 2009 , 167 ( 1 ): 810 - 816 .

Sun Y , Chen L , Cui L , et al . Molecular dynamics simulation of cross-linked epoxy resin and its interaction energy with graphene under two typical force fields [J ] . Computational Materials Science , 2018 , 143 : 240 - 247 .

Ikeshoji T , Hafskjold B . Non-equilibrium molecular dynamics calculation of heat conduction in liquid and through liquid-gas interface [J ] . Molecular Physics , 1994 , 81 ( 2 ): 251 - 261 .

Jund P , Jullien R . Molecular-dynamics calculation of the thermal conductivity of vitreous silica [J ] . Physical Review B , 1999 , 59 ( 21 ): 13707 .

Brown W M , Yamada M . Implementing molecular dynamics on hybrid high performance computers—three-body potentials [J ] . Computer Physics Communications , 2013 , 184 ( 12 ): 2785 - 2793 .

Brown W M , Kohlmeyer A , Plimpton S J , et al . Implementing molecular dynamics on hybrid high performance computers—particle-particle particle-mesh [J ] . Computer Physics Communications , 2012 , 183 ( 3 ): 449 - 459 .

Brown W M , Wang P , Plimpton S J , et al . Implementing molecular dynamics on hybrid high performance computers—short range forces [J ] . Computer Physics Communications , 2011 , 182 ( 4 ): 898 - 911 .

Nguyen T D . GPU-accelerated Tersoff potentials for massively parallel molecular dynamics simulations [J ] . Computer Physics Communications , 2017 , 212 : 113 - 122 .

Nguyen T D , Plimpton S J . Accelerating dissipative particle dynamics simulations for soft matter systems [J ] . Computational Materials Science , 2015 , 100 : 173 - 180 .

Plimpton S . Fast parallel algorithms for short-range molecular dynamics [J ] . Journal of Computational Physics , 1995 , 117 ( 1 ): 1 - 19 .

Boone P , Babaei H , Wilmer C E . Heat flux for many-body interactions: corrections to LAMMPS [J ] . Journal of Chemical Theory and Computation , 2019 , 15 ( 10 ): 5579 - 5587 .

Wirnsberger P , Frenkel D , Dellago C . An enhanced version of the heat exchange algorithm with excellent energy conservation properties [J ] . Journal of Chemical Physics , 2015 , 143 ( 12 ): 124104 .

Hoover W G . Canonical dynamics: equilibrium phase-space distributions [J ] . Physical Review A , 1985 , 31 ( 3 ): 1695 - 1697 .

Ohara T , Chia Yuan T , Torii D , et al . Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer [J ] . Journal of Chemical Physics , 2011 , 135 ( 3 ): 34507 .

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