SCIENTIFIC ABSTRACT YE.M. DENISOV - YE.T. DENISOV

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• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000310120019-4
• Release Decision: RIF
• Original Classification: S
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• Document Creation Date: November 2, 2016
• Document Release Date: June 12, 2000
• Sequence Number: 19
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

VERNIKOVSKrr, X.,B.; LUBENE7S, I.P.; CIRLOV, V.S.; .',)HCHELKANOV, r
DEN]ISOV, YeA
Induced block caving at the Gora Blagodat' mine. Gor, Zh
IWO
no. 12:29-32 D 165. (MIRA 18;12)1"-~i'lt~'
1. Gorobla fp~'4ihelezorudnoye mestoroishdeniya (for
V)dat&M
tbrriko~j*,-1k%11e~ts, Orlov). 2. Institut gornogo dela,
Sverdlovsk (for Shcbelkanovp Denisov)e

DENISOV, Ye.N.,- HITVEYENKO, le.G.
Purification of radioiodine-labeled Rose Bengal from admixtures
of unbound radioiodine. Mod. rad. 10 no.11:65-66 N 165.
(KRA 19-1)
1. Laboratoriya radioisotopLoy diagnoatiki (zav. - prof. M.N.
Fateyeva) Inatituta meditainskoy radiologil AMN SSSR. Submitted
Dece:-.nber 3.2, 1963.

~.707h-66 EWT ( 1 )jIT - ---J',K
AP6013759 SOURCE COME: UR,/02/J/65/010/011/0065/0066
AUTHORS: Daniso-7, Y 3. N. Matveyeako) Ye . G -
R
ORG.- Institute of Medicinal Radiology# AMI SSSR,-Laboratury of Radioisotopic
Diagnostics, Professor M. H.-Nallay8ya-.- Director (Institut-tt meditainskay radiologii
MIN SSSRI Laboratorl;ra radioizotiopnoy diagnostiki
TITLE., Removal of f~roq 1131 frcan I133--labolled Bengal rose
SOURCE: MeditsinBkaya. radiologiya, v. 10, no. l1,.1965, 65-66
.,nootic. medicine, a4U4704-A-)
TOPIC TAGS: radiation ohemistry, chemical labellingg diaf.,
iodinated organic compound, ion exchange chromatography / AV-17 anionite
131 ko
ABSTRACT: A method for the removal of free I cont.-oardmiting industrially rxe-
pared I131-labe2-led Bengal rose is described. The procedure is of importance
because the presence of free I 3~-11 distorts the diagnostic data obtained by using
I131-labelled Beingal rose in liver diseases. The method consists of passing Berigal.
rose in glycine buffer solution through an ion exchange column filled with anionite
AV-17 (in C17 form) at a rate of 0.5-1 ml/min. The amount of free 1131 in the
UDG: 63.6-073.916:615.42

L 37074-66
ACC NRt AP6013759
technical preparation was reduced from 9.28 to 0.35%. The purified preparation
was considerably more stable to sterilization by boilfii'g. Orig. art. has: I figus-9
aW 1 'table
SUB COM 07p 06/ SUBM DATEt Moc63,
C.,d 2/2

S/481/63/M)5/004/026/047
B102/BI66
AUTHORS i Shohemelave V No 9,::Rume h qU. A.0 and Denisov, Ye. P.
'%1T LE i cknesa and efficiency of the yield zone of!
Determination of thi
true secondarT.eleotron emission based on ar investigation of
the energy spectrum';of X-ray photoemission
PZRIODICALs Pialka tirerdogo te1at To 5,P noe 4o 1965, 113-2 1137
TEXT t The X-ray~,
-photoemiesion 'energy spectrum of NaM, XCI and KBr photo-
cathodes, condeneled in.vacuP onto Al or Au substrata were! analyzed in order;
.to determine the Ihickness of t:h"e yield.zone 1 and its efficiency S-v-1,
where V is the'mOan nimber of electrons contained in the wave packet. (Of.
4, 2795, 1962)9 1/1 Ibeing the total current in the case of
r
zero delay, and I the current-,41'Re to X-ray photoeleictrons. The layer thick-
investigated wors betweea~eeversl tens and soveral thousands of
about ten different cathodes were measured.foreach pair substratum-ealt,
'placed in a sphei,iical'capaoltorot -The electrometer %mod had a sensitivity of
10 14a so that V: I/I obisineCtron tbb" volt-ampere characteristics was
_9ard. 1/3

ii:!~ mechanism most probab y beoi~mes &ppgjTtnt OnlY when besides irradiation alsot
an electric field acU on tite cei'ho4oli.in the presiDnt case this field
was
-.1i.;1kv/cm. Thelfolloivin~g rosultis werip.obtaineds
so
Nac 1 1000voo 22~~ 21. .18 S (I-i
D'. xcl 600+10D I q, So. (I-i )/i
15
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SHCHEMELEV, V.N.; YELISEYENKO, L.G.; DENISOV, Ye.P.; RUYS:J, M.A.
Current and pu:Lse meatturements of the X-ray photoemission from
a massive cathode. Fiz. tver. tela 6 no.9:2574-2579 S 164.
(MIRA 17:11)
1. Leningradak.':y gosudarstvennyy univeraitot.

,---DMUSOV, Ye.p.
7ormation of the low-lying shores of the southern Maritime Territory.
Soob.DVFAN SSSR no.10:246-248 139. (KIRk 13: U)
1. Balinevostochnyy-filial Sibirskogo otdeleniya AN SSSR.
(MBritIme Territory"hore lines)

DINISUV, Ye.F.
Stratigraphy of upper Cenozoic formations of the soukthweatern Maritime
Territor7. Boob.DV.FAN SSSR no,12:19-21 160. (MIR& 13:11)
L Dallnevostochnyv. filial imeni V.L.&)mrova Sibirskogo otdoleniya
AN SSSR.
(Maritime Territory-Geolog7, Stratigraphic)

m 4 21 V 01
'4 1:1 P
14
Rl

DENISOV , Ye.p*
New data on the basalts of the Maritime Territory. Geol, i geofiz,
zio.12:1+8-56 16o. (MIRA 14:5)
1. Dellnevostochriyy filial Sibirskogo citdeleniya AN SSSR, Vladivostok.
(Maritime Tarritory-Basalt)
I

S/5ly6O/OOO/OO8/O23/031
D051 DI-13
AUTHORS: Denisov, Ye. Pe; Smirnovp A. Mo
TITLE: On the latest tectonic movements of the southern coastal region
of the Primorskiy kray and adjacent territories
SOURCEt Akadomiya nauk SSSR. Sovet po seysmologii. Byulleten', no. 8,
Moscow, 1960. Vop:rosy seysmicheskogo rayonirovaniya, 179-183
TEXT: A brief survey of -the geologic-tectonic development of the south-
ern coastal region of the Primorskiy kray and adjacent territories is given.
Continental conditions were established as a result of folding and uplifts in
areas which were inundated by the sea before the end of the Cretacious period.
A number of depressions mid axially oriented elevations formed durinc the
Paleogene, but 'the main cliara-ateristic, however, was planation. The corre-
lation between depressions and elevated zones did not remain constant and
some depressions rose to different heights, even up to 600 m, a process due
to increased tectonic activity at the end of the Mocene. The post-Miocene
formations stretch practically horizontally. Differentiated movements gra-
Card 1/3

S/519/60/000/008/023/031
on the latest tectonic movements of ooe D051/D113
dually weakened and general planation begran once more butp however, did not
establish a peneplain. The pliocene basaltic flows did not engulf the axial
sections of mountainous structures which emerged like inselbergs from the
basalt sheet* The lower basalt surface marks the old relief, the upper
layers gradually assuming a sloping position and the top layers being prar-ti-
cally horizontal. In the south,the basalt sheet surface shows collapsed
voleartic cones along an old mesozoic fault. A close connection between cea-,
ters of basalt discharge and lines of intermittent faults could be observed.
In this respact,olivine-Dyroxene inclusions discovered by the authors in
different lavas and basalts are important, Preliminary data concerning theil-r
spoctral analysis are given. Uplifts in the concerned area occurred toWards
the end of the Pliocene and are still occurringe Accordin- to G, P, Gc-T-ch~-Ie)-,!
the territory is located in a zone of seismic intensities 6 and 7n It if
stated,that this activity is related to recent intermittent faults located
on the edges of large depressions and stretching submeridionally and 311b
latitudinally. Scientists A9 Z. Lazarev, Yao Ye. Pashchenko, G. M. Vlr,,S(-"-
P. N. Kropotkin, B. M. Shtempelf, A. IL Siairnov, N* Ao Lebedeva, V. 1, Du
Card 2/3

9/519/60/000/008/023/031
On the latest tectonio movemonts of 9oo D0501-13
and G. S. Ganeshin are mentioned. There are 1 figure and 15 references:
13 Soviet and 2 non-Soviet* The Englisb.-language references are: Ho Kuno,
Plateau Basalt - Lavas of' Eastern Manchuria. Proc. 7-th Pac. Scio Congr.,
2, 1953; C. S. Ross, M. D. Foster ao Ao T. LVers. Origin of Dunites and of
Olivine - Rich Inclusion$ in Basaltic Rocks. The American Uineralogist,
No 9-10, 1954-
ASSOCIATION: Dallnevostochnyy filial All SSSR (Far Eastern Branch of the
AS USSR)
Card 313

DENISOV, Ye.P.; NIKOH)VA, R.I.
Reoent tecton:Lc wivements in the southern Maritime Territory and
ad,facent regions. Biul.MOIP.Otd.geol. 35 no.2:28-37~ Ht-Ap 160.
(KERA 14:4)
(1hrtime Territory-Geology., Structural)

DENISOV, Ye.P.
Age of blanket basalts in the southe* jart, of the Maritime Territorye
DOkl.AN SISSR 136 no,l..167-.168 Ja 163.* (MIRA 14:5)
1., DallneqrostochW filial Sibirskogo oiAeleniya AN SSSR.
Dvdstavleno akademikom D.V."vkinym.
(Writime prritory-l"alt)

SAKHNO, V.G.; DENISOV, Ye.P.
Origi.n of the Inclusions of ultrabasite rocks in basalts in the south-
ern part of the Far East. Izv. Jai SSSR.Ser.geol. 28 no.8:43-55 Ag 163,
(MIRA 17:2)
1. Dallnevostochnyy ireologichaskiy institut Sibirskogo otdeleniya AN
SSER, Vladivostok.

