SCIENTIFIC ABSTRACT SHLYAPINTOKH, I.YA. - SHLYAPINTOKH, V.YA.
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SCIENTIFIC ABSTRACT
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SHLYAP INT OKH, I.Ya.
I,-, '~-- --w
State Institute for the Design and Planning of Iron and Nonferrous
Ore Mining Industries. Shakht.stroi. no.11:32-33 H 157. (MIRA 10:12)
1. Nachal'nik tekhnicheakogo otdela instituta Girporud~&.
(Iron mines and mining) (Nonferrous metal industries)
(Research, Industrial)
1A
AUTHORS: Tsepalov, V. F., Shlyapintokh, 1. Ya. 20-4--31/51
TITLE: Note on the Intermediate Products in Redox Photoreactions
of Xanthine Dyes (0 promezhutochnykh produktakh v
okislitellnovosstanovitelinykh fotoreaktsiyakh ksantenovykh
krasiteley).
PERIODICAL: Doklady AN SSSRy 1957, Vol. 116, Nr 4, pp. 641-644 (USSR)
ABSTRACT: The xanthine dyes eosine, erythrosine and bengal
pink are frequently utilized photosensitizer of oxydation
and polymerization processes. A potentiometer method was
employed for studying the photo reduction and photo
oxydation of xanthine dyes. In the present paper the
measurements of the photo galvanic effect permitted the
recording of the formation of the intermediate products in
the redox- reactions of some dyes. The experiments were
conducted in a container with platinum electrodes. The
authors established the following facts in complete
accordance with the results obtained from chlorophyll
theophitine (feofitin) and other pigments. The illumination
of an alcoholic solution or of a pyridine solution of a
xanthine dye ( C = 10-6 -10-3 ,01/1) shifts the electrode
Card 1/3 potential towards the positive in the presence of oxygen.
Note on the Intermediate Products in Rodox Photoreactions 20-4-31/51
of Xanthine Dyes
An illumination in the presence of reducing substances
(alcohol, pyridine, ascorbinic acid, aldehyde) shifts the
electrode potential towards the negative. A diagram
illustrates the kinetic curves of the modification of
potential of a platinum electrode, which is immersed in a
pyridine solution of eosine. The measurements were conducted
with different light intensities from I = 1 to I = 0,08.
On illumination the potential decreases, reaches a certain
minimum, the increases again and returns to the original
value. The modification of the photo potential observed here
is connected with the existence of an intermediate product.
The condiderations institute by the authors also explain
the dependence of the kinetics of the modification of the
potential on the concentration of the dye, which has been
observed experimentally. An increase of concentration of
eosine shows in Ueneral the same influence on the kinetics
of the process as an increase of the light intensity. On
a cooling down the velocity of the potential reversal
decreases quickly. The character of the dependence of the
Card 2/3 kinetics of the modification of the potential on temperature
Hote on the Intermediate Products in Redox Photoreactions 20-4-31/51
-of Xanthine Dyes
distinctly speaks in favour for a stage-like character
of the reduction process. Finally, a few words are said
concerning this reaction at various pigments.
There are 4 figures, and 3 Slavic references.
PRESENTED: April12, 1957, by A. N. Terenin, Academician
SUBMITTED: February 7, 1957
AVAILABLE: Library of Congress
Card 3/3
AUTHORS. Seli7Enov,., V. V.,,.-Shiyapintokhp I. Ta. 76-32-3-27/43
TITLE: The The=modynamic Proper,t,:L-,of Air in Thermal IonizatiorL
and the Shook Va-,?,,e (Termodinamicheskiye evoystva
vozdukha pr--' termicheskoy -ionizatsii i udarnaya voina)
PERIODICAL-~ Zhurnal Fizicheskoy Khimii~ 1958o, Vol 32~ Nr 3,v
pp 670-678 (USSR)
ABSTRACT- AccordIng to-Davies (reference 1), full dissooiation
of the air is practically obtained a'. temperatures of'
10 000-15 OOOOC, whereas at still higher temperatures,
thermal radiations play an important part. The data
of the thermodynami'c properties of air at several 1 OOOOC
are to be found in the papers by Davies (reference 1)V
M. P. Vukaiovuch (i-eference 2), Ya. B. Zelsdovich and
A. I. Polya-.nyy (reference 13), as well as Llyr-is and
Ellbe (reference 4)9 whereas the present work performs
determinatlons of the thermodynamic properties of air
at temperatures where the dissociation-is finished and
Card 113 where only ionization and radiation take place. The
The Thermodynamic Properties of Air in Thermal 76-32-3-27/43
Ionization and the Shock Wave
investigations were not made in natural air, but in a mixture of
79.1% nitrogen and 20.9% oxygen (by volume). In the calculation
of the statistical sums, it is emphasized that the number of
energy levels shall be limited, for the solution of this problem
is considered complicated and the selection of the number of levels
is practically arbitrary. In the present work the number 10 was
never surpassed. It is said that a wrong selection of numbers
exerts little influence upon the final results. The obtained
experimental results show that at temperatures of 200,000 - 400,000 OC
the gas mixture mainly consists of free electrons and nuclei of
nitrogen and oxygen with 2 helium electrons, this being explained
by the higher dissociation energy of the two last-mentioned electrons.
The results of the calculation of the thermodynamic quantities are
given in tables. From the obtained results and diagrams follows
that a great influence of the dissociation and ionization upon the
Card 2/3 front parameters of the shock wave is exists, the latter propagating
The Thermodynamic Properties of Air in Thermal
Ionization and the Shock Wave
with velocities up to 115 km/sec.
D. A. Frank-KELmenetskiy and Ya. B.
There are /+ figures, 6 tables, and
Soviet.
76-32-3-27/43
Finally the authors thank Professor
Zelldovich, Corresponding Member.
10 references, 8 of which are
ASSOCIATION: Akademiya nauk SSSR, Institut k7himicheskoy fiziki, 'Moskva
(AS USSR Moscow Institute of Chemical Physics)
SUBMITTED: December 28, 1956
SHLYAPI19T OXH, L.
A machine for the duplication of drawings. Prof.-tekh. obr.
12 no-5:29 MY '55- (XLHA 6:8)
1. Zamestitell direktora, po uchebno-proizvodetvennoy chast
remeslennogo uchilishcha No. 9 (Moskva)
(Multigraph)
"V a z
-Z ;OLI
3 V
=-~Vi az' rc; 2-t-
L~L- Gf
LCTI, i9,~2,
KITAIIIN, Valintin Tev'grin'yevich-, PTUROV, Vadim Kona tantinovich;
'SiLLYPTINTOKII, L6v Samoylovich; KUKHMV, D.A., dotsent,
redaktor; KOPTEVSKIY. D.Ya.
redak-t,-,r; OSTRIWV, N.S., tekhnicheskly redaktor
[31 15~
I- lectric r-?,- inaering] El6ktrotekhnika. Moskva, Vses. uchebao-
p6dagoi~.izd--vn Trudrezervizdat, 1955. 219 p. (MLRA 3:10)
('21actric engineering)
KITAUV, Valentin Yevgenlyevich, kandidat tekhnicheskikh nauk; PETROV.
TVAD 0
Vadim Konstantinovich, iazhener- SHLYAPINTO I's , oylovich,
inzhener; KOPTZVSKIY, D.Ta., reaiaiKmorpr, AB'XUUIUJL, r Ij.9 ek c e-
Bkiy redaktor
E.9lectric engineering] Alektrotekhnikas Izda 2-oe, perer. i dop.
Moskva. Vaes.uchebao-padagog. izd-vo Trudrezervizdat, 1956. 271 P.
(Blectric engineering) (M1RA 10:9)
f/ ?7- 7
GRAMRATIKATI, Vera Mikhaylovna; PETROV, Vadim Konstantinovich; �H,L-IYAPINTOXHO.....
Lev Samoylovich; BILINSKIY, M.Ya., red.; BARANOVA, N.N., tekhn.
[Teaching electric engineering; a concise practical manual]
Prepodavanie elektrotekhniki; kratkoe metodicheskoe posobie.
Moskva, Vses.uchebno-pedagog.izd-vo Trudrezervizdat, 1957. 102 p.
(MIRA 11:1)
(Electric engineering--Study and teaching)
At
KIMRUK, Alaksandr Fedorovich DUKOV, V.M.'
redaktor; KOZLOVSXA M.D., takhnichaskiy re" tor
[Practical manual of electric engineering; a texbtook for students
An the tenth grade] Rukovodsto k praktikumu po alaktrotakhnike;
uchabnoe posobie dlia uchashchikhsta I klassov. Moskva, Goa.
uchabno-padegog.izd-vo H-va proav. RSFSR, 1957. 175 P. (MIj3A 10:9)
(slactric angInearing)
SHLYAPIYTOKH. L.S - BAKINOV, V.N.
........... mmmm~
CIRops used in electrotechnical installation work. Politekh.
obuch. no.4:84-85 Ap 10. (MA 10:7)
(19lectric apparatus and appliances)
SHLYAPINT . - -.- . -I.. .
A good visual aiA. Politekh, obuch. no-5:-89-92 My '57. (MLRA 101-6)
(Visual aide) (Woodwork (Manual training))
PETROV, Vad~m Konstantinovich, inzh. ; Z~A~IHTQKH, Lev Samoylovic!~,'-Inzh.;
METER, Yakov Solomonovich, nauchny-Y'i6'a.'!,!'KOPTEVSK'tt,-V.-tT.,' red.;
ROGACFM.V. F.V., red.; RAKOV, S.I.. tekba.red.
