SCIENTIFIC ABSTRACT KRYLOV, O. V. - KRYLOV, O. V.

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

USSR/Chemistry Physical Chemistry
Card 1 1/1
Authors I Krylov. 0. V., Memb. Correa. of Acad. of 5c. USSR., Roginskiy, S. Z. and
F'oZk_na_'.___n_1".
Title Investigation of the absorption method characterizing the alkaline pro-
perties of oxfda catalysts
Periodical i Dokl. AN SSSH, 96, Ed. 6, 1183 - 1186, June 1954
Abstract In order to investigate the catalytic properties of surfaces, acting ac-
cording to the acid-basic mechanism, one must have proper methods of de-
termining the number and quality of the acid ary] alkaline centers of the
surface. The most effective methods are thone based on the measurement
of the value and stability of snecific absorptions for such weak baoes
as: ammonia, pyridine, quinoline, and the methods based on the study of
the noisoning effect of alkalis on the activity --if catalysts. Twelve
references. Graphs.
Institution :
Submitted : March 12, 1954

AF701597 TREASURE ISLAND BOOK REVIEW AID 842 - 3
KRYLOV, 0. V. and YE. A. FOKINA (Instttute of Physical Chemistry,
Aca-a-emy of Sciences, USSR).
0B IZMERENII KISLOTNO-SHCHELOCIfNYU SVOYSTV POVERKHNOSTI
(Determination of oxidation-reduction properties of surfaces).
In Problemy kinetlki i kataliza (Problems of Kinetics and
Ua-talysis), vol. 8. Izdatel'stvo Akademil Nauk SSSR., 1955.
Section V: New experimental methods. p. 2118-255.
The adsorption of phenol was studied in order to develop a method
for the determination of the number and nature of acid and alkaline
centers on the surface. It was determined gravimetrically on a
quartz spring balance connected with an ampule containing phenol.
The adsorption of phenol was conducted at 23-250C~ desorption,
at 25, 100, 200, 300 and 0380OC; adsorption at go C, desorption
at 100, 200, ~00 and 380 C; adsorption at 200 C, desorption at
200, 300 and ~800C. A study of the kinetics of adsorption and
decorption of phenol was carried out on acidic, alkaline
and amphoteric adsorbents. BeO, MgO, ZnO, CdO, CaO., Ca (0H)21
A120~, silica gel, and the alumInosilicate cracking catalyst.
The atSlytic activity of the above catalysts were also studied
In the decomposition of Isopropyl alcohol. The experimental
1/4

KRYLOV, 0. V. and YE. A. FOKINA An 842 - S
data are comptled In Table I (p. 250). The adaorption of phenol
byall the catalysts except Slop and A'2_'03-SIO2, Is very stable
(chemisorption).
The curve -in Fig. I (p. 251) shows the quasi-isobar3 of adsorption
(calculated from the saturation points of the kinetic ad orptIon
isotherms), The amount of phenol adnorbed at 250C on Im
catalytic surface Is approximately the same (5-8mm) on different
catalysts while -the stability of the bond between phenol and
catalyst differs for different catalysts. Data on the desorption
of phenol from BeO and MgO at various temperatures are compiled
in Table 2 (p. 252),
Kinetic isothermB of adsorption of phenol on BeO are shown in
Fig. 21(p. 253). Analogous isotherms were found for ZnO, MgO,
A120~, etc., with the exception of Cao, ca(OH)2,silica gel and
alum nosilicate. Kinetic lootrierms of adsorption of phenol on
aluminosilicate at various temperatures are shown In Fig. 3
(p. 253).
2/4

KRYLOV, 0. V. and YE, A. FOKINA
AID 842 - S
To eatabll8h the acIdic nature of tile catalytin surface, adsorption
of pyrtdln(! wan conductbd In the same manner as the adsorption of
phenol. The experimental data are compiled In table MP. 254),
Study of the decomposition of isopropyl alcohol showed that the
dehydration ability of the catalyst changes as in the adsorption
of pyridine, and the dehydrogenation ability of the catalyst as
in the adsorption of phenol.
The adeorption of phenol can be used for quantitative determination
of the basic nature of the surface, Other volatile substances
with low acidity my be used.
Adsorption of pyridine may be used for determination of the
acidic properties of the surface. It Is advisable to determine
also the heat of adtiorption and the energy of activation. A
similar method may be used for determination of the electronic
nature of the catalytic surface.
The effect of the adsorption of mercury, an electron-donor,
and oxygen, an electron-acceptor on the catalytic nature of
3/4

KRYLOV, 0. V. and YE, A. FOK114A
AID 842 - S
oxides of Be, Zn And Cd wan studied, Mercury and oxygen were
supplied to t,he catalyst slmultaneoitV with the vapers of
luopropyl alcohol. Oxygen decreasefl the rate of decomposition
of half of the initial value - see ref. 19. Three tables,
3 dingrama. 19 references, 12 Russian (19116-1954).
4/4
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USSR/PAysical Chemistry Kinetics. Combustion. Explosives. Topochemistry.
Catalysis, B-9
Abst Journal: Referat Zhur - xbimiya,, No 19, 1956, 61093
Authort Krylov, 0. V., Roginskiy, S. Z.
Institution: None
Titlet Concerning the Possible Mechanism of Catalytic Oxidation of
Hydrogen op Metals
Original
Periodicalt Izv. AN SSSR, Otd. khim. n., 1956, No 2, 145-149
Abstract: Presented is a summary of principal results of studies of kinetics
of oxidation, f H2 on Pt. It is assumed that the stai~*hich limits
the process if oxidation of H2 on Pt is the adsorption of 02 without
breach of molecules into atoms. Oxygen having undergone strong
surface combination (probably in the fom of ions) with the partici-
pation of d-elee-trons of Pt is not reduced by H2 but activates Pt
as concerns the reaction of oxidation of H2. H2 is adsorbed at
thoue active centers of Pt, reversibly poisoning them. The
Card 1/2

