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

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000412110004-8
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: January 3, 2017
• Document Release Date: July 27, 2000
• Sequence Number: 4
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

.USSR/Pbysical Chemistry Kinetics. Combustion. Explosives. Topochemistry.
Catalysis, B-9
Abet Journal: Raferat Zhur - AhImiya, No 1., 1957, 411
Authort Vasillyev, R. F.p and B=uel,, N. M.
Institution: Acadow of Sciences USSR
Title: Kinetics of the Oxidation of Acetaldehyde by Acetyl Hydroperoxide
Original
Periodical: Izv. AN SSSR, section on chemical sciences, 1956, No 4, 387-396
Abstract: Two possible mechismismo are discussed for the reactions: CH.-CHO t
CH3COOOH :kA Y -,) 2CH COOH (1) and CH3CHO + CH3CO0OH ' Yj and CA cHo +
CH COOOH vh 2CH CON (Y Is the peroxide product for'mced during 4: re-
a2ion). 'The rl.netics~af-the disappearance of CH3COOOH and the ac-
rum"I COOK have been investigated in toluol soli~Uons at
18-400 and are Mquately described by the step mechaniam (1j; in
particular, the ratq of forviation of the acid shows an initial in-
crease. Thus, I appears to be an intemediate and not a side-
product.of the reaction. The value 1.6-10 exP(-5,500/RT) mol/liter
Card 1/2

USSR/P~ysical Chemistry - Kinetics. Combustion.
Catalysis) B-9
Explosives. Topochemlstr)%
Abst Journal: Referat Zhur - Xhimlya., No 1, 195T', 412
Author: Vasillyev, R# Fe, Terenin, A. N.; and Emanuel, N. M.
Institution: Academy of Sciences USSR
Title; Spectroscopic Investigation of the Intermediate Product and the Transi-
tion Step in the Oxidation of Acetaldehyde by Acetyl Hydropwoxide
Original
Periodical: Izv. AN SSSR, section on chemical sciences, 1956, No 4, 397-402
Abstract: The intermediate peroxide product (I) formed during the reaction of
CH3CO09H (II) With CH3CHO (III) (see preceding abstract) has been
crystallized from tolaene solution at -500 and dissolved in nitro~-
methane. The solution was placed in a cuvette with polyethylene
windows,, and its spectrum recorded with an IR a ectrophotometer. In
,produced by the va-
the spectrum the average intensity band 847 cm-I
lency oscillations of the -0-0- group, was found. From the 847 band
and the 586 (11) and 947 cm-1 (III) bands in the temperature range
Card 1/2

USSR/Physical Chemistry - Kinetics. Umbustion. Explosives. Topochemistry.
Catalysis, B-9
Abet Journal: Referat Zhur - Xhimiya, No 1.. 1957, 412
Abstract: -20 to 200, the kinetics for the establishment of the equil-ibrium
II t 1110 1 were studied qualitatively as well as the kinetics for
the formation of acetic acid. The small shift in the 847 band of I
relative to the II band (856 cm-1 indicates that I apparently has a
hydroperoxide structure, e.g., CH3CH(OOH)OC(O)-CH3'
Card 2/2

------------------- -- --------------- ------
USSR/Physical Chemistry - Kinetics. Combustion. Explosives. Topochemistry.
Cata3yols, B-9
Abst Journal; Werat Zhur KhImiya, No 1, 1957, 413
Author: Vasillyev, R. F., Terenin, A. W.,, and Emanuel, N. M.
Tnstitution: Academy of Sciences USSR
Title; The Effect of the Solvent on the Rate of Oxidation of Acetaldehyde
by Acetyl Hydroperoxide from the Point of View of Hydrogen-Bonding
Original
Periodical: Izv. AN SSSR, section on chemical sciences, 1956, No 4, 403-407
Abstract: The rate for the first step of the reaction (see preceding abstract)
at 24.20 is the same in CHM 3) C05CH31 C06) and C6H -W020 the rate
is somewhat higher in CC14 and considerably lower in K30H), CHIN02
and CH 3COCH In the,IR absorption spectra of CH3COO0H solut'~`ns in
CH3NO2 and & 3COCH there are observed, in addition to the bands due
to intermolecUar drogen bonding in CH3r'OOOH (3,310 am-1), broad
bands with maxima at 3,385 and 3,285 cm-1., which are ascrDed to intra-
Imezmolekulyarnyy vodorodniv svya
molecular hydrogen bonding (MVC - qT)

USSR/Physical Chemistry Kinetics. Combustion. ftplosives. Topochemisti7.
Catalysis,, B-9
Abst Journalt Referat Zhur - Xhimiya, No 1, 1957., 413
Abstract: between the solvent and CH3COOOH' In the-spectrum of the solution of
CH3COOOH in C6H N02 there are observed only the 3,310 cm-1 bands: KVC
is either abseng or very weak. At the same time it can be assumed that
MVC takes place in the system CH COOOH + CH30H. In the revaining
solutions WC is not possible . K authors are of the opinion that
the inhibition of the reaction observed in a nxmber of solvents is due
to the hindering effect of the molecules which are joined to the
CH3COOOH by hydrogen bonds.
II.-A 0/0

VSSR/Physical Cheral-stry - Kinetics. Combustion. B-9
Explosives,,Topochemistry. Catalysis
Abs Jour Referat Zhur - Khimiya, No 2, 1957, 3784
Author Sedova M.F. F Doalq~~-
Inst Departrient of, Mienical Sciames, AcadeW of Sciences UISSR
Title Kinetics of Ethane Oxidatiou ii-i the Presence of Hydr-oGen
Orig Pub Izv, AN SSSR, Otd. khim. A., 1.9505, No 6) 65M67
Abstract
Kinetics of oy-qdatioa of C H6 In the presenco of HBr was
a ~s) aiA, O.If-
studied at 205-2450, pro s?Q of 100-200 mi Hr
ferant proporti-or'is of C061 0, and Hbr. The min product
of the reaction is CH 3COOH, aiid its fornation ceasc!s long
before expe&,ituro of the starting mterials, Yiculrl of
""3tcOOH increases with itcreasing co;icemitratiun of Mr,
up -^~4o% of the in,tial
0 15%, and remins corstant (,:
C2fff) on further increase of HBr concentration. Diergy
U
of activation of CH3COO11 form-tion is 23 Kcal/Mia.
Card 1/2 117 -

Category: USSR
Abs Jour: Zh--Kh, No 3, 1957, 7547
B-9
Author : Blyumberg, E. A., Pomanskiy, A. N., and Emanuel, N. M.
Inst : Academy of Sciences USSR
Title : Concentration Limits for Flame Propagation in Mixtures of
Hydrogen and Oxides of Nitrogen
Orig Pub: Izv. AN SSSR, Section on Chemical Sciences, 1956, No 7. 764-770
Abstract: The region of flame pr:pagation in mixtures of H2and oxides of
N? and N. has been determined and is presented graphically; the
mixtures were ignited by a spark. The lower concentration limit
(percent Hz, first number) and the amount of NZ (percent in mix-
ture) required to render the mixture completely insensitive were
found to be as follows: for Nz0, 5. 0, 86. 0, 75. 0; for NO, 11. 4,
60. 0, 40. 0; for an,equflibrium mixture 2N02 N?O , 24. 0, 87. 6,
4 O-NO
60. 0. The region of flame propagation in mixtures of H2_N2
has also been determined.
Card 1/1

CIM 4A1 q e ~ '7 /V.
USSR/ Pbysical Chemistry - Kinetics. Combustion. Explosives. TopochezEstry. B-9
Catalysis
Abe Jour : Referat Zhur - Xhizi~%) No 4. 1957, 11229
Author : Vartanyan L.B., Rhorre D.G., Mayzus Z.K.$ EMnuel' I.M.
Title : Xinfitic'Characteristic6 of n-Decane'Oxi on Formin-vi the initial
Macroscopic Stage of Catalyst Transfor-Astion
Orig Pub : Zh. fiz. kbinli, 1956, 30) No 3., 665-673 (ftalish summary)
Abstract : Co ste6rate a6d -Ma- lauiate which -catalyze oxidati6n of a-de=e'at 1W,
undergo'-Izi the-couisei of'thd r"ction A 6~cle'of valincy-transf6rmations
which Urninates,by a separation-of the catalyst into the precipitate
Rzhftim.. 1955 - 36911- 1956J. 35357)'. *Remo4al of catalyst rrecipitate
)'d6es'not_a'ff6ct alcohols, carbonyl
0
~6*~ouddi' acidi 6~A'eateks._- -Con6entration of peroxide Iiiareases after
renovAl of CP_t6 avalue chiracteristic of'non-catalyzed .o:ddAtion. it
is sh6i& by'palciulati6ris thit-the results obtained can n6t'Oexplaimd in
the icope of*the generally adeepted'ehaiti'schaie -of oxidatton'of"hydro-
carbons, since this d6heme-asii6es'-that'rat6'of accumulation of final
oxidation products) after remolml'of CP, should decrease, and kinetic
1/2

USSR/ Physical Chemistry - Kinetics. Combustion. Explosives. Topochemistry. B-9
Catalysis
Abe Jour ReferatZhur - rhinlys, No 4. 19571 11M
curves approach the curves of non-catALlyzed oxidation. The authors
consider that during the initial macroscopic stage of catalyst trans-
formation there are formed metal-free intermediate compounds vhich
ensure progress of the process at a rate characteristic of catalyzed
oxidation, also after removal of CP.
.2/2

US6W_Fh/si&ffCheP tX/Vities) Combustion) Explosions) B-9
04 ry) ne
Topochemistry, Catalysis.
Abs Jour Ref Zhur - Xhimiya, No 7, 1957, 22396.
Author N. M.-iban=11.
Inst Not given
Title Liquid Hydrocarbons Oxidation$ initiated by Gaseous Catalizers
in the Original Period of Process Development.
Orig Pub Zh. fis khimii, 1956, 30, No 4, 847-855.
Abstract An important consequ6-nca of N. N. Semenov's theory of chain
reaction with degenerated ramification is stressed. 7his
consequence consists in a possibility of efficient conduct of
such reactions after only a short stimulating action, ot the
process in its initial stage of development. The methcd pro-
poeed by the author earlier (R. Zh. Khim 1956, 50223) cV ori-
ginal g-iscous initiation of chain-reactionu of hydrocarloon
oxidation in liquid phase is applied to reactions of n- hexa-
d"cane (I) and paraffine initiated by N02. The rata of for-
maticn. of carbonyl compounds and acids by I oxidation at 1270
increases rapidly upon additions of % which is incoming for
oxidation and 10% Of N02 during the first lo minutes of the re-
Card 1/2 -129-

USSR/Physical Chemistry) Kinetics) Combustion) Explosions) B-9
Topochemistryp Catalysis.
Abs Jour Ref Zhur - Khimiya, No 7, 1957 22396.
action. Further oxidation is conducted by pure 02. Sijailar-
-ly initiated oxidation of the "Kepsen" brand of paraffine
produces an acid number of 70 mg in 24 hours, whereas without
N02 the ruaction doesnot even begin within 370 hours.
Card 2/2 -130-

USSR/ Physical Chemistry -.Xinetics. Combustion. Explosives. Thpochemistrj.
Catalysis
Abe Jour Referat Zhur - Xhimiyap No 4, 1957,, 32231
B-9
AUthor Vartanyan L.S... Mayzus Z.K., Ihmuell N.M.
Title Kinetic Characteristic of HjEBFe_r_oZ1e-9&e Tatermediate Pmlucts of
the Reaction of Oxidation of im-Decane
Orig Pub Zh. fiz. khimli) 1956) 30, No 4, 856-861
Abstract Decomposition of hydroperoxide formed on oxidation of n-decans (1) at
120-1400 was 6tudied-in a medium of 1) oxidized to different extent.
M2e reactio'n in of I-at order i6d values of velocity constant decrease
with increasing extent of oxidation'of 1. Z~ergy of activation of hy
drdperoxide d6c6iposition,'with a constaht:extent of oxidation, is 24
k6al/mole. Compari6on-of aWmtive kinehic-cux-io of the *Ate of for-
mtion of final reaction prcklucts (alciohols, carbonyl-compoiinds., acids
ana'eaters) with,kinbtic dur*jS of Lhydropeioxide deco=positioa rate, ,
shows that the main poiti6n of final oxidation products(- 80%) is for-
med as a result of decomposition of intermediate hydroperoxide.

