SCIENTIFIC ABSTRACT MAYZUS, Z.K. - MAYZUS, Z.K.

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• Collection: Scientific Abstracts
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• Document Creation Date: November 2, 2016
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• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

Oxidation of Wdrocarbons in the (Cont. )
r3OV/3663
Khorre, D.G.0 L.G. Chuchukinap and N.M. Emanuel' (Institute of Cbemical
Physics]. WF11 Function of Metal Stearates in the Hydrocarbon Oxidation
Reaction 145
7he dual role of copper and manganese stearates as both catalysts and
inhibitors of oxidation of iso- and n-decanes is described. The
authors determine the critical concentration of cupric stearate
( - 0.03% per mole) above which the induction period for n-de
oxidation increases.
Hkvzus Z.K., L.G. Privalova, and N.M. Mani, 11 (Institute of Chemical
in the Wchanism of n-Decane Oxidation in the Course
of the Pleaction 14 152
The authors have used C tagged n-deeane to Investigate changes
in the rates of formtion and consunytion of n-decyl hydropero3ddes
during the oxidation of n-decan . The hypothesis that variations in
the activities of radicals carrying on chain reactions are proportional
to the accumulation of oxygen-containing oxidation products in the
reacting mixture is offered as a possible explanation of the
phenomenon.
card 8/X

5W
AUTHORS: Babayeva, A. A.,
M ~is SOV/62 -6/42
M~ 1 -59-8
__
--
Emanuel', N. M.
TITLE: Oxidation Kinetics of Isobutane in the Presence of
Hydrogen Brftldt
PERIODICAL: Izvestiya Kkademii nauk SSSR. Otdoleniye khimicheskikh nauk,
1959, Nr 8, pp 1378-1385 (USSR)
ABSTRACT: In the present paper the investigation of the catalytic
oxidation -)f hydrocarbons is continued and the oxidation
kinetics of ramified hydrocarbons (in this case isobutane in
the presence of HBr) is investigated by means of NBr. This
reaction is very sensitive to the surface condition of the
reaction vessels. Thus molybdene-glass vessels covered with
a layer of boron oxides were used. The oxidation was carried
out an a vacuum unit under static conditions. A figure shows
the unit used. The way in which the reaction products were
removed from the vessels is described. The peroxides obtained
in the reaction were identified polarographically (peroxides
of tertiary butyl, tertiary butyl alcohol, and acetone). Very
definite stages were observed in the reaction process. In the
Card 1/2 first stage isobutane is mainly oxidized so that it forms the

Oxidation Kinetics of Isobutane in the Presence of SOV/62-59-8-6/42
Hydrogen Bromide
hydroperoxide of tertiary butyl; in the second stage the
oxygen consumption drops and the reaction takes place via
the formation of the hydroperoxide of butyl alcohol and the
decomposition of the peroxide while acetone is formed. These
facto were obtained by means of the determination of the
yields under varying reaction conditions (changes in the
concentration of initial materials) (Figs 3,4). The summary
reaction process is represented by the following equations:
i-C4 H10 +02---r~ (CH3)3 COOH? (CH 3)3 COOH + (CH 3Ya__~' (CH 3) 3COH +
+ (CH 3)2CO + CH4* There are 5 figures, 4 tables, and 14 ref-
erences, 9 of which 4re Soviet.
ASSOCIATION: Inotitut khimicheskoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences, USSR)
Moskovskiy gosudarstvennyy universitet im. M. V. Lomonosova
(Moscow state University imeni M. V. Lomonosov)
SUBMITTED: December 27, 1957
Card 2/2

BABKTSVA, A.A.; M&TZUS, Z.K.; EM&IRM'. N.M.
Changes in the chemistry of the oxidation of isabutane in the
presence of HBr as affected by additions of reaction and
products. Dokl.A.N Azerb.SSR 15 no.11:1009-1013 '59.
(MM 13: 4)
1. Kafedra kbimicbeekoy kinatiki Moskovskogo goeudiiretvonnogo
universiteta im3ni Lomonoaova I Institut khimichoskoy fiziki
AN SSSR. Predatavleno akademikom AN Azerbaydzhanskoy SSR M.F.
Nagiyevym.
(Propane) (Oxidation)

5W
AUTHORS: Knorre, D, SGV/76 - 33- 1-- 36/45
Markin, jj' T~
. , Em a ntre 1 N ~ M.
TITLE-. The Kinetics of the Valence Changes of Manganese Stearate an
the Course of the Initial Macroscopic Stage of the Catalyti,~
Oxidat3.on ef n-Decane (Kinetika valentnykh prevrashcheniy
stearata margantsa v khode nachallnoy makroakopicheskoy stadii
katalizirovannogo ok-isleniya n-dekana)
PERIODICAL-, Zhurnal fizicheskoy khimii, 119591, Vol 33, Nr 1, pp 213-218
(USSR)
ABSTRACT: A short t--me ago it was found (Refs 1-3) that on the oxidat-,On
of n-de,^ane (1) several changes take place in the laurates and
stearates of manganese and cobalt, A valence change of the
catalyzer takes place which causes its falling out and be,~ominE
ineffective (Ref 4). In the case under diSCUSSIOn the kinetics
of the accumulation of colored intermediate products of these
catalyzers are investigated. The oxidation of (I) took place in
a way already described,, The samples were examined in the wave
length of 400 m/(( by the spectrophotometer SP-4, It is stated
that the effective activation energy of the accw-iulation of the
Card 1/2 intermediate products of manganese stearate is 8,1 kcal on the

The Kinetics of the Valence Changes of Manganese SOV/76-33-1-36/4,'
Stearate in the Course ,F the Initial Yacroscopic Stage of the Catalytic
Oxidation of n-Decare
ASSOCIATION:
SUBMITTED:
Card 2/2
oxidation of (I), whereas the activation energy of the further
reduction of the intermediate compound is 16.1 kcal. The
absorption coefficients of the intermediate compound were
determined in sumene (since it is simpler than in (T) ) and at
400 m 4, the value 780 1/g-mol cm was found. Beer's (Ber) law
is followed up to a catalyzer concentration of 0,016 mt/Fig 7).
Tests With (I), tetralin, and cumene showed that the absorption
coefficient of the intermediate compound obviously does not
depend too much on the hydrocarbon to be oxidized (Fig 6).The
kinetic of the accumulation of colored intermediate
products show an initial acceleration (Pig 7). At the curve
maximum cumene and tetralin show a complete transition of
manganese stearateto alli-her valence stage and (I) a 30~5
transition only. There are 8 figures and 4 Soviet references,
Akademiya nauk SQSSR Institut khimicheskoy fiziki,11oskva
(Academy of S-iences, USSR, Institute of Chemical Physics,
Moscow)
July 17, 19571

H1 S G., :'n~%,z
TITLE: Ki !~ ot i c s of t',e ?onct-nn Pcti-x(,E~r D-`1
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involvirt- or
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t,,~ t1iin 2,- 0. 1 hy t
Ye. Do r v a r, d E- !ii,! "o'.
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of thr,-)t,,:r,-:
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V
Kinetics of the -'eaction Between Decyl Hydroperoxide "76--,
and Yan-anous Ste,rate in n-D-are
12 rof,~re-cer-, )f iwhic,. are ".ovi -t.
ASSOC 1ATION Aka-1. emiya r-iuk I r,:i Ii + i:t khi~nichies~oy f i z i !- i,
(A c ad emy of Scie- c,-s, V-; R, :n!,ti tute of icA
MO P, cow,!
SUPMIT'ED: July 17, V~57
Card 3,'3