[Collection of problems In electric engineering for communication
scbools] Sbornik zadach po elektrotekhnike dlia romeslennykh
uchilishch sviazi. Izd.2., ispr. I dop. Moskva, Irses. uchebno-
pedagog. izd-vo Trudrezervizdat, 1958- 154 p. (14IRA 12:1)
(Electric engineering--Problems, exercises, etc.)
PETROV, Vadim Konstantinovichi inzh.; MMTAPINTOKH, Lev 01=71ovich,
inzh.; POLTANSKAT-A, T.D., na-66- MWMA -9 - G-.-A. . red. -,
TaM, A.M., tekhn.red.
[Collection of problems in electrical engineering] Sbornik
zadach po elektrotekWks. Izd.3., ispr. i dop. Moskva, Voss.
nchebno-pedagog.izd-vo Proftekhizdat, 1960. 173 P. (MIRA 13:5)
(Electric engineering-Problems, exercises, etc.)
KITAYEV, Valentin Yevgenlyevich- SHLYAPINTOKE Lev Samoylo-vich; SVITKOV,
I -
L.P., red.; SMIRNOVA, M. -,iekbn. rede'.
f
[For the young electrical engineer] IUnomu elektrotekhniku. Mo-
skva, Gos. uchebno-pedagog. izd-vo M-va proav. RSY5Rq 1961. 134 p.
(MIRA 14:7)
(Electric engineering)
KITAYEV, Valentin Yevgenlyevich; PIRROV, Vadim Konstantinovich [deceased];
SHLYAPINTOKH. Lev Samoylovich; SIMOMOV, -A.F., nsuchnyy red.;
'--IOFFE, M.L., red.izd-va, fd=F9 I.M., tekhn.red.
[Electrical engineering] Elektrotekhmike. Izd.'01,., perer. i dop.
Moskva, Vses.uchebno-pedegog.izd-vo Proftekhizdat, 1961. 351 P.
(MMA 14:3 )
(Electric engineering)
SHLY preDodavatell.elektrotekhr,.iki;
SKITEVA, R.A., red.; NESMiSLOVA, L.M., tekhn. red.
[Methodological aid in electrical engineeringjMetodicheskoe
posoble po elektrotekhnike; dlia prepodavatelei brigadnoi i
individuallnoi podgotovki stanochnikov na predpi.144tiiakh.
Moskv&, Proftekh:Lzdat, 1962. 57 p. OCIRA-16:2)
(tlectrid engineering)
GH&MATIKATI, Vera 1-iikhaylovna; SHLYAPINTOKH., Lev $E_a._aZ1qiricht
PETROV, Vadim Konstantino-vich [deceased]; kMfft~, 1.S.,
nauchn. red.; SILIVERSTROVICH, G.A., red.; DORODNOVA,
L.A., tekhn. red.
(Teaching electrical engineering together with the
fundamentals 'of industrial electronics) Prepodavanie elek-
trotekh'niki s osnovami promyshlennoi elektroniki. Moskva,
Praftekhizdat, 1963. 174 P. (MIRA 17:3)
PETROV, Vadim Konstantinovich [deceased]; SHLYAPATOKH Lev
oylovich!, GETLING, B.V., nauchr~.-'~ed.; MUP!fflrA-;---
V.G., red. -
[Collection of problems in electrical engineering with
industrial electronics fundamentals] Sbornik zaclach po
elektrotekhnike s osnovami promyshlennoi elektraniki.
Moskvay Vysshaia shkola, 1965. 174 p.
WRA 18:1-7)
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77
SOV/62-59-4-10/42
AUTHORS: Tsepalov, V. F., Shlyapintokh, V. Ya.
TITLE- Mechanism of the Photoreduction of Xa.,it',!--"e D~,estuffs
(l,',ekhanizm reaktsii fotovosstanovleniya ks-=tenovykh krasiteley)
PEdIODICAL: Izvestiya kkademii nauk SSSR. Otdeleniye khimicheskikh nauk,
1959, Nr 4, pp 637-643 (USSR)
ABSTRACT: The photoreduction of xanthene dyestuffs consists in a trans-
formation of the dyestuff into a colorless leuco -~;,;mpound; the
dyestuff is completely bleached out when the reaction is
completed. Eosine, erythrosine, chemically pure Bengal pink and
("ch.d.a")ascorbic acid were used in the present work whereas
ethanol and pyridine were used as solvents. A typical kinetic
curve of the potential change of the platinum electrode dipped
in the dyestuff solution exposed to light is shown in figure 1,
It is seen that the potential changes quickly in the negative
direction upon exposure to light to reach the minimum and return
to the initial value. This course has been ascribed to the
presence of an intermediate product formed during the reduction
of the eosine. With the aid of potentiometric measurements it
Card 1/3 has been found that the intermediate products formed during the
Mechanism of the Photoreduction of Xanthene Dyestuffs SOV/62-59-4-10/42
reduction of the dyestuffs are sufficiently stable and have a
life of -300 to -400 minutes. In view of the data found on the
life and on the conditions under which the highest concentra-
tions of intermediate products can be obtained the photoreduc-
tion of the xanthene dyestuffs has been subjected to spectral
analysis. The spectra of the intermediate products are shown in
figure 3. As the spectrum of an intermediate product depends
neither on the dyestuff nor on the reducing agent this compound
can be assumed not to form any complex with the dyestuff or the
reducing agent. Figure 4 shows the kinetic curves of the inter-
mediate products of eosine and the potential change of the elec-
trode determined during an experiment conducted at room tempera-
ture. These data indicate that the concentration of the inter-
mediate product at the time when the light is removed is
cEff>7 10- 6 or 20% of the initial concentration of the
,_ - 11 -
eosine. The highest concentration reaches 354,. Based on the same
data the molar absorption coefficient of the intermediate prod-
uct has been obtained (E EN)427 1.1 . 104 1/mole-cm. As is ap-
Card 2/3 parent from figure 5 the highest optical density of the inter-
Mechanism of the Photoreduction of Xanthene Dyestuffs sov/62-59-4-10/42
mediate product at -350 reaches 0.62, which means that it is
about five times higher than at room temperature. The estizia-
tion of the maximum concentration in view of the amount of dye-
stuff regenerated after the removal of light has led to the
values c... ~/>42% of4the initial eosine and
(E EN) 427,,:~,4-4 - 10 1/mole-cm. The cause for the great varia-
tion of the EEN values with temperature has not been clarified.
It becomes evident from figure 6 that the potential reaches the
zero level more quickly at a higher concentration of the reduc-
ing agent. This shows that the intermediate product is consumed
more quickly than it is formed. There are 7 figures and 5 ref-
erences, 2 of which are Soviet.
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR (Inotitute of
Chemical Physics of the Academy of Sciences, USSR)
SUBMITTED: July 10, 1957
Card 3/3
5(3), 5(4), 24(7) 391/.51-7-1-19/27
AUTHORS: Bubnov, N.N., Kibalko, L-A., Tsepalor, V.F. and Shlyapintoich, V.Ya.
TITLE: On the Nature of the Intenaediate Product in the Reaction of Photo-
reduction of Eo'sin t0 prirode promezhutochnogo produkta v reaktsii
fotovosstanovleniya eosina)
I
PERIODICAL: Optika i suektroskoviya, 1959, Vol 7, Nr 1, m3 117-119 (USSR)
ABSTR.ACT: Eosin solution in pyridine (10-inole/litre) was photoreduced in the
presence of ascorbic acid (10-3 mole/litre). A SVDSh-250 lamp was
used as the light source and the reaction was studied using an
electron- ps. rama Snetic-res onance (e.p.r.) spectrometer with high-frequency
modulation of the inagnetic field. The e.p.r. spectrum kthe upper
figure on p 118) was a triplet with the component intensities in the
ratio 1:2-1 (the hyperfine-structure splitting mas AH = 4.6 7t 0.2 oersted)
The a.p.r. sDectrum was due to an intermediate prodact in the photo-
reduction reaction; the shaDe of the spactruat confirmad earlier
Card 1/2
SOV/51-7-1-19/27
On the Nature of the Intermediate Product in the Reaction of Fhatrireduction of
Eosin
suggestions kRefs 1, 2) that (1) the intennediate product is eosin
semiquinone, and that (2), in the photo chewi;:a 11 y -a otive APta, eosin
is a metastable biradical. There are 2 figures and 10 references,
4 of which are Soviet, 3 German, 2 English and I French.
SUMUTTEDs November 25, 1958
Card 2/2
2 4 7
T" SOV148-23
Bubnov, N. N., Tsepalov, V. F., -1-0-36139
SJ~Ljy~~Pintokh, V. Ya.
TPITLE; The Spectra of Paramagnetic Electron Resonance of Eosin
Semiquinone in a Live Leaf
i:EI?IODICAL: Izvestiya Akademii nauk SSSR. Seriya fizicheakaya, 1959,
Vol 23, Nr 10, pp 1265 - 1266 (TJSSR)
kEBSTIUCT: The present paper intends to explain the nature of the inter-
mediate products in the photochemical reactions of eosin and..
chlorophyll. The investigations were carried out at room
temperature with high-frequency modulation of the magnetic
field. Method and apparatus are described in references 1
and 2. First, some results concerning the photoreduction of
eosin are discussed. This reaction consists in the transforma-
tion of the dye into a leuco-compound and has already been
potentiometrically and spectroscopically investigated
(Refs 30). The authors assuined that a comparatively stable
intermediate product is formea (semiquinone dye), Aich may
have a life of several seconds at room temperature. An investi--
gation of the paramagnetic electron resonance spectrum of
Card 1/2 eosin (solvent: piridine, reducer: ascorbic acid) showed a
Tlio Spectra of Paramagnetic Blc~.tror Resonance of SOV146-23-10-36139
Eosin St-amiquinone in a Live Leaf
triplet splitting (intensity ratio 1:2:1,,4H = 4.6 + 0.2 Gs)
which is caused by the interaction between the unpaired elec-
tron and two protons. The photochemical reaction which de-
velops by way of a biradical, is shown schematically and has
already been described by Schenck (Ref 5). The authors of the
present paper were the first to investigate the resonance
spectrum of a live leaf. A leaf of agrophyrum repens was used
for this purpose. The resonance signal showed a doublet, hyper-
fine splitting amounted to AH = 1.8 + 0.2 Gs. There are 5 ref-
erences, 4 of which are Soviet.
