SCIENTIFIC ABSTRACT EMANUEL, N.M. - EMANUEL, N.M.

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• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

51.4)
AUTHORSt Knorre, D. G., Mayzus) Ze Ket SOY/76-33-1-36/45
Markin, M. I., Emanu*11, N. M.
TITLE-. The Kinetics of the Valence Changes of Manganese St-garate in
the Course of the Initial Macroscopic Stage of the V'atalytic
Oxidation of n-Decane (Kinetika valentnykh prevrashcheniy
Btearata margantsa v khode nachallnoy makroskopichuskoy stadii
katalizirovaiinogo okisleniya n-dekana)
PERIODICAL: Zhurnal fizicheskoy khimii, 1959, Vol 33, Nr 1, pp 213-218
(USSR)
ABSTRACT: A short time ago it was found (Refs 1-3) that on V-ie oxidation
of n-decane (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 becoming
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 (1) took place in
a way already described. The samples were examined in the wave
length of 400 m ( by the spectrophotometer SF-4- :[t is stated
that the effecteve activation energy of the accumulation 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--l-36/45
Stearate in the Course of the Initial Macroscopic Stage of the Catalytic
Oxidation of n-Decane
oxidation of (I), whereas the activation energy of the further
reduction of the intermediate compound is 16.1 kca:.. The
absorption coefficients of the intermediate compound were
determined in cumene (since it is simpler than in (I)) and at
400 m A the value 780 1/9-mol cm was found. Beerli; (Ber) law
is followed up to a catalyzer concentration of 0.0,16 m(Fig 7)-
Tests with W, tetralin, and cumene showed that the absorption
coefficient of the intermediate compound obviously does not
depend too much or. the hydrocarbon to be oxidized (Fig 6). The
kinetic ourves of the accumulation of colored inte:!mediate
products show an initial acceleration (Fig 7). At ihe curve
maximum cumene and tetralin show a complete transi-:ion of
manganese stearateto ahigher valence stage and (I) a 30.5;4
transition only. There are 8 figures and 4 Soviet xeferences.
ASSOCIATIONs Akademiya nauk SSSR Institut khimicheskoy fiziki$Mi)skva
(Academy of Sciences, USSR, Institute of Chemical Yhysicop
Moscow)
SUBMITTEDt July 17, 1957
Card 2/2

561) SO-1/7,5-33-2-25/45
AUTHORS: Knorrep D. G.p _S'.Tayzus,-Z. K., ."arkin, J. I., _17mannal', ". 21.
TITLE: Kinetics of the Reaction Between Decyl Hydroperoxide and
I
Manganous Stearate in n-Decano (Kinetika vzaimodeyFtviya
gidroperehisi, detsila. so stearatom mar-antna v zi-lekane)
PERIODICAL: Zhurnal fizicheskoy khimii, 1959, Vol 33, Nrr 2,
PP 398 - 4o4 ("S3R)
ABST"ACT: Several papers on the oxidation kinetics of hydrocarbons
involving manganese or cobalt catalyots report th7..t the
catalyst is observed to acnume a higher valence number. In
re.-ard to this soversl hypotheses have been cet forth by
Ye. T. Deninov and N. 1M. Emann-211 (Ref 6), D. V. Yerofeyev
and L. I. Chirko (Ref 7), and others (Re"s 4,5). The quention
ofthrough what reaction the chanL:-,e in the valence of tile
cat.lyet tnKes place has until now, however, not been ex-
plained. The first experiments carried out in the work re-
ported in this paper showed that the renction mentioned
in the title occurs very fast. It was for this reason that
an apparatus was constructed (Pi- 1) which could lirectly
Card 1/13 measure the optical density of the reaction melium. The

K~netlcn of the Reaction Between Decyl Hydroperoxide SOV/76-33 -2-2.1 /45
and Manganono Stearate in n-DecAne
apparatus is similar in principle to the SF-4 spectrophoto-
meter. The kinetic curves obtained with var -'oud concentra-
tionn of the manganrije atearnte (1) show (Fig 2) that the
reaction is complex. The reaction in a first order reaction
(Fian 3,5). The kinetic cxirves (Fig 4) for 850C show that
a maximum transformation occurs with ration of (1): docyl
hydroperoxide (TT) of 9-7-80%, at 4-83-56;.')jand 3.2,7-40',4.
An increase in tenporqture increases the velocity of the oxi-
dation reaction an well an its depth, wheroby thure is
also a deareatic in the induced docompocition of (11), which
occurs in aldltion to the accumulation of the oxidi-ed form
of (1). Since tho rule of the induced decompovition of (11)
Is unknovin only the upper limit of the activation enerGy
couN be reliably.detormined (22-5 kcal), but for a firet
approximation of the hOtivation energy a value of 18 kcal
wan obtained. The rate constant for the reaction giving an
accumulation of the colored reaction prodi)ct (oxidized forn
of (I)) in written as
Card 2/3 k- 2.8.10 11 e- 13000/RT 1/mole.cee. There are 7 fisilre-3 and

r,
Xinetics of the Reaction Between Decyl Hydroperoxide 30V/7'-33-2-25/45
~nd 111anganous Stenrate in n-Decane
12 referencess 5 of which are Soviet.
ASSOCIATION: Akademiya nauk SSSR Institut khimicheakoy fizikiUoskvs,
(Academy of Sciences, USSR, Institute of Chemical Physics,
Moscow)
SUBMITTED: JulY ITv 1957
Card 3/3

