SCIENTIFIC ABSTRACT Y.T. DENISOV - YU.M. DENISOV

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• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000310120020-2
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: November 2, 2016
• Document Release Date: June 12, 2000
• Sequence Number: 20
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

PHASE I BOO,'K EXPLOITATION SOV/6319
Berezin, '111ya, Vasillyevich, je~yg!pT,~j_ TiMDfeyevich Denisov, and
NikolaiY Markovich Emanuell
Okisleniyo taiklogel:sana (Oxidation of Cyclohexane) (Moscow]
.Izd-vo Mosk. univ., 1962. 301 P. Errata slip inserted. 3500
copies printed.
Ed.; N. A. Korobtsova; Tech. Ed.: T. A. Kozlova.
PURPOSE: This book is intended for chemists and chemical engineers
engaged in the industrial oxidation of cyclobexane.
COVERAGE: The book discusses current theory and technology of
cyclohexane oxidation. Although the text is based primarily on
non-Soviet materials, the discuss~ion of.kinetics Is taken entirely
from N. N. Semenov's theory of degenerate-branched chain reactions.
The oxidation of cyclohexane is presented in the broadest range,
e.g., from elementary reactions to the technological procass.
References are given at the end of each chapter.
Card 1/4

DENISOV, Ye.T.,; KHARITONOV, V.V.
Kinetics of hydrogen peroxido consumption in the oxidation of
cyclohexanol. Neftekhimiia 2 no.5:7150-765 S-0 162. (MIU 16:1)
1. Institut khimicheskoy fiziki AN SSSR.
(Cyclohexmol) (Oxidation) (Hydrogen peroxide),
I

DENISOVP Ye.T. (Mosccw)
Mod'Is of degenerate chain-branching reactions with several
intermediate products. Zhur. fiz..khim. 36 no.11:2352-
2361 N162, (MIRA 17:!i)
1. Institut khimicheskoy fiziki AN SSSR.

W570
e., S/020/62/'146/002/012/013
B101/B144
AUTHOR: Denisov, Ye. T.
TITLE: Formati~on of free radicals on interaction of hydroperoxide
and cyclohexanone
PERIODICJ~iL: 'Akadeaiya nauk SSSR.* Doklady, v. 146, no. 2, 1962, 394-307
TEXT: The author and V. V. Kharitonov found that o3rclohexanone and if 2 02
obtained by the oxidation of cyclahexanol, combine reversibly to form a
hydroxy cyclohexyl hydroperoxide, disintegrating into free radicala more
rapidly than 11202. Tort-butyl hydroperoxido and cyolohexanone in ohloro-
benzene vere examined to fini out whether such a chain branching aluo
occurs when hydroperoxides react.with ketones. The consumption of
a-naphthyl-,amine (inhibitor) was measured to determine the formation rate
of fre.e radicals. Results: Hydroperoxide C 6H10" OOR which decomposes into
OH
free radicals more rapidly than tert-butyl bydroperoxide, is formed even
Card 1/3

S/020/62/146/002/012/013
Formation of free radicals ... B101/B144
in the presence of inhibitors. At an inhibitor concentration, of'
1.10-4 to 20-10-4 moles/l, the inhibitor consumption does not depend on
the concentration. The formation rate of free radicals is a linear
function of the hydroperoxide concentration LROOH]. The following data
were obtained at 12 0C:
Ketone [InHI . 10" 1rROOH] Wi-10 8 )c 106 sec- J!
ill,. bv volume mole,s/l i moles/1-seo
10 2-5 10-050 5 1.00
15 2.63 10:050 13-7 2.74
.20 3.26 0 042 20.8 4.95
26.o 6.05
170 4.41 10. 043
1100 11-5 0 047 30-5 6-50
100 21.7 10:108 67.0 6.20
k1 k k-
It is inferred that. ROQH --:. RO *+OH ; _ROOH 4- ke t one -!"X; X i rc
(k + k ~! ketone3 )/(I + K !,ketone] ).
radicalsi k i U 1 2 Xetone peroxile
formed with the liberation of,approximately 11 kcal/Mole; its dcl,~ :;-~,n
Card 2/3

S/020/62/146/002/012/01~;'
Formation'; of free radicals... B101/B144
energy of decomposition is 26 kcal/mole. The reaction tonstants were':
k 1.8-10 12 exp(-330OO/RT)Sec:_1i k2 'i.a.lo9exp(-26000/RT)sec-1;,
K 6.~-io-7exp(11000./RT) 1/mole. The simultaneous addition of ketone
and hydroperoxide initiates the oxidation more intensively than their
SE~parate addition. There are 4 figures and 2 tables.
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the.Academy of Sciences USSR)
PRESENTED: April 4, 1962, by V. N.-KondratlyeO, Academician-
.SUBMITTED: March 30, 1962
Card 3/3

ACCESSION NR: AT4olo620 S/3051/6:1/000/000/0420/0427
AUTHOR: Emanuel I, No Me;; Denisov, Y*o To
TITLE: Stimulation and Vnhibition of the reaction of liquid-phase oxidation In
the light of the chal.-i theory
SOURCE: Katallticheskiye reaktsil v'. zhidkoy faze. Trudy* Vsesoyuznoy konferentsil.
Alma-Ata, 1963., 420-427
TOPIC TAGS: oxidation stimulation, oxidation Inhibition, liquid phase oxidation,
oxidation, chain theory, branched chain, free radical, chain reaction
ABSTRACT: The article discusses the Semenov theory (1q. N. Semenov, Tsepny~rye
reaktsii, L. Goskhimizdat, 1934) of chain reactions with a degenerated, branched
chain. The latest concept of these chain reactions includes the fol)owinc
.1 main
points: 1) The formation of free radicals in an oxidation reaction is primarily
due to the stimulation caused by hydroperoxides, although acids and ketones such as
cyclohexanone may also play a role. 2) The formation of free radicals may also
involve nonperoxide substances, as in the oxidation of methylethylketone which
yields diacetyl; diacetyl rapidily decomposes to free: radicals. 3) The lcm, initial
rate of hydrocarbon oxidation iTwiy be increased by adding initiators such as pero-
xides, azo-compounds, a.nd salts of. metals with variable valences. Salts of metals
Carcl 1/2

