Kinetics and mechanism of the carbonylation of methanol to methyl formate
The rate of carbonylation of methanol to methyl formate in methanol solutions of sodium methylate within the range 1-4 MPa and 80-110/sup 0/C obey the first-order equation with respect to the concentrations of sodium methylate, carbon monoxide, and methanol (k/sup ..-->../ = 10(/sup 7.84 +/- 0.23/) exp (-15,000 +/- 400)/RT, liters/sup 2//mole/sup 2/ x min). Under the same conditions the rate of decarbonylation of methyl formate is proportional to the concentrations of sodium methylate and methyl formate to the first power (k/sup ..-->../ = 10(/sup 13.43 +/- 0.37/) exp (-24,200 +/- 600)/RT, liter/mole x min). When methanol is replaced by a form enriched (98%) with deuterium in the hydroxyl group,the kinetic isotope effect of the reaction is equal to one. It is concluded that the charge on the C-atom of the intermediate carbanion is too low for the splitting-off of H+ from the methanol molecule, introduced into the activated complex of nucleophilic attack of CH/sub 3/O- on CO and the stabilizing carbanion.
- Research Organization:
- N. S. Kurnakov Institute of General and Inorganic Chemistry, Moscow, USSR
- OSTI ID:
- 5735148
- Journal Information:
- Kinet. Catal. (Engl. Transl.); (United States), Journal Name: Kinet. Catal. (Engl. Transl.); (United States) Vol. 27:5; ISSN KICAA
- Country of Publication:
- United States
- Language:
- English
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400201 -- Chemical & Physicochemical Properties
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALCOHOLS
ALKALI METAL COMPOUNDS
ALKOXY RADICALS
ANIONS
CARBANIONS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLATION
CARBOXYLIC ACID SALTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHROMATOGRAPHY
DEUTERATION
DEUTERIUM
ELEMENTS
FORMATES
HYDROGEN
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
HYDROXY COMPOUNDS
IONS
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
METHANOL
METHOXY RADICALS
METHYLATION
NONMETALS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RADICALS
REACTION KINETICS
SEPARATION PROCESSES
SODIUM COMPOUNDS
STABLE ISOTOPES
YIELDS