5W
AUTHORS i Knorreq D*G,o Chuchukina, L. Do, SOV1*33-4-20132
Fkanuel!j 14M,
TITLEo On the Phenomenon of Critical ConcentratiQn of Cu(C 17 a35 coo)2
in the Reaction of Uatalytia. Oxidation of n-Decene
(0 yavlenii kritioheskoy kontsentrataii_ou(C 17'35CGO)2 V
,reaktaii katalizirovannogo okialeniya a dekanaj
PERIODICAL: Zhurnal fizicheskoy khimii, 1959, 'tol 33, Nr 49 PP 677 - 882
(USSR)
ABSTRAM In the present paper a new example is given of the c:.-itical
phenomena in reactions with degenerated branchings in liquid
phase which.were observed in the investigations of n--decane
oxidation in the presence of copper stearate (1). At a certain
concentration of (1) a complete stop of the reaction was
observed while at this concentration a self-accelerai--ed
reaction with a small induction period takes place. it-decane
(II) was produced electrolytically (Ref 5) and (1) at-cording
to a method of production described. (I) and (II) were
dissolved in a nitrogen current and the moment where oxygen
Card 1/3 was introduced was regarded as the beginning of reaction.

dn the.Phenomenon of Uritical Uonoentration SOV176-33-4-2013'9-
of Uu(c 17R39COO)2 in the Reaction of Catalytic Oxidation of n-Decane
0-03 - 0-10 m01% of M were used and the peroxides, carb6,4,1
compounds, acids, and copper were determined according to the
course of oxidation; the latter according to two methods:
CU 2+ and the entire copper. A catalytic effect (Fig 1 for
0 030 (1)) could be observed until a concentration of 0.06--mexo--
(i) is attained. A change in the copper valency in the induction
period is explained by a reaction of (1) with intermediate
oxidation products of (II) (e.g.hydrogen peroxides) which
causes the self-aocel-eration proper of the process. The increase
of the induction period at an increase of concentration of (I)
is indicative of a secofid- the inhibiting - ef feat of (I) which
ap arently is based on a destruction of the chains at the
(I5-molecules-. The critical concentration is at 0.065 mol% M
at which the induction period is longer than 15 hours and
where the oxidation rate also changes. The phenomencn of the
critical concentration of (I) in explained by the radical-chain-
mechanism of hydrocarbon oxidatIon* There are 5 figures, 1 table#
and 9 references, 6 of which are Soviet.
Card 2/3

OIL the Phenomenon of a Critical Concentration SOV/76-33-4-20/32
of ft(C 171E35COO) 2in the Reactiom of Cata37~U'.., Oxidation of n-Decane
ABSOCIATIONs Akadeaiya naukEBBRpInstitut khimicheskoy fiziki Moskva
(Academy of Sciences of the USSR 7Institutt of Kemical
Physics )Moscow) ,
SUBMTTEDi Beptember; 28p 1957
Card 313

5W SOV/76-33-7-29/40
AUTHORS: Gagarina,A. B., Emanuel', N. 9
TITLEs Kinetic Rules Governing the Reaction of Methane and Nitrogen
Dioxide
PERIODICAL: Zhurnal fizicheskoy khimii, 1959, Vol 33, Nr 7,
pp 1641 - 1647 (USSR)
ABSTRACTt Small additions of NO 2 to air or oxygen in gaseous-liquid
phase oxidations of hydrocarbons are known to have a strong
stimulating effect (Refs 1,2). Among numerous articles on
the reaction of paraffins and NO there are only two (Refs
9, 10) dealing with the kinetic ireatment of this process. Since
an unsuitable method was applied in (Ref lo), the authors inves-
tigate.in this article the afore-mentioned subject within the
temperature range where NO 2 dissociates noticeably. For this
purpose, an ordinary static vacuum apparatus was used, i.e.
a reaction cylinder (15 cm long, vol-ame of 200 cz3). The authors
applied a method by which the reaction vessel. was filled with
CH4 as soon as the dissociation of the previvasly introduced
Card 1/2 NO2 wasin equilibrium. The kinetic rules governing the reaction

Kinetic Rules Governing the Reaction of Methane and SOV/76-33-7-29/40
Nitrogen Dioxide
were determined by plotting &L'.Aio curves on the basis of
the pressure rise (measured by means of a diaphragm gauge)
as well, as of NO2 consumption (photocolorimetrically deter-
mined). Measurements were made at 360 - 4200 and an initial
CH4 pressure of 50, 100, 200 and 300 torr. The authors further
made experiments with additions of NO or oxygen. Experimental
results led to the following oonclusicnss The rate of the
total pressure rise of the zero-th order, whereas that of the
initial pressure of CH 4 is of the first order, The pressure
rise is *ooelarated by NO additions, while the addition of oxy-
gen strongly inhibits the reaction. The resultant effective
activation energy of the process amounts to 42 kcal/mal.There
are 9 figures and 10 references, 5 of which are Soviet.
ASSOCIATIONs 1kademiya nauk SSSR Institut khimicheskoy fiziki Moskva
(Academy of Sciences of the USSR, Institute cf Chemical Phy-
sioe, Moscow)
SUBMITTEDs February 21, 1958
Card 2/2