5(4')
AUTHORS: Denisov, Ye. T., MayzuB# SOV/20-128-4-33/65
9 17. M.9 corresponding Member, AS USSR
Skibida, I. P. , It= t[#
TITLE: Kinetic Laws for Autocatalytic Reactions in Open Systems
PERIODICAL: Doklady Akademii. nauk SSSR, 1959, Vol 128, Nr 4,
PP 755-758 (USSR)
ABSTRACT: In chemical technology, the continuous process of reactions
is attempted more and more, i.e. of reactions in open systems.
While the kinetics of simple processes had already been in-
vestigated (Refs 2-4), no data are available on autocatalytic
processes. Therefore, the continuous oxidation of cyclo-
hexanone to adipic acid by oxygen at 1300 was studied. The
apparatus 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 value I indicatas the avera,-,e duration of stay of the
v
liquid in the reaction vessel. The content of hydrogen per-
Card 1/3 oxide, adipic acid, and CO 2 in the reaction product is

Kinetic Laws for Autocatalytic Reactions in SOV/20-1213-4-33/65
Open Systems
determined for different v. In the continuous process, a
stationary state appears, i.e. the reaction rate and the
discharge of the end product are in an equilibrium relation
to each other. Figure 1 shows the dependence 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 ig formed
corresponding to v, irrespective of the oxidation degree
attained. While for simple reactions the rate rises mono-
tonously with v, there i-s a different dependence for auto-
catalytic reactions since not only the concentration of the
initial. product but also that of the resulting intermediate
product (hydrogen peroxide) is decisive. Figure 3 shows that
the reaction rate passes a maximum at a certain v; if v keeps
on rising, 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 SOV/20-128-4-33/65
Open Systems
occurs because the reaction products remain in the
reaction zone for a shorter period. There are 3 figures
and 6 references, 3 of which are 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

8560b
S/062160100010061023/02-, ' X
/J 10 0" 2205 B02O/BO6O
AUTHORS: Babayeva, A. A.,,PyZus' Z. K., and Emanuel', N. M.
TITLE: Part Played by the Surface in the Macroscopic Stages of
IsobutanelOxidation Peaction in the Presence of HBr
PERIODICAL; Izvestiya Akademil nauk SSSR. Otdeleniye khimicheskikh nauk
1960, No. 61. pp. 976-980
TEXT: The oxidation mentioned in the title consists of two distinct
macroscopic stages separated in time (oxidation of isobutane with oxygen
on tert. butyl hydroperoxide, and decomposition of hydroperoxide and its
-eaction with the initial hydrocarbon).
The differential-calorimetric
method suggested by A. A. Kovallskiy (Ref. 5) was used for the atudy of
the oxidation kinetics, and furthAr evidence was found for the two-otage
reaction course. and the part played by the surface in the macroscopic
stages of this reaction was defined. The reaction was studied in a static
vacuum system. A Mo-glass reaction vessel was washed out with a boric acid
solution for surface stabilization (Ref. 6). The differential thermocouple
Card 1/4

856OL
Part Played by the Surface in the S/062/60/000/006/023/025/XX
Macroscopic Stages of Isobutane Oxidation B02O/BO6O
Reaction in the Presence of aDr
consisted of a constantan wire and several copper wires entered into
0.44-mm quartz capillaries. The junction for the measurement of temperatur"-
in the central zone was fixed in the central capillary, and the junction
for the measurement of the wall temperature was fixed on the vessel wall,
The heat flow between the temperatuie in the renter of the reaction
mixture and on the vessel wall was measured by a mirror galvanometer with
an accuracy of 2.8.10-9 a/'mm/m. The kinetic curves of the accumulation of
tert, butyl hydroperoxide and the heating curves of the reaction mixture
during the isobutane oxidation in the presence of HBr are shown in Fig.
while the temperature dependence (-,f 'Tmax (heating maximum) is illtistrated
in Fig. 2. The activation energy determined from the inclination of the
straight line is 16.8 kcal/mole, which Is in gocd agreement with the value
of 16.4 kcall/mole found earlier from the kinetic curves of the
accumulation of tert. butyl hydrcperoxide. Tests made by applying a KCI
layer first onto the reaction surface vessel and then onte the surfane
of the central capillary revealed that the heating of the react-ion mixture.
which corresponds to the reaction rate in the hydrrpercyido formation,. is
Card 2/4

8cf6oll
Part Played by the Surface in the S/062/60/000/006/02~/025/'X,;
Macroscopic Stages of Isobutane Oxidation B020//BO60
Reaction in the Presence of HBr
caused by the liberation of heat in the reaction vessel interior and not
on it6 surface, For a proof of the heterogeneity of the second reaction
stagej the reaction vessel was filled with packing material the kinetic
curves of the hydioperoxide aocumulation with packing material in the
vessel (Fig. 3) distinctly showing the different effects of the packing
material upon the first and the second reaction stage, The effect'cf the
packing material is the same at 11~00 and 1700C, The missing effe~-t of *he
packing material upon the kinetics )f -the process in the first stat-,e ~T-oves
the homogeneous character of the ter'. butyl hydroxide formation with a
heterogeneous initiation of the chains. The rate increase in the second
reaction stage with enlaiged vessel surface prcves the heterogeneous
chara,:~ter of this stage. In the oxidation of isobutane in the presence of
HBr there ocTurs partly a decomposition of tert, butyl hydroperoxide under
formation of acetone, and partly its reantion with isobutane to form
tert. butyl alcohol, In the presence of packing materia'- (Fig. 4) the
amount of resulting acetone is increased. and that of tert, butyl alcoh-1
is decreased. There are 4 figures and 6-references; 5 Scviet and ' US,
Card 3/4

85604
Part Played by the Surface Jln the S/'062/'60/000/ 006/1023/'O,",,/'XX
Macroscopic Stages of Isobulane Oxidation B020 B060
Reaction in the Proooncc- of' 11Br
ASSOCIATION.- Institut khimicheskcy fiziki Akademii nauk SSS
0 R (Institute
of Chem"cal Physics of the Academy cf Sciences USSR) I /
SUBMITTED. December 16. !958
Card 4/4

82654
11195 '6 0 'r C, I'3C
AUTHORS: Mayzus, Z,. K~, Skil-Ida, 1. Emanuel', r,,
Yakovleva,_7 I -
. T,
TITLE-. Chain- and Molecular Reactions of T1,,te r-r.( ntu,,3 -.i tlie
Oxidation of n-Decane
PERIODICAL: Kinetika i kataliz, 1960, Vol 1, No.. 1, Tp '----,')2
TZXT: The authors studied the decomposition kinetics of the hy~ilr(--
peroxides of n-decy lin r-decane in the presence of t>(- -n--iphithone a,~tiz,,.
as an inhibitor. Thelatter was added at various stages of the rtjucti~,r.
The constant of hydroperoxide decomposition without chain roL,C11,-,r
calculated from the kinetic curves and was found to equal 1.7 -
- i.,,.io-3 min.-'. It is rear the value of the reaction ruto -_c-~t-!r;~
of the reaction chain branchinL in the, oxidation of n-duoano
=111-lo-3 min.-'). From this the authors concluded that, be!.id s the
decomposition of the hydroperoxidc molecules into radicals without
reaction, there also takes place a molecular decomposition tirdur, the
formation of ketcnes and water. c~L -naphthene was found to rii.-;~c~ not o, 11
Card 1/3 Vr

