Summary
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1.
In the synthesis of hydrocarbons from carbon monoxide and hydrogen over nonhydrogenating oxide catalysts (Al2O3, ThO2), which is called the iso synthesis, the hydrogenation processes are in the nature of semicatalytic reactions: carbon monoxide molecules are activated at be catalyst surface and are attached to the surface during the reaction, but the hydrogen molecules are thermally activated and react by moving from the gas phase, without becoming attached to the catalyst.
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2.
It has been suggested that semicatalytic reactions are not confined to the iso synthesis, but have a more general character.
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3.
In semicatalytic reactions, those atoms, in molecules attached to the catalyst, that enter the reaction must themselves be attached to the catalyst surface.
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4.
In the iso synthesis, CHOH groups, as well as CH2 groups, take part in the. formation of carbon chains.
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5.
Semicatalytic hydrogenation in the iso synthesis leads to increase in the concentration of CHOH groups and to the occurrence of hydroxyl groups at secondary carbon atoms in carbon chains.
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6.
Iso compounds are formed by catalytic condensation with elimination of water (dehydrational condensation).
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7.
The mechanism discussed readily explains the peculiar nature of the products and other experimental characteristics of the iso synthesis.
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Eidus, Y.T. Semicatalytic hydrogenation and dehydrational condensation in the mechanism of the iso synthesis. Russ Chem Bull 2, 913–920 (1953). https://doi.org/10.1007/BF01167536
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DOI: https://doi.org/10.1007/BF01167536