SCIENTIFIC ABSTRACT VOYEVODSKIY, V.V. - VOYEVODSKIY, V.V.
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Li
USSR/Chemistry - Chain- Reactims, Apr 53
Atomic Energy
"The The.ory of Chain Reactions in the Calculation of
the Diffusion.of Active Centers," N. S. Akulov
Zhur Fiz Khim, Vol 27,, No 4, pp, 614-615
In all chain reactions which occur :in nature, dif-
fusing active centers interact vith the medium,
forming active centers of another.type. The view of
V. V. Voyevodskiy and A. S. Ko=Daneyets (Zhur Eksp i
Teor Fiz, Vol 23, p 229,1952) that there is only
one type of active center in the chain fission of U,
i.e. the neutron, is erroneous. One must consider
270T23
at least 2 types of centers, i.e.-slow and fast
neutrons. Although Vo-yevodskiy and Kompaneyets use
vith small changes equations developed in the
author's (Akulovs) book, they claim credit for in-
dependent work in arriving at the same result as the
author.
270T23
VOYEVOwnys V. V.
USSR/ChemistrY - Combuzion Kinetics Sep 53
"The Problem of the Existence of Three Limits of
Spontaneous Ignition o;' Combustible Mixtures
;V. V. Voyevodskii~'~Iinst of Chem Phyw, Ac C-TUoiii
Zhur Fiz Khim, Vol 27, No 9, pp 1420-1426
~%e alleged theory of three limits of ignition about
which N. S. Akulov talks and for which he claims
credit does not exist. Akulov's deductions are riot
in accordance with exptl facts. His criticism of
W. N. Semenov's theory, which does explain exptl re-
sults satisfactorily, is not justified and involves
26sIT26
rejection of everything that has been done by USSR
workers in this field during the past 20 yrs. There
is no reason for ;acceptance of Akulov a empirical
formulas, because all phenomena can be explained
from a unified theoretical point of viev.
A M--h--l 1, thq tas
of sr't'
Val ~C-: :v", rt
v-
A-Z
b), s A' i are 11~11.ed in t'rMZZ dO
All Winm j,Aymrnzrd in the Ms-nce n(
4 v*1y"wrtx3(fvC (~--Urv at 30% trjn~
mmonltr imt,wl d 42% wficn pure IIjO iv
Wvwn thr ~ah.,e is C"% and
t,, N.011, 50% V.,(h ~~ and art ims 'lect
"L~tw- r.t~, (h, .1nin" '64 1,Wm,-j durtng th~ t-A~-
tm-fi~,atkrl must act 15 a (hpolm im It. W Werster
L~ L L
Tte CcMmittce an Stalin PrI26S i0f the Council of Ministers LWR) in the flelds of
salence and Inventions annotmeev that the following oclentIrIc works., po7~ular sclen-
tifit bwkft, ",nd nextoookv riave oern vubmItttd for campetitIm fvr -13talln fIrIzve for
thip ytme. 1952, =d 1953. (SOVCWI'11,~,~, K'~~lttrdj )Wcov, 110- 20 F*b 3 Apr 1954r:
h _.M of
V.V. nnrl ComIrl',q-
t--,n r)-f'
of S~Acn
so. w-306o4, 7 jAy j9%h
VOYLIJUDSKIY, Vladislav Vladislavovich.
A cademic degree of Doctor of Chemical Scienceso based on
his defense., 29 December 1954, in the Council of the Inst
of Chemical Physics Aced Sci USSRP of his dissertation
entitled: "Free Radicals in Chain Gas Reactions ".
.A cademic degree and/or title: Doctor of Sciences
SO: Decisions of VAK, List no 8, 2 April 55, Ryulleten'
MVO SSSR, No. 14,, July Moscov pp 4-22, Uncl.
JPRS/WY-429
tA W,
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OY157 V 0,-D 51?
AID P - m8
Subject
Card 1/1
Authors
Title
Periodical
Abstract
USSR/Chemistry
Pub. 119 - 1/5
: Kursanov, D. N. and Voyevodskiy, V. V. (Moscow)
: Some new data on hydrogen exchange between organic
radicals and ions
: Usp. khim.., 23, no. 6j, 641-653, 1954
Hydrogen exchange of free organic radicals and of organic
cations is reviewed. Experimental data on the hydrogen
exchange of carbonyl compounds with D S04 are compiled in
a table. One table, 38 references (13 Russian: 1934-54).
Institution : None
Submitted : go date
Vwnfthemistr7 - Analysis moUods
Card 1/1 Pubs 247 - 13/27
-Authors Mrdale7shvilip R, Es; Lavrovskaya, G. K.1 and Voyovudskiy,, V. V.
-Title ftro-wthod of analyzing heavy water
Porlodical_-'s --- --- Zhuro-fiz*-,kidm.__29/32,,-.2195-0~,913,,Dea 1954
Abstract I A new compensation mothod for measuring vapor pressuroa wa3 utilized
in determining the deuteri= content of water. This mrthod porrdto
carrying out heavy water analyses (deuterium content in water) in
A%5--mg of water wit;, an accuracy of up to I - 0.05 mol/~,, reGirdless
of the D cont-ent--In-the-wrater. The Im-W-~ation3 used ~.n connection
with thig compensation method 4r-e-described. Eight references A.
5 USSRI 1 UBA; 1 En&Iish and 1 German (1936-1953). Table; graphs;
drawings V
Irstitution AeaderV of Sc. LBSR,, Institute of Chemical Physics and the V. M.
Lomonosov State Universityp Mwcow
Submitted June 23, 1954
OR
MAN
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AF701597 TREASURE ISLAND BOOK REVIEW AID 803 - S
VOYEVODSKIY, V. V.-(Institute of Chemical Physics, Academy of
C n -s, USSH).
DISKUSSIYA (Discussion), In Problemy kinetiki i kataliza
(Problems of Kinetics and Ua-talysis), vol. 8. Izdatel'Btvo
Akademii Nauk SSSR, 1955. Section 1: Effect of illumination
on the adsorbability of solids. p. 73-74.
An outline of the photodesorption of CO froni a Ni-8urface is
given. The process consists of the absorption of light, de-
activation by means of recombination, surface reaction pre-
ceding desorption of CO, and desorption of CO.
1/1
AF701597 TREASURE ISLAND BOOK RVIEW AID 807 - S
-VOLWODSKIY., V. V. (Institute of Chemical Physics, Academy of Sciences,
U
0 TSEPNYKH MEKHANIZMAKH V GETEROGENNOM KATALIZE (Chain mechanisms
in heterogeneous ,atalysis). In Problemy kinetiki i kataliza
(Problems or Kinetics and Catal-ysia), vol. 8. Xzdatel'stvo
Akademii Nauk SSSR, 1955. Section M General problems of the
theory of catalysis. P. 97-109.
An explanation of the mechanism of catalytic processes is given,
based on the formation of intermediate products with a higher
reactivity than the initial substances. Three types of hetero-
eneous active centers are discussed: 1) free lattice valence
formed by thermal or chemical action); 2) heterogeneous radical,
T
i.e., a particle chemically combined with the surface and 3)
homogeneous radical (or atom), whose bond with the surface is
intermediate between a strong chemical bond and physical
adsorption. The mechanisms of hydrogenation,of catalytic
cracking in the presence of carbon and formation of hydrocarbons
and alcohols from CO and H are discussed at some length. The
processes determining the girection and velocity of heterogeneous
chain transformation are governed by the action of the catalyst
1/2
S
0 1 mekhanizmakh V ........... AID 807 -
voyEVODSKly, V. V., 0 tsepnykh ation (and breaking) of the
& Dntimation and 2) initil 4-1955).
on 1) the c1 .5 14 Russian, (194
chains# 22 ref -,
2/2
0 1,
AF701597 TREASURE ISLAND BOOK REVIEW AID s
VbyEvoDsKIY, V. V. (Institute of Chemical Physics, Academy of Sciences,
'USSR)-
DISKUSSIYA (Discussion). In Problemy kinetiki i kataliza (Problems
of Kinetics and Catalysis)-,vol. 8. Izdatel'stvo Akademii Nauk
SSSR, 1955. Section II: General problems on the theory of
catalysis. P. 154-155.
In reply to his opponents, Voyevodskiy states that his theoretical
explanation of catalysis by chain reactions, though in need of
experimental or theoretical confirmation introduced clarity into
the mechanism of heterogenous catalysis. The further study of the
chain theory of heterogeneous catalysis should be concerned wilu;
1. the properties and structure of active heterogeneous
compounds and 2. the kinetics of catalytic processes.
1/1
I - I
rmp
, ,
1-401,020 NII-ONFRORMIR, - -. ,- I'll,-;I.....,W-1- ~
"t"':50 LIT O-N
VOYEVODSKIY, V. V. and TIKHOMIROVA, 11. N.