Chain- and Molecular Reactionn of Intermediates 7
in the Oxidation of n-Decane B015/Bo6o
with the RO* radical but also with RO' radicals developin[- in the
2
hydroperoxide decomposition. The formation of free radicalaiwity, the
chain branching occurs i.n parallel to two reactions: the monomolocul~ir
decomposition of the hydroperoxide ROOH--~>-RO + OH and the reactioT~ of
the hydroperoxide with the hydrocarbon ROOE + RH-->RO + H 20. The ~i--Ahorc
established the effective reaction rate constant of the chain bra.-i-LinE:
reaction in the oxidation of n-decane as the sum of the eqnstants of t,'-.i?
monomolecular decomposition of the hydroperoxide (in chlorobenzene as all.
inert solvent) and of the bimolecular reaction of the hydroperoxide with
n-decane. The re4ction rate constant of the bimolecular tranchini- reaction
rises with the weakenine of the C-H bond in the hydrocarhon in the
following order: decane< isodecare O,Ay -.,0 or 6x R*, chain forination.
k I k 2
Chain lengthening: R* + 0 )RO and RO, + R11 ROOH + R - Cleava,ye:
k 2 2 k k.
ROOH 3a, RO-+ OH .. Chain rupture: RO, Ro,-~Al~and RO2+ InIl- I-.-"ROOH + In'
(In - inhibitor). According to V. M. Andreyev who obtained
[InHl,,, =2 21hkswg 2alk, + !t U.
I//" kv(ka +T) + ki (k#+ vv
for the critical inhibitor concentration nDd
ki -21RHIks I
k.+u (B)
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Critical phenomena in...
S/020/61/140/00 ~ /0 1 5:'024
B127/B10'.
cr ) for the ratio. The authors determined the ratio k,/k',, for
naphthol as an inhibitor, using the experimentally determined constant,
nHj cr = 9-10-9 mole/ml, and the following constantst v = 0.5hr
RHJ 5.2-10-35mole/mi, 4) 1.8-10-9 mole/ml, It was found that
J
k /k 1.33-10 . The activation energy of the reaction of RO' w2tY.
1 2 ?
n-decane equals 19.1kcal/mole, and that of the reaction of' RO, with
a-naphthol equals 5.4kcal/mole. v is determined by W/V. W is the volume
of the substance entering the reaction vessQ1 per unit time, and V ia thf-
volume of the ronction mixturo. Thure art, ~ FIR1.1ron lind 'I Soviot r,t'i.r
ences.
ASSOCIATIONz institut khimicheskoy fiziki Akademii nauk SSSIR (Institute
of Chemical Physics of thP Academy of Sciences USSR)
SUBMITTED: May 20, 1961
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LIS 00
28674
S/02 61 /140/002/01 9/02_3
B1 30YB1 10
AUTHORS: Zaikov, G. I., Ma~rzus, Z__Z., and Emanuel, N. M., Correspond-
ing Member AS USSR
TITLE: Mechanism of chain ramifications during oxidation of methyl
ethyl ketone in liquid phase
PERIODICAL: Akademiya nauk SSSR. Doklady, v. 140, no. 2, 1961, 405-408
TEXT: The authors found that the degenerate chain ramification during
oxidation of methyl ethyl ketone (I) in liquid phase proceeds through the
decomposition into radicals of two intermediate compounds, keto hydro-
peroxide and diacetyl. (I) was oxidized with atmospheric oxygen in an
autoclave at 50 atm and 100-145'C. The oxidation products (acetic acid,
ethyl acetate, diacetyl, ethanol, peroxides, 00, and C02) were analyzed
chemically or by paper chromatography. From the course of the kinetic
curve for the (I) consumption (Fig. 1) it may be concluded that the oxida-
tion is a reaction of the first order. In fact, a complicated process
takes place, which is suggested by the chain reaction and the anomalously
low factor before the exponential function in the equation for the constant
Card 119-4

28674
S/02 61/140/002/019/023
Mechanism of chain ramifications ... B130YBIIC
1
of the reaction ratep k m 5.2-10 exp(11,200/RT) sec- . The chain
character of the process was proven by addition of a-naphthol (II) as
inhibitor. In the presence of (II), a noticeable induction period occurs,
the duration of which rises with increasing inhibitor concentration. The
rate of formation of chains during oxidation of (1)_gas determined from
the kinetics of inhibitor consumption: cio = 1.5-10 mole/liter-sec at
1450C. During the process, the rate of initiation rises as compared with
% due to the formation of degenerate ramifications. The rate of
initiation during the reaction was determined by measuring the consumption
of inhibitor (II) freshly supplied at different time interv4~s. Fig. 3
shows that the oxidation of (I) proceeds like a chain reaction. The rate
of initiation, however, rises to double its value only. For ~he rateci of
oxidation of (T), it is written down: ej - (k2/V-k5) [RCOR,](,),' /2. An
increase.of the reaction rate 0 to double its value changes the initiation
rate L), 1/2 by the 1.3-fold only, which leads to a linear dependence of the
reaction rate on the concentration of (1), i.e., to a reaction of the first
order. The rate of chain ramification during oxidation of (1) rises in
proportion with the accumulating amount of keto hydroperoxide only at the
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28674
S10201611140100210191023
Mechanium of chain ramifications ... B1301BI10
beginning of the reaction. Later on, a higher total rate of formation of
radicals is observed than corresponds to the decomposition of keto
hydroperoxide into free radicals. This shows thatp besides keto hydro-
peroxide# other intermediates participate in the chain ramification
during oxidation of (1). The assumption of a cooperation of diacet~l
(formed in this reaction and readily decomposable into two radicals was
confirmed by an increasing rate of chain ramification on 'addition of
diacetyl. The dependence of the ramification rate on the total concentra-
tion of keto hydroperoxide and diaoetyl is calculated:
u1j-kjjDj,+ksjPjj=kj IDII+t'[Pll
ki
Here, ol is the rate of initiation at a certain instant of the reactionj
[I)] and [P]. are the concentrations of diacetyl and keto hydroperoxide. On
admixture of an additional amount of diacetyl, Eq6 (1) obtains the form:
tV2=kjjDj2+kqjPJj=k, ID19+~[PI11 (2).
k,
From (1) and (2) we obtain:
01/02 - ~[D]j + ~k 2/ki) LP], [D ]2 + (kA [P] I.- k2A, can easily be
Card 3/6