Sill VY V.41J.; YELISEYE111"cl, L.G.; -TENIS'Ov, Ye.p.; I.A.
14--asuring X-ray photoemission from metals by r%eans of o;~en type
secondary-ele.-tron multipliers. Prib. i. tekh. eksp. 9 no.O':ID,-
118 N-D 164- (MIRA 18:3)
1. Leningraoskiy gcsudarst,.renn-.Yy universitet.

DENISOV, Yep,
Some characteristics of basaltoids with ultrabasic rock
inclusions. Gool. i geofiz. no.4:168-1715 165.
(MIRA 18:8)
1. Dallnovostoohnyy geologicheskiy instltut Sibirskogo otdelenlya
AN SSSR, Vladivostok.

AP60.22499 SOURCE CODE: UR/00,54/66/000/00:L/0057/oo68
WHOM: Dqni ov Ye, Humah, M. A.
RG.& none
,-/ -7
7
&
ITLE: Determination of the characteristics of the movement of the
lectron fluxes in a solid body by the method of -the external x ray
botoeffect 9~1
OURCE: Leningrad. Universitet. Vestnik. Seriya fiziki I kbimii,
0. 1, l966,_5_7_-_0
OPIC TAGSt electron fluxt pbotoeffect, x ray photography
BSTRACT: The article gives a calculation of the extrapolated end
inximum ranges of pbotcoolectrons from the experimental values of the
.uantum -yield for normELI and inclined incidence of the x-rays on the
botocatbode. After a short Introduction, the article proceeds to a
iscussion of' the basic; principles determining the propagation of
lectron fluxes in a sc;lid body, and then goes on to a quantitative
alculation of the quantum ~,ield of pbotoelectrons, Calculated results
sing the mathematical theory developed in the article are listed in a
able an,3 arc found to be in agreement with the data of other authors.

~ 42296-66
A& NRI AN,022499
3 C)
Orfg. art* bas: 27 formulas, 7 figures and 1 table.
SUB CODE: 20/ SUBM DATE: 3.6Jun65/ ORIG REF: 010/ OTH REF: 007
c,,d 2/2

Ed ~-'
INN
USSR/Chemiatz7 Physical Chem.Latry
Card 1/1
Authors i Berezin, I. V... and Danisov E T
Title Basic prcductW of liqikid-phase.oxidation of cyol.ohexane with atmospheric
oxygen and the,~ role ol these products in processes of phase-formstion
Periodical D61cL. AN SSSRI;! 97, Ed. 2, 273 275, July 3.954
;-Ab Two are f6rii:d during the oxidation of cyclohexane
~abios-pfiviiri-c oxygem-'16-, 1~yei'repreemnts a solution of reaction
witl upper
products . in wrelohexane; the lower layer c'onsisI;s of liquid oxidation pro-
due t s and ac6nsider6ble amount of solidacids. Quantitative separation
of-Lippor layer products showed that 95 mol. % of all alcohols consisted of
cyc. lohexanol,Dnd 97 mol. % of all carbonyl compC-unds consisted of cyclohex-
ane Thei lower layer contained the sama products plus adipic and formic
acii;s. J'jVe references. Tables.
Institution The M. V. Lov6nosov State University, Moscow
Presented by Academician 11. N. Samenov, March 20, 195-4

USSR/Physical Chemisti.7"- Kinetics, Combustion,, EKplosions, Topo-
chendstry, Ce.talysia. B-9
.I.Abs Jour: Referat. 2bwmal Miimiya, No 3, 1958, 7210.
Author : IN. Berezin, Ye. T. Denisav. N.M. Emanuel' .
Inst : Academy of S--fe-nees Of USSR.
Title : Ydnetics and Chemism. of Cyclohexane Oxydation in Liquid Phase
by Oxygen from Air under Pressure.
Orig Pub: in symposium: Voyr. Iftim. kinetiki, kataliza i reaktsionnoy
sposobnosti, M., izd-iro AN SSW, 1955, 273-291.
Abstract: Cyclohexane (I) oxidation vas carried out with 02 frm the air
perstures from 135 to 1550
in an autoc%ave installation at tem
and. under the 2ressura frm 10 to 100 atm. During the reaction
cotrse, sa3qples were -taken and analyzed for cyclobexanone (II),
cyclohexanol (III) ani cyclohexyl peroxide (IV) contents, and
the total contents of acids M and eaters (VI); waste gases
were analyzed for 02 and CO,,?. The oxidation reaction of I has
Card : 1/4* -1 P_

USSR/-nysical Chemistz~, - Kinetics, Combustion, Explosions, Topo-
chemistry, Cetalysis - B-9
Abs Jour: Referat. Zhinnal 1(himiyaj, No 3, 1958, 7210-
an Etutocatalytic character; the kinetic curves of 11, 111 and
IV have the raw shape and pass through a maxim=, and the con-
centrations are II > III > IV along the total reacti on duration.
After a rapid rise at the reaction start the rate of 0 absorp-
tion re ins nearly constant for some time, after Vhi2 it starts
slowly to drop. V and *VI appear later thEm other products.
Traces of aldehides were detected at great depths. The active-
tion energy according to the 02 and IV curves is Z?'.2 and 29 kcal
per mole correspondingly. The waximun concentrations of II, III
and IV rise with the teaperature rise. Additions of 11 (4-5,
12.5%) and butyraldehide (0.8%) accelerate the oxidation of I
very much - An addition of IV, as well as of the mixture of II,
III and IV in concentrations produced at the reaction., increase
the oxidation rate of I, the autocatalytic character of the kine-
tic curves is preserved, whicli indicates the existence also of
Card 2/4 -13-

UNWPbysical Menistry - Kinetics, Combustion, Explosions, Topo-
chemistry, Cat4aysis. B-9
Abs JOUr-0 Flafe,Xt- ZhUrnA1 MIJUdAy No 3, 1958, 7210-,
Other intermed.Late products responsible for the self-secelera-
tion of I oxicthtion. The stu(b* of the IV dissociation showed
that it proceeded at 1350 in a steel auticlave according zo the
firal; orde;r with constants of o-48 hot=- (0-39 M 133 pure I),
0.52 hour' (0.06 M of IV + 0..1%, M of ii), and 0.6 bour-1 (in
oxiclized I medium) and produced. an equimolecular mixture of
II and III - The authors asm ! that the mdu amount of II is
prockeed by the dissociation of the hydropeAroxide radical, and
that III is Obtained at the expense of the recombination of
the ]*%UWeroxLde radicAl with OH with the liberatica Of 02-
IV docozVoses with formtion of' caprone and -oxycaprone &I-
dehides, which oxidize at a great rate to corresponding acids.
The formation of adipic acid.. (VII), the final react-ion product,
Card 3/4 -14-

DVIIIT5011, Ye. T
DENISOV, Ye. T.: "The kinetics of the catalytic cocication of cyclohexanes
from the point of view of the chain theory of degenerate branches.*
Moscow Order of Lenin and Order of Labor Red Bannar State U imeni
M. V. Lomonosov. Chemistry Faculty. Chair of Chemical Kinetics.
Moscow,, 1956. (Dissergation For the Degree of Candidate in Chemical
Scienco. )
Knizhnaya letopis'
No 32, 1956. Moscow.

USSR/Physical Chemistry - Kineti,as,
cheidstry, Catalysis.
Combustion, Explosions, Torpo-
Abs Jour: Reforat. Zhurnal W-1ya, No 2, 1958, 3855.
Autphor : Ye. T. Denisov, N.M. 30-e1' -
Inst : iF*~O-V~FUhiversity-
Title : Meckanism of Catalysis by Cobalt Srearate at Initial Period
of C~mclohexane Oxidatitm.
Orig Fab: Zh- fiz. khinii, 1956, 30, No 3-1, 2499 - 21M.
B-9
Abstract: At the beginning of eyeldhexane (1) oxidation reaction catalyzed
by cobalt stearate at 50 to .1100 in an autoclave equipment (Bere-
zin I V Dissertatsiyei, Mrj, 1953) a rapid transition of C02+
C* ~
into 4 takes place vith the formation of insignificant amounts
of alcohol and ketone. Iater a period of a retarded reaction
occu.rs, after vhich the! formttion process of Co3+ and oxidation
products is resumd. at a gmt speed. AddItions, of cyclohexanone,
(0.61MMOle per lit) to the initial I result in an increased yiell.d
Card 1/2 -7-

USSR/Physical Chemistry - Kinetics, Combustion, Explosions, Topo-
chezaistry~ Catalysis. B-9
Abs Jour: Referat. Zhun2al Khimiya, No 2, 1958, 3855-
of the initial stage products; additions of cyclohexanol (3.35
M-MDle per lit) increase the duration of 'the retarded reaction.
Tf St2Co coataining cr5stallization water was added to I, the
transition of' C02+ into Co3+ and the initiation of the oxidation
process do ncit take pItLee. The authors think that in the initial
oxidation peilod a rapidly retarded macroscopic initiating stage
teles place, in which otage Co2+ converts into Co3+ and the latter
catalyzes the faether process course. Experilumts with different
St,,~D concentiations arul with additions of Co2+ to the developed
resiction indleate that Co2+ retards the reaction. In the opinion
of the authois, initiwhing is not connected with the reaction be-
tween St~D ard peroxicI!, but it occurs with the participation of
the St 2C002 complex with I.
Card 2/2 -8-

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-AUTHORSo Emanuell, N*. Id. Denisov, Ye. T.
TITLEt 2heoratical Potsibility of Oxidation of Benzene to Phenol
in the Liquid khase (0 printsipi~.llno,, voz~..-ozluioati zhidkofaznogo
okialeniya benzola v fenol)
PERIODICALs Doklady AD SSSR, 1957, Vol. 117, Nr 3, pp. 458 - 461 (USSR)
ABSTRACTs The authors here endeavor to de Sormine the oxidation of benzene at
temperatures of from 230 - 270 and at a pressure of 50 atmospheies
Experiments were carried out in an autoclave device for the oxida-
tion of hydroca:rbons in the liquid phase tinder pressure. At each
experiment 200 imm of benzene were introduced into the reactor. Oxi-
dation was carried out by the o4rgen of a nitrogen oxygen mixture
with the composition 1 1 1 . During this process samples were taken
of oxidized banzene and were analyzed with respect to their phenol
content. With a photooalorimeter also 0the optical density of.the
oxidized benzeno was measured. At 250 oxidation of the benzene in
the liquid phase takes place with noticeable rapidity. With the
oxidation -of benzene phenol and resins are produced, The kinetic
curve of the accumulAtion of phenol is of S-like character. How-
ever, the maximiam concentration of phenol in this process amounts
Card 1/3 to.aiy 0,16 mol percent. In the oxidation of benzene with cobalt