"Deterzrdnation of the,Velocity Constants of the Reaction of Hydrogen Atons with
Hydrocarbons at Increased Tjenperature5," pp. 172-186 of the book Chain Reactions of
Oxidation of !!Zdrocarbons in thj_2ts Poase, AS USSR, Moscori, 1955,
Translation 1071268
VThe role office valrhcj~-
tjr, ~,,eu YP" c4tjdrirfffl~ V.-.
V. Vu-tv-c4:6-Ljl, F
~z '~
r ~-- Iv.
",, "it :."11
VdPiozy 10im. , --
AI:jJ. Sj4A S,S tv~5 -10 A Preliminary
exctch cl the pfirnpal t-, - .4 ~ ~h,oj A catalrus. A
catalyst crysw am be %ittz i Lq smgtr Ki:111% troul. that id-
fects heterErgencol, leactii- m ".. Eimilar to thst of free
radicals ill bolmolcu'Al"i in N:tb =Xs. reactions
proceed by essenibIly slunflar In ajj'c;ttjIyjk
17"ctlova the procm b mu5ftl ~i:d Ifirc. ted b7 I;tc vuleadta, -
and the mulyst p6ys a nAr iv,i un!ikc tigit ,( a "radicill".
The PhYS. IL'ttorC of jFCC' V:,JLo-j- I)o the MtAIYL.*t ClySt2l
,fam, and the difftstut typ~-s between tbti (mlsorbed
audrs and We in-yatal butficr aic di-,~,uuKA I'lie- reaction
mechamnLum Qru txm-d oil th, ill the re-takus
of (rot ~alrncki md Cf Oim ~i, radicals ("ToCll
durinx the pro"" in Eb%: C.MN!V51 mirf;ice 'I'lie tritroduc,
t;on c4 a cbAin "talyia5 rn~hzt,i~- Kivc.4 a m)vcl explAnation
U the merhAzi3tu cf accele-i-ri, tjs;~vd by the cutalyit.
This acccl~raticz, in;Ay be a tviiilt A f-mati"n vI (fee valen-
ci" (liat -cauivi-lm~aia vneraut?a ,,, the catalyst at much
bigher velt)-citics lban La t6 ga5 pl,.i:, A 2nd evalyst luitc-
tjKm cniy eLnlut in thcrF=
cxm the cqiW turfioe. y %-1y 0 N, lWh "C=
fkM ve rearivA. The chain-graAth-tilay frequently bli
lopcdod by the high end.thti-micity of the comp&. forrized
La the c1cluentary smgt~q- Wb,n ille Q"x deirclDpirtent
V12 [be htltTOgl!j2CGu; T.Wk.;Js t,-) be enefgetkully
Mofe pmLuble, mtalpili cart Vv;htly arculerate the process.
A compka abst-tice (A InNiumak.-n im ith rtrmd to hijud curr.
gies of single aloins and of at. rm~j, with the catalyst may
be the principal dfirmilty tha! "t vief~:ut ivwfercs with the
evaluation cif %n:l,.,city fcja~~us I's r!"I;eritafy
raillcal muctior-A. A mw9h cvAuAtica ul the heits of re-
actioal at cLem4mrary 5tag-. mlk, It ufiqe3 .1ppear proll-
aue, but cnm L71te . I Je cumider
Pl!rdy hyglvtical~
v!)
4p
416
s s
,,12645
AV
I,, r
-~.U- "e nIld T-.u in
d'i",1111,14 11~ 1) C",tt!nt "I *All' At a
-ter
(G Y
V VZ
.; X
0 y v-_ v p 4 > i r V. V, Catalysis B-9
emistry-
Och
TO
P
mbustion* EXPlosionse
C
f USSR/Kinetics .
o
No 61 1957) 16564
Khimiyaj
Referat Zhur
Chirtove
Abs JOur N.M.
io~
:_
tkoVO-)
:
Author
. ,
T6ve
I of Science- Of USSR' n 140noxide.
Academy dation of Carbo
; oxi
Slo.
Inst
l '
Kinetics 0 380-389; in symposium
AN
e
Tit 1955) 29) No 2) eazovoy faze, 14f)
khimii
v
orig Pub ,
t-
Zh* fi"
e reakt0ii uglevodoTOdOV
y
TsepnY
55, 161-171-
10
,
6300 and a
Lation at 450 to
column in presence
ves of Co Oxid
tract mercurY rami-
The kinetic cur
acteristical of non-
f 150 to 500 va of
the
Abs char
pressure o
team or H2 have a shape ( sho~m that ji2 catalyzes
menon of
t is
)f s
0
The pheno
hain reactionse I
vea c' times more than steam was disclo-
team and
d
pproache
reactioTt six ith s
turation" Of the mixture ion speed 11
e substances
t the react
11
sa
of thes
sed; it consisted in tha
itude vinen the contents ion energy Of the
at
a constant maga
ture increased- The activ
in the mix
235
card 1/2
for I I
g% -g - ~!
..... .. ..............
VOY6-vo-Dsck;~') V.v,
~~W_~ical Chmiatry - Kinetics, Combustion., Explosionsy Topo-
chemistry, Catalysis. B-9
Abs Jour: Beferat.Zhu;val MmIyaj, No 3,, 1958.9 7186-
Author R. Ye. MLrdaleyschvi1i., G.B. Pariyokiy., V.A. Poltorak,
V.V.
last of Sciences of USSR.
TItle Reaction of Deuterium Atoms with Alkenes. Dependence of
Methane Deuterization on Owcentration of Deuterium Atoms
in System.
Orig Pub: I=. AN SM. M. Idtim. n.2 1956., No .5, 516-524.
Abstract: The,exchange reaction of alkyl radicals Vith D2
1956., 74392) was stuxiied with the application of the naam-
spectrometric analysis of D content in the being produeed
methar The ratUcals were formed according to the reaction
D + X R, where M was CAI CA, and iso-CILU8. In the
cases of C2H4 and iao-04%, the D content in mef1ine increased,
Card 1/2 -4-
>/ V,
z
USSR/Physical Chemistry - Kinetics. Combustion. B-9
Explosives. Topochemistry. Catalysis
Abs Jour : Referat Zhur - Khimyaj 11o 2, 1957) 3774
Author : voyevodskixav.
Title : Interchange of Free Alkyl Radicals vith Molecular
Deuterium
Orig Pub : Mro Min. zh-j 1956, 22, Ho 1, 42-44
Abstract : There is proposed a new hypothetical elei-wntal reaction
of isonerization of alkyl radicals in beta-position,
with formation of a hyc!rogen bridge, which supplements
tho author's notions concerning the mechanism of Inter-
change and isonerizantion of free radicals (HUMin,
1956, 74392),
Card 1/1 - ilk -
CHIRMT, ~.M. -, VOTLFVO~D;SKlr, TOT. ~
Nikolai Nikolaevicb Se"anov, famder of the theory of chain
reactions; on the 60th anniversary of his birth. N.M# CbIrkov,
V.V. Voevodakit. Z.hur.fit.khim. 30 no.49722 Apr. '56. (MLRA 9:9)
(Semenov. Rikolai Nikolaevich. 1893-) '*
4
V,
USSR/-Phyeical Chemistry Molecule. Chemical Bond
Abe Jour : Referat Zhur - nimdya, No 2) 1957, 3462
B-4
Author : Vedeneyev V,'L,, Voyevodskiy V.V.
Title : Cleava."e Euer6y oftr---Z ~,na-sof Different Chlorides
Orie Pub -156
: Zh. fiz. I:nimii, 2
30, No 4) 789-793
.
,
Abstract : Fulfillment of the correlation F = cK Di(l),
wherein E: i -- enerLrj of activation of exothermic reac.
tion, D. -- cleavage energy of Rix molecule (Ri -- alkyl
radica!~, and r-< and q --constants., is illu~tratcl by
Y-
.
several exomples. Equation (1) is used to calculate the
cleavage energy of C - C! bonds on tha basis of known va-
IlLes Of D(CnH~-Cl) and D( Calculated values of
CH3'cl)'
cleavage enera are in sati5factory agreement with the
available experizental values. The conclusion is c3trawn
that equation (1) can be utilized to evaluate the elea-
vage eaerEW values of bonils on the basis of known values
of enerCy of activation, and vice ver3a.
Card 1/1 - 5 -
V0 V V v/
USSR/Physical Chemistry Kinetics. Combustion. Explosives. Topochemistry.
Catalysis, B-9.
Abst Journal: Referat Zhur- Khimiya, #o 1, 1957, 390
Authort Voyevodskiy, V. V., and Kabachnik, M. I.
Institution: None MWMNWMM*ft
Title: On Completing the Reactions Involving Isomerically Active Particles
Original
Periodical: Zh. fiz. khimii, 1956, Vol 30, No 4, 94-5-948
Abstract: On the basis of the Polanyi relations for single-type free radical
reactions, it is shown that whenever during a chemical reaction the
formation of free radicals which are sufficiently rapidly intercon-
vertible is possible, the direction of the reaction will be deter-
mined preferentially by the moot stable of these radicals. Its re-
duced chemical actiifity Is compensated by its considerably greater
concentration.
