SCIENTIFIC ABSTRACT BAGASARYAN, K. S. - BAGDASARYAN, K. S..

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• Collection: Scientific Abstracts
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• Sequence Number: 11
• Publication Date: December 31, 1967
• Content Type: SCIENCEAB

BAGDASARIYANJ, Kh. S.
I'Photochemical Polymerization of Vinyl Compounds,"
Chem. Sci. Sub. 26 Jun 50, Sci. Res. Order of Lenin Red
Inst. im. Karl>ov-, Mosc(rr
Thesis for degree of Dr.
Banner Phyeical Chemistry
Sum. 713 4 Sep 52

_J -r. ) I'll -- 41
irs and departure from the ildittYlly, two
in hydrfarb!na. Kh- & Alagda-aq'Yall (1!Qrt)Ov Phys.-
Chetll. Inkt.. Nto~a-uw). Zhur. Fis. KAim. 24. IM14-38
01145)).-A new vt of 1,ond encfgies is InolxwA. based tali
the value of 170 kcal. for the sublimation beat of diamond:
11-11 104; C-C F-1; C-C 1455; C-T;C 195. C-11 (r, .5;
C-11. 97.5 X 2; C If. toaS X 3: CZ-;!If. 99 X 4. This
set gives co""I v4hns ("ithin 0.2 kcal./noole) fortlachrats
of fortuation of all wKinal mul. hydromboas and of
Call,. I'm. (Pi anti urg. (N) deparlurrs front additivity
Are obtained lav comparing called. values with heats of
voolbu%tion J16-inil anj of hydtogeliathail (Kitallakowsky)
for various ronilhk For buladirne, the additive hydro.-
grotation beat is 1(2 x 841 4- (4 X 97.5) + (2 X 1.5)) -
1(2 X IN) + (2 X 115 5)1 - (12. Th,t expd. value is
57.1 and thu% the rv~,nanvr varixtr is 4.9. which is in
good
agrernient %ith.5.2. file N Altar olstained from
thectainbustion
heat. For iso %j(d. coniptis.. tables shoir that (1) a Me
group in the 2-limition dom not give notireable departures
from Iclitiviiy; :4 Jnfi of tile group towards more
crutrial ,
Itsoitiom, frivm N. Ft grouln give Wtonger N. This
ellect is 1xis%iblir due to stific hindrance. (2) The pre*.
ence of two or thrm Mr groups oil a 2-C atoin gives P(e.g.
HtChlrs) but it N effect is displayed by MCNIesEt anti
simi-
lar conliads. ;3) Tno Nle gr~ur on, 0 neighboring C-
atoms live a N effect ~ This A r ect t ecarruses when the
Me troujA are zntjvvd a%ay from each oth" ulong file
chain. Cyclopenlanu give, N - 6.5. whereas cyclohexAne
give$ V - 0.6 (SIL1110. StIlIS11111tiOll Of Mt group$ At 4
double bond gives P ial,tKat 11. This 11 effect increases
-Aith the too oil sub.tiltitions &fill is oft(inger for
asym. than
#(it xym. substiltilions (hyltefconjugaitican and steric
effects).
All cyclic comos. uith I double bond givePeffects. latols.
.iih 6olated dwiltle it%,- Olvit, %hich ate appo-%.
the %out of the eff~ts title to r.tch dotible 6,nd. e.g.
for
fi-onene P - 6.4 h-- 11 - 2-slor Nfr.c~clhalld P -
3.2 for Me.C:1011.11e. llduli. with eonjuxaled double
bou& present large effect, (r",nmice). The calcA.
resonance Von rgy of Cal Is i, 3S 7 (hoill "11111111%tiOn
1 41111
11"litaill..11% 4.1 NIV, E'I. Anti
.18.6 (fruit% hydrogroation). S
i1r gToulet in tile Call, fing give I' t:tlrcl, Conjugation
of Calla with a double loond gives I' t-114-01 i0vicror. 1)
Data also show that hyloerculljURAtiOll a% inore
inaloortant
with triple than nith double Iltnid, Alictirs lort-sent N
effects (Approx. 11). AlIYI ate. rat, , N - to .5. " Inch
is
anotioalous. Rcson.ince Isrt,%%,n viml anti cAflu"Iti-I
groups is 3A local (caled. fm \IvCll:clici[O!. For
EtO the resonance energy is 4 3 kcal. R~,nancc energies
E of various radicals safe ralrd with the help of file
lifo-
lolled set of Ixond rnrfji~ and thedala --f Slracir,
Rolk-Ittt,
an(] Ssware. /-.' - I*x - Is -- And V, - V - I). %hur
LIN is the exl)tl. beat of formation of the radical; CK ad
is the caled. valtic bj-,rd oil ill,, additivity title; V
is the
heat of (mination of tile un.1 %ilh ild Valence%: 1) is
tile
dissocn. energy into radicaak A 14-1 of lbe easal'itlealey
of the set of tvond etl"Kies (an-I in I~ArfiLULLT of the
VAIUr
170 for the sublimation heat of diamotill i is provided by
the
good agreement twi%cell caled. anti rtlid. di%macn.
eneftim;
this itgreement is ol,tainod unhout Ix-cial assumptions.
\Iiclici houdart
1131

USSR/Chemistry Aromatic Hydrocarbons Jul
52
Examination of Aromatic Hydrocarbons by
the Elec
(letter to
tronic Gas Metfiod," 'Kh. S. Bagdasarlyan,
the Editor), Physicochom Inst imeni L. Ya.
Karpov, CA
Moscow
Zhur Fiz Khim, Vol 26, No 7, PP 1053-1056
In aromatic hydrocarbons, the Ir-electrons
are "free",
analagous to valence electrons in metals.
This sug-
gests, the author states, that the
clectronic gas
method be applied to an examination of the
properties
of aromatic hydrocarbons. Use of this
method to calc
248T15
polynuclear aromatic hydrocarbons led to
results co-
incident w1th the results of quantum-chem
calcs.
However, the electronic gas method does
not reflect
differences in the energies of conjugation
of iso-
meric hydrocarbons - IThis method gives
lower values
of 6 for hy,~trocarbons like pyrene and
perylene'than
the method of molecular orbits. For
hydrocarbons in
which the aromatic nuclei are conjugated
together, or
with a double bond, the electronic gas
method gives
results approximately coincident with the
results of
the molecular orbits method. Calcn of the
potential
energy. of electronic gas, the author
states, will
permit more precise computations by the
electronic
gas method. This, he adds, is being done.
CZ>
248T15