USSR/Pbysical Chemistry - Kinetics. Combustion. Explosives. Topochemistry.
Catalysis, B-9 -
Abst Journalt Referat Zhur - Xhimiya, No i9, 1956, #03
Abstract: assumption is made concerning the possible role of Ions and
radicals during the subsequent stages of the process. Regu-
laritieB of =dation of H2 on Pt are retained also in the
case of ?d and other noble metale, which makes qWable the
existence of a single mechanism. Bibliography, V-33 titles.
Card 2/2

ical Cheraistry - Thermodynuaica. Thernochemistry.
Equilibri'vis Phyaico-ChMiCal A1lA1Yri3. 1-11','ts,,
Abs Jour : Referat Zhur - 19iiniya, No 2, 1957, 3734
Luthor : Kirillov T.P., Krylov OOV,, Uckneyev ,.M.
111fit Ivanovo Chemtco-11O'C=7,q~1,'1CCLl IllatitutQ
Title Study of -r-bysicochemical Properties of Sy9ten PbO
FC.2031
Orig Pub Tr. Ivanovok, kiiim.--telthnal. in-ti.. 1956, No 5, 61-68
Abstract Stuly of PbO.Fe,)O 3 systen produced by co-precip-Itation
of the hylroxiden from a mixture of nitrates of Fe and
Fbj with 1111 - Aftar a prulininary drrinc; (90-1200) the
systera was XtIcined within 200-800 r-_rGc at intervals
of 1009. In the coTxsu thercof warc investigated the
rLLmetlc susceptibility, adsorption power nr.14 soLubility
(relati7e i-ae of dissolution of Fe,O 111, 1.0 N HC1 aid
PbO in 0.25 11 C11 COO. 1-6 wns founil ;Iat tile systen un-
dur stuO-y pasueG3 throuCb a series of Interm-diante atates
C~, rd 1/2 - 83
WSRIMYsictLl Chemistry - lLierriDdynardcs, Therwchonist,,j. B-8
Equilibriun. MY91co-Chmical iluialycis, -Phase TranSitiOns
Abs Jour Referat Zhur - KliLdya, No 2, 1,957.. 3734
oil calcining: 1) Decouposition of nitrates aii;i hydro-
xi'les (100--35c0); 2) Crystallization all,! ~olymrphoua
transformtiono of FbO and Ye2O (350-5000); 3) Inter-
nal, diffusion, characterized by 3iiieorporation of wre
nobile mleculva of PbO Into the crystal Lattice of
FO 00 (500-7000); 4) Forvation of crystal-line reaction
pr'.)Act leni forritc PbO.FeOO 3 ('[,'C-BCDo):
Card 2/2 34
USSR/Physical Chemistry Yinetics. Ccobustion

USSR/,-Fhysfca1 Chemlety - Klnetica. Combustion. Explosives. Topochemistry. B-9
Catalysis
Pbs Jour Referat Zhur - Xhimiyao No 4, 1957.. 1194
Author py1gy 0,Vj, floginekly S#Z.9 Yokins Ye. A,
inst Department of Chemical Sciences, Academy of Sciences USSR
Title Study of the Dejendence of Catalytic Activity of Binary Compounds of
Metals of-the Second (froup with Non-Ketals Upon e Position of Elements
in the Periodic System of Mendeleyev. Communication 1. Catalytic Decom-
position of Isopropyl Alcohol over Oxides of Alkaline-Earth Metals.
Orig Pub Izv. AN SSSR, Otd. khim. n-, 1956, xo 6, 668-675
Abstract In a flow-unit, at 314-46es a study was made of decomposition of isopro-
pyl alcohol in the presence of the catalysts CaO (1), Sro (II), B&O, (M),
CaCO (IV), B&CO M or *002 (VI). rz the 1-111 series catalytic ac-
tiVNy of the o2des increases. Over all the oxides dehydrogenation of
alcohol predominates over'the'dehydration. Energies of activation I of
dehydrogenation (in cal/mole), 1 12000-16000, on rI 11000., on 111 6000.
Values of E of dehydration are higher (in cal/mole): on 1 22000-26000,
on rI 25000, on 111 12000. At the same time 9 values of dehydration
1/2

USSR~ Phyiical Chemistry Kinetics. Combustion. Explosives. Topochemistry. B-9
Catalysis
Abe Jour Referat Zhur Xhimiya, No 4) 195T, 11284
over carbonates (24000 on 'IV, 17000 on V) are lover than dehydrogenation
E values (39000 on IV, 26000 on V) and approximate the dehy4rogenation
E over oxides. On the basis of these data the assumption is made con-
cerning the presence in oxides of carbonate admixtures which cause the
dehydration. Dehydrogenation R over V1, of 16= cal/mole, is close
to dehydrogenation I over 1. Literature data concerning catalytic pro-
perties of solid alkalies indicate widespread use of alkaline catalysis.
2/2

fo

"Study of the Acid-Dase Properties of catalytic Sul-fact--3 by the! Differential
Isotop,2 Method.
4 J%'i