5(4) SOY/76-33-6-331/39
AUTHORS: Gagarinap A. B., Emanuel,# it. M.
TITLE: Kinetics and Chemism of the Reaction of Methane With Nitrogen
Dioxide
PERIODICAL: Zhurnal fizicheskoy khimii, 1959, Vol 33, Wr 8, PP 1872-1879
(USSR)
ABSTRACT: In continuation of a previous paper, aft investigation of
the intermediate and final products of the reaction between
methane (I) and nitrogen dioxide (II) was carried out and
the kinetic behavior of the reaction products was examined.
Besides the analytical methods described in publications,
analysis methods particularly developed for that purpose
were used as well. The analyses showed that the reaction
products are nitromethane (III), Go (IV), CO 2 (V), NO (VI),
and traces of formaldehyde, and HCN (VII). The kinetic be-
havior of these substances was examined in a static vacuum
unit with t.. reaction vessel made of molybdenum glass (200 =3).
The kinetiov of the formation of (III) was examined thorough-
ly. It was :ound that (III) forms as an intermediate product
Card 1/2 and further decompoees.,.A complete analysis of the reaction

SOV/76-33-8-33/39
Kinetics and Chemism of the Reaction of Methane With Nitrogen Dioxide
products renderod it possible to determine a material balance
with respect to carbon and nitrogen (Table 1). The following
rate constant is suggested: CH~j U021
w - k Pq_10121
(k - summary rate constant, 3 r_O,] and pressures
[C H41 P N] =
of M, (II)s, and.oxygen). Data for the value of w/k are given
in mm Hg for up to 15 minutes after the beginning of the re.-
action (Table 2). Various thermodynamic constants relating
to the reaction inveati at d are computed$ and it 4s found
that the reaction of (I~ a:d (Ii ) followo two separate direc-
tions - the nitration of (1) while (III) forms, and the In-
tensive oxidation of (I) with the oxygen from (11), while
(IV) and (V) are formed. There are 4 figures, 2 tables, and
12 references, 4 of which are Soviet.
ASSOCIATION: Akademiya nauk SSSRyInstitut khimicheskoy fizikiMookva
(Academy of Sciences USSR; Institute of Chemical Physics,Moscow)
SUBMITTED: February 21, 1958
Card 2/2

BOV/26-59-1-19/34
oAUTHOR: Emanuel', N.M.,; CorrvsVonding Wwbero AS USSR
TITLE: The Control of Chain Reactions in Chemistry (Upra-
vleniye tsepnymi reaktsiyami v khimli)
S
P~RIODIOAL: r 1 pp 46 - 56 (USSR)
Piiroda, 1959.
'A
ABSTRACT: The article gives a historical and physical survey
on the phenomenon of,ehain reactions in chemistry
and stresses especially the merits of Academician
N.N. Semenov and his investigations of cataly,-,ers
and inhibitors in chemical chain reactions, which
he carried out in the thirties and for which lie was
awarded the Nobel Prize in 1956. -These fields of
the mechianism of chemical reactions and chemical
kinetics have assumed new importance with respect
to the objectives of the 7-Year Plan in the field
of synthetic-material production. The author, to-
gether with Z.K. Mayzus, K.Ye. Kruglyakova, M.F.
Sedova and other researchers, discovered interest-
Card 1A ing peoularities of the action of positive c3Ltalyz-'
4L

'The Contrbl'..4T Chain Reactiona in Chemistry SOV/26-59-1-19/34
ers in oxidation chain reactions of hydrocarboas. In
addition to formerly known elementary reactions, ag-
gregate interactions take place. The reactionme-
chanisms on their-way from one macroscopic stE.ge to
the.next and the occurring changes were studied
(Figure 1). Ye.T. Denisov together with the author
succeeded in increasing the yield of cyclohexanone
by over two times by merely removing the cataLyzer
from the reaction zone after an initiator action of
brief duration. While new concepts, with respect to
sudden breaks of chain reactions on the walls of the
reaction vessel, were found by Profassor A.B. Nalban-
dyan in 1946 together with the possibility of influ-
encing these breaks (Figure 2) similar to eff'Pets
upon nuclear reactions '. , CorrespandiM r
'AS UNH A,A, Kovallskiy discovered solid surfaces
that bring about a chain reaction process. Con-
cepts on these homogeneous-heterogeneous reaetions
had been formed earlier by Professor M.V. Polyakov.
Recently, Academician N.N. Semenov, Co=eOmAing Men-
Card 2/4 b6r'' AS USSR ; V.V. Voyevodskiy and Profesecr F.F.

The Control of Chain Reactions in Chemistry SOV/26-59-1-19/34
Vollkenshteyn formed new concepts on reactions of a
merely heterogeneous catalysis by way of the chain
mechanism brought about by free radicals. If these
concepts can be proved by experimentation, new ways
of influenoing the processes of the heterogeneous
catalysis would be given. Speeding up of slow reac-
tion processes by way of diverse stimulation
(Figures 3-6) is being studied by Professor M.A.
Proskurnin, B,A. Blyumberg, D,M. Ziv, V,L, Mi-kay-
,eva, V.K. Tsyskovskiy, V.K. Zeynalov, and the author.
The problem of free radical.s and chain reactions in
biological processes is being studied by L.P. Lip-
china and Professor B.N. Tarusov (Figures 7 and and
8). The author,concludes that there are various
ways of influencing chemical and biochemical chain
Card 3/4 reaction processes, many of which may lead to inter-

':teCv'ntrol of Chain Reactions in Chemistry SOV/26-59-1--19/34
esting re3ults and further possibilities. Thore are
8 graphs and I Soviet reference.
ASSOCIATION: Institut khimicheskoy fiziki AN SSSR /Moskva ,The
Institute of Chemical Physics of the AS USSR IMos-
cow)
Card 4/4