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR (Institute of
Chemical Physics of the Academy of Sciences, USSR)
Card 2/2
5W SOV/20-124-4-43/67
AUTHORS: Tsepalov, V. F., Shlyapintokh, V. Ya.
TITLE: The Determination of the Elementary Constants of the Reaction
of the Oxidation of Ethyl-benzene by the Method of Intermittent
Illumination (Opredeleniye elementarnykh konstant reaktsii
okisleniya etilberizola metodom preryvistogo osveshcheniya)
-PERIODICAL: Doklady Akademii nauk SSSR-, 191-9, Vol 124, Nr 4, PP 883--886
(USSR)
ABSTRACT: According to present-day concepts, the oxidation of hydro-
carbons in the liquid phase develops according to a chain
mechanism accompanied by the formation of hydrogen peroxide
as the primary stable product of oxidation. At moderate tem-
peratures hydrogen peroxide is also the final product, and
in this case the reaction develops in accordance with the
folloving scheme; Production of radicals A or RO , rate w i
k2 - ko 2' i
(I). Continuation of the chain k ~ 0 2 2
~O2 + RH ~" RO2H + R (III). 2i inactive products
k k 6
(IV)~ R + k0 2 ~:"- inactive products (V); 2iQ,--~4 inactive
Card 1/4 products (VI). Here RH denotes the hydrocarbon, h - an alkali
SOV/2o-124-4-43/67
The Determination of the Elementary Constants of the Reaction o]" the
Oxidation of Ethyl-benzene by the Method of Intermittent Illumination
radical, and ;0 2 '* a peroxide radical. Next, an expression
is written down fo*he rate of the reaction for this scheme
for the case of long chains, and is then specialized for the
case of sufficiently hi.'rh concentrations V-021 of oxygen:
d ~02] 1/2 ./2 [RHJ . In the case of short chains
- = w k k
dt 1 3 6
the initiation rate w i must be added to the right Dart. The
last-mentioned equation contains 3 unknown quantities wi9
k3 and k6, and accordingly~ three independent relations are
required for the separate determination of these three quan-
tities. The theory of the method of continuous illumination
of such a decomposition has already been discussed in an
earlier paper (Ref 3). By means of this method it is possible
to measure the mean life of this chain, or, which is ihe
Card 2/4 same thing, the mean life T of the radical. Formulas for the
SOV/20-124-4-43/67
The Determination of the Elementary Constants of the Reaction of the
Oxidation of Ethyl-benzene by the Method of Intermittent illumination
determination of T are written down. Carrying out of the
experiments is described in short. The rate of reaction is
determined from the absorption of oxygen in a vacuum device
with automatic recording. The light source used was a mercury
lamp SVDSh-250. which was fed with direct current. The next
chapter-deals with the determination of the initiation rate.
The experimentally determined dependence of d 10 21 /dt on
the concentration i/[Bj of the inhibitor,is shown by a dia-
gram. The straight lines for 4' inhibitors at different tem-
peratures intersect at one and the same point, which is
indicative of the fact that the additions of these inhibitors
do not modify the initiation rate itself and that the latter
also does not depend on temperature. This fact was used for
the direct measurement of the quaritity w.. For this purpose
the dependence of the reaction rate on temperature was deter-
mined. In the case of sufficiently low temperatures (5-15')
the reaction rate does not depend on temperature. Within this
temperature rIn e the length of the chain is near zero, and
it holds that df021 /dt = w'. The values of w. determined
Card 3/4 by the inhibitor method ani from the temperaiure-dependencG
SOV/2o-124-4-43/67
The Determination of the Elementary Constants of the Reaction of the
Oxidation of Ethyl-benzene by the Method of Intermittent Illumination
of the reaction rate are in practical agreement. Furthermore,
the initiation rate was determined by means of the second
method, because more accurate results may be obtained in this
way within a shorter time. In the last part of this paper
the life-times of peroxide radicals are determined. There
are 4 figures, 1 table, and 6 references, 1 of which is
Soviet.
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR
(Institute for Chemical Physics of the Academy of Sciences,
USSR)
PRESENTED: October 11, 1958, by V. N. Kondrat"yev, Academician
SUBMITTED: September 2o, 1958
Card 4/4
5W
AUTHORS: Vasillyev, R. F, Karpukh-'Ln,, 0,. IV,, SOV/20-1 24 -6-21/5 5
Shlyapintokh,, V~ Ya. , Emanuel 11, 114. ,. Corresponding Member,
AS USSR
TITLE: Gas In-itiaticn by Ozone in the Reaction of the Oxidation of
Isodecane and tb- 01--iluminescence Connected With It
(Gazcvoye. ~ *.7 -,_ _%. ,e zonom v reaktsii okisleniya izc--
dekana i svyaziz-,~.tp. s nim khemilyuminestser-ts-iya)
PERIODICAL: Doklady Akademii nauk SSSRI 1959., Vol 124,, Nr 6~ pp '125B-1260
(USSR)
ABSTRACT: The present paper deals tith the staL-,e of initiation by ozone
in segregated form,, i.e. the authors investigate such phenom-
ena and processes as ozeur during the short action of the
initiator. Isodecane (2.7-dimethyl-octane) was used as test
object. Preliminary tests shcwed that if ozone is blown past
during a short time the reaction is accelerated considerably.
The authors recorde& a weak glow which was produced during
the bubbling of oxygen (containing 2-3 % ozone) by isodecane.
This isodecane was in a glass cxidatlion cell at temperatures
of 20-900. By glow the photomultiplier FEUz-19 served as an
Card 1/3 indicator of the glow. The photoelectric current was recorded
Gas Initiation by Ozone in the Reaction of the SOV/20-124-6-21/55
Oxidation of Isodecane apd the Chemiluminescence Con-nected With It
by means of tha alectroni.-% potentiometer EPPV-51. The first
diagram shows the intensity of glow as a function of time
during the uninterrupted b1cwing-through of ozone and iso-
decane at a temperature of '~qO. Tntensity increases gradu-
ally and, after 2.-5 hours, it attains a maximum after which
it gradtially decre-asps. As soon as the adding of ozone is
interrupted, the glow immediately vanishes in all stages of
the reaction.. If ozone Js again supplied,, 41-,he previous inten-
sity i.3 qu-iol~~,y restored. Acitlording to these results the low
is caused in the --r-terantion between ozone and a compound,
which was formed alxeady before this interaction as the
-.esult of a reactlon of ozone with 3arbono The above mentioned
intensity maxim-= indi,-,ates that the concentration of this
hypothetical compcund passas through a maximum, In this case
the kinetics of the accumulation of this compound agrees
with the kinetics of the accumulation of the intermediate
product in the case of successive chemical reaction. An other
possibility of explaining the phenomena discussed is re-
jected on the Grounds of being unsuited, A further proof of
Card 2/3 the intermediate 1-ha--ac-Ier of the product of primary interaction
Gas Initiation by Ozone
Oxidation of isodecane
ASSOCIATION:
the Reaction of the SOV'/20-124-6-21/55
the Chemiluminescence Connected With It
with ozone was supplied by experiments carried out with
higher temperatures, Thus,, the interaction between ozone and
normal hydrocarbons at moderate temoeratures is a complicated
process in the course of which a relatively stable inter-
mediate compoirid is formed, There are 3 figures and 4 Soviet
references,
fizicheskoy khimi4i Akademii nauk SSSR (Institute of
Chemistry of the Academy of Soien,_.es.-, USSR)
5 (4 )
UT HORS x Vaftillyev, R., F., Farpukhin, 0, 14, SOY/20-125-1-28/67
Shlyapintokh, V.. Ya.
TITLE. Chemiluminescence in Reactions of Thermal Decomposition
(Khemilyuminestsentsiya v reaktsiyakh termicheskogo rasnada)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 12:3, Nr 1, )p 106-109
(USSR)
ABSTRACT: The present Daper describes the results obtained from
exueriments, in which a very weak luminescence was detected.
The luminescence in question occurs with the decomposition of
some or.-anic compounds in hydrocarbons as solvents. A figure
illustrates the scheme of the apparatus used for recording the
luminescence. The reaction takes place in a cuvette placed in
a transparent chamber. The cuvette is enclosed by a water-heated
outer glass wall which acts as a thermostat. The image of the
clavette is then projected onto the photocathode of the
ohotomultiplier FEU-199 and the current supplied bj the latter
is recorded by an electronic potentiometer EPPV-51c The authors
investigated the thermal decomposition of the hydrogen peroxides
of Tetralin; 2.7-dimethyloctane; isopropylbenzene; benzoyl
Card 1/3 peroxide and isoazobutyronitryl. Chlorobenzene was used as a
in Reactions of Thermal Decom,-,o.--,it i r, n
S07 20-12'-J-1-26/67
D 1j
solvent in all reactions, A table specifies the conditions
under which the reaction was investi.-ated. According to the
experimental results the intensity cf luminescence increases
with rising temperature. In the case of 'the hydrogen peroxides
of 2-7-dijaethyl octane and of tetralin as well a-I of benzoy!
peroxide., the law I-.f--xp(--A/IIT) holds with good accuracy for
the interisity of luajinescenc:e.. For these substances 'the
tem-oerature coefficients amount to 29.~+1.0; 26,5j~1-5; .31.9�1-0-
At a given temperature, intensity remains unvaried for many
hours; however, there is a limit temperature for each substance,
beyond which inten,,--ity decreases accordint-, to an exponential law.