20-3-28152
Iheoretical PDssibility of OAdation of Beazene to PheAol
in the 14qaid Fbam
stearate -this oatalyzer directs the reaction into the direction of
the condensation of benzene with the production of soot; only small
quantitiea of phonol are produced on this occasion. Small quanti-
ties of easily oxidizable substances such as cyclohexane and cyclo-
hexanon aooelerate the oxidation of benzene. The corresponding ki-
netio ourves are given. The experimental data obtained here con-
cerning the oxidation of benzene tend to show that this process
is a chaiia-like deomerated, ramified, self-decelerating reaction.
The experimental data agree well with a mechanism, which is de-
scribed in detail. The present pqper proves that, in principle,
it is posgible to attain the oxidation mentioned in the title at
temperatures that are near critical temperature. The-Irinciple
of gas initiation applied on this occasion furnished the beat re-
sults. Tho processes for the removal of the self-slowing-down of
the proceasee will have to be examined. There are 3 figures and
4 referenoes, 3 of which are Slavic.
Card 2/3

2N3-28/52
.1booretical ftexibility-of Oxidation of Benzene to Phenol in the
Uquid. Pbaw
ASSOCIATIONs Institute for Chemical Physics A.V USSR
(Institut khimi.chesk6y fiziki Akademii nauk SSSR)
PRESENTEDs
SUEHITTEDs
AVAILLBLEo
May 15, 1957, by N. N. Semenov, Academician
May 15, 1957
Library of Congress
Card 3/3

AUTHORS: Denisov, Ye.T. , Emanuel' , N.M. (11,03001W) 74-27-4-1/8,
TITLE- The Effective Mechanism of the Inhibitors in Chain Reaction-3 of
the Liquid 03d.dation Phase (Me1rhanizm deystviya ingibitorov v
tsepnykh reaktsiyakh zhidkofazriogo okisleniya)
PA~JODICAL: Uspekhi Khimii, 1958, Vol. 27, Nr 4, Pp- 365-402 (USSR)
ABSTRACT: The report begins by dealing with the importance of inhibitors and
the research vrork carried out in this connection during the past
decades,. Mention is made of the works by Muro and Dyufre!s (Ref 7)
on antioxidatton. After the function of inhibitors had, in their
general outlines, become -known and the chain theory supplied r---
lative.l.r simple formulae for the description of slowing-down ef-
fects theoretlical interest in `Lnhibitors began to die down. It
only recently that one of the 4Luthors of this paper pointed out
that in numerous cases oxidation processes have a far more compli
cated mbchanizim than that of the slowly growing and ramified chain
avalandtie. The present sur7ey is devoted to the analysis of the
chemics:1 effective mechanism oT inhibitors and to the theoretical
interpretation of and the particular affect exercised by inhibitors
Card 1/3 on the basis of the theory of ohain reactions with degenerrate3

The Effective Mechanism of the Inhibitors in Chain 74-27-4-1/8
Reactions of the Liquid Oxidation Phase
ramifications as developea by Semenov. The report is divided into
the following parts: The chain meclumism of the oxidation of hydro-
carbons. The "abain-interrupting!' chemical effect exercised by in-
hibitors; on the separation of the li-atom from the molecule of the
admixture InH; on the connection of the free radical with the mole-
cule of the admixture Q; the mechanism of the inhibiting effect of
pbenols; the mechanism of the inhibiting effect of amines. The
next chapter deals with the kinetic characteristic of the effect
exercised by inhibitors: i.) The theory of the effect produced by
strong !Lnhibitors. 2.) The theory of the effect produced by weak
inhibitors. - The following chapter deals with antioxidizers whiob
exercise a retarding effect upon the velocity of degenerated rami-
fioation. Mention is made in this connection of the destructive
effect oxercised by sulfides upon hydroperoxides, of the problem
conoexm~Lng the. modification of the kinetic curve of oxidation of
hydrocarbon, of the slo%,ing--aown effect produced with respect to
the oxidation process of alkaline subst8noes and acids. In conolu-
sion the report deals with the joint effect produced by 2 arti-
Card 213 oxidize-s. In this connection the fact is stressed that the join".

The Effective Mechanism of the Inhibitors in Chain 74-27-4-1/8
Reactions of the Liquid OadLdation Phase
effect produced by two substances which are able to destroy
peroxides caji often produce a greater effect than may be assumed
on the streq3th of the rule of additivity. There are 10 figures p
6 tables, anil 81 references, 23 of which are Soviet.
1 -. . -Chain ieactiob8"-Inhibition 2. Oxidation inhibitors-Ans.2,ysia
Card 313

D
AUTHOR: Denisov, Ye. T. 76-1-15/32
TITLE: The Specific Action of Inhibitors on Dee-anerate Branching
Chain Reactions (Osobennost'L deyfjtviya ingibitorov na
tsepnyye vyx-ozhdenno-razvetvlenn:fye reaktsii).
PERIODICAL: Zhurnal Fizicheskoy Khimii, 195a, Vol. 32, Er 1,
pp. 99-108 (.USSR)
ABSTRACT: By means of the chain theory the various processes connected
with the influence of inhibitors on chain reactions with
deE:ene3-ate branches are investi(:ated. Some facts regarding
the effect of inhibitors on the oxidation of liquid hydro-
carbons are explain~ed. Based on a Eeneral investigation of the
influence of various inhibitors a kinetic explanation of the
cozice.-D,.ionn on force and effectivenens of the slowinc-down
effect of inhibitors are Eiven. The hydrocarbon oxidation
procesaes are deEenerate branching chain reactions. The
slowing down effect of inhibi+ors is dependent on the -ir
in-tera.,.tion with free radicals. This leads to a slowing down
of the chain extension reaction. Three ponsible processes
of the interaction are shown. The author states that a
Card 1/4 weakening cf the slowine down effect Of some inhibitors with

The Specific Action of Inhibitors on De,;~enerate Branching 76-1-15/32
Chain Reactions
their introduction in to the already developinL process
of degenerate branchin6 chain reaction takes -.lace indei)endent
from inhibiting,from the character of the disconnection of
the chains in reaction. Thin characterlstic makes a differunce
between the daGenerate branchinE chain reactions the non-
branching chain reactions (the latter are slowed down when
the inhibitcrs are introduced at the be,-inning of the reaction,
as viell as -.ihen the introduction takes place durinE7 a reaction
already in proCress)(ref. 8). The cause of the wea.'ening of
the slowine down effect of inhibitors on the del,enerate
branchinU chain reactions w4~th the development of the latter
is that the reactions develop automatically. The ruaction
velocity with degenerate branchinCs is determined at any
moment by the concentration of the substance which injects
the chains and forms durinE,' reaction. The inhibitor slows
down the formation of this substance. The sloyrinC, down is not
only determined by the intensity of the slowinj: doun effect,
but also by its duration. The intensity of the slowine down
Card 2/4 effect of ari inhibitor is determined by the ratio between

The Specific Action of Inhibitors on DeCenerate BranchinE 76-1-15/32
Chain Reactions
the velocity constant of the reaction of the radical formed
of -the inhibitor and the radical effeotint: the oxidation with
the hydrocarbon. The smaller this ratio is the stronGer is the
inhibitor. The effectiveness of the slowing down effect is
determined by the magnitude of the constant of reaction
velocity of the radical effecting oxidation with the
inhibitor. The greater it io the L:~reater is the constant,
The explanation for the opposite effect on the oxidation of
various hydrocarbons with the addition of some substances is
given. The activity of the radicals through which the
oxidation of hydrocarbon takes place changes from one hydro-
carbon to the other. The radicals forming with the oxidation
from such related hydrocarbon compounds, as there are
alcohols or acids, apparently do not differ much as recards
their activity from those radicals forming with the oxidation
of hydrocarbons. Therefore cases are easily possible where
the radicals forming with the oxidation of such a substance,
are less active than the respective radicals of a hydro-
carbon, but much more active than radicals which effect the
oxidation of another hydrocarbon. In the first case an
Card 3/4 addition of this substance will slow down .). * - - t; ~ , -, ':. '. ...-

The Specific Action of Inhibitors on Degenerate branching 76-1-15/32
Chain Reactions
oxidation, in the second case it will accelerate it. In the
end the author shows thUt when a weak inhibitor is intro-
duced to a reaction already in progress the slowing down of
the chain reaction could occur because of the change of the
composition of radicals in the course of' the chain process.
There art) 3 figures, and 13 references, 9 of which are
Slavic.
ASSOCIATION: Moscow State University imeni M. V. LomonoBOT.
(Moskovsl:iy gosudarstvennyy universitet im. M. V. Lomonosova)
SUBMITTED: October 8, 19ri6
AVAILABLE: Library of CortUress
Card 4/4

AUTHOR: Denisoy, YD 76-32-6-13/46
TITLE: On the Participation of Salt Catalysts in the Chain Propagation
Reaction of the Liquid Phase Hydrocarbon Oxidation (0b uchastii
solevykh katalizatorov v reakteii prodolzheniya, teepi pri zhid-
kofaznom okislenii ugleyodorodov)
PERIODICAL: Zhurnal fizicheskoy khimiip 19589 Vol. 32, Nr 69
pp. 1269 - 1276 (USSR)
ABSTRACT; Owing to the complicated nature of the problem and insufficient
experimental evidence various standpoints have hitherto been
adopted papers concerning the mechanism of the catalysis with
metal salts and organic acids. The results of the catalytic oxr*,.
idation of cyclohexane leadto the assumption that processes of chain
propagation are caused by such catalysts. In the present paper
factors are pointed out on the strength of the theory of chain
reactions with degenerate ramifications indicating such a reaction.
New experimental data are evaluated and the correctness of the
assumptions is proved. It is found that a reaction of the free
radicals with hydrogen peroxide must be assumed apart from the
Card 1/3 transformation of the ROO-radicals in hydrogen peroxide.. The

On the Participation of Salt Catalysts in the Chain
Propagation Reaction of the Liquid Phase Hydrocarbon Oxidation
scheme of :reaction derived herefrom, however, is unable to explain
all experimental evidence obtained. It appears, among other
things, that an interaction of the catalyst with the ROO-groups
takes place under the formation of another radical, as for
example OH and molecular products which differ from hydrogen
peroxide a6i do a ketone or an alcohol. Proceeding from this as-
sumption corresponding equations are derived. Experiments were
conduoted, determining the content of hydrogen peroxide, ketone
and alcohol.. The kinetic curves showed that all three products
are formed in parallel in the presence of salt catalysts. Thus
the assumption is provedAhat an interaction of the catalyst with
the radical ROO takes place under the formation of a new radical,
of alcohol and of ketone. Salts with cations containing smeared
electrons must react particularly actively with the free radicals.
This is substantiated by the experimental evidence concerning
the oxidation of cyclohexane with cobalt and manganese stearate,
in which the production of hydrogen peroxide is particularly
small in Vie beginning. There are 4 figures, 1 table, and 11
Card 2/3 references, 6 of which are Soviet.