U-qbR/ Physical Chemistr~y - Kivet$ca. Combustion. Explosives, Topochemistry. B-9
catalysis
Abe Jour : Referat Zhur Dimiyal No 4., 1957,, 1M0
Author : Vartatyan L.S., X%yzus Z.K.) b"UW-L".
Title : On Sequence of Armtion of Oxidation Pro4uate of a-Decane
Orig Pub : Zh. fiz. kbimlip 1956, 30., ito 4) 862-870
Abstract : To determine the sequence of formation of oxidation products of n-decane
use vad made 6 f the kineti6'procedure of removing from the reaction mix-
ture (at a certain moment of the reaction) the intermediate product'of
oxidation :- the hydroperoxide(I). 'Study of the subsequent kinetics of
acemmlation of the final reaction products shove that removal of pero-
xides affects mostly the "kinetics - of forp0ion of alcohols, to a lesser
extent the kinetics.df-carbohyl compounds,, and bAs'piaticall'y no effect
on kin6tics**of acdumaation 6f-the'acids. Trodiiete-of decomposition of
10 formed on oxidation of 'dicAAep &re'ilc*6hols and "carbo4l compoiinds.
Acids are notformed direL-tly'~:6m.-~dedotiposittonrofal~.--)IiMha redUltslobt,&-
ned indicate the foUowing sequence in the formatFon of products:
1/2

TJBSR/ P~ysical Chemistry Kinetics - Combustion. lxplosives. Topochemistry.
Catalysis
Abe Jour : Referat Zhur Fhlmlya, No 4, 1957, 11230
alcohols
ketones--) acids. YAthenatical analysis of the form of kinetic
111111ren of oxidation'proftct accumilation after removal of peroxides,
yields in the case of such a sequence, results that coincide with ex-
perimental data.
2/2

~z
USM/Physical Chemistry - nuetics, Combustion, Explosimsp TOPO-
cbeWstry, Catalysis. B-9
Abe Jour: Referat. Murnal Kbi-Im No 2, 1958, 3855.
Author to To. T. Derd Ov, N.x* Iftnuelf .
j
Inst :Moscow Stat: DaVe3;i-
Title :Mechaulim of Catalysis by Cobalt Srearate at Initial Period
of Cyclob=ane 03ddetion.
orig Pab: zh. fiz. kb-i-ii, 1956.. 30, No 11, 2499 - 2509.

USSR/Physical Chemistry - Kinetics, Combustion, Explosions, Topo-
chemistry, Catalysis. B-9
Abs Jour: Referat. Zhunial KbImlys, No 2, 1958, 3855.
of the initial stage products; additions of cyaldhexanol, (3-35
m-mole per lit) increase the duration of the retarded reaction.
If St2Co conte W crystallization water was added to L the
transition of CoNginto OFand the initiation of the oxidation
process do not take place. The authors think that in the initial
oxidation period a rapidly retarded macroscopic initiating stage
takes place, in which stage Co2+ converts into Co3+ and the latter
catalyzes the further process course. Experiments with different
StpO concentrations and with additions of Co2+ to the developed
reaction indicate that Co2* retards the reaction. In the opinion
of the authors) initiating is not connected with the reaction be-
tween St2O and peroxide, but it occurs with the participation of
the St 2C002 complex with I.
Card 2/2

A-ItMEL, N- 14, Ii'ETIVT, 1-1- B-, IIALIJJVfD=I, A. 1.I..
"Employing the method of labelled atow in studying the successiva
stages of hydrocarbon oxidation," c paper oubmitted at the Internatioral
Conference on Rddioisotopes in Scientific A"%escarcli, Paris) 10-20 $eP 57-

PHM I BW UPLOVATION 439
041
jimovs ILkalq ZkolgeAch
0 tsipn7kh reaktalyah 1 tooril gorenlya (Main lba*ticns and the MwcKr7 Of
CasbustLon) Moscow,, Is"tallaWD Nami".0 Series 8,, Ir 17,, 1W.
31 V. 46j.500 aqpias-prln~ed.
Rot Pspbo3u, 1. Be; Tisch. Xd..e 00in,, Me 1.1 Corrector: Bawr,, 0. 114
FU The pasphlat publicizes No No'Semenov's paper read at the NobeL Prize
presentation ceremony in Stockholm, 1956.
COVERAGS., 7ble paper reviews progress In tae study of eballn reactions. Besearch
van divided into two groups 1) &~pllcatlou of chindcal kinetics to~ Uw tbeory
of combustion sud detanatlont afid 2) study o-f the xechanism of cbaLLea reQc-
time, IA'particular,, chain reactions. The author points out the great contri-
bution of Soviet scientists to the-development of chaln-reactioL coacepto, to
the theory of thexml detonation, and to the general theory of ccatintion. Me
paper covers Western as vell as Soviet achlevementas Mw second part of the
paWhlet is a biography of Nikolay NikolayevIch Benanav written by :Drof.
Semenov's contribution to the theory of chain reactions is the
JUO" ULM=
Card 1/2

. -~ -, z: ~,- ,
- .z r-~;,- -- 7t - - - ;Nr
- IL . - -, ~~ -~
-,- - ~-, ~t ~~. A ~,, -, , , ~ L; ,

AUTMRS: Yruglyakova,, K, Is,, and Emanuell,, Ne Me 62,1,2/21
-------------
TITLEs Kinetic Characteristics of the Reaction of Propane Oxidation with
Oxygen with Chlorine Admixtures in Quartz Crystal Vessels (K4-net-
icheakiye kharaktaristiki reaktaii okislaniya, propana kielorodom
a dobavkwd khlora,v kwartsevykh sosudakh.,
FERIODIGALs Izveatiya Akademii Nauk SSSR, Otdeleniya Ddmicheskikh Hauk, 1957,
No. 11 pp. 18-28 (U.S.S.R.)
ABSTRACT: Investigations were conducted to determine the effect of chloxAne
admixt,ures in oxygen used for the oxidation of propane at various
atmospheric preBat=B and temperatures ranging from 250 to 35510,
It was found that small additions of Cl accelerate the propane
oxidation process and increase the Yield of oxygen-containing
compounds. An increase in temperature from 25C to 3550 is folloved
by a noticeable increase in the amount of peroxides in the oxidation
products and the tire needed for maximum concentration of the peroxides
Card 113

6Z.2m: /21
Kinetic Characteristics of the Reaction of Propane Oxidation wTth
Oxygen with Chlorine AdmixtureB in Quartz Cr7stal Vessels
decreases. The introduction of larger Cl-additions was found to be
impractical because it does not increase the yield of valuable
oxygenous products and the deep-burning processes are stimulated.
The total f.Aount of carbonyl. compounds was determined by tho ordinary
hydroxylamins method and it is shown that the error in determining
the carbonyl compounds, due to the presence of peroxides vbAch also
react with the hydrochloride of the hydroxylamius, was no higher than
3 - 5% of their total content. The content of acetaldehyde., formaldehyde,
organic acids and peroxides machos its maximum within 1 min. The
peroxide, being an intermediate molecular product., is being slowly
consumed, whereas the acetaldehyde, formaldehyde and organic acids
remain unchanged during the continuing oxidation process. TU gaseous
reaction products includet GO2. Go., and unsaturated hydrocexbons. The
nature of the peroxides forming during Cl- catalyzed oxidatiDn of pro-
pane is described as a mixture of hydrogen peroxide of isopropyl and
hydrogen peroxide,
Card 2/3 Graphs., drawing, There are 9 references,, of wbich 7 are Slavic.

6P-1-2/21
Kinetic Characteristics of the Reaction of Propane Oxidation with
Oxygen with Chlorine Admixtures in Quartz Crystal Vessels
ASSOCIATION: Acadevq of Sciences USSR, Institute of Chemical Physics
PUSENTED BYs
BUBK=l june B., 1956
AVAnAMZs IdbrW of GOOM85
Card 313

AUTHOPj EHANUELJ N.M. PA - 2198
TITLE: _1%1-Zh1m1md--ch&in reactions and the processes of combustion and
explosions.(In connection with the awarding of the Nobel Price to
PERIODICAL: Atomnais, Energiia, 1957, Vol 2, Nr 1, pp 61 - 65 N.N.SEMENOV.
Receivede 3 / 1957 Reviewed3 4 / 1957-
ABSTRACTi N.N.3WWNOVt9 discovery of branched chemical chain reactions (espe-
cially the ohainlike inflammation), his general theory of chain re-
actions, his theory of thermal reactions, and the determination of
the connections between combustion, explosion, flame propagatio#1
and the laws for the process of combustion soon found world-wide
acknowledgement. For the investigation and the development of
SEMENOV's new ideas the Institute for Chemical Physics of the
Academy of Science of the U.S.S.R. was established in 1931. The
laboratories of this institute carried out many fundamental in-
vestigations on chain reaotionav processes of combustion, and
explosions. N.N.SEMEWOV carefully investigated long before the
discovery of the chain mechanism of the fission of uranium and
plutonium nuclei, the mechanism of the chainlike ramifications at
chemical reactions. In 1926 SEMENEV and his colleagues detected in
the Laboratory for Electronic phenomena of the Leningrad Physical-
Technical Institute, that during the influx of oxyde into a con-
tainer filled with phosphorus vapor phosphorescence does not-occur
at once but only after reaching a certain "critical" pressure of
Card 1/2 oxyde. This threshold of the pressure also depends on the diameter

A 2198
The chemical chain reactions and the processes of combustion and
explosions.
of the reactor. Besides, the reaction in systems with dimensions
which are smaller than certain "critical" dimensions ,,annot ac-
celerate by itself to an explosion. SEMENOV explainer; this be-
havior with chains of chemical reactions. The notion "critical
diameter" in the case of ohainlike chemical reactions fully cor-
responds to the notion of the "critical dimension of the reactor"
in nuclear physics. In this theory the idea on the breaking off
of the chain on the walls of the reactive container and inside the
reacting mixture was formed. The loss of free %tome and radicals
which causes the breaking off of the chemical reaotion chain is
completely analogous to the looses of neutrons during nuclear
chain reactions. '1hese numerous investigations of the Institute
for Chemical Physics prove the frequent occurence of chain re-
.actions in chemistry. SEMENOV proved the general theories of chain
reactions very thoroughly by experiments. Besides, he set up a
Card 2/2 theory for the interaction of chains. In conclusion scme examples
and applications are discussed.
ASSOCIATIONt Not given
PRESENTED BYt
SUBMITTEDt
AVAILLBLE: Library of Congress.