Card 1/1
VOYEVODSKIYI Y.V.; VEDRIUMV, M,
Possible mechanism of degenerat6d branching In hydrocarbon
oxidatiou reactions. Dokl.AN SSSR 106 no.4-.679-68Z F 056.
(MLRk 9:6)
1.1natitut khimichaskoy fiziki Akademii nauk SSSR Mookovskly
gosudarstyennyy universitat imeni M.Y.Lomonosovao
(Hydrocarbons) (Oxidation)
I K--
ll~ ffi.
OW-1-1- I
.1
-.1 = ~ . 111 ~- -3 ~ 4 ~~ff ;" ::-~m U:M --l
~ ~ - i~
Explosions,
Topochemistry, Catalysis.
Abs Jour Referat Zhur - Khimiya, 110 1, 1958, 501
Author V.V. Voyevodskiy.
Inst
Title Heteroeeneous Catalysis and Chain Proceosea.
Orif; Pub Khim. nauka I prom-at, 1957, 2, No 2, 16o-i66
Abstract Review.
Bibliography with 14 titles.
D-9
Card 1/1
N
VoyjjV0DS v denterium
-- ljl~ous and noteroge7o (MIRA 11o)
Moobanism Of homogf 44 5Z6 hosolytic
-obl. VAne i kat. 9:33- (catalysis)
exchar-ge. P, (Deuteriun)
AUTHORS: Lyadovaj Yu. I., Vedeneyevp V. I.p 20-1.144-36/54
VoyeYodokiy, V.
TITLE: Investigation of the Kinetics and the Mechanism of the
Thermal Decomposition of Isobutylene (Issledovaniye
kinetiki i mekhanisma termicheskogo raspada izobutilena).
PERIODICAL: Doklady AN SSSRt 1957, Vol- 114P Nr 6, pp. 1269-1271 (USSR)
ABSTRACT: The third author (references 1,2) suggested a chain-reaction
of the thermal decomposition of olefines which is based upon
the redistribution of the H-atom between a radical of the
allyl-type, and the olefine-molecule, where an alkyl radical
and a diene develop. He succeeded in determining from this
point of view the composition of the products of this
composition of olefines of various structure. It was,
however, not possible to extend these conceptions to the
cracking of such simple olefines as C 3H6 and i-C 4HS 9 as
no H-atoms capable of redistribution reactions exist in the
allyl-radicals developing of it . In another paper
(reference 2) the third author advocated the opinion that in
the case of the two above-mentioned olefines the formation
Card 1/4 of the reaction products is always preceded by an addition
Investigation of the Kinetics and the Mechanism of the Thermal 2D-IU-.6,36/54
Decomposition of Isobutylene
of the allyl-radical to the double bond of the olefine. The
authors intended to obtain additional data on the chain
character of this decomposition as well as to check the
hypothesis concerning the transfer of the H-atom to the
olefine double bond. The cracking of isobutylene was
studied at between 542 -and 6200 and at a pressure of
100-500 mm torr. Furthermore experiments with a mixture
of i-C 4H8and C2H4 were made at 542-6000 and 200-600 mm
pressure. The thermo-chromatical gas-analysis showed that the
main products (gases) of the isobutylene-crackifig are
C3H6' CH4, i-C4 a10' C2H4and H2 beside small quantities
of 02H6 and C 3H.. Figures 1 and 2 show the modification of
the composition of these gases with a modification of pressure,
as well as the percentage of conversion. The extrapolation of
the curves which describe the dependence of the composition
of the gas products on the percentage of conversion to the
zero-percentage of the conversion makes it poonible to
determine the primary reaction-products and their relations.
Card 2/4 From the cracking of i-C 4H8 up to 10% isobutane is obtained
Investigation of the Kinetics and the Mechanism of the Thermal- M414-439/54
Decomposition of loobutyleno
as one of the primary products. This quantity Increaneo with
increasing pressure and with decreasing temperature. This
shows that the addition reaction of the H-atom to the
double bond of isobutylene takes place under the conditions
given here. In order to further determine the problem of the
transfer of the H-atom to the olefine double bond, the
cracking of mixtures of i-C 4H8, with 02R4was studied. The
results in table 1 permit the following conclusions:
1) They confirm the conception on the chain mechanism of the
reaction. On the other hand the development of ethane in large
quantities furnishes another proof that the transfer reaction
of the H-atom, to the olefine double bond is possible. The
authors are of opinion that their tests confirm the assumed
reaction in isobutylene-crackings:
A + i-C4H8 M + 6 4H9*
The same applies to the mixture of isobutylene-ethylene;
i + C2 H4---- > M + 62H5*
Card 3/4 The comparison of the analysis results of the primary gas
investigation of the Kinetion and the Thermal 20-114--6--.36/54
Decomposition of Isobutylene
products and the composition of the liquids leads to the
conclusion that the cracking-scheme sugggested by the third
author of C H and i-C H is insufficient. New ways of the
3 6 4 8 0
transformation of the radical i-C 4H7 must be introduced
to this scheme. The decomposition to bH, and "allene" may
be supposed as such, as well as the transfer reaction of the
methyl-radical from i-b 4H7 to the isobutylene molecule. Allene-
formation was observed in the cracking of isobutylene
reference 4). Under the conditions given here it isp however,
unstable and completely disappears from the gas phase during
the duration of test. There are 2 figures, 1 table, and 5
references, 2 of which are Slavic.
ASSOCIATION: Institute for Chemical Physics AS USSR (Institut khimicheakoy
fiziki kkademii nauk SSSR)
PRESENTED: January 14, 1957, by ff. It. Semenov, Academician,
SUBMITTED:* January 12j 1957
JI ':i-
Card 4/4
VOYEV0051,~11'-I) V
TSETKOV YU.D. VOYLVODSKIY V.V.,RAZUVAYLT G.A., 20-1-32/54
S 0 R 0 K I I I Y u . V . , 1) ;tEd-C-r__V" -^ T'.-r
iITLE Electron Spin Re3onance in Some Sandwich Type Chro=aroriatic Co=poands.
(Elektronnyy. paramagnitnyy rezonans v nekotorykh khro-marc=atich~s-
kikh soyedineniyakh sandvichevogo stroyeniya -Russian)
PERIODICAL Doklady Akad.Nauk SSSR,1957,Vol 115, Nr 1, pp 118- 121 (U.S.S.R.)
ABSTRACT In recent times increased interest was devoted to the study of the
mentioned compounds of the ferrocene type,(Fe(C5H5)2),the ferrocene
ion and analogous molecules with aromatic addenda.In spite of a great
number of papers on this subject,there hitherto exists no eeneral
theory which might explain the present data on the 1'sandwich"struc-
ture of these m-oleculea.Their formation and steadiness cannot be ful-
ly explained by the generally accepted conception of valence.The da-
ta obtained indicate that in the majority of compounds of this type
the linage of addenda with the complex-forming atoms is of a cova-
lent character.This Is especially indicated by magnetic measurements.
According to the latter these materials are either diamagnetic or
they possess a magnetic mo=entum which correspond s to one,two cr
at most three non-paired electrons.The ion salts of these metals of
such compounds by the method of electronic paramagnetic resonance
(called EPR in the following) have hitherto been described in pu-
blications.The present paper given measurements of the ;OR spectra
of the following compoundst Cr(C6H6)2J (I),Cr(C6115)2J (II) and Cr
Card 1/;J, (C6H5 - C6H5- C6H5)2oC6H5 (III). The static magnetic susceptibility
Electron Spin Resonance in Some Sandwich Type Chromaro- 20,rl-32/54
matic Compounds.
of these materials correspondsto a single- non-coupled electron.The
presence of a hydrogen-overrefined structure of the absorption line
in solutions of the materials II and III can be explained in two
wqys. 1.The non-coupled electron and the positive charge of the
complex are located onthe chromium atom. The estimation made on the
basis of this assumption shows that the density of the non-coupled
3d-electron on the positions of the hydrogen atoms of the aromatic
rings is sufficient to effect an "overrefined" cleavage of the EPR
spectrum.2.The non-coupled electron and the positive charge are loca-
ted on the aromatic addenda of the complex.The overrefined structu-
re is in this case due to the interaction of the non-paired x.elec-
tron of the aromatic rihg with the hydrogen atoms of this ring.The
extent of cleavage, the number of components and the ratio of their
intensities are in this case dependent on the distribution of elec-
tron density on the addenda molecule.The following facts speak in
favor of the first aesumptiont a) presence of the anisotropy of the
g-factor in the materials I and II, b) the value of the g-factor is
less than that of a free electron.The true picture of density di-
stribution of the non-ooupled electron is probably a superposition
of the two extemua cases mentioned above.