The existence- of a chemilur.,iinesQence signifies that the reaction
3one contains excited particles, In all of the chemical systems
investigated by the authors, only recombination reactions of
radicals briniz about an excitation. The follovinn- deDendence on
time and temDerature applies for the intensity of luainescence:
E/RT -kt-
I-e e ,Most of the reactions investigated here agreed
w-~ll rith this lay.. The tem-.)eratur- coefficients A deter--.iinecl by
Card 2/3 the authors are in agreement with 'the activation energies of the
Che:Aluminescence in Reactions of Ther.,:,,al soir/ "67
Decomposition
decomposition of the correspondinE substances, Chemilumminescence
reactions mad- videly occur everl ir, simple reactions- The
authors probably observed the lum-inescence of primary excited
particles, There are 3 figurcs, 1 table, and 6 references, 2
cf which are Soviet.
ASSOCIATION-, Institut khimi~ahesko- fiziki. &kadei:iii nauk SSS? (Institute
of Chem-'cal Physics of the Academ,,,r of Sciencc.,-,
T
PRESE.NTED October 29-. 1958, by V, -11, Kondrat~yev, Acadenician
SUB".TTT':D Se-itembc-r 20., '.958-
Card 3/3
ENTELIS, S.G,;--,--SHLYAPINTOKH, V.Ya.; KARPUKHIN, O.N.; NESTEROV, O.V.
Chemiluminescence in the reaction involving the formation of
nylon when the process to carried out in solution and at the
ph-Rae boundary. Vysokom. sced. 2 no. 3:463 Mr 160.
(MMA 13:11)
(Nylon) (Luminescence)
86408
2 2- 12- 0 8, 12 14 S//062/60/000/008/015/033/xx
5'.1190 B013/BO55
AUTHORS: Vasillyev, R. F., Kozlova, Z. G., C~huchukina, L. G.,
_,.~ Ya.., and Emanuel', N. M.
J11
TITLE: On the Change in Catalytic Activity of Nickel Stearate
During the Oxidation of Ethyl Benzene
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk,
1960, No. 8, pp. 1337-1341
TEXT: The present publication treats a phenomenon observed during the
nickel-distearate catalyzed oxidation of various hydrocarbons. The authors
observed that in these reactions the maximum concentration of the hydro-
peroxide fairly eQuals its concentration in an uncatalyzed reaction. It
was shown that the anomalous course of the kinetic curve of the hydro-
peroxide during the oxidation of ethyl benzene is connected with an in
activation of the catalyst. Various experiments were cade to establish the
cause of the reduced activity of the catalyst during the oxidation process
(Figs. 3, 4). These experiments lead the authors to assume that products
reacting with the catalyst and reducing its activity are formed during
Card 1/3
86408
On the Change in Catalytic Activity of Nickel 3/062/60/000/008/015/033/XX
Stearate During the Oxidation of Ethyl BenzeneBO13/BO55
the reaction. Since acids accumulate during the oxidation of the decompo-
sition products of hydroperoxide, it seems likely that these very acids
inactivate the catalyst, e.g. by forming insoluble salts (Refs. 2-4). Ex-
periments performed in this direction showed that tile reduced activity
of the catalyst is indeed related to its reaction with these acids (Fig.
5). Theestablished reduction of catalyst activity during the reaction
permits a simple explanation for the accumulation of peroxides during the
nickel-stearate catalyzed reaction (Pigs. 1, 2). Till the maximum peroxide
concentration is reached, the nickel salt is completely inactivated. The
reaction is then practically uncatalyzed and the maximum peroxide concen-
trations are therefore in agreement. At the same time the maximum concen-
tration is reached more quickly in the presence of nickel stearate since
the latter has a strong catalytic effect at the outset of the reaction.
The results of this investigation furnish further proof that in the cata-
lytic oxidation of hydrocarbons metal salts are no catalysts but rather
initiators of the process. Their activity, and frequently also the
mechanism of their effect, change during the process. The observed reaction
kinetics therefore reflect not only the properties of the reacting system,
but also the changes in the activity and action of the catalyst in the
Card 2/3
On the Change in Catalytic Activity of Nickel ~"/6t/UOO/O0'8/015/O33/XX
Stearate During the Oxidation of Ethyl B013/BO55
Benzene
individual stages of the reaction. In studies of the catalytic mechanism,
stabilization of the catalyst is particularly important. This would con-
siderably facilitate the explanation of the mechanism of the catalytic
effect of metal salts. There are 6 figures and 4 references: 3 Soviet
and 1 British.
ASSOCIATION: Institut khimLcheskoy fiziki Akademii nauk SSSR
(Institute of Chemical Physics of the Academy of Sciences
USSR) V
SUBMITTED: February 16, 1959
Card 3/3
BUBNOV, N.N.; KRASNOVSKIY, A.A.; UMRIKEINAq A.V.; TSEPALOV, V.E.;
SHLYAPINOTOKH9 V.Ya.
Electron paramagnetic resonance spectra observable during the
illimination of plant leaves and photoreduction of chlorophyll
and its analogues. Biofizika 5 no. 2:122-126 160. (MIRA 14:4)
1. Institut khimicheskoy fiziki AN SSSR i Institut biokhimii im.
A.N. Bakha AN SSSR, Moskva.
(CHLOROPHYLL)
(PARAMAGNETIC RESONANCE AND RELAXATION)
VASILIYEVP R.F.; KOZLOVA, Z.G.; CHUCHUKINA, L.G.; SHLYAPINTOKH, V.Ya.;
F14ANM I J, N.M. I - .
Change of the catalytic activity of nickel stearate in the process
of ethylbenzene oxidation. Izv.AN SSSR Ortd.khim.nauk no.8:1337-
1341 Ag 160. (IGRA 15:5)
1. Institut khiin+chesko fiziki AN SSSR.
(Catalysta, Nickei~ (Benzene) (Oxidation)
S/076/60/034/007/040/042t/,X
3004/Bc68
AUTHORS: Entelis, S. G., Shlyapintokh, V. Ya., Karpukhin, 0. N.,
and Nesterov, 0.
TITLE: Chemiluminescence in Reactions of Acid Chlorides With
Amines and Ketones
PERIODICAL: Zhurnal fizicheskoy khimii, 1960, Vol. 34, No. 7,
p..1651
TEXT: It was established by the authors that the acylation of amines
and ketones by organic acid chlorides is accompanied by chemilumines-
cence. Luminescence can be observed with an~)9-29 (FEU-29) photomulti-
plier sensitive to the range from 350 - 610 mg. The following reactions
of the components dissolved in organic solvents are mentioned:
Card 1/3
Chemiluminescence in Reactions of Acid S/076/60/034/007/040/042/XX
Chlorides With Amines and Ketones B0041Bo68
Reaction Signal*
C6H5NH2 + C6H5COC1 0 (dissolved in chlorobenzene)
C6H5NH2 + C6H5coci 0.55 (dissolved in benzene)
C6H5NH2 + C6H5COU 2-5.5 (dissolved in acetone)
v
C6H5NH2 + ClOC(CH 2)4 coci 6.5 (amine in acetone, chloride in toluene
)
C6H5NH2 + ClOC(CH 2)4 coci 7 (amine in benzene, chloride in toluene)
CH3COCH3+ C6H5coci 0.35 (ketone in acetone, chloride in benzene)
CH3COCH3+ CIOC(CH2)4 coci 0.7 (ketone in acetone I chloride in toluene)
C 6H5NH2+ HC1 0.01 (dissolved in chlorobelizene)
* The intensity of the signal is expressed in relative unita. About
2-104 quanta/sec.cm3 of the reaction volume are taken as unit. There is
1 table.
Card 2/3
Chemiluminescence in Reactions of Acid S/076/60,/034/007/040/042/XX
Chlorides With Amines and Ketones 3004/Bo6a
ASSOCIATION: Akademiya nauk SSSR, Institut khimicheskoy fiziki, Moskva
(Academy of Soiences USSR, Institute of Chemical Physics,
Moscow)
SUBMITTED: December 29, 1959
Card 3/3
-VASIL'YEV, R.F.; SHLYAPINTOKHq V.Ya.; EMANUEL', NII.M.
Mechanism of the initiating action of nitrogen dioxide in the
oxidation of 2,7-dimethyloctane by molecular oxygen. Izv. All
SSSR. Otd. khim. nauk no.2:218-225 F 161. (MIRA 14:2)
1. Institut kbimicheskoy fiziki AN SSSR.
(Octane) (Nitrogen oxide)
23567
S/062/61/000/'005/002/009
2ZO9 IZ51 '7-19 B118/B206
AUTHORS-, Korsun.4 A,G., Shlyapin-vokh, V. Ya.,,and Emanue~, N. M.
TITLED Catalytic decomposition of ethyl benzene hydroperoxide
PERIODICALt Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no, ~?,. 1,961, 788 - 796
TEM The systems consisting of a metal salt of variable valence and a
peroxide are frequently used as catalysts in the oxidation of hydrocar-
bong and as initiators in the radical polymerization, The mode of action
of such systems is based on the fact that they produce free radicals and
L . --
,hus -increase the ~n-i"ation rate of the chains, The salt catalysts under-
go a change during the ~xidatiori process in the oxidation of hydrocarbons.
