吸附过程的热力学误差问题的研究

doi:10.16046/j.cnki.issn2096-5680.2023.01.009

河北水利电力学院学报 ›› 2023, Vol. 33 ›› Issue (1): 50-55.DOI: 10.16046/j.cnki.issn2096-5680.2023.01.009

吸附过程的热力学误差问题的研究

聂佳馨¹, 司展², 胡晶晶³, 周华锋¹

1.沈阳化工大学理学院,辽宁省沈阳市铁西区经济技术开发区11号街 110142;
2.沈阳化工大学化学工程学院,辽宁省沈阳市铁西区经济技术开发区11号街 110142;
3.东北大学计算机科学与工程学院,辽宁省沈阳市浑南区创新路195号 110819

收稿日期:2022-03-23 修回日期:2023-04-21 发布日期:2023-10-26
作者简介:聂佳馨(1998-),女,河南平顶山人,在读硕士,主要研究方向:吸附剂的研发及其在污水处理中的应用。E-mail:niejiaxin99@126.com
基金资助:
国家自然科学基金青年基金项目(41807350)

Study on the Thermodynamic Error Problem of the Adsorption Process

NIE Jia-xin ¹, SI Zhan², HU Jing-jing³, ZHOU Hua-feng¹

1. School of Science, Shenyang University of Chemical Engineering, 110142, Shenyang, Liaoning, China;
2. School of Chemical Engineering, Shenyang University of Chemical Engineering, 110142, Shenyang, Liaoning, China;
3. School of Computer Science and Engineering, Northeastern University, 110819, Shenyang, Liaoning, China

Received:2022-03-23 Revised:2023-04-21 Published:2023-10-26

摘要/Abstract

摘要： 吸附热力学中物理量的误差自上世纪就被学者关注,这种误差被归因于熵焓补偿。对于化学和生物学中类似的物理化学过程,线性焓-熵补偿(EEC)现象是一个热力学谜,长期无法解释。基本的热力学规则并不严格地支持EEC现象,在某些受限条件下,EEC可能呈现出不现实的线性状态。文中将从吸附过程的误差入手,综述对这种误差的解决方式的修正思想与统计力学观点,深入研究熵焓补偿的现象,分析现象产生的原理,认为补偿现象的存在并非数学和量子级别的物理问题。

关键词: 熵焓补偿, 修正思想, 统计力学, 量子分析

Abstract: The error of physical quantity in adsorption thermodynamics has been concerned by scholars since the last century, and this error is attributed to the entropy enthalpy compensation.For similar physicochemical processes in chemistry and biology, the linear enthalpy-entropy compensation(EEC)phenomenon is a thermodynamic mystery that cannot be explained for a long time.The basic thermodynamic rules do not strictly support the EEC phenomenon.Under some restricted conditions, the EEC may present an unrealistic linear state.Therefore, In this paper, we start with the error of the adsorption process, review the correction of the solution of this error, and deeply study the phenomenon of entropy enthalpy compensation, analyze the principle of the phenomenon, and think that the existence of the compensation phenomenon is not a mathematical and quantum level physical problem.

Key words: entropy-enthalpy compensation, correction thought, statistical mechanics, quantum analysis

中图分类号:

聂佳馨, 司展, 胡晶晶, 周华锋. 吸附过程的热力学误差问题的研究[J]. 河北水利电力学院学报, 2023, 33(1): 50-55.

NIE Jia-xin , SI Zhan, HU Jing-jing, ZHOU Hua-feng. Study on the Thermodynamic Error Problem of the Adsorption Process[J]. Journal of Hebei University of Water Resources and Electric Engineering, 2023, 33(1): 50-55.