Card 2/~~ (2 illustrations, 2 Slavic references.)
/Slo'iz , U 'L
iel'141z_~' /// f 4 .11 /jj
VIVI
AOTHORS: Kazanskiy,
144 TITLE;
V. B.'v Voyevodskiy, V. V. 20-4-29/51
Note on the R81e of Hydrogen Atoms in the Catalytic
Oxydation of Hydrogen on Palladium (0 roli atomov Yodoroda
v reaktaii katalitioheskogo okisleniya vodoroda na palladii).
PERIODICAL: Doklady AN SSSR, 1957Y Vol- 116, Nr 4, pp. 633-636 (usn)
ABSTRACT: Wagner (vaguer) and Hauffe (Khauffe) (reference 2)
investigated the mechanism of the catalytic oxydation of
hydrogen -on metallic palladium by comparing the
stationary concentration of hydrogen atoms at the surface
of the catalyaator with the concentration corresponding to
equilibrium. On this occasion the authors established, that
a chain-like mechanism of this reaction is posaible. The
authors of this paper examined the final conclusions by
Wagner (Vagner) and Hauffe (Khauffe) by an independent
method, using a different experimental procedure. According
to modern conceptions a dissociation of the hydrogen
molecules at the surface of the metal takes place in the
adsorption and dissolution of hydrogen in metailic palladiuz,
Card 1/3 resulting in the formation of adsorbed atoms, The solution
Note on the R81e of Hydrogen Atoms in the Catalytic 20-4-29/51
Oxydation of Hydrogen on Palladium
and diffusion of hydrogen within the metal apparently
takes place in the form of ions. The authors compared
the stationary concentration of the hydrogen atoms on the
surface of the palladium with the concentration corresponding
to equilibrium with the help of a diffusion process In a
vacuum circulation apparatus. A capillary tube consisting
of palladium served as a catalysator. The numerical data of
the experimental arrangement are given here, and the occurse
of the experiments is explained. The results from some of
the experiments of the authors are compiled in a table.
According to these data the stationary concentration of
the hydrogen atoms in the reaction zone in considerably
smaller than the concentration corresponding to equilibrium.
For the purpose of a more precise investigation of the
mechanism of the reactiont the authors computed the deviation
of the stationary concentration of the hydrogen atoms at
the surface of the catalysator fro m the equilibrium coacentra-
tion with the assumption of a radical mechanism. The data
computed in this way were then compared with the experiment.
Card 2/3 Oxygen does not modify the mechanism of this reaction. The
Note'on the R81a of Hydrogen Atoms in the Catalytic 20-4-9-0/4
."r A
Oxydation of Hydrogen on Palladium
good accordance of the experimental data with the computed
values speaks in favour of the radical mechanism of the
oxydation of hydrogen on metallic palladium. The data
obtained here without doubt speak for the factp that in the
case of palladium the reaction takes place with an inter-
action between the hydrogen atoms adsorbed at the surface
of the oatalynator and oxygen.
There are 1 figure , 2 tables, and 11 references, 5 of
which are Slavic.
ASSOCIATION: Moscow State University imeni M. V. Lomonosov (Moskovakiy
gosudarstvennyy universitet im. M. V. Lomonoao* Institute
for Chemical Physics AN USSR (Institut khimi ahes~oy fiziki
kkademii nauk SSSR)
PRESENTED: April 12, 1957, by N. N. Semenov, Academician
SUBMITTED: April 5, 1957
AVAILABLE: Library of Congress
Card 3/3
5 071'i" -,-, I .. 1-1/i9
voycirodskly, V,V., 1!oliii, Y~x.% aad 01-tlbri;ciri,
,5 Tr,! OZ3
s Eloctron Paraaagzmz3tic Razona, So ~f
JTLP
, I Various Substli;aw-Ats (3rt.-.rj Aaktrcanoorl
with
razonansa Cr-arajutichoskikh r.-- enlys razlich-qyA
IIZ,q I OD I CU sOPtika i SPektrOul-COplya, 1956, 'rol 6, 11r 1, pp 00-~-2 (U""~(l
ABS M.UCT., The oresent noto reportj cor.4-juautloa of iho work do:icr1'-O,J ia
Ref 1-2 on alectron par,%."6netl,~ rosonaapa apo.tra of fjoluti-,ij
I
or (06H6.- 2 Cri, (C6H5 . G6'ill)2 Orl, (Ce-5 . C61i8)(06H6)"
jH5)2 CrI. These cot-,ipoundz are danot 1 1, 11.. 111 ard
(CtiHS . C(
IV respectively In the present nota. Tho piA~rpoia of rho .1or'.,C
to find tho effect of substibition of I%-,ha distriWt-ioa of 14-an3ity
of unpaired elacbroau. Isopropyl alco*.-ol, acatone, pyridlnj aryj wat.)r
were used au solvents. All moaw-,re., ixatz wara made -at ra--.,
a SpaCtrOU31W-3r workin6 at 91,00 -1 J3pt'. of
using Z Mc/s . The itlo-
the nagnotic field was 2 Oo. Tha 6-factor, tho to-"l
in Oe, the separ.-vsion of tho hyparfina stractur3
and the nizaboi of re3olvad hyp.,)rfine stz-,.;,cbra (h.f.;;-)
Card 1/2 for tile compounds I-IV in isopropyl alcohol are given i~. t-"*1-1-3
Electron Para0agnotic Resonaric3 Spactra of Grnilraaatic Corjpa4nda with Variouj
Substituent3
on p 91. The convistoncy of L: atul AH in tlrk-~) 3aries vf
I-IV indicates thii; introdiAcPioa of a substittiont Into f;!v,) ~onzona
ring does not iauterially chanra tho dirtrilyAt-Icn to-V tlatialty of
unpaired oleetrons betfriaa Cr and the benzene rinj;s. Imprwu,3at
of the resolution of the apactnx4 (see +.he figure en p 92'~ -r- Golinr,
from the coiapouud I to the cwpound IV was observed. TM a,!-hora U~,a
the folloytinG coilclusions . (1) In dilute jolatiors the
coi-iponeat vidth coases to depand on concantrlt~.oa below a cartain
concentration which is differant for different raolvont;i. (2, !?.G
,,-Jidth of h.f.a. cotaponeats in dilute sol-ations depends or; the i.,at-Ira
of the solvent-. (3j On inzraase of the solut-ion tho
h-f-u. disapp.:~ars at differeat ccneentrations in different sol-anta.
Th3 main reason for the disappearance of the h.f.s. is tho
13
interaction bot-nean paramagnatia particles. The auth3rs Uhank
Professor G.A. RazuMyev (Gorlk# Institute of Organic, Chemlsl~ry) and
Profassor F. Hain (Institute of' Inorganic Cheirtstry, Jena, B.";terr-
,'J~trd 2/2 Germany) for supply of Itho -_aap,)a_ndr. studied. There a.-,) I fij;Ur-,j,
1 table and 5 rofarencas, Z~ of nlilch are Americ.-in and 2 So-.11A.
ASS0=170111 Inatitut. ~~himicheskoy fiziki, All SSSR (Institute of Ghw,".al Irbysics,
.Aaade;ay of Sciences of the U.S.S.R.) 1. Motalorganic compormds-Spectro-
SUBLaTTSD: January 9.7, 1958 graphic aralysis 2. Metalorganic couTcumds-Ma&netic
properties 3. Cyclic compounds-Prtgortles 4. Chromi=
iodine compounds-Properties
AUTHOR: Molin, Yu. N., Voyevodskiy, V. V. 57-1-19/30
TITLE: Investigation of Action of the Ionizing Radiation on
Quartz by the Method of Electron Paramaenetic Resonance
(Issledovaniye vozdeystviya ioniziz-uyushche,,go izlucheniy;%
na kyarts metodom elektronnogo paramagnitnogo rezonansa)
*PERIODICAL: Zhurnal Tekhnichozkoy Fiziki, 1958, Vol. 28, Nr 1,
P9. 143-149 (USSR)
ABSTR.ACT: The investigation of the paramagnetic reDonance absorption
was carried out on a spectrometer of the Superheterodyn
type with 9.300 me and of a sensitivity of 5.1014 of the
diphenylpierylhydrazil - (DFPH) - radical-particle. (ref.
10, 11.) The samples of the crystalline quartz are pro-
duced of rock -crystal. 6o
The quartz samples were irradiated with V-rays of Co
Irradiation and measuring were carricd out at room
temperature. On the occasion of the investigation of the
temperature influence on the behaviour of the defects the
samples were heated in the electric furnace (outside of the
resonator). Molten quartz whi,,.h has be-2n irradiated with
y-rays and crystalline ij-cartz irradiated with, 7-raya and
Card 1/5 neutrons were investigated. The molten quartz which had
Investigation of Action of the Ionicing Radiation on 57-1-19/30
Quartz by the Method of Electron Paramarnetic Resonance
not been irradiated ouve no signals of paramapetic
absorption. On the occasion of irradiation the quartz
became -violet and showed two abuorption lines. Thece
lines are called a and P signale according to their
sequence in th,- magnotic field. The parama,-netic sentres
which L-ive the a and P 3iCvals are here called a and P
defects. The a siCnal showed no sien of saturation.
Saturation of thP p signals oc--urred without change of the
signal. Width ana ohape of the p eigmal seem to be due to
the anisotropy ~f the 0-factor. The shape of the saturation
curve of the P-sianal was analysed according to the methods
dencribed in Ref. 13 and 14 and a value of the order of
-
=Cnitude of 10'
Isek ras obtained for the time of the spin-
-lattice-relaxation T1. The investigation of the dependence
of the concentration of the a and P-defects an the
irradiation dose showed chat in the case of doses of an
order of magnitude of 10 the defect concentration reaches
saturation. In the first part of the curve the concentration
of the P-defec'. is proportional to the square root of the
irradiation acae. Because of insufficient accuracy of the
Card 2/5 spectiometer the first section of the curve for the a-effect
investigation of Action of the Ionizin '- Radiation on 57-1-19/30
quartz by the blethod of Electron Paramagnetic Resonance
could not be recorded. In accordAnce with ref- 7 and 6
it could be observed that on the occasion of the heating
of the irradiated molten quartz up to 300 and 4000C it
turned from violet into blue. Thu heating was accompanied
by chanUes, in the spectrum of the paramaenetic absorption.
It could be observed that when the a-sigmal disappears
the P-oijnal increases aimultaneoanly. The initial cor-
centrntion of tho a-dofects is about throe times greater
than that of the P-defects. The b-ginding of irradiated
quartz into powder does not change the intentity of the
a and P-sienals. It influenceop however, the behaviour of
the P-aiGnal on the occasion of heating. Due to the
Erinding the temperature at which the P-defect disappears
changes by 3500. The following was observed on -the occasion
of the investigation of cryntalline quartz:
1) The monocrystal C;ave no signal of pftrama,-~nctic absorption
after irradiation with y-rays (107r6i,tgan), neither at
room temperature nor at the temperature of liquid nitrogen.
2) At the same irradiation fine polyarystalline powder
Card 3/5 gave a weak siGnal which as to its 3ha;;e and position on
Investigation of Action of the lonizina Radiation on 57-1-19/30
Quartz by the Method of Electron Faxamagnetic Resonance
the spectrum was similar to the P-signal in molten quartz.
In the case of (;reat amplitudes of the radiation-frequency-
-field this sigmal 11oaturated" like the P-signal.
3) After irradiation by means of a nuclear reactor (y-rays,
neutrons) the monocryntal anve the same mi,-nal as in case
2, it was only soLewhat more intense. Besides, some weak
siGnals were observed in the ran,,-e of C 2. The dependence
of the conce,--ration of the P-defects on the irradiation
dose observed here, can be explained 1by considerin(.: the
finite number of traps and by takin(; into consideration
that nimultaneov-sly with the process of capturing of free
electrons arid holes throuj;h the traps also prooeases of
recombination of free electrons with the captured holes
and of the free holes with the captured electrons occur.
It is presumed that paramagnetic absorption in irradiated
quartz is due to the electrons and holen captured by the
structural defects. It. simple table iz; r-liven on the basis
of which the fundamental qualitative rules of the
accum-alatior.-kinetics of pararria~;natic defects can be ex-
plained. The behaviour of the a and P-defects on the
Card 4/5 occasion of heatin.rr can equally be explained on the basis
Investigation of Action of the Ionizing Radiation on 57-1-19/30
quartz by the .1fethod of Electron Paraiagnetic Riso-t--nce
of this model. There are 6 fieures, and 14 references,
1 of which is Slavic.
ASSOCIATION: natitute for Chemical Physica All USSR Moscow
~Inntitut khimicheskoy fi?iki All SSSR Mockva)
SUBMITTED: May 3, 1957
AVAILABLE: Library of Conu-,ress
Card 5/5
AUTHORS: Ivanov, 0. A.p Fokp N. V., 2o-U8,-6-26/43
Voyevodakiyp V, V.
TITLE: Reaction Between Methyl Radicals Obtained According to the
Method of PolawAliand Deuterium (Reaktsiya metillnykh
radikalov, poluchennykh po metodu Polyani, s deyteriyem)
PERIODICAL: Doklady Akademii Nauk SSSR, 1958t Vol- 118, Hr 6,
PP. 1142-1145 (USSR)
IBSTRACT: First previous papers dealing with the same subject are
shortly referred to. The authors produced the methyl radicals
according to the method of Polanyi (Polyani) according to the
reaction CH 3J + Na. - CH3 + NaJ. The reaction passed in presence
of molecular deuterium which was used as carrier gas for sodiun
vapors. The acheme of the experimental arrangement is
illustrated in a figure. The reaction container in ihich the
jets of CH 3J combine with those of deuterium consisted of a
quartz cylinder with a nozzle. In one series of experiments
the inner surface of the reaction container was covered with
Card 1A sodium which was applied in form of drops or ae.reflecting
20-118-6-26/43
Reaction Between Methyl Radicals Obtained According to the Method
of Polydni and Deuterium .
coating. The deuterium used for the experiments was produced
electrolytically from D 0. The authors detected the composition
of the methanes obtaineg in a pure quartz container in the
temperature interval of from 20-4800C- Under these conditions
mainly CH 4 and CH3D are obtained. The quantity of the semi-
deuterized methanes- is small and reaches the value 18-20% only
in a small temperature interval near 2000C. The ratio CH 3 D/CH4
increases in the interval of from 20-IOOOC from 0,6 to 2, and
remains constant in the case of further temperature rise. The
deuterium content in the investigated methanes is considerably
changed in the case of a deposit of metallic sodiun on the
surface of the container. Here the connection between the
portion of the different deuterized methanes and the temperature
depends on the kind of applying of sodium to the surface. In
coverming the container surface with a reflecting sodium the
Card 2/4 percentage of to a great extent deuterized methanes (CD 4, CD3H
20-113-6-26/43
Reaction Between Methyl Radicals Obtained AccordinL.- to tio,
of Polyani and Deuterium
and CD2H2) is at room temperature by 5 to 8 times greater than
in a pure quartz container. In the case of a temperature rise
the percentage of the to a great extent deuterized methanes
decreases. In the case of sodium drops the surface reaction
is insignificant and its portlon of the volume of the methane
produced amounts to totally only 1/5- Here the methanes
obtained from the radicals CH contain much more deuterium
3
,than in the case of a reflecting coating sodium. The maximum
,of the deuterization at 70-8000 is striking. At higher
temperatures CH4 and CH 3D predominate again. In the case
of sodium drops the light methane is not exchanged with D2 as
it is the case in the oaae of existence of a reflecting
coating. This exchange has to take place with participation
of the methyl radicals independently of the kind of mechanism
Card 3/4 of the production of CH211 2' CH3 D and CD 4'
20-118-6-26111-
Reaction Between Methyl Radicals Obtained According to the Method
of Polyani and Deuterium
There are 3 figures and 0 references, 3 of which are Soviet.
ASSOCIVION: Kafedra khimicheekoy kinetiki Moskovskogo gosudarstvennogo
universiteta im. M. V. Lomonomova
I
tChaiy~ of Chemical 'Kinetich,~ Moscow State -University
imeni M. V. Lomonosov
Institut khimicheskoy fiziki Akademii nauk SSSR
(Institute of Chemical Physics.1s USSR)
PRESENTED: July 26, 1957p by N. N. Semenov, Member, Icademy of Sciences
of USSR
SIBMITTED: July 19p 1957
Card 4/4
AUTHORS: Chernyak, N. Ya., Bubnov, It. IT., SOV/2o-12o-2-34/63
V olak, L. S., Tavetkov, Yu. D.
TITLE: The Formation of Free Radicals and of Atoms in the Radiolynis
of Hydrocarbons at a Temperature of 77 0K (0b obrazovanii svobod-
nykh radikalov i atomov pri radiolize u-,lcvodorodov pri tem,.cra-
U
ture 770K)
PERIODICAL: Doklady Akademii nauk SSSR, 1950, Vol- 12o, Ur 2,
PP. 346 348 (USSR)
ABSTRACT: Refererc i are made in publications to free radicals forned
during the action of ionizing radiation, as by X-rays, y-
radiation, fast electrons etc. This in causedby a rupture of
C - C and of C - 11 bindino,s. When fluid hydrocarbons are
radiolysed, the life of the free radicals is very short. The
main products of radiolysis, apart from liquid products with
one or two conjugated double bindlngc, are 11 2 and C14H30' The
latter compound is connidered to be a dimer of the heptyl
radical. The method of determining the radical in chortly
Card 1/3 described. The followin- hydrocarbons sere investig~.ted: hexare,
1~
TheYormation of Free Radicals and of Ato-is in the SOV/2o-12o-2-34/63
Radiolysis of Hydrocarbons at a Temperature of 770K
heptune, octane, dodecane, cetanc, isooctane, cyclohexane,
benzene and toluene. In all cases intensive signals of para-
magnetic electron resonance with a g-factor of,-v 2,0 are
observed. In paraffin-type hydrocarbons and in cyclohexare a
hyperfino structure was very clenrly observed. According to
the attached photot;rapha the hyporfine atriicture is c=jiderably
changed if the structural properties of the initial molecule
change. Another peculiarity of the spectra pf parama~rnetic
electron resonance of tha hydrocarbons which are irradiated in
a frozen state is the existence of considerable concentrations
of hydrogen atoms. This is aloo indicated by two narrow signals
-which are located symmetrically at a distance of about 250
Oersted (Ersted) from the si,:nals of the alkyl radical, The
hydrogen atoms probably do not become stabilized in the volunc
of the frozen hydrocarbons but on the internal surface of the
quartz ampoule. In a table the quantitative measurements per-
formed on the basis of the example of heptane concerning the
concentration of the free radicals with a dose of^j jo7r are
compared with the data of the chemical analysis of a sample
Card 2/3 irradiated under absolutely identacal conditions. Th-- results
The Formation of Free Radicals and of Atoms In Me
Radiolysis of Hydrocarbons at a Temperature of 770K
obtained by both measurements agree in a satisfactory manner.
There are 2 figures, 1 table, and 4 references, 2 of ithich are
Soviet.
ASSOCIATION: Institut nefti. Ali SSSR (Petroleum Institute,, AS USSR) Inatitut
Ithimicheskoy fiziki, AN SSSR (Institute of Chemical Physics
AS USSR)
SUB1-1ITTM: Janua--Y 11., 1958
1. fact!~r:; 2. Free radicals
-Fro67-'otion 3. Atonx-Production 4. V'Ydrccarl.ona
-Test results
Card 3/3
~'W SOV/20-122-2-27/4-2
AUTHORS: Tikhomirova, 11. 11., Lukin, 13. V., Pazumovn, L. Lp,
.Voyevodskiy, V. It., Corresponding Member, Academy of Sciences,
TITLE: Using Electron Paranagnetic Resonance and Roentgenography in
StudyIng the Structure of the Carbonization Products Obtained
From Carbon-Containing Substances
(Is.,.-ledovaniye atrcyoniya produktov karbonizataii
uglerodsoder-,hashchikh veshchestv T-etodon clektronnof,,-o para-
ma,-nitno3o rezonansa i rentgonografiyey)
PERIODTCAL! Doklady Akademii nauk SSSR, 1958, Vol 122, Ur 2, pp 264-266
(USSR)
ABOTRACT; The method of paramaEne-tic electron resonance permits im-
mediate detection of free radicals in the investigated system
and a measurement of their concentration. In order to find
the possibilities which are given by the investigntion of
.the structure of carbonized subttances bythe
method of paramagnetic electron resonance (and simultaneous-
ly by radiography), the authors investigated the structural
Card 1/3 variations caused by the carbonization of polyvinyl chloride
SOV/20-122-2-27/42
Using Electron Paramagnetic Resonance and Roentgenography in Studying the
Structure of the Carbonization Products Obtained From Carbon-Containing
Substances
and polyvinylidenechloride. The carbonization was carried
out in an inert atmosphere in the -temperature interval of
350-7000C. The signalof the electron paramagnetic resonance
(which indicates the existence of free radicals) appears in
the first stages of the carbonization of polyvinyl chloride
and polyvinylidenechloride(beginning with 3500). A diagram
shows the variation of the signal width for the 2 investigat-
ed substances as a function of the carbonization temperature.
A relatively wide line (7 Gauss) in poly-vinyl chloride is
an argument in favor of an essential influence of the hyper-
fine splitting up on hydrogen nuclei. Such great widths are
characteristic of some natural coals. In the case of poly-
vinylidenechloride (especially in the initial staees of
carbonization) the line of paramagnetic electron resonance
is by far narrower than that of the product of the carboni-
zation of polyvinyl chloride. According to radioC.~aphic data,
an increase of the calcination temperature to 450 0 only
slightly changes the character of the products of the carboni-
Card 2/3 zation of polyvinyl chloride. Other results are then discussed.
SOV/2o-122-2-27/'42
Using Electron Paramagn6tic Resonance and'Roentgenography in Studying the
Structure of the Carbonization Products Obtained From Carbon-Containing
Substances
."ccordint-, to these results, the appearing of a wide signal
is connected with the existence of free valences near the
individual carbon nets or blocks in which conduction elec-
trons appear. There are 2 figures.
SUBMITTED: June 28, 1958
Card 3/3
SOV/2o-122-6-27/49
AUTHORS: Tavetko-, Yn. D., rhibnoyt N. 7.1 Yal.Ul'akly; Y. A.,
Laourkin, Yu. S. , Voyevoclakiy, It. V. tCorresponding Member,
AS USSR
TITLE: The Investigation of the Spectra of the BlectranParamagnetic
Resonance of Some Polymers Which Were Irradiated at 77 K
(IBolegovaniye spektrov e.p.r. nekotorykh polimerov,obluchennykh
pri 77 K)
PERIODICAL: Doklady Akademii nauk SSSR, 1958, Vol 122, Nr 6j PP 1053-1056
(USSR)
ABSTRACT: The athors carried out the above investigation for the pur-
pose of solving several problems connected nith the structure
and chemical behavior of organic radicals in the solid phase
as well as with the mechanism of chemical transformations
in solid organic bodies under the influence of ionizing radia.-
tion. Poly?th~lene, polyvinyl chloride, "Teflon" (polyethylere
tetrafluoride , polydimethyl siloxane, polyisobutylone, poly--
methyl methacrylate and natural rubber were investigated oCar.-
13 rying out of the experiments is described in short. At 7~ K
Card I a.very intensive signal of paramagnetic electron resonance
SOV/2o-122-6-27/49
The Investigation of the Spectra of the ElectraiParama,-,netic Resonance of
Some Polymers Which Were Irradiated at 77 0K
with a g-factor near 2.0036 was observud In all samples. After
"thawing" of the sample down to room temperature the signal
was in all cases found to change. In some cases, the signal
vanished completely as a result of "thawing" (polyisobutjlene,
polydimethyl siloxane, natural rubber). In the cane of other
materials the character bf the signal and its fine structure
changed considerably. A comparison of all data obtained gave
the following result; The character of the spactra obtained
by investigating not "thawed" samples can be fully explained
by the assumption that the predominant primary chemical act
in irradiation is the atrippin.r', of one of the C-11 bonds in
the main chain (or in the absence of a main chain the strip..
ping of a C-H bond in a laterall chain). The opSetrun of
paramagnetic electron resonanne recorded at 77 K consists of
6 components. The even number of tho spectrum in this as well
as in other cases is connected with the formation of the radi-
cal -Ch 2- 611-CHi-, . The authors then discuss several details;
especially such as concern the investigation of Teflon. By
Card 2/3 the irradiation of Teflon at low temperatures it is possible
SOV/2o-122-6-2T/49
The Investigation of the Spectra of the Electron Paramagnetic Resonance of
Some Polymers Thich W;re Irradiated' at 77 0Y
to obtain materials with fully satisfactory mechanical
properties. These substances contain a large quantity
(,vO.1 %) of free radicals. There are 2 figures and 7 ref-
erencesq 4 of which are Soviet.
ASSOCIATION: Institut khimicheekoy fiziki Akademii nauk SSSR
(Institute for Chemical Physics of the Academy of Sciences )
USSR)
SUBMITTED: July 24, 1950
Card 3/3
AUTHORSt
TITLEt
~:-PXRIODICAL:
ABSTRACT:
Card 1/4
SOY/20-123-2-23/50
Moiseyev, V. D., Lyadova, Yu. I., Vedeneyev, V. I., Neyman,
B., Voyevodskiy, V. V., Corresponding Member, AS USSR
Ways of the Formation of Propylene and Ethylene in Isobutylene
Cracking (Puti obrazovaniya propiiena i etilena pri krekinge
izobutilena)
Doiclady, adexii nauk SSSRf 1958, Vol 123, Nr 2, pp 292-294
(USSR)
As is known, up to 50% of the initial substance in thermal iso-
butylene-dedomposition are transformed into liquids (olefins,
Akbmalic compounds). Apparently the polymerization of the
ini'tial dlefin rorms the first stage of the liquid formation,
with dimerid and trimeric olefin being formed. The latter them-
selVes are capable of being transformed in various ways with
thb'ffnal result being liquid cracking products. The ratio
b~6t*een ca)rbon and hydrogen in the~e'products is about 1 (Ref 2),
*hekeas'it is 2 in isobutylene. From this may be supposed that
hydrogen and methane'-are separated in the formation of'the
liquids; in principle, also heavier cracking gases with 2 and
73 carbon atoms each in the molecule can be formed. The problem
SOV120-123-2-23150
Vays or the Formation of Propyleno and Ethylene in Isobutylene Cracking
epneerning the type and amount of the gases escaping from the
liquids or in their formation is not'investigated at all.
P3~601'ene 'is one of the main productis 6f isobutylene cracking.
If"iV*6rb fo:emed from isobutylen# only, its formation veloc-
itt viodld-d6dre7ase with the'exhaustion of the isobutylene. 11'
pftp.Ylo~ne' however, - formed trost the 'liquid or from any other
~fiVeroefdf6te' pr6duct*of' low 'stiability (not from radicals), its
'-,rb'fm'iitVon 'velocity'in -the beginnipg of the reaction must be
6qual to zero, and then increase According to the law of sue-
dei~siVe reactions. If both'*AYA,of the formation of propylene
drd-6orrect the two pidtdke's: dubt agree. This wan the case in
thb pieseht'_ekperim6nts. The dhan&o''of the forma%izn velocity of
propilene-was investigated by the isotopic kinetic method (Ref
3)-.Ye.. D...-Fedorov took part in the synthesis of the marked
]~jF6pyIIen6'(with C14 on the hydroxyl group)'. This piopylene
(15_.toi'�)'wa`s.'aubjedted together with isobutylene (285 torr)
0
:to. a., crackdng-In --iracuum at - 542 -:.The-course of the specific
activtty cc and of the C H concentrations are given in figure I.
3 6
Card 2/4 Figure 2 gives the formation velocity of propylene w.,' In the
SOV120-123-2-23150
Ways of the Formation of Propylene and Ethylene in Isobutylene Cracking
.begi.nning..of-the reactions this value wi is not equal to zero;
Lt.'increases during the first 10-12 minutes, i.e. to about
20%,isobutylene.transformation. This,wi increase tends to show
'th'at"a^dbhdi`derable propylene amount in isobutylene cracking is
ho't"':rormhd*f`rom isobutylene but from any intermediate products
bf-the cracking,'obviously from liquids. As may be seen from
'fi:gure 2, the formf~tion velocity of propylene passes a maximum
*fthih the range 0t 10-:14 minutes and then decreases. The
authors' condider'it to be prematu:ee' to draw any conclusions.
The"ethylene activity determine'd in some experiments besides
IU dpe6ific'a6tivity of propylene is given in figure 3- As
this activity is much lower t4an that of propylene, this tends
to show that only part of the ethylene is formed from propylene.
Also ethylene can be 'formed either from isobutylene directly
or'from liquids. Based on the experimental results obtained it
is-not possible to make a decision as to the way of formation
prevailing;'The fact that propylene is formed from liquids
tends to show the possibility of the ethylene formation from the
Card 3/4 latter. There are 3 figures and 4 'references, 2 of which are
SOY/20-123-2-23/50
Ways of the Formation of Propylene and Ethylene in lsobutylene Cracking
Soviet.
ASSOCIATION: Institut, khimicheskoy fiziki Akademii, nauk SSSR (Institute of
Ch6mical Physics AS USSR)
SUBMITTED; July 28, 1958
Card 4/4
-'5M . SOV/20-123--5-31/50
AUTIJ )RS: Molin, Yu. 11., Koritskiy, A. T., Buben, N. Ya.,. Voyevodse:iy,V-V-'1
Corresponding Member, Academy of Sciences, USSP
TITLE: The Investigati,on of Free Radicals Formed in Zolid 11o,lion in
the Process of Irradiation by Fast Electrons (Isslerjovaniye
avobodnykh radikalov, obrazuyuehchikhoya v tverd.,T1zh tela'1:11
v protsesse oblucheniya bystrymi elektronami)
PERIODICAL: Doklady Akademii nauk SSSR, 1958, Vol 123, Nr 5Y pp 882-88)
(USSR)
ABSTRACT: The authors endeavored to detect radicals of short life-,times
in solid bodies formed by fast electrons. The present paper
gives data concerning radicals of life-timea of some minutes.
The authors constructed an apparatxis for t4o' immediate re-
cording of the spectrum of the paramagnot-'6 electron resonance
during the irradiation of the investigated specimen. Prepara-
tion of the samples is.discussed in short. The experiments
wore carried out at room teoperature. The authors observed a
signal of paramagnetic electron re.;onance (luring the irradin-
tion of the specimen and after the interruption of the irradia-
tion. 4"fore than 20 various substances wore investigated,
Card 1/3 namely polymers (polyethylene, nylon, caprone, polymethyl
The Investigation of Fr,-e R;~Iicca_!:~ For:-e!1 Sz~1i-' _-r~ces_-
of Irradiation by Fast _i_lectrono
metacrylate, teflon, and varirua ijpacimena of rubber), 3olid
organic acids and their salts (oxalic acid ond their salts,
succinic acid arfd theJr sodium atr~ar-'to acid and citric
acid), aromatic compounis Oru---Jhthalen,~, a--naphthol, P-naphthol,
bonzoyl peroxide. matol). In all tho investigatod samples,
the concenLration of the radicals reachod naturati,,-n at dones
of some dozens of me~-,arad. In the ca.--P. c.f tha najority of the
investigated substances, the protl-.Aced radicali were rather
stable, their life-tire amounted to ionu hoiirn(in some cases
also to longer pariodj). Some dotail~ are ,-ivr,,n in short.
During the irradiation of po1yot'ql'jn,.), the authoi-3 could re-
cord tho radical which is not stable at room
2
temperature. The spectrum of this radical is shown in a fig-
ure. According to measurements at temperatures below room
temperature, the rate of converaion of the primary radical
into the second one decreases with a de,-.rease of temperature.
There are I figure and I Soviet referenne.
C';lrl 2/3
BOV/2o-123-5-31/50
The Investigation of Free Radicals Forned in Solid Bodies In the Process
of Irradiation by Past Electrons
ASSOCIATION: Inatitut khimicheskoy fiziki Akademii. nauk SSSR
(Institute of Chemical Physiou o. the Academy of Sciences,
USSR)
SUBMITTED: Auguat 11, 1958
Card 3/3.
I
~IOYE-Vouskly V. v
VOEVODs,ay, v. v.
"Lmr-Temperature Radical Reactions in Solid Bodies."
paper to be submitted Fourth Intl. Symposium on Free Radical Stabilization) Washington,
D. C-) 31 Aug - 2 Sep 1959.
0 D'5 Y
SOGWY Ot UG "A bald LU AnAwd MSOUAJ 28 UG%A 'lot. 1958 In Adivoic.
IYA following ps"re wers proomted bj W MA dolodstift
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%orneschs wom
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latalyestaraft.4
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bet Lanpoom
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der b1ologlacbm Istaly" 1A Kebt der dirkampolso der =a2a"yow.
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der Chosioche ~qqollvcuft is 4kr KIN, foodeften, 1959, unal.
KORITSKIY, A.T.; 14DLIN, yU.N.; SHAHSM, V*116*s BUBVI, N.Ya.;
YOYBVODSKIY. Y.Y1,.-
Study of radicals by means of electronic paramagmetic re-
sorAnce duringtbe irradiation of polyethylene by fast elec-
trons. Vymokou.soed. I no.8:118Z-1193 Ag 159-
(MM 131?)
1. Inatitut khImicbeekoy fiziki LH SSSR.
(Polyethylene) (Radicale(Chemitry))
TSVMTKOV, Yu.D.; LRBRM, Ta.S.: VOTNOXEMY, V.V.
. 7rea radical reactions in irmdiated polytetrafluoroothylanso
Part 1: Use of electron resowince (IM) In studying radi-
cal conversions and in the determination of the coefficient
of diffusion of oxygen in pol]rtetrafluoroothylene. Vysokon,
soed. 1 no.10;1519-1525 0 '59. MU 1343)
1. Institut khimicheskoy fiziki AN SSSR.
(Radicala(chemietry)) (Bthylene) (oxygen)
TSVPMV. Tu.D.; LIMXDU, U.S.; VOTIMMY, V.V#
Reactions of free radicals in irradiated polytetrafluoroethylones
Part 2: Determination of the rate constant's for the reactions
R02-#R* Oi-andR+ 02 4R02. V7sokow.soed. I no-11:1634-1642
H 159, (MIRA 13:5)
1. InAtitut khimicheekoy fiziki AN SSSR.
(Radicals (Chemistry) (Sthylene) (oxygen)
TSVETKOV. Tu.D.;, NDLIN, Tu.N.; VoriwoDsxly. V.V.
Blectron rooonanco spectra of some irradiated polymrs.