During the reaction the valence of 'he metal changes, and complexes are
formed from the metal salt and the reaction products with the metal salt
being preripitated in certain cases. The catalyst may play a part not
only 1-n the in.Lriation of the chains, but also in the chain rupture and,
apparen7 Ij in the 9P--)ngation of the chains. Such changes of the catalyst
and i's manifold functions highly complicate the reaction kinetics and
Card
23587
0
S/062/61/000/005/002/009
Catalytic decomposi~icn of- B118/B208
make it difficiilt to under3tand ~he mechanism of the catalytic effect of
metal salts. In order to solve this general problem the authors analyzed
the reaction of the catalytic oxidation of hydrocarbons, and studied each
single 3tage In the present paper one of the most important reaction
stages of the catalytic reaction is studied, i., P., the reaction of a
hydroperoxide with a me-al salt whose metal has a variable valence. The
k-,nE,tjcs of thQ catalytic decomposition of ethyl benzene hydroperoxide was
inv:?stagated. The initial dpccmposition rate is proportional to the con-
centration of the -:catalyst (of copper stearate anQ hydroperoxide). At a
high hydroperoxide excess, rhe catalyst is converted to the inactive form
cf monovalent copper during the reaction, which is stopped. The amount of
decomposed hydroperoxi-de increases with increasing concentration of the
catalyst and of hydroperoxide, as well as with rising temperature. Decom-
position mainly proceeds accord-Ing to the catalytic mechanism; the chain
mechan:sm is of minor importance. When 'the reaction was carried out in
the presence of an inhibitor (diphenyl picryl hydrazyl) it was found that
the rate constant of the inhibitor consumption considerably exceeds that
of the catalytic decomposition of the hydroperoxide. The diphenyl Dicryl
hydrazyl was synthes,.zed in the institut arganicheskoy khimiiANSSSi
Card 2/3
23587
S/062/611/000/005/1002/009
Catalytic decomposition of-.. B'18/B208
(Institute of Organic Chemistry, AS USSR). The ethyl benzene hydro-
peroxide was obtained according so K. I. INanov (Ref". 5: Promezhutochnyye
produkty -. prome-zhutochnyye reaktsi-i avtookisleniya uglevodorodov (Inter-
mediate products and Intermediate reactions of hydrocarbon autooxidation)
Gostoptekhizdat, 1949)L There are 9 figures and 8 referencesi 6 Soviet-
bloc and 2 non-Soviet-bloc. The 2 references to English-language publica-
-t-ions read as follows! EL A, Braude, A. G. Brook, R. P. Linstead, J. Chem.
Soc.. 1954, 5.~;74~. C &H- Bawrl. S~ T_ Mellish., Tran3~ Faraday Soc. 47, 1216
ASSOCIATION-, 1-is7i7ut khimicheskoy fizik~ Akademii nauk SSSR (Instizute
of Cheml-cal Physics of the Academy of Sciences USSR)
SIUBMITTED: April A, ;960
Card ~//'A
ZAKHAROVJ. I.V.; SHLYAPII~ZQKH, V,--Ya.
Chemiluminescence in the decompouition of diphenylethane hydro-
peroxide, and its relation to the kinetics of this process,
Kin. i kat. 2 no.2:165-171 Mr-AP 161. (MIRA 14:6)
1. Moskovskiy fiziko-tekhnicheskoy institut, kafedra khimicheskoy
kinetiki i goreniya.
(Ethane) (Luminescence)
28654
S/020/61/139/006/021/022
B103 B101
AUTHORS: Lebedev, Ya. S., Tsepalov, V. F., and Shlyapintokh, V. Ta.
TITLE: The possibility of using the method of electron paramagnetic
resonance to record the active centers in the oxidation of
hydrocarbons in the liquid phase
PERIODICAL: Akademiya nauk SSSR. Doklady, v. 139, no. 6, 1961, 1409-1412
TEXT: The authors studied the applicability of electron paramagnetic
resonance (epr): a) for determining free radicals; b) for measuring the
steady concentration of these radicals in the oxidation of hydrocarbons.
A continuation of these studies will probably contribute to the knowledge
of the kinetics of processes of other types. From the measured values it
is possible to determine directly the rate constants of the elementary
reactions that constitute parts of the entire process. Since the
concentration of the radicals is low, their determination under steady
conditions is difficult. For this reason the active radicals could not be
identified during the oxidation of hydrocarbons in the liquid phase. 2
types of active centers take part in the oxidation of hydrocarbons:
Card 1/5
2865
S/020'N1/139/006/021/022
The possibility of using the itethod ... B103/3101
hydrocarbon radicals k and peroxide radicals R0*2, At a given initiation
rate the steady concentration is known for several substances. It is
approximately equal for the following substances: cyclohexene, methyl
cyclohexene, 1-octene, dihydromyrcene, ethyl linoleate, digeranyl,
tetralin, ethyl benzene, cumene, n-decanal, and benzaldehyde. Under
w
d(RO w
2
steady condition.. dt 0, and (R02) = F-ki, (1). Hence, the steady
6
concentration of the R62, at a given initiation rate, is the higher the
lower the rate constant of R62 recombination. An increase of the constant
to the threefold increases the steady concentration only to the 1-7-fold.
In aromatic hydrocarbons, tetralin and ethyl benzene, in which the
peroxide group is located at a secondary hydrocarbon atom, the recombination
constant is by 1-2 orders of magnitude higher. Among the substances
mentioned the cumyl peroxide radicals recombine with the smallest constant.
In order to prove the existence of the peroxide radicals their concentration
must amount to at least 1-1015 to 5*1015 radicals/CM3. The authors studied
Card 2/5
28654
S/020/61/139/oo6/021/022
The pcasibility of using the method... B103/B101
z;u.'-,P_rie since they expected the highest concentration in this substance,
They usGd an epr-spectrometer RX&2 (lKhF-2) with high-frequency
mo,_~ulqtion of" the magnetic field (A. G. Semenov, N. N. Bubnov, PTE, 19
r)2 (19-))). During the oxidation, oxygen was continuously bubbled tiTiough
tha h.,!drocarbon. The folloving substances were used for the oxidation:
T) azoblel4sobutyronitrile, II) dicyalohexyl peroarbonate, III) cobalt
stearatq, and IV) cobalt acetate. Different initiators give identical
spectra. The spectrum is a wide, almost symmetrical singlet
(&H~_,18 +2 oersteds) with a g factor of 2.015 tO.001. According to the
Shi+'z of the g factor and the effective line width, this spectrum is
similar to the epr spectrum of the peroxide radicals in the solid phase.
in control tests in which isopropyl benzene was replaced by ethyl benzene
no epr spectrum was observed in any of the initiators mentioned. Besides,
epr absorption disappeared when the oxygen supply was stopped and when
.'rogen was blown through for a short period. Ad I) The authors
1 5 4
n
calculated the steady concentrations of the cumyl peroxide radicals at
different initiation rates from the known values w and k of Eq. (I).
1 6
These concentrations were also measured between 70 and 900C and a
Card 3/5
28654 S102016111391006,110211022
The possibility of using the method ... B103/B101
concentration of I) between 0.05 and 0-55 mole/I. The absolute values of
the concentrations of (R6 lie between 2-1015 and 4-10 16 radicals/CM3.
2)meas
The measured steady concentration of RO2 radicals was close to the
calculated one. In experiments with II) the authors measured concentra-
tions of 4-1015 to 2*10 16 radicals/CM3. The rate constant of decay of
10 into radicals is unknown. The authors assume that its decay rate is
equai tc the decay rate into radicals. Thus, they calculate the initiation
rate and find that the measured concentrations of the RO2 radicals are
114 to 4,'12 of the calculated values. Since this rate is unknown in
ex*perim,~nts with III) and IV) the mest;ured and calculated radical
concentrations could not be intercomrared. There are 2 figures, 1 table,
and I' references: 4 Soviet and 7 noi-Soviet. The four most important
references to English-language publi:ations read as follows: Ref. 1:
H. W. Melville, S. Richards, J. Cheu. Soc. 1954, 944; Ref. 4: H. R. Ccoper,
H. W. Melville, J. Chem. Soc,, j9 - - 5: L. Bateman, G. Gee,
-251, 1993; Ref
Trans, Farad. Sac 471 155 1951); fef. 6: T. A. Ingles, H. W. Melville,
Proc. Roy. Sac., 163 (1953).
Card 4/5
28611
S102~611139100610211022
The possibility of using the method... B103 B 101
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences USSR)
PRESENTED: May 20, 1961, by V. K. Kondratlyev, Academician
SUB MT TTED: May 20, 1961
x
Card 5/5
ZAMAROV, I.V,,; SHLYAPIRTIOXE, V.Ya.