28674
S10201611140100210191023
Mecha~ of chain ramifications ... B13C/B110
calculated since the other data are experimentally determined. The
1 o-io-5 eec-1 , for k -4 see 1.
re found for k at 14500: 1.4-10
autho 1 2:
There are 4 figures and 14 references. 11 Soviet and 3 non-Soviet. The
three references to English-language publications read as follows: W. D.
F4mons 9 Go Be Lucas 9 j o Am# Chem* Boo. p 77 # 2287 (1955)1 J. So P. Pods We A -
Waterej J6 Chem, Boo., 1956P 7171 We A. Watera, J. Chem. Soc., 1946, 1151-
ASSOCIATIM Instiiut khimicheakoy fiziki Akademii nauk SSSR (Institute
of Chemical.Physics of the Academy of Sciences USSR)
SUBMITTED: May 20, 1961
Figi I.. Kinetic curves for the consumption of methyl ethyl ketone and the
a ou ulation'of reaction products at T -, 14500, pressure a 50 atm, and air
6
velocity a 20 litere/hr. (1) consumption of methyl ethyl ketone, (it) semi-
;!:.'logarithmic ariamorphoais of curve 1, (2) accumulation of acetic acid,
(4) Got J5) ethyl acetate$ (6) diacetyl )(7) keto hydroperoxide
iights-hand scale s'(8)
-ethatiol (right-hand scale
Lege~ds* (a) hr, (b) M014.
V,

S/062/62/000/007/002/013
B117/BI80
AUTHORSs Zaikov, G. Ye., and Mayzus, Z. K.
TITLEi Reasons for the different mechanism of oxidation of organic
substances in gas or liquid phases
PERIODICALt Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no, 7, 1962p 1175 - 1184
TEXT: Methods described in previous papers (E. A. Blyumberg, G. Ye. Zaikov,
and N. M. Emanuel', Dokl- AN SSSR: 159, 99 (1961); Neftekhimiya 1, 235
(1961); E. A. Blyumberg, G. Ye. Zsikoi~ Z. K. Mayzue, and N. M. Emanuel
Dokl. A-N SSSR 133, 144 (196o); Kinetika i kataliz 1, .510 (1960);
G. Ye. Zaikov and Z. K. Mayzus, Kinetika i kataliz (1962); E. A. Blyumberg,
Z. K. Mayzus,..&-.-&d N. M. Emanuel', ob. "Okieleniye uglevodorodov z
zhidkoy faze" ("Oxidation of hydrocarbons in the liquid phase"), Izd.
AN SSSR, M., 1959, P. 125; G. Ye. Zaikov, Zh. analit. khimii 15, 104
(1960); 15, 639 (1960); 17, 117 ~1962)) were used to study the oxidation
of ethyl alcohol and methyl-ethyl ketone with different amounts of benzene.
Experiments with ethyl alcohols 200009 50 atm-9 alcohol s benzene ratio
Card 1/3

S/062/62/000/007/002/013
Reasons for the different mechanism... B117/B180
= 8 s 1, 2 : 1, 1 s 1, 1 1 2, and 1 j 3. Experiments with methyl-ethyl
ketonei 1450C, 50 atm., ketone i benzene ratio w I j 1, 1 j 2, 1 t 3. In
both cases, an increase in benzene, which reduces the dielectric constant
of the medium, was found to alter the composition of reaction products.
With ethyl alcohol, the amount of products obtained from the bimolecular
reaction of peroxide radicals was 20% at I 1 3, and 80% in 'pure alcohol.
With methyl-ethyl ketone, (1 1 3) the reaction products had the same
composition as with oxidation in the gas phase. Differences in the oxida-
tion mechanisms of polar organic compounds in goo and liquid phases are
due to the rate of the reaction between the peroxide radical and the
oxidizing substance (bimolecular reaction), the dielectric constant of
the medium, and the formation of intermolecular hydrogen bonds. The bi-
molecular reaction between RO~ and the test material, is between two
dipoles and slows down as polarity decreases. Good agreement between
experimental and calculated dipole momenta confirms the structure assumed
for the activated complexes in the.case of methyl-ethyl ketone, but not
for ethyl alcohol. This shows that the reaction rate of ROi and ethyl
alcohol is not only dependent on the polarity of the medium but also on
Card 2/3

5/062j62/000/007/002/013
Reasons for the different mechanism... B117/B18O
the formation of intermolecular hydrogen bonds. It is not the individual
molecules (RH and RO~) which react, but aggregates consisting of five or
more particles linked by hydrogen bonds. There are 5 figures and
3 tables.
OSOCIMONs Institut khimicheskoy fiziki Akademii nauk BSBR (institute
of Chemical Physics of the Academy of Sciences USSR)
SUBMITTEDi January 30, 1962
Card 3/3

s/195/62/003/oo6/002/011
E075/E436
AUTHORSs Z,,%ykov, G.Ye., ?~a '__Z'Y_'
I -Y IZU a
TITLE: Oxidatiop of methylethy]~42tone in the liquid and gaseous
phases
PERIODICAL; Kine*tika i kataliz, v.3, no.,6,-1962, 846-854
TEXT: A comparative study of the mechanism of oxidation of
methylethylketone in the liquid and gaseous states was undertaken
to elucidate the effect of polarity and*the al;sence of hydrogen
-the phase oxidation was,
bonding in oxi-dkrpe7d molecule--ri TYpip 41quid
studied :Cor--the first time. Both the~liquid and gaseous
oxidation were carried out at 1450C and 50 atm. The liquid
oxidation Was a complex chain reaction.imttating a first order
reaction. Individual stages of the roactions were studied by
adding a-naphthol at various times durtng the reaction, this
stopped the chain reactions and peemifted to characterize
the non-chain reactions. Diacetyl, ketchydroperoxide and
ethylacetate (intermediate oxidation ptoducts) undergo non-chain
decomposition, the hydroperoxide in this case decomposing much
more rapidly than hydrocarbon hydroper#xides. Diacetyl decomposes
Card 1/3

S/195/62/003/006/002/011
Oxidation of meth ylethylketone ... E075/E436
at a higher rate than that calculated from the consumption of
a-naphthol which indicates that the branching reaction is not the
only decomposition process. Ethylacetate is decomposed by water
forming during the oxidation, acetic acid thus produced being a
part of the total acid formed. The remaindVr of the acid is
formed from the decomposition of diacetyl. Acetic acid is also
formed from ketohydroperoxide via diacetyl. In the gaseous phase
oxidation there is formation of formaldehyde, acetaldehyde,
acetone, formic acid, methyl acetate, methyl alcohol and CO,
whichare not produced in the liquid phase oxidation. Conversely,
the formation of ethylacetate and diacetyl decreases during the
gaseous oxidation. There is little difference however in the
formation of acetic acid. Comparing the rates of formation of
the oxidation products during the two types of oxidation, the
authors conclude that the specificity of the liquid phase oxidation
is due to the polarity of the oxidized subatancq. Comparison
with the oxidation of ethyl alcohol indicates that hydrogen bonds
also affect the mechanism of oxidation* The mechanism of chain
branching in the same for the liquid and gaseous oxidations which
Card 2/3

s/195/62/oovoo6/002/011
Oxidation of methylethylketone ... E075/E436
indicates that the polarity of the oxidized substance affects all
the stages of the oxidation process. There are 6 figures and
2 tables.
ASSOCIATION: Inst,itut khimiche6koy fiziki AN SSSR
(Institute of Chemical Physics AS USSR)
SUBMITTEDi October, 7, 1961
Card 3/3