Vysokon.soed. I no.12:1805-1811 D 159, (RIRA 13:5)
1, Inatitut khimicheekoy kinetiki i Coreniya AN SSSR
(Sibirskoye otdelerAye),
(Polyzers-Speotra)
'up), 5(3) SOY/51-6-1-26/29
AUTHORSs Chernyalc, N. Ya., Babnov, N.N., Polyak, L.S,, Tsvetkov, Yu. D. and
Voyavodskiy, V.V.
- 1Z ---------- Z--~
TITIS.- On Certain Ro6ularitioa in the i;lactron Paramagnetic Resonance Spectra
of Allcyl Radicals (0 nekotorykh rakonomernostyakh Y spektrakh
slaktronnogo peramagnitnogo rezonansa alkilinykh radikalov)
Plr;RIOUICAL iOatika i Spektrookoplya, 1959, Vol b, Tir 4, pp, 564-565 (US3R)
ABSUMOT: In the study of the electron paramagnetic resonance (o.p.r.) spectra
of radicals for-mod on 4-irrsdiation or frozen hydrocarbons (at 770K), it
vas found that the hyperfine, structure (h.f.s.) varies with tho position
of the hydrocarbon in its homologous series. Fig I shows the spectra
of radicals of normal paraffin hydrocarbons frcm Cl1H23 to ClbH33
obtained under conditions described earlier (Ref 1). The samples were
of 97-98% purity. Fig 1 shows that h.f.s. of the even kG,2%, C,4%,
C16H33) and odd (GlIH23, C131127, ClSH31) hydrocarbons differ
considerably. in odd hydrocarbons the n.f.s. is well resolved and the
intensities of the central components differ only slightly from one
another. In even hydrocarbons the resolution in much poorer and the
intensity distribution is close to binomial. In paraffin hydrocarbons
N rd 1/3 frcm n-C* to n-Clo the spectra are more complex and more similar to
SOV/.51-6-4-26/29
on cartain Regularities in the :electron Parw&agnetic Resonance Spectra of Alk-(l
Radicals
one another. 'rwo of theta are shown in Fig 2, where curves 1 and 2
ropresent the e.p.r. spectra of C61il.3and C7H,5 respectiveiy. The spectra
of radicals of cyclic hydrocarbons kwith five or six C atoms, shown
in Fig 3) are In many respects similar to the corresponding spectra
of the odd and even terM3 of the series C11-C16. The simplest spect.-Im
is that of cyclO-'r,6- ~rne hyperfine splitting and canponent iatencities
may be explained by assuming that the spectrum it; a triplet (vrith
37 oerst3d splitting and 11:2:1 ratio of intenGities of the empo'nont-s)
and each components of the triplet ir. split into two lines (20 Der.5ted
separation). Such a apectram ozeura in the radical cyclo-06'-'ill-
Following Ingram (Ref ~) it is assumed ~iere that of fnnr by-irngen
atoms in the p-positioa, the free valence, only two take part in the
hyperfine splitting. This proauces a triplot. . Interaction with a
hydrogen atan in the d:-position prodilces trr- doublet splitting a
., of a ch
triplet component. In the case of cyclo-05Flo the molecule is almoit
planar and both nydrogon atoins of tno#3-Grouns CHZ in tho) radical should
be equivalent with respect to free valance and the number of h-f-s-
components should increase. Tne spectra shown in Fig 3 confirm these
deductions. The authors conclude by pointing out that the a.p.r. spectra
card 2/3
VO
W V/51-6-4-26/29
On Certain Regularities in the Llectran ParaLaagnetic Resonance Spectra of AlIcyl
11adicals
can be used in molecular structurt: studies and in chemical.
analysis. Tbero are 3 figures and 3 references, 2 of which are
Soviet and 1 English.
SUBM,rTED. August 28, 1958
Card 3/3
2:1(7), 21(l) SOV/51-6-4-27/29
AU THORS Bubnov, N.s., Voy9vodskiy, V.V. , Folyak, L.S. and Tsvetkov, Yu. D.
TITLE: 'Electron Paramagnetic Resonance Spectrwn of Hydrogen Atoms Stabilized
on Solid Surfaces (0 spektrakh elektronnogo paramagnitnogo razonansa
atomov vodoroda, stabilizirovannykh na tverdykh poverkhnostyaich)
PisRIODICAL; Optika I Spakrroskopiya, 1959, Vol 6, Ur 4, pp 565-566 (USSR)
AB.3 TRACT. It was reported (Rofc. 1. 2) that H atoms ' formed on y-irradiation of
frozen hydrocarbons and other compounds, can be statfiizod on various
.surfaces. The present paper reports studies of the effect of the
nature of the staUlizing surface on the magnitude of h.f.3. splitting
of the electron paramagnetic resonance (e.p.r.) spectra of H atoms and
the width of the e.p.r. absorption lines. The K atoms 'were stalRized
on quartzsillea gel and molybdenum glass. -they were formed by
irradiation of these three substances with y-rays at '170K. It may
be assumed that formation of H atoms Is due to rupture or bonds in
HZO molecules adsorbed on those surfaces or rupture of bonds in SiOH
groups (Rof 3). .rho magnitude of h.f.s. splitting in all the three
cases was found to be close to .500 oersted which does not differ greatly
from splitting in a free H atom (Ref 4). Width of the components of the
hydrogen, doublet depends strongly on the nature of tha suriace: on
card 1/2
SOV/51-6-4-27/29
Electron Paramagnetic Resonance Spectrum of Hydrogen j~.toms Stabilized on Solid
Surfaces
quartz It is close to 0.8 oersted tcurve 1 in a figure on p 56U), on
silica gel It Is near 2.4 oersted (curve 2) and on molybdenum glass it
is 4.5 oersted (curve 3). Since the hyperfine splitting in the a.p.r.
spectra of H atoms stabilized on various surfaces is close to the
hyperfine splitting of free atoms, the binding of H atoms to these
surfaces does not alter greatly the spin density of the unpaired olectron
in hydrogen. On the other hand, dependence of the width of the hydrogen
doublet components on the nature of the stabilizing surface indicates
that there Is a definite interaction between the unDaired electron and
the surface. in view of this the authors suggest further studies of tne
nature of binding of H atoms to solid surfaces. This is an abridged
translation. There is I figure and 4 references, 2 of-which are Soviet
and 2 English.
SUBMITTSDi August 29, 1958
Card 2/2
24co 5W SOV/51-6-ti-18/34
,AUTHORS.- Buben, N.Ya., Koritskiy, A.T., Molin, 'YU.9.1
Ghkheidze, I.I. and Shamsher, V.31.
TI TLE Electron VSranagastic Resonance Il'tudiss of Free Radicals Formed by
Irradiation with Fast Blec+.rons (Iseledovaniye matodcm elaktronnogo
naramagnignogo, razonansa evobodnykh radikalov, obratuyushchikhxya v
protsesse oblucheniya bystryni eleictronami)
. rl`
PMODIGAL-.(YptX'ka i spektrookopiya, 1959, 1rol 6, Nr 6, pp 606-007 (USSR)
ABSTRAM An 6 lectron paramagnetic resona-ace (e.p.r.) spectrometer with high-
frequency modulation of magnetic field -working at 9400 Me/s was used
to measure the affects of fast-electron irradiation in eltu. The
sample& Irradiated were kept at temperatures from -160 to +1500C and
the radiation dose reached 106- 107 rad/sec. At room temperature
radicals produced in various polymers , solid organic acids and their
salts and in some aromatic com'?P'Ounds were found to be stable ttheir
lififtme vas of the order of so-raral hours and sometimes longer). At
low temperatures *.p.r. reson&aco showed the presence of atomic hydrogen,
in irradiated aqueous solutions of sulphuric acids and some of its salts.
Card 1/3 Irradiation at low temperatures and subaeqaent warming up produced changes
in the e.p.r. spectra which cculd be either reversible (caprone) or
Blectron Parmpetia Resonance studios of Fres Radicala Formed by IrradiatL on witj2
Past Ilectrons
irreversible (dicarboxylic &aide, polyformldshyd*). Such studies were
Made on radicals produeed by electron Irradiation in oxalic acid,
polyethylene and paraffin. In Mlic acid the e.p.r. signal is a single
line whose width is due to interaction between an unpaired electron and
magnotic moments of protons. The observed e.p.r. spectrum of oxalic
acid in not related to the presadCe of vater of crystallization Ixat it
is due to radicals of the type
R - 01 0 1
formed by remo~ml of the bydroges atom from the carboxyl group. I.p.r.
studies shoved that radicals foized by electron irradiation of oxalic
acid had disappear-A at the ratts given by dn/dt - An (Lt 260C
K - 10-21 CM3/;ee) - The presence of water of crystallimtlot af fecta
strongly the rate of disappearance of theae radicales the value of
K In anhydrous e6cid is higher than In the hydrated compourA. Irradiation
of polyethylene at room temperature produeet CH2--