The Nature of Autocatalysis in the Butlerov Reaction
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Translated
|
| Journal |
Kinetics and Catalysis
ISSN: 0023-1584
, E-ISSN: 1608-3210
|
| Output data |
Year: 2007,
Volume: 48,
Number: 2,
Pages: 245-254
Pages count
: 10
DOI:
10.1134/S0023158407020085
|
| Authors |
Simonov A.N.
1
,
Taran O.P.
1
,
Matvienko L.G.
1
,
Parmon V.N.
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis SB RAS
|
|
Funding (4)
|
1
|
The Ministry of Education and Science of the Russian Federation
|
2.1.1.1969
|
|
2
|
Council for Grants of the President of the Russian Federation
|
НШ-6526.2006.3
|
|
3
|
Russian Foundation for Basic Research
|
05-03-32862
|
|
4
|
Президиум РАН
|
|
The effect of the nature of an initiator on the kinetics of formaldehyde consumption and on product composition in the Butlerov reaction was studied in a stirred flow reactor and a batch reactor. It was found that, under flow conditions, the kinetics and the product composition of this reaction are independent of the nature of the initiator. The reaction schemes proposed previously for an autocatalytic process mechanism based on the formation of glycolaldehyde from two formaldehyde molecules are incorrect. A correlation between the initiating activities of various monosaccharides and the rates of their conversion into an enediol form was found with the use of a batch reactor. Solid enediol complexes with Ca2+ ions were isolated for glucose, fructose, ribose, and sorbose; the initiating activity of these complexes was found to be much higher than the initiating activity of pure monosaccharides. A self-consistent mechanism was proposed for Butlerov reaction initiation. The formation of the enediol forms of monosaccharides followed by degradation to lower carbohydrates plays a key role in this mechanism. In turn, the initiating activity depends on the position of the carbonyl group in the monosaccharide molecule. The condensation reactions of glycolaldehyde, glyceraldehyde, and dihydroxyacetone with each other were studied. Based on data on the condensation products of lower carbohydrates, a scheme was proposed for the Butlerov reaction. According to this reaction scheme, C2 and C3 carbohydrates mainly undergo an aldol condensation reaction with formaldehyde, whereas the formation of higher monosaccharides occurs by the aldol condensation of lower C2–C3 carbohydrates with each other.