S/02 62/143/002/016/022
B1 45YB1 38
AUTHORS: Emanuel N. M. , Corresponding Member AS USSR,
Zn-d Yakovleva, V. N.
TITLI~: :4echanism of chain formation in n-decane oxidation
PEAi0DlIC,',_L: Akademiya nauk SSSR. Doklady, v. 145, no. 2, 1962, "'69
Ti;.~T: The mechanism was experimentally investigated for liquid-phn8e
n-decane to find out whether the reaction concerned is trimolecular
k2 RH + 0 "RI + H 0 + R9 q ) or bimolecular (RH + 02~ R9 + HO'
2 2 2 2 2 - q').
The chair. formation rate W was measured withoL-naphthene as inhibitor,
whose concenlration was measured by spectrophotometry after reaction
with p-nitrobenzodiazonium chloride to form an azo dye at 1500C. The
inhibitor consumption is liaearly time-dependent up to a )0 - 40716o conver-
sion. The rate of inhibitor consumption, W InIl' determinded from the
foregoing, grows with the inhibitor concentration, i. e., the radical
formation rate is so low at the beginning of oxidation as to become
Card 1/3

Mechanism of chain ...
5/020/62/1115/002/016/022
B145/B138
comparable to the rate of inhibitor oxidation by 0 2' The resulting
equation reads: - d rInH /dt = W + k,1 7InH~ n10,. W is linearly
0 1 - - L 2: InH
r YIH]2 (n=l.~5 was found from the straight line in the
dependent on [I
coordinates d,[InH_!Vdt, log,InH_.,). WO = 2.6-1o-9 mole/liter-sec was
determined from section cut off by the straight-line on the ordinkte of the
IN 1 -12 -1 2 2,
Inff -InHil diagram, and k i . 1.2-10 liter /mole see from the slope.
'The same value for ki was also found when oxidizing with a 53- 02 + 47'f, N2
mixture. Measurements at different partial pressures of 0 2 and of
n-decane - p-dichloro benzene mixtures of various compositions showed the
chain formation reaction to be of first order with respect to the 0 2
concentration, and of second order with respect to the decane concentration.
Card -2/3

Mechanism of' chain
S/020/62/143/002/01~/022
B145/Bl'16
-1 2 2
k 5.2-10 liter /mole .sec, i. e. a higher value, was established in the
reaction in n-decanc - p-dichloro benzene mixtures, evidently due to the
polarity of the solvent. There are 3 figures and 7 referencesi 6 Soviet
and 1 non-Soviet. The reference to the English-language publication reads
as follows: C. A. 114c Dowell, J. H. Thomas, J. Chem. Phys., j2, 558 (10/49).
ASSCCIA",'IUN: Institut khimichesk-oy fiziki Akademii naak SSSR (Institute
of Chemical Physics of the Academy of Sciences USSR)
SUB_..',!TTED: December 11, 1961
Card 3/3

SKIBIDA,, I.F.; MkYZUSI, Z.K.; EMUMLI, S.M.
Study of kinetic regularities of conplex chain processes aa a
method for determining the rates of formation and consunption
of-intermediate products. DokI.4B SSSR 1" no.1:170-172
VV 162. (MIRA 15:5)
1. Institut khimicheskoy fiziki AN &%R. 2. Chlen-korrespondent
AN SSSR (for Fmanuelf).
(Hydrocarbons) (Chemical reaction,, Rate of) (Oxidation)

C.V, ifz":~
1. Tnsti,,-,t -I.-'

b/062163/ODID/00 03/022

-
iv!'qvw~za
X
_
' tw'
'dibg ts~:~zbli
bet
s"-_l*:ac#*ity'o A e.'radU &'-I" a7 re
'43 lttvraAli6:~:bf ~-tbe':pbrmdd6. radic' witb. C:rease: of Asse
bf-th
I~Mhllimrffi_ls Ox
the bf tlii- &aid fo=ed,- In -the

limtitutlib~~Cbmk fWJd'-Akadmdl:'z'~ii:'s~5m -oziAi"
af_a
cy
z' b Mid%W .56iiiid4: US'
all'bysics of:
15 0

7_Q

P
.

910201631148100610211023
B190/B102
AUTHORS: Skibida, 1. P., Kulitskiy, Z. I., Mayzus, Z. K.
TITLE: Reactivity of isomeric decanols, the intermediates of
n-deoane oxidation
PERIODICAL: Akademiya nauk SSSR. Doklady, v. 148, no. 6, 1963, 1358-1360
TEXT: The reactivity of decanols with hydroperoxides was determined from
their consumption when added to the reaction mixture. The pure initial
product n-deoane was added to the reaction mixture at a certain rate
until a stationary concentration C of the intermediate (alcohol) set in.
1
A mixture c~f decane and 0.205 mole/l of decanol-2 was added at the same
rate, whereupon a higher stationary conoentration C 2 of the intermediate
became established. If, instead of this mixture, mixtures of decanol-4
and subsequently of decanol-5 having the same concentration were added,
then the stationary concentration C remained constant. The hydroperoxide
2
concentration also remained constant during the experiments. Hence it
L -Card 1/2

S/020/63/148/006/021/023
Reactivity of isomeric deoanols, Bigo/BI02
follows that the decanole used exert no effect on the radial concentration
in the system and have the same reactivity. The gross velocity of the
formation of the alcohols in n-decane oxidation was found to be
vgr - 7-4-10 -4 mole/l min.
There is 1 fijzure.
ASSOCIATIOYA: Iniititut khimicheskoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences USSR)
PRESENTED: YLly 28, 1962, by V. N. Xondratyev, Academician
SUBMITTED: July 23, 1962
Vard 2/2

SKIBIDA, I.P.; MAYES, Z.K.; MANUEL', NJL
Activation energy of the chain reactions by which
alcohols are formed and consumed in the oxidption of
no-decane. Dokl, AN SSc;R 149 no.5.-IUI-1114 Ap 163. (MIRA 16:5)
1. Institut khi-icheakoy f'LzW AN SSSR. 2. Chienkorrespondent
AN SSSR (for &mmelc).
(Decans) (Alcohols) (Chemical reaction, Rate of)

ZAIKOVO G.Te.; MANUS, Z.K.
Polarity of the medium as effecting the activation energy of the
chain continuation reaction in the oxidation of ethyl alcohol and
methyl ethyl ketone. DAL AN SSSR 150 no.1:116-119 Yq 163.
(~aRA 16:6)
1. Institut khimicheskoy fiziki AN SSSR. Predstavleno akademikom
N.N.Semenovym.
(Rthy! alcohol) (Butanons) (Oxidaticn) (Activation energy)

L 19o14-63 EPF(c)/EWPQ)/EWT-(=)/BD5 Pr-4/Pc-4 RM/'NW/JW/MAY
ACCESSION NR: AP3007235 S/0020/63/152/001/0110/0113
AUTHOR: Karpukhina, G. V.; Mavzus. Z. K.; Emanuel', N. M.
(Corresponding member, AN SSSR)
TITLE: Interaction of two inhibitoralin hydrocarbon oxidation
SOURCEs AN SSSR. Doklady*, v. 152, no. 1, 1963, 110-113
TOPIC TAGSi antioxidant, oxidation inhibitoro inhibitor, oxida-
tion, hydrocarbon oxidation. hydrocarbon. synergism, synergistic
effect, synergistic inhibitor, Neozone D, 2-naphthylamine. N-phenyl-,
phenol. 2.6-di-tert-butyl-, benzene, ethyl-, isobutyronitrile.
azodi-, Ionol, p-cresol.'2.6-di-tert-butyl-, phenolphthalein.
tetraisopropyl-, diphenylamine, inhibitor consumption, consumption
rate, free radical,hydrazine. tetraphenyl-
ABSTRACT: The consumption rate of two inhibitors (antioxidants)
of the fftenol and aromatic amine type in hydrocarbon oxidation has
been studied to clarify the mechanism of the synergistic effect of
two inhibitoiz 4:,eZ simultaneously. Neozone DI(N-phenyl-2-naphthyl-
a-mine)l and 2.6-di-.tert-butyl h0n^1_N_1_F -were used I-o-W -separately
&--n-a- simultaneously in ethylbenzenetoxidation initiated with
'Card

