SCIENTIFIC ABSTRACT VOLKENSHTEYN, M.V. - VOLKENSHTEYN, M.V.

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• Collection: Scientific Abstracts
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• Document Creation Date: November 2, 2016
• Document Release Date: August 9, 2001
• Sequence Number: 19
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

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AUTHOR: Vol kenshtein, V. , Luc, tr m.-,ical 3o-I 1-22/23
Sciences
a r--
TITLE: An International Symposium on the -Hyclro;,en 15ond _Ln Liub.L,;
(Mezhdunarodnyy zi-m-puzia", po vodorodnoy i;v,azi v 11yubl,--_ne)
'L.
PERIODICAL: Vestnik ATSSIR, 1957, Vol. 27. Nr 11, pv. 157-139 (USSR)
ABSTRACT: Scientists from Yugoslavia, the ~,est- and kasteurojean countriez,
Au:;tralia, the USA, Canada, the USSR, Scandinavia and the state
of Israel participated in thu symposiumheld from Jul.y 29 to Au-
gust 3. More than 6o speakers got a hearing. The goviet delega-
tion read 6 papers;: Yu.F.Grozz talked on "The vibration &;,;ectrum
of the hydro,~en bond!'. D.N.Shiaorin on "The nature of the h~r-
dro-en 'bond anu itz influence upon the vibration- and elec-
tron-spectra of the molecules", V. Tyl. Chula novs ":i,- an "The spec-
troscopic investigation of the hjdrogen bond" Vol 1 1~~n-
~ ~te r in vitrifica-
..sht _~ on "The behavior of the hydrogei bonds
tion (steklovaniye)", N.D.;jokol(.;v "On the iuaatum -theory of the
h,,drogen bond" I A.I.I.Turunin and V.Fili,;iorov "Th,_t
bond OeLaeu.-. adsorbed moleculew, and the ~itructAral OH-8,1rual,si
on the surface of ~jolid bodicii". YiaiV paperki were devoteAjo the
Card 1/1 3 spectroscopy of the- h~jarogE;n bond. . Ir-portant information was

An International Sympoi;ium on th(:: H,uro,,~en Bond in Ljubljana. Jc-11-22/23
given by Dzh.Pimc:ntel (LISA) on the apeettrul pro~,evie~; of tne
compound6 at low temperatures and G.1,1arrinar, (England) on the
inveatig tion-res,411-t; of the oryztalline modifications of cel-
luloGe by meani.; of the method of polarized itifrarecl spec .tra. E.
Lippert (Germaxi Ft~dt~nal Republic) gave an extensive survey of the
influence exerted by the hydrogen bonds upon tht:! electron-
spectra. The session in which the participants capeciallj dealt
with the problems of the crystallography of the compounds with
those of hjdro-en, was opened by Dzii.Bernal, England, with an
extensive report on the part played by the hjdrogen bonds
in solids and in li-,uidz for *hich the particilants sho-,,jeci gre *at
interest. R.Pepiniikiy (USA) talked on the investigation of the
h,yd-rogen bond oy :~ieang of the X-raj and neutronographic me-
thod. U.ShneycLer (Canada) and others also dealt wit~i t' is methor-
The following seasions mainly dealt with problems of the theory
of the hydrogen bond. Speaker wag; Ch.Koulzon, EnSland. Hiu
st,tement caused a liveij diAcuswion in which above all the
Amurican iicientigtk; participatud. AlthouCji there exiots no -itrict
definition on the conception of the hiarogen bond all par-
ticipants in the discussion agreed that the eviuence of the
quantura-mechanical process of the formatioii of a donor -acct~pt or
Card 2/3 bond 'donorno-aktseptornaya svjazl) were necez~;ary for the
UJIM 3;

Ail International Sympoi;ium on the H,,drogep Bond I Ljubljsna- 30-11-22,123
determinat ,n o-4" the hydrogen bond.
1-0
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AVAILABLE: Librarj of CongreQm
Card 3/3

/Optical propLrtfee and the chemical 9tructure 01
V. V. V
0
h All 13, -v, A
h.und to styrene. When the 9.1u-H --toms in A were sub-
tituted the optical propextics of the polymer were not
ged by polymerization. Part of th~-. 9-Cl-A and Q-
=
ML-A beewric attacbeA to the polynu:r chain with the uub-
Atitution of the IG-H atom. The interaction of A and It3