Kinetics of chem:Lluminescence in the reaction of the thermal
decomposition of diphenylethane hydroperoxide. Trudy 1,TTIL
no.8:137-14.9 162. (MIR.A. 15 - 5)
(Luminescence)
(Bibenzyl)
s/195/62/003/006/oo5/oll
E075/E436
AIUTHORS! Tsepalov, V.F., Shlyapintokh. V.ya-
TITLE:. Rate constants of elementary reactions-in-the oxidati on
of ethylbenzene with molecular oxygen
PERIODICAL: Kinetika i kataliz, v.3, no.6, -1962, 870-876
TEXT: The method of intermitt-ent illumination was used 'to
determine the rate constants for the elementary reactions of chain
propagation and stoppage. The rate of' oxidation was measured by
02 absorption in a vacuum apparatus with an automatic pressure
regulator. Light was emitted from a Hg lamp, the pulse duration
ranging from 0.002 to 10 see. Anthrachinone .(1.4 x 10-4 mole/1-itre)
,was used as a photosensitizer. The reaction vessel was shaken to
make the oxidation not dependent on diffu'sion Of 02- The
oxidation was carried out at 1 atm between 50 and 900C, the degree
of oxidation'of ethylbenzene not exceeding 0.5%. The oxidation
scheme considered was: chain initiation
W R or R02, rate of initiation Vj; chaln propagation
k2 . I k3
(II) k + 02 R02 and (III) R02 + RH R02H +
Card 1/4
',S/195/62/003/006/005/011
Rate constants 1-iM/E436
Chain ruptu re gives inacti-;r.e products As" follows:
k4' k I k6
(IV) 2h (V)'.k + R62 (VI)'2RO2 and
k
7
(VII) RO' '~+-inhil;it7or The re'Action rate applicable
2
to short and long chains is given by
d[O~ = k k-1/2 W [RH] + 1 Wi
dt 3 6 2
'Wi was determined by inhibiting the reaction with a-naphthol.
As (d[023)/(dt) varied linearly with the reciprocal of the
inhibitor concentration (1/[Bj) the va lues of Wi were determined
graphically by extrapolating 1/[B] to zero. The values of
1/2
k3 x k6 were determined by three.independent methods
(inhibition with a-naphthol, inhibition with azo-bis-isobutyro-
nitrile, oxidation in the presence of cobalt acetate catalyst)
and ranged from 4.00 at 500C to 22.2 U mole x sec)1/2x 1o-4 at
1000C. The agreement between the values determined by the three
Card 2/4
N/195/62/oc3/oo6/oo5/011
Rate constants ... E075/E436
m3thods indicated that in the photosensitized oxidation
ff 02 rad.Lcal-s did not take part in chain rupture, the rupture
occurring via peroxide radicals.., The-,mean life of radicals R02
is given by
[R 21 1
and. r k7'Zwi 2 (4)
k6[i(02] 2 k 6 ~kO 21
1/2
The quantity T x Wi did not change with temperature, which
indicated that the activation teniperature.of the radical
recombination is zero. The mean value of k6 was
3.2 x 10-4 cm3/sec. From this value the'consta for the
chain propagation was jound to be 1.6 * 1o-15 e M5001T CM3
x sec
The constant k was calculated using,the equation
7
d[02] W I + k [RH] (5)
i k; [B]
dt
Card 3/4
Rate constants ...
For the inhibition by a-naphthol,
k = 1.7 x 10- 12 e -6800/RT CM3
7 sec
There are 3 figures and 2 tables.
S/l95/62/0O3/oo6/oo5/oi1
E075/E436
ASSOCIATION: Institut khimicheskoy fiziki AN SSSR
(Institute of Chemical Physics AS USSR)
SUBMITTED: October 31, 1961
Card 4/4
01
S165816210001010100810co
A059/A126
AUTHORS: Zakharov, IN., Shlyapintokh,'V.Ya., Candidate of Chemical Sciences
TITLE: Kinetics of chemoluminescence in-the reaction of catalyzed oxida-
tion of ethylbenzene-
SOURCEt Moscow. Fiziko-tekhnicheskiy institut. Trudy, no. 10, 1962. Is-,
sledovaniya. po fizike i radiotekhnike. ill -118
TEXT: The assumption that oxidation as a chain reaction taking place with
the participation of free radicals should be accompanied by luminescence is ex-
perimentally demonstrated on the example of ethylbenzene oxidation catalyzed by-
cobalt acetate, the kinetics of which has been described before. Oxidation was
performed in a special constant-temperature vesseli with the photomultiplier
0Y -18 (FEU-18) placed behind it. In the course of the experiment, air was
passed, which had been dried with~CaC12- Glacial acetic acid was used as the in-:
ert solvent. Chemoluminescence was 'measured-at temReratures between 50 and 00C.
with catalyst concentrations between 0 and 20 - 10 -1 moles/1, and ethylbenzene-
ume-
concentrations between 5 and 40% by vol Luminescence is recorded only in ~he
Card 1/3
,S/658/62/000/01 0/10~~O~~]
Kinetics of chemoluminescence in the reaction of .... A059/A126
presence of oxygen, which shows that the chemoluminescence observed is due only T:
to oxidation. After some time, which increases with increasing catalyst concen-
tration, steady luminescence intensity is established, which shows a maximum. A
linear relation between chemolur~inescence.intensity and oxidation rate is found.
The introduction of hydroperoxide leads to the disappearance of the initial stage:
of growth of luminescence intensity, which Increases with increasing concentra-
tion of the hydroperoxide added. The development of luminescence in time is re-
lated to the accumulation of hydroperoxide In the system, and the steady lumi-
nescence intensity corresponds to steady oxidation~ in which the decay velocity~"
of hydroperoxide is constant. The intensity was found,to be proportional to the
square of ethylbenzene concentration. As a result, chemolumi-nescence in the--re-
action studied is assumed to be excited by the energy set free in peroxide-radi--i
cal recombination, which is the only exothermic stage in oxidation. This energy
which is in excess of 50 - 60 kcal/mole-is sufficient to excite luminescence:in
the visible part of.the spectrum in the sensitivity range of t.he.photomultiplier
used. As A result of kinetic studies,it-i a fowid that the rate of hy~droperox
ide decay is, a-t all catalyst concentrations 'proportional to'the concentration
of thenondecomposed hydroperoxides
Card 2/3
1-14.. -;JILYAPINTI)Yt~, V,.Yit~, QW)VALOVY
Chwffb. I ii,.,j !In --- 7~-3e n,~,~ -', n ll-ht~ P-;" -3 0;~ ir' 'I 'j Lon c, f a -10 tra 2rlo ~,yde ,
I ~ . 11
36 noJ0.22"84-2286 0 162. (MIRA 17-4)
1. Inc.-IJ.~ii-il fl.ziki AN SSSIR.
B/062/63/000/002/006/0*2a
B144/8186
AUTHORSt Kulitakil Z. I., Terman# Le Mol Teepalov, Vo F., and
Shlyapintokh, V. Ya.
TITLEI Determination of the rate constants of initiator decompoetiolt
and of the initiation efficiency
PERIODICALt Akademiya nauk SSSR. IZVe3tiyG,% Otdoleniye khimicheektkh
nauk, no. 2, 1963, 253 - 257
TEXTs The rate constants of initiator decompos'ition,oah be -det ermin Qd from
the relation between oxidation rate and conaentrati:b~&. T he oxidatio'n rates
of cumol and ethyl benzene containing iso-bis-isobutyra nitrile (I) ana- di-
cyclohexyl peroxy dicarbonate (II) as initiatord'were studie,! at. 60 900C
in an apparatus described previously (Kinetika k'.katirl-iz- (4962), no &~.
The 0 2 absorption-vers us -time curves showed tha~f the ozidation rate is. Oon.
stant at low temperatures, where the initistoe concentration remailut eom-o
stantp 'but decreases at higher temperatures owirij to initiator decomposition.
The order of the initiation reaction was detarmtied using'the' equation.
-1/2 1/2.(Y)n/.2
-d(0 21)/dt - k 3k6 (RH)(e-k eff) (3) 'for the rate of 0 2 absorptionr
Card 1/3
5/�6y65/OOO/CO2/006/V.'-O
Determination of the rate... ]M4 a 186
where RH is the substance to be oxidized, e. tl~e fnitintion efficienoll Ikelf
the effective rate constant of initiator decompapWltion# Y the initiator#
and n the order of the initiation reaction. If
-ke ft
(Y) - Mo e is introduced into (3) under t4e assumplion.of a first-
order reaction for the decomposition of the initiatox-t loll(-d(02 )/dt)
log(-d(02)/dt)o - kefft/4.6 is obtained, where (-d(0?)/at*)o is the, initial
reaction rate and Y the initial concentration of the ititiator. PlotAing
curves for the time dependenioe of log (d(O,)/dt)/(d( 02) # dt)o eatablishled
that both initiators decompose in a first-order reaction., The rate cob-
stants of initiator decomposition., keff, were calculate"I'from this graphe
The activation energies were 29.6 kcallm for II angoVA.2 koal/it for 1.
-W51 29 T
The decomposition rate constants were 2.71 e- for 11P and
2.63-1015e- 31200/RT for 1. The initiation efficiency wan calculated fron
the initiation rate and the rate of initiator decomposition. The values
Card 2/3
El/062/63/000/002/006/020*
Determination of the rate*#& B140186
obtained were 1.1 for I and IA for II.. There are 5 figures and'2 tables.','
ASSOCIATIONs Institut khiImioheskoy fisiki4kadeinii nauk SSBR (institute
of Chemical-.Physics ofthe Academy of Sciences USSR),
SUBMITTEDi May 14, 1962
KARFUKHIN, O.N.; RUSINA, I.F.J NIKIIPOROV, G.A.; SHIZAPINTOXH,, V.Ya.
Sterically hindered phenolphthalains and the poasibilit7 of
using them for the study.of inhibited cxidation processes.
Neftekhimiia 3 no-4:579-583 Jl-Ag 163. (MIRA 16:11)
1. Institut khimicheakoy fiziki AN SSSR.
m
)/FrS AFTTIC/ASD Pc-Vrr--~h
ACCESSION NR-, AP30014817 S/0195/63/GW002/0239/0243-
AUTHOR. Zakharov, Is V.; Shlya2intokh, V.