On the Participation of' Salt Catalysts in the Chain SO" i,"76-32-6-13/46
Propagation Reaction of' the Liquid Phase Hydrocarbon Oxidation
ASSOCIATION: Moskoyskiy gosudarstvennyy universitet im. M. V. Lomonosova
(Moscow state University imeni M. V. Lomonosoy)
SUBMITTED: January 18, 1957
1. Hydrocarbons (Liquid)--.Oxidation 2. Metal salts-Catalytic
propertleia 3. Organic acids--Catalytic, properties
Card 3/3

-~ (4)
1UTHORS: Denisov, Ye.T., Emanuel', N. M. SOV/76-32-1o-2V39
TITLE: The Liquid Phase Oxidation of Benzene to Phenol at
Temperatures Close to the Critical Point (Okisleniye
benzola r fenDl v zhidloy fa~:e pri temper-ti,,ral~h, bliz-
kilch k 1-1:?iticiieskoy)
PERIODICAL:. Zhurnal fizicheskoy khimii, 1958, Vol 32, Nr 10,
pp 2374 - 2382 (USSR)
ABSTRACT: In an ea-:,~lier 1)a-)er (Ref" 1) it was pointed out that
a series of hi.,-h-temperature oxidations can be carried
out in the Gas phase Ct low tem-cratures, and in
P
the liquid phase. In the presenb paper t' Ie oxidation
of liquil benzene is carried out at 230-2700 (especially
at 2500) and at a pressure of 50 atmospheres absolute
pressure. An autoclave serving for the investi~;-ntion
of the kinetics of proc-ooses in liquid phase (Ref 5)
was used. Benzere oxidizes in the li~Luid phase rather
rapidly at 2500; phenol and resins are formed as
reaction products. An addition of 2 mol,,~'D c.-clohexane
Card 1/4 causes an acceleration in the process, whereas 1 mol%

The Liquid Phase Oxidation of' Benzene to Phenol at S07/76-32-1o-21/39
Temperatures Close to the Critical Point
cyclohexarione shows a still stron~;er effect. The
addition of 0,'5 moll/fo cobalt stereate led to the
opposite offect, i.e. a small formation of plienol
took plac(!;how(!ver, with a 'lari;e formation of soot.
Experiments carried out with jas injections yielded
the best :7esults when ZitroC;cn dioxide was used.
Nitrobenzene was qualitatively determined amon- the
oxidation products in this case. The interruptlon
of the ga:3 passage leads to a slowi.nG down of the
reaction so that a stimulation by riitro~~en dioxide
should ta'Ke place throughout the oxidc.tion process.
It is assumed that benzene oxidizes also in the
licluid phase according to the chain mechanism. The
maxi,mum phenol formation depends on the self-im-
pedance of the benzene reaciion.The present reaction
is considered in relation to the theory of chain
reactions by N.N.Semenov (Ref.9), and the experimental
data obtained-are compared. The self-impedance of
the chain reaction is ex'Plained by the accumulation
Card 2/4 of p:~oducts that inhibit the reaction by ar exchai-,Ge

The Liquid Phase Oxidation of Benzene to Phenol at SOV/76-32-1,:)-21/39
Temperatures Close to-the.Criti.cal Point
of activo radicals against less active ones. According
to a scheme the weakly active free radicals react
with intermediate products and the maximum concentration
of the intermediate products is lower the higher the
inhibition by the oxidation products. On the other
hand, the final product will be formed at a maximum
velocity in the case that the maximum concentration
of the intermediate products is obtained. There are 6
figures and 10 references, 8 of which are Soviet.
ASSOCIATION: Akademiya nauk SSSR,Institut khimicheskoy fiziki (AS
USSR)Inc-titute of Chemical Physics)
SUBMITTED: May 15, 1957
Card 3/4

F&A I BDOX EVWrWWN SDV/3663
nauk SSSR. InstItut W-4cheskoy f1siki
oidsleniye uglevmoroftv v zhidkoy fase; abornik statey (O)ddation of Hydro-
carbons in the Liquid Rase; Collection of Articles) Moseow, Izd-vo AN SMI,
1959. 334 p. Errata s3lp Inserted. 2j,200 copies printAid.
Ed.: N. M. lmsxuells, Corres"nding YAmber,, Academy of Sciences USM; Ed. of
Pablishing Ebuse: K. M. Dyumayev; Tech. Ed. *. 1. F. fts lain.
PURM: 2his collection of articles to Intended for cl~wdxts interested in
hydrocarbon oxidation reactlonsp particul&rly for those Vactalizing in petrol-
eum fuels.
CCYVX": This collection of A,5 articles represents iJ* reoults of Investigations
.ovdr a Varied of several years on problems . ' on oxidation. The
authors preeent their aim tkadketical'and,experimental data and also draw fren
current lit4rature, No pereanalities an mentioneds lieferenoes accompany
most of the articles,
Card 1/18

Oxidation of Hydrocarbons in the (Cont.) SOV13663
Knorre, D.G. (Institutg- of (benical Physics], Some Elemt!ntary Stages in
the Liquid-Phase Oxidation of Hydrocarbons 46
This stucky, based on data from the literature indicates that hydro-
peroxide tormation is the initial stage in the formtion of stable
hydrocarbon oxidation pr&luats. Reaction activation energies and
reaction xates are computAid both theoretically and experimentally.
Denisov Ye r. [Moskovskiy gosudarstvannyy universitet imeni M.V. IA)mono-
University imeni N.V. Lomonoso%)]. Inflivnee of Products
so
of a Slowly 'Developing Chain Reaction on the Length of the Unbranched Chain 55
The influiBnce of oid.dation product concentratioa on the! length of side
chains is investigated. Ch this basis,, a number of phenomena observed
during thB liquid-plase oAdation of hydrocarbons is explained: self-
retardation 6f the oxidation process,, rectification of the kinetic
curves during low-temperatun oxidation, the iniorease in effective acti-
vation energy with lowered temperature, etc.
Card 3/18

Oxidation of lbArocarbons in the (Cont.) SOV13663
Dealsov Ye.T, [Moscow Statq 'Mdversity imenj M. V. Lomonosov].
;~;~s of the Action of Inhibitors on Side-Chain Dacbmposition
Reactions 66
lvanov., K.I.., and Ye.D. Vilyanskays [Vsesoyuznyy tep~otekhnicheskiy nauch-
no-issledovatmllokly institut imeal, F. E. Dzershinskogo (All-Union Beat
Engineering Scientific Ruawch Institute imeni P. H. Dz(.zrzhinskiyl.
Effect of InMoitors on the Kt3etiee JfL the Autoxidation of Wdro-
carbons 77
Me authors investigate the effect of various Inhibitors on the
mutoxidation of bydrocarbons from petroleum crudes, as vall as
various stages in the development of the oxidation process.
Card 4/L8

Oxidation of ILydrocarbons in the! (Cont.) SOV/3663
pol7valent metal salts in thei decowposition of peroxides and the
oxidation of hydroosa-bons Is discussed.
Blyumberg, E.A.,, Z.K. Wqzus., wid, N.M. Rmauell [Institute of Chemical
Pbysics]. Liquid-Phase Oxidation of n-Butane at Bear-Critical Temp-
eratures and Pressures 125
The authors discuss the kinetics and chemistry of a purportedly new
method for liquid-phase oxidation of a-butane. Initiating the re-
action with N02 and catalyzing with C*St2 resulted In a
shorter Induction period, by Increasing the initial rate of chain
growth. Acetic acid and =ethyl ethyllmtone are the principal
products of the reaction.
.'Deniggy, Ye.T. [Moscow StAte University imeni K.V. Ta=osov] Kinetics
_~f_6;d~mie Oxidation Catalyzed by Cobalt Stearate 136
The author finds that the catalytic action. of cobalt salts (stearates)
both breaks down andinitiaties chain growth during the oxidation of
cynaldhexane. The relationsIcip between these functions is substantial-
ly changed as the reaction eLevelops*
Cw-d 7/18 ,

5.4300
77062
sov/62-59-12-6/43
AUTHOR: Denisov, Ye. T.
TITLEi Causes for Changes in Concentration of the Intermediate
Product in the Course of Chain Reaction
PERIODICAL: Izvestlya Akademii nauk SSSR. Otdeleniye khimicheskikh
nauk, 1959, Nr 12, pp 2100-2111 (USSR)
ABSTRAM. During oxidation reactions with degenerate branching,
the concentration of the molecular intermediate
product (hydroperoxide, ketone, aldehirde), after
reaching a maximum, often starts to decrease rapidly.
The author considered possible Cases in which the
concentration of the intermediate! in the reaction
RH---), P .--.)K (w,'.,iere RH is starting compound, P is
intermediate, K is final product) is decreasing:
(1) reaction, in which the intermediate is formed
and consumed *by a chain process; (2) the intermediate
is consumed by a nonchain process, in whichthe
accumulating products alter the consumption rate of
Card 1/3 the intermediate; (3) formation of ionic'products

Causes for Changes in Concentration of the 77o62
Intermediate Product in the Course of Chain sov/62-59-12-6/43
Reaction
takes place, oatalyzing ionie.distiociation of the
intermediate. Two main causes for the decrease of
intermediate-product concentration are; (1) change of
radical composition and their activity in the cour3e
of reaction. When the inter-mediate is formed and
consumed by a chain process, its concentration changes
when the relative reactivity of the radicals changes,
i.e.
ko, + -L"- k 1
k. kio ,or F_- ratio is not constant.
0
Here ko and k 1 are rate constants of the radicals
with RH and P, respectively, I denotes free radical
(from 0 to i)j 0 denotes RHj I denotes P. This
Inequality takes place when the heats of the four
reactions do not have the same sign. (2) Rate increase
of the interniediate-product consumption by a nonchain
Card 2/3 process. This takes place due to accumulation of