I ---- , - -
,~A- 111,41V 61 e Z; /4/. A/I
KNORRI, D.G.; LYASKOrSKAYA. Th.l.;
Oxidation kinetics of fats. 1xv. AN SSNR Otd. khtm. nauk no.6.-678-
683 Jo 157. (MML lotil)
1. Institut
dovatellskiy
khIsdaheskoy f Wki AIT SSSR I Yessoyunyy nauchn*-ionle-
institut Wasuoy provVehleimosti,
.(Mle and fats) (Oxidation)

BLTJKEW#4e`eA.,;mVifiIL1TV, Tolol 2KANEMLIt- M.''.
3iffect of hydrocarUn, O"ne ou the. concentration limits of
flame spreading in gas mixturas containing hydrogen. Isy. AN SSSR.
Otd, khime nauk no.10:1172-1180 0 r57, (MM. 11:3)
191astitut khtmicheekey fisiki AN SSSR,
(Combustion) (4drocarbons) (Inhibition (Chemistry))

A#THORt Emanuel, I He me 62-11-3129
-
TITLEt Now Problems in the Field of Chain Reactions (NOTYY9
problemy v oblasti tsepuykh reaktsiy).
PERIODICAM Izvestiya AN 833R, Otdelenie Khimicheskikh Nauk, 15-57P
Nr 11, pp. 1298-1313 (USSR)
ABSTRACTt The following can be Baid based on the survey given her&.
Many properties and partioularities of a branched obain
process can serve as fundament for elaboration of new
principles for the controlled execution of the oxydation
prooesses of hydrocarbons. The capacity of the degenerated
branched chain reaction in the oxydation of hydrocarbons
In liquid phase for self-maintaining and self-accelerating
development offers the possibility to stimulate these
reactions by means of influence for a short time of gas-
initiatoral penetrating rays, malt-oatalysts and the like
in the initial phase of the process development ("taking
away" the induction period)* In homogenous catalycis
(induction) of the-oxydation processes of hydrocarbons the
phenomena of a reaction process are distributed according
Card 1/2 to ph&sosp in the form of successive# chronologically

low Problems in the Yield of Chain Reactions. 642-11-3/29
seyarstgat macroscopic phases, In some cases an smalogical
process according to phases also becomes manifest in non-
catalyzed oxydation* Additions of negative catalysts
(inhibitors) can have a different effect on the development
of then* phases* In connection with this high differeno*e in
the mode of action of the inhibitors can occur whod
introducing them into the initial and the reacting mixture.
The presence of chronologically separated macrosoopio phases
permits to direct the oxydation processes by modification of
the conditions after the reaction proossel with transition
from one macroscopic phase to the next. There are 12 figures*
ASSOCIATIONt Institute for Chemical Physics of the AN USSR (Inatitut
khtmiohookoy fiziki Akademiii nauk SSSR).
SUBMITTEDs September 171 1957-
AVAILABLEt Library of Congress
Card 2/2

&J':
IKANLMLI II.M.., professor,
Nobel prixe'winner Academician Nikolgi Hikolaevieh Semenov.
YestAosk.". 12 no.1:18~-187 '57. (MLRL 10:8)
(Semenov, Nikolai Hikolaeviob, 1893-)

Fjvj6NUE_LJ%, N-M
AUTHORs EMANUEL NW PA - 2618
TITLEt -V-5-hYr-lbutivil-of the Development of Chemical Physics.
On the Occasion of the 25th Anniversary of the Existence of the
Institute for Chemical Physics of the Academy of Science of the
U.57S.R. (Vklad Y rasvitiye khimioheskoy fiziki. K 25-letiyu
Institute, khiaicheskoy fisiki Akademii Nauk SSSR, Ru Ian)
PERIODICALs Vestnik Akademil Nauk SSSR# 1957, Vol 27, Ir 3, pp 6;:- 81 (USSR)
Received, 5 / 1957 Revieveds / 1957
ABSTRACT: In his article the author mentions the revolutionizing effect pro-
duced by the progress recently made in physics in various fields.
The work performed by the above Institute is described as consisting
in "making physics the basis of socialist industry and technical
engineering In the U.SeS.Re". The institute began vtork at Lenin-
grad in 1921 as an independent.State institution under the name
"Leningra d State Physicel-Technical Radiological Institute
(GFTRI - Gosud4rstyyonVy fiziko-toohnicheakiy ryentgyenovskiy
Institut) under the management of A.F.1offe, member of the
Academy. The laboratory for electron chemistry, vhi.ch van establish-
ed at that time under the management of N.N.Syemyenov, is de-
scribed as the most important department of that Inst;tute. A short
outline of the history &n& of the achievement@ of the institute
(1921 - 1956) is given. It was incorporated in the Academy of
Card 1/3 Science in 1939. The first work carried out under the supervision

PA - 261e
Contribution to the Deveopment of Chemical Physics.
of N.N.Syeayenov concerned the investigation of electric fields#
the analysis of electric breakdown in the vacuum and in guess.
Later, the host theory of combustion, and explosion processes was
developed and research work was carried out in the fields of con-
densation, adsorption, polenerization, and colloidal chemistry.
In the period of 1925 - 1928 important discoveries were made under
Syemyenov with respect to combustion of phosphorus gases under
pressure, and the theories of "critical pressure", "chain explo-
sions", and the general theory.of combustion processei were do-
velop1d. The work performed by the Institute in 1931 is described
as particularly important because it was at that period that the
Institute gained a leading position in world science by its scienti-
fie research work in the field of chain reactions. In 1934 N.N.
Byemyenoy published a monography on "chain reactiors" which
attained world fame. It was followed by the vionography on "Some
problems of chemical kinetics and some properties of reaction",
in which W.N.Syemyenoy mainly dealt with the investigation of the
mechanism of chemical reactions, for which he was awarded the Nobel
Prize in 1956. Following a suggestion made by N.N.Syemyenov the
first research work in the field of nuclear physics, the formation
Card 2/3 and adsorption of neutrons, the metastability of the excited

Contribution of the Deveopment of Chemical Physics. PA - 2616,
nuolene't *to were beiun in the U.S:S.R. The Institute is
continually being extended# partioularly.by soliciting the servi-
ces of the most talented scientists of the countryl and is ex-
peated t6 make a great contribution towards " enhancing the
glory and the power of the U.S.O.R.".
ASSOCIATIONs Not given
PRESENTED Bri
SUNITTEDi
ATAILLBLEt Library of Congress
Card 3/3

ZXANULI N.M. professor.
Important contribution to world science; award of the Kobel Prize
to Academician K*N.Semenov. Priroda, 46 no.2:43-0 7 '57. OILHA 10:3)
19 Institut khImichaskoy fisiki Akadsvii nauk SSSR (Moskva)
(Sesenov, Nikolai Nikolaevich,1893)

. XKAMLIp N,*)I,o, professor@
~Ivl on an the mechanism of chemical reactions* Pr1roda
w
46 ne.3344-48 Xr. 157. (KM 10:3)
1. Institut khimicheskor fisiki Akademil navk SSOR (Xoskya).
(xinshelvood, Cyril. 1897-)

EMHNUt-O~ N. MI
KHDRRI, D.G.; MATZTJS, Z.K. L==h"
Activation enorgy of the elementary reaction RD2+ RH in the
1 oxidation of n-decans. Dokl. AN SSSR 112 no-3:457-460 Ja 157.
(MLRA 10.- 4)
I* Predstavleno akademikom V.N. Kondratlyevym.
(Chemical reaction.-Hechanism)
(Decane) 1 01.

I-Ito W!~/52
AUTHORSo Emanuell-g Xt Me I Denisovo Yee To
TITLEt fteoratical Possibility of Oxidation.of Benzene to Phenol
in the Liquid khaeo (0 printaijil:.tl1noj vo"ozanosti zhidkofaznogo
okieloniya benzola v fenol)
PERIODICALo Doklady AN SSSRt 1957, Vol* 1179 Nr 39 PP. 458 - 461 (USSR) -
ABSTRACTs Tho authors he're endeavor to do Sermine the oxidation of benzene at
temperatures of from 230 - 270 and at a pressure of 50 atmospheies
Experiments were carried out in an autoolave device for the oxida-
tion of hydrocarbons in the liquid phase under pressure. At each
experiment 200 mm of benzene were introduced into the reactor. Oxi-
dation was carried out by the oxygen of a nitrogen oxygen mixture
with the composition i t 1 . During this process samples were taken
of oxidized benzene and were analyzed with respect to their phenol
content@ With a photocalorimeter also the optical density ofthe
oxidized b-nzene was measured, At 2500 oxidation of the benzene in
the liquid phase takes place with noticeable rapidity. With the
oxidation of benzene phenol and resins are produced. The kinetic
curve of the accumulation of phenol is of S-like character. How-
ever, the maximum concentration of phenol in this prooess amounts
Card 1/3 to.criy 0,16 mol percent, In the oxidation of benzene with cobalt

20-% 52
,11heoretic&l'Possibility of Oxidation of Benzene to..Phanol
.:Lu Us Liquid PMn
stearate this oatalyzer directs the reaction into the direction of
the oondeneation of benzene with the production of soot; only small
quantities of phenol are produced on this occasion. Small quanti-
tioa of easily oxidizable substances such as cyclohexano and cycle-
hexanon accelerate the oxidation of benzenes The corresponding ki-
netio ourves-are given. The experimental data obtained here con-
cerning the oxidation of benzene tend to show that this process
is a chain-like degmerated~ ramified, self-decelerating reaction.
The experimental data agree well with a mechaniamt which is do-
scribed in detail. The present pqper proves that, in principle,
it is possible to attain the oxidation mentioned in the title at
temperatures that are near critical temperature. "The-principle
of gas initiation applied on this occasion furnished the best re-
sults. The proceesee.for the removal of the self-slowing-down of
the processes will have to be examined. There are 3 figures and
4 referencesp 3 of which are Slavic.
Card 2/3

20-3-28/
52
.2heoretloa ft#11b131V of 0,44Afton of lknzezw to Phenol in tbe
.14qcdd FmAe-
ASSOCIATIONs Institute for Chemical Physics AN MR
(Institut khimichesk6y fiziki Akademii nauk SSSR)
MSBYM# may 15, 19579 by N. N. Semenovq Academician
SUBMITTBD# May 15, 1957
AVAILABLEo Library of Congress
Card 3/3