1RY1OV O.V.; ROGINSKIY, S.Z.: YOXIII. Te.l.
Investigating the dependence of catalytic nctivity of binary
metal compounds of the second grolyp with nonmetals on the position
of the eleikente in M.I.Mendeleev's periodic table. Report No.2:
Catalytic decomposition of slopropyl alcohol on oxides of metals
from the side subgroup of the second group. IzY.AN SSSR Otd.khia.
nauk no.4:421-430 Ap 157. (MIRA 10:11)
1. Institut fisichaskay khtmii AN SSSR
(Catalysts) (Isopropyl alcohol) (Oxides)

KRYU)V, O.T.; YOKINA, Ta.A.
ftudy of sulfide stability vith the aid of $35 during catalytio
dooonposition of isopropyl alcohol. Probl, kin. i kat. 9.,294-303
'57. (MIRA 1113)
(Sulfides) (Cataly-sim) (Sulfur-Isotopes)

XEtTWV, O.V.; YOICIXA# Te.A.
Stud.v of acid-bass properties of catalytic mLrface bT the differ-
ential Isotope method, Probl, kin, I kat, 91304-3,3 57,(KINA 1113)
(Adsorption) (Cresol) (Carbon-Inotopos)
N5 U

tit 'i

AUT11ORS3 ~Krylov, 0. V., Pokina, Ye. A. 62-5a- 3-2/30
TITLE: The Investigation of the Catalytic Activity of the Binary
Compounds of Metals of the Second Group With Nonmetals as
Dependent on the Position of the Elements in the Mendeleyev
Periodio System (Izuoheniye zavisimosti kataliticheskoy
aktivnosti binarnykh soyedineniy metallov vtoroy gruppy v
nemetallami ot polozheniya, elementov V periodioheskoy sisteme
Mendeleyeva). Communication 3. The Catalytic Decomposition
of Isopropyl Alcohol on the Sulfides of Metals of the Second
Group (Soobshoheniye 3. Kataliticheskoye razlozheniye izo-
propilovogo spirta na sullfidakh, metallov vtoroy gruppy)
PERIODICALs Izvestiya Akademii Nauk SSSR Otdeleniye Khimicheakikh Hauk,
1958, Nr 3, pp. 266-276 (uss~j
ABSTRACTs This paper represents part of the systematic investigations
of the catalytic properties of binary metallic compounds
(metals of the 2nd group) with metalloida of the 6th group.
Beside the sulfides of the 2nd metal group some sulfide
samples (of Pb and Bi) were also investigated. The present
Card 1/ 2 paper describes the investigation of sulfurous zinc ZnS and

The Investigation of the Catalytic Activity of the Binary 62-58-3-2/30
Compounds of Metals of the Second Group With Nonmetals as Dependent on the
Position of the Elements in the Mendeleyev Periodic System. Communicetion
3~ The Catalytic Decomposition of Ioopropyl Alcohol on the 3ulfides of
Metals of the Second Group
similar types of zinc. Table I shown the results of the per-
formed experiment. The dehydrogenation and dehydration of
iaopropyl alcohol on the sulfides were also investigated (see
tables 3-6). It became evident that all investigated sulfides
except PbS are dehydrogenizing catalysts. The catalytic
activity of the sulfides Zn and Cd is higher than that of ZnO
and CdO. It was further found 'that a modification of the
method of synthesis of the sulfide causes a modification of
its catalytic properties. Under the conditions of the de-
composition of isopropyl alcohol (in the layer) the activity
of ZnS is higher than of ZnO, The activation energy of the
dehydrogenation (in the layer) increases with an increasing
filling of the surface. There are 8 figures, 6 tables, and
17 references, 16 of which are Soviet.
ASSOCIATION3 Inatitut fizicheakoy khimii Akademii nauk SSSH
(Institute for Physical Chemistry,AS USSR)
SUBMITTEDs January 8, 1957
Card 2/2

:30V/30-58-7.-34/49
AUTHOR: Krylov, 0
Candidate of Chemicul Sciences
TITLE: Physics ind Physical Chemistry of Cutalyais (Fizika I fi2iko-
-Knimiyu kataliza) Transactions of the All-Union Conference
(Vaesoyuznaya konferenteiya)
PERIODICAL: Vestnik Akademii nauk SSSR, 1958. Hr 7, pp. 119 - 122 (USSR)
ABSTRACT; This conference convened in Moscow between March 20 th and
March 2 3rd. It was called by the Department of Chemical
Sciences and the Institute of Physical Chemistry of the AS
USSR (Otdeleniye khimimheakikh nauk i Institut fizicheskoy
khimii Akademii nauk SSSR~It was attended by more than 600
persons from different towns of the Soviet Union as well as
from countries of the people's democracies. Nearly 100 re-
ports were submitted, 78 of which were given to the parti-
cipants for discussion. The remainder was read. The follow-
ing reports were heard:
1) S. Z. Roginskiy, (Inatituteof Physical Chemistry,,AS USSR),
spoke about the selective methods concerning semiconductor
Card 1/5 catalysis.

Physics and Physical Chemistry of Catalysins SOV/ 30-56-7-34/49
Transactions of the All-Union Conference
2) V. V. Boldyrev, Tomsk University, used electron repre-
aentations for the explanation of the course of topo-
chemical reactions*
5) N* Pe Keyyer, (Institute of Physical Chemistry)AS USSR),
used electron representations for the clarification of
the characteristics of heterogeneity of the active sur-
face of semiconductor contacts.
4) F. Fe Vollkenshteyn, Ve Be Sandomirskiy and She Me Kogan,
(Institute of Physical Chemistry,AS USSR), investigated
the influence of exposure as well as of an external elec-
tric field on the absorptive power of a semiconductor.
5) A. He Terenin spoke about the investigation of the struc-
ture and the behavior of jurface formations in the case
of adsorption and catalysis.
6) V. F. Kiselev (Moscow University), dealt with problems
concerning the elementary act ofcatalysis.
7) G. Ke Boreskoyt Physical-Chemical Institute imeni Le Yao
Karpov (Fiziko-khimicheskiy institut im. L. Ya. Karpova),
reported on the dependence of the catalytic activity of
metals on their position in the periodic system of ele-
Card ments.