L 190!1+-63
ACCESSION NRi AP3007235
an
azobieisobutyronitrilel d conducted at 70C. This oxidation
I Kas the advantage of being an "unbrandhad" chain reac-
tion. Changes in inhibitor concentration in the cou::se of oxida-
tion were deterfained spectrophotometrically by formation of an
azo dye from the inhibitor and added diazotized p-nitroaniline.
It was found that a single inhibitor iB spent at a rate equal to
one-half the initiation rate, indicating that one inhibitor mole-
cule reacts with two R02 free radicals. When the two inhibitors
are used together, consumption of Neozone D is slight until prac-
tically all of the phenol I is spent. Neozone D is subsequently
consumed at a rate close to the half-rate. , This amine-consump-
tion inhibition is observed at various ratios and total contents i
of the two inhibitors. The same inhibition was observed with other:
pairs of phenols and amines; e.g.. Neozone D with 2,6-di-tert-
butyl-4-methylphenol (Ionol) or with tetraisopropylphenolphthalein.'
Replacement of Neozone D with another amine, diphenylamine, also
resulted in considerable slowing of amine consumption in the presence
of the phenol. In an attempt to explain this phenomenon, the rate
constants of the reaction between inhibitor and RO free radicals
2
Card 2 /J* _a

ACCESSION NRt AP3007235
were determined by~the chemiluminescence quenching method (0. N.
Karpukhin, V. Ya. Shlyapintokh, N. V. Zolotdva, Izv. AN SSSR, OKhN,
1963, No. 10). It was clearly indicated that inhibition of amine
consumption in the presence of phenols in not caused by the dif-
ference in the vialues of the constants, i.e., in the effectiveness
of the inhibitor. It is assumed that a free radical formed by the
reaction of the amine with R02 radicals abstracts a hydrogen atom
from the phenol,thus restoring the amine. Hence, amine concentra-
tion changes only slightly until all of the phenol is consumed.
This assumption was confirmed experimentally by establishing that
diphenylamine accumulates during ethylbenzene oxidation inhibited
by Ionol and tetraphenylhydrazine. The latter is a source of
(C6H029 radicals which form diphenylaminefon reacting with Ionol
(by ebstracting Rn H atom from this phenol). Oxidation of the
RR,N free radicals does not occur, since the reaction rate with
Ionol is higher than the RiR2A oxidation rate. The results of
the study may also contribute to an understanding of the synergistic
effect of Inhibitor pairs at higher temperatures. Orig. art. has:
4 fl urep and 1 table.
01Y
.Card - 3/6:~

EMANUEL$,, N.M.; DRONOVA, L.M.; KONOVALOVA, N.P.; MAYZUS Z.Y,.-
SKIBMAY I.P. ----l - - p
Antileukemic effect of 2.6-di-tert.-butyl-4-methylphenoI
(ionol). Dokl. AN SSSR 152 no.2:481-484 S 163. (MIRA 16:11)
.9

PRIVALOVA, L.G.; 14AYZUS, Z.K.
1.1-- --l ~ 4-F .,- "
Effect of organic acids on the mechanism of chain branching
during oxidation of decane, Iz,AN SSSR.Ser.khim. no.2:281-286
F 164* (MIRA 17:3)
1. Institut khimichedDy fiziki AN SSSIR,

ACCESSION NR: AP4024407 9/0204/64/004/001/0082/0090
AUTHOR: Skibida, 1. F.; Hayzus, Z. K.; Emanuel" N. Mo
.... ........
TITLE: Reactivity of intermediate materials in hydrocarbon oxidation reActions.
SOURCE: Neftekhimiya, v. 4. no. 1, 1964, 62-90
TOPIC TAGS: hydrocarbon oxidation, reaction rateg hydroperoxide, alcohol, ketone,
Ro sub 2 radical, ethylbenzene oxidation, decane oxidation, kinetics, aceto-
phenone, methylphenylcarbinol, reactivity
ABSTRhCT: The rates of reaction of hydroperoxides, alcohols and ketones with RO
2
radicals in the oxidation of ethylbenzene and n-decane were determined by a method
developed by the authors (Uspekhi khimii 26, 416, 1957) wherein the rates of
formation and consumption of reaction products in an open system may be determined.
The various parallel and consecutive reactions by which the chain oxidation of
hydrocarbons may proceed were investigated and the reaction rates determined:
Card 1/8

ACCESSION UR: AP4024407
0) R If + 0l R + 1101
(Y) 21111 + 01 tv 11 + Iflog+ R
1) R + ot it -10.110,
k. c A,&i-
2) Rol -1- Rif 0. 11001-1 + R)
ka
3) J10011 --* no + OH
T) 110011 + Rif k~" n0+ a -4- HsOl
4) 1100114- RO,
41 Roil + R%*-. CAA,. PRO.& Ir-P
k,-
4-) n,con- + not
kb
5) Rooll - *
k, I
51 Roll 2.
6) llot 4- 1109
Card 2 /8

ACCESSION NR: 4024407
The kinetic curves of ethylbentene consumption And hydroperoxide Accumulation
(fig. 1) and alcohol (methylphenylcarbinol), hydroperoxide and ketone (aceto-
phenone) accumulations (figs. 2 and 3) for reactions run at 118 C were drawn.
Acetophenone is the end product of ethylbenzene oxidation; its rate of consumption
k4"(RO2) : 0 kj : 0, and k 3 - 0.82 x 10-3 mol/l.hr. The reactivity of ethylben-
zene and its ox datio~ products with R02 increases in the,;Wes eihylbenzene
(k 2 : 8.3 x :0-3 hrs- ), alphs-h~droperoxide (k 4 : 7.8 x hrs- ), and methyl-
phenylcarbinoi (k4l = 10.2 x 10- ); the relative reactiviries are 1:9.5:12.
k6 = 7.8 x 10 0 1/mol.hr. IThe rate consta 2ts of the elementa _rf reactions were
determined: k2 : 1.3 x 10 ' k : I .2 x 10 and k W - 1.6 x 10 Ilmol.sec. Th-
reactivity of n-decane, its hyMperoxide and its isomeric alcohols formed by
oxidation at 140 C was determined (fig. 4). The rate of rVactioQ with R02 radi-
cals-ior all the isomers is ~he same. k2(RO2) : 3.8 x 10-4 min L; k4v(ROZ) : 2.6
x 10 ; k4(RO2) = 0.51 x 10- ; hence the rate of reaction of RO increases in the
order n-decene, alcohols, hydroperoxide In the ratio of 1:6.3:3. As with ethyl-
benzene, the reactivity of n-decane with the R02 radical is less than with their
respective hydroperoxideB or alcohols. Unlike ethylbeazene, the reactivity with
the decyl alcohols is two times less than with the hydroperoxide. leading to the
formation of different products, in this case alcoholat
C,-rd 3/8