41
'p
ono
s4dl 6
up '01 clectrMl-, L50torristo, dill v. 10 fliud
eft of em
)~Itowbwt-' 10~ e6h t d Tdth rgual 60:'h~ lensth, the e exp
mcra. of h and excUnged 4nitgrals Ij the 9,~tjjc rol.%Li
Md. frorp th* daWOI thi.' wat o
6 v-vccf :Penderwe Of die C~ersy of W-clcjtr6jj3 Oa tU7
'found by compari4
nil`
'r litit,of ugat=6 is ti, _thh energy witli the
L
dz~ni,pqz. t responding numbu 6412-elturol r-b3ads atthe il t
-trohs vrh
pall t iftstances. ThLIattedhpagnItndChsMRUtrth
dia c
wrinit At` and thI3 difference is a Nconjusated tnijtwv~
s tre -
tW fric
twtm, OM Q
pa" i Zero in aw-nc,- of C~aju on, and itta
0-00 d9
jjj~&_ '' n~L of~.&OM
tW. bco5 na tht rum at n
V -r
sho-InF a Ultan
()Uahtiln, cbtm6
-trY at P !ricraiencv on the !Aructt
tabec , t andcu

which'puin~Ld the theory ~VijdltWt
~

t!"
opinlo~, -calcm of devjgj~m7. Trojn..-4dd &jt~r:jci~- J450ttz

I
hydrocarbons does 3mt,bAif'ajy-phy
are ISO dimple nd douhl Wrliw, Y

A,
standAtd tetrabodral b6hdi imd tiW,ill.

1110jeCWe With ConjUpted b~o d,
at M. I

to
46.
M

Mt

-?T-1~,; :c -F,i
d6&oinpa- a6l
rT-o&A' . it z&~ 7 fitnet; is fast in AcQM.-
4 tL es
&staminAwnushicna. Triacclunatber4teof
v c6lb -in C-c4i - Ph;Clll - diT
butyl Pbtlialatc. ---rid Pneudortanow ADO the --wrie aq in
Cilia, With dc~-rmsing conen. ,f Rz.0i in Ctlis the yield
of BzOH dcc-.va-~. In AcOFt wh a rclarit- do,; n-it
hold for either C(~ cr BzOl 1. A : a c,.n, n. of (). 1S.5 mol, 1
in Ph,CH. t~v vicid of BzOj! i, th~jf in C,11,; 1;;
liolf", 11~ 3
Mort.; ~n fe's: 1:1 m
ALOH un-' AcOLt, Iii n:~~. Dcrt-nupn. in Ent PTC,enf eOf
vinyl co;~mh. in Ctil, :it 75* re-OtN its -. dmrea~cd im;d
ofBzOllanc)CO~.
dc,nmpn. of Bz,O.. There ;im 2 tv~.r, of
~Ininlc~l. (:-Ci)Tnpll of j'f-'1oxHc illt.~ )~- :' " .*' .,:. I.:
tmactioll"Of PCID.We with tnPi. rru~ting components.
Jack Weimr

1509. Mechanism of pirroxid 'witia(ion during

vinyl pol merisali K.
S. HAGDASAWYAN. Z1111r.
14m 10
Rubber Abstracts
Fiz. Khbij., 1951. 27; A42. 9;

April 1954
195:1, 6, 74H. 'I'lie polyinciis-Mion k 6peadent mi

the
dissoCialioll of fill- liefoxii1v into radii-als. lly
Synthetic
Rubber
addilion of these tadicak to tire mrsaluraic-I
and Like
Froducts
Illorlonlers, It Chaill reacdmj k started, oild tire

dept-nilence (if !lv~ of thk icaution (it% the

Volicentlatioll (if
Illulluiller k explailled by Ille

presence tif a W-11101crillar
teautioli livilveell ladical

und villyl Colvill(lund, The speed
Callixtit be gicatur

than the pritriaty dissociatiori into
railicali, bill

rather smaller, r.g., if the inilially fumitil
wilicak

Ilike patt ill Some other reliclikin h6lic addili'lli 141

are
double bond. They rill tcact with ench other 0,

i Torm difilienyl
nod cafhoti dioxide, or fir4ime Ow

chnin-polymerLsittiop, T- 1! 112

BIGDASAPYAN,,
KH..S..

Card 1/2

Authors
13agdasaryan, Kiii and
Milyutinskaya, R. I.
--Title
Carbon tetrachloride with vinyl-
Photochemical Reactions
uf -.

.
.
ompounds
Periodical
Zhur. Fiz. Khim. 28, Ed. 3,.498-506, March 1954
Abstract
The exposure of.carbon,tetrachloride mixtures to the affect
of

vinyl compounds leads to-a mm*e or less considerable increase in

the
rate of polymerization or the formation of carbon tetrachloride

addition products with double bond. Typical is the behavior of

styrene
and viWl butyl other. Styrene dissolved in carbon tetra-

chloride
polymerizes much faster than in an inert solvent. The

molecular weight
of polymers decreases simultaneously., Styrene is

a photoacti*re
component; the tnc rease in the
ratoof polymerization

-
.
16~ caused b.~-the_ increase in the rate of formation of primary
radi-

cals. VirVibutyl other mixed with carbon tetrachloride forms an

addition product with composition ratio of 1 t 1. The rate of

reaction
is proportional to the first degree of light intensityp

ths thermal

Zhur. Fiz. Xhim. 28s Bo. 3, 498-506,, March 1954
Card 2/2
Abstract coefficient is close to ow, It is a chain reaction The
quantum
yield increases during tkii reduction in the other concentration
and reaches several thousands in diluted solutions. Hexachloroethane
chloroform,, and allyl_chloride also accelerate the photo-
polymerization of vinyl ompounds but to a much lesser degree than
carbon tetrachloride. Seven USSR references. Table , graphs.
Inntitution t The L. Ya, Harpov Physico-Chomical Institute, Moscow,
USSR.
Submitted t June 19p 1953,

WDASWAN, -Eh. Se~
Card 2/1
Authors i Milyutinskaya, R. I., and Bagdasaryan, Kh. S.
Title I Study of the mechanism of radical reactions. Part 3.
Decomposition of
benzoyl peroxide and its p, pl-dinitro- and pt
pl-dimethoxy-derivatives
in bonzene and nitrobenzene.
Periodical s Zhur. Piz. Dim., 289 FA. 5) 797 - 800., May 1954
-Abstract The., d scomDosition .of - benzoyl o'eroxide and its
dinitro- and"dimetboxymn
derivatives in benzene and nitrobenzene was used as an example to
prove
the value of the mlarity of molecules and free radicals for the
process
of radical reactions. The polarity of radicals may at times have a
dou-
ble effect on the rate of radical reactions. At distances up to the
sum
of the van der Waals radii, the opposite polarity of the reacting
compo-
nents should be favorable for the radical reaction by Increasing the
nwn-
bar ar collisions. Seven references: 6-USSR; 1-USA. Table.
-Institution t The L. Ya. Karpov Physico-Chemical Institute, Moscow.
Submitted t July 3, 1953

Va. Ma-pov phys.-Chtm. InAr--Ii Fit.'
Kkim. 28, 10118-]IMIDU): cf. CA. 48, 119Ml.-A
theorEtical disrusaim. Tfte rleehrn-gas mttlivd for mols
CDllt_-. -e~e"TO~S (1) i5 developed on the bnxis of the b~L-
11=~~ of po.~itwely char:ged ~Iekwns Tl~e entire cloud
of I forms a s)stem. of cci-juga" elvctrov~c 5ph-cm crn-
temd on tliz mLAdle Hm-r-. o-hon.&- -lim-troms--
vylmia-,~a sphere thm-kinetic-rimrsyl-r-
--bri is-irria, 6y the statistical tnelPad. ThepMentialetierv
of I iseak-l.from tbe0mtrostp6cir,ter=Aktzo1 the I with
the pos. skclttfms and each other, The critrz, trswd.
with ovErJ:tp;drS of I and e-electrunsiscm furctischemat-
Ically. Fir seveml trial. t)-ties ike d6tributim; is gimi of
I arrimig the tyon& (spLzres) cowvsponiling 10 Mn. enc~gy
T-he bond hntg I b if ccrca5es as t lie clt~, tron d. it Prmsz-q, The
d-vitribution of Ouctron d. Ls miinly do'.d. b~ the r-pnNion
1'rtwern I culd adjurvrit bonds. In stibitilutim on tl-,- 1~n-
ri,:i the tub,tituent cither a 1W. pflA. crntel
I- the ~mg m ~h.ngc~ ine efir-cfiye cbatirt:
M-mileementot
el'~CuQn Pairs in buteru-nt-Ums atlavW to thr. i1na dmi not
occur In mols, of Ft-NIJ, FhOH, or MCI, but takei Place
(for NH. or OR. but not CO upon introdv:tion into thz~
ring of a S=rd elertroneg, substitnent ~v in the trwmition
--t d triz maction with a cationald reagent.
1. W. XAVATJ~,,-f. Yr.

Activation Illeviry of rc;lction 1'1.1Aiil=L_ M S
-
xhi
Ki

,
m
m,
N, rek S.S.S.R. 1955, h9-7-1-

A inethod i% prop aA of charmnvrizirg
hydiwaibon inoli.

ut'd radicali With
Cottlurated bordi. Every Illol, gmull is

,
Ornacktiled by it valov. thr. 6,ujugatiou

COOT. The Conjillatioll
CtION. Urt: C"Ilmocd widk ;% group

-illdex of thebond ibrough which
tilt nu,L groups tire bound.

at d tile localiraition.cnergy of
electrons on the given atonis.

The connection betiveen the 2 values is
given ctaphically,
'

system is studied -is if it were a quasialul. with
a

--Iii-aiialogy-witithydromtbc)nt----
conjugatQ systcinol-bbifffis_
-
system
with cnnjugated bonds, tilt energy of the ratcting

'
call be expressed as all eneryy !wm ni the principal re-

action
complex (e.g., the quasiallyl radical, a C H C

Mraplex), independent
(31 the attached Ri. R3 groups, and

-the reaction compicz conjugation
energy with the groups

R, and Rj. In strongly honutlytic reactions,
the con-

jugation energy during the course of tile reaction is as-

surned to be capable of being represented as a linear func-

tion of 2
variables, a gnd -y, that depend on the nucleus

7
configuration. The conjugation cnergi,-. of R, and R2, in

tli~lr
initial and final forms, -LrL parairettrs c,f thiq function,

42 + :1.
throughout tilt-, raacliim. . ix and -f asnuint:

definite values in
the iwerniediate stage, thm- vMues &itit;-

'-fyi~lg the above
relatioti, and the -gmu: value f,,r the. whole

series of reactioru of
a giver. type. This leads up t~- the

Tolanyl rule, to the teactivity
of radicals. The

location of the trols. -ar-d ratik-als in the
mictivity scries is

detd. by the conjugation c~wff, values of tilt-.
R, and l4t

groups, A semiculpirical formula is prc,pniscLd for the

evaluation of the uctivatiun energy of the rudicAl adda.

to a double
bond, using the conjugation coeff. In tile pres-

ence: of polar groups
in the reacting mols., the conjugation

cittergy is 4VPimd to be
ine-alible of being exprcsstd by a

litvt&~ kiiattan of tile a and -V
valiables. The deviations

I "lols,
Own regularities of rigidly. homolytic rc-ictions o

int! radicals
contg. polar pronits are connected with a I'll, I

not Wng "pressible
aq linvar function-i. W-M.-s-

merhation of C11,:CMCCOSM
-K k, y I
V
e

OA,c 6thLi en msse solaw
PhCH;C
& In

with EtOAc, Wis. aud CM, lNem examid. uDd" 7-radiation

from Co".
The inite of pol,,nnaimtIon In PhCll~Ctlj or

CHl-C_MtCO*Me WBttms in-
~CCI& rises througli a max. in

mpect to wmpn. of the sok.; . such
curves cannot be ex-

plained by primary radical lonnution from the
inaW cora-

N4hatiow sire deriyed for formation of primary

in
2-compontut mixts, by taking into account a rL-

distrihut6n,of the
abscatied nviliaut cnergi% Tht-equation

is vrell ouppowted by the
upti. datA which are shown graphi-

yield of primuy.:WtLiting radicals
per 100 t.v.

entily art, PhCli:Clll 0.4. Cll,:CKIeCOAlc

-3.6. CHI-CHOAc
5.0. The mlituve of radimls was at-

tained fit sonic of the runs by
the use of diphcaylpl,:,Ylhy-

dmzvl.

M~F
WN T-7 F

R.*
dill
O

I~__

M MON

E
R Ewa
Mi
RE
- NO

!.-LN - -, - - - --
A ~
_::I j 2~~.,~~ . , -. .. - I - _--
i

,'l C', , / -) - -/ -- , &`3
" - , I I f
a
vj~ -

BAGDASAR I YAN, Kh. S.
-o- --
nniction between the structure of the molecules and
their re
activity in the polymerization processes. Usp. khim. i
tekh. Pollm.
no.2,.62-80 157. (M3MA jjrj)
(Molecular structure) (Polymerization)

5,q e;_ b os 6 /~ ; yf-) it" ~/,j - S'.
USWPhysical Chemistry? - Radiation Chemistry,
Photochemistry,
Theory of Photographic Process. B-10
Abs Jour: Referat. Zhurnal Xhimiya, ITO 3, 7268-
Author T.S. Nikitina, Kh. S. Bagdasarlyan.
Inst
Title Addition of Carbon Tetrachloride to Vinylbutyl
Ester under
j'-Radiation Action.
Orig Pub: Zh. fiz. Mynii, 1957, 31, 170 3, 704-707-
Abstract: A producT, of addi*uion of mrb= tetrachloride
to Vizqlbutyl ester
(1) in theproportion of 1:1 is formed by the action of
1--r&cU&-
tion of COW on mixtures of I and CC14. The reaction rate
de-
pending on the mixture caVositim passes through a
maximum at
65 mol- % of CC14; the yield from such a mixture is 4500
per 100
ev of absorbed energy. The yield of radicals from I and
from the
equimolecular mixture of I and CC14 is 4.8 and 13
(determined
with diphenylpicry1hydxazyl). A chain reaction mechanism
is pro-
posed. See also IRMEhin, 1956, 445-
card 1/1 -8-

MILYUTINSKAYA. R.I*; BAGDASAROYAN, Kh.S.; IZRAILFIVIGH,
Ye.A,.
Studies on the mechanism of radical reactions. Part 4: The
mecha-
nism of formation of diphenyls in the decomposition of
benzoyl and
4-nitrobenzoyl peroxides in benzene and nitrobenzene [with
ffwmr'y
in ftligh]. Zhur. fiz. khIm. 31 no-5:1019-1026 my 157.
(MIRA l0r1l)
1. Tiziko-khtmicheakiy institut im. L.Ta. Karpova, Mbskva.
(Benzene) (Benzoyl peroxide)

AUTkORS: Krongauz, V. A., Ba dasar.yan Th S 20- 114-4-41/63
TITLI: Energy Transfer on the Occasion of the Radiolysis of
Benzoyl
Peroxide Solutions (Peredacha energii pri radiolize
rastvorov
perekisi benzoila)
PERIODICAL; Doklady Akademii Nauk SSSR, 1957, Vol. 114, Nr
4,
pp. 829-a32 (USSR)
ABSTRACT: Under the influence of ionizing radiation upon
organic
solutions the primarily absorbed energy may be transferred
from one component to another. In order to determine the
influence which the quality of the solvent exerts upon the
energy transfer, the authors studied the radiolysis of
benzoyl peroxide solutions in benzol, cyclohexane and ethyl-
acetate. The radiolysis was carried out by I-rays C060 in
the
absence of air. The initial velocity of the peroxide
decomposition was measured iodometrically. Its decomposed
amount did not exceed 10-M4 of its initial concentration.
Figure 1 shows the dependence of the initial velocity of the
radiolysis on the initial concentration. The benzoylperoxide
absorbs part of the total energy absorbed by the solution,
Card 1/4 this part corresponding to the electron share of
the peroxide

I
Energy Transfer on the Occasion of the Radiolysis of Benzoyl
20-214.4-41/63
Peroxide Solutions
mechanism. One may assume that the high radiation yield in
the
radiolytic decomposition of the peroxide is due to the energy
transfer of primarily produced benzol molecules upon the
peroxide molecules. A comparison of the results obtained from
radiolyses of benzoylperoxide in different solvents shows
that
the energy transfer from the solvent upon the solved
substance
is dependent on the quality of the solvent. The individual
stages of the radiolysis are as follows: 1) Formation of
excited benzol molecules at the absorption of the-radiation
energy, 2) a spontaneous disactivation of the same molecules.
3) energy transfer of the excited benzol molecules upon the
peroxide and the decomposition of the latter, and 4) decompo-
sition of the peroxide by absorption of the y-rays by the
peroxide itself.
There are 4 figures and 12 references, 2 of which are Soviet.
ASSOCIATION: Nauchno-iseledovatellskiy fiziko-khimicheskiy
institut im.
L. Ta. Karpova (scientific Research Institute for Physical
Card 3/4 Chemistry imeni L. Ta. Karpov)

P,4C,DA,S'AP"YAA,,'
AVTHORSi Krongauz, V. A., 3agdasarlyan,' Kh. S. 20-5-27/48
TITLE: Radiation Chemical Effect of Excitation Energy Transfer
in Three-Component Solutions ( Radiatsionnokhimicheskiy effekt
perekhoda energii vozbuzhdeniya v trekhkomponentnykh
rastvorakh).
PERIODICALt Doklady AN SSSR, 1957, Vol- 116, Nr 5, PP- 817-819
(USSR).
ABSTRAM The authors showed already in preliminary works
(reference
1-2) that with the radiolysis of solutions of benzene-super-
oxide in benzene the primary absorbed energy is transfered
from the excited benzene molecules to the molecules of
superoxide. In order to closer study the mechanism of energy
transfer of the radiolysis of the three-4mmponent benzene +
phenantrene + benzoyl-superoxide, the present work
investigates the kinetics of the radiolytic decomposition
of benzoyl-superoxide of these compounds within a wide range
of phenantrene concentrations. (0 - 1 mol/1) with three
different concentrations of benzoyl-sul-eroxide (0,0125
0,0083 ; 0,0042 mol/1). The radiolysis of the solutions was
Card 1/3 carried out under the influence of I - rays of Cc 60
with

Radiation Chemical Effect of Excitation Energy Transfer
20-5-27/48
in Three-Component Solutions.
no air present. The differential dose was 1,5-1015
eV/ml.sec.
A diagram shows the dependence of the initial velocity of
the radiolysis of benzoyl-superoxide on the concentration
of phenantrene for three concentrations of superoxide. With
increasing concentration the velocity of radiolysis
decreases at first, passes aminimum and then increases
linearly. The authors study seven processes occuring with
the radiolysis of the compounds investigated. They take the
following simplified conditions as basis: As the concentra-
tion of benzoyl-superoxide in the solution is small the
decomposition of the superoxide by direct influence of
radiation can be neglected. The decomposition of the
excited molecules of benzene and phenantrene to their
radicals is not taken into account because of the small
yield of radiation of the radicals of these hydrocarbons.
The excited phenantrene molecules obtained by means of two
certain (mentioned) reactions are kinetically identical. A
formula is given for the velocity of the radiolytic
decomposition of benzoyl-superoxide and it is specialized
for sufficiently great concentrations of phenantrene. In
the
Card 2/3 end the authors still estimate the mean life of
the

AUTHOR: Bagdasarlyan, Kh.S. SOV-77-3-5-13/21
TITLE: The Mechanisin of-the Action of Dye-desensitizers
(K mekha-
nizmu deystviya kra.,iitele~,-deconnibilizatoi-ov)
PERIODICAL: Zhurnal nauchnoy i prikladnoy fotograf-ii i
hinermatoi;ralf'iij
10/56, Vol 3, Nr 5, PP 381-382 (USSR)
ABSTRAM Roferrlin& to R.C. Nelsonlq recent article on the
clectron
affinity of dye-desensitizers, the author points out that
one of his own works, published in 1944, deals with the
saine qubJect and arrives at much the -,;ar:~e
conclus~Jons.
There are 3 references, I of which is Soviet ana 2
A-Merican.
ASSOCIATION: Moskva, Fizi'lCo-kh--micheskiy institut imeni
L.Ya. KF%rpcva
(The Physico-Chemical. Institute imeni L.Ya. Karpov)
SUBMITTED: June 3, 1958
1. Photographic emulsions--Processing
Card 1/1

AUTHORS: Milyutinskaya, R. I., Bagdasarlyan, Kh. S-,
76-32-2-29/38
Kopytovskiy, Yu.
TITLED Investigation of the Mechanism of Radical Reactions
(Issledovaniye mekhanizma radikallnykh reaktsiy)
V. Decay of 4-Nitrobenzoylperoxide in Toluene
(V. Raspad perekisi. 4-nitrobenzoila v toluole)
PERIODICAL*. Zhuxnal Fizicheskoy Khimiij 1958, Vol. 32)
Nr 2~ Pp. 428-432
(USSR).
ABSTRACTr Data were obtained in earlier works by the
authors (reffrence
which prove the assumptions of rederence 3 concerning the
scheme
of the formation of diphenyl in the decomposition of
nitroben=
zoylperoxide and its substituents in aromatic sol-vents
according
to (1) and (2). The radical occuring in (1) and (2) can
in a
special case also be a benzoate radical. The there
obtained re=
sult agrees with the mechanism of the formation of
nitrobea-zoio
acid (according to reactions (1) and (2), where X denotes
a
nitrobenzoate radical,) from reaction (3). In this
connection the
following problem appaers: can a nitrobenzoate radical
dissolve
Card 113, out a movable hydrogen from the alkyl group
belonging to the a~o-

Investigation of the Mechanism of Radical Reactions 76-32-2-29/38
V. Decay of 4-Nitrobenzoylperoxide in Toluene
matic ring? In order to solve this problem the authors investi-
gated the decomposition of 4-nitrobenzoylp--roxide in toluere
partly deuterized in the methyl group, as well as in toluen-
partly deuterized in the ring. The results obta4-ned showea
without any doubt two ways for the formation of nitroberaoi,.
acid: the reaction (3) that is R = NO 2C6H4) R1 - CH 3.0 and the
reaction (4). Data are given by means of which the share of
nitrobenzoic acid obtained oy reaction (4) as well as the
kinetic isotopic effect in this reaction can be determined.
The equations (5) and (6) for the deuterium content -J'n n�t:~oben=
zoic acid (obtained in the toluene deuterized in the ring or the
methyl group) are given. From these the equation (7), for the ic7o=
topic effect is obtained. The values calculated according to thizn
equation are within the limits of from 1,79 to 2,1-. The ie:~topic;
effect in the reaction of the dissolving out of hydrog-?n from the
toluene by the No C H r'00 radical (reaction M) is equal to !,92'o
2 6 V
The share of the nitrobenzoate radicals which react according to
reaction M-in the concentration of peroxide in the solution from
0,16 M and looo - amounts to 0,365.
Card 2/3 The work was discussed with S. S. Medvedev.

Investigation of the Mechanism of Radical Reactions
76-32-2-2-9/38
V. Decay of 4-Nitrobenzoylperoxide in Toluene
There are 1 table, and 7 references, 2 of which are .'soviiate
i6SOCIiiTION: Physic o-ch-emical Institute imeni L. Ya.
Karpov, '."Oscow
(Aziko-khimicheskiy institut im. L. Ya. Karpova, L-.oskva)
SUBMITTED: December 12, 1956.
. ~:.; 'i. _ . . ~1 '6 i;Nit;ro,-donpo~UndS+rDecoml-os it ion
3. Toluene--Chemical reactions
2. Benzoyl peroxide--Decomposition
Card 3/3

AUTHORS: Krongauz, V~ A.,,_Lag a 76-32-3-36/43.
TITLE: The Radiolysis of Solutions of Tertiary Butyl
Peroxide
(Radioliz rastvorov perekisi tretichnogo butila)
PERIODICAL: Zhurnal Fizicheskoy Khimii, 1958, Vol 32, Nr
3,
P 717 (USSR)
ABSTRACT: It had already been shown earliei- that alvM
y-raOiation
of benzoyl solutions (in benzene))a transition of the
primarily absorbed energy excited benzene molecules
to the molecules of peroxide,takes place. It is interesting
to find out whether the taking up of energy of benzoyl
peroxide is to be traced back to the presence of the weak
peroxide bond or to the aromatic molecular structure of
peroxide. In order to verify the assumption that the Sormer
is-not the causelthe investigations in benzene and cyclo-
hexane solutions mentioned in the title were performed. The
concentrations of the solutions were 0002 -0,,5 mol/1;' the
y-radiation was obtained by Co6o. From the small yield
of the radiatj.(j%tr,&-,tr of tert-butyl peroxide in
benzene
Card 1/2 and cyclohe.:a'.1(.~,u~-, be concluded that no
energy transfer

76-32-3-36/43
The Radiolysis of Solutions of,'-N~rtiary Butyl Peroxide
from the solvent to peroxide takes place. In connection
with the earlier observations Pit can be maintained that
especially effective transfers of excitation energy only
take place in cases where both solution components possess
an aromatic structure. Individual data of concentrations, as
well as energetic quantitien and measurements are given.
There are 3 references, 1 of which is Soviet.
ASSOCIATION: Fiziko-khimiches1ciy institut im. L., Ya.
Karpova,Moskva
(Moscol, Institute imeni L. Ya. Karpov)
SUBMITTED: February 21,1957
Card 2/2

AUTHORS- Sinitsyna, Z. A., Bagdasarlyan~. Kh. S.
SOV/76-32-.6-20/46
the Elementary
TITLE: The Determination of the Velocity Constan
Reactions in Methylacrylate Polymerization (Opredeleniye
konstant skorostey elementarnykh reaktsiy polimerizats1i
metilakrilata)
PERIODICAL: Zhurnal fizicheskoy khimii, 1958~ Vol- 321, Nr 6,
Pp..1319--1327
(USSR)
ABSTRILCT: It was found earlier that the photopolymerization
of methyl-
acrylate proceeds with a constantly increasing velocity. De-
terminations of the reaction constants were conducted by
Matheson et al. (Ref 2), Mellville et al. (Refs 3, 4), and
by Mahadevan and Santhappa (Ref 5). The problem is inventi-
gated. at a certain concentration of the initiator (dinitrile
of azodiisofatty acid) a giverx-,Iength of the molecular
chains
a given initiation velocity and mean life of the kinetic
chains, From the experimental part may be seen among other
things that the polymerization velocity was determined by
dilatometric methods. The experimental arrangement is
represent-
ed schematically. The mean life of the kinetic chains was
Card. 1/ determined according to the method of intermittent
illumination.
.3

SOV/76-32-6-~)o/46
The Determination of the Velocity Constant of the
Flementary Reactions in
Methylacrylate Polymerization
by using a collection of' slotted disks. The obtained
functions
of the logarithm of the polymerization velocity versus the
logarithm of' the concentration of the initiator are plotted
in a graphs In the calculations the author proceed from the
equation by Khauvink. Agreement is foun&vtth the data by
Furman and Meerobian (Ref 8). The initiation velocity is de-
termined from the duration of the induction period in the
presence of ava-diphenyl-p-picryl hydrazyl. From a compari.,
son of the initiation velocity with the decomposition vel-
locity of the dinitrileazofatty acid the efficiency of
initia-
tion is determined. The mean life of the polymer radicals
was computed from an rqttation which is derived from
measure-
ments carried out accorLAitig to the above mentioned method
at
a continuous or a discontinuous illumination. From the,
values obtaine(i the kinetic constants for the given case
are
computed. They are compared in a table with the data obtain-
ed by othar authors. There are 6 figures~ 4 tables~ and
12 referenvesp 5 of which are Soviet.
Card 2/3

SOV/76-32-6-2o,/46
TI.,p -i'-E,~arminatlon of the Velocity Constant of the
Elementary React.-ons
Polymcrization
A-'-, ijC I* T 1 ON i1irtitut irm. L. 'r".
(Motitute of aples and MMJ 9try IMzd- L.Ta. - K&Mrp
7MOsaw)
**UBMT
11111-;i"D February 9, 1957
1. Acrylic resins-Polymerization 2. Acrylic
resins--Chemical
reactions
Card 3/3

,AUTHORS:
Krongauz, V. A.,-Zagdasar'yanq_.K SOV/76-32-8-22/37
TITLE:
The Investigation of the Radiochemioal Effect of the
Excitation

Energy Transfer In Binary Systems by Means of the
Polymerization

Method (Issledovaniya radiatsionno-khimicheskogo
effekta

perekhoda energii vo2buzhdeniya v dvukhkomponentnykh
sistemakh

metodom polimerizatsii)
PERIODICAL:
Zhurnal fizicheskoy
khimii, 1958, Vol. 32, Nr 8, ppo 1863-1868

(USSR)
ABSTRACT:
Continuing earlier papers the investigation mentioned above
was

carried out to further explain the corresponding problemsi
the

authors investigated the radiation polymerization of
styrene

alone as well as together with methyl methacrylate in
the pre-

sence of benzoyl peroxide and the dinitrile of a2oiso
fatty

acid. The polymerization was carried out under the
influence of

I'-rays of C060 at 30,200 in the dilatometer
described already.

The experimental results show that the
addition of 0,01 mole/1

of the peroxide to styrene increases
its polymerization rate

by a factor of three, I. e. the
formation rate of the radicals
Card 1/3
(initiating the
polymerization) is increased by a factor of nine.

SOV/76-32-8-22/37
The Investigation of the Radiochemical Effect of the
Excitation Energy
Transfer in Binary Systems by Means of the Polymerization
Method
In the case of an addition of dinitrile no energy transfer
from
the solvent to the dissolved substance was found. This is (as
in earlier papers) explained by the fact that the nitrile
does
not contain an aromatio ring (like the peroxide), as the role
of the energy acceptor is dependent on the aromatic
structure.
In connection with the observations made by T. S. Nikitina
.L
and Kh. S. Bagdasarlyan (Ref 6) the time course of the common
radiation polymerizaVon of styrene and methyl me-thacrylate
is
investigated. An addition of styreneconsiderably decreases
the
polymerization rate. The starluing rate is ca!3ulated
according
to an equation by Melville (Melvil) (Ref 12). A difference
between the data obtained and those by Nik-,tin and
Bagdasariyan
Is explained by a difference between the methods employed. An
agreement of the data obtained with those by Walling (Uoling)
(Ref Q~) is found. Pinally the authors express their
gratitude
to S. S. Medvedev, Member, Academy of Sciences, USSR.
There are 4 figures and 18 references, 5 of which are Soviet.
Card 2/3

SOV/76-32-8-22/37
The Investigation of the Radiochemical Effect of the
Excitation Energy
Transfer in Binary Systems by Means of the Polymerization
Method
ASSOCIATION: Fiziko-khimicheskiy institut im. L. Ya;
Karpova,Moskva
(Physical and Chemical Institute imeni L. Ya. Karpov,
Moscow)
SUBMITTED: March 23, 1957
Card 3/3

AUTHOR: Bagdasarlyan, Kh. S. SOV/76-32-11-24/32
- - - - - - - - - - - - - - - --_
TITLE: The Inhibiting Effect and the Structure of Inhibitors
(Ingibiruyushchiy effekt i stroyeniye ingibitorov) I. Kinetics
of Inhibited Polymerization (I. Kinetika ingibirovannoy poli-
merizatsii)
PERIODICAL: Zhurnal fizicheskoy khimii, 1958, Vol 32, Nr 11,
pp 2614-2623
(USSR)
ABSTRACT: In the present paper a method suggested already
earlier by the
author (Ref 1) is further developed for the investigation of
the
subject mentioned in the title.-The described method serves for
the analysis of kinetic data of inhibited polymerizations and
is similar to the method by Kice (Kays) (Ref 2), so that by
some modifications of the final equation the equation mentioned
by Kice may be obtained. The method makes possible a good
classification of the function of the inhibition reactiDn
versus the concentration of the inhibitor. Moreover, the values
q and Ax (q = coefficient of the "regeneration" of the reaction
chain) can be determilicd forvar-ious values of the inhibitor
- The
Card 1/2 values ao q and A x were calculated for two different
inhibitor

307/76-32-11-24 .32
The Inhibiting Effect and the Structure of Inhibitors. I.
Kinetics of ~n-
'ibited Polymerization
concentrations in polymerizations of methacrYlate (Ref 6),
methyl methacrylate (Ref 2), and vinyl acetate (Ref 3); they
are given in a table.(Table 1). It was found that the inter-
esting conclusions on secondary reactions in the case of an
inhibition nay be obtained from a comparison of the kinetic
data and the length of the polymer chains. The inhibiting
mechanism apparently consists (in vinyl acetate by isopropy"
benzene) in a separation of the mobile hydrogen atom from
the
isopropyl benzene molecule by a polymer radical.
Corresponding
to the obtained data (Table 1) the formed dimethyl-phenyl-
methyl radical reacts with the -Dolymer radical. There are
4 figures, 2 tables, and Do references, 3 of rhich are
Soviet.
ASSOCIATION; Fizi.ko-khimichpskiy inqtitut im. L. Ya.
Karnova Moskva
(Physico-Chp.mical Institute imeni L. Ya. Ka~pov' nnscnw)
SUB141 I TTE.D: May 30, 1957
Card 2/2

5W
.AUTHORS.- Sinitsyna, Z. A., Bagdasarlyan, Kh. S.
SOV/76-32-12-2/32
------------
TITLE: The Inhibiting Effect and the Structure of Inhibitors
(Ingibiruyushchiy effekt i stroyeniye ingibitorov) 11. The
Inhibited Polymerization of Methyl Acrylate (II.
Ingibirovannaya
polimerizatsiya metilakrilata)
PERIODICAL: Zhurnal fizicheskoy khimii, 19589 Vol 32, Nr 12,
pp 2663 - 2672 (USSR)
ABSTRACT: A study was made of hydrocarbons with an unstable
hydrogen
atom, hydrocarbons with condensed or conjugate rings and
nitro-compounds. The reactivity was compared with the hydro-
carbons in which deuterium was substituted. R. I. Milyutinskaya
determined the deuterium content. Because of contradictory
results it was not possible to determine whether the formation
of polymers was by disproportionation or combination of
polymer radicals. In the case of hydrocarbons with an unstable
H-atom the cooperation of the latter in the polymerization
process has been confirmed; triphenyl deutero-methane has a
weaker effect than triphenyl methane. - Fluorene and triphenyl
Card 1/3 methane have an inhibiting effect whereas diphenyl
methane,

The Inhibiting Effect and the Structure of Inhibitors.
SOV/76-32-12-2/32
Il. The Inhibited Polymerization of Methyl Acrylate
dibenzyl and toluyl nitrile are ineffective, With condensed
or conjugate ring hydrocarbons the effect decreases rapidly
from anthracene to phenanthrene and stilbene; naphthalene,
diphenyl, m-diphenyl-benzene and quinoline are ineffective.
This gradation corresponds to the series found by M. Szwarc
(Ref 12). Amines and phenols (phenol, aniline, diphenyl amine,
diphenyl ether, hydroquinone, triphenyl carbinol) have no
inhibiting effect.a.-naphthol inhibits, but naphthalene and
a-fluoronaphthalene do not, All nitro-compounds inhibit. The
effect of further sabstituents is in accordance with Hammett's
rule,Hammett's constant being 0.8. Nitrobenzene and nitro-
deutero-benzene are equilly effective. A polymerization by
the traiisition of an If-atom from the phenyl ring to the
polymeric radical does not take place in this case. C. Price
(Ref 14) assumed a binding of the polymeric radical to the
phenol ring with a simultaneous formation of an inactive
radical. Bartlett and Hammond (Ref 16) assumed a binding of
the polymeric radical to an O-atom of the nitro-group. How-
ever, the partial reduction of the nitro-group and
polymerization
Card 2/3 by disproportionation is also possible. Polyani's
rule on the

The inhibiting Effect and the Structure of Inbibitors.
SOV/76-32-12-2/32
II. The Inhibited Polymerization of Methyl Acrylate
effect of electron-acceptor substituent8 on the reaction
heat
was confirmed. With all inhibitors studied one molecule
interrupts two kinetic chains. - Professor S. S. Meavedev
cooperated in an advisory capacity. There are 3 figures,
3 tables, and 17 references, 6 of whic-h are Soviet.
ASSOCIATION; Fiziko-khimicheskiy institut im. L. Ya.
Karpova Moskva
(Physico-Chemical Institute imeni L. Ya. Karpov, Moscow)
SUBMITTED: May 30, 1957
Card 3/3

5W PHAsE I BOOK MawinTION SOV/2649
Bagdasarlyanj, I&ristofor Stepanovich
Teoriya radikallnoy polimerizataii (Theory of Radical
Polymerization) Macaw.,
Izd-vo AN SSSR, 1959. 297 p. Errata slip inserted. 4,000
copies printed.
Sponsoring Agency: Akademiya nauk SSSR. Institut
nauchno-tekhnicheskay
informatsii,
Ed.: S.S. Medvedev, Academician; Ed. of Publishing House;
A.L. Bankvitser;
Tech. Ed.: I.F. Kuzlmin,
PURPOSE: This book is Intended for scientists working in
the field of polymer
chemistry.
COVERAGE: This monograph reviews the present state of the
theory of radical poly-
merization in connection with the general theory of radical
reactivity.
The first part of the book covers the chemistry of
elementary reactions and
their kinetic characteristics and the polymerization
kinetics and length of
polymeric chains formed under different conditions. The
second part discusses
Card 1/ 8

Theory of Radical PolymerIzatior SOV/2649
PART I. KITOT CS AND MECffWSM OF POLYMERIMION
Ch. 1. Polymerization Kinetics and the Mean Iength of
Polymeric Chains
1. General characteristics of elementary reactions
2. General characteristics of polynerization kinetics
3. Initial stationary rate of polymerization
4. Mean length of polymeric chains
5. Distribution function for polymeric molecules
6. Determination of Pn from the viscosity of polymer
solutions
Ch. II. Reaction of Pol*erization Initiation
1. VArthods for determining rates and efficiencies of
initiation
2. The theory of primary recombination
3- Initiation mechanism in solutions
4. Initiation with benzoyl, peroxide
5- Initiation with azo compounds
6. Redox initiation
7. Initiation with systems: benzoyl peroxide - mines
8. Thermal initikion
9. Photochemical initiation
5
5
9
11
15
19
24
29
29
32
35
38
49
51
52
57
60
Card 3/ 8

Theory of Radical Polymerization SOV/2649
3-
Intramolecular segment distribution
127
4.
Kinetics of
copolymerization
130
Ch. V.
Chain Transfer and,Inhibition
Reactions
136
1.
General classiftistion
136
2.
Kinetics of
inhibited polymerization. Presence of an efficient inhibitor

in very small quantities
138
3.
Origin of induction periods
142
4.
Kinetics of Inhibited polymerization. Inhibitors witli lov
efficiency

present in large quantities
143
5.
Mean length of
polymeric chains in chain-transfer reactions
149
6.
Chemistry
of,the reactions of chain transfer and inhibition
154
Ch. VI. Rate of Polymerization and,the Length of Polymeric
Chains in Exten-
sive Polymerization 167
1. Chain grovth and termination reactions 167
2. Chain transfer reactions 171
3. Kinetics and mechanism of the6J-polymerization 173
PART U., SOM PRORLEW IN THE THEORY OF RADICAL REACTMTr
Card 5/8

Theory of Radical Polymerization
2. Addition of radicals to aromatic rings
3. Addition of-radicals to quinones
Ch. XI. Relative Radical Reactivity
225
232
236
Ch. XII. Polar Effects in Radical Reactions 242
1. General concepts - 242
2. Applicat 'ion of the Hammett equation to radical
reactions 249
3. Polar effect in copolymerization reactions 256
4. The Alfrey and Price Q and e constants 260
Ch. XIII. Quantum-Chemical, Methods for the Qualitative
Interpretation of

Radiala Reactivity
265
1.
Localization energy
265
2.
Free-valence
i0dices
268
3.
Method of the incoherent molecular orbit
271
4.
Method of conjugation coefficients
272
5.,
Perturbation method
276
SOV/2649
Addenda. Application of the Method of Molecular Orbits to
Molecules With Conju-
gate Bonds 281
Card 7/8

,5(4),' 21(6) SOV/20-127-5-32/58
AUTHORS: Krongauz, V. A., Bagdasarlyan,. Kh. S.
TITLE-
The Transfer of Excitation Energy and the Sensitization
of

Chemical Reactions in the Radiolysis of Solutions of
Aromatic

Azocompounds
PERIODICAL
Doklady Akademii nauk SSSR,
1959, Vol 127~ Nr 5, pp 1047-1050

(USSR)
ABSTRACT:
In preceding
papers (Refs.1,2) the authors investigated the

radiolysis of
benzoyl peroxide dissolved in benzene, and found

a considerable
sensitization to occur. The decay rate of benzoyl

peroxide was
twenty times as high as corresponded to the direct

action of
the radiation. It was concluded herefrom that the

solvent
traftefers energy on to the dissolved substance. Accord-

ing to
reference 6, small additions of phenanthrena and

anthracene
decrease the velocity of the radioly3is, because

(Aef 7), they
are also energy acceptors. For the purpose of in-

vestigating
the influence of the structure of the dissolved

substance on
the energy transfer, the radiolysis of. the follow-

ing
aromatic azooompounds was carried out: Phenylazotriphenyl
Card
1/3
methane(PhATM), diazoamincbenme,benzylphenyl triazenep and
methy.1-

SOV/20-127-5-32/58
-The Transfer of Excitation Energy and the Sensitization of
Chemical Reactions
in the Radiolysis of Solutions of Aromatic Azocom-pounds
phenyl triazene. Radiolysis was carried out by means of a- -
rays of co6o in solutions from which dr had been carefully re-
moved. The primary yield of decay products per 100 ev of ab-
sorbed energy was determined. Figure 1 shows the course taken
by the radiolysis of PhATM . The yield in decay products in-
creases rapidly up to a PhATM concentration of 0.01 mol/l,
after
which it becomes linear. This coursed which proves a more in-
tense decay of PhATM than would correspond to rad.-lation, con-
firms the opinion that benzene transfers its excitaticn energy
to PhATM. The radiollysis of benzoyi peroxide I's considerably
hampered by the addition of PhATM, which is proof of the fact
that the latter is Just as active an ene:.-gy acceptor as
benzoyl
peroxide. DAB, BPhT, and MPhT do not, decay with noticeable
velocity under the action of,~_rays (Table 1). In the case of
azobenzene a transisomerization which increases linearly with
ir:radiation (Fig 2) occurs duxing irradiat-ion. The results
ob-
tained prove that, between the structure of the molecule and
its
ability of taking up the energy of electron excitation and'
utilizing it for the carry4ng out vi chemical reactions, there
Card 2/3 is no direct connection. There are 2 figures, 2
tables, and

SOV/20-127-5-32/58
The Transfer of Excitation Energy and the Sensitizat-icn of
Chemical Reactions
in the Radiolysis of Solutions of Aromatic Azooompounds
13 references,. 8 of which are Soviet.
ASSOCIATION: Nauchno-issledovatellskiy fiziko-khimicheskiy
institut im.
L. Ya. Karpova (Physico-chemical Scientific Research Institute
imeni L. Ya. Karpov)
PRESENTED: April 15, 1959 by S. S. Medvedev, Academiuian
SUBMITTED: April 11, 1959
Card 3/3

0
AUTHORSi
TITLEi
PERIODICAL:
ABSTRACT:
Card 1/2
058348
S/076/60/034/01/043/044
B004/BOO7
A New Method of Investigating the Reactivity of Organic Com-
pounds to Radicals
Zhurnal fizicheakoy khimii, 1960, Vol 34, Nr 1, pp 234 - 235
(USSR)
The authors describe a variant of the method of competitive
reactions, which was worked out by themselves. It is based
upon the application of tagged radicals and the determination
of the reaction products by means of isotope dilutiDn. Thus it
is possible to use the tagged radicals in low concentration
(0.01 m1/1), so that the reactions of these radicals may be
neglected. The authors describe carrying-out of their method
in the case of the reaction of the phenyl radical with aro-
matic compounds. A table gives the data for the reaction of
benzoyl peroxidelin a mixture of benzene + CCI 49 nitroben-
zene + Col 4' naphthalene + CCI4, and cumene + cc'4 at 1000.

683h8
A New Method of Investigating the Reactivity of S/07
60/034/01/043/044
Organic Compounds to Radicals B004YB007
The reaction constants found agree with the data obtained by
employing other methods. At present the authors employ the
method described for systematic investigations. There are
I table and 3 references, I of which is Soviet.
ASSOCIATIONt Fiziko-khimicheakiy institut im. L. Ya. Karpova
Moskv.--
(Institute of Physical Chemistry imeni L. Ya. Karpov, Moscow)
SUBMITTEDi June 18, 1959
Card 2/2

68856
AUTHORSa Milyutinakaya, R. I., Bagdasarlyang
B/076160/034/02/021/044
Kh. S. BO1O/BO17
TITLEi Investigation of the Mechanism of Radi_q&l Reactions. VI.
On the
Reaction Mechanism of Benzoyl Peroxido'[With Amines
PERIODICAL% Zhurnal fizicheskoy khimii, 1960, Vol 34, Nr 2, PP
405-412 (USSR)
ABSTRACTs S. P. Gambaryan (Rofo 112) had already observed that
&mines roaot
rapidl with bonsoyl peroxide. 0, At Gbaltykyan (Rof 4) and Horner
(Ref 5~ found that free radicals are formed in this connection.
Since the reaction kinetios proper has been little investigated
the authors tried in the present case, in continuation of
previous
investigations (R*f 7), to obtain a direot proof of the formation
of free radicals n the reaction of benzoyl peroxide with
secondary
&mines. The polymerization method and the reaction with diphonyl-
piory114--raesine more applied, and the kinetic isotope effect
in the
exchange of the hydrogen atoms in the amino group with deuterium
was determined. N-douterium aniline and N-doutorium diphonylemine
were produced by shakii out with heavy water, c