Physics and Physical Chemistry of Catalysis, SOVI 30-58-7-34/49
Transactions of the All-Union Conference
8) V. L* Bonch-Bruyevich and V. B. Glasko, (Moscow University),
reported on the results of the adsorption computation of
metals.
9) A. A. Balandin, Institute of Organic Chemistry AS USSR
(Inatitut organicheakoy khimii Akademii nauk SSSR), re-
ported on new data concerning the Ale played by structure
factors in heterogeneous catalysis*
10) V. V. Voyevodskiy disproved his (and 11. No Semenov's) hypo-
thesis of the existence of surface lattices and a hetero-
geneous catalysiso
11) Ya. T. Eydus and No 1. Yershov, (Institute of Organic
Chemistry AS USSR), 0. 1. Golovina, M. M. Sakharova, So Z.
Roginskl~ and Ye. So Dokukina, (Inatitute of Physical
Chemistry)AS USSR), proved the existence of polymerization
lattices in heterogeneous-catalytic processes of hydro-
carbon synthesis.
12) N. No Tikhomirov, Po No Bubnov and V. V. Voyevodskiy,
(Institute of Chemical Physics)AS USSR), reported on the
application of the method of paramagnetic resonance of
Card 3/5 electrons for the purpose of investigating the interaction
v

Physics and Physical Chemistry of Catalysis, 30V/ 30-58-7-34/49
Transactiona of the All-Union Conference
of molecular oxygen with the free carbon valences.
13) Ya. K. Byrkin, (In3titute of General and Inorganic Chemistry
AS USSR' (Inatitut obahchey i neorganicheskoy khimii
Akademii nauk "."SR), reported on problems concerning the
molecular mechanism in catalysis.
14) X. V. Topchiyev, Moacow University# gave a survey on the
data concerning catalytic activity of aluminum silicates.
15) L. I. Piguzova aq'd M. A. Kaliko, All-Union Scientific He-
search Instituteof Mineral Oil Industry (Vaesoyuznyy
nauchno-iseledo,,rtk!tel1skiy institut neftyan*y promyshlonnosti)
reported on problems concerning characteristics of active
acid centers in cracking and in catalytic reactions with
aluminum silicates.
16) No M. Chirkovj Institute of Chemical Physics,AS USSR,
proved the proton character of the mechanism of homogeneous
acid catalysis.
17) 0. V. Xrylov, Institute of Chemical Physics,AS USSR, spoke
about the heterogeneouo catalysis of acids.
18) Go M. Zhabrova, V. I. Vladimirova and Ye. I. Yegorov,
Institute of Physical ChemiatrylAS V,6R, spoke about the
sorption of ions in the production of q zinc oxide cata-
Card 4/5 lyst.

Flhy:3ica and Physical Chemistry of Catalysis. SOV/ 30-58-7-34/49
Transactions of the All-Union Conference
19) 0. M. Poltorak, Moscow University, reported on problems
concerning the genesis of catalysts.
Card 5/5

5(4) 50V/62-58-1 2-3/22
i ~
AUTHORS: Kryloyl 0. V., Kushnerev, M. Ya., Fokina, Ye.
TITLE: Intestigation of the Dependence of the Cu*.aly'..-'c Activity of
Binary Compounds of Metals of the Second Group With Non-Metaa
Upon the Poeit�cn of the Elements in the Mendeleyev Periodic
System (IzuchGnl.ye zavisimooti kataliticheskoy aktivnosti bi-
narnykh soyedineniy motallov vtcroy grurpy s nemetall'aml ot
polozheniya elementoo-v v periodicheakoy sisteme Mendoleyeva)
Communication 4: Catalytic. Decompoeltion (if Isopropy! Alcohol
on Zinc Selenide and Telluride (Soobahcheniye 4. Katalitiches-
koye raziczheriye izoprop~lovogo spirts, na splenide i telluride
t
--linka)
PERIODICAL: Izvestiya Akademii na-ik SSSR. Otdeloniye khimicheskikh nauk,
1958, Nr 12, PP 1413-1421 (USSR)
ABSTRACT: The present pape- deals with the in-testif;ation of the catalytic.
activitly of selenides and tellurides of metals oil the second
group w4th respect to the dehydration and dehydrogenation of
isupropyl alcohol, It is a continuatior. of the investigations
carried out with the ox-ides and sulf1d4,-t; of metals of the same
Card -1/3 groul, (Ref!j 1-3). The ~nvoistiguzkion mothods vmployod are dt~-