17 1.3)
AUTHORS: Emanu;el No Mo. Corresponding Member, SOY/20-124-5-56/62
AIV USSR, Lipchinag L, Pop Pelevina, 1. 1., Lipato,ral To E.
TITLE: The Selective Inhibition of the Aotivity of Reduction-Oxidation
Enzymes in Tumoral Cells When Acted Upon With Inhibitors of
Chain Reactions (Izbiratelinoye podavleniye aktivnosti
okislitellno-voestanov4.tellnykh fermentov v opukholevykh
kletkakh pri vozdeyatvii ingibitorov tsepnykh reaktsiy)
PERIODICAL: Doklady Akademii nauk SSSRj 1959, Vol 124, Ur 5, pp 1157-1159
(USSR)
ABSTRACT: Since many years the idea of a selective inhibition of
fermentative processes in tumoral cells, as a rational
principle in oanoer chemotbarapyj focuses the interest of the
scientists (Ref 1). The first two authors (Ref 2.) proved an
inhibition and a retrogression of leucosis in mice under the
action of non toxic inhibitors of the oxidative chain reactions
(butyl-oxy-anisole, ionone, propyl gallate)(Ref 2). There aere
reasons (the radical mechanism of the reduction.-oxidation
processes) for assuming that the inhibition meLtioned in the
title is one of the reasons of the tumor inhibiting effect of
the mentioned substauces. This disturbs the formation processes
Card 1/3 of some energy-rieh compounds which are necessary for the

The Selective Inhibition of the A-3tivity of SOVP,0_12~-5-56/62
Reduction-Oxidation Enzymes in Tumoral Cells When Acted Upon Wit~a Inhibitors
of Chain Reactions
intense biosynth9sis in the neoplastia growth. In the present
paper resitlts could be obtained which confirm the above
assumption. The authors irivestigated enzymes of tbe
suceinoxidase sjritem. The ascitto cancer of Ehr2ich (Erlikh)
in mloe, leucasis of Ilan* mize (line C-57, strain LOP
aoridine sarioma of m-L~o and the Braun-Mrs tumor of rabbits
served for the exper-Almente. Cells of the ae-~itlo cancer. as well
as tumoral tissues of other new firmations reduce,! to small
pieces were incubated for 30 minutes in 0.75, 0.15 and 0.075%
propy! gallats solution, These con.,)entrations inhJbit the
activity of succino dehydrogenase in the cells of all tumors
investigated (Figs'2' 9 2). The activity of this enzame is not
sappressed In healthy liver and spleen calls by p:-opyl gallate
solutions of 0.15 and 0#075% (Figure 3). Incubation in a 0.75%
solution is, however, inhibiting. Thin inhibition is reversible
in afflioted as well as in sound cells. The diffe-ences in the
propyl gallate effect on the reduction-oxidation -)rocesses iA
normal and tumoral ae3ls are probably due to a di:'ferett
card 2/3 permeability of the calls and their components (6. r. m1A-.chcnd_"i0)

The Selective Inhibition of the Activity of SOV120-12e,1-5-56162
Reduction-Oxidation Enzymes in Tumoral Celle When Acted Upon %7'Lth Inhibitors
of Chain Reactions
to propyl gallateo Thusl propyl gallate has a sele:tive effect
on tumoral cells in certain concentrations. This is expressed
by the inhibition of the aotirity of dehydrogenases which. :
participate in various reduction-oxidation processes as well as
of cytochrowcxidase. The thus influenced cells locee their
implantatiou power. There are 3 figures and 6 refcrenoes,
5 of which are Soviet.
ASSOCIATION: Institut khimicheskoy fiziki Akad.emii nauk BSSR
(institute of Chemical Physics of the, Academy of S.-,:iences USSR)
SUBMITTEDs November 25Y 1958
Card 3/3

5.( A.)'
1
xUAids. Vasillyev, R. F-9 Karpukhin, 0. ff., SOV/20-124-6-21/55
Shlyapintokh, V. Ya., Emanuel', N. M., Corresponding Member,
AS USSR
TITLE: Gas Initiation by Ozone in the Reaction of the Oxidation of
Iaodcoane and tbn PI-Aluminescence Cortnected With It
(Gazovoye initslllr-va,%~ye -.~zonom v reaktaii okisleriiya izo-.
dekana i svyazu"adya u nim. khemilyuminestsentsiya)
PERIODICAL: Doklady kkademii nauk SSSRq 19599 Vol 124, Ur 6p pp 1256-1260
(USSR)
ABSTRACT: The present paper deals *ith the stage of initiation by ozone
in segregated form, i.e. the authors investigate such phenom-
ena and processes as otcur during the suort action of the
initiator. Isodecane (2-7-dimethyl-octane) was u:3ed as te4t
object. Preliminary tests showed that if ozone i3 blown post
during a short time the reaction is accelerated .,onsiderably.
The authors recorded a weak glow which was produeed during
the bubbling of oxygen (containing 2-3 % ozone) by isodecane.
This isodecane was in a glass oxidation cell at temperatures
of 20-900. By glow the photomultiplier FEU-19 served as an
Card 1/3 indicator of the glow. The photoelectric current was recorded