~F (VIA The ametical A"toty it uw am mid its afta mattimc 20 Qlt.-I Now. 1956 two tolovig.
nw (4114"Lag Papers Imm presm"d 6r 04 a" W*Otlm
F. fuse" old A. Ismis - hq*Loo Ano., VW 1?Mtodo"mLsobs Amissfam dw
Obort2sedw win
To. ShUvw m# A. Tamtkof - JANS. -rcomis OWmIltry, AS OU -W"r den 4ebmalawas
der astolytisebm "Is& was 4suosearem in dom Oventonam der tirtymolverbindmorm.0
A. Obekhtor - Ames. bvis"Ifig Aaf~tm, U VW 'lap Ilektrommalkro"to boteralmor
It. 4MIC41 haste*, AS WU 6110wome OSWYM mat Chwmtocbo Andmitt"S
be, P.Am
A. To. prowaskup last. owegical & f4dual owatts AMS UU 'Alliewbe Prove
der bialsomebeft 14taly" to AIe" der wirkwrolso diMMAISR-ros.
1. failke"Mon - JoO. N01841 %WSUT, AS OU $Zkr laaktromeatho"ris der Qwd-
forptias led lately" a R4bL*IMM.*
1. Ifivaskly MMY. Voye"dakly - AW. Qlasioal hyetes. AS NU Itloor des ftchostams
Staiser AstalrUfther AsodrUeaft t1a as r4ledimmometAU StOr MILUUICag M Wailrostaft
.orlimatoW
0. 9. Ibropbor - Amarew ftstoodAmodeal Use, $asom "Weaboalwirtmag swiftban 4tayeater
us Al*tUw"T%-m.
A.* A. SaImAM AI OU 91ps AWb" agg"Itsuearis der, hotsjyft.~
901 MUSSUSAIdANAAL "ban As der M. loodsturs. 1959.
Q-A

a ff) A /V L&
LI

50)
AUTHORi FmanUell _ N-M-j, Corresponding Member, SOV/55-58-5-1/34
cadeMy of Valences , USSR
TITLEs Chemical Science on the Threshold of new Tasks (Khi.micheakaya
nauka na poroge.rovykh zadach)
PFMODICALs Vesinik Moskovokogo universitet&,Seriya Wsmatiki khmlklo
&Atronomilj, ftzildq kbkI41958,Nr 59 pp 3 - 6 (USSR)
ABSTRACTs The author writes on the tasks which arise for Soviot chemistry
from the resolutions of the 21-th Conference of the Comunist
Party of.thiUSSR. The chemical production is to be trebled
during the following seven years. The production of synthetic
substances from by-products of petroleum hauling, particularly
the application of hydrocarbon gases to the production of
rubber and fertilizers is to be increased extensively. Tn this
connection the scientific aounail of the Chimioal Department of
the Moscow University concluded the research of the synthesis
.and of the properties of the monomer, of tho polymer aff well
as of the highly molecular combinations$ the foundation of a
laboratory for condensed ("frost-bound") radicals, the en-
largement of the laboratories at all, and the increase of the
Card 1/2

Chemical Soience'on the Threshold.of now Tasks SOV/55-58-'5-1/34
standard of education of new chemists, For several times the
author refers to the theses of N.S. Khrushchev.
Card 2/2

- -E-KIWIrWO K. M4 (correspondent -members AS USSR)
"New Investigations in the Field of Chain Reactions."
Lecture to be delivered by Soviet Scientists at the Brussels Exhibition,
August 1958- The delivered lectures will be available in English, French,,
Flemish and German as Individual brochures.
(Priroda, 1958, No. 8, p. l16)

SOV--3,58-e -3126
AUTHORt Eman1t&1JT-4h*-., Lenin Prize Laureate, Corresponding Member
of ihe USSR Acadewy of Sciences
TITLE: Important Questiona of Higher Education in Chemis-,ry
(Vazhnyye voprosy vysshego khimioheskogo obrazovaniya)
PERIODICAL: Vestnik vyeshey shkolyt 1958, Nr 8, pp 11 - 19 (USSR)
ABSTRACTt During the Soviet regime chemistry has reached a high level,
but still does not meet the requirements of the national
economy and the chemical industry. In the production of
artificial and sythetic fibre, plastics and other synthe-
tio materials, Soviet chemical production is still be-
hind. It is of utmost importance to intensify scientific
research and experimental work in this field. Th-i teach-
ing of chemistry does not pay sufficient attenticn to the
up-to-date subjects (petrochemical synthesis; the problems
of high molecular compoundsl the theory of chemical pro-
cesses)~and the relations between chemistry and paysioa,
biology and medicine. The chemistry faculties shDuld pre-
pare more qualified research chemists. Every ahe:nist
Card 1/2 should have a command of quantum chemistry and el3etronic

Important Questions of Higher Education in Chemistry BOV-3-58-8-3/2f
calculating devices. The program of the faculties shculd
also contain subjects such as biochemistry, biophysien
and medical chemistry.
ASSOCIATION: Moskovskiy gosudarstvennyy univereitet imeni M.V. Lomcno-
sove(Moscow State University imeni M.V. Lomonosov)
Card 212

AUTHOR: Emanuel N.N.9 Holder of the Lenin Prize, SOV/29-58-lo-11/28
-ToMr'Maponaing member, Academy of Sciences, USSR
TITLE: Scientists Greet.the Komsomol t(Uchenyye privetstra)-ut
komsomol 00hemistry as Eobby (Lyubite Khimlyu)
PERIODICAL: Tekhnika,molode.zhi, 1958, Nr 19. pp 12 - 12 (USSR)
ABSTRACT: Among other things the author writes: Within many
centuries mankind took the goods from nature which
were used in an almost unchanged form. Thanks to the
work of several generations of chemists about 300 000
simple and complicated substances - chemical compounds
of the inorganic, lifeless matter could be discovered.
When scientists, however, started their experiments with
the living naturej e.g. organic substances they were faced by
unlimited, unexpected and inexhaustible possibilities.
More than 3 000 000 chemical compounds are already known.
Today chemistry is the most fascinating field of zcience.
Chemistry supplied man with everything he needed !.n the
course of social development and with which he waa not
supplied by nature. Chemists started to create nature
Card 1/2 once over. They produced substances which had not been

Scientists Great the Komsomoll Chemistry as Hobby SOY/29-58-10-11/28
known beforei and those substances had wonderful and
strange properties. Chemistry has a great future . Without
exaggeration it may be said that the twentieth century
is not inly the century of atomic power, of electronics
and exploration of outer space but just as well the
century of chemistry. With full conviction scientists may
invite young people to devote themselves to chemistry.
"You wbalt be-'aorry- *since you will enter a field of
wonderful transformations, a field where man starts to
areate another nature". That is how the author closes hiq
paper. There is 1 figure.
Card 2/2

- -. -
__ - -- ~4. - M__ -
BOV/62-58-12-4/22
AUTHORS: Knorre, D. G., Lyaskovskaya, Yu. N., Piultakaya, V. I.,
__EmanuvT+-,-N-;--Mi -
TITLE: Inhibition of Oxidation Processes of Fats by Ascorbic Eaters
(Tormozheniye protsessov okielen-'ya zhirov efilrami askorb-4novoy
kisloty)
PERIODICAL: Izvestiya Akademii nauk SSSR, Otdeleniye khimicheekikh nauk,
1958, Nr 12, PP 1422-1427 (USSR)
ABSTRACT: In the present paper the antioxidation properties of ascorbyl
palmitate 'and of mixtures of ascorbyl, palmitate with tort.
butyl oxy-anisole in the oxidation of molten lard by means of
an accelerated kinatio-oxidation method at increased tempera-
ture (Ref 3) was investigated. The possibility of substituting
palmitio
acid in the production of antioxidants by a mixture
.
of n. acids obtained in the oxidation of paraffin was also
determinod. It was found that ascorbyl palmitate in a mixture
with tort. butyl axy-anisole can effectively maintain thE,
oxidation procesues af melted animal fats caused by atmospheric
oxygen. The substitution of palmitic acid by a mixture of
Card 1/2 synthetic fatty acids (fraction C 14-C 16 ) doea not exercise any

SOV/62-56-12-4/22
Inhibit,ion of Oxidation Processes of Pats by Ascorbic Esters
unfavorable effect on the antioxidation properties of the
preparation in the production of ascorbic ester. The efficiency
of the mixture of 0.01% tert. butyl oxy-anisole and 0.02%
ascorbyl palmitate as an antioxidant of molten animal fate
does not depend on temperature* There are 7 figures, 1 table,
and 21 references, 2 of which are Soviet.
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR (Institute of
Chemical Physics Academy of Sciences USSR) Vsesoyuznyy nauchno-
-iseledovatellskiy institut myasnoy promyshlennosti M i MP
SSSR (All Union Scientific Research Institute for Meat Industry
MPM and MP USSR)
SUBMITTED; May 22, 1957
Card 2/02

~" NKOMO, N.M.
Chemical science on the threshold of now problems. VesteMookoune
Beremateemakhopastronelfist,khim, 13 U0,50-7 138. (IIrRA 12:4)
1e Chlen-korrespondent AN SSSI.
(chemistry)

AUTHORS: Deniaovj le.T., Emnuell , N.V. (Moscow) 74-27-4-0
TITLE: The Effective e am of the Inhibitors in Chain Reactions of
the Liquid Oxidation Phase (Hekhanizm deystviva ingib4.torov v
tsepnykh reaktsiyakh zhiakofaznogo okialeniva)
PMIODICkL: Uspekhi Khimii, 1958, Vol. 27, Nr 4, PP- 365-402 (USSR)
ABSTRACT: The report begins by dealing with the importance of inhibitors and
the research work carried out in this connection duririg the pa3t
decades. Mention is made of the works by Muro and Dyuf'res (Ref 7)
on antioxidation. After the function of inhibitors ha~, in their
general outlines, become known and the chain theory supplied re-
latively simple formulae for the description of slowirg-down ef-
fects theoz,etioal intere3t in inhibitors began to die down. It was
only recently -that one of the authors of this paper pointed out
that in numerous maes oxidation processes have a far more compli-
cated mechanism than that of the slowly growing and ramified chain
avalanche. The present survey is devoted to the analysis of the
chemical effective mechanism of inhibitors and to the theoretical
interpretation of and the particular effect exercised by inhibitors
on the basis of the theory of chain reactions with deginerateJ
Card 1/3

The Zffective Mechanism of the Inhibitors in Chain 74-2-,1-4-1/8
Reactions of the Liquid Oxidation Phase
ramifications u devslopea by Semenov. The report is divided into
the following parts: The chain mechanism of the oxidation of hydro-
carbons. The "chain-interrupting" chemical effect exercised by in-
hibitors; on the separation of the H-atcm from the moJecule of the
admixture InH; on the connection of the free radical uith the mole-
cule of the admixture Q; the mechanism of the inhibiting effect of
phenols; the mechanism of the inhibiting effect cf amines. The
next chapter deals with the kinetic characteristic of the affect
exercised by inhibitors: 1.) The theory of the effect-Droduoed by
strong inhibitors, 2.) The theory of the effect praduc'..a by weak
inhibitors. - The following chapter deals with antioxillizers which
exercise a retarding effect upon the velocity of degen )rated rami-
fication. Mention is made in this connection of the de;ttruotive
effect exercised by sulfides upon hydroperoxides, of the problem
,concerning the modification of the kinetic curve of ox-aation of
hydro=bon, of the slowing-down effect produced with ,!espect to
.the oxidation process of alkeLline substances and acids, In conclu-
zion the report deals with the joint effect produced b.,i- 2 anti-
Card 213 oxidizers. In this connection the fact is stressed tha- the joint

The Effective Mechmniem.of the Inhibitors in Chain
Reactions of the Liquid Oxidation Phase
effect produced by two-substanceg which are able to Ieatro*y
peroxides can often produce a greater effect than mAF bo aasuud
on the strength.of the rule of adaitivity. There are W figures,
6 tablea, =d 61 references, 23 of which are Soviet.
14"Ohdn reidtidfib~lnhibition 2. Oxidation inhibi-=a-Analyais