SOV/62-58--12-3/22
Investigation of the Dependence of the Cataly-~ic Activity of Binary CompounlD
of Metals of the Bactind Group With Non--Motalr Upon thr., Position of the
Elements in the Mondnleyev Feriodio Syntom. Communloation 4: Catalytic
Deramposition of Itt..,propyl Alcohol on Zino. Sol-an1de and TolluTlde
scribed 'Refs 1-3). The ZnSe preparation was supplied by M. S.
BRInnlkiy, the ZnTe preparation by N. A. Goryunova, and chem-
ically piire telliirium by A. V. Novoselova. The decomposition
of is-)pzopyll alcohcl on ZnSe and ZnTe witnin the temperature
rangs) 20-140o was investigated. It was found that the reaction
in p:7incipla develops in the dirncti,~n of dehydrogonation. In
the reaction a decrease of the catalytic activity of ZnSe and
ZnTa is observed. The activation energy of the dehydrogenation
of al-~;ohol on ZnSe increases from 15 to 21 kcal/mo-1- The ZnSe
sample annealed :~n a'-r at 6000 was less acttve -1han that not
annealed. Elementary tellurium has a low cataly".-ic activity.
Rftdiographia a-lid alectroacgraphic inveitigations as a result
of numrar~aon of thermodynamic characterf-st~cs slowed that the
phase ahangett of the catalyst are due to impurities in the
basip sample and on temperature affect3, but in, no case on the
course of catalysfs. Thera are 11 fig-L~rss, 3 tablon, and
!0 references, 7 of whiz-h a-re
Card 2/3

SOV/62-58-12-3/22
Investigation of the Dependence of the Catalytic Activity of Binary Compounds
of Metals of the Second Group With Non-Metals Upon the Position of the
Elemants in the Mendeleyev Periodic System. Communication 4: Catalytic
Decomposition of Isopropyl Alcohol on Zinc Selenide and Telluride
ASSOCIATIOV., Inatitut fizioheskoy khimii Akademii nauk 33SR (Institute of
Physical Chemietry,Academy of SciencesUSSR)
SUBMITTED: June 1, 1957
Card 3/3

_AUTMIRS:
TITLE:
PERIODICAL:
Krylov, 0. V., Ruginsl.j, S.
Member AIN USSR
". Corresponlin,; 2o-3-5o "511
OtIaljuiu on Intrinsic Semi c on~l tie. torn (0 katalize na
poluprovodrikakh v oblanti sobutveni,o,, iirovollmosti)
Do!,-lady All SSSR, 1958, Vol- 118, Ir 3, pp. r23-525 (USSR)
ABSTRACT: Although tl~,e same mechanism of the primazy act of the inte.-
action of a semicondtictor-catalyst with the substrate
prevptlls the catalysis In the domain of Intr1noic conduction
raust (liffer in many regards fro!n the catalycis in the domain
of the admixture-conduction. For the catalWcis in the domain
of Intrinsic conduction I.Ye followin6 must te characteristi-
cal: 1) A lieht dependence of the catalytic activity on the
"structure-sensitive" propertiesi 2) A conrection between
the catalytic properties end the substance propertieul 3) A
connoction between the catalytic properties and the width of
the forbidden zon(-,, which resulto from this; 4) High values
of the factor In front of the exponential function; A
compensation of the differencei, between the n- Lint! the p-
Card 1/3 -cernicondii-tora. The dati~ rhich rere obtriinod by tho authors

C4talysit; on Intrinsic Semiconductora 2o-3-3o/59
together with Ye. A. Pokin,,. are ~I-;er, In L table, they show
the sharp increase of the catalitic activity -,,-ith re6ard to
the dehydration of the isopropyl-n1co)1ol at t%e trantition
from. ZnO to Zs-.Te. At tYe same tiz.e tilc activztion energy of
the d-hydration deercaaed, whereby this cuctivation energy
depends much on the filline up. Th~, rj~.',e of dehydration was
low, in cane of all catalynts, where!!~r the percentage of
dehydration decreased tit the trnnniti,)n from ZnO to ZnTe.
When the other propcrtie5 in the series Z-0 --q- ZnS --)- ZnSo-~'
---.>ZnTe were investigated tht, follow!:,C could b,: stated: The
catalytic activity and the dielectric constant C increase,
but the differerce of the electron uct;ativity and the width
of thL' forbidden zono deceusv. An oxcepti.-)n in this vieyr
is ZnO with U - 3,2 eV. The catalysis takes -oluce in a
temperature ranfep In which iire -at least 3 of the here
examined binLry compou,~ds (ZnS, Zj.Se, and ZnTe) ir. the domain
of intrinsic conduction. At the ctumte time with the in-
creasinf, of the deh,~,dratln,- activity the lattice parameter
of the US increases. Thus In the case of thu here examined
binary compounds a simpler correlation betreen the width of
Ue forbiddez: zone, and tht catalytic uctivity is observed.
Card 2/ 3 Such inveotigatio.,.s would be icairable also for other graups

Catalynin on Intrinsic Semiconductors 2o-3-3o/'59
of compoundo. There are 1 figure and 19 referencec, 15 of
which are Slavic.
. ASSOC IATION; Institute for Physical Chemictry AN USSR (Institut
fizicheakoy khimii Akademii nauk SSSR)
SUBMITTED: September 9, 1957
AVAILABLE: Library of Congress
Card 3/3
LL~~~77777~

AUT"IORS Krylov 0 V., Fo%ina, Ye. A. 1 2e,-2- ',rl(~3
TITLE: On the Catalytic Properties of Calcium O~:i,le (0 1rat;-.1itichooki~h
avoyntvakh ohiai kalltsiya)
-PERIODICAL: Doklady Akademii nauk SSS11, Vol. 12o, 111- 2,
PP- 333 - 335 (USSR)
Ar~STRACT: First, reference in nade to varioiio pertinent j)apers publichod
previously. The invosti,_--~tion of the rules ;overnini; the basic
catalyDis an aGainst the ncid catalynin ani the oxidation-
reduction catalysis is very intoresting. The dehydration of
cyclohexane, the decompocition of loobiityl alcohol and of
hydrazines on calcium oxide in investi,;,,ted. The calcium oxide
was produced by a dehydration of Ca(011) 2 at 6000 in a vacuum
in the same container, in which tile ~:at~Llytic reaction was
investigated. The reaction products were analyzed by freezing out.
Bonidest an additional analysis for H 2 was carried out. The
bydro,t-on was made to pans throtil, dium tapillnry. The
kinetic curves of the deh-dration of inopropyl alcolial in tho
Card 1/3 adsorbed layer at 100- 200 are -iven in a diaeran. The a-mount
M

