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An investigation of the crystalline hydrocarbons of the higher fractions of romashkino oil
Abstracts
477
The /'act that the inhibition is independent of the chemical mechanism of the formation of the various radiolysis products is probably duo to the fact that the inhibitor abstracts part of the excitation energy from the electron levels of a n excited molecule or iron to the extent that one chemical reaction or another takes place. The transfer of excitation energy from a molecule of the irradiated hydrocarbon to a molecule of the inhibitor during the radiolysis of n-hexane containing benzene sati.~fle,~ a relationship correspondin~ to the direct electromagnetic transfer of energy. CHROMATOGRAPHIC MATOGRAPHS
SCHEMES
V. G. B e r e z h i n al)(t S . K . 1961.
AND STANDARDIZED
P A R T S FOR
GAS
CHRO-
K r a s h e n i n n i k o v , N e f t e k h i m i y a 1: No. 5, 7 0 0 - 7 0 5 ,
~IMPLE standardized parts for gas chromatographs which permit the rapid selection of a chromatographic scheme giving the optimum conditions for each particular case have been developed. Some new variants of ehromatogwaphie schemes have been proposed, ineludin~ a series-parallel scheme. A method for evaluating the influence of the chromatographic apparatus on the efficiency of separation has been proposed. *SELECTION OF CONDITIONS F O R T H E G A S - C H R O M A T O G R A P H I C OF COMPLEX H Y D R O C A R B O N M I X T U R E S
SEPARATION
M. S. V i g d e r g a u z a n d K . A. G e l ' b e r t , N e f t e k h i m i y a 1: No. 5, 706-715, 1961. .\ METHODof calculation of the worst-separated components in the elution of substances belonging to a n y homologous series is given. At sufficiently high molecular weights, the efficiency of separation of the members of a homologous series remains practically constant. The possibilities of separating complex mixtures of substances on compound cohmms linked in succession have been considered and an equation deduced for the calculation of the m a x i m u m breadth of the fraction being separated. The basis of a general scheme of analysis of multicomponent mixtures is given in which they are separated in a first stage according to their numbers of carbon atoms or their boiling points, with subsequent distribution of the narrow fractions among the cohunns of a second stage, upon which their detailed analysis is carried out. A method for evaluating the breadth of a fraction sent to the second stage of separation has been l)ropose(I. A N INVESTIGATION OF T H E CRYSTALLINE FRACTIONS OF R O M A S H K I N O OIL
HYDROCARBONS
OF T H E H I G H E R
P. I. S a n i n a n d N. K . D r u z h i n i n a , N e f t e k h i m i y a 1: No. 6, 7 2 5 - 7 4 1 , 1961. THE crystalline hydrocarbons present in the 325-375 and 375-500 ° fractions of FComashkino petroleum have been investigated. Crystalline hydrocarbons which form complexes with urea have been isolated from this fraction. Two methods of fractionation were used to separate the hydrocarbons The Publisher will be pleased to quote for the supply of a fllll English translation of any papers abstracted in these pages.
478
Abstracts
of this fraction; distillation in a rectification column of 30 theoretical plates, and molecular distillation in a multi-stage apparatus. F o r the further investigation of the narrower fractions, the method of liquid-phase dehydrogenation was used to determine the naphthenic hydrocarbons containing a hoxamethylene ring and nitration b y Konovalov's method to deter~nine the hydrocarbons with a t e r t i a r y carbon atom. The combined use of these methods allowed conclusions to be drawn on the nature of the hydrocarbons investigated. The crystalline hydrocarbons of the 32;)-375 ° fl'action contain about 12% of cyclic hydrocarbons with a hexamethylene ring and about 600/o of normal paraffinic hydrocarbons. As a previous investigation tins shown, the crystalline hydrocarbons isolated from the broad 375-500 ° fraction contain a b o u t 15% of naphthenie hydrocarbons with a hexamethylene ring. The largest p a r t of the naphthenic hydrocarbons (85%) consists of naphthenic hydrocarbons which form complexes with urea. The content of notarial paraffinio hydrocarbons in the fraction is more t h a n 57~o. I n the course of the investigation it was shown t h a t when hydrocarbons are nitrated b y Konovalov's method, tertiary nitro compounds are formed not only from branchedchain paraffinic hydrocarbons but also from naphthenic hydrocarbons containing a t e r t i a r y carbon atom. These results make it possible to give a new interpretation to the results of the nitration of the crystalline hydrocarbons of petroleum obtained by other authors. *THE SYNTHESIS OF 3-ALKYLPENTAMETHYLENE SULPHIDES AND A STUDY OF THEIR INFRA-RED ABSORPTION SPECTRA
Yu. K . Y u r ' e v , Y u . A. P e n t i n a n d O. M. R e v e n k o , N e f t e k h i m i y a 7 4 2 - 7 4 8 , 1961.