H r L5 Y",
AUTHORS PokrovskiyU-JI., and Vollkenshteyn, M'V1' 20-3-306/59
TITLE A Study of I3otactic Polypropylene by-M-leans of Infrared Spectra.
(Issledovaniye izotakticheskogo polipropile-na mtodow infrakrasnykh
spelctrov).
PERIODICAL Doklady Akademii Nauk, 1957j, Vol. 115, Nr 3, pp. 552 - 553 (USSR.).
ABSTRACT Specimens obtained from different methods were investigated in the
form of membranes W2 mm thick,, Bands vrere found at 720, 730, 790,,
, 285o, 2924
81aj 839, 935, 969s 992, 105o, 1108, 117o, 1376, 146a
.
1. .1
and 2975 cm-.00 only-one of these bands- 935 cm diverges from the
spectres mentioned by-NATTA and his collaborators. This extremely soft
band doem not appear in all specimens. The occurrence of the bands
894 and 992 emm -1 is characteristic for the isotactic crystalline
polymer. They are very soft, if the fraction is extracted with ether*
When the polymer is-,heated to 14o - l5o0C. the spectrum change,-, so
that the-bands 81o, 839, 894 and 992 cm-1 are softened. This proves,
that the melting point T pl- of isotactic polypropylen is at about
16o - l7o0C. Apparently the latter bands can be considered aa bands
of crystal state, From the cuante of the dependency of the transmissi-
vity-at-the band maximum 992 cm ::1 the melting temperature of the
polymer can be determined. The value of the degree of crystallization
Card 1/2 was found to be 75, go and loo0/b respectively in the case of three

20-3-36/59
-propylene by Means of Infrarel Spectra*
A Study of Isotactic Pol~,
specimens. Thene values do not claim to be of high quantitative
exactness, for the measurements were made according to the method
of differential intensitye There is good reason to maintain, however,
that this value is very high in the case of the samples under inve-
stigation, (There are 2 figures, and 2 Slavic references.)&
ASSOCIATION Institute for Polymolecular Compounds AN USSR. (Institut vyaokomole-
kulyarnykh soyedineniy Akademii Nauk SSSR.).
PRESENTED by Academician A.V.Topchiyev
's February 13, 1957
SUBMITTED February 6, 1-957.
AVAILABLE Library of Congresff.
Card 2/2

20-2-1?/50
The Forming of Glass of Fluctuations and the Scattering of Li-E7ht
also the fluctuation of orientation freeze in. These fluctuations
thus, make their contribution towards the central component in
glasses. The fluctuations in the concentration freeze in in the
inhomogeneous liquids, so that the velocity of their dissolving
caused by diffusion depends to a considerable extent upon ter,
perature. This theory is suited apparently also for viscous liquids.
In the case of fluctuations & v rrlass formation partly can start
sooner than in the other liquids. '2here are 16 references, 15 of
which are Slavic.
ASSOCIATION: Institute for Highly Molecular Compounds AY USSR
(Institut vysokomolekulyarnyf'-.h soyedineniy ~'kaderaii nauk SSSR)
PRESENTED: May 15, 1957, by A. F. Ioffe, Academician
SUBMITTED.- May 13, 1957
AVAILABLE: Library of Con-gress
Card 2/2

voialORTM11 M. V.
"Amorphous and Crystal-line State of Polywra."
report presented at the Conf. on Mechanical Properties of Non-Metallic Solids.
Leningrad USSR, 19-26 may 1ceos 125
tkplmlll--~, O.A. N14 V-7. M-IriLnin. AnIBV-.r~y of Flertrlrml
CCndacL1v.1%F -f Fu1jed O!,Ica ~d 11,oriu~ In Fjcv 125
Card .1 Ix,
Vitreous State (colit. S(71/5035
yomolcn.ko' S.N. r~' t. ;-ral- 0: 01A.'s Fomln~; 123
Chect-11n, V.A., .0 C.A. Ye~j.. El"trolynt., of Liq,IA Al~lt-.Itcm,c I
SrYVollb, or.1i C.A. Y-Io. Prcl~rtlem of tll!-
of
Kerl.mnlLn of V!tritIcat!on
P..V. C- t-c -1 Kln~tic Pf U,
Aourri)~-, T-Y., t."! P.V. On the Y.~!hm of'
t , %'1trif1-t!~----1rT-'1-. 11ki
I.$- sO VHr1fi,.,tjc:j
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VOLIMSHTMH red.; T IN, X.L., red.; BIUMA. M.A.,
tekhn. red.
(Physics of -polymers; collected articles] Fizika polimerov;
sbornik statei. Koskva, Izd-vo inostr.lit-ry, 1960. 551 P.
(Polymers) (MIRA 13:8)
a