TITM Chemiluminescence in slow chemical reactions. .1. The mechanism governin
chemiluminescence in -the catalyzed reaction of ethylbenzene oxidation
SOURCEs Kinetika i katalizo v. 4. nos 2, 1963# 239-243
TOPIC TAM chemiluminescence in oxidation benzene, cobalt acetate, hydro-
peroxide
ABSTRACT: Chemiluminescence was observed during,'the oxidation of ethyl-benzene
in a reaction catalyzed with cobalt acetate. q1ts intensityis proportional to
of the
the rate of reaction and it changes th the temperature, ooncentrati--
_catalyst, concentration of the hydrocarbon, and the rate of oxidation. The
proposed kinetics explains the principal mechanism governing chemilumineacence.
The experiment confirms the assumption of chemiluminescence in reactions and
dt22m ~osit~ionslof hydroperoxides by using the ordinary salt catalysts. The
discovered proportionality between the intensity of glow and the rate of chemical
conversion can be utilized in the investigation of kinetics and also for the
control and direction of the process of catalyzed oxidation. Orig. art. hast
Card
- - - - - - - - - - - - I -
-------------
VASILIYEV, R.F.; VICHUTINSKIY, A.A.; KARPUKHIN, O.N.; SHLYAPINTOKH, V.Ya.
Chemiluminescence in slow chemical reactions. Part 2: Effect
of the chemical composition of the system on chemiluminescence
intensity. Kin. i kat. 4 no.3:382-387 Ilq-je 163,
-(MIRA 16:7)
1. Institut khimicheskoy fiziki AN SSSR.
(Luminescence) (Chemical reaction, Rate of)
ZAKHARGVY I.V.; SHLYAPINTOKH, V.Ya.
Chemiluminescence in slow chemical reactions. Part 3:
Chemiluminescent method used for studying the kinetics of
hydroperoxide accumulation in the reaction of catalyzed oxidation
of ethylbenzene. Kin.i kat. 4 no.5:706-712 S-0 163.
(MIRA 16:12)
1. Moskovskiy fiziko-tekhnicheskiy institut i Institut,
khimicheskoy fiziki AN SSSR.
KARFUKHIN, O.N.5 SHLYAPINTOKH,_,IYa._; ZOLOTOVA, N.V.
Chemiluminescence in the reactions of inhibited oxidation and Uie
activit-Y of inhibitors. Report No.lz Theory of themilumineseent
methods for determining the activity of inhibitors. Izv,. Alt SSSR
Ser.khim. no.lOgl7l8-1721 0 163.
Chemiluminescence in the reactions of inhibited oxidation and the
activity of inhibitors. Report No.2-. Measurement of the activity
of Inhibitors by the-chemiluminescent methods. 1722-1727
09RA 170)
1. Institut lkhimicheskoy fiziki AN SSSR.
KARPUKHIN, O.N.; SHLYAPINTOKH, V.Ya.; RUSINA, I.F.; ZOLOTOVA, N.V.
Chemiluminescent method for determirdn- the inhilbitors of free
0
radical reactions. Zhur.anal.ki-dm. 18 no.8:1021-1025 Ag 163.
(MIRA 16:12)
1. Institute of Chemical Phynics, Academy of Sciences, U.S.S.R.,
Moscow.
L 9865-63 EPF(c) IEW(1) /EW(b) /tDS-AFFTO/ASD-Pr4--RM/WW/)fAY/IJP(G)
ACCESSION NR: AP3001349 S/0048/63/027/006/0735/073 18
AUTHOR: Postnikov, L. M.; Shuvalov,~V. F.;6blyapintokh, V. Ya.
TITIE: Nature of chemiluminescence associated with low7temperature oxidation of.
acetaldehyderNEReport of the Eleventh Conference on 1=inescerLae held in Minsk
from 10 to l5kSeptember 19621-
SOURCE. AN SSSR. Izv. Seriya fizicheskaya, v. 27, no. 6, 1963, 735-738
TOPIC TAGS: chemi-luminescence, vapor phase reactions, reaction kinetics,
acetaldehyde
ABSTRACT: Chemiluminescence luminescence accompanying chemical reactions.- has-
been under study at the Irz=iAte of Chemical Physics...of-the Academy of Sciences
S&qR_for several years, and it has been_~siablished t*hat the emission appea-rs as
a result of radical recombination. Most of the previous studies, hawever,*Were
concerned with reactions in the liquid phase. Accordingly, it.was deemed of
interest to investigate reactions in the vapor phase. Chemiluminescence has been
observed (in some cases for the first time) incident to decomposition of methyl
Card 112
L 9865-63
ACCESSION NR: AP3001349
hydroperoxide, oxidational decomposition of deuteria butyl peroxide and
azomethane, slov oxidation of n-butane, ethyl ether, acetaldebyde, etc. The
present experiments were carried out in a 550 cc molybdenum glass reaction vessel
at temperatures from 100 to 2000C and Initial pressures from tens to hundreds-M-M
Hg. The variations in chemiluminescence and pressure vere recorded automatically;
vhen indicated, the end products were sub.jected to chemical analysis. The time
variation of the chemlluminescence incident to oxidation of acetaldebyde proved
to be distinctive; most curves exhibit two peaks; one sharp, the crther flat (the
time curves and spectra for oxidation of acetaldehyde are reproduced). This
-; icates that the reaction
ind proceeds in two stages. Hence observation.of
chemiluminescence provides a means for stiidying the kinetics of some chemical
reactions. Orig. art. has: 3 figures.
ASSOCIATION: Institut khimicheskoyfiziki Akademii nauk'SSSR .(Institute of
_.Chemical Physics, Acade-wi of Sciences- SSSR)
SUBMITTED: 00 DATE ACQ,. 01JU163 ENCL: 00
SUB CODE: PH CH NR FmF Sm. oo6 orm: oo6
Card 2/2 -. JaAa
KARPUKIIIN, C.N.; SHLYAPINTCKH, V.Ya.; ZOLOTOVA, N.V.; KOZLOVA, Z.G.; RUSINA, I.F.
Mechanism of the weakening of chemiluminescence by inhibitors of free
radical reactions. Zhur.fiz.khim. 37 no.7:1636-1638 Jl 163.
(MIRA 17:2)
1. Institut khimicheskoy fiziki AN SSSR.
.,Sff,LYAPINTOKH, V.Ya.; POSTNIKOV, L.M.; KARPUKHIN, O.N.; VERETIL'NYY, A.Ya.
Chemiluminescence during alternating current electrolysis. Zhur.fiz.
khim. 37 no.10:2374-2375 0 163. (MIRA 17:2)
45160
c/020/63/148/002/037/037
;124/B1806
AUTHORS: Shuvalov, V. F., Vasillyev, R. F., Postnikov, L. M.,
5
yhlyA2~intokh, V. Ya.
TITLE: Formation of excited formaldehyde molecules in low-temperature
oxidation of acetald-ehyde
Pj~'RTODICAL: Akademiya nauk SSSR Doklady', v. 148, no. 2, 1963, 388-390
TEXT: The project consisted in determining the chemical nature of I he_.
luminescent particles in the oxidation of acetaldehyde. It is pro4khat
in this reaction the luminescence is connected with the formation of 6x-
cited formaldehyde molecules. Chemi-luminescence in reactions which pro-
ceed under formation of alkoxy radicals is ' also explained in this way. The
luminescent particles in the slow oxidation of acetaldehyde in the gas phase
are identified experimentally by taking the chemi-luminescence spectra With
a high-power spectrometer developed by R. F. Vasillyev, S. It. Petukhov and
T. N. Zhuchkova; the instrument is described in ZhvKh, V- 36, No. 10, 2284
(1962). The chemi-luminescence spectrum of a mixture of 50 mm. Hg acetalde-.
hyde and 47 mm Hg oxygen was taken at 1820C, chemi-luminescence having a
maximum valuz. The kinetic c4*rve of chemi-luminescence has two peaks. I n
Card 1/-1
--/020/63/148/002/037/037
Formation of excited formaldehyde ... B124/-B186
the section following the necond peak the intensity of luminescence changes
but little with time. Tt has,been found that the Spectrum taken in this
section practically coincide 's with the fluorescence spectrum of formalde-
hyde. The formation of formaldehyde in the reaction products is proved
also by chemical analysis. With the aid of,light filters it was shown that
between 180 and 1200C the oosi,tion of the luminescence maximum and the total
shape of the spectrum do not change. Hence it can be concluded that also
at temperatures below 1800C th 'e second luminescence maximum is related t*o
the formation of formaldehyde. The kinetic curves of 1 ,uminescence at 1820C
and with a composition of the mixture of 50 mm Hg CH3 CHO and 35 mm H9 02
were taken at 370, 425, and 510 mi;. It.was found that the intensity ratio
remains practically constant. This prov'es that also in the region of the
first DC-ak, luminescence is connected with excited.formaldehyde molecules.
This example shows that the reactions necessary for the formation of excited
formaldehyde molecules take place not only in cool flames but even at much
lower temperatures. There are 3 figures.
ASSOCIATION: institut khimicheskoy fiziki Akademii nauk SSSR-(Institute
of Chemical Physics of the Academy of Sciences USSi)
Card 2/3
s/020/63/148/002/037/037
Formation of excited formaldehyde... B124/3166
PRESENTED: June 11, 1962, by V. N. Kond'ra,tlyev, Academician
SUBMITTED: July 10, 1962
Card 3/3
POSTNIKOV, L.M.; SIILYAPINTOYH.,-V,.Y4.-
Machanism, of the formation of excited formaldehyde molecules in
oxidation reactions. Dokl. All SSSR 150 no.2:340-342 Yq 163.