On the Catalitic Properties of Calcium Oxide SOV/2o-12o-2-30/63
of desorbod hydro6en at 150-2000 i.,: cqu,-1 to the amount of
acetone. At lower temp 2rat tires a 10-2a,141 excesa of hydro,-en is
found. This is explained by the more pronounced adsorption
of acetone on CaO. With an initial pressure of C 6H12 a.-nounting
to 0,2 nm the dehydration of cyclohe:eait1 proceeds at 300-450 0
with a satisfactory velocity. Further details are given. These
renults are well reproducible. The activation ener:;y of de-
hydration in 30,5 Kcal/ mol. A 3toicho-ictric deco-aposition of
C61112 into C 6H6 + 3112 was not observed. In another diaGram the
kinetic curves of the decomposition of hy;lrnzine upon the
absorbed layer at 50-2000 are Given. Thin investij-,ation proven
that it is possible to carry out three reactions of hydrogen
separation upon CaO. Two of these reactions, the dehydration
of alcohol and of cyclohexane proceed in the same direction
an upon electron semiconductors. The direction of the third
reaction, the decomposition of hydra-.ine differs from the
direction taken by the reaction upon metala %nd semiconductors.
The authorn express their gratitude to the Corresponding Member
AS USSR, S.Z.Roginskiy for hin advice and a number of valuable
Card 2/3 nuLfZeationa. There are 4 figiiroo and 13 references, 9 of which

On the Cahalytic 'Proportion of C.%lciun Oxl~!e 1 2~-2- 3o1
are Soviet.
PRESE11TED: January 2, 195t;, by 3.1.Vollfl:ovich, of
Sciericeo, US"'R
SUBMITTED: December 31, 1957
L. Geld= oxide-XaUlytia properties
cara 3/3

5(4) SOV162-59-1-3138
AUTHOM. Krylovp 0. V., Roginskiy, 3. Z.
TITLE: The Dependence of Catalytic Activity of Binary Compounds
of Metals of the Second Group With Non-Metals on the
Position of Elements in Mendeleyev's Periodic System (Izu-
cheniye zavisimooti kattilitichcskoy aktivnosti binarnykh
soyedineniy metallov vtoroy gruppy a nemetallami ot -polozhe-
niya elementov v periodicheskoy uizteme Mendeleyeva)co-nmu-
nication V. Reg-alaritles in the Change of Properties of the
Series ZnO, ZnSp ZnSe, ZnTe (Soobnlicheniye 5. 0 zakonomor-
nostyakh izmeneniya avoyctv v ryndu ZnO, ZnS,ZnSe,ZnTe)
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk,
1959, Nr lt PP 17 - 24 (USISR)
ABSTRACT: The connection between the position of elements within
the solid body in the periodic systern on the one hand and
the catalytic properties of this body on the other hand in
insufficiently inveati,rated. Systematic papers hitherto
published primarily refer to simple bodies and mainly deal
with explaining the role played by empty points of d-obells
Card 1/4 of the atom in catalysis. In view of the development of

The Dependence of CatAlvtic Activity of Binary Compounds SOV/62-59-1-3/38
~1
of 4"Ietals of the Sec(md Irroup With Non-Metals on the Position of
Elenonts in Merideleyev's Periodic Syntem. Communication V. Re-ularities
in the Change of Properties of the Series ZnO, ZnS, ZrSe, ZnTe
semiconductor chemistry and the connection between their
electronic and catalytic properties, which frequently has
been observed, it neem.~d to ~o important to investigate the
effect exercised by the non-metallic component upon the
latter. Hor have there been any experimental data available
which might serve an basis for generalizations. In some
earlier papers the authors tried to fill this gap by inves-
tigating the catalytic properties of semiconductors. The re-
sults obtained and data recently published indicate certain
reg,ularities which in future might be of gcneral. mportance.
In the present paper the authors investir,-ated the effect
of non-metal referring to the compound of the type
II VI II
A B with zinc as a positively charCed atom A . In order
to determine the corre3ponding rc,,ularities they compared
the chanve in the catalytic properties in the series
ZnO --4ZnS ---i Zti!;e -~ ZnTo tin to tho decomposition of Iso-
Card 2/4 propyl alcohol with tho clvin,-,es of a number of electric

The Dependence of Catalytic Activity of Binary Compounds SOV/62-59-1-3/38
of Metalt of' the Beemd ;roup With flon-Met-Is on the Porition of
Elements in Mendeleyev's Periodic System. Communication V. Regxilnritien
in the Change of Proportion of the Series ZnO, Zn5, ZnSe, ZnTe
characteristics of these semicon3uctors. It was stated that
the catalytic activity of the binary "eX compound chane;cs
as to the dehydrogenation of alcohol simultaneoiisly with
the change of binding polarity which becomes manifest by
the change of a numl,.er of electric properties. On the In-
crease of the atomic weight of th,~- non-metal in the MeX
compound the activation energy of the dehydrogenation of
alcohol decreases, wheruas dielectric constuRnt, increases,
and the width of the (ian;,(..r zone fin rell as the difference
of electronegativity decreases. The dependence in complicated
by the change of E (activation energy) with the occupation
of the -urface. According to data of publications it was
assumed that the catalysts ZnS, ZnSe, ZnTe (possibly also
ZnO) primarily act within the ran,,-,e of their own conductivity.
Definite conclusions can be drawn only when electric pro-
perties of Bemico0uctors during catalysis have been measured.
It is supposed that the position of the level of impurity
Card 3/4 conductivity may he also determined according to the

