Quantumchemical study of the isobutane cracking on zeolites

被引：106

作者：

Kazansky, VB ^{[1
]}

Frash, MV ^{[1
]}

vanSanten, RA ^{[1
]}

机构：

[1] EINDHOVEN UNIV TECHNOL,NL-5600 MB EINDHOVEN,NETHERLANDS

来源：

APPLIED CATALYSIS A-GENERAL | 1996年 / 146卷 / 01期

关键词：

alkanes; carbenium ions; carbonium ions; cracking; isobutane; isobutene; transition states;

D O I：

10.1016/0926-860X(96)00060-9

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：

The ab initio quantumchemical investigation of the elementary steps of the catalytic isobutane cracking is presented. A reasonable agreement between experimental and theoretical activation energies is found. The obtained results demonstrate that the adsorbed carbenium and carbonium ions represent not the really existing reaction intermediates, but the high-energy transition states of the corresponding elementary reactions. This results in much higher activation energies than for the similar reactions in homogeneous super-acid solutions.

引用

页码：225 / 247

页数：23

共 43 条

[1] C-13 NMR IDENTIFICATION OF INTERMEDIATES FORMED BY 2-METHYL-2-PROPANOL ADSORPTION IN H-ZSM-5 [J].

ARONSON, MT ;

GORTE, RJ ;

FARNETH, WE ;

WHITE, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (03) :840-846

[2] DENSITY-FUNCTIONAL THEORY CALCULATIONS OF THE TRANSITION-STATES FOR HYDROGEN-EXCHANGE AND DEHYDROGENATION OF METHANE BY A BRONSTED ZEOLITIC PROTON [J].

BLASZKOWSKI, SR ;

JANSEN, APJ ;

NASCIMENTO, MAC ;

VANSANTEN, RA .

JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (49) :12938-12944

[3] DETERMINING ATOM-CENTERED MONOPOLES FROM MOLECULAR ELECTROSTATIC POTENTIALS - THE NEED FOR HIGH SAMPLING DENSITY IN FORMAMIDE CONFORMATIONAL-ANALYSIS [J].

BRENEMAN, CM ;

WIBERG, KB .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1990, 11 (03) :361-373

[4]

Brouwer D.M., 1972, PROGR PHYSICAL ORGAN, V9, P179, DOI DOI 10.1002/9780470171882.CH4

[5] EXCHANGE REACTIONS OF TERTBUTYL CATION [J].

BROWNSTEIN, S ;

BORNAIS, J .

CANADIAN JOURNAL OF CHEMISTRY-BACK YEAR, 1971, 49 (01) :7-+

[6] A THEORETICAL DESCRIPTION FOR THE MONOMOLECULAR CRACKING OF C-C BONDS OVER ACIDIC ZEOLITES [J].

COLLINS, SJ ;

OMALLEY, PJ .

JOURNAL OF CATALYSIS, 1995, 153 (01) :94-99

[7] THE ROLE OF REACTION TEMPERATURE AND CRACKING CATALYST CHARACTERISTICS IN DETERMINING THE RELATIVE RATES OF PROTOLYTIC CRACKING, CHAIN PROPAGATION, AND HYDROGEN-TRANSFER [J].

CORMA, A ;

MIGUEL, PJ ;

ORCHILLES, AV .

JOURNAL OF CATALYSIS, 1994, 145 (01) :171-180

[8] CONTRIBUTION TO THE UNDERSTANDING OF THE REACTION CHEMISTRY OF ISOBUTANE AND NEOPENTANE OVER ACID CATALYSTS, .1. [J].

ENGELHARDT, J ;

HALL, WK .

JOURNAL OF CATALYSIS, 1990, 125 (02) :472-487

[9] PECULIARITIES OBSERVED IN H-D EXCHANGE BETWEEN PERDEUTERIOISOBUTANE AND H-ZEOLITES [J].

ENGELHARDT, J ;

HALL, WK .

JOURNAL OF CATALYSIS, 1995, 151 (01) :1-9

[10]

Frisch M.J., 1992, GAUSSIAN 92 REVISION

← 1 2 3 4 5 →