Nucleophilicity and Accessibility Calculations of Alkanolamines: Applications to Carbon Dioxide Absorption Reactions

被引:29
|
作者
Jhon, Young H. [1 ]
Shim, Jae-Goo [2 ]
Kim, Jun-Han [2 ]
Lee, Ji Hyun [2 ]
Jang, Kyung-Ryong [2 ]
Kim, Jaheon [1 ]
机构
[1] Soongsil Univ, Dept Chem, Seoul 156743, South Korea
[2] Korea Elect Power Res Inst, Global Environm Res Grp, Environm & Struct Lab, Taejon 305380, South Korea
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2010年 / 114卷 / 49期
关键词
ELECTRONIC POPULATION ANALYSIS; REACTION-CENTER CONGESTION; MOLECULAR WAVE FUNCTIONS; ATOM FORCE-FIELD; AQUEOUS-SOLUTIONS; OVERLAP POPULATIONS; CHEMICAL-REACTIVITY; ORBITAL THEORY; BOND ORDERS; FREE-ENERGY;
D O I
10.1021/jp105914c
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Both nucleophilicities and accessibilities of three alkanolamines [monoethanolamine (MEA), (2-(methylamino)ethanol (MAE), and 2-amino-2-methyl-l-propanol (AMP)] were calculated to predict their reactivities with CO2. After DFT geometry-optimization calculations, the global, group, and atomic nucleophilicities of each amine were obtained using MP2 quantum mechanical calculations. Only global nucleophilicity matched an experimental pK(a) order (MAE > AMP > MEA). However, it failed to predict the slow rate of the sterically hindered AMP and the order of rate constants, MAE > MEA > AMP. The accessibilities of amines to CO2 have been calculated by MD simulations by monitoring collisions at the reaction centers: N atoms in amines and C in CO2. The accessibility results indicate that global nucleophilicity needs quantitative correction for steric effects to predict better reactivities of amines with CO2.
引用
收藏
页码:12907 / 12913
页数:7
相关论文
共 50 条
  • [1] REACTIONS OF CARBON DIOXIDE AND HYDROGEN SULFIDE WITH SOME ALKANOLAMINES.
    Maddox, Robert N.
    Mains, Gilbert J.
    Rahman, Mahmud A.
    Industrial and Engineering Chemistry Research, 1987, 26 (01): : 27 - 31
  • [2] ABSORPTION OF CARBON-DIOXIDE IN ALKANOLAMINES IN THE PRESENCE OF FINE ACTIVATED CARBON PARTICLES
    SAHA, AK
    BANDYOPADHYAY, SS
    BISWAS, AK
    CANADIAN JOURNAL OF CHEMICAL ENGINEERING, 1992, 70 (01): : 193 - 196
  • [3] REACTIONS OF CARBON-DIOXIDE AND HYDROGEN-SULFIDE WITH SOME ALKANOLAMINES
    MADDOX, RN
    MAINS, GJ
    RAHMAN, MA
    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1987, 26 (01) : 27 - 31
  • [5] Effect of alcohol chain length on carbon dioxide absorption into aqueous solutions of alkanolamines
    Yamada, Hidetaka
    Chowdhury, Firoz A.
    Matsuzaki, Yoichi
    Goto, Kazuya
    Higashii, Takayuki
    Kazama, Shingo
    GHGT-11, 2013, 37 : 499 - 504
  • [6] Study on carbon dioxide absorption in aqueous solutions of potassium carbonate activated with alkanolamines
    Binczak, Grzegorz
    Pohorecki, Ryszard
    Moniuk, Wladyslaw
    Mozenski, Cezary
    Cwalina, Janusz
    Mordecka, Zofia
    PRZEMYSL CHEMICZNY, 2013, 92 (03): : 321 - 324
  • [7] The adsorption of carbon dioxide by tertiary alkanolamines
    Gomes, MTSR
    Barros, CMF
    Santana-Marques, MGO
    Oliveira, JABP
    CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1999, 77 (03): : 401 - 408
  • [8] NUCLEOPHILICITY IN REACTIONS AT A VINYLIC CARBON
    RAPPOPORT, Z
    ADVANCES IN CHEMISTRY SERIES, 1987, (215): : 399 - 421
  • [9] NUCLEOPHILICITY IN REACTIONS AT VINYLIC CARBON
    RAPPOPORT, Z
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1985, 190 (SEP): : 244 - ORN
  • [10] Absorption of Carbon Dioxide into Aqueous Solutions of Alkanolamines in a Wetted Wall Column with Film Promoter
    Rodriguez, Henry
    Mello, Lilian
    Salvagnini, Wilson
    de Paiva, Jose Luis
    PRES 2011: 14TH INTERNATIONAL CONFERENCE ON PROCESS INTEGRATION, MODELLING AND OPTIMISATION FOR ENERGY SAVING AND POLLUTION REDUCTION, PTS 1 AND 2, 2011, 25 : 51 - 56