17n
The Dependence of Catalytic Activity of Binary Compoun'f7 3011/62-59-1-31.)
of Metals of the Second Group With Non-l-letaln on the Position of
Elements in MendeleyevIn Periolle System. Com-ninication V. JPjularities
in the Change of Properties of the Series ZnO, ZnS, Zn')e, ZnTe
position of elements (of which the nemicondtu:tor is -tinde up)
in the ppriodic system. The authors thank F. F. Vollken-
shteyn and V. B. Sandomirskiy for the discuscion. There are
I table and 31 references, 20 of which are Soviet.
ASSOC IATION: Inntitut fizicheakoy khimil A~Poo.,Al rauk SSSR (InBtitute
of Physical Chemirtry of the Acadf~my of ScIprees, USSR)
SUBMITTED: May 31, 1957
Card 4/4

J~2 00
444) 66869
AUTHORS: Krylovp O.V., Yokina, Ye.A* SOV/76-33-11-31/47
TITLE: Investigation of Some Catalytic Reactions on the Surface of
Calcium Oxide
PERIODICAL: Zhurnal fixicheskoy khimii, 1959, Vol 33, Nr 11, pp 2555-2558
(USSR)
A.BSTRACT: In continuation of a previous paper (Ref 1) the authors
investigated the decomposition of isopropanol and hydrazine
as well as the dehydration of ethane and cyclohexane on
calcium oxide. The decomposition of iaopropanol was carried
out In an adsorbed layer according to a method described
earlier (Ref 2). The curves (Fig 1) are given of the decom-
position of isopropanol at freezing out (-116"(1)"f the reac-
tion products (acetone), in which case in the eas remained
mainly hydrogen and the product of dehydrogenatiq,7 jLenee
The hygogen content was as 1000b - 6403%, at 15-0 - 7proi]%rp
at 180 - 78.8% and at 2gO C- 84.0 -86.3%. The activation
energy varied at 100-150 Cin dependence on the degr Of
filling in the range, 21-30 kcal/mol and at 180-2002;from 32
to 36 kcal/mol. Ethane did nos show any change an calcium at
Card 1/2 0-4 da-119 uP to 600'q, above 600 Ca small degree of pressure

66869
Investigation of Some Catalytic Reactions on soy/76-33-11-31/47
the Surface of Calcium Oxide
Increase could be observed and hydrogen was found in the
-reaction products. The dehydrogenation experiments carried out
wi h a a ex G.V Isaguly
t LSloh ane put at diaposal by A auto, showed
(Fig 3 kine-tf-c-Ae-oomposition curve at 400-C dhd varied initial
pressure) that the dependence of the initial reaction rate is
linear with the pressure of the cyclohexane (Fig 4). The
activat n energy of the dehydrogenation is 30-5 kcal/mol at
300-450~which is in accordance with data by A.A.Balandin and
I*I.Brueov (Ref 4), and M.Ya.Kagan and R.M.Flid (Ref 5).
Hydrogen was determined an the dehydrogenation product. The
hydrazine decomposition was also investigated in the adsorbed
layer 8f the oalbium oxide and it was established that at
50-200 Cthe main reaction products are hydrogen and nitrogen.
There are 6 figures and 7 references, 6 of which are Soviet.
ASSOCIATION: Akademiya nauk SSSR jInstitut fizicheskoy khimii,)Ioakva
(Aqademy f sciences , USSR, Institute of Physical Chemistry
Moscow)
Card 2/2

3 '(3)
AUTHORS: Frolov, V. M., K S071-20-12(-1 -29/62
RoGinakij, S. Z., Corroapinling Member,
AS USSR
TITLE; Catalytic Dithydrogonatir.,.-. of Ethanol -,n G.-rmanluzl
(Katal1ti,tw.!c)yo "4egtdri::,-,ian1yu na gervanit)
PERIODICAL: Doklady Akadezil nauk SSSR, 19r1q, Vol 126, Nr 1, pp 107 - 110
(USSR')
ABSTRACT: Germanium .n abio, to oatoilyza several rede~x rerictiz;ns (Rafe
1,2). The atithore waitel t~ investl6ate the !~Ineticn of some of
thooo reactions In the caou of various Go-samples with differ-
'ent crill"I~!tirity J.n th,) c%so (,f a r,~,n~-"ntraticr. ohane,3 of the
current c&:-riurc withir. a ~,'Lde -:arE;,-_. This can facilitate the
-understaniinC of the rrt~chaniaz, of the scuiconduntor catalysis.
The k1-.-.ati,-a of the reactiop. renti(_-.~Yd in tha title ;ias iwiest-
igated under utatic va-.u,im onlitions in a -,uart!z ranotor. Pow-

der w-~th a np5)uJ.f1c 3~.rfac,- (if 0.05 -- 0.1 by ;rl-
2/,; r

pr-cee.. The
verization In the mortar ir. air for thin
.9
Ge-powder was trained before th,~ ex~erimort at 050 D or a'. 650
Card 1/4