F
ACCESSION NR: AT4010620
however, may also act as inhibitors, as exemplified by KMn04 in the oxidation of
n-decane. This inhibition suggests the existence of a Mn2+ critical concentration,
which reverses the stimulation. 4) The oxidation of paraffin to fatty acids can
be initiated by ~ -radiation frcxn a cobalt source. 5) Heterogeneous catalysts
such as metallic oxides act as !itimuli in reactions of liquid-phase oxidation, as
exemplified by a Mn02 catalyst In the oxidation of Isobutylene. The article con-
tinues with a discussion of the critical factors in an inhibited reaction. The
inhibitor concentration that effects a break in the chain and the use of inhibitors
in studies of complex chain-nonchain reactions yielding free radicals are also
mentioned. Orig. art. has: 40 chemical formulas and 4 figures.
ASSOCIATION: Institut khimicheskoy fiziki AN SSSR (Institure of Chemical Physics
AN SSSR)
SUBMITTED: OC,
SUB CODE: GC'1 'GP
DATE ACQ: 25Jan64
NO REF SOV: 015
ENCL: 00
OTHER: 001

L 12733-6,,1 3 'M
PF(c)A~T( )IBDS Pr-4 iLm/Wint
ACCESSION NR; AP300=2 S/0062/63/OCO/006/0980/0991
AUTHOR: Denisov, Ye. T.
TITLE;, Tb~;e mathematical modibls of complex chain reacticAf oxidation
SOURCE: AN SSSR. Izvestiyiri: Otdeleniye khi micheskikh nau%, u0. 6, 1963, 980-M
TOPIC TAGIS. complex chain dl~generate-branched reactions
ABSTRAM, The author studi0s, theoretical models of complex chain degenerate-
branched zeactions followed 'j)y transformations of four Intermediate products into
each other, occurring with tie.participation of various sorts of free radicals.1
The influence of separate fai6tors (activation of vidicals, their c-o-n-sia-R-of re-\
combination) on th~ rate and~accumulation of intenaediate products in the complex
chain process is also establ~Lshed. "I express my deep gratitude to the mathemati-
cian V. T. Gontkovskoy for t1te progimmming and solution of systems of differential
equatfoi-ns. g. ai . hasv', 11 tables and 16 figures.
ASSOCIATION- Inatitut khimioheskoy fiziki Akademil. nauk SSSR (Institute of Chemi-
cal Physics, Academy of Sciences, SSSR)
Card
...............

DE2?ISOV,, YowT.; DENISOVA, L.N.
Meohaniom underlying degenerated chain hra~ching in cyclohexanone
during Its oxidation. Izv. AN SSSR Ser.-khim. no.lDsl731-1737 0
163. (HIRA 17:3)
1. Inatitut khimicheskoy fiziki AN SSSR.

DENISOV, Ye..T.
Decomposition of initiators into radicals studied by the method
of inhibitors. Izv. AN SSSR. Ser. khim. no.11:2.037..2039 N 163.
(KRA 17:1)
1. Institut khimicheakoy fiziki AN SSSR.

DENISOV, Ye.T.; KHARITONOV, T.V.
Special features of the inhibiting action of -naphtbyl-
immine in cyclohexanol oxidation. Izv. AN SSSR, Ser. khim.
:ao.12:2222-2225 D 163. (MIRA 17:1)
1. Institut khimicheskoy fizild AN SSSR.

NA-
_ZBii~ _~P' A
L 1-4513-6)
j~__ 60/0366
CCESSIOM NR: Ap3bo2776- S/0204/63/003/003/03
AUTHOR: Denisov, Y4. T.; Sq1yanikov*, V. M.,
A
"TITLE : The study W~ the kinetics of oxidation \of ~vopropyl al-c o
oh I
SOURCE:, Neftekhimi
;~a, vs 3,.noo 3, 196~~ 360-366
TOPIC TAG.): alcohol., alpha4naphthol,,hydrogen peroxide, oxidation kinetic
isopropyl alcohol o3:idation,~
ABSTRACT:~ This vork. is dedle
ated to the study of the chaim mechanism of the
oxidation of isoprol7l alc6kiol. The quantitative characteristics of isopropyl.
alcohol oxidation ir., the foxm of elemental constants and ac'ivatuion ertergy
have been obtained. ~ The iscipropyl alcohol was cixidized in a glass reactor
with oxyg(m from the air at a temperature of 86 to 2380 and a pressure of 10
-lv-o 15,4M.. Peroxide of tert.-butyl,was added to initiate-the reaction.
The rate cof oxidation was measured by the speed of H sub 2, 0 sub 2 accirmLatim.
The experiments were, also conducted using other types of initiators. The rate
of'decompcisition of the initiator Jnto radicals was measured by the irLibitor
method with alphs,-naphthol* ':.During t.he reaction, the inhibitor was ccins=ned
at a constant rate which ind icates the constant fo=ation of free radir.,alls in
-Card. 1/2