IKANMW, No' doktor khiionauk; EMU, Do, kandekhim,nauk; LTASIOTSILUO
kanil.takhoonauki PIUMSKAU, To, inzh.
ImWoving the stability of animal fate with antioxidants. Mao.
ind. SSSR 29 no.2:52-55 158. (MIRA n:5)
1.1notitut khimichaskoy Iftild AN SSSR (for Imanual, K=rr,q).
2,Vsasoyuznyy nauchno-iseledovatellskly inetitut mysenoy IrroxVehle=
promyshlonnosti (for IWaskoTakaya, Plullskays).
(Oils and fate, Witle-Preservation)
(Antioxidants)

5W
SOV176-:32-10-2Y39
AUTHORS: Denisovj Ye.T.r-F
TITLE: The Liquid Phase oxidation of Benzene to Pbenol at
Temperatures Close to the Critical Point (Clcislenije
benzola v fenol v zhidkoy faze pri temper-aturakh, bliz-
kilch k kriticheakoy)
PERIODICAL: Zhurnal fizicheakoy khimii, 1,9589 Vol 32, Nr 10,
pp 2374 - 2382 (USSR)
ABSTRACT: In an earlier palvr (Ref i) it vas pointed out th,-~,t
a series of high-temperature oxidations can be carried
out in the gras phase at low temperatures, and in
the liquid phase. In the present paper the oxidation
of liquid benzene is carried out at 230-2700 (espocially
at 2500) and at a pressure of 50 atmospheres abso:lute
pressure. An autoolave-serving for the inve-lGation
of the kineticB of processes in liquid phase (Ref~5)
was used. Benzene oxidizes in the liquid phase rnther
rapidly at 2500; phenol and resins are formed as
reaction products. An addition of 2 mol~61 cyclohexane
Card 1/4 causes an acceleration in the process# whereas 1 mol%

The Liquid Phase Oxidation of Benzene to Phenol at SOY/76-32-10-21/39
Temperatures Close to the Critical Point
oyclohexanone shows a still stron,er effect. The
addition of 0,15 mol'i't cobalt otereate led to the
opposite effectf i.e. a small forrlation of phenol
took placelhowever, with a large formation of soot.
Experiments carried out with gas injections yielded
the best results when nitroCon dioxide was used.
flitrobenzene was qualitatively determined among the
oxidation products in thiu case. The interruption
of the gas passage leads to a slowing do-,m of the
reaction so that a stimulation by nitro.,ren dioxide
should take place throughout the oxidation process.
-It in assumed that benzene oxidizes also in the
liquid phase according to the chain mechanism. The
.maximum phenol formation depends on the self-im-
pedance of the benzene reaction.The present reaction
in considered in relation to the theory of chain
reactions by K.N.Semenov (Ref 9), and the experimental
data obtained are compared. The self-impedance of
the chain reaction is explained by the accumulation
Card 2/4 of products that inhibit the reaction by ar, exchani,-,e

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

2o-119-6-37/56
AUTHORS: 'Emanuelly No Mop Blyumberg# E. A., Zivy Do Mot Pikayevap V.L.
TITLE: The Initiating Effect of the Radiation of Radon in the Process
of the Oxydation of Isodeoane (297-Dimethylootane)(Initaiiruy-
ushoheye doystviye islucheniTa radona v protsesee okieloniya
izodekana (2t7-dimetiloktana)
PERIODICAL: Doklady 1kademij n-%uk SSSR, 1958P Vol. 1199 Ur 6,
pp. 1183 - IiS6 (USSR)
ABSTRACT: The application of the radiations of radioactive gases for the
initiation of chain reactions can be very effective ana this
not only in slow chain reactions in the liquid phase. Besides,
the application of radioactive gases allows interesting ex-
periments with chain reactions in the gaseous phase. This work
uses as test object the oxidation of isodecane (2,7-dimethyl-
octane) on the notion of a-particles of radon. The authors star-
ted from the fact that the processes of the oxidation of the
hydrocarbons in the liquid phase represent degenerate-branched
chain reactions. Therefore ouch processes can be stimulated only
Card 1/3 in the initial period in the development of the process. The

Tge'Initiating Effect of the Radiation of Radon in the 2o-119-6.-37/56
Process of the Oxidation of Isodecane(2#7-Dimeth.Tlootane)
action of radon radiation leads to the occurring of active
particles (free radicals and atoms), i. e. to the Increase of
the initial velocity 'of the production of the chain;3 woo The
experiments were made in a glass device with oxidation cell.
The device and the performance of the experiments axe illu-
strated by a figure. 2 diagrams illustrate the curvas for the
accumulation of the peroxides and acide in the oxidation of
isodeoane, initiated by a-radiation of radon ( and also by the
a-and P-radiation of the decay products of Rn). The short sti-
mulating action of the radon radiation is enough for a consi-
derable decrease of the induction period in the production of
the h.ydro-peroxides. Also the maximum yield of the ?eroxide
compounds is increased. The very strong increase of the production
velocity of the active centers must lead to a considerable
diminution of the induction period, which also expe:^imentally
is observed. Still more effective is the action of the a-radia-
tion of Rn upon the reaction velocity after the end of the in-
Card 2/3 duction period. The autho-rs thank V. M. Vdovenko fo= his inter-

Tirg-Ihitiating Effect of the Radiation of Radon In the 2o-119-6-17/56
Process of thelOxidation of loodsoane (2#7-Dimetbylootane)
eat in this work and V. M. Permyakov and his collaborators
for the production of the radon preparationa used in this work.
There are 3 figures and 3 referencest 3 of which are Soviet.
ASSOCIATION: Institut khimichaskoy fiziki Akademii nauk SSSR (Institute of
Chemical Physics AS USSR)-Radiyevyy institut Akademil. nauk SSSR
(Radium Institute AS USS4
PRESENTED: December 28t 19579 by V. ff. Kondratlyev, Member, Academy of
Sciencee" USSR
SUBMITTED: December 25, 1957
Card 313

AUTHORS: Knorre, D. G.9 PikayeYat V* L., SOV /2o-12o-l-;!8/63
Smanuelt, N. M.
TITLE: On--f-h-e -Role Played ~y the Unsteadiness of the Procesc in the
Stimulation of the Deaenerated Branched-Chain Reactions in the
Liquid Phase (0 roli nestatsionarnosti protsessa pri stimuliro-
Yanii vyrozhdenno-razyetrlennykh tsepnykh reaktaiy Y zhidkoy
faze)
PERIODICAL: Doklady Akademii nauk SSSR, 1958t Vol- 12o, Nr 1,
PP. 107 - 110 (USSR)
ABSTRACT: In the present paper the kinetics of a chain reaction with
degenerated dislocations and quadratic disconnection of the
chains are calculated, taking into account the unstendiness of
the processin the initial period of development of the process.
The problem of the influence of the duration of initiation on
the Initial stage of the reaction, mainly on the dur!.tion of
the induction period, is of basic importance. Therefore the
calculation is carried out without taking into accownt the con-
sumption of the intermediate product which begins to exert in-
Card 1/4 fluence on the kinetics of the process only in the deeper phases

On the Role Played by the Unsteadiness of the soVI 2o-12o-1-28,63
Process in the Stimulation of the Degenerated Branched-Chain Reactions in the
-Liquid Phace
of the transformation. It is further shown that the brfsking
is realized by the recombination of the radicals noi p which
as a rule takes place at oxygen pressures close to atmcapherie
pressure. On these conditions the system of equatiom describing
the kinetics of the filling of the intermediate product has the
form
d CRO~2 + kp [ROOHJ - k [R0;] 2, d 1111 - k [1.0~ [RR]
dt 0 recomb dt
k or kv respectively, denote the constants of thit recom-
recomb :
bination velocity of the radicals N~ and of the propaE:ation
reaction of the chain:ROi + RH --~ HOOH + R* . These differential
equations are transformed by the introduction of dimen!.ionleas
variablesp and then are integrated. The discussed calcvlation
was carried out for'a model ramification of a paraffin, theiso-
decane.,A diagram shows the kinetic curves of the accurulation
of hyd ogan Iperoxide calculated for the cases k recomb /k*. 103
Card 2/4 and 15 9 as well as the curves calculated by

On the Role Played by the Unsteadiness of the soy2o-12o-1-28/63
Process in the Stimulation of the Degenerated Branched-Chain Reactions in the
.Liquid Phase
using the condition of the quasisteadiness. In either case
qualitatively similar renults are obtained. The calc%Jation
carried out on the condition of the quaoisteadiness cf the process
supplies a completely wrong impression on the intensity of the
action of the initiator on the kinetics of the oxidation. The
rigorous solution of the system of differential equations for the
kinetics of the accumulation of the intermediate product in the
reactions of the oxidation of the chains with quadratic breaking
makes possible the explanation of the experimentally Dbserved
induction periods and promotes the understanding of tie effects
of the initial stimulation of these processes. There are 3
figures and 11 references, 9 of which are Soviet.
PRESENTED: December 25o 1957, by V.N.Kondrattveyl Member, Academ:r of
Sciences, USSR
SUBMITTED: December 22, 1957
Card 3/4

AUTHORS: Emanuel's N.. M., Lipchina, L. P. SOV/2o-121-1-40/55
TITLE: Leucosis in Mice and Some Characteristic Features of 1;9
Development Under the Action of Certain Inhibitors of Oxidizing
Chain Processes (Leykoz u myshey I osobenno.sti yego ra:ivitiya
pri Yozdeystvii ingibitorov tsepnykh okislitelinykh pr;3taessov)
PERIODICAL: Doklady Akademii nauk SSSR,.1.958, Vol. 121, Nr 1,
PP- 141 - 144 (USSR)
ABSTRACT: The progressive development process of a malignant ulcer is
very similar to the course of a unsteady chemical procesep e.go
of the branched chain reactions (discovered by N.N.Samenov,
Ref 1), It is possible that the observed similarities are based
upon the similarity of the nature of the active intermediate
substances responsible for the self-accelerating type of
processes In vivo and in vitro. The active centers of the chain
reactions yield the free radicals. In the slowly progressing
(not explosive) branched chain reactions furthermore inter-
mediate substances are formed which decompose sometimes under
formation of free radicals. Consequently degenerated (retarded)
Card 1/4 ramifications are formed and the process is only to a small

Leucosis in Mice and Some Characteristic Features of SOV/20-121-1-40/55
Its Development Under the Action of Certain Inhibitors of Oxidizing Chain
Processes
extent accelerated with respect to time. Certain data exist
on the fact that the free radicals and the chain reactions
play a Ale (Ref 2) in the mechanisms of several bioc,.emical
processes. It is especiall important that the reactions of
a biological (fermentative5 oxidation which produce the
energy necesaary for the growth of the malignant ulcer are
considered from this point of view. We may also assumo that
the free radicals in the biosubstrate stimulate the r4dical
(chain-) reactions and thus represent in many cases the
mechanism of cancer formation. A number of proofs of ~;his
assumption is given. All this leads to the conclusion that it
might be expedient to act upon the malignant ulcers br the
introduction of substances which react easily with fr,!ie radicals
(chain breakers)q Stron% non-toxic inhibitors of the oxidizing
chain reactions (nutrition antioxidants): 1) Butyloxy-anisol
~(Isomeric mixture); II) jonol (2,6-di-tert. butyl-4-m3thyl
phenol)l III) Propyl gallate and others were tested tj the
authors as such substances.Leucoses with acute course which
Card 2/4 can be re-inocculated (perevivayemye) were used as disease