(MIRA 16;5)
1 Institut khimicheskoy fiziki Ah SSSR. Predstavleno akademikom
V.N.Kondratlyevym.
(Formaldehyde) (Oxidation) (Reaction., Rate of)
Ewp(j)/kw q M /"D:,., Pe-4/T~k
L 12629:J6 )/EWT(i)/BPS ',ARM,
I*VWW/JD
ACCESSION NR: AP3002878 s/mq/63/i ~q/qw/i o6g/i 672
AUTHOR: Zakharov, I* V.;.Shlyapintokh~ V. Yae
TITLE: Chemiluminescence 'and reaction mechanism of tLe catalyzed decomposi
of ethylbenzene hydroperoxIde
SOURCE: AN SSSR. Dok3.adv*, A
noo 5.. i q6% lo69-im
TOPIC TAGS: chemiluminescence, cobalt acetate, trivalent cobalt
ABSTRACT: This study is a continuation of the vork previoudly done on the law
of chemiluminescence in the oxidAtion of etby1benzene using cobalt acetate-As a
metal salt catlyst vith a variable valence. The chemiluminescence in thisteaction-
depends on the recombination of peradde-radicals formed as a result of the'
catalyzed decomposition of hydropervxide~ The intensity of chemiluminescence is
proportional to the speed of decomposition. 7he value obtained from the light
intensity curves and from the analysis of hydroperoxide decomposition are in agree-
ment. This gives a possibility of utilization of.chemiluninescence methodfor
the investigation of the kinetics of catelyzed.hydroperoxide decomposition. -it
Vw found that the higher the concentration of catalyst, the higher is the
maxEm= intensity of the chemiluminescence. The rate of decanpogition is doubled
tard
ACCESSION NR: AP4016517 S/0195/64/005/001/0064/0070
AUTHOR: Lebedev, Ya. S.; Tsepalov, V. F. ~into~k&,. V. Ya.
TITLE: Measuring the stationary peroxide radical concentration in the cumene F
oxidation reaction by the EPR method
SOURCE: Kinetika i kataliz, v. 5, no. 1, 1964, 64-70
TOPIC TAGS: peroxide radical, concentration determination, cumene oxidation,~:
peroxide radical formation, liquid phase oxidation, recombination rate, cobalt
stearate catalyst, azobisisobutyronit vile, dicyclohexylpercarbonate, EPR
analysis, cumyl peroxide
ABSTRACT: A study of the liquid phase oxidation of hydrocarbons showed that
the peroxide radical recombination rate constant is approximately the same for
olefinic materials, and 1- 2 or d e r s higher for aromatic hydrocarbons. Cu-
myl peroxide was selected for further study since it has the smallest recorabina-'.
tion rate constant. The oxidation of cumene was then effected in the resonator
Card 1/2
ACCESSION NR: AP4016517
of the EFR spectrometer. The reaction was catalyzed with cobalt stearate or
initiated with azobisisobutyronit rile or-with dicylohexylpercarbonate. In chang-
ing the concentration of the latter from 0. 02-0. 55 mol. /1. , at 68-50C, the ini-
tiation rate changed by a factor of 50, from 5x !or-6to 2-4x1o-4mo2/1_rec. The EPR:.'
spectra, determined by the cumyl per-oxide radicals,are identical, although
oxidation was initiated by different radicals. The peroxide radical concentration;~
measured in this work essentially approaches the values calculated from the I
known rate of initiation and the recombination rate constant. The slightly lower
measured values are explained as due to experimental errors such as insuffici-
ent 02, incorrect placement of the ampoule in the resonator, etc. Orig. art.
has: 2 figures, 4 equations, 1 formula
ASSOCIATION: Institut khimicheskoy.fiziki AN SSSR (Institute of ChemicRI
Physics AN SSSR)
SUBMITTED: 26Apr62 DATE ACQ: 1OMar64 ENCL: 00
SUB CODE: CH, PH NO REF SOV: 007 OTHER: 013
Card 2/2
KOZLOVA, Z.G.- TSEPA T
I LOV9 V.F.; SHLYAPINTOKHS V.Ya.
-~.- - - .. -,-- ..
Mechanism of hydrocarbon oxidation catalyzed by cobalt salts.
Kin. i kat. 5 no.5:868-876 S-0 164. (KIRA 17:12)
1. institul. khimicheskoy fiziki AN SSSR.
TSEPALOV, V.F.; SHLYAPINTOKH, V.Ya.; CHZHOU PEY-KHUAN [Chou Plei-huang)
Kinetics of cooxidation of cumene and ethylbenzene. Part 1.
Zhur. fiz. khim. 38 no.1:52-58 Ja'64. (MIRA 17:2)
1. Institut khimicheskoy fiziki AN SSSR.
ACCESSION NR: ILP4019513 3/0076/64/038/002/0351/0355
A TimS: "i'sepaloy, V.F, (Moscow); Shlyapintokh, V.Ya.(Moscow);
JMU " "
Chou, Vei-huang (Noscoir~~~~
MLEE: Kinetics of cooxidation of oumene and ethylbenzene 11. Deter-
mination of rate constants of cross reaotions of chaIn extensions and
rupture.
SOURCE: Zhurnal fizicheskoy khimii, V-38, no.2, 1964, 351-355
TOPIC TAGS: cumene ethylbenzene cooxidation, ethylbenzene peroxide,
cumene neroxide, cumene, benzene
ABST-RACT: This Is a continuation of the work by the same authors
(Zh.F.Kh.,38. 1964) covering the kinetics of cooxidation of the same
cor.-oounds at 6C) and 800. The purpose of the present work is to cor-
_reci data concerning the rate constant of recombination of peroxide
radicals of cument~ as given by H. Melville, S. Richards (J.0hem.Soc.
944, 1954) which were based on an erroneous assumption on the initia-
tion of tuvo chains. The kinetic regularities observed in the coozida-
tion of cumene and ethylbenzene are qualitatively interpreted. Values
Card 1/2
Ov., V'11.'~~ LEHEDEV, Ya,9.- T,-'vEPALOV, V.F.,, V.Ya.
E,-Ieo~.ron para-.,magntel~f~ resonance spactra rf pn-ox,cv- rad~.0.3
pi".3 I
Ir. -~ho I~quid e. Zhur. f'-z. kh-,*m. 38 no.,1287 Mly f61~.
(MMA 18:12)
r,,Ic-t% '.. .I -!~d March
I. ingtitut, kh-ljnll,~.rienkoy Nziki AN our-MIL,
28, !963.
rb
lt26657-65
Pc-47Pr7t7Ps-4/Pad/Peb: IJP(c)/RPL RmA4wlj S
ACCESSION HR: AT5002264
ell
AUTHOR: Lebedev, Ya. S.; Tsepalov,,V. F.; Shlyapintokh., V.~ Ya.
41
TITLE: , Use of electron paramagnetic resonance f or. the study of active centers,
in liquid-phase oxidation reactions
SOURCE: Soveshchaniye po%izicheskim metodam issledovaniYa stroyeniva molekul
organicheskikh soyedineniv i khimicheskikh protsessov. Frunze, 1962. Trudy.,
Frunze, Izd-vo Ilim, 1964,190-195
TOPIC TAGS: electron paramagnetic resonance, liquid phase oxidationj active.
center, EPR spectrum, Reroxid radical, Cumene oxidation
ABSTRACT: This investigation was undertaken to,4determine the- steady concentra-.
tions of peroxide radicals in liquid phase id t' reactions by-means of EPR
_,,ox a ion
spectra. Experiments were conducted on an'-ftKliF-2:s~ectrometerle~ith.a'-high-fte-
quency modulation fields The instrument recorded-the first derivative-of the EPR
line of the peroxide radical, simultaneously with thesignal from the standard.
sample (carbon)& The reaction was conducted directly in an EPR,resonator of the*
spectrometer. For this purpose, an ampule of cum-ene was placed iwthe resonator
and heated with a stream of hot air. Oxidation was catalyzedby cobalt.s earate
oF initiated by azodiisobutyronitrile (I) or dicyclohexylpercarbo;n~a-te (ftX
Ca d 2
Card .2/2
D.-I I )IE'.'rr )IE-i G)/rI
r
ACCESSION NR; AT5006090 JPSWO00/64/00SO/000/013710145
11
AUTHOR: Vasil'yev, R.F.; Vichutj~g~ki , A.AL.,' Zakharov 1. V.; Karpukhin, 0. N.
Postnlt*~,,-.7~,-=,-..-s,=y,~pi.tokh, V. Yn.
TITIX: Cliemiluninevenc. n the study of the kinetics and mechanism of chemical
reactions of organic compounds
icheskim metodam issledavantya argnntcheakikh rove----
SOURCE: Soveshchani
dtneniv f lhp;rN V.
khimichesk ':c;s. Frunze, 1962t Trudy. Frunze, Izd-vo Ilim,
1964, 137-145
TOPIC TAGS: reaction kinetics, organic mechanism, themtluminescence, radical re-
combination, luminescence spectrumr hydrocarbon oxidation, hydroperoxide decompo-
sition
ABSTRACT: The article deals with the chemiluminescence, produced by recombination;
in radical reactions. Measurement of the intensity of chemiluminescence at var-
ious temperatures provides a rapid method for determining the initiation rate or
the activation energy of decomposition of the initiator of the reaction..fThe tem-1
1 perature dependence of the intensity of chemiluminescence in the course ox 44,
tion of various hydrocarbons initiated by different hydroperoxides is discussed,
Card 1/2N