L13513-63
ACCESSION.NR.- JLP3002776
~the courbe of the re46tion: as! a- result of the inLtiator. From the kinetic.
curves, the connumptibn of irkbitor of al-am-naphthol and the accuumulELtion
of hydrogen permide durimg the oy-Wation of isoproinyl alcohol at a corstant,
of rate of reaction of the peroxide radical uith the inhibitor and isopropyl
alcohol hat beeii fomd,. TheActivation energy of the first reaction is
4400 cal/nole. Orig.. art. ha'b: 4 tables, and 4 figvres.
ASSOCIATICN: Listitut khindcheskoy tiziki AN SSSR (Institute of Chendeal
Physic a,! lezz.~:, df Sciences 4LBR)
SUBMITTED; 29&~-p62 DATE--A 2,2Ju'-' 63 ENCL: 00
GQ.
SUB CODE: '00 NO.REP SOV: 004 OTHER: COS
Card 2/2

L1548o-63 LM'(J)/FjPM)/M(m)/BPS PcT4,/Pr_4 PIV, WW
ACCESSION NR t AP3005452 SI(Y,? 64/~;3/003/004/05 5 E V05 64
AUTHORSt k)enisov, 7
! -Kharitonov, V. V..
4
TITLE: KLnetie equilibrim of the concentration of the intermediate
products during o~,Idation reaction of cyclohexanol
SOURCEt Reftekhimi7a, V-3, no. 4, 1963, 558-564
TOPIC TAGSt cyclohexanol~loxidation, cyclohexanol, hydro,5,en
peroxide,cyc~lohexanone kinatic equilibrium
ABSTRACTi, Authors attempt!ed to finq the imeentration limits of
i hydrogen peroxide and cyc3~ohexanonel~n the oxidation of cyollo-
hexanol. -Authors di* 6v-eFecl that malxim~m concentrations of HsOq
and cyclohexanone depend upon-the initial addition of these
products to the reaction. Kinetic equilibrium of hydrogen per-
oxide ooncentration in thet oxidizing cyclohexanol under the above
conditioni .t was 2-7 moles/31ter at 120C. An analogous experiment
was made with an initial addition of cyclohexanone. Results show
that about 20% af thea added cyclohexanone is oxidized by a c1hain
Card

;L,i548o_63
AccEssioN ~VR t AP3009452
reaction and that tho resli it! oxidizedby H90g. Thus, it was
shown that the oxidation p~rodvcts of cyclohexanone accelerate the
decomposition of hydrogen peroxide during the oxidation of cyclo-
hexanol. It was establislifipd that the h1gher the addition of cyclo-
hexanone at the begi,.3nIng:.of the reaction, the higher is the kinetic!
equilibrium' of the cycloho~xanone In the oxidized'eyelohexanol.
Orig. art. hasi 6 figures, 1 table and 5 formulasi.
ASSOCIATIONi linstitut khIm'icheskoy fiz1ki AN SSSR (Institute of
olmemical physics, AN SSSR.).
SIUBMITTEDi 21S,ep62 DATE ACQ:, 06Sep63 ENC'L t 00
SUB CODE: CH NO REP ScrVI OOT OTHER: 000
2A
Card

9070SO
AUTHOR i Vehisc y4i.
an o
IrXTLZ: The f corriia f fi-ee in the system RH + 02~
Tel..rali#, eye,lohexanol,' cyclohexanonis
PERIODXCAL.t linitika i ','.kata4x v. 4A, ~'no, 11; 1963, 53-59
out.'iA view' of, insuffi-cient knowledge
-TEXT i The trark iias - ci~rriisd~:'
chahi#m+ 4 1)f k ili~Ltlati .on. in tbe -system.
of the me chi in The author
considered 'that the mojoA lixoly chain initiation process in a
trimolecular, reacti
2RH. + 0 "L4 210~ + H'O - UV)
2 ~2 2.
The experimental (let& iOere a:lialysed to-dimicover, whether they fit
Anto Eq. (IV) The Iiijuid b~rdrocarbona weire oxidlzed in a quartz
~reactor through which 112 wadil-Apaissed-at thet ratc of 0.2 ml/sec..
The formation of Irree i~.A.dicdls van follow4id by measuring changes
in, -the conceatratlon o:r a-n4phthol (oxidation lnbil4tor) . For
tetralin the chain ini-iiatic'6i -was studie~d an a function of thei
concentration of, dissolved (i.es its pairtiial pressure) at 3.410C,
the concentration. of co-naphthol beirg 2'x 10-3 mole/litre. Free
shout the ~~Ipartic4~tion of O:a at !the rate of
radicali forimed yll
-Card -1/3

S/195/65/004/001/oWoog
Thel; -formation of free..;',,, 9075/943,6
-6 x 10-9 mole/litrib see., . (acti,vation 4p.nergy = 48 kca.1/mole) ancl
-a 180 by the reoption of' tetralin witl~ 02 at thei rate,of
18 x 10 9 mole/ S'C (acl~ nergy AA + 2,,kcal/mole).
tivation'.0
The veloc'i eqnatant for reaic, tion IY at 1300C, wa;
2.1.8 x 10-8 2 Is
42/0p~e sect. ab olute velocity constant was
K = 3.5 x lo3 exp(_20j~!O/RT):.t2/mole2 sec. The ac,t~vation energy
for- reaction 1twas 201: /mole Thin experimental value
I � 2'keal 0
is in good agre4ment with th(p: calculated one. Ford: -Yclohexanol
the rate of free radical forinlation at) 1110C inoreased linearly with
the partial pre~peure,:J;'.02 from- 2 x. 10-9 at pj) = O~O mm Hg
The chains were-init 1, d viik 'the reaction of (.,~ciohexanol with 02
arid also direct1y from cyc.Xo10exanol Vithout O~. The free radicals
~_,~Were formed by ~,6actiori IV with thet activation energy of 16 + 2, kcal/
- The,absiolute velocitk-constant for renation IV was
8 3: o exp(--1fiOOO/M~'-).-- for cyclohexanone -the inhibitor waim
-2 .10-0. mole/litre sec at 1200C ands
.consumed at the., rate oC
4 X 10-8 mole/1-itre Bei.- at-IWC. In this case the formation of
free radicals also pronieeded:.according to reaction IV with the
activation of+ 1.70 4.kcal/mole and the absolute vplbcity cowstant
Card 2/3
it