Gas Initiation by Ozone in the Reaction Of the SOV/20-12-~-6-21/55
Oxidation of Inodecane and the Chemiluminescence Connected With rt
by means of the electronic potentiometer EPPV-51& The firet
diagram shows the intensity of glow as a function of time
during the uninterrupted blowing-through of ozone and iso-
dooane at a temperature of 550. Intensity increases gradu--
ally andq after 2.5 hours, it attains a maximum after which
it gradually decreases. As soon.as the adding of ozone is
interruptedg the glow immediately vanishes in all, stages of
the reaction. If ozone is again suppliedv the provious inten-
sity ia quickly restored. According to these tesults the glow
is caused in the interaction between ozone and a compound,
which was formed already before this interaction as the
result of a reaction of ozone with carbon. The a'oove mentioned
intensity maximum indicates that the concentratiDn of this
hypothetical compound passes through a maximum, In this case
the kinetics of the accumulation of this oompowid agrees
with the kinetics of the accumulation of the intermediate
product in the case of successive chemical reaction. An other
possibility of explaining the phenomena discussed is re-
jected on the grounds of being unsuited. A further proof of
Card 2/3 the intermediate character of the product of primary interactka

'Gas Initiatio-n by Ozone in the Reaction of the SOV/20-124-6-21/55
Oxidation of Isodecane and the Chemilumineseence Connected With It
with ozone was supplied by experiments carried out with
higher temperatures. Thus~ the interaction between ozone and
normal hydrocarbons at moderate teaperatures is a complioatod
process in the course of which a relatively stable inter-
mediate compowA is formed, There are 3 figures and 4 Soviet
references.
ASSOCIATION: Institut fizicheskoy khimii Akademii nauk SSSH (Institute of
Physical Chemistry of the Academy of Sciencesq USSR)
SUBMITTED: October 29f 1958
Card 3/3

17(3)
AUTHORS: Emanuel $-No Mo, Corresponding SOV/20-125-2-49/64,
-Vember, AS USSRt LIpchina, L. P., Pelevina, I. Is '
TITLE: Selective Decrease of the RNA Content in Tumor Celle and Their
Lose of the Ability to be orafted when Acted upon by Chain-re-
action Inhibitors in Vitro (Izbiratellnoye umenlaheniye soder-
zhaniya RNK v opukholevykh kletkakh i poterya imi sposobnosti
privivatleya pri vozdeystvii in vitro ingibitorov tsepnykh
re&tsiy)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 125, Nr 2, PP 411-413
(USSR)
ABSTRACT: The authors found a principal possibility of the inhibition
andretrogression in the forination of tumors by use of the
aforesaid inhibitors (Ref 1). The activity of importAnt.
redox ferments in tumor cells is suppressed by propyl gallate
in vitro (Ref 2). Thus these cells are deprived of the* ~?.
energy they need for intense biosynthetic processes which
are typical of blantoma growth. Among these processes the
biosynthesis of ribonucleic acid (RNA) is of special interestp
whiohp according to modern yiews, forms a matrix for albumin
Card 1/3 synthesis (Ref 3). There is a certain connection between the

Selective Decrease of the RNA Content in Tumor Celle SOV/20-125-2-49/64
and Their Lose of the Ability to be Graftei v4hwa Acted up9n ti Chain-reaction
Inhibitors in Vitro
intensities of albumin synthesis and the re-formation of
RNA. Also rapidly growing cells of tumor are known to possess
a high RNA content (Refs 4-6). The%r'e are also some indications
(Ref 7) that the decrease of RNA content below a certain
value stops albumin synthesis. In the present paper it was
found that a considerable selective decrease of the RNA con-
tent in tumor cells is caused by propyl gallate (as compared
to a regular cell) so that these cells lose the capability
of being implanted. Ehrlich- (Erlikh-) cancer of micep care-
fully minced tissues of leucosis mice, Brown-!,~~erce- (Braun-
Pirs-) tumor of rabbits, acridine sarcoma of mice, sarcoma
45 of rate and Rous-sarcome of hens were used for the ex-
periments. Already after an action of O-T5 % propyl gallate
solutions for 15-30 min neither plasm RNA nor nuclear RNA
is visible under the luminescence microscope (Fig 1 a,b).
The'ehange of the RNA content are reversible and can be
eliminated to a certain extent (Fig 1, v). Experiments with
sound liver cells have shown that the inhibitor (0.15 %)
Card 2/3 insignificantly reduces the RNA content within a short time;

Selective Decrease of the RNA Content in Tumor Celle SOY/20-125-2-49/64
and Their Lose of the Ability to be Grafted when Acted upon by Chain-reaction
Inhibitors in Vitro
SUBMITTED:
on the other hand, a complete adaptation of the cells follows
and the regular state is restored (Fig 2 a,b). Thus it was
possible to draw the important conclusion on the selective
effect of propyl gallat.e on tumor cello, which explains the
therapeutical effect of the inhibitor in vivo without
damage of the organism as a whole. The cells of the enumerated
tumors are therein completely deprived of the capability of
implantation. If they are washed out with physiological
common Balt solutiont this lost capability is restored. There
are 2 figures and 8 Soviet reference3.
November 25t 1958
Card 3/3