AG':ESSION NR: AP4024407
R1 H OH R1 If R1 H
\I_ I I-. \J-0.+
C 0-0..
C-OH+R-
R1
Orig. art. has: 21 equations and 6 figures.
ASSOCIATION: Institut khimicheakoy fiziki, AN SSSR (Institute of Chemical
Physics, AN SSSR)
SUEMITTED; 26Jul63 DATE ACQ: 17Apr64 ENCL: 04
SUB COM NO REY SOVI 007 OTHERI 001
Card 4/8

ACCESSIOP NRs.AF4024407
IMIZ, *- ,
fig. 1
ENCLOSURE t 01
Kinetic curves ofthe consumption of hydrocarbon (curve 1, external scale) and
accumulation of hydroperoxide (curve 2, internal scale). Ethylbenzene oxidized in
open system v/V = 0. 102 hr-1. 1180,
Card 5/8

ACCESSION NRi AP4024407 ENCLOSIME 1 0 2.
W - (8)
f ig. 2
Kinetic curves for the accumulation of alcohol (1), hydroperoxide (2) and ketone
(3). Ethylbenzene oxidation in open system with ethylbenzene feed (part a) and feed
of methylphenylcarbinol solution in ethylbenzene, containinf 0. 106 mol/1 alcohol
(part b) and 0. 17 mol. i1. alcohol (part 0. v/V r- 0. 102 hr- , 118c).
Card 6/8

ACCESSION NR: AP4024407 ENCLOSVREi 03
Fig. 3. Kinetic curves for the accumulation
of hydroparoxida, katona and alcohol. oxi-
dation of ethylbenzene in open system with
ethylbenzene feed (curves la, 2a, 3a) and 4a -440
feed of ethylbe'nzene containing 0.055 mol/l.
acetophenone (curves lb, 2b, 3b), 1--hydro- q071 -4j#
peroxide (internal scale); 2--acetophenone;
3--methylphenylcarbinol. v/V : 0.102 hr-l. 4aw -4z#
Card 7/8

ACCESSION NR: AP4024407
Ftg. 4. Stationary concentration of alcoholB
(1) and hydroperoxide (11) in oxidizin n-
decane in open system; v/V 7 2.7 x 10- 1 min'l
0
140 . Section 1--pure n-dacane feed; 2--
mixture of n-decane with decanol-2; in
amount of 0.205 iLol/l.; 3--mixture of n-decane
with the same amount of decanol-4; 4--mixture
of a-decane with decanol-5.
V-1
ENCLOSUREt 04
ard 8/8

ZAIKOVJ1 G. Ye.; RAYZUS~ Z.K.; EMPIMELI., N.M.
Initiation of chains in the liquid-phaBe oxidation of methyl
ethyl ketone and ethyl alcohol. Neftekhiffiiia 4 no,101-95'64
(,'.,IRA 17t6)
1. Institut khimicheskoy fiziki AN SSSR.

- ict b" effk,,~
'In'h bitot-s --in, 6 iddion reac ore has.- ten': at thibi
iol-

T: - -- H ~- - - - 1 1, ; -~ ---, r-. -
: R Ir
- " - +R(h~tAmm.+ - 04a
: , - - f- - -~Il -1 , '. ~ - - -
w -

ANDRONOVY L.M.; EYJNUEL', N.M.
Kinetics of oxidation of aqueous solutions of glycer-oldehyde
by molecular oxygen. Izv. AN SSSR. Ser. khim. no.9-.15,19-
1523 165. (MIRA 18:9)
1. Institut khimicheskoy fAziki AN SSSR.

-~66-
ACCESSION.NR:: APS021420

a:3m during oxidation itbout tbe:*:_add3*Ltio_-n:of the products
bt of: n-~decane-w Addition
6
~JoUthe ~alc6h6l vas, -found' to decrease c6n6idei"Ij-the activity- Of the radicals prop.
e- Oxi
RD with
~th daticin chains. The-radicals-formcid byltha'reaction~of
2-
the
_
alzofi6l'.. are 5't 2times less active.' than -the RO '- radicals -The -rea6tiOik Of R02-
20 Witl

the alcohol e represerite as
may b f0 It*

+ C
H

OH OH)

-radical.- In the latter,
substituted for th
Th u B the R02- rad cal-is' an
.
J~
OL-_
0
form-d- which-16 were the activity of
I intraradical iy"em~ bond ~mayl e thii

Card

Oli

in
~hie f i5i7&t cals
'ue-n-dec-and .4
00. -66 t -dro
b ca 6f hy
Ta_
e:-And- e- a
ecular-reac ion- e dki --hydrdbarb6n. As
tween-lij-dr
operpx1d th
oxidat -ion- -increas egy- t SP41 i t -Mee
anism ecolneu more ~CcjmD e
. he-
-0 -,ac
at. ~-~Of rganic ids lle_rdaction:pioduct~) le-AdS.-to a:marke'd. inw
amone
-1 'It ht,- b ed ~lhwl;':th -
ati~- 6f-- h~droperoxidp,-~ deov --to rallica 3, - on 0 OS
pr p
irmliy clabbioositio-IX-bf. an--intarmediata- o-omp etvidenAvhe )~y~roperpxide:::
0 i3y develotmeht- ot-~,,u~terMAecul:aa~-_ 6& _-.bonds.'~-,~To:tebt;
fhe-- Wthors~~~ed.: the, dependence- of - dooomweiti. -rate on- aoid':
on
this

I

MAYZUS Z.K.; SKIBIDA, I.P.; FMANUELI, N.M.
P
Mechanism of the catalytic decor-posItion of hydropercarides
under the effect of copper stearate. Dokl. AN SSSR 164
no.2:374-377 S 165. (MIRA 18:9)
1. Chlen-korrespondent AN SSSR (for Emanuel').

L h2
-66 7-r,1'r(m)ZmT0),'T 1,11' ( c
It AP6021960 SOURCE CODE: UR/0030/66/000/006/0076/0080~
AUTHOR: Mayzus, Z. K. (Candidate of cherp-ical sciences)
ORG: none
TITLE: Symposium on chain and fre-e-ra-d4-c,-il'.re-,ici,ion-.
SOURCE: AN SSSR. Vestnik, no. 6, 1966, 76-PO
TOPIC TAGS: chemical confcrence., radical pcolynieri7~,t'ion, oxid-ition k"netirs,
chemical personnel, free radicil, re;iction, cheniilcai reaction, r-action
mechanism, polymer-Lzation k.inetics, chemdcnI detection, chemical syntly--sis
posiwn on ch~~n Te,.3-ctions was held in Moscvw
ABSTRACT: A sym
,from 11 to 14 Aprl-l.-Yhe sym-pos ium was dedicated to -Academician -N. N.
Semenov on the occasion of his 70th hirthday and 50th year of scientific
activity. Semenov himself made the opening address to some 500 Soviet
and foreign scientists by outlining Lhe history of development of his
theory of chain reactions and combustion processes and by discussing the
.theory of branched chain reactions, including the latest developments
wnich have resulted from experimental work at the Institute of Chcmica_~
_f~ ~si~s, AS US SR. A significant new contribution to the theory of
branching was made when Semonov introduced the idea that molecules in the
excited state participate in branchIng. Semenov also a4vanced a hypothe-
sis of the exciton mechanism to explain low-Leipperature". ipoly-merization in
the solid phase without activation Pnergy.
Card

L 42118-.'~6
_ACC_ NR. AP602-1960
In addition to others branched chain react ions; in the gas phase were
In._.A. B. On6titute of Cf,emical
treated in several papers: Nalbandy,
Physics, AS USSR), and__Yoy~vodskiy_,__V. V., and V. 14. Panfilova (Institute
of Chemical Kinetics and _9ombustion, AS USSR, Siberian Departrent)
rarefied flame reactiijns,'bf sulfur and sulfur compounds, and bydrogen
with hydrocarbon additives, respectively; Sabo, --- Z.-(Institute of Inorpanic
-garlan AS) -- d~ 91. ion reactions.
and Analytical Chemistry, Hun comp. t o______
Liquid phase reactions were discussed in a scries of papers, the mos,
interesting of which were: Emanue I ' , N. -r-1. ( I ns t i t u t e o f Chemi c a 1 Phy s i cr, ,
AS USSR) -- oxidation of organic compounds, specifically mild oxidation
of low-molecular weight compounds under pressure and co-oxidat~on of
aldehydes and olefins, which yields large quantities of epoxy~tompound-;
,NeyTan_, M. Yu. A. Shly i~ov, V. B. Miller, and V. P~_dcv (InstituLe
of Chemical Physics, AS USSR) oxidation inhibiting activity-of biphpnols
with narrow-spaced active groups; Roginskiy, S._ -Z., Andrianov, T.-T.,and
Yu. N. Rufov (Institute of Chemical Physics, AS USSR) -- the role of oxy-
gen-free radicals in hydroperoxide formation and the discovery of new
solid catalystsqand inhibitors of this process; Yenikolopyan, N. S.
(Institute of Chemical Physics, AS USSR) the chain-transfer with breaking
mechanism of the formation of heterochain polymersqby ionic polymerization;!
and Dolgoplosk, B. A. (Institute offetrochemical SXnthes1s1V4.*4.&.Y.
y", AS USSR) -- stereo-specific polymer~zatiokA dAM
.Topchi of J~jt i -
~cally p6lybutadiene via r-allyl and w-ctotyl complexesof tran &Le t a IS
Card 2 /1 4~ -

L.M.8-66
ACC NRi A P6 0~1_9_6 _0
Free-radical reactions were, stualed, in addition to others, in the
papers by: Kondrat'yev, V. N. Academician -- review of the state-of-the
art of research with emphasis on kinetic measurements of elementary free-
radical reactions, specifically of thermal peneration, exchange, and re-
;combination reactions; Azatyan,.V. V.,and Dodonov, A. F.PG. K. Lavrovskaya
and V. L. Tallroze (Institute of C ical Physics, AS TISSR) -- determina-
,tion of rate constants of the reactions of atomic hydrogen, oxygen, and
hydroxyl radicals and of atomic hydrogen with ethylene molecules, respec-
tively; Shlyapnikova, N. L., A. P. Ballod, and V. Ya. Shtern detection
,of CH NO NX CH ON02. in products of the
20, CH30 radical C1130NO, and CH3
reaction of methyl radicals with nitrogen dioxide; Bagdasar'yan, Kh. S..
(Karpov Physicochemical Institute) -- the problem of reactivity of free
radicals; Freydlina, R. Kb (Institute of Heteroorganic Compounds, AS
USSR) -- investigation of the ree-ra ical mechanism of telomerization
and intramolecular rearrangement of free-radicals; and Razuvayev, G. A.,
and N, S. Yyazanki (Laboratory of Polymer Stabilization, AS USSR) --
new research data on chain reactions with organometallic compounds, e.g.,
bis-[triethylgermyl] cadmium with_M~~to yield J(C If Ge)2'C'2 at -75C.
2 5) 3
[ATD PRESS: 5030-F]
SUB CODE: 07 / SUBM DATE: none
Card 313 af

6030451 SOURCE CODE: UR/0204/6610061004iO6O3/060
AUTHORj Karpukhina, GO V.; Mayzus' Zt-J.6-4, Hatlyenko, L. 1.
ORGt lna&itM&e of Chemical Ph_ysics, AN_SSSR (Institut khimich.eskoy4e
fiatki AN SSSR)
TITLEi Interaction of phenol and aromatic-amine inhibitors in
hydrocarbon-oxidation reactions
SOURCEt Neftokhimiy&, v. 6, no. 4, 1966, 603-607
TOPIC TAGSt oxidation. inhibition, antioxidant additive, combustion
modifier, synergism Y n & k VL POE A309-)~reff #V~010IC09A- ~S 7'#q J3 / J- / Z A 7-,,4V
ABSTRACTs A relations'.ilp has been established between the occurrence
of synergies between two oxidation inhibitors-an aromatic anine (ASH)
and an alkylphenolA(PhOH) -and the structure of the alkylphenol. This
synergism Is assu:;~ to be due to a free-radicaltreaction of the two
Lnhibitorse
MaH + ROO 4 Am- + RO H (1)
2 2
An* + PhOH A=H'4%+ PhOe. (2)

-L 43750-66
ACC N1, AP6030451
The effect of phenols having different substituents ortho or par& to
the OH group, in conjunction with N-phanyl-B-naphthylanineq (Neozont 4)
was studied in the azebtalmobutyronitrile-initiated low-temperature
(60-700 oxidationiof ethylbensene,lby a chesiluminescenne technique &4
and by chemical analysis. It was sh6wn that the sypergion.occur in
the case of o,o'-dialkylphenole but not in the case of o-alkyl a:d
nonsubstituted phenols. This was attributed to the fact that the rste~
of &nine regeneration (reaction (2)) Increases with increasing PhOO
radical stabilityg which in turn increases with increasing steric
hindrance of the phenol's OH group. A relationship was also estab-
lished between the inhibitor effectiveness of the phenols [in the
absence of the amine) and their structure. The criterion of inhibitor
effectiveness used was the constant of*the'reaction of the phenol with
ROJ radicals, The activation energy of the reaction of 2,4,6-tri-
tert-butylphenol with ROi radicals was found to be 3.4 kcalluol. The
U -- V__ .- - - A-6 -_ -
i:ho__r_i7_ihank N. -k.-Emanuel , A7. A. Bailin . a-n-d- V.- V-. fersEO_-vf_or i-
&
cussing this study. Orige art. hass 4 figures. ISM]
SUB CODE101.116 21/ SUBM DAM '02Jul65/ ORIG REFS 005/ OTH REF: 00
ATD PRE6S11 5076

0357-66
'~Cc ` NRI AP6013383
constant.,for the formation of t6l complex N 6910 -5 exp(IGOD/RT)
the equil"Aui
Tbe~results Indicate that-tbe great effectiveness of cobalt lt as a cata-
clue to the(,hIgt value,of the rate constant of.deccmpositic Le hydro
~IySts 2*8, O'njf t
t
ide.into, radicals '1whi6h is almost 163-~.tilies. greater. than the te constant of
perox
ec~poilii-on in thwabsen6e of catalyst. Orig-4 art has t 3 figures, 10

'. '
F
SLT - OD
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SUBM DATti'---""--04DecS4 REF: 003
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