DENISOVS Ye~T#
Kinetics of consumption of an inhibitor introduced at the start
of oxidation reaction. Kin. i kat. .4 no.4:508-516 JI-Ag 163.
(MIFLA 16:U)
1. Institut khimicheskoy fiziki AN SSSR.

1. 18304-63 EWP(j)/EPF(c)/EWT(m)/BDS Pc-4/Pr-4 RWWWIJWIJFW
AQCESSION M AP3004989 S/0076/0/037/6osA896/i899
MUM ReAsovj~.7e~.,
TIMM Formation of free radicals by the rea:otion of hydroperoxides with ketonee
S(XRCE1 Zhurnal fiz- khimii, v-, 37, no. 8, 1963, 1896-1899
TOPIC TAGSt free radical formWtionp tertiary butyl hydroperoxide-eyelohox!Lnone,
cumyl hydroperoxide-cyolohexanojieg ourWl hydroperoxide-methyl ethyl ketone,
free radical
ABSrRA r Pros radical formation was investigated in tertiary butyl hydroperox-
ide4cyclohexanonelo I 4ydroperoxide-oyclohexanonot and cumyl hydroperoxide-
met IVI-eW laystems by the method of inhibiting consumption of Alp].-ia-
naphthylamineo. Hydioperoxide alde reverkbly to ketones with the formatia.'l of
peroxides which rapidly decompose to free radicals. With cyclohexanone, tl-.ie.
greater its concentrations the greater the amount of peroxide and the faster the
free radical formation, Two aotive7 forms of peroxide are formed with methylethy!
ketone. Acetic acid accelerates the reversible addition of hydroperoxide to
ketone. Rates were calculated for the reactions studied. Orig, ae~. hass 4
figures, I tables 4 equations and 2 formulas.
Card 1A

-L 7226.52-6L5" E P _'k P -4 MAW:
C r
ACCESSION. NR: ATM~D=l ~$4/000)!000/1)201/0204
S100001
N V
AUTHORe Denisov, Y'b.
TITLE: T he rAechaWlSira of pxjdAtion to cy6lohexanone
t "inte2; I svoystva moncrmerov
SOURCE AN SSSR. Kn titut n4Bkfiiinicheiskogo sin cza. IS
(The synthesis and properties ofmonomers). M-o`scoW_,Sd-vo Nauka, 1,9664, 2OV-204
TOPIC TAGS- cyclcb~e~ol oxUation, -:,cyclobOxanone synl6sic, hydrogen permade
pmduction
Pl T: Tlie kilq6tws of OX~6tion.of cyclobexanol In 02 have been studied tD estabUsh
ASSTJU
0cmaitions for i2le MWAMUM coni~entration andyield of cyc.11oliennone and hydrogen per-
oxide, Cyclohexamlwas oxidlz~d in a laboralbry reactor at 110-130 C,With oxyjgdn or in
ark inert atmosphere vrith.hydrogt~en peroxide. The.chain roacUan was shown to involve
100-1000 steps with li~ydrogea p6roxide participat-Ing in chitin branching. Hydrogen per-
OxWe is exanol anil by heterogeneous devomposi-
- con mi-ned dwUg the mild.Work of cycloh
ti Dn ,Cy f0hex6mol i$; oxidlied l6y'hydrogen peroxide and by freie peroxide radiv4s, and
Its 6etice equilibriumi concimtration increases if a ketone, is dided to the cyclobexanol
foed. lbe Idnetic, eqtkillbrium concentration of hydrogen peroxide goes through a maximum
Card

NO REF SOV: 001
OTHER: 000

ya.,j,. ; I'll! 14 V. I
14 " " ,., i~.k$ 1 .
:ymergatic, mffect of alcohcols ~n ~.tie InhibitIvin I-ourr of a-c.7r.8,tjc
.I I I
amines. n,~,- 5~9ii-921 l-V fi~jU J.'7,6)'
~. Instit-at. khiwinhesk,~;.y 'N " ")'! ~,'
i -

InH
iffl R0014 R n
0
eact ~.naphfthol and 4K -naph_
~6th iD~13 j~jjitjjo~~
contaihin cohols' kqtor4ps. and hydroixilroxides
f 1b)
action o cyc Iexai, i6l and,c. clohexanone~ on the
:.y
an -of-n-bi4tand . cycloheiii .knonei and cui~nyl
Abi i~it~ei~-naphthylamine~*as quanttati,~ejy
.1 1
f
,,,d 0 the ~)Te ~A~O-H. formed beiiween
ol (butahol) hinders r'up'ture of the hydrogen
t 'US lower's its r6actfvlty..''~ :Similar redu;rtion in
blUtanolwilSrndt6d.rrT)iel'D~ver*eilinhib )ractivi--,
1,.explalned~rt]Ud W the IcIrMaHon:cpf an ami,ne-hydro-
~ydiojen.--bon~~. i~aly.' ~* 2 1 fie JeCj
rhe e. . ct of the die
examitie&,_. inerreasjj~6g .: ulc6hol content from 0- 10%
itok activily,was 16,Wer3d three times. Thus
)n.inhibit6t'b'vithRO24INAfi,i,kttrib,utedlarigely to tie
I the pxygen-ent4"11-compounds and the inhibi-1--
777-7