Leucosis in Mice. and Some Characteristic Features of SOV/2o-121-1-40/55
Its Development Under the Action of Certain Inhibitors of Oxidizinig Chain
Processes
in mice suffering from severe leucosis of the line alb,
rate 31 IV,: and in the mice of the line 0 , race 31 A which
were practically immune from leucosis. T21 latter was
achieved by the re-inocoulation of leucosis which was caused
in the 10 mice by'x-ray irradiation. The healthy control
animals ald not show dyspepsy or other pathological changes
after a single administration of the preparation. In them
afb m.iole. which w.ere~.8. weeks old a pXol.ongation of life and a
hep;ling of the leucosis pr9cess.was oVserved. After 14 days
.the blooO was.opmpletely normalized-The pured mice were
immune from furtherjeucosis Inocculations.-If the above
mentioned facts turn out to be right,we may expect that the
class of chemotherapeuticewill be effective in a va-st,range
of mAlignantiulcers. Ye.Ye.Pogosyants (Institute of 'Experimental
Path *ology and Cancer Therapeuties,kcademy of Medical Sciences
'USSR - Institut ekSDerimental"noy patologii i terapii rqka
ANN SSSR) placed specimeng suffering from leucosis at the.
Card 3/4 authorte'dispoeal. There are 3 figures and 5 references, 4

Leucosis in Vioe.and Som~,Characteriatio.Features of SOV/2o-121;-1-4o/55
its Development-Under the Aotion of Certain Inhibitors of Oxidizing Chain
Processes
of which.are Soviet.
ASSOCIATION, Institut khimicheakoy fiziki Akademii nauk SSSR (Inatitute,of
Chemical.Physics.)ALS USSR) Laboratoriya anizotropnykh struktur
Akademii nauk SSSR (Laboratory 'of Anisotropic Structures AS
USSR)
PRESENTED: May 69 19589 by K.N.Semenov', Member,'Academy of Sciences, USSR
May 5t 1958
l.-Leukemia-Therapy. 2. Cancer res6arch-USSR 3. Chenotherapeutic
agents"Development 4. Chemotheialleutic agents--4Materials
5. Chemotherapeutic agents--Teat results'
Card 4/4

514)
'AUTHORSt Knorre, D* Gp Mayzue, Ze Kap SOV/20-123-1-3~/56
Emanuel19 N. M.gCorresponding Member, Academy of Sciences# USSR
TITLEs On the Rate of the Degenerate Branching of a Chain In the
Oxidation of n-Decane (0 skorosti vyrozhdennogo razvetvleniya
teepi pTi okislenii u-4*kana)
PE2IODICALt Doklady Akademii nauk SSSRv 1958, Vol 123t Nr 10 pp 123-126
(USSR)
A13STRACT: The authors determined the above-mentioned rate by the method
of inhibitors* The n-decane was oxidized in the liquid phase in
an oxidation cell which was located in an oxygen flow. From the
rate of oxidation conclusions were drawn as to the a3cumulation
,of hydrogen peroxidesp the concentration of which was
determined iodometrically.efionapht 'hol was used as in~~ibitor.
A diagram shows the kinetic curves of the accumulati,)n of
hydrogen peroxides in the oxi4ation of n-decane at 1300 in the
presence ofod&naphthol (2 .10 OM/ml), the cc-naphthol 'being
introduce'd at various instants of time. The forming Df free
radioals is sharply accelerated in the initial period of the
reaction. Tho later the inhibitor is introduced, the shorter
Vard 1/3 will be the induction period of oxidation.

OnIthe Rate of the Degenerate Branching of a BOT/20-123--l-33/56
Chain in the Oxidation of n-Decane
After the introduction of o4snaphthol into the n-decan-i about
to oxidize, the solution gradually becomes yellow. Ifqftvamg&thO1
is introduced in comparatively advanced stages, preci-pitation
is even brown. The compound produced has a charaoteri3tic
spectrum In the visible domain with a maximum absorption at
420 meA . The optical density Of the solution attains a maximum
after which it decreases. The solution is therefore cl)lored by
means of an intermediate compound, which is formed by the
participation of e(r-aaphthol. An addition of the preci-pitation
of this compound to the fresh n-decane showed that thii
intermediate compound acts as an inhibitor. The oe-nap!ithol yield
follows the.reaotion of zero-th order only up to a %,'101;
transformation, after which distinct deviations from the
equation of the first order are observed. Several possible
causes of this phenomenon are pointed out. The values of the
rate of consumption of the iphibitor in the n-decane En the state
of oxidation at 1300 at a concentration 0#02 M/1 of tav hydrogen
peroxide and at various concentrations of the inhibit)r are
given. This rate of consumption d M /dt does not depead on the
Card 2/3 concentration of the inhibitor* The inhibitor does thirefore

Oh the Rate of the Degenerate Branching of a SOV/20-123-1--33/56
Chain in the Oxidation 9f n-Decane
not take part in the production of free radicals and is
merely an "instrument" of measuring the quantity wp M -~d[l]/dto
A fu:rther diagram shows the dependence of the branching rate
obtained in this way at 1300 upon hydrogen peroxide
concentration. Thusi direct proof was given of the fw)t that
hydrogen peroxide is the mort important factor cau3iA!; I
branching in n-decans oxiaation. For the temperature 4opandence
of the rate constant it holds that
~ k -,,6.1o8 exp(-24800/RT)eec-1
Degenerate branching is probably a bimolecular reaction with a
hydrocarbon ROOR + HR-+ RC# + B40 + Ro . There are .") figures
and 6 referenceag I of which is Soviet,
ASSOCIATIONs Institut khimicheskoy fiziki Akademii nauk SSSR (Inst4.tute for
Chemical Physics of the Academy of Sciences, USSR)
SUBMITTEDs July IN 1958
Card 3/3

ZZMF.ALOV, B.Z.;I-IMANUM.I. laureat Laninskoy premii. red.;
DOLa0V. T.-T.
[Kinetics and mechanism of oxidation of the paraffinic distillate
and practical uses of the oxidation producteJ KinetUm i khirizz
okislenila perafinistogo distilliats i ispollsovanie produktcv
okislaniia v praktike. Baka, Isd-vo Amd.nauk Axerbaidshanskol
WRO 1959. 253 P. (MIU 13iQ
1. Chlon-korrespondent Akademii nauk SSSR (for Imanuall),
(Paraffins) (Oxidation)

PUM I BOOK NEWT=ON ODV/3663
Usdemlys, nex* SSSR. Institut cheskoy flzlJd
Okisleniye uslevodorodoy Y zhidkoy fami sbornik statey (Oxids6tion of Vydro-
carbons in the Liquid Phasej Collection of Articles) Moscow., Izd-vo AN IMUS
1959. 334 p, Irrata, slip insbrted. 2,0200 copies printed.
Ed.: It-14. Emanuel,# Corresponding Member., AcadezW of Sciences U=j Ed. *f
Publii"j_lWset K. M. Wunsyevj Tach. Id.t 10 IN IWAIMIA.
PURPOOB: This collection of articles is intended for C~Qmlsts intevestea in
hydrocarbon oxidation reactions.. particularly for those specUUming in petrol-
eum fuels.
COVERAGS: We collection of 35 articles represents ihe r seats of investi^tions
,,.ovdr a Veriod of several years on problems. an oxidation. The
authors present their = theoreldml ia,exjpirlmental data and also Maw from
current literature. No perwulities are mentioned. Befennoes acccMany
most of the articles,,

,.6ddation of Hydrocarbons in the (Cont.) eovl3663
VM3 OF CC==:
Foreword
3
Emanuel' N.M. (Thatitut khImic skoy flaiki (3hatitute of Chemical
--iWisre-all.-Problem of Controlling Wdrocarbon Oxidation Chain Re-
actions in the Liquid Phase 9
This article gives the general characteristics of hydrocarbon oxida-
tion processes and describes the various principles involved in
accelerating branched chain reactions. The yhen na, Aich accompany
the oxidation reaction, including +,he macroscopic stagesp an in-
vestigated from the point of view of their-utiliza Ion for control-
ling chemical procescass
W,Vzua, Z.K. [Institute of Chemical Physical. The Role of Peroxides
in Hydrocarbon Oxidation Processes in the Liquid Phase 35
This article deals with the role of peroxides In liquid-phase
oxidation processes. 7be article demonstrates that the rate of
a low-Umperature hydrocarbon oxidation reaction In the liquid-
plase is determined by the rate of decooWosition. of the intereed-
IsAe peroxide compounds.

Oxidation of Hydrocarbons In the (Cont.) SOV13663
from ketone a-hydroperoxides.
021ppintokh, V*Yaop and N#X# IMU01,11astituts of Chemical Physics].
mechanism of the Optical Sensitization of Liquid-Phase Oxidation by
Molecular Oxydation of 2j, 7-DinethVlootane 13.3
The coiebined effects of photocheW~q actixation, and the catalytic
action of po3rvalent metal (On and Fe ` ) stereates on the oxld&tLon
of 2J-dimethyloctane are investigated. Additions of metal malts p*r
the role of photoinitiators. The augors, de%ct reaction acceler-
ation caused by the photolysis of CU and Is atereates,, and confiru
the formation of free radicals which cause this acceleration.
Tinyakova.. Ye.I.., F.A. Dolgoplosk, and V.9. Fleykh [rustitut vysokomo3,e-
kulyarmykh soyedineniy AN SSSR (institute of High molecular cmmpounds,
AeadezW of Sciences USSR; Vaesoyusnyy mAuchno-issledovatel'skiy institut
sinteticheskogo, kauchuka (All-Ukdon Scientific Research Institute of Synthetic
Rubber)], Oxidation-Reduction System for Initiating Oxidation Processes
In Hydrocarbon VAdis and the Meabanism of Their Action 13.7
The authors show 1hat oxidation-reduction systemso widely used for
initiating low-temperature polymerization processeaj, can be success-
fully employed for initiating oxidation reactions. The role of

OxIdation of 93rdrocarbons in the (Cont.) 90V13663
P01YVA10at Metal salts In the decomposition of peroxWo and the
oxidation of hydrocarbons is discussed.
Blyumberg,, R.Ao. ZeL "not andjg.M.- it jTj2stitute of Chemical
Fasical. Liquid-Pbase Oxidation of n-Butans at Bear-Critical Temp-
eratures and Pressures 325
The authors discuss the kinetics and chemistry of a purportedly new
method for liquid-phase oxidation of a-butane. Initiating the re-
action with N02 and catalning'with CoSt2 resulted In a
shorter induction period by increasing the initial rate of chain
growth. Acetic &aid and methyl ethylketone an the principal
products of the reaction.
Denisovj, Ta-T. (Moscow State Wiversity Imul N.V. Uumosov) Kinetics
of Cyclobexame Oxidation C&.toJYftd by Cobalt Stearate 3,36
The author finds that the catalytic action of cobalt salts (stearstes)
both breaks down and Initiates chain growth during the oxidation of
cyclohexane. 7he reUtionship between these Zzactions is stibstantial-
ly changed as the reaction develops.