参考文献

[1] Anastopoulos I, Kyzas G Z. Are the thermodynamic parameters correctly estimated in liquid-phase adsorption phenomena？[J]. Journal of Molecular Liquids, 2016,218:174-185.
[2] Milonjic S K. A Consideration of the Correct Calculation of Thermodynamic Parameters of Adsorption[J]. Journal of the Serbian Chemical Society, 2007,72(12)1363-1367.
[3] Yu L. Some consideration on the Langmuir isotherm equation[J]. Colloids & Surfaces A Physicochemical & Engineering Aspects, 2006, 274(1-3):34-36.
[4] Liu Y. Is the free energy change of adsorption correctly calculated？[J]. Journal of Chemical & Engineering Data, 2009,54(7):1981-1985.
[5] Sawalha M F, Peralta-Videa J R, Romero-González J, et al. Biosorption of Cd (II), Cr (III), and Cr (VI) by saltbush (Atriplex canescens) biomass: thermodynamic and isotherm studies[J]. Journal of Colloid and Interface Science, 2006,300(1):100-104.
[6] Chen T, Zhou Z, Han R, et al. Adsorption of cadmium by biochar derived from municipal sewage sludge: impact factors and adsorption mechanism[J]. Chemosphere, 2015,134:286-293.
[7] Sharp K. Entropy-enthalpy compensation: fact or artifact？[J]. Protein Science, 2010,10(3):661-667.
[8] Krug R R, Hunter W G, Grieger R A. Statistical interpretation of enthalpy-entropy compensation[J]. Nature, 1976,261(5561):566-567.
[9] Privalov P L, Gill S J. Stability of protein structure and hydrophobic interaction[J]. Advances in Protein Chemistry, 1988,39:191-234.
[10] Milne J S, Xu Y, Mayne L C, et al. Experimental study of the protein folding landscape: unfolding reactions in cytochrome c[J]. Journal of Molecular Biology, 1999,290(3):811-822.
[11] Ben-Naim A, Marcus Y. Solvation thermodynamics of nonionic solutes[J]. The Journal of Chemical Physics, 1984,81(4):2016-2027.
[12] Gallicchio E, Kubo M M, Levy R M. Entropy-enthalpy compensation in solvation and ligand binding revisited[J]. Changes, 1998,5(6):13-15.
[13] Eftink M R, Anusiem A C, Biltonen R L. Enthalpy-entropy compensation and heat capacity changes for protein-ligand interactions: general thermodynamic models and data for the binding of nucleotides to ribonuclease A[J]. Biochemistry, 1983,22(16):3884-3896.
[14] Khakhel', Oleg A, Romashko, et al.Extrathermodynamics: Varieties of Compensation Effect[J]. 2016,120:2035-2040.
[15] McPhail D, Cooper A. Thermodynamics and kinetics of dissociation of ligand-induced dimers of vancomycin antibiotics[J]. Journal of the Chemical Society, Faraday Transactions, 1997,93(13):2283-2289.
[16] Liu L, Guo Q X. Isokinetic relationship, isoequilibrium relationship, and enthalpy-entropy compensation[J]. Chemical Reviews, 2001,101(3):673-696.
[17] Lumry R, Rajender S. Enthalpy-entropy compensation phenomena in water solutions of proteins and small molecules: a ubiquitous properly of water[J]. Biopolymers: Original Research on Biomolecules, 1970,9(10):1125-1227.
[18] Rosenberg B, Kemeny G, Switzer R C, et al. Quantitative evidence for protein denaturation as the cause of thermal death[J]. Nature, 1971,232(5311):471-473.
[19] Schwarz J A, Felton L E. Compensating effects in electromigration kinetics[J]. Solid-state Electronics, 1985,28(7):669-675.
[20] Constable F H. The mechanism of catalytic decomposition[J]. Proceedings of the Royal Society of London. Series A, Containing Papers of a Mathematical and Physical Character, 1925,108(746):355-378.
[21] Sharp K. Entropy—enthalpy compensation: Fact or artifact？[J]. Protein Science, 2001,10(3):661-667.
[22] Starikov E B, Nordén B. Enthalpy-entropy compensation: a phantom or something useful？[J]. The Journal of Physical Chemistry B, 2007,111(51):14431-14435.
[23] Chen L J, Lin S Y, Huang C C. Effect of hydrophobic chain length of surfactants on enthalpy-entropy compensation of micellization[J]. The Journal of Physical Chemistry B, 1998,102(22):4350-4356.
[24] Cooper A, Johnson C M, Lakey J H, et al. Heat does not come in different colours: entropy-enthalpy compensation, free energy windows, quantum confinement, pressure perturbation calorimetry, solvation and the multiple causes of heat capacity effects in biomolecular interactions[J]. Biophysical Chemistry, 2001,93(2-3):215-230.
[25] Pan A, Biswas T, Rakshit A K, et al. Enthalpy-Entropy Compensation (EEC) Effect: A Revisit[J]. The Journal of Physical Chemistry B, 2015,119(52):15876-15884.
[26] Mandal B, Rakshit A K, Moulik S P, et al. A Rational Study of the Origin and Generality of Anti-Enthalpy-Entropy Compensation (AEEC) Phenomenon[J]. Zeitschrift für Physikalische Chemie,2017.
[27] Moulik S P, Naskar B, Rakshit A K.Current Status of Enthalpy-Entropy Compensation Phenomenon[J]. Current Science, 2019,117(8):1286.
[28] Urry D W. Entropic elastic processes in protein mechanisms. I. Elastic structure due to an inverse temperature transition and elasticity due to internal chain dynamics[J]. Journal of Protein Chemistry, 1988,7(1):1-34.
[29] Krug R R. wG Hunter, and RA Grieger[J]. J. Phys. Chem, 1976,80(21):2325-2351.
[30] Griessen R, Boelsma C,Schreuders H, et al. Single Quality Factor for Enthalpy ntropy Compensation, Iso-equilibrium and Isokinetic Relationships[J]. Chem Phys Chem, 2020,21(15):1618-1618.
[31] Ryde, Ulf. A fundamental view of enthalpy-entropy compensation[J]. MedChemComm, 2014,5(9):1324-1336.
[32] Moulik S P, Naskar B, Rakshit A K. Current Status of Enthalpy-Entropy Compensation Phenomenon[J]. Current Science, 2019,117(8):1286.

吸附过程的热力学误差问题的研究

Study on the Thermodynamic Error Problem of the Adsorption Process

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 0

编辑推荐

Metrics