Z`324~Z
S105( WOW PC-
I -J
P RPL J JFWIM
Accurssion im: J05002 F27 ~',/,Dlg$/64/CO5/006/ooBi/ogOS.,
D
aniistw, Yei T tiD'Oj-VsNij IMOW& YOt No.
L i V,
s by interan-bion of I.V&ogen i~eroxid Ith
':TITIX: Formati(in of free r, 0 Wl
cyclLohmanono
A
:'I 1J, SOURCE., Kineti ta i 'kataiis v8 n6l'~ 6'~..:Lqfi' 9m-.988
TUN T'kGS 3 hy&rogen peroxidei freavadiva,, oxidatiOn reduction reaction,
I aafor concentration., inuLl#aiitm cowtutp
One -Eu
ABSIMACT: The iilole ct eydlo"Ibiail was Stu ed in tha: formation of free radicals
by oxidation,q1t -i~s E;hv#m that.cyclohexanane, unLtes with hydro'gen
!~i -76 tc~ f ont .a ) I I ;
-m I .,I ormddo Wilch As quickly i
freo!radicalsv This Man.$ bf 0~ -nmphthylardne inhibitrmq.
Finit) the rate'of fies radil~al ~~'-armptioh ftcm the, t ertiary-bubyl peroxide as aan
'Latiat-tvas d0ormir.- -at ivariow.uIrp attires) anO'sibsoqueWy it was ~~hown
or.
tha-rate-o!r a-Ar,
that A), C-Ofisuvti6b~vU., ahd consequent"lly
;j La ~~_C roei Chan _ 3,
th~ dyclohemand yelohexanom Tho-intbraction of the amme
vith hydrogen varoxUle, was v~ufto tw4j. 3A.Imth oxygeh wA, in argon atmoupheras,
,card

-.. . ''I ; I , , .. I 1~ -. :., 1-1 . -- , " -% : . , . I -.-. . ~ 7 , F : .~ -- t : ~o . , 1 1. . . ] -, I . - . , . , I

'24 6
Ii 251, 5
:'AGGJZSION,IlRf AJ~500279 7.
ASMIAT ION Xn6tAut', WAmi &o-t3k' p:y ~-fiidkll Ali M.,(Institube ~Df ChOMiO &I RW6109
,
:-4fi scso .

SM
DCODE
Go

m REIF WV i

cord

ACC4ESSION NR: AP4011434 S/0076/64/038/00:L/0003/0015
AUMOR: Denisov, Ye. T.
TITLE: Elementary reactions or rorming free radicals in liquid
phase oxidation
SOURCE: Zhumal fiz. khim, V. 38, no. 1, 1964: 3-15
TOPIC TAGS: free radical, free radical formation, liquid phase
oxidation, free radical mechanism, monomoleoular reaction, bimole-
cular reaction, trimolecularreaction, chain rormation, carbon-car-
bon bond rupture, oxygen-oxygen bond rupture, kinetics, activation
energy, bond strength, reaction rate., carbon-hydrogen bond rupture
A BSTRACT: This article relates to analysis of' free radical forma-
'6
tion during l';quid phase oxidatolon, study of metchanisms proposed for
various types of free radical reactions and evaluation of the kine-
tics, reaction rate constants, bond strengths, activation eneraAes,
including extensive data from the literature. The t.,Fpes of reac-
tions discussed include: monomoleoular reactions Including rupture
Card :L/2

ACOESSION IM: AP4011434
of the C-C bond, or of the 0-0 bond in the case of by4roperoxLde
decompositions, or reaction of hydroperoxide with ketones; bijuole-
cular reactions such as reactions of hydroperoxides with hydrocar-
bons, decomposition of byd:voperoxides by rupture of the 0-0 and the
ROO-H bond with formation of H-OH, zmd chain forning reactions; tri-
molecular reactions of chain formation (generation of-two alk7l
radicals) as in liquid pbase chlorination or reaction with hydrogen
peroxide. Orig. art. has: .4 figures, 4 tables and 20 equations.
ASSOCIATION: Akademiya n&uk 53SH, Institut khimicheskoy fiziki
(Academy of Sciences SSSRI Institute of Chemical Physics)
SMKITTED: 02Apr63 DATE ACQ: 14Feb64 ENCL-0 00
SUB CODE: CH.. PR NO REP SOV: 019 OTM: 017
Cord 2/2

ACMSSION NR: AP4019528 S/00;'6/64/038/002/0491/0494
AUTHOR: Denisov, Ye Tq_#1eksandrov, A. L.
TITLE:' Determination of relative reaction rates of peroxide radicals with
inhibitors
SOURCE: Zhurnal fixichesikoy khlniio vo 38, no. 2, 1964, 491-494
TOPIC TAGS: inhibitor peroxide reaction, alpha naphthol, betha naphthol, alpha'
napbthylamine, beta'naphthylamines cyclohexanev cyclohexanone
ABSTRACT: Having reviewed different methods for determining the mechanism of
inhibitor action in oxidation reactions, the authors propose two new methods of
determining the relative constants of reaction rates of peroxide radicals with
inhibitors. Complex mathemati-cal formulas are derived, curves are plotted,
tables set up and concluvions imade a's follows. The proposed methods are based
on the consumption rate of the inhibitor introduced in a very low co'neent-ration.
According to these methmls, the relative constants of reaction rates of peroxide
radicals with o( and 6-xiaphtoL and a~ and naphthylanitim inhibitors f or
oxidation of cyclohexans and cyclobexano- dve- been detersinede Orige airt,
Card 1/2

ACCESSION NR: JiF4019523
has: 3 figures,, 14 fonulasp I itables.
Assocr~Tzom ThstLtut klWeLehielgoy flzLkL AN USI (lutitute of Chud"I
Physics, AN SS31t)
SU 34VM t 28vjir63 OM AO~: 3lMr64 RML: 00
SUB CODE: 6C ID M SOV 8. 003 OrM 002
2/2
Card-

1-6

;REF SPV.-.,005 OTHER: 003

COESSION NR ~AP404
350
lea blinolecular Te'
action between
dical-formation mi~eeds i~
P,
hydToperomide-sud st3n~ejae imill jby themuch slover _mbnomolsciilar de-
I compryaltion of the: hp~roperoAde;.radloals, according to the ra"Ce
equation:
k, JR001 +kj JR00H)
At 900, 6 x ID d .-5.9 x 10-7 Vmolei.eec. By convaring
8jan
.the radl%cl f ormat'lott rate bi Up.presence of styrene and In the
n- i~~ne ,IVI s determined that the increasvd rate
~Ves6nce. of ethylb~ Z. ed
ist due ond in styrene.
-the probmblt~ liiterv~titlon with the doublLe ~
t' ialcu3ated to 'be 17.2 - 0 5 kcal/mole
mepnorgy of activa %on wa s
for:_a, sufficiently lw~ge con ontratim of styreno (729~ mole/11 ter)
leal'
speari e"t Nere aleo calctlated for several oteps iii tha rad
Xormation mechanism, smd it vr-m lound that the more energetically
favorable reaction is;:
RO ko
OH + P! ~H MM-1 RO' + 06H CHCH,)GH 4. 15*2 al/mole:
g , 162 A 0
a 8 Opposed to the rewt n pr posed by 0. W211inij and. 1. W. (",hang
(J. An~ Ohem 300. 761~ 1918- (054)):
RWH + 0 'R OR CH
'x6.9 kcal/
ROO* + 1)6llr-CH()H3
6~;
nole. Orig. art. hilL;: 3 figur and equation13

PENISOY, Ye.T.; DEIVIISOVA, L~N.
Mechanism of cyclohexanone oxIdation. Izv. All SSSR,, Ser,. khim.
no.6:1108-1110 Je 164. (MIRA 17:11)
1. Institut khimichesko,y fiziki AN SSSR.

DENISOV, _YjZ.; SOLYANIKOV, IT.M.
I
Mechanism of the UquAd-phave oxidation of isopropyl alcohol.
Neftekhimia 4 no.3:451~-465 Ybr-Je 164.
(MIRA 18:2)
1. Institut khImicheskoy fiziki AN SSSR.

- ALEKSANDROV, A.L~; HU-'EREDIII, V.P.
DENISOV. Ye.T.;
.1
Effect of hydrogen bonds or, the activity cf ox-*.diitJc)n inhibitors.
Izv.AN SSSR.Ser.khim. no.9:1583-1590 S '64. (MIRA 17:10)
1. Institut khimicheskoy fiziki AN S-'-,9R.

i- -2tri tr-,nd'Lng in on
k'.-.i-ir ohe,
j ic 9 Irl

DENISOV, TooT.; XMRITONOV, V.V.
Fomation of free radicals from hydrogen peroride in oyolo-
heranol. -Ein. i kat. 5 no,5081-786 S-0 164, (MIM 171,12)
1. Institut khimioheakoy fimiki AN SSSR.

DEENISOV, Ye.T.; KHARITONOV V.V.; JUSPOPOVA, Ye.N.
Formation of frae radicals in the reaction of hydrogen peroxide
with cyclohexanone. Kin.i kat. 5 no.6:981-988 N-D 164. (MI-RA 18.3)
1. Institut khiinicheskoy fiziki AN SSSR.

RM_
IL 1654-66 DJTNVEUW/gk,~~(D
iACCESSION NR: AP50214:20 UR/01)76/65/039/008/1965/3.969
V 541.124/.128
tp
WJTHOR: Privalova, L. G.; MAYZus, Z. K. Denisov, Ye. T.
! , _1
!TITLE: Effect of the t)xidat ion products of n-decane on :radical activity in the
;chain propagation reaction
SOURCE: Zhurnal fizicheskoy khimii, v. 39, no. 8, 1965, 1965-1969
ain
decane oxtdation, fi reaction rate, reaction k' ch
.TOPIC TAGS: ree radicall inetics
ion
propagat
ABSTRACT: The purpose1of the study was, to determine the role of one of the int8v~
Mediates (alcohol) in ithe chain propagation reaction involved in the oxidation of n-.
Aecane, Its influence im the:compositicn and activity of the radicals, anEfFe- con-
,'tribution of the formation of tbe alcohol to the change in the overall oxidation
xate of n-decane. To -this eInd,, the value of w/luli'ERNI (where w is the rate of the
~chain process of oxidation of the hydrocaorbon and wi the initiation rate of radi-
cals) was measured in -the course of oxidation of n-decane in experiments involving
1
ithe addition of the alt,.ohol (5-nonanol) and compared ifith the corresponding values
Card