Catalytic Dehydrogenation of Germanium SOV/20-126-1-29/62
-5 torr. The mentioned dohydrogen%tion was In-
and at 10 10
0
vestigated at 200-270 , A reduction of the reaction rate (Fics
1:1-4 cursive) took place in the case of sutsequently carried
0
out ethanol compoaiti~jna on Ge, trained at 850 . This vas stop-
ped after the fourth experiment. Beside hydrogen and acetal-
dehyde also ethylene was found to exist in the gas phase. Its
content was reduced from experiment to axpol,iment. The hydrquen
pressure was in all experiments equal to the summed pressure
of acetaldohyde anl othylene (uieuracy The authors as-
oume that the fresh Ge-surface adsorbs an oxyC;en mcleoule from
ethanol (reaction 1) thanks to Jts Gr~!at afflnit~r to oxy4;en.
The cov,-jrinG of the Go-ijurface with adsorbed vxy,;E-n leads to
tho breakitif;-off of the reacti(in (I). As late as from the 'fourth
experiment on only the process of t1he catalytic dehydroGenation
takcs place on the Go-po-ader. The chemosorrtion if oxyL:on was
carriad Qut after th,, fourth Qxperft~cnt in order to clarify the
effect of a cooplete ~,overir,- of the Ce-surface with oxy6en.
The curves 5-0 (FiC 1) belon- to th,,:~ a: bsaj.-uently carriod out
experiments. They dnccribe tile kinctics of thi hydroZ;en separa-
Card 2/4 tion under the glklven conditions. Sirce V,o prcssure of the

Catalytic Dehydrogenation of Ethanol cn Germanium 507/20-126-1-29/62
acetaldehyde formod un the ti-irface jourpass-~o consider.-
ably the h1droger. prasa~tra the removal of the adsorbel oxj&en
accarding to the raacticn (III) is to be assumel. The cataltic
roaction (II) ;roceods ther. ~)r. the curface from jxyden.
Thus, adsorbed oxyGen ran in th.--t case !:~f tho systom Cormanium-
-athanol approach to the staticnary a-,tivitv cf the k7atalytic
dehydroganation fror, the side of th,,, nurfac~ free fr)m oxygen
as well as frcm the side of thn aurfa~.e Qompletel;f cc-;ered by
the adsorbod cxy,-e-,,. FiCure I shows th!:~ electronic character-
istics of the alloyed Go-sar;)los, the loearithm. of tha pre-ex-
ponantial multiplier (k d and of the seeming activation energy
(E) of the catalytin -)thanul dvhydroZ;onation. The reslilts des-
cribed clarify to a -,q:rtain extent the often dis(,ussed problem
of the catalytic equivalence of the p- and n-semiconductors.
The authors assume with a certain security with respect to the
reaction mentioned in the title that the activation energies on
the p-germanium ara "-ansidorabl., lower than on n-jrer=ari'.im.
This conclusion does, howo-ier, nDt hold in the -ase :~f all other
reactions (Refs 6,7). The ranro of the invpstigated systems is
Card 3/4 to be widened and thi catalytic processes are to be more thc-
-7Z7

Catalytic Dehydrogenation of Ethanol on Germanium SOV120-126-1-29162
roughly investigated. Data concerning the change of -the elec-
tronic charaotoriatice of the surface during the reaction pro-
oess are to be used. There are 3 fieiiros, 1 tablet and 7 ref-
orencest 4 of which are Soviqt.
ASSOCIATION: Institut fizicheekoy khimii Akademii nauk SSSR (Inatitute of
Physical Chemistry of the Academy of Sciencee,USSR)
SUBMITTED: January 28, 1959
Card 4/4
t _rn 4

E s 5
VIA
VV
all
3 Big 3
:t2
Ali '3
33
Jul 11
Ell
t3

a
pit
oil;
all
"Al
41 i 11 1

FROLOVI V.M.; KRYWVl O.V.; ROGIIISKIYp S.Z.
Catalytic propertieo of gormwUum., Probl, kin, i kat, M102-107
160a (MIRA 3-40)
1. Inatitut fizichookoy khimii AN SSSR,
(Garmwdum)

KRYLOVj _Pfy.j RMTUSKTY, S,Z,; F
DKINA,
Catalysis on semiconductors in the Aigion of natural conduction.
Proble kin, i ka'v-, 10IU7-120 160, (MIRA 14:5)
L Institut fizicheskoy khImii AN SSSR,
(CatalYsis) (Semiconductors)

KRYLOV 0 V
Catalytic action of solid baass. Prpbl. kin. I kat. 10:273-278 160.
(MMA 1-4: 5)
1, Institut fizichookoy khIm4i AN SSSR*
(Catalysts) (Bases (Chemistry))

KRYLOV, O.Y.; FOKLNA, Te.A-
'Isotopic study of the heterogeneous surfaces of oxide
catalysts used in the decomposition of isopropyl alcohol.
Part 1: Calcium oxida. Kin. i Irat-1 no. 3:421-410
&o 16o. (MIRA 13:11)
1. Institut fisichaskoy khtaii AN MR.
(Isopropyl alcohol) (Catalysts) (Carbon-Isotopes)
.44
:5

S/195/60/001/004/006/015
B010055
AUTHORS: Krylov, 0. V., Fokina, Yo. A.
TITLE: Application of the Isotopic Exchange Method for the
Investigation of Surface Inhomogeneity of Oxide Catalysts
by Deenmposition of Isopropyl Alcohol. II. Aluminum Oxide
and Zino Oxide
PERIODICAL: Kinetika i katalisp 1960, Vol. 1, No- 4, PP. 542-547
TEXT: Studies on the nature of active centers on the surface of1120 3
were carