Thermal reaction of 2-methyl-2-butene in the presence of azomethane: Enthalpy of formation of the radicals (CH3)2ĊCH(CH3)2 and tert-Ċ4H9

Z. Király, T. Körtvélyesi, László Seres

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Abstract

The reaction of ĊH3 and 2-methyl-2-butene (2MB2) was investigated in the temperature range 540-610 K. Azomethane was used as the source of ĊH3. The addition of ĊH3 to 2MB2 was concluded to be an equilibrium process: ĊH3 + (CH3)2C=CHCH3⇆(CH3)2̇CCH(CH3)2. The equilibrium constant of this reaction was determined from the rates of formation of the combination products (E)- and (Z)-CH3CH2C(CH3)=CHCH3 and (E)- and (Z)- (CH3)2CHC(CH3)2CH2C(CH3)=CHCH3. Finally, the enthalpy of formation of the adduct radical, Δ(f) H298/°[(CH3)2ĊCH(CH3)2] = (3 ± 10) kJ mol-1, was obtained from the temperature dependence of the equilibrium constant. On the assumption that the group additivity rule was valid for the adduct radical, the following group value was obtained: Δ(f)H298/°[Ċ- (C)3] = (179 ± 12) kJ mol-1. Through use of this datum Δ(f)H298/°(tert-Ċ4H9) = (53 ± 12) kJ mol-1.

Original languageEnglish
Pages (from-to)349-354
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume2
Issue number3
DOIs
Publication statusPublished - Feb 1 2000

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Equilibrium constants
butenes
Enthalpy
enthalpy
adducts
Temperature
temperature dependence
products
azomethane
2-butene
Hot Temperature
temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Thermal reaction of 2-methyl-2-butene in the presence of azomethane: Enthalpy of formation of the radicals (CH3)2ĊCH(CH3)2 and tert-Ċ4H9",
abstract = "The reaction of ĊH3 and 2-methyl-2-butene (2MB2) was investigated in the temperature range 540-610 K. Azomethane was used as the source of ĊH3. The addition of ĊH3 to 2MB2 was concluded to be an equilibrium process: ĊH3 + (CH3)2C=CHCH3⇆(CH3)2̇CCH(CH3)2. The equilibrium constant of this reaction was determined from the rates of formation of the combination products (E)- and (Z)-CH3CH2C(CH3)=CHCH3 and (E)- and (Z)- (CH3)2CHC(CH3)2CH2C(CH3)=CHCH3. Finally, the enthalpy of formation of the adduct radical, Δ(f) H298/°[(CH3)2ĊCH(CH3)2] = (3 ± 10) kJ mol-1, was obtained from the temperature dependence of the equilibrium constant. On the assumption that the group additivity rule was valid for the adduct radical, the following group value was obtained: Δ(f)H298/°[Ċ- (C)3] = (179 ± 12) kJ mol-1. Through use of this datum Δ(f)H298/°(tert-Ċ4H9) = (53 ± 12) kJ mol-1.",
author = "Z. Kir{\'a}ly and T. K{\"o}rtv{\'e}lyesi and L{\'a}szl{\'o} Seres",
year = "2000",
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T1 - Thermal reaction of 2-methyl-2-butene in the presence of azomethane

T2 - Enthalpy of formation of the radicals (CH3)2ĊCH(CH3)2 and tert-Ċ4H9

AU - Király, Z.

AU - Körtvélyesi, T.

AU - Seres, László

PY - 2000/2/1

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N2 - The reaction of ĊH3 and 2-methyl-2-butene (2MB2) was investigated in the temperature range 540-610 K. Azomethane was used as the source of ĊH3. The addition of ĊH3 to 2MB2 was concluded to be an equilibrium process: ĊH3 + (CH3)2C=CHCH3⇆(CH3)2̇CCH(CH3)2. The equilibrium constant of this reaction was determined from the rates of formation of the combination products (E)- and (Z)-CH3CH2C(CH3)=CHCH3 and (E)- and (Z)- (CH3)2CHC(CH3)2CH2C(CH3)=CHCH3. Finally, the enthalpy of formation of the adduct radical, Δ(f) H298/°[(CH3)2ĊCH(CH3)2] = (3 ± 10) kJ mol-1, was obtained from the temperature dependence of the equilibrium constant. On the assumption that the group additivity rule was valid for the adduct radical, the following group value was obtained: Δ(f)H298/°[Ċ- (C)3] = (179 ± 12) kJ mol-1. Through use of this datum Δ(f)H298/°(tert-Ċ4H9) = (53 ± 12) kJ mol-1.

AB - The reaction of ĊH3 and 2-methyl-2-butene (2MB2) was investigated in the temperature range 540-610 K. Azomethane was used as the source of ĊH3. The addition of ĊH3 to 2MB2 was concluded to be an equilibrium process: ĊH3 + (CH3)2C=CHCH3⇆(CH3)2̇CCH(CH3)2. The equilibrium constant of this reaction was determined from the rates of formation of the combination products (E)- and (Z)-CH3CH2C(CH3)=CHCH3 and (E)- and (Z)- (CH3)2CHC(CH3)2CH2C(CH3)=CHCH3. Finally, the enthalpy of formation of the adduct radical, Δ(f) H298/°[(CH3)2ĊCH(CH3)2] = (3 ± 10) kJ mol-1, was obtained from the temperature dependence of the equilibrium constant. On the assumption that the group additivity rule was valid for the adduct radical, the following group value was obtained: Δ(f)H298/°[Ċ- (C)3] = (179 ± 12) kJ mol-1. Through use of this datum Δ(f)H298/°(tert-Ċ4H9) = (53 ± 12) kJ mol-1.

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