L 165h-66
!ACCESSION NR: AP5021420
~obtain during oxidation of n-decane without the addition of the products. Addition
of the alcohol was found to decrease considerably the activity of the radicals ' prop-j
wagating the oxidation rhains. The radicals formed by :he reaction of R02. with the
t
~alCDhol are 5.2 -times less active than the RO radicals,, The reaction of RG-2. withl,
a 2-
i i
'the alcohol may be rep:reeented as follows.,
it 7 OR
C ROO11 +
\bH
0-0.
OH,:
17hus, the R02, radicalls s0stituted for the radical., In the latter, an
O-W-:
whic
~intraradical hydrogen may be formed h lowers the activity of this

L 1654-66
IACCESSION NR.- -- AP'5021420
1radical. Differences in the nature of thel dependence of w I'YZ D113 on ROOH obtained
4rom the ex erimental datit and calculated by allowing for the effect of the alcohol
p
indicate that the effect Of the oxidation products of n-decane is not limited to the!
;inhibiting influence of the alcohol, and that on the cc.ntral-j, other products pres-
lent in the reaction mixture have an accelerating effect on the oxidation procp-ss.
',The overall effect of all the oxidation products causes first an, increase, then a
:decrease in the activity of the radicals. Orig. art. bas: 3 figures and 9 formulas,
1ASSOCIATIONt Institut khlmicheskoy fiziki, Akademiya nauk. SSSR (Institute of Chemin
:gal Ph cs Acad4,,-m Sciences SSSR)
':SUBMITTED: 29Jun64 ENCL: 00 $UB CODE: GC
NO REF SOV: 012 OTHER: 000
Card 3/1 i

ANTONOVSKII*,
,,J,,; KUZNETSOV, I.A.; MEKHRYUSHEV, Yu.Ya.;
SOLNTSE".. L.V.
Mechanism of the liquid-phase oxidation of cumene studied by the
inhibition method. Part 1: Chain initiation. Kin. i kat. 6 no.4:
607-610 J1-Ag 165. (MIRA 18:9)
1. Novok-uybyshevki-y filial liauchno-issleflovatellskogo instituta
sintetichealikh spirtov i organicheskikh produktoy.

DENISOVA, L.N.; DFNIS(-AT, Ye-T.
Fonnation of rad3cels during the reaction of oxygen with the
double bond of sytrene. Izv. AN SSSR. Ser. kh--'m. rto.9;11102-
1704, 165. (MLR-A 18: 9)
1. Nnstitut Ithimiclieskoy ftziki AN SSSR.

4-y
~1,1;
EWMEL I, Nihr,::,P-7 Markovich, _LEN
Zpp. __TiuAWey vichi
1"mvis, Zinaida Kusbelevria. Prinimall uch&!3iAei
ANTOOVSKIY, V.L.,- IILYUMBERG~ B.A.; VASILt"1,70 R.F.j,
GAGARINAO A.B.- GOLIDBERG, V.M.; Zpapov, G.Ye.; DORIXOV,
v 31
Yu.D.; OBUKROVA, LA.; TSEPALOV, V.P.;, SHU!J,PINTOKH,
V.Ya,~ SKIBIDAy I.P., red,
[Oxidation chain reeictiorw of hydrocrrbons In the liquid
phase] TSaprve reaktsii okislonallp- uglevodarodov v
zhidlioi faze. Moakma., flauka, 1965.. 374 P.. (MIRA 180)

ANTONOVSK3Y9 V.Lo; DENISOV, YejT.1 SOLNTSEVA, L*V.
Inhibition method in etudying the wohanism of liquid-phave
oxidition of armcanal, Part 2a Mechaniam of dagenerittAk chain
branohingq lin,i keo;,-6 no.",:815419 S.-O 1,55,, (NIRA 18811)
1. Hauabno-iseledonktallskiy institut. sintetichaskilch spirtov
i organiehookikh produktov, NovokuytVshevskly filial.

L 387?0-66 aa T (m) (J) MAW
AdC NR. 6024022 SOURCE CODE: uR/0062,166/ooo/oo6/1O95/1097
AUTHOR: Denisova, L. N,i,~enisov, Ye. T.; Deglgrareva, T. G.
-~3
ORG: Institute of Chemical Physics, Academy of' Sciences SSSR (Iiistitut'.
khimic skoy fiziki AkademiT nauk SSSR)
TITLE: -Free ra,dicallfoirmation by the reaction of oxygen with styrene
and cobalt
SOURCE: AN SSS-R. Izv. Ser khim, no. 6. 1966, 1095-1097
TOPIC TAGS: oxidation, catalysis, free radical, reaction mechanism,
oxidation kinetics, cobalt
ABSTRACT: The mechanism of catalysiAby metals able to assume several
valences, of liquid-phai3e oxidation reactions has been studied. The
formation of free radicals by a reaction between styrene, oxygen, and
Co(II) was established. The reaction was carried out with Co(II) as
the atearate or the acetylacetonate in organic-oolvent solution at
115C in the presence of an inhibitor (a-naphthylamine). The reaction
kinetics were studied and a reaction mechanism was proposed. The
rate of formation of free radicals was determined from the rate of
consumption of the inhibitor, on the assumption that two free radicals
consecutively react with one inhibitor molecule. The reaction mechani
C.,
42-97+547.024+541.124

L-3879o-66
ACC NR1 AP6024022
proposed involves the reversIble formation of a 1-,AARIM; between oxygen
and Co(II) and the subsequent, reaction of this complex with styrene to
form the free radicals:
Coll IC
+ Oj;: Cq... Ol
W
CO.. -.0s +CHo =CHR - GO-00-ClIj-CftR
Orig. art. has: 4 figures. (SMI
SUB CODE: q,4. 21/ SUBM DATE: 22Nov65/ ORIG REF: 002/
OTH REF; 002