,Oxidation of Ardrocarbons In the (Cont. BOV/3a3
MlOrre 111 D*G.p L.O. Chuabukinsix end N.M. Enamel' frustitute of Chemical
Physics . DiAl function Of 1bul steftraie`mln~ Wdrocarbon Oxidation
lbaction 145
2he dual role.of cqMer and manginese stearates an both caUaysts and
inhibitors of oxidation of I*o- and n-decams is described. 7he
authors determine the critical concentration of cupric steLrate
( - 0.03% per-mole) above vhich the induction period for n-decane
oxidation Increases.
WYzus.' Z.K. s L,G. Privalovap and NX Smamel I 11jastitute of Chemical
Pbyaics3. Change In the Meebanism of n-Decann Oxidation in the Course
of the Beaftion 14 152
The authors have used C tagged n-decane to inventlipte cLaqps
in the rates of formation and consumption of n4ecyl hy&operoxides
during the oxidation of n-de 0 The hypothesis that variations in
the activities of radicals carrying on cliedn reactions are proportional
to the accumulation of o5qaen-containlng oxidation products in the
reacting mixture is offerad as a possible explanation of the
phenomenon.

5(4) 1 SOV/62-59-1-4/30
AUTHORS: Blyumbergt E. A.0 Voronkov, V. G., Emanuellp N.
TITLE: Gaseous Initiation by Ozone During the Process of.Partiffin
Oxidation (Gazovoye initaiirovaniye ozonom v proteesso okis-
leniya parafina)
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimicheakikh nauk#
1959t Ur 1, pp 25 - 29 (USSR)
ABSTRACT: ~In the-present paper the authors investigated the protlem
of the applicability of ozone as a gaseous initiator in
the oxidation of liquid phases. The method of oxidatioi
described in (Ref 3) has been already applied. The par-iffin
"Kepsen" was oxidized from brown coal supplied by the ilerman
Democratic Republic. Experimental data show a number a--'
particular features which occur in the addition of ozorte
during the oxidation of liquid hydrocarbons. The kinW-c
curves of the increase in the acid numbers in paraffin
oxidation are presented in (Fig 1). The effect of the itimula-
tion with which the reaction was excited at the beginning
may be seen from it. If ozone acts in it for a longer jeriod
Card 1/4 a very peculiar phenomenon is observed. The reaction it

Ghseoue Initiation by Ozone During the Process of Paraffin SOV/62-59-1-4/38
Oxidation
accelerated (the period of inriuction is shortened) whilc
the limiting yield of acids is aimultane,usly reduced.
Similar phenomena were also observed in the application
of other stimulants. In this connection the experiments
with uninterrupted transition of ozonized air were some-
what startlingfor the respective kinetic curve indicat,is a
reaction course with maximum velocity and a very high d,)gree
of oxidation. It was assumed that the process of oxidation
changes in this case and oxidation is produced no longe::
by molecular oxygen but by ozone. If molecular oxygen
participates in the reaction it is included only in verr
small quantities. (Fig 2) confirms the conclusion that a
strong stimulation of the process causes, apart from its
acceleration, a reduction of the transformation degree. Inter-
esting results were obtained (Fig 3) by the applicatior of
different temperature conditions during the initial at4-gcan,
the development of the oxidation process effected by a "shock"
at the beginning. It may be neon from it that the kine,;ic
curve of acid numbers does not vary in any cane. At prrisent,
Card 2/4 the paraffin in oxidized by menna of the manganese exile

Gaseous Initiation by Ozone During the Process of Paraffin 307/62-59-1-4//38
Oxidation . .. I
catalyst under commercial conditions, whereby the proi;ess
is very complicated, however. Production is simplifiel
and continuous conditions of oxidation are establishe,1
by the application of ozone as a gaseous initiator. 11.
must be emphasized that oxidation by ozonized air ens-,ires
good quality of the oxidation product which meets the
requirements called for synthetic fatty acids. Simult,-.neousIy
a complete utilization of raw material will be achieved.
For comparison some properties of the oxidation produ--ts
synthesized in the presence of the manganese catalyst on
the one hand and by uninterrupted oxidation with ozonited
air on the other hand are shown in the table. These data
were obtained at the laboratory of the Vsesoyuznyy nauchno-
isaledovatellskiy institut zhirov (All-Union Scientific
Research Institute of Pats) in the Shebekinskiy Kombinat
under the supervision of H. K. L'anlkovskaya, There aie
3 figures, I table, and 15 references, 8 of which are Soviet.
Card 3/4

I Gaseous Initiation by Ozone During the Process of Paraffin SOV/62--59-1-4/38
Oxidation
ASSOCIATION: Institut khimicheskoy fiziki, Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences, US'3R)
Moskovskiy gosudarstvennyy universitet im. Y. V. Lomonocova
(Moscow State University imeni M. V. Lomonosov)
SUBMITTED: May 299 1957
Card 4/4

SOY/sc-501-1-28/44
AUTEORSi Berezin, IoV., Vagnorg G. and, I.F.'riwnuell,
P~_. ra 1, N o 1(11 i !: tlr~n *1 n i Tby Chlorine -])wing the Initial
Stage, of the. Reaction
r- i; v i t i
PE'JODICAL. Zhurnal prikladnoy khimiit 141- 1, PI) 173-IBC (USSIO

ABSTRACTs The method of atimulating,liquid-phose oxidation reaotiona by
moano of small admixtures to the air of certain oatalyzing
r.a3es (NOZI HBr, etc) was named the mothed of i,?as'initiation
ZRef. I --b I i.;'- -
J. "'ho present inveoti.-ation wa3 aimed at ent A

'I
ini: main rejularitiezi of t- e in! t iation of t'ect cc.used by a d-
mi~turcz of chlorine-in the oxidation rocess of li~lnite i:~ -~ ra
fin of the "Upnen" type (East f~erTIAPI
,. Aj the main pro-
ducts of oxidation are aliphatic acids, the principal atten-
tion was paid to the kinetids of their formation and ac2
cumulat *ton. The results of experiments are presented in
Graphical form. It can be concluded that the gas initiation
of the x,eaction by chlorine has a strong stimulating efZ--,,jt
on the paraffin oxidation process; at that the initiation
is brought about during a short initial poriod in the de-
velopment of the process. The accumulation of acids is do-
scribed by the kinetic curves obtained experimenially. It
tlha low Mayimllm Affpnt in thp Icirptin

SOVBC-59-1-28/44
I Paraffin Oxidation Initiated by Chlorine During the Initial Stage
of the Reaction
curves of acid formation is due to the prezence in "Kgpsen"-
type paraffin of aromatic substances.
There are 6 f;raplz, 1 diagram and 4 Soviet, references.
SUB'"'ITTED: . Douember 20, 195C
Card 2/2

5(1,3), 21(8) SOV/153-2-4-12/32
AUTHORS: Burlakova, Ye. B.1 Dzantiyev, B. G., Sergeyev, G. B., Emanuel',
N.
r-
TITLE: Radiolytical Oxidation of Fat
PERIODICALt Izvestiya vysehikh uchebnykh zavedeniy. Khimiya i khimicheakaya
tekhnologiya, 1959, Vol 2, Nr 4, PP 533 - 540 (USSR)
ABSTRACTs The investigation of the kinetics and processes of fat oxida-
tion is necessary for an economical production technology of
edible and technical fats and oils as well as for the investi-
gation of the assimilation mechanism of the fats consumed by
living organisms. The oxidation reaction of fats,tormi"a chain
reaction with degenerate ramifioations (Semenov, N. N., Acade-
mician, Ref 1). It has been pointed oat recently (Tarusov, B. N.,
Refs 2,3) that the oxidation processes proceeding in the lipo-
protein phase of the cell structures play an important role in
radiation damageof the organism. The initiation of oxidative
chain reactions can be achieved by a short effect or catalysts
(initiators) At the beginning of the reaction (Refs 4,5)- This
dynamics of
phenomenon has many analogies in the developmental
Card 1/3 radiation damages (Ref 6). Purified fresh cod-liver ail was

iadiolytical Oxidation of Pat BOV/153-2-4-12/32
chosen for the investigation. It was oxidized by means of
atmospheric oxygen at 20-1300 in a glass cell (Ref 7). It was
irradilied with gamma rays from C06o X-rays, and beta part"la"Rk-
from P and 1098. ?igure I shows typical kinetic curves of
the peroxide.aggragation with thermal oxidation at E.5-1000. They
are characterIzed by an induction period which is shortened
with increasing tomperaturej 8 hours at 6501 the period is al-
most entirely missing at about 1000. The curves of a.cid aggre-
gation aeon in figure 2 are analogous to the above .:urves. Acid
formation, however, is somewhat retarded since acids are ee-
condary oxidation products (Ref 9). The effect of i.,nizing'radia-
tions on fat containing dissolved oxygen leads to the appearance
of oxidation products already at room temperature. The intensi-
ties of oxi ati?n in the range of doses used, howevor, are not
high (N.10i-10 p). The bxtent of the effect depends on the
temperature at which the fat is irradiated. The yield rises with
increaping temperature (Pigs 3,4). This seems to be connected
with the attaining of conditions favoring the chain extension
(Pig 3). The authors introduce the symbol G for the value of
the radiation effect. Equations are derived for G as well as for
Card 2/3 the reaction rate W. Curve 1 (Fig 5) concerning the oxidation

Radiolytical Oxidation of Pat
SOV/153-2-4-12/32
of irradiated and nonirradiated fat at 1000 illustrates the
presence of an "upper temperature limit". Above thie limit the
irradiation dose does no longer affect the oxidation kinetics.
The effect of a previous irradiation at 200 on the formation
.kinetics of peroxides in fat with an oxidation at a higher temper-
ature is analogous (Pig 6). Thus, the separation oJ' the irra-
diation period and the oxidation period with respect to time only
affects the duration of the induction period wherean the cheMiBM
of the process remains unchanged. The types of radiation mentioned
at the beginning neither influenca the kinetics nor the chemism
of fat oxidation. The quantity of radiation yield depends on the
temperature extreme. There are 8 figures and 11 references, 8
of whioh are Soviet.
ASSOCIATIONs Moskovskiy gosu"rstvennyy universitet imeni M. V. Lomonosova.)
Kafedra khimicheskoy kinetiki (Moscow State University imeni
M. V. Lomonosov~ Chair of Chemical Kinetics)
SUBMITTEDi May 16t 1958
Card 3/3

5 (4.1?
AUTHORS: Kruglyakoval K.-Ye.g Emanuellq N. M. SOV/62-59-3-6/37
TITLE: Som e Particular Features in th-e-le-Wavior of Intermediate
Molecular Substances During Propane Oxidation (Osobennosti
povedeniya molokulyarnykh promezhutoohnykh veshebestv pri
okislenii propana)
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimiche,3kikhinauk9
1959, Nr 3t pp 417-424 (USSR)
ABSTRACT: In the present paper the attempt was made to explain the role
of some oxidation products - acetaldehyde, methyl alcoholt
acetic acid - during the development of the reaction by -
kinetic methods. Besides, the problem of the nature of-the
maximum yield of one of these products (acetaldebyde) was
experimentally investigated. In figure A the kinetic curves of
the formation of intermediate products are presented. Under
given experimental conditions it could be seen that propane
is consumed during the formation of acetaldehyde,,form4ldebyde,
and methyl alcohol in practically equal quantities. Tho
effect exerted by acetaldehyde additions (1.789 11.3, 5-5 %)
on the formation kinetics of the intermediate productslis given
Card 1/3 in figure 2. It was proved that these additions increase, the

Goiie Particular Features in the Behavior of Inter- .. SOY/62-59-3-6/37
mediate Molecular Substances During Propane Oxidation
oxidation rate of propanewhereby acetaldehyde, formaldehyde,
and apparently methyl alcohol tre formed. The maximum ooncen-
trations of the oxidation productp remain the same as in
experiments without additions. The addition of acetic acid
(0 '28 %) and methyl alcohol (2-7 ~) does not affoct their
yield (Table). By means of tagged atoms it was proved that the
ma-imnm concentration of acetaldehyde represents a special ,
case of the dynamic equilibrium. Apparently in the moment of
the maximum concentration both the formation and consumption
of this product are retarded. This might be due -.o an Inter-
action of the intermediate products with the radicals of ' the
chain, wherein less active centers are formed which guarantee
the retarding effect. The lacking activity in diiaedone)-.
derivatives of formaldehyde confirms the assumption that the
latter is not formed from acetaldehyde but indep-andently of.it.
The value of the specific activity of carbon mon3xide a 125
impulses per minute. mg and C02 (132 impulses per minute mg)
indicates that CO and C02 are not only formed from
Card 2/3

Some Particular Peatures in the Behavior of Inter- SOY/62-59-5-6/37-
mediate Molecular Substances During Propane Oxidation
acetaldehyde but also in another way. There are 4 ligures,
1 table, and 18 Soviet references.
ASSOCIATION: Institut khimicheskoy 1*iziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences, USSR)
SUBMITTED: May 30, 1957
Card 3/3

5M SOV162-59-6,-8136
AUTHORSt Kruglyakovaj X. Yo. ,,,E:,manu9i N* Id'.,
TITLEs Kinetics of the Oxidation of Propane Induced by Chlorine!- in
FA*ked Vessels at IY;.fferent SIV (Kinatika
initsiirovannogo khlOrom okialeniya propana v aosudakh a nasadkoy
pri raznykh S/V)
PERIODICALt Izveatiya Akademii nauk 6SSR. Otdeleniye khimioheakikh nauk,
1959, Nr 6t PP 1005 - lolo (USSR)
ABSTRACTs By way of introduction the different possibilities -of observing
the chain reiction which occurs with the process menticned in
the title are dealt with in brief (Refs 1-17)- It could be ob-
served that a considerable influence is exercised upon the
process by the walls of the vessel, that is to say, by their
shape and the material they are made of. For the investigation
reportid on'in the present paper a vessel.was used made. of
sodium glass which was equipped with an insert consisting of
glass ball's'of tne same type but with different diameters
(5091-7 mm). Oxidation was inve atigated with a mixturo of.
a398tO2-1si at-,-a temperature of 346 # at first in a vensel
Card 1/3 without-ad insert.(Curves of the reaction kinetiosin figure I).

Kinetics of the Oxidation of Propane Induced by Chlorine in 3OV/62-551-6-8/36
Packed Vessels at Different S/V
In this case already no agreement with the data given in
reference 18 could be found. (These data were obtained by using
a quartz vessel f6r the reaction). When using the ball shaped
inserts the reaction was considerably accelerated (mostly if
the balls had a diameter of 1.7 mm)# but on the other hand the
yield in aldehydes decreased. It is because of this accelera-
tion that the reaction way also be carried out in the presence
of chlorine without inflammation of the mixture (Fig 2). In
this case the chlorine (0-5%) 4espite of its accelerating the
process also secures a high yield in aldehydes. The kJ.netic
curves which all (with, and without addition of chlorine that
only influences the yield in aldehydes) exhibit an S-3hape may
easily be represented by the autooatalytic function of the first
ordert if only not the initial but the final concentration of
the product is taken as standard for the reaction intensity.
Thus the reaction is splf-accelerating and the insert only
influences the raml'ication of the chains an with this ball
shaped insert a reaction surface is formed which takes part
Card 2/3 in the process of ramification. The peroxide which otherwise

Kinetics of the Oxidation of Propane Induced by Chlorine SOY/62-59-6-8/36
in Packed Vessels at Different SIV
as intermediate produot disturbs the reaction may without any
difficulties be decomposed on the burning surface. There are--
8 figures and 18 references, 13 of which are Soviet.
ASSOCIATIONs Institut khimicheskoy fiziki Akademii nauk SSSR (InstLtute
of Chemical Physics of the Academy of Sciences, USSR)
SUBMITTEDs August 23, 1957
Card 3/3

.'3 (2)t 5 (4)
AUTHORS., Kruglyakoval K. Ye., Emanuel', 11. M. SOV/62-59-7-9/38
TITLE: Activation of the Container Surface by the Reacting Mixture
03H8 + 02 in the Presence of Chlorine (Aktivatsiya poverkhnosti
soanda, reagirayushchey smeyslyu C3Ha + 02 v prisutstvii khlora).
PERIODICALt Izvestiya Akademii nauk SSSR. Otdeleniye khimichaskikh nauk,
1959, Nr 7t pp 1211-1215 (USSR)
ABSTRACTs 1~r way of an introduction there is a brief reference to own
papers and to papers of Sergeyev and 5htern (Ref 2), Kalinanko
and voyevoaskiy (Ref 3) being in connection with tho problem
under review, This paper reports on the discoveredactivation
affect as it is called in the title. The existence of the effect
was conoludea from the.initiating effect of the surl'aoe of the
container on the oxidation in the absence of chloriae following
experiments with chloroinitiated oxidation of propaae.
The apparatus on which the experiments were carried
out is deacribed in paper reference 5. The reaction kinetic
curves with and without t~e addition of chlorine at 3350 are
plotted in figure 1. The chlorine influences strongly the yield
Card 1/2 of acetaldehyde. This influence of the chlorine could only be

Activation of the Container Surface by the ReactinC SOV/62-59-7-9/36
Mixture C H + 0 in the Presence of Chlorine
3 8 2
noticed in quartz containers with a Glass splinter filling. in
containers made of other material also the formation of
formaldehyde was influenced. There are accordingly two ways
independent of one another to produce both aldehydes. A
production scheme of both aldehydes in Given (for the formaldelVda
according to the scheme of Semenov and Shtern (nef* 4, 6)).
Furthermore, the yield of formaldehyde and acetaldehyde is
investigated in dependence on the reaction temperature and
addition of chlorine. In figure 3 also the secondary effect of
chlorine is to be seen (decrease of the yield of aldehydes at
high temperatures). There are 4'figures and 6 Soviot references.
ASSOCIATIOTTs Institut kbimicheskoy fiziki Akademii nauk SSSR (Institute Of
Chemical Physics of the Academy of Sciences, USSR)
SUBMITTED: October 24v 1957
Card 2/2

5W
AUTHORS: Babayeva# A. A., klayzust Zolot SOV/62-59-8-6/42
Emanuellf Nil me
TITLE; oxidation Kinetics of Isobutane in the Presence of
Hydrogen SOM0
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauko
1.9599 Nr at pp 1378-1385 (USSR)
ABSTRACT; In the present paper the investigation of the catalytic
oxidation of hydrocarbons is continued and the axidation
kinetics of ramified.hydrocarbons (in this case.isobutane in
the presende of HDr)-is investigated by means of HBr. 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 on 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 (per xides
of tertiary butyl, tertiary butyl alcohol, and acetone3. Very
definite stages were observed in the reaction :prooem In the
Card 1/2 first stage isobutane is mainly oxidized so that it forms the

Oxidation Kinetics of Isobutane in the Presence of SOV162-59-8-6142
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
facts were obtained by means of the determination of th
yields under varying reaction conditions (changes in th:
concentration of initial materials) (Figs 3,4). The summary
reaction process is represented by the following equations:
i-C a +Or-:v (C11 (CH3)3COOH + (CH V ~(CH ) 009 +
4 10 3)3COOE' 3)3""-' 3 3
+ (CH 3)2CO + CH 4. There are 5 figures, 4 tables, and 14 ref-
erences, 9 of which qre Soviet.
ASSOCIATION: Institut khimicheskoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences, USSR)
Moskovskiy gosudaretvannyy universitet-im. M. V. Lomonosova
(mosoow state University imeni M. V. Lomonosov)
SUBMITTED:, December 27t 1957
Card 2/2

-BABLYINA, A.A.; VAYZUS, Z,K,; WARMI, N.M.
Changes In the cberdstry of the oxidation of Isobutano in the
presence of HBr as affected by additions of rsaction and
products. Dokl.AN Azerb9SSR 15 U091191009-1013 '59.
(MIRA 13:4)
1. Wedra khimicbeekoy kinettki Hookovskogo-gosudarstvannogo
universitsta imeni Lomonosova i lustitut khimichookor fisiki
AN SSSR. Predetavlano, akademikom AN Aserbeydzbanakoy SSR M.7.
Maglyevym.
(Propane) .(Oxidation)

BRUZIN, I.Y.; VAMM, G. I ZMANUAL', Me
-0 ..
Chlorlwi-init late& oxidation of paraffin. Zhur.prikl.khlxo
32 no.11 173-180 j& 139. (XIBA 32; 4)
(ftraffing) (Oxidation) Oblorins)

'5 .3) SOV/80-12-4-33/47
AUTHORS: Berezing I,V.: Denisovq Ye.T., Suvorova, S.N., Smolyan, Z.B. and
Emanuel', N.M.
TITLEt The Oxidation of a Mixture of Cyclohexane and Cyclohexanol +.a
Adipic Acid (Oki 11 leniye smesi tsiklogeksana i tsiklogeksanola v
adipinovuyu kislotu)
PERIODICAL: Zhurnal prikladnoy khimii, 1959, Vol 32f Nr 4, pp 888-892 (USSR)
ABSTRACT: Production of monomers for plastics and synthetic fibers is one
of the important tasks of modern chemistry. The utilization
of various waste materials can contribute to the solution of this
task. One of theae waste materials is the mixture of cyclohexane,
80 mol.~, and cyclohexanol, 20 mol.%. The authors studied the
kinetics of the oxidation of this mixture, called 11anol head",
with an aim of obtaining cyclohexane and adipic acid. The oxidation
was c:arried cut in an autoolave at a pressure of 20 atm by mole-
cular oxygen at temperatures of 130 and 1500C. Kinetic curves of
accumulation of the reaction products were obtained and the
possibility of producing adipic acid by oxidizing the "anol head"
was proven. It was shown that some peculiarities in th,) oxidation
Card 1/2 kinetios were determined wholly by the concentration of cyclohexanol

SOVJ80-32-4-33/47
The Oxidation of a Mixture of Cyclohexane and C.Yclohexanol into Adipic Acid
in the nanol head". The Drocess of oxidizing "anol head.n is to
be carried out with continuous removal of adipic acid obtained in
order to prevent its burning into lower dicarboxylic acils, and
the process thereby acquires a continuous character.
There are 3 sets of graphs and 7 Soviet references.
SUBMITTED: November 1, 1997
Card 212