S/829/60/000/000/001-/00.5
D243/ '308
VolIken-'atcy-, 1, V
TITLE Lar-c raolecii1cs. a-ad biology
C~11
SOU-ICE: 7Iizi'o-'ji-.:jic-Licsj:iyc i strulturnyyc osnowj biologich-
~c --
cs1j.r.i!,:h y.:ivlc1-iiy : sloornik rabot. Inst. biol. fiz.
*d~, " 11
Noscow, Izd-vo ,U4. SSSR, 1960, 7-11
TL;XT: The aut'Lior co-iisiders some distinctive features of
the 1.-xk,lrc ziolccule-s i-.iLjortaut in the structure of organisms.
7 T
L&C discusses. tiucir groat i--1cI-:'.v-i(,IuaJ-ity, tahing plassria alin-Lmens ,:,id
nucl-cic acids as an -.,d the role o.-C stercoisorneric atorLic
groir-)s; t1ic work of Cwclchovich's school 'is referred to. Considering
tlic-sc su'Dsta-acer, ap, -polyclcctrolytes, the coiiseqUent relation be-
twcou mccLianical worl: 311 cF- the medium, , and the indivisibility
&Z plrysico-mcchanical -i-Li(L clicmicial processes are discussed. Their
role as information carric-i-n. and transmitters is described and sug-
gestions arc made for :-irc.-Ling the DNA code. Here sonic of Gamov's
worl: is criticizcd on the ~)asis of ignoring the chemical interaction
Card 1/2

Large rIOICCUICG a,,fl biolo,,-
3/329/60/000/000/001/005
D243/0303
L)et-,MCI.L nucleic aci(IS einally, these oubstance:7. arc
briefly cons-i.dcrcd at the abov--molecular level, -,rith particular
reference to their propcrtics ii-i the crystalline state.
ASS)OC LVION:
v,, soyedinciUy MI S,iSR,
Lenin- crad (I-astitute of High Molecular GOVIVOI-111day
Lc-aingrad)
Card 2/2

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24666
S/081/61/000/009/01311/015
B101/B205
AUTHORS: Anufriyeva, Ye. V., Vol'-kens-hteyn, 14. V~
TITLE: Luminescence method of investigating the vitrification of
polymers
PERIODICAL: Referativnyy zhurnal. Khimiya. no. 9, 1961, '037,
abstract 9P31 (9R31)(V sb. "Stekloobrazn- soatoyaniyell,
M.-L., AN SSSR. 1960, 138-142, Diskus., 153-154)
TEXT: The authors studied the effect of the vitrification of polymers
on the intensity of fluorescence of molecules with a non-rigid structure,
which had been introduced into the polymer (auramine, crystal violet,
Michler~s ketone) in polyvinyl acetate, polyvinyl alcohol, and other
media between 20 and 1000C. All curves obtained show a break for T= T
v
If T is greater than Tv, the local viscosity of the medium changes
accordingly to such an extent that a mutual rotation of the parts of the
luminescing molecule and a quenching of luminescence become possible.
The (I)T curves of auramine in polyvinyl alcohol show a further break
Card 1/2

2h6-66
S/081/61/000/009/017/ols
Luminescence method of ... B101/B205
at 550C, which is caused by hydrogen bonds. When investigating the
system polymer - luminescing molecule with a rigid structure, a break
is observable only with a certain choice or the system,. When investigating
the polarization and the "retarded" phoophorescencP of rhoduline orange
in polyvinyl alcohol, a break appears only in the latter case,. Investiga-
tions of this kind give new and essential information about the mobility
of macromolecules with which luminescing molecules are connected.
r
LAbstracter's note: Complete translation-i
Card 2/2

S/051/6o/oO9/004/008/034
E201/E191
AUTHORS: Vollkenshteyn, M.V.~ and Kruchek, M.P,,
TITLE$ Calculation of the Optical Activity of Molecules
PERIODICAL: Optika i spektroskopiya, 1960, Vol 91 No 4, pp 467-4-71
TEXT: A theoretical calculation of the optical activity is
illustrated in the case of 3-methyleyelopentanone.1
The calculation was. a quantum-mechanical one and it showed that
polarization interactions of constituent groups played the major
role in the optical activity of molecules of 3-me-thyleyclo-
pentanone type which contained one chromoform group and had no
conjugated bonds. The paper is entirely theoretical.
There are 2 figures and 13 references; 4 Soviet and 9 English.
SUBMITTED: February 51 1960
Card 1/1

3 J
B004/B056
AUTHOR- Volikenshteyn, M, V., Doctor of Physical and Mathematical
~_&Iences --
TITLE. The Physics of Polymers
3D
PERIODICAL: Vestnik Akademii nauk SSSR, 1960,,&No, 12, pp. 3 - 10
TEXT: The author gives a survey of the physical properties of polymers
as linear atomic systems and of the methods and theories necessary for
their investigation. The :onsiderable achievements of Soviet research
workers in this field are stressed, In this connection, reference is made
to the work done by the Institut vysokomolekulyarnykh soyedineniy Akademi
nauk SSSR (Institute of Macromolecular Compounds of the Academy of
Sciences USSR) (V. N. Tsvetkov et al.). The variety of the possible
rotation-isomeric configurations of polymers led the collaborators of this
Institute to develop a statistical theory on configuration, on the basis
of which they calculated the dimensions of macromolecules, their
electrical and optical properties by using modern physical methods such as
measurement of light scatter, measurement of the birefringence in flow etc.
Card 1/3

Z59
The Physics of Polymers S/030/60/Coo/012/001/018
B004/'BO56
Whereas the configuration statistics for elastic polymers
4 (natural
rubber, polyisobutylene) is already well developed (S.. Ye, Bresler,
Ya. I, Frenkell), there exists as yet no theory for relatively hard
macromolecules, for such as form intra- and intermolecular hydrogen
bridges, as well as for polyelectrolytes. In the case of rubber, the
rotational isomerism could be proved to exist by means of polarized infra-
red spectra. The investigation of the kinetic behavior of the polymers
(A. P. Aleksandrov, Yu- S. Lazurkin), such as relaxation, dielectric
losses (G. P. Mikhaylov), mobility of macromolecules and their links, are
now investigated by means of ultrasonics and magnetic resonance. In spite
of voluminous material, a clarification of the nature of the relaxation
spectrum (V. A~ Kargin, G.. L, Slonimskiy) of macromolecules in interaction
has at yet not been successfully carried out., The mathematical formulation
of the vitrification temperature (P. P. Kobeko, Ye. V., Kuvshinskiy,
S,, N. Zhurkov) has hitherto shown only a qualitative agreement with the
experiment. The existence of crystalline and amorphous regions in polymers
is mentioned, and the molecular packets are pointed out as a preliminary
stage of crystallization (V. A. Karginj A. I. Kitaygorodskiyj
a L. '~lonimskiy)~ In this case, the application of the general principles
Card 2/3

The Physics of Polymers S I!
3004/B056.
of solid state physics, especially of the dislocation theory is promising,
The application of the chain-method according to Markov permits the
thermodynamic analysis of reduplication of desoxyribonucleic acl-d, upon
which mitosis is based. The D01yelectrolytic nature of albumin and the
muscular contraction basing on it has boen proven by V~, A. Engellgardt
and M. N. Lyubimova., The physics of polymers thus becomea the basis of
the further development of biology. As regards the electrical and magnetic
properties of polymers, papers by A,. V, Topchiyev, V_ A. Kargin,
B, A. Krentself. and L. S. Polak are pointed out, who obtained substances
of high conductivity from thermally treated polyacryloni.trile, which have
semiconductor properties, Electrical properties are found also in the
polyphenylenes obtained by A- A. Berlin. L. A. Blyumenfelld found a high
unpaired electron content in desoxyribonucleic acid and its albumin com-
pounds. Together with V. L. Ginzburg, he developed the theory of an
ionic state of the desoxyribonucleic acid chains. Problems of adsorption,
adhesion and polymerization are not discussed in the present paper,
because they are rather to be ascribed to physical. chemistry than to
physics.. There are !6 Soviet references..
Card 3/3

VOLK7NSHTFYN, M. V. (USSR)
IlCo-onerative Precesses and the Reduplin-atlon of D--oxyrib:~nucl--ic Acid.11
Report presented at the 5th Internitional Biochemigtry Congress,
Moscow, 10-16 Aug 1961

_1VOLKENSHTEYN, M._V., GODZHPIPV, N. M., GCTLIB, Y11. YA., YaYASHEVICH A. M.,
PTITSIN, S. B., and BIRariTE-YN, G. M. (USSR)
y of Biosynthesis.1'
"Statistic Thermodynamic and Kinetic Model Theor
F,--port pr&sented at the 5th International Biochemistry Congress,
Moscow, 10-16 Aug 1961

VOLIKENSHTEY14 M.V.- GODZHAYEV, !1.M.-, GOTLIB, Yu.Ya.; PTITSYN, O.B.
Kinetics of the reduplir-;~'.ion of Uch-. zap.
AGU. Sar. fiz.-mat. i khim. nauk no-41105-112 61. (MIRA 16:6)
(Nucleic acids)

M.V.; KI'UCIIEK, M.P.
__1
Optical activity of amino acj-'.ds. Zhur. strukt. k-11-3m. 2 no. 1:4.0,
62 Ja-F 161. (HTRA 14:2)
1. Leningradskiy pedagogicbeskiy institut im. A.I. Gertsena.
(Amino acids-Optical properties)

AiJTHORS:
24107
S/192/61/002/003/001/001
D257/D305
Borisov&, N.P..and Vollkenshteyn, M-V.
TITLE: Van der Waals forces between hydrocarbon molecules
PERIODICAL- Zhurnal strukturnoy khimii, v. 2, no. 3, 1961t 346-349
TEXT: This article deals with the van der Waals "interaction energy" or
so-called van der Waals "potential energy" between molecules of methane.
The results found in the literature for potential energy between two non-
bonded hydrogen atoms - H...H were represented in Fig. 1. where potentials
energies - 11U11 in Kcal/mol were plotted against thecorresponding inter-
nuclear distances - 'Ir" in X. LAbstractor's note: In this article two--
non-bonded hydrogen atoms are represented as follows: H ... H, and analo-
gously two non-bonded carbon atoms - C ... C, two hydrogen molecules
H ...H two methane molecules - CH ..CH etc.
2 2' 4' 4 ] Curve 2 in Fig. 1 is the
experimental curve found from potential energy between two hydrogen mole-
cules. Curve 1, Curve 3 and Curve 4 in Fig. I represent the potential
Card IV9
5

24107
S/192/61/002/003/001/001
Van der Waals... D257/D305
energy between H2-H2 i.e. the potential energy between non-bonded hydrogen
atoms which have a bond with an atom of H (i.e. between R - H...H - H)
calculated by various equations derived independently. The potential for
I
H ... H-C- represented by curve 5 in the range 2.2 I-rZ_3.0 X is nega-
4- 1
tive, i.e. it represents the forces of attraction while the potential for
H-H...H-H represented by curves 1. 3 and 4 in the above mentioned range
of 'Ir" is positive, i.e. it represents forces of repulsion. It can be
assumed that C bonded with H causes the deformation of the electronic shell
of hydrogen atom, leading to the decrease of repulsive forces between
kydrocarbon molecules. The carbon atom in a methane molecule is not
compldely shielded by the four hydrogen atoms and, therefore, the calcu-
lation of potential energy between methane molecules does not refflice to
the calculation of the potential energy between non-bonded hydrogen
atoms; the potential energy between two carbon atoms C...C as well as the
potential energy between hydrogen atom of one molecule and carbon atom of
the other moLecule H...C should be considered. The potential energy
Card 2/6

24107
S/192/61/002/003/00001
Van der Waals... D257/D305
between two non-bonded carbon atoms was found by A.I. Kitaygorodskiy:
U_ 37-10 3 e-3.6r - 330 (4) The notential enerry
r 6 for C...C plotted
against internuclear
distances 'Or" is represented in Fig. 3, LAbstractor's note: no more ex-
planation referring to the potential for C ... C could be found in this
article,3 . Eq. (7) for the potential energy between C...11 is then given:
UC.*oH (r,X) = 36 - 10 3 exp G-4.6-r) - 80 r_6 (7) FAbstractor's note-
No further explanationreferring to the potential for C ... H could be
found in thiLs article?~ When calculating the potentialenergy between
methane molecules, their relative spatial orientations of one molecule
in respect to the other should be taken into consideration. One methane
molecule can have different spatial orientations in respect to the other.
Total potential between methane molecules is the sum of three potential
energies namely: the potential between non-bonded hydrogen atoms H...H,
the potential between non-bonded carbon atoms - C ... C and the potential
Card 3/0
6

Van der Waals ...
S/Ayffli/002/003/001/001
D25?/D305
between non-bonded carbon and hydrogen atoms - C ... H. As the potential
energy depends on the distance betwe~en atoms, each of the three above
mentioned potential energies are different for the different relative
spatial orientations of methane molecules. The potential energy H ... H
is pronounced mostly -Jr. the "all relative orientations of molecules, the
potential energy C...C is pronounced mostly in the 11c; r, 11 orientations
of molecules and the potential energy C..oH is pronounced mostly in the
"B" orientations of molecules. Eq. (3) used for calculating potential
energy between non-bonded hydrogen atoms was derived for the -calculation
of potential energy between hydrogen molecules. The assumption that it
can be applicable for hydrocarbons is, therefore, wrong.
U (r, 12 - 102 exp (._2, 85 r-) - 160 (3) Eq. (3) was derived
r6 assuming that the po-
tential energy
t~etween hydrogen molecules is equal to the sume of 1/4 the potential
for two hydrogen atoms in the single state and 3/4 the potential for
two hydrogen atoms in triplet form-,
Card 4/*
3

M107
S/192/61/002/003/001/001
Van der Waals... D:257/D305
U 1 U1 U3 (2) CAbstractor's note: Eq. (3) was not
H ... H 4 4 derived and no more explanation re-
ferring to it could be found in this article3. Talcing into account the
equations for calculating potential energy between methane molecules,.
the potential energy between non-bonded hydrogen atoms in methane
molecule H3C - CH3 was calculated to be equal -0.2 Kcal/mol which re-
presents attraction and was found to be practically independent of
the rotational angle of the CH.-group around the C - C bond. There
are 5 figures and 14 references: 1 Soviet-bloc and 13 non-Soviet-bloc.
The references to the~most recent English Language references read as
follows: C.A. Coulson, D. Stocker, !klol. Phys. 2, 397 (1959), K. Howlett,
J. Chem. Soc., 4353 (1957), L. Pauling, Proc. Nat. Acad. Sci. USA, 44,
211 (1958), G. Harris, F. Har'ris, J, Chem. Phys., 31, 1450 (1959).
ASSOCIATION: Institut vysokomolekulyarnykh soyedinyeniy AN SSSR
Leningrad (Institute of High Molecular Compounds, AS
USSR, Leningrad)
SUBMITTW: July 4, 1960
Card 51- (For- Figs. 1, and 3 see next card)

FJORISOVA, N.P.; VOL11 1111~v.
Internal rotation in i-~rcpane arZ r---butan-e-
2 no.4:469-475 j-1-g 161. Q,fiR---- 14:9)
1. Institut v-jsokomo1ek:ulyarnykJi soyedineniy AN SSSR,
Luningrad.
(Proparie) (Butane) (Molecular rotation)

BAZHENOV, N.M.; KOLITSOV, A.I.;MILCHATUROV, A.S.
Nuclear magnetic resonance study of polymers. Part 1: Temperature
dependence of molecular mobility in different stereoisomeric forms
of poly(methyl methacrylate). Vysokom. soed,3 no.2:290-291 F 161.
(MIRA 14:5)
1. Institut vysokomolekulyarnykh soyedineniy All SSSR.
(Methacrylic acid)
(Nuclear magnetic resonance)

201-18
Ll 1 3/181/61/003/002/016/050
10 D B102/B204
AUTHORS: Vollkenshte V Ir Gotlib, Yu. Ya., and Ptitsyn, 0. B.
TITLE: The kinetics of cooperative processes
PERIODICAL: Fizika tverdogo tela, v. 3, no. 2, 1961, 420-428
TEXT: The solution of the kinetic equations describing the cooperative
processes occurring in'changes of sta:te (e.g. in fluids) is connected with
considerable mathematic difficulties, if the state parameters change
continuously with the coordinates and the momenta of the interacting
particles. However, it is mostly sufficient to investigate two or more
discrete values of the parameters of state, which simplifies calculations
considerably. The authors now developed a method permitting solution of
the kinetic equations for cooperative systems by means of discrete state
parameters by successive approximations. The interrelation between this
method and others (e.g. as developed by N. N. Bogolyubov) is discussed;
the present method is suited for studying cooperative kinetic processes
of the structural change in liquids and solids. Such chemical processes
are considered to be cooperative as occur on a certain matrix; in
Card 1/12

20118
s11811611003100210161050
The kinetics of cooperative ... B102/B204
heterogeneous catalysis, e.g. the catalyst plays the role of such a
matrix. The synthesis-of albumens and nucleic acids, e.g. occurs only on
matrices with the participation of ferments. It may be assumed that in
biosynthesis, the cooperative processes play the main part. Here a
system is investigated which consists of N correlated subsystems; the
probability of the change of a state of a subsystem is assumed to depend
not only on its state but also on the state of the neighboring subsystems.
Thus, the probability of a change in state (transition),depends only on
states and not on the transition of the neighboring subsystems, so that V
only a single transition need be investigated. For the state disturibution
a F'a" the kinetic equation
function F(al, a2l N L
dF(-) - -F (a) W.
dt I I
j
F(L,,,, "21 'j-11 a" a,,,,
ao 49
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The kinetics of cooperative ... B102/B204
holds, where w denote the transition probabilities. The partial distribu-
tion functions of n-th order, which depend on the state n of tfte sub-
system are introduced with
FM V F (2).
(koil' 3.... In)
and finally one obtains for the partial.distribution functions
dF(I) (.,) = -"IF. F('-') (ai, x
dt
x
W., a,,)
F('-"*')
a aw a
dF~.) (a', ak) x
F(--1)(a,,
t
(k=l, 2.... z)
x W" (Xi' a~' ai"
U"t+,. UI'e
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The kinetics of cooperative -Bl02/B204
F(,+Ik+l) a, aj., aj,'
Irv
Ik
all, ... aI., (a',, a,,, - - - a,,) x
x
a'sp ... a aj) X
.X ,,,t, a,, a,,, ... a
Ik
(a,, a,,. a,,) x
dt I, aj,, a
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S1181,1611003100210161050
The kinetics of cooperative ... B102/B204
cL,,)
X
at
'a M
we ~ 4, ("'t
F"") (at, a,,, ... a.) W., (d" att
.j F('
cx,,, aq a, , aik*" at's
't-1 sit
Mi't Miol aji, Mi').
q-1" ail) X W.it -.0. Q'j; (a,
which may be solved according to the method of successive approximations.
Here the first approximation agrees with the zero-th approximation of
the Bogolyubov power expansion. In first approximation,
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The kinetics of cooperative B102/B204

(n)
1 a
(a n

a FT
)
(1)
F
(1)
(a holds; for F (ai) one
)
1 1
,
1 k-1
2 n , k
obtains the system
dF(')(0
I
(a
)
I a,, a ... a")
][I FM w (ail is)
,
I
dt k=1

S
F1,I) (a,,) vj.~ (14, 0 j, a,,- - - - aio) (6)
k=I

From the equivalence of all subsystems one obtains as normalization
condition F 1, independent of 1. (6) supplies the
P=j
function F(i)(a) in first approximation; in order to obtain this
function in second approximation, it is necessary to substitute
S/181/61/003/002/016/050
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The kinetics of cooperative ... B102/B204
function F(z+lk+l) in first approximation into the last equation of (4),-
whose solution gives F(0+1) in second approximation. If then F (Z+1)
2
is substituted into (3),
dFM F('-#-')(ai, at,) ay ... a )X
dt
XVW a d a
at
-I-D (d
F
V a,,) U'., N, av at,. a,.,)
F(a) a
k0 i J,# i
F(al, a2' ... aj-11 a~l a...,, am) X
k i i
(3)
x W.,
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201-18
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The kinetics of cooperative B102/B204
one obtains F(l)(a) ih sebond approximation. In order to obtain
F(l)(a) in third approximation, it is necessary to know p(z+lk+l) etc.
2
This method is explained on the basis of the example of a linear
cooperative system (e.g. macromolecule). The equations (10) (12)
are obtained, by means of which the distribution functions of arbitrary
order may be determined.
K
a a
di 2 C'i'
'51F(3) (cei (10~
4L.J (-t-1) U~' -.. gi(Ili-it "1, 0'1'
8/19

The kinetics of cooperative ...
(av
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2C118
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B102/B204
a ail ar CE
dFM (. a(, a(4-0 --NF(3) a,-,.i) w., i
(ail
1.2) We
F'3) (a,-,, ail
ail C ai4-11 ai-4-2)
F(3) (ail
H nPjt
(ail ai+11 ... at-4-M-1)
--~dt
L-2
W, (a i4-P-11 ai+jP ai4-pt
-I
, a'+)
N-I, ail al-1.17 ... a',
Mi+X-11
F("+')
a i-ol ai+11-11

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The kinetics of cooperative ... B102/B204
u-2
Fcn) a# a a
P=I ai-t-P-1 i+P+I X
X .1 a 'F F(n-1)(a a,, a,.,_,,
ail ai-1-04-
x
X w
-Card .1.0/1.2-l'..
_j

