Kinetics of the Photolysis of Methyl Iodide and the Hydrogen Halides I. Photolysis of Hydrogen Iodide in the Presence of Iodine, Hydrogen Bromide and Hydrogen Chloride

1947 ◽  
Vol 15 (10) ◽  
pp. 691-696 ◽  
Author(s):  
Russell R. Williams ◽  
Richard A. Ogg
1967 ◽  
Vol 20 (6) ◽  
pp. 1143 ◽  
Author(s):  
RL Failes ◽  
VR Stimson

Hydrogen iodide catalyses the decomposition of isopropanol into propene and water at 356 to 457�, viz. �������������������������� i-C3H7OH+HI → C3H6+H2O+HI This is followed by the faster reactions �������������������������� C3H6+HI → i-C3H7I ����� ��������������������i-C3H7I+HI → C3H8+I2������������������������ i-C3H7OH+I2 → (CH3)2CO+2HI The rates of the initial reaction fit the Arrhenius equation ����������������� k2 = 1012.24 exp(-31900/RT) sec-1 ml mole-1 and it is believed to be homogeneous and molecular. It is faster than the corresponding reactions with hydrogen chloride and hydrogen bromide in the ratios 100 : 1 and 5 : 1, respectively. For the overall reaction the amounts of the products formed to 70% reaction, computed with the use of rate constants of the individual reactions, agree well with the amounts found by analysis.


1968 ◽  
Vol 21 (3) ◽  
pp. 687 ◽  
Author(s):  
JTD Cross ◽  
VR Stimson

Hydrogen bromide and hydrogen chloride catalyse the decomposition of methyl trimethylacetate into isobutene, carbon monoxide, and methanol at 370-442� and 450-48O�, respectively. The kinetic form, which is basically 1 : 1, is severely modified by the effect of methanol either produced in the reaction or added initially. Water or alcohols react with an intermediate in the catalysed decomposition of trimethylacetic acid or its methyl ester in esterification-like reactions; some of the resultant esters subsequently decompose to olefin and acid.


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