170)
AITHORS S
'~ -
IbAnusio, N. U , Corresponding Member AS USSR, SOV/20-125-5-53/61
*
O
- T
~ a ~Iz
.
f p Ec
TIME: The Loss of the Blastomagenio Properties of the Virus of Rowso
Sarcoma Under the Action of Propylgallate (Poterya blastomageMkh
avoysty virusa, oarkomy Rouna pri vozdeystvii propilgailata)
PMODICAL: Doklady Ikademii nauk BSSR, 19590 Vol 125, Nr 5, pp 1148-1150 (USSR)
ABSTRACTz Several malignant tumors are known which can be revaccinated not
only by the transplantation of tumor cells, but also by the
introduction of filtrates of tumor tissues free from cells. This
cayacity vanishes after the influence of one of the inhibitors of
the oxidative chain processes, of propylgallate (Ref 1). This doeB,
however, not occur in consequence of the protein denaturation. The
cello from which the inhibitor was washed out with physiological
sodium chloride solution belsome anew blastomagenic. This in as well
the case with cells (Ref 2) of such tumors which can be revaccinated
by means of filtrates free from cello (Rowel sarcoma of fowls,
mouse leucosis). The authors are witb respect to the r8le of the
free radicals in the growth processes of the -hmor (Ref 3) of the
opinion that the spreading of the virus takes in many cases place
Oard 1/5 by the transformation of the cell cytoplasm, not by separation

The 14as of the Blastomagenic. Proportion of -the Virus of Rowel BOV/20-125-5-53/61
Samoms. Under -the Action of Propylgallate
(Ref 4). In suob cases the prognssive virus propagation has a
character similar to the nonsteady chemical processes which an
stimulated by free radicals (Ref 5). The references 6,7 deal with
the possible autooatalytic character ~of the virus apraading. A
slight inactivation of the virus by the oxidation with oxygen in,
as well interesting (Ref 8). All that may prove free-radical
character of the virus particles. Thus may be assumed that the loss
mientioned in the -title after the influence of the inhibitors is
related to the loss of the free-radical properties by the virus.
As a consequence of this may be assumed that an inactivation of
the tumO4 forming viri and -the loss of the blastomagenio properties
of filtraltes free from cells is possible by the influence of
inhibitors of the free-radiaal (chain) processes. The addition of
propylgallate did not cause abrupt shifts1of the pH-value in the
experiments of the authors (it remained between 6.7 and 6.9). The
filtrates (control with 1:1 physiological sodium chloride solution
and experiment with propylg&llate in an equal solution: 0.75, 0-150
and 0.075%) were kept 30 minutes in the propylgallate nolution an
ice. Experimental- and control material was at the same moment
Card Z/3 injected into the right or left wing respectively of one and the

Th6 14se of the Blastomagenic Properties of the Virus of SOV/20-125-5-53/61
ROW80 Sarcoma Under the Action of Propylgallate
same fowl. The latent period up to the formation of the tumor
took 7-12 days in the case of the filtrate without propylgallate.
The fowls died after 18-20 days. As a rule, no tumor,waa produced
in the case of a filtrate inhibited with 0.75% propylga:Llate
(Fig lga#b)- Only 3 of 30 fowls had tumors the rate of irrowth of
which was, howevero to a great extent inhibited (pea-si:sed instead
of chicken egg-sized like in the control). 0615% propyltrallate lead
to an inhibited tumor formation, whereas 0.075% was in&3tive.
Finally the authors make the attempt of interpreting tha obtained
results. Propylgallate suppreB83d the activity of the radox ferments,
e. g. of the dehydrasea. R. H. Radzikhovskaya helped in this
investigations There are 1 figure and 14 references.
ASSOCIATIM Institut kbizioheakoy fiziki Akademii nauk SSSR (Instit-Ite of
Chemical Physics of the Academy of ScienoesUSSR)
SUBUTTEDt February l1v 1959
Card 3/3

50)
AUTHORS: Denisov, Ye. T., Mayzus, Z. K.? SOV/20-128-4-33/65
Skibida, I. P., Emanuel I
Corresponding Member, AS USSR
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 cont inuous proneae of reactions
is attempted more and more, i.e. of reactions in open systemse
While the kinetics of simple processes had already been in-
vastigated (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
producta. 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 un.1A of times
The value I Indicatoo the average duration of stay of the
v
liquid in the reaction vessel. The content of h:ydrogen per-
Card 1/3 oxide, adipic acid, and CO 2 in the reaction product is

Kinetic Laws for AUtocatalytic Reactions in SOV/20-128-4-3'3/65
Open Systems
determined for different Y. In the continuo" process, a
stationary state appears, i.e. the reaction rate and the
discharge of the end product are in an equilibriun relation
to each other. Figure I shows the dependence of the equi-
librium concontration 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 r, irrespective of the oxidation degree
attained. While for simple reactions the rate r1s*,s mono-
tonously with v, there is 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
tho reaction rate passes a maximum at a certain Yj 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 920

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: Ins titut khimioheskoy fiziki Akademii nauk SSSR (institute
of Chemical Physics of the Academy of Sciences, UISSR)
SUBMITTED: June 22, 1959
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s/595/60/000/000/004/014
zl96/E535
AUTHORS: Emanuel', MM01 Berezin, I.V. and Denisov, Ye.T.
TITLE: The oxidation of cyclohexane
SOURCE: Vaeaoyuznoye aoveshchaniye po khimicheskoy per#a~rabotke
neftyanykh uglevodorodov v poluproduRty dlya sinteza
volokon i planticheakikh mass. Baku, 1957. Baku, Izd-
vo AN Azerb.SSR, 1960, 143-156
TEXT: The kinetics of oxidation of cyclohexane were Lnvesti-
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 cyclohexyl hydroperoxide. A
second liquid phase appears when the reaction mixture becomes
Card 115

The oxidation of cyclohexane S/595/6o/ooo/000/004/Oi4
9196/E535
saturated with water and adipic*acid, which have limited
solubilities in cyclohexane. As the reaction in 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, urith an
activation energy of 27 kcal/mol. The log of the conversion
coefficient to cyclohexyl, hydroperoxide over the first part of the
reaction varied linearly with the inverse of the temperature, with
activation energy 29 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 carbon as marker and the following sequence was
found
OH 0
0. 2
adipic 0 CO + monocarbon
2
acid 4 2 acids
V/
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The oxidation of cyclohexane S/593/60/000/000/004/014
E196/E535
In glass vessels the hydroperoxide breaks down equally into
cyclohexanol, formed entirely by the decomposition of cyclohoxyl
hydroperoxide, and cyclohexano:ae, from decomposition of the
hydroperoxIde and oxidation of cyclohexanal. Adipic acid is
formed exclusively by oxidation of cyclohexanone whilst the
eaters 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 130*C the concentration of Co(III) besomes
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
E196/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 two functions - initiation of the reaction
and regulation of the proportions of the products. The rate of
absorption of oxygen in the uncatalyzed reaction remains
constant after the inductlon period; in the catalyzed reaction
MM
it rises to a maxiu 17-d6creases to a constant value whi,-h is
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 initiation
and the final constant velocity attained was found to be higher
than for the uncatalyzed reaction. A new method of stimulating
liquid phase oxidation, using NO 29 was studied, The air was
saturated with NO, (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 cntaly-st. A table is
Card 4/5

The oxidation of cyclohexane S/595/60/000/000/ooti/014
n196/E535
included which gives yields of acid and ketone for the 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. Landeborg and N,N,Semenov
are mentioned in the paper. There are 10 figures and 2 tables,
Table
Test Depth of Yield of Yield of
oxidation acid.% ketone,%
Autooxidation 14.8 30 37
Oxidation with
St 2Co
18.5
.58
23
Oxidation with NO 2 19 57 22
Oxidation with
St2Co + NO 2 22 51.5 27
Card 5/5

826%
S/195/60/001/001/003/007
BO15/B06O
AUTHORS: Mayzus, Z. X., Skibida, I.P., Emanuel',
Yakovleva, V. - Y.
.TITLE: Chain- and Molecular Reactions of Intermediates in the
Oxidation of n-Decane,
PERIODICALs Kinetika i kataliz, 1960, Vol. 1, We. 1, pp~ 55-62
TEXT: The authors sjudied the decomposition kinetics of the hVro-
peroxides of n-decyl'lin n-decane in the presence of o'- -naphtbene acting
as an inhibitor. Thelatter was added at various stages of Cie reaction.
The constant of hydroperoxide decomposition without chain reaction was
calculated from the kinetic curves and was found to equal 1.7 -
- 1.9-1073 min.-1. It is near the value of the reaction rate conatant
of the reaction chain branching in the oxidation of n-decane (-;(
1.1-1o-3 min.-I). From this the authors concluded that, besides the
~
ecompoaition of the hydroperoxide molecules into radicals without chair.
reaction, there also takes place a molecular decomposition under the
formation of ketones and water. r>/--naphthene was found to react not only
Card 1/3 VK

***Chain- and Molecular Reactions of Intermediates si'.195,'601001 /00 111003/00 7
in the Oxidation of n-Decane B015/BO60
with the RO radical but also with RO* radicals developing in the
hydroperoxide decomposition. The formation of free radicals1with the
nhain branching occurs in parallel to two renctionai the monomolocular
decomposition of the hydroperoxide RCOH--*RO + OH and the reantion of
the hydroperoxide with the hydrocarbon ROOH + RH-->RO + H 20. The authore
established the effective reaction rate constant of the chain branchinG
reaction in the oxidation of n-docane as the sum of the constantn of tho
monomolecular decomponition of the hydroperoxide (in chlorobenzene as an
inert solvent) and of the bimolecular reaction of the hydroperoxide with
n-decane. The reaction rate constant of the bimolecular branchin,3 reaction
rises with the weakening- of the C-H bond in the hydrocarbon in the
following order: decane"'isodecano 4) and AY 0*> 0 or Axo< 0 and 46yo< 0.
Here A XQ = X0 and A Yo y "Overshoot" can occur at
a It tho VA11.1es of V if 4xo> 00,,6y.< 0 or Anxo 0.
The sign of the differential (dAy/dt)t=t is determined only by
0
the sign of Axo. Fig.6 shown the rules of accumuintion of hydro-
peroxides and acids (curves 1, 2, respectively, left-hand ordinate)
and of ketones and acids (curves 3,4, respectively, right-hand
ordinate) as functions of v (hours- ). These curves show thEit by
changing v the relative yie Ids of the components can be changed.
In general. the maximum rate of acclimulation of component c in
kI kr) k3
A -"* B --=-) C --!.?r) occurr at gr;-ntev valties of v than if the
Card

Peculiarities of the kinetics S/I 95/61/Oo2/oo4/otj6/ocj8
9111/F985
loAt stage were absent. Furthermore, except when k k2' the
maximum rate of accumulation of each successive product is attained
ot values of v Ie-m than that corresponding to the maximum rate
(st' accumulation of: the preceding prodtict. The conclusion can be
drawn thpt acids arp not formed in n-decane oxidation from kvtone);
t-nd alcohols, In an open system the alcohols, ketones and acids
;ive formed diroctly rrom hydroperoxides, but for a clossed system
L, S, Vartanyan, top:ether with the present nuthors Z. K. Mayzus
and N, M. Emanuel', have shown (Ref.8- Zh.fiz.khimii, 30, 862,1956)
that the acids are formed from hydroperoxides via an intermediate
stage of ketone formation. There are 6 figures and 11 references,
9 Soviet-htoc and 2 fion-Soviet-bloc. The English-language
reference.q read as follows: Ref.4: K. G. Denbigh, M. Hicks.
F_ I-L Page, Trans.Faraday Soc., 44, 479, 1948; Ref.10: L.J.1hirliam,
H.S.Mooser, J.Amer.Chem.Soc., 80, 327, 1958.
ASSOCIATTON- - Institut khtmicheakoy fiziki AN SSSR
(Inmtitute of Chemical Physics AS IJSSIO
UBMITTI'D - I't-1,rijarY 7*, IL961
card 4

KNORRE, V.L.; M&NUELT 0 N.M.
Kinetics of 1..2-diphenylethane oxidation with potassium
permanganate in aqueous solutions. Kin.i kat. 2 no.6:816-WO
N-D 161. (MIRA 14:12)
1. Inatitut khim4chook6y fiziki AN SSSR.
(Ethane)
(PoUssium Parmanganate)

317IJi
S/133/61/004/005/001/005
9134/9483
AUT11ORSj Durlakbva, To.b., Gorban', M.I., Dzantiyev, B.G.,
Sergoyov, G.B., Zmanuall N *H.
TITLZ& The effect of gamma radiati n on the oxidation of
mothyl cleat* in the presents of inhibitors of free
rgidiefal processes
PZRIODICALs Izvestiya vysshikh uchabnykh zavedonly SSSR.
Xhimiya i khImichaskaya t*khnalogiya, Y.4, no.5, 1961,
TEXTs In previous work on the radiological oxidation of natural
fats (Ref.11 IzV. VUZ SSSR. Xhimiya I khim. takhnologiya, y.2.
533 (1959)), the present authors had'related a reduced induction
period with destruction of inhibitors by radiation. In view of
the complexity of natural fats, in which the quantity and xtructu-rs-
of antioxidants Is unknown, the authors decided to study rAthyl
cleat* - inhibitor sys~oas.. Diphonyl&nine and hydroquinone, boC!j
known as inhibitors of fro* radical reactions, wore employed.
The authors had previously (Ref.2t Xxv. VUS SSSR. XhImiya I khim.
takhnologlya, V.3, 265 (196o)) studied the effect of radiation on
Inhibitor free mothyl olexte, and considered that radiation leading
-C&-rd 1/4

31744
S/133/61/004/005/001/005
The effect of gamma radiatl~n Z134/Z485
to free radical formation would destroy the inhibitors by
re4otion with free radicals. Samples were exposed to gamma
radiation from Cobalt 60 in apparatus 11YI-400 (GUT-400) and %hs
destruction of the inhibitor was followed spectrophotom-trically,
irradiation took place at 20"C. Oxidation experiments on
Irradiated and non-irrAdiated nothyl oleate were carried out at
60'C with continuous passAge of air. Experiments with Inhibitc..-
freo.methyl oleate were carried out simultaneously under identical
,onditions to obtain the rate of free radical formation.
Experimental details and methods of analynin were as das;ribmd in
11cr.2. Curves showing the rate of free ra,licai rorwaxi;r, -4r,
inhibited and non-Inhibitod methyl oleato wore founJ to be
parallel and differed only in their induction period. The tottil
induction period cor-aists of the basit indu-ticit pellod for the
oxidation of inhibif~or free methyl oleate ani dn additio=a! -fnd--;Z#-0M
period related to the concentration of inhil4itor, the latter 11
practically completely destroyed before free peroxide radicals *,r*
cbeerved. The additional induction period is directly
proportional to inhibitor concentration, which in tharartert3t1a
of inhibitors reacting with radicals. 1nd"4ti3n peria3z for
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317L4
S/153/61/004/005/001/005
The effect or gamma radiation ... E134/Ek85
irradiated material were lower than for non-irradiat*d material
due to inhibitor destructiong and the decrease in induction paricd
was found to be proportional to the quantity of radiation.
Curves showing the relation between inhibitor concentration and
induction period, and the decrease in induction period of
inhibited methyl cleats with total quontity of radiation, are
given an well,ae correlating equations. It has been shown that
quantity of radiation is controlling, and that intensity has
virtually no effect. At the low temperature of radiation, the
Induction period of non-inhibited m*thyl oloate was practically
unaffected by'rAdistion. The correlation between the Induction
period of inhibited methyl oleate and the quantity of radiation
made it possible to calculate the number of radicals formed per
unit or radiation. Experiments, carried out in the presence and
absence of oxygen respectively, lead to the suggestion that
removal of a hydroquinane type inhibitor takes place essentially
bytreaction w1th an R02 type radICAL. There are 5 ftgurls.
I table and 3 Soviot-bloo references,
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317h4
S/153/61/004/005/001/005
The effect of xa-- radiation ... 9134/9485
ASSOCIATION: Moskovskly gosudarstv*nnyy universitat
im. M.V.Lomonosova. Kafedra khimichaskoy kinetiki
(Moscow State University Im, H,V,Lomonoxov,
Department of Chemical Xinetics)
SUBMITTEDs January 28, 1960
Card 4/4