The kinetics of cooperative
S118I16i1003100210161050
B102/B204
The scheme of successive approximations is represented in Fig. 1.
The first and second approximations are calculated. -There are
2 figures and 4 references: 3 Soviet-bloc and 1 non-Soviet-bloc.
ASSOCIATION: Institut Vysokomolekulyarnykh soyedineniy AN SSSR
Leningrad (Institute of High-molecular Compounds
AS USSR, Leningrad)
SUBMITTED: MaY 4, 1960
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2970
S/1 90/61/003/0-1 1/015/016,
B1 10/B 147
AUTHORS, Vollkenshteyn, M. V., Sharonov, Yu, A,
TITLE: Effect of fritting of polymer glasses on the course of
specific heat in the softening range
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v.. 3, no. 11, 1961,
1739-1745
TEXT: Aim of the present work was to obtain exact quantitative data on
the dynamics of vitrification and softening processes, and to investigate
the effect of fritting on the softening of glass. Changes of the
amorphous structure and increase of the interaction of the kinetic units
take place during prolonged fritting, The irregular specific heats were
measured, S. N. Zhurkov and B. Ya. Levin (Ref. 13: Sb, rabot,
posvyashchennYY 70-letiyu akad. A- F, Ioffe (Collection of papers
dedicated to the 70th anniversary of Academician A. F,, Ioffs), Izd,
AN SSSR, M.-L., 1950, p, 260) found that the specific heat lias a maximum
in the softening range, the position and height of which de-end on the
heating rate.. The fritting of samples should additionally be taken into
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Effect of fritting of polymer- B110/B-147
consideration. In order to measure the heat effects linked with the rate
of relaxation, concentrated polymer solution was applied to three copper
wires. A O~14 mm wire of 98 mm length served for heating, the other
0,05 mm wires of -J17 mm length each for temperature measurements and "or
producing adiabatic conditions. A strip of a 0.15 to 0.20 mm. thick
polymer layer was obtained, which was coiled up and placed into a vacuum
flask. The thermal equilibrium occurred in fractions of a se-old at a
heating rate of 0.5 degrees/min, Measurement was made at 5-10~'~ mm Hg.
A thin, nickel-plated Al foil which was wrapped with R P-3 (R NE ) heati--,).g
wire and two coils of R P1 (RAEO and RA)2 (RAE2) Cu wire for adiabati-c
conditions served for preventing heat radiation., The heating circuit of
the foil contained 1he rheostats R1 and R (Fig, 2). Thyrairon rela y TV
2 .11
and the bridge circuit' diagram I with mirror galvanometer in the diagcnal
bridge kept the temperature of the foil -,b.0,030C lower than that of" the
sample,, The bridge consisted of the resistors RAO (RAO) and RA30 (R
AE1~4
The photoresisior ~~-2 (PSK-2) was thapickup for the thyratron relay. In
order to keep the sample-fcil temperature difference constant, the -acuum
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Critting of polymer.... B11O/B147
flask containing the apparatus was placp) -in an electr-,C fl~rr,.a.-
colder The rate of coollng from te=eratiiros > '11 "hu frit!'Inc
ic,:-rre -/min to 6de~~reeo/min. The third bridge
circuit diagram III with the mirror galvanometer r3c-47 (GZS-47) -,n ~hq
diagonal bridge served for temperature measurement- The tempe-ratut-P ef
the sample mczisured between 0 and 1200C with 0,01'C relative accurac,,,,
The tcl--_~l specific heat of polymer and Cu wire was calculated according
to; Cp= 0,239 u 2/Rt, where u =voltage of the heating battery; R =mean
resistance of the heating wire in the range of temperature measurement;
,-ti.me required for heating by 101", The measurement interval was 0,50"!
in the softening range O..250C. Dissolved and reprecipitated polyvinf'
acetate (PVA) and polystyrene (PS) (molecular weight -v10 6 were
0
investigated, Fritting took place at 21 C for 24 hr, For PVA, the curves
rl, ) the softening range. Amount and temperature of
pass a maximum in
the maximum increase with increasing heating rate- The amount increases
linearly with increasing fritting time (Fig.. 4). Relaxation times are
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2 7 1
S/190/61'/OOA/O11/O-.-/.076
iritting of oolymer... B110/ B147
measured for < T v in 10 hr so that equilibrium is approximately achieved
during prolonged fritting, A maximum of C P may occur during iubsequent,
heatlna~ it is not observed %nen fritting does not occur
EnthaIDY alloc -i~DDends on the fritting time, Its change was e_--t-_,_qjated
aC4:ording to the change of -the total amount of heat which waB passed to
ritting temperature to > T
the polymer at subsequent heating from the f, V VX
Glass may reach the state with 11 0 at T0