1: No. 6,
TI~]~ catalytic conversion of oxygen-containing heterocyclic compounds into rings containing a different hetero-atom has been successfully used for the production of 3-methyl-, 3-ethyl-, 3-propyl-, 3-butyl-, and 3-isobutylpentamethylene sulphides from the co)'responding 3 -alkyltetrahydropyrans. A study of the infra-red absorption spectra of the 3-alkylpentamethylene sulphides has shown t h a t the assignment of the frequencies characteristic for the tetrahydrothiopyran ring proposed earlier are, in the main, also valid for this ease. The results obtained in the study of the infra-red absorption spectra of the 2- and 3-alkylpentamethylene sulphides can be used both for the identification of individual representatives of these series of compounds and for the analytical determination of each of the components of a mixture of 2-alkyl- and 3-alkylpentamethylene sulphides. *THE PRODUCTION OF a-OLEFINS BY THE CATALYTIC DEHYDRATION OF PRIMARY ALCOHOLS
L. K h . F r e i d l i n , - V . Z. S'h a r f a n d Z. T. T u k h t a m u r a d o v , N o . 6, 7 4 9 - 7 5 1 , 1961.
Neftekhimiya
1:
A CATALYTIC method for the production of individual C4--Ce a-olefinic hydrocarbons b y dehydrating normal primary alcohols in the presence of calcium triphosphato containing caustic alkali has been developed. The yield of pentenes amounts to 88.5%. The p u r i t y of the pent-l-eno obtained is the same (98%) as t h a t from the pyrolysis of amyl acetate. The yield of hoxenes amounts to 80.6%, and the content of hex-l-ene to 97.6o/o. The catalyst has considerable stability and is readily regenerated.
477
The /'act that the inhibition is independent of the chemical mechanism of the formation of the various radiolysis products is probably duo to the fact that the inhibitor abstracts part of the excitation energy from the electron levels of a n excited molecule or iron to the extent that one chemical reaction or another takes place. The transfer of excitation energy from a molecule of the irradiated hydrocarbon to a molecule of the inhibitor during the radiolysis of n-hexane containing benzene sati.~fle,~ a relationship correspondin~ to the direct electromagnetic transfer of energy. CHROMATOGRAPHIC MATOGRAPHS
SCHEMES
V. G. B e r e z h i n al)(t S . K . 1961.
AND STANDARDIZED
P A R T S FOR
GAS
CHRO-
K r a s h e n i n n i k o v , N e f t e k h i m i y a 1: No. 5, 7 0 0 - 7 0 5 ,
~IMPLE standardized parts for gas chromatographs which permit the rapid selection of a chromatographic scheme giving the optimum conditions for each particular case have been developed. Some new variants of ehromatogwaphie schemes have been proposed, ineludin~ a series-parallel scheme. A method for evaluating the influence of the chromatographic apparatus on the efficiency of separation has been proposed. *SELECTION OF CONDITIONS F O R T H E G A S - C H R O M A T O G R A P H I C OF COMPLEX H Y D R O C A R B O N M I X T U R E S
SEPARATION
M. S. V i g d e r g a u z a n d K . A. G e l ' b e r t , N e f t e k h i m i y a 1: No. 5, 706-715, 1961. .\ METHODof calculation of the worst-separated components in the elution of substances belonging to a n y homologous series is given. At sufficiently high molecular weights, the efficiency of separation of the members of a homologous series remains practically constant. The possibilities of separating complex mixtures of substances on compound cohmms linked in succession have been considered and an equation deduced for the calculation of the m a x i m u m breadth of the fraction being separated. The basis of a general scheme of analysis of multicomponent mixtures is given in which they are separated in a first stage according to their numbers of carbon atoms or their boiling points, with subsequent distribution of the narrow fractions among the cohunns of a second stage, upon which their detailed analysis is carried out. A method for evaluating the breadth of a fraction sent to the second stage of separation has been l)ropose(I. A N INVESTIGATION OF T H E CRYSTALLINE FRACTIONS OF R O M A S H K I N O OIL
HYDROCARBONS
OF T H E H I G H E R
P. I. S a n i n a n d N. K . D r u z h i n i n a , N e f t e k h i m i y a 1: No. 6, 7 2 5 - 7 4 1 , 1961. THE crystalline hydrocarbons present in the 325-375 and 375-500 ° fractions of FComashkino petroleum have been investigated. Crystalline hydrocarbons which form complexes with urea have been isolated from this fraction. Two methods of fractionation were used to separate the hydrocarbons The Publisher will be pleased to quote for the supply of a fllll English translation of any papers abstracted in these pages.