Causes for Changes in Concentration of the 77062
Intermediate Product In the Course of Chain sov/62-59-12-6/43
Reaction
ASSOCIATION:
SUBMITTED:
Card 3/3
compounds, reacting with the intermediate, or due to
accumulation of acids, which cause Ionic decomposition of
the Intermediate. In actual oxidation processes, one may
find cases in which either both, or predominantly one
of the causes exist. There are 4 figures; and 1b ref-
erences, 7 Soviet, 4 U,K., 5 U.S. The 5 recent U.K.
and U.S. references are: J. E. Hay, N. M. Johnstone,
C. F. Tipper, R. H. Williams, J. Chem. Soc., 1954,
629; E. J. Gasson, A. F. Millidge, G. S. Primavesi, J.
Chem. Soc., 1954, 2161; F. H. Seubold, W. E. Vaughan,
J. Amer. Chem. Soc., 75, 3790 (1953); C. F. Tipper, J.
Chem. Soc., 1955-, 1675 M. S, Kharach, J, S, Burt, J.
Organ. Chem., 16, 150 14951).
Institute of Chemical Physics of the Academy of Sciences
USSR (Inotitut khimicheskoy fiziki Akademii nauk SSSR)
March 22, 1958

5(3)
ZOV/80- 3 2-4-- 33/117
AUTHORS: Berezin, I.Y., Denisov, Ye,.T., Suvorova, S.N,, Smolyan, Z.S. and
Emanuel', N.M.
TITLE: The Oxidation of a Mixture of Cyclohexane and Cyclohexanol -.0
Adipic Acid (Okisleniye smesi tsiklogeksana i tsiklogeksanola v
adipincvuyu kislot-a)
PERIODICAL: Zhurnal pri-Icladnoy khimii, 1959, Vol 32, Nr 4, pp 888-892 (USSR)
ABSTRACT: Production of monomers for plastics and synthetic fibers is one
of the important tasks of modern chemistry, The utilization
of various waste materials can contribute to the solution of this
task. One of these waste materials is the mixture of cyclohexane,
80 m01.%, and cyclohexanol, 20 mol.%. The authors studied the
kinetics of the oxidation of this mixture, called "anol bead",
with an aim of obtaining qclohexane and adipic acid. The oxidation
was carried cut in an autoolave at a pressure of 20 atm by mole-
cular oxygen at temperatures of 130 and 1500C. Kinetic curves of
accumulation of the reaction Droducts were obtained and the
possibility of producing adipic acid by oxidiz--'-ng the 11anol head"
was proven. It wai3 shown that some peculiarities in the oxidation
Card 1/2 kinetics were dete3!mined wholly by the concentration of cyclohexanol

SOV/80-32-4-33/47
The Oxidation of a Mixture of Cyclohexane and Cyclohei~anoj Tn-o Adipic Acid
in the "anol head". The process of oxidizing "anol head" is to
be carried cu-t with.continuous removal of adipic acid obtained in
order to prevent its burning into 4ower dicarboxylic acids, and
the process thereby acqoirer z~ continuous character.
There are 'A se-ts of graphs and 7 Soviet references.
SUBMITTED: Povember 1, 1957
Card 212

5(4)
JWM=t Deniwv,, Yeo T. WV/76-33-6-6/44
Tr=t Investigation of the Wdation of Cy-olahexane by an Wlibiting
Method During the Course of
tsiklogeksana metodom ingibirovaniya po khodu reaktEiii)
PMUODICALs 2burral fizicheakoy khimiip 19599 'Vol 33, Vr 6, pp 1198-1208 (USUR)
ABSTRAOTt To oliaraoterime a chain-oxidation przoesa it, is necessary to know
the chain formatLon rate and the ohaSn length as well as the
kinetics of the veAstion of both these queztitias ditring reaction,
A rather aimple method of determl-n!mS +,has@ qrawtities, in the oase
of oxidation in the liquid phaeaq Is that of InhibitirIg the reaction.
There are two basic possibilitiGs in a ohain reaoti= with the
formation of da~wnerated ramifications, with an intermediate and: an
end produot. 1) The molecular intermediate product (Z), from which
the degenerated ramlfioation Is *xliginated, occurs after a chain
reaction, and &1so deocaposes after & ohdh- rea-1tion. 2) (Z) is
formed by a chain reactions it does not, however, decompose after a
ohain reacticz. Both thass oases are thoroua4ly dealt with
theoratioally, and it is stated that in tha firat oase the addition
of an inhibitor (1) effsvto a mark3d ralmrda-tion of th~.4 aacumulation
Card 1/3 of (Z), whila La tha &eoczA tags tha W addilu'lo.i causes the

Invegrtig&tion of the Oxidati-n cif Cyoldhaxane by to Inhibit-1.71g WITC-33-6-6/44
Method During the Gourse of
consumption of (Z) already in the. oaarse of henoe,, the
meabanism of thm ams=ption of (Z) vneAr rertirent rewtion conditicus
may be interpreted on tho strength ot the v&r4.at:'-om cf the kinetic
ourve of the (Z:) isi,~mamulatic:,. fc1lowLng th4 aid.-I'tion of a strong (Ij~.
Tht preseint, papir deals with the 1m-#-stigat:'-xn of thu oxilation, of
200 ml eyolohemm* (II) I--- a speulal autocla-re systum. At 1400 and
30 3.tm pitissura a nitro6vin-oxygez rdxtura (1:1) was tlcwn thrortcph
with & vislocity of 30 3-!hocr, ~x-y-aphthvl (1-II) ~elng lised as
(I)p Rq4rimemtia resil-144 ~:how (Pip 3-6) that inhibits the
formatim of this ketcmq of an!. cf avids, i.e. the (II)
oxidaticna is b&qio-.LUv a 311min 1"af, ULZa,, Tte kinetin craxws of the
af,.6r a (1) addition (Fig 6)
A
sh,-~w +~hzit %JV) does r.-)t att-er a ,Bin vaa:;tion. There is
no dimot reaction between and (IV) (Table 1)+. Data a-re supplied
oancerr4mg ohab2 irit-leting rate and t;tain length (Table 2). An
explanaUcin is gl-mn :~f the pam;.Ilar or-%zzaa of the liagram of the
Chain I(Mgtl- r-a-3t-lan, ,m-AL the totaa aotivity of the
free vuLicmlz 6inmr-ming f,--, t:-, jh.=g- ji id rably
Card 2/3 d-jrJng Xealat:-Co, Thes-3 ~u.'aagez vtmcngly pr:z-,at-s t~,--3 im--rease in

Investigation of the Cticidation of Cyclohexane by an rnhibi-ting W7176-33-6-614A
Method During the Course of Vao Reaction
oxidation velooity of (11)9 wbidh is observable in the oauzoe of
reaction. There we 8 figures, 2 tables, and 17 references,, 13 of
which us Soviet.
ASSOCIATICK: Akademiya nauk SSSR Institut kbimiohoWcoy fizild (Academy of Soiwmes
of the) USSR, IrsIftate of Chemical Physics)
SUMMED: MaY 15, 1957
Card 3/3

5 (4)
AUTHORS: DeniEtov, Ye. T., Mayzust Z. I%, SOV120-128-4-33165
Emanuel', N. M., Corresponding Member, AS USSR
TITLE: Kinetic Laws tor Autocatalytic Reactions in Open Systems
?ERIODICAL: Doklady Akade-aii nauk SSSR, 1959, Vol 128, Nr 4,
PP 755-758 (USSR)
ABSTRACT: In chemical technology, the continuous process of reactions
is W;tempted more and more, i.e. of reactions in open systems.
While the kinetics of simple processes had already been in-
vestigated (Pefs 2-4), no data are available on autocatalytic
processes. Therefore, the continuous oxidation of cyclo-
hexanone to ELdipic acid by oxygen at 1300 was studied. The
appa:catus used permitted the automatic maintenance of the
inflow of raw material and of the outflow of the reaction
products. The term of "specific velocity" v is defined as
the -volume of the liquid initial component supplied to the
unit of volume of the reaction vessel in the unit of time.
The valuel indicates the average duration of stay of the
v
liquid in the reaction vessel. The content of hydrogen per-
Card 113 oxide, adipic acid, and CO 2 in the reaction product is

Kinetic Laws for Alito-~-atalytic Reactions in SOV/20-128-4-33/65
Open Systems
determined fox different v. In the continuous process, a
stationary state appears, i.e. the reaction rate and the
discha.rge of the end product are in an equilibrium relation
to each other. Figure 1 shows the lependence of the equi-
librium concentration of adipic acid on v. In the transition
from the periodic process to the continuous one, it is of
no importance in which phase of reaction this transition
takes place since the equilibrium concentration is formed
corresponding to v, irrespective of the oxidation degree
attained. While for simple reactions the rate rises mono-
tonously with v, there is a different dependence for auto-
catal 'ytic reactions since not only the concentration of the
initial prod~uot but also that of the resulting intermediate
product (hydrogen peroxide) is decisive. Figure 3 shovs that
the reaction rate passes a maximum at a certain v; if v keeps
on risingf the reaction rate falls since the concentration
of the hydrogen peroxide becomes lower. The equation for the
maximum reaction rate is written down. It is pointed out
that in the continuous process, in comparison with the
Card 2/3 periodic process, a smaller amount of burning to CO 2 and H20

Kinetic Laws for Autocatalytic Reactions in SOV120-128-4-33165
Open Systems
occuxa because the reaction products remain in the
reaction zone for a shorter period. There are 3 figures
and 6 references, 3 of which tire Soviet.
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences- USSR)
SUBMITTED: June. 22, 1959
Card 3/3

S/081/60/000/023/001/021
AOO5/AOO1
Translatlon from: Rf3ferativnyy zhurnal,. Xhimiya, 1960, No. 23, P. 59, # 91595
AUTHOR; Denisi","e 41
"UMM00%
TITLE: On the Effect of the Products of a Slowly Evolving Chain Reaction
on tho Length of a Non-Ramified Chain
PERIODICAL: V sb.:: Okisleniye uglevodorodov v zhidkoy faze, Moscow, AN SSSR,
1959, pp. 55 - 65
TEXT: The kinetic equations are derived and analyzed for the case of noll-
ramified and degenerated ramified chain reactions,, Activity variations of the
radical-carriers of the chains are taken into consideration. These variations oc-
cur in the ciourse of the conversion because of the! accumulation of reaction pro-
ducts in the! reaction system, which react with the radioal-carriers with the
formation of' radicals differing from the radical-carriers in their reactivity.
On the basis of the results obtained, the following experimental facts are ex-
plained which can be observed at the chain oxidation of hydrocarbons: self-inhibi-
tion, rectification of the kinetic curves at low temperatures, increase of the ap-
parent activation energy at decreasing temperature, the existence of a sharply
Card 1/2

3/081/60/OC)0/023/001/021
A005/AOOI
On the Effect of the Products of a Slowly Evolving Chain Reaction on the Length of
a Non-Ramifi-ed Chain
expressed peak in the kinetic curves of the accumulation of intermediate products,
the opposite effects of additions of the same substance on the oxidation of dif-
ferent hydron.arbons, the difference in the effectiveness of an Inhibitor depending
on the conversion depth at which the inhibitor was introduced into the reaction
system, the i3imulation of regularities in the process of a degenerated ramified
reaction by a non-ramified chain reaction (and vice-versa)
G. Korolev
Translator's note: This is the full translation off the original Russian abstract.
Card 2/2

5 -4100
S OVI/6) 2 - '6 i --D 7
AUTHOR. Derlisoir, Ye- T.
TITI,E: Concerning a Pcssibility al' Hydroren Bond Forma-lticn
Between a Peroxide Radical arn Molecules Containinc,
an OH Group
PERIODICAL: Izvestiya Akademii nauk SSSR. Otde-leniiye khimicheskikh
nauk, -1960, Nr 11, PP 54-,58 (USSR)
ABSTRACT: This paper presents a theoretical substantiation
and experimental proof of the formation of a ccinplex
hydrogen bond between a peroxide radical and molecule3
containing an OH group. ROG ... HOX, where X is,,.
H, R, RCO, 110. The rate of' ox1dat.ion is determIned
by the concentration and activity of the 'Lree radicals,.
In the presence o-f compounds conta-Ining OH groupq, e,g,,
water, formation of the above complex takes place,
FTO * + If 0 -- R0, if 0
Card 1/2 2 2 2 2

concerning a PossIt.,1 A ty of' Hydroge- cnd
Formation Between a PE-roxide Radical and ,:.,ov/-62 I
Molecules Containing an OH Group
ASSOCIATION~
SUBMITTED:
Formation' of the above complex woul.d cause a decrease
in the rate of' oxidation, Experiments conducted with,
oxidation of anhydrous cyclohexanone and cyclchexanone
containing different amounts of water eilth a 0mixture
of nitrogen and oxygen in a Izi ratio at _12-0 , show
that addition of water to the reaction mixture de-
creases the rate of eyelohexanone oxidation, n-
hibiting action of water indicates that the formation
of the above complex takes place. There are I T:able;
fJgures; and 6 references, German, 5 S:)v-lei:,
Institute of' Chernical, Physics, Acadamy of Sciences,
USSR (Institut khimicheskoy lfizlki Akademil- nauk
SSSR)
March 31, 1958
Card 2/2

S/595/60/000/000/004/014
E196/E535
AUTHORS: Emanuel', N.M., Berezin, I.V. and Denisov, Ye.T.
TITLE: The oxidation of cyclohexane
SOURCE*. Vsesoyuznoyt9 soveshchaniye po khimicheskoy pererabotke
neftyanykh uglevodorodov v poluprodukty dlya sinteza
volokon i plasticheskikh mass. Baku, 1957. Baku, Izd-
vo AN Azerb.,SSR, 196o, 143-156
TEXT: The kinetics of oxidation of cyclohexane were investi-
gated without using: catalysts, with catalytic salts and with a
stimulating gaseous initiation. The aim of this study was to
gain more information on the oxidation of cyclohexane which is
important in the production of cyclohexanone and adipic acid for
the nylon fibre industry. A further aim was to determine the laws
governing this simple liquid phase oxidation and to apply these
laws to more complicated hydrocarbons. Without a catalyst
satisfactory velocities can be attained at pressures of 10-100 atm
and temperatures of 135-1550C. The main intermediate products
are cyclohexanone, cyclohexanol and cyclobexyl bydroperoxide. A
second liquid phase appears when the reaction mixture becomes
Card 1/5

The oxidation of cyclohexane S/595/60/000/000/004/014
E196/E535
saturated with wate.r and adipie'acid, which have limited
solubilities in cyclohexane. As the reaction is a chain
degradation-branching reaction, no single parameter can be used
to characterize it. The maximum absorption rate of oxygen is a
function of temperature and obeys the Arrhenius equation, with an
activation energy of 27 kcal/mol. The log of the conversion
coefficient to cycl43hexy:L hydroperoxide over the first part of the
reaction varied linearly with the inverse of the temperature, with
activation onergy 21) kcal/mol. For the intermediate cyclohexanone,
the log maximum concentration varied linearly with the inverse of
the temperature, the activation energy being 8 kcal/mol. The
transformation of the intermediate products was studied by the
use of radioactive i.-arbon as marker and the following sequence was
found
OEI
02 02 adipic 0 CO + monocarbon
4o acid 2--4 2 acids
Card 2/5

The oxidation of c:yclohexane S/595/6o/ooo/ooo/oo4/0l4
E196/E535
In glass vessels the hydroperoxide breaks down equally into
cyclohexanol, formed entirely by the decomposition of cyclohexyl
hydroperoxide. and cyclohexanone, from decomposition of the
hydroperoxide and oxidation of cyclohexanol. Adipic acid is
formed exclusively by oxidation of cyclohexanone whilst the
esters are formed by direct esterification of the adipic acid
with cyclohexanol. In. a steel vessel, however, cyclohexanone
is also formed by decomposition of the cyclohexyl hydroperoxide
radical. In the reaction withcatalyzing salts, cobalt stearate
dissolved in cyclohexane was used as catalyst. During the
reaction, the cobalt changes into the trivalent state. and after
a few minutes at 1300C the concentration of Co(III) becomes
constant, then begins to decrease until after about 1.5 hours
it is all once more in the divalent state. With the appearance
of adipic acid the cobalt begins to precipitate as cobalt
adipate, but part of the catalyst remains in solution throughout
the reaction, The catalyzed and non-catalyzed oxidations differ
as regards the reaction, rate and concentrations of the inter-
mediate products. Experiments with different concentrations of
Card 3/5

The oxidation of cyclohexane S/595/60/000/000/004/014
EI.96/E535
the catalyst (0.06 to 0.00023 mol %) showed that the higher the
amount of catalyst, the faster the rate of reaction, demonstrating
that, in the initial periods, it is a chain reaction whose rate
of initiation is proportional to the concentration of dissolved
catalyst, Similar results were obtained using cobalt adipate,
The catalyst has thus tvro functions - initiation of the reaction
and vegulation of the proportions of the products, The rate of
absorption of oxygen in the uncatalyzed reaction remains
constant after the induction period; in the catalyzed reaction
it rises to a maximum arL ~/-decreases to a constant value whi~,h
less than that of the uncatalyzed reaction, This suggests a
self-delaying action, To confirm this supposition the catalyst
was removed from the reaction zone some time after initiatioi~
and the final constant velocity attained was found to be highr--~r
than for the uncatalyzed reaction, A new method of stimulating
liquid phase oxidation, using NO 2. was studied, The air was
saturated with NO 2 (0.4%) at a rate of 50 litres '/hr, At 1400C
the reaction was markedly accelerated,, The method was also tried
in combination with cobalt stearate catalyst, A tabl e i s
Card 4/5

The oxidation of circloh,exane S/595/60/000/000/004/ol.li
E196/E535
included which givets yields of acid and Iretone for tI-)e various
methods of oxidation, A mathematical analysis of the reaction
is made on the assumption that it is a simple chain reaction
with a single intermediate and a single final product; the chain
is assumed to be broken by recombination of the free radicals,,
Academicians B. A. Kazanskiy, G. S. Landeberg and N,N-Semenov
are mentioned in the paper. There are 10 figures and 2 tables,
Test Depth of
oxidation Yield of
acid,% Yield of
ketone,%
Autooxidation 14.13 30 37
Oxidation with
St 2C0
18.,)
58
23
Oxidation with NO 2 19 57 22
Oxidation with
St 2C0 + 1402 22 51.5 27
Table
Card 5/5

DINISOV Te 2 1
'0 '
Oxidat!Lo7n of acetone, Initiated by benzeyl peroxide. Izv.AB
SSSR Otd-lchlm-nauk no.5:812-815 My 160. (MIRA 13:6)
1. Institut kbimi-heBker fiziki Akademii nauk SSSR.
(Acetone) 13suzo7l peroxide)

E;/074/60/029/012/003/004
13010078
AUTHORS: Denisov, Ye. T., Emanuel', N. M.
wurft"W.
TITLEs Catalysin With Metals of Variable Valence in Oxidation
Reactionn in the Liquid Phase
PERIODICALt Uspekhi !chimii, 1960, Vol. 29, No. 12, pp. 1409 - 1438
TEXT: This is a survey of experimental data published over the past
decade concerning oxidation processes in the liquid phase under the
catalytic action of metals of variable valence. The review offers a broad
outline of mechai,.iisma by which the salt-catalysts act upon the oxidation
of aldehydes and hydrocarbons. The existing experimental material con-
cerning the catalytic oxidation of crganic compounds (Refs.4-6, 8, 10,
16-49;,Figs.1-6; Tablos 1-3) indicates that catalysts of variable valence
take an activ e part in the initiation of chains. The basic difference
between these catalysts and the peroxides an well as azo compounds is that
each molecule of the catalyst.may repeatedly participate in the initiatio4n
of a chain by causing the transformation of molecular products into free
radicals. The mechanism of the initiation of c-hains., however, has not bee
Card 1/3

Catalysis With Metals of Variable Valence in 5/0%60/029/012/003/004
Oxidation Reactions in the Liquid Phase B013 B078
investigated more closely. A. further function of catalysts of variable
valence, e.g., the tearing of chains has been examined in Refs.11, 20-23,
27, 38, 50-52. (Tables 7-1111. Such a reaction takes place when the
catalyst reacts with free re,dicals. The inhibiting effect of the catalystst."
is in most cases non-apparent due to the stronger acting effect of
initiation. A thorough study of the inhibiting effect of catalysts is
still in its initial stage-Physioo-chemical properties of catalysts in
hydrocarbon solutions were investigated in Refs.3, 5, 20-24, 43, 53-64
(Fig.12, Tables 4,5), where salt molecules were found to associate into
micellas. About the dependence of oxidation rate on the concentration of
the catalyst, opirtions diverge. Just as with the oxidation of hydrocarbons
in the gas phase in the presence of catalysts (Ref.65), also in the liquid
phase in the presence of catalysts of variable valence the reaction course
was observed to take place in successive macroscopic stages limited in
time. (Refs.8, 7, 10, 59, 6,ri, 551 Figs.13, 14). The causes of such a
stepwise course could, up to now, only be explained in rough outlines *The
study of the regulating actfon of the catalyst during oxidation is dealt
with in Refs.10-129 179 219 67-73 (Figs.15-20, Table 6). On the basis of
existing experimental materials, the following may be stated on the
Card 2/3

Catalysis Witit Metals of' Variable Valence in S/074/60/029/012/003/004
Oxidation Reactions in the Liquid Phase B013/BO78
catalytic effect of metal salts of variable valencet The effect of salt
catalysts upon oxidation is complicated and has various aspects. The
catalysts reaot with oxidation products such as hydroperoxides and
aldehydes undar formation of free radicals. At the same time, several
catalysts reai,.t with free raAicals under tearirg of chaina. Under certain
conditions, such catalynts have an inhibiting action upon oxidation.
Besides, salt catalysts contribute to the lengthening of chains and
regulate the composition of the resulting oxidation products. While the
catalysts have an effect on the process of oxidation, they undergo com-
plicated physicochemical transformations in their turn. Products of the
developing reaction, particularly acids, extract the catalyst in the
precipitate, which causes the further course of reaction to take place
under a weaker pa3 *'ticipation of the catalyst. In spite of the complicated
mechanism of catalytic oxidation, a number of symptoms could be determined,
the knowledge of ithich will undoubtedly help in working out rigorously
controllable oxidation methods. Mention is made of V. K. Tayakovskiy,
N. A. Kiseleva, and B. G. Freydin. There are 20 figures, 6 tables, and
73 referencess 31 Soviet.
ASSOCIATIONs Institut khimicheskoy fiziki AN SSSR (Institute of Chemical
Card 3/3 Physics of the AS USSR)

S-,- -?,~ C 0 (~A) 68616
lrt#
AUTHOR: Denisov, Ye.T.-. S/020 '60/130/05/028,/061
ZWK B0047BO14
TITLE: A Dew Reaction for Initiating Chains in Liquid-phase Oxidation
PERIODICAL: Doklady Akademii nauk SSSR, 1960, Vol 130, Nr 5, pp 1055-1058
(USSR)
ABSTRACT: of the initiation
The author presents an estimate of the rate W
0
of chain reactions according to the equation RH + 0 2~' +
+ Hoj - q, (1). Table I lists experimental values of Wo

(kcal/al) for benzaldehyde, decanal, oyclo-
(ml/l.sec) and 33
0
hexane, n-deoania, Tetralin, and cyclohexanol. Calculation
~
yields values which are too low and deviate from the experimenta
values by 5-10 orders of magnitude. As the values of E and of
the steric factor f, assumed for calculation cannot lead to
such great deviations, the author investigates the trimolecular
reaction HH + 0:2 + HR-+E* + E202 + R* - q2 (2). The values
calculated for W
according to equation (2) are compared in
o
table 2 with those following from equation (1) and experimental
CELrd 1/2 values which aria partly quoted from publications (Refs 2-6).

A blew Reaction for Initiating Chains in
Liquid-phase Oxidation
68616
S/020/60/130/05/028/061
B0041BO14
The differonces 'between W from equation (2) and experimental
values amount to 1-2 ordeis of m94;nitude only. In consideration
of the unavoidable errors of such an estimate, the author notes
that the trimolecular reaction 2RH + 02 proposed by him is in
satisfactory agreement with experimental data. Furthermore,
this reaction forms the principal source of free radicals at
the beginning of liquid-phase oxidation. This applies parti-
cularly to substances with easily separable C-H bonds
(aldehydeov 1,4-diene hydrocarbons, and 1,3-diphenyl alkanes).
There are 2 tables and 9 references, 4 of which are Soviet.
Institut khimicheekoy fiziki Akademii nauk SSSR (Institute of
Chemical Physios of the Academy of Sciences, USSR)
October 9, 1959, by V.N. Kondratlyev, Academician
October 2, 1959
ASSOCIATION:
PRESENTED:
SUBMITTED:
Card 2/2

S/020/60/132/03/29/066
B011/B008
"~13.200
Danisov, Is, _wiKharitonov, V. V.
AWHORS:
TITLE:- Oxidation of Cyolohexanol by Ozonized Oxygen
PERIODICAL- Doklady Akademii nauk SSSRp 1960, Vol. 132, No. 3,
pp. 595-597
TEXT: The authors oxidized 25-30 ml cyclohexanol by means of bubbling
with oxygen which contained 0-3�0-03% ozone, at a volume rate of
6-7�0-7 1/h At 50-1000C. Cyclohexanone, H202, adipinic acid and several
eaters develop by oxidation. The aggregation kinetics of the cyclo-
hexanone and the H202 is at first linear, at a considerable intensity
of the oxidation (^.,10%) the ooncentrations of the ketcneand H202 pass
a maximum. Data concerning the composition of the products after an
oxidation lasting 2 hours are mentioned in Table 1. Compared with the
thermal oxiaatiori at f20001 the products of the ozo;Lized oxidation
contain large amounts of acids and esters (10-20% instead of 1-2%). It
follows from Table 1 that oiygon does not participate in the oxidation
Card 1/4

Oxidation of Cyclohexanol by Ozonized 9/02 60/132/03/29/066
Oxyllen B01 1 Y3008
at 1500C, but undoubtedly at higher temperatures. The authors presumed
that all 3 oxygen atoms from the absorbed ozone are absorbed into the
oxidation products. The authore further used hydroquinone as an
inhibitor in order to'check the chain mechanism of the reaction. It
follows from Fig. I that it chain mechanism is hare aotu&lly present.
The problem whether the eiitire.cyclohexanol or only part of it ie
oxidized in this way, rOMILined unsolved. The authors found the answer
thereto in their previous paper on the thermal oxidation of the cyclo-
hexanol. Accordinglyq the inclusion of the oxygen into the oxidation
and the slowing down of the reaction by the inhibitor indicates that
the reaction mechanism is chain-like. The assumption, however, that
the reaction takes its course only chain-likeg contradicts the data
of the thermal oxidation of the cyolohexanol. There remains the only
assumption that 2 oxidation mechanisms are present here: a chain
mechanism with a rate vV and a non chain-like with a rate v03' v03
eqiuils the entering rate of the 03 into the reaction vessela vj~:*vo 3
at lower temperatures, vV increases with the temperature rise
Card 2/4

Oxidation of Cyclohexanol by Ozonized S/02 60/132/03/29/066
Oxygen B011YB008
(Table 2). From the energies of activation the authors come to the
conclusion that the inititition of the chaino'by'the decomposition of
the ozone into 0 and 02 does not play any signifimat role. The authors
determined that the concentration of the oyclohexanone decreases at the
introduction of the inhibitor eA 1000C. This indicates a non chain-like
reaction mechanism of the ozone with cycl.ohexanone (at the thermal
oxidation cyclohexanone is only consumed on the chain way). A special
experiment showed that the ozonized 02 10ads at 800C and with an
inhibitor to a non chain-like oxidation of the cyclohexanone. Acids are
developed thereby (the inhibiior does not hamper tl~e reaction). A
z
p~ssi&e scheme on the basis of the reaction of the ozone with the enol
form of the ketone is mentioned. The authors conclude from the data that
ozone reacts 20 times more quickly with oyclohexanone than with cyclo-
hexanol. The authors thank V. G. Voronkov for his assistance with the
experiments. N. M. Emanuell is mentioned, There are 1 figure, 2 tables,
and 3 Soviet references.
ASSOCIATION: Institut khimicheEikoy fiziki Akademii nauk SSSR
(Institute of Chemical Physics of the Academy of Sciences
Card 3/4 USSRT-

.0
Oxidation of Cyolohexano:L by Ozonized S/02 6o/132/03/29/066
Oxygen BOJIYB008
PRESENTED: January 28,, 1960l by V. N. Kondratlyev, Academician
SUBMITTED. January 22, 1960
Card 4/4

23588
S/062/61/000/005/003/009
B118/B208
AUTBORs Denisov, Ye. T.
TITIE~- The probability of self-inhibition of complicated chain
reactions
PERIODICALa Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no. 5, 196% 796 - 803
TEX91s A eelf-inhibition of complicated chain reactions, as in the oxida-
tion of hydrocarbons, is a frequent phenomenon. It was studied for the
firEA time by N. M. Emanvel I (Ref . 1 ~ St "Voprosy khimicheskoy kinetiki,
kataliza i reaktsionnoy spcsobnoatill (Problems of chemical Kinetics,
Catalysis and Reactivity) Izd. MISSSR, M, 1955~ P 11'7)- One of the causes
of the self-inh-Lbition of' this reaction may be the change of the composi-
tion of the radicals during the reaction. The present paper deals with
the probability of a self-inhibition of complicated chain reactions due to
a change of the composition of the radicals. It is confirmed that this
probability is very high, The composition of the radicals in a compli-
cated chain reaction changes because the reBilting intermediates react
with the free radicals and give rise to the formation of radicals of
Card I/A

The probability of...
23588
S/062/61/000/005/003/009
B118/B208
another type. The complicated oomposition of the radicals occurring dur-
ing the reaction affects the reaction rate.. The author derives a formula
expressing the change of the rate of consumption of the initial product as
a result of the change of the radical composition! F -2a,,n'/VD nt.
i t-fli
a., eciuals k /k wherE- k, denotes the constantaf the reaction rate of
i0 Go, lo
the 1-th radicali n9 ~. n /ni n. - concentration of the i-th radical;
i t . :1
n - total concentration (if the free radicals; k,'/ko. With a very
high probability the complication of the radical composition during the
reaction causes a self-inhibition of the complicated chain reaction, These
calculations explain the cases of splf-jnhibit~on of oxidations and crack
reaction, which frequently OCCUr in experiments. and indicate the change
of the radical composition to be a fundamental cause of this fact. Apart
from the immediate effec-~ on the rate of the chain reactiongthe radical
composition may also exeTt an indirect effect on this rate, i. e., by the
concentration of the dmtarmediate warranting the anomalous branching of
the chains. This problem was discussed in the author's paper (Ref. 10s
Izv, AN-SSSR,,- Otd. kh:Lm. n. 1959~ 2100), where it is confirmed that the
Card 2/3

The probability of'..
1
235
S/062 61/000/005/003/009
B')18/B208
reduction of the function F which shows the ohange of the reaction rate
only as a result of the changel radical composition, usually reduces the
kinetic equilibrium concentration of the intermediate and, in addition,
the reaction rate, The effect of the composition of the radicals on the
intermediate conoentration increases the probability of a self-inhibition
of the anomalously branched chain reactions, contrary to the unbranched
chain reactions. There are 5 figures and 10 Soviet-bloc references.
ASSOCIATIONs Institut kh.imicheskoy fizik! Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences ITSSR)
SUBMITTEDt April. 2, 1r-60
Card 3/3

8/076/61/035/002/014/015
B107/B220
AUTHORS: Denisov, Ye. T. and Kharitonov, V. V. (Moscow)
TITLE: Oxidation mechanism of cyclohexanol in liquid phase
PERIODICAL: Zhurnal fizicheskoy khimii, v. 35, no. 2, 1961, 444-451
TEXT: The aim of the study is to clear up the oxidation mechanism of aecond-
ary alcohols; the oxidation of pure cyclohexanol at 110, 120,and 1300C and at
atmospheric pressure has been chosen as an example. 6 1 of oxygen per hr
'ts
were passed through a layer of 70 ml cyclohexanbl. The reaction produc. V
were mainly peroxides (H 0 and oxyalkyl hydroperoxide), cyclohexanone, wate4
and at the beginning of ihie reaction, also higher eaters and acids. The
peroxides were determined iodometrically, and the ketones with the help of
hydroxylaminel the acids were titrated against phenolphthalein; the es'.'ers
were determined by saponifaction with alcoholic soda lye. Moreover, tile
peroxides were determined again potentiometrically. The curve for the in-
crease of cyclohexanone (Fig. 1) shows that the reaction proceeds Luto.-
catalyticallyl the curve for peroxide (Fig. 2) indicates that peroxide is
an intermediate product of the reaction. a-naphthol was added as inhibitor
Card 1/6

S/07 6/61 /03 5/002/014/015
Oxidation mechanism of ... B107/B220
to study the kinetics of reaction. The curves for cyclohexanol (Fig. 3)
show that the reaction proceeds according to the chain mechanism only; this
is different with peroxide: It can be seen from Fig. 4 that it is decom-
posed during oxidation without free radicals being involved. Furthermore,
the rate of chain initiation was investigated (Fig. 5): At 1201C it in-
creases from 0.27-1c)-7 mole/1-sec to 10- mole/1-sec. The oxidation of
cyclohexanol is, thits, a degenerate branching chain reaction; its auto-
catalysis is caused by the formation of peroxide and further chain-initiatbg
products (Pig. 5). At 12000 the rate constant for the decomposition of the
peroxide into free radicals is 1-34-10-6 sec-1. The chain length is re-
duced frum 1000 at 'the beginning of the reaction to about 100 (Fig. 6). Me
activation energy of the chain lengthening amountsto 7.7 kcal 'mole. The
relative reactivity of cyclohexanol (k1) and cyclohexanone (k 2) with per-
oxide radicals amounts to k2 /kl,; 2.1-2 between 120 and 1300C. The oxida-
tion mechanism of cyclohexanol shown in the two schemes
Card 2/6

, I : ~
I f I
.. i; "

8/076 61/035/002/014/015
Oxidation mechanism of B107/M
There are 6 figures, 4 talDles, and 8 references: 6 Soviet-bloc. The refer-.
ences to English language publicati6ne read as follows: Patent Brit.
J'08339 5-V-1954 (according to Chemical Abstracts 48, 11017, 1954); N. Brown,
..Amer. Chem. Soc., 77, 1765, 1955.
ASSOCIATION: Akademiya nauk SSSR sInstitut klimicheskoy fiziki (Academy of
Sciences USSR, Institute of Chemical Physics)
SUBMITTED: June 26, 15159
Legend to Fig. 1: Kinetic curves showing the increasing content in'cyolo-
hexanone for the oxidation of oyolbhexanol (1) at 1100C, (2) at, 12i)00
(3) at
130OC- (x) t in hr, (y)cin moles/1.!
Legend to Fig. 2: Kinetics showing the-increasing content(in peroxide for
the oxidation of cyclohexanol (1) at 11000, (2) at 1200 1 3) at"1300C.
(x) t in hr, (y) c in moles/l.
Legend to Fig.-3: Kinetics ok ketone formation with a-naphthol as inhibitor
at 1200C. The arrows inclicate thf Ii instant at which the inhibitor was added.
(x) t in hr, (y) c irrmles/lo.
Card 4/6

S10761611035100210141015
Oxidation mechanism of ...
Legend to Fig. 4! Kinetics of pero'jcide formation in ordinary -eest. (2)
and (3)..with a-naphthol as inhibitor. (x) t in hr, ~y) c in moks/l.
C. 1,10flSIA
;2
QS
2 4 6 8 /V 09C r
U-90/0
F. IG vac
CY
114 - 42
OL
s 1 10 t. WC 2 vac
Card 5/6

DENISOV, Ye *T. Woskva)
Various~m&Lels of degenerated branching chain reactions with
one intermodiate. Zhur.fizkhim. 35 no.9.1906-1974 161. (MITRA 14:10)
1. Akademi.ya nauk SSS.R, Inotitut khimicheskoy fiziki.
(Chemical roaction, Rate of)
(Radicals (Chemistry))

AUTHOR. Denisov, Ye. T.
30032
S/O:? 6,1/141/001/017/02,
B I 40.YB -1 () I
TITLE- Chain formation mechanism during cyclohexanol oxidation
.PERIODICAL: Akademiya nauk SSSR, Doklady, v, 141, no. 1, 1961, 131 -134
rEXT% It was experimentally found that the formation of free radicals
Juring C6H11OH oxidation in liquid phase was not RH 4 02- R'-~ HO; (1)
as had been assumed but RH + 02 + R11 -42R* + H202 (2). The experiments
were conducted in a qua.rtz vessel with reflux condenser, The vessel was
heated and filled with 20 ml of C6H11 OH containing an a-naphthol
(10-3 _ 1.5-10-4 moles/i.iter) solution. The veS S E! I was heated for anotlier
5 min, and then an 02 flow of 0.2 ml/sec was let in, a-naphthol was used
as inhibitoT: InH + RO,', ---.* Ih + ROOH, IA + RO'---.~InOOR. Thus. its rate
d. 2
of consumption corresponded to the formation rate of free radicals:
Wo = 2(-dE InHj/dt). Samples were taken during the urocess, and their
Card 1/

3 0" "1 - 2
S/02C/61/141/031/017/021
Chain formation mechanism during ... B140/B!01
a-naohthol content was stud:Led: Parasulfophenyl diazonium sulfate in
methyl alcohol containing !-)w amounts of alcoholic alkali was added to
the sample, The dye thus forming -gas determined colorimetrichlly using
a green fiLter. The accuracy of inhibitor concentration determination
was + O~7 Ifo. At 1210C, the inhibitor only reaoted with 1'ree radic,-Lls.
During the first 100 min, the rate of inhibitor consumption was constant;
then, it increased as the peroxide content increased, From the in-
clination of the kinetic curve for a-naphthol consumption., the forination
rate of free radicals was calculated to be 8,3*10"'9 moles/li+er *aec,
(A) The author studied the dependence of W 0 on the 0, concentrat:on at
f
7710C, an a-naphthol concentration of 2 1 -4
~5. 0 mojes/liter~ and at a
pressure of I atm. The partial pressure of 0 2 was changed by adding
nitrogen. A linear increase of W was observed: W W aP (Fig~-")-
0 02"
Without o_-4ygen. W0;1, 0 ,Hence, the formation, of free radicals vas az~smad
Lo be due to the relc.ction of impurities withcut. 02 participation The
use of a pyrex glas~i ve9sel did not. change the forma-.-_-on rate of frer-
Card 210 Ulk

.3 0 G;2
S/020/6-1/141/00 I A 17/021
Chain formation mechanism during Bi .40/B101
radicals. (B) The depenience of W on the C H OH concentration was
6 11 _'4
studied at 1-910C and an a-naphthol concentration of 1 5110 moles/liter,
When dissolving C 6Hill OH in chloro bEtnzene., reduction of the C 6 F11,0H con-
centration caused a decrease of W . With pure C,11.-Cl. "1 0. The curve
02 0 02 r
shows that Wt -[RHIand W I [RHI ' with W being the for.,,rii-iori rate. of fhe
0 0 0
radicals during the reaction of C 6H11 OH with 0 2' For [",HI between 9.6
02/a log [RHI 0 1) =
and 5~8 moles/liter log W o 2, 3 0 ~ 2 1 Vio k LRHI 'P 02
A log W02 = n A Iog [IIHI i. 4log P Hence,
02 2"
4 log W 0 6109 P02 &log P02
n = P was 393 mm Hg in
0 IIRT - 2.3 - -Z-1-0-6-TR- HI, 0
0 RHT - -6-1-6-T
50 ~a mixture of C 6H,JOH and C 6 H501 at 120C'C,, Hence,
log P / ~a log LRHI= M5/0.30 = 0.5; n = 2,,3 0.5 = 1,8 0 3. i. e
0 2
Card 3/6t-11

3093,;
S/o20//0"1/'-4!/0D!/017/02'
Chain formation mechanism during ... 3140/3101
n practically equals 2., Hence, Eq. (2) proved to be correct. PC, Was
12
630 mm Hg at 1110C, 1 atm, an 02 concentration of 1.9-10 molesiliter,
and a C6H.1i OH concentration of 9.6 moles/li.tor., Hence. the coni3tant of
2 1?
the reaction rate: k = 0.7-10, liter /inale For reat:tion Eq (2)
an activation energy of 12 kcal/mole was obta.ined by studies in varicius
temperatuxe ranges. The real activation ene--gy is somewhat higher due
02 concentration reduction in the liquid phuee caused by a te-mperature
elevation.. a pressurEt increase of C HJ-1OH, and a P0_ reduction, At
!300C. the real activation energy is 16-kcal/'M~~le, and
k = 8,3*exo(-16000,/RT)liter2/mole2-sec.. There are 2 fiF;ures, 1 table,
and 4 references: 3 Soviet and 1 ncyn-Soviet~ The veference tc, the
English-language publication reads as follows: C- E- Boozer. G S~
Hammond, C. E. Hamil-~on, J, N. Sen, J Am- Chem So-~- 7?
ASSOCIATION: Tnstitut khimicheskoy fizik-i A-adE!Ml3. nauk SSSR (Instlllute
of Chemical Physics of the Academy of Sciences USSP)
Card 4/0A