AW NR, AP6034616 SOURCE CODES UR/0062/66/000/010/1737/1743
AUTHORI Alekiandrovp. A. Ls;, D9nimgrj-)Uk.-T&--,
ORGs Institute ot Chemical ftelcog Acadeny of Sciencasp SSSR (Institut khimiohookoy
fimiki, - Akademii nauk SSSR)
TITLES Elementazjr'rote constants of radical reactions in exclohexanol undergoing
oid.dation
SOURCES AN SSSR. Isvestlya. Seriya khisicheakayag no. 10p 19669 1737-1743
TOPIC TAGS: cyclohexanoig reaction rate, wcidation kinetict;q free radical
ABSTRACTS The chain wddation of an alcohol RH (cycloheocancil was studied) can be
represented as follows (I being the initiator)
I - free radical W*
R + M
Ri?R%H + R
RO~oo (2)
R0z4+ R%* -mol. products (6)
The aim of the study was to.detemLne the absolute rate constants of reactions (2)
and (6). The values obtained for those constants made it possible to analyze these
elementary reactions in greater detaUs To wcplain the effoot of the medium on the
~J. A

oxidation of cyclahexanolp the rato'constants of (2) and (6) were measured in mix-
tures of cyclohexanol and chlardbenzeneo The ratio of the constants kd~~k 1948
found by measuring the rate of Initiated oxidation and the initiation rate math ofj
inhibitors), and the method of photochemical aftereffoot was used to measurethe
ratio k2/k6t whencte k2 and k6 were daterodnede Orig. art. hast 3 figurem and 4
SUB CM91 07/ BUM DAT91 1()Xmy6~( aM RM 009/ OrK Wo 009

ACC NRI AP7007076
SOURCE CODEs UR/0048/66/030/010/X577/1580
AUTHORi- Dentsov, Ye. V.; Dedenko, L. G.; Dubrovina, S. A.; Kotallnikov, It. A.;
0. F.; Sokolovskiy, V. V; Slavatinskiy, S. A.;
Fetisov, 1. N.
ORG: Physics Institute im. P. P. Lebedev, AN SSSR (Fizich-askiy institut
AN SSSR)
TITLE: Nuclear cascade process In an Ionization calorimeter &-aper
presented at the All-Union Conference on Cosmic radiation physics, ~bscov,
15-20 Nov 196V
SOURCE: AN SSSR..Izvestiya. Serlya fizicheskaya, v. 30, no. 10, 1966,
1577-1580
TOPIC TAGS: pi meson, calartmet(Dr, proton
SUB CODE: 20
ABSTRACT: Results of the calculation of the nuclear cascade process in an Iron
absorber were correlated with experimental data obtained an the Ionization ca-
lorimeter of the Tyant-Shan' Cosmic Ray Station. It was established that at
ED - 300 Bev approximately 307. of the energy spent being carried away by
Ionizing particleo ("black tracks") j and the rest by protons with an
energy of - 150 Mev (11grey tracks"). Errors in the measurement of ED - 200
Bev associated with fluctuations In the recording of strongly Ionizing parti-
cles amounted to -_* 12% ( -- 11% for "black tracks" and - 4% for "grey
tracks"). In measurements by means of an Ionization calorimeter of the energy
transmitted to TrO mesons, Ionization prq~duced by particles originating from
nuclear splitting must be considered. The authors thank N.~ At Dobrotin and V, So
Marzin for valuable '~~jj_tjeal' observations, V. G. Ignattyevaya, Z. G. Yereminaya,

NR, AP7007076
L. Vo Shibayeva, and No So YWchurkinaya for processing the i erimental
Ya
data* Orig. art. has: 2 figures, 2 formulas and 1 table. IJPRSt 39,618]

20451
B/056/61/040/002/00,1/047
/0, )PkeI3 B113/B214
A'UT HORS s Zatsepin, V. I., Nikollokiy. S. I.,
Pomanakiy. A. A., Subboting B. V., Tukish,. Ye. I.,
Yakovlev, 11. 1.
TITLEs Observation of nuclear-active particle a and electron-photon
avalanches with energies greater than 101"! ev at a height of
3860 m above sea level
PERIODICALs Zhurnal eksperimentallnoy i teoreticheskoy fizikip v. 40,
no. 2, 19619 419-425
TEXTe The nuolear-aoti-re and eleatron-photon component of high-energy
cosmic radiation were studied to obtain additional datEL on the nature of
nuclear interaction at energies >0 1013 ev. The observations were made in
1959 on the Pamir. The detector consisted of four rows of ionization
chambers between which were placed lead and carbon and over which were
10 hodoscope groups oon-taining 12 counters (330 cm ~ each). Besides, two
cylindrical chambers were plaoed at a distance of 7 m from the middle of
this setup, a hodoscopio point and detector of the energy density of the
Card 1/3

20451
B/056/61/040/002/004/04.7
Observation of nuolear-aotive... B113/B214
electron-photon oomporient were at a distance, of 18 m from the cei,.iter
and served to stacly the fluctuations of the particle flux. If the axis
of the extensive atMOElpheric shower hits the recording area of the
detector, the number of particles in the shower may be determined from the
formula N - 1000 Q'2w here Q is the effectivo particle density of the
particle flux per m . Assuming that in every event, nucleons and pions
impart 1/3 of their energy to the new resulting pions, the energy of the
nuclear-active partio3les was found to be given by E - 2.3-10 6N1.04ev which
holds for the range '10 11 ev,