478
Abstracts
of this fraction; distillation in a rectification column of 30 theoretical plates, and molecular distillation in a multi-stage apparatus. F o r the further investigation of the narrower fractions, the method of liquid-phase dehydrogenation was used to determine the naphthenic hydrocarbons containing a hoxamethylene ring and nitration b y Konovalov's method to deter~nine the hydrocarbons with a t e r t i a r y carbon atom. The combined use of these methods allowed conclusions to be drawn on the nature of the hydrocarbons investigated. The crystalline hydrocarbons of the 32;)-375 ° fl'action contain about 12% of cyclic hydrocarbons with a hexamethylene ring and about 600/o of normal paraffinic hydrocarbons. As a previous investigation tins shown, the crystalline hydrocarbons isolated from the broad 375-500 ° fraction contain a b o u t 15% of naphthenie hydrocarbons with a hexamethylene ring. The largest p a r t of the naphthenic hydrocarbons (85%) consists of naphthenic hydrocarbons which form complexes with urea. The content of notarial paraffinio hydrocarbons in the fraction is more t h a n 57~o. I n the course of the investigation it was shown t h a t when hydrocarbons are nitrated b y Konovalov's method, tertiary nitro compounds are formed not only from branchedchain paraffinic hydrocarbons but also from naphthenic hydrocarbons containing a t e r t i a r y carbon atom. These results make it possible to give a new interpretation to the results of the nitration of the crystalline hydrocarbons of petroleum obtained by other authors. *THE SYNTHESIS OF 3-ALKYLPENTAMETHYLENE SULPHIDES AND A STUDY OF THEIR INFRA-RED ABSORPTION SPECTRA
Yu. K . Y u r ' e v , Y u . A. P e n t i n a n d O. M. R e v e n k o , N e f t e k h i m i y a 7 4 2 - 7 4 8 , 1961.
1: No. 6,
TI~]~ catalytic conversion of oxygen-containing heterocyclic compounds into rings containing a different hetero-atom has been successfully used for the production of 3-methyl-, 3-ethyl-, 3-propyl-, 3-butyl-, and 3-isobutylpentamethylene sulphides from the co)'responding 3 -alkyltetrahydropyrans. A study of the infra-red absorption spectra of the 3-alkylpentamethylene sulphides has shown t h a t the assignment of the frequencies characteristic for the tetrahydrothiopyran ring proposed earlier are, in the main, also valid for this ease. The results obtained in the study of the infra-red absorption spectra of the 2- and 3-alkylpentamethylene sulphides can be used both for the identification of individual representatives of these series of compounds and for the analytical determination of each of the components of a mixture of 2-alkyl- and 3-alkylpentamethylene sulphides. *THE PRODUCTION OF a-OLEFINS BY THE CATALYTIC DEHYDRATION OF PRIMARY ALCOHOLS
L. K h . F r e i d l i n , - V . Z. S'h a r f a n d Z. T. T u k h t a m u r a d o v , N o . 6, 7 4 9 - 7 5 1 , 1961.
Neftekhimiya
1:
A CATALYTIC method for the production of individual C4--Ce a-olefinic hydrocarbons b y dehydrating normal primary alcohols in the presence of calcium triphosphato containing caustic alkali has been developed. The yield of pentenes amounts to 88.5%. The p u r i t y of the pent-l-eno obtained is the same (98%) as t h a t from the pyrolysis of amyl acetate. The yield of hoxenes amounts to 80.6%, and the content of hex-l-ene to 97.6o/o. The catalyst has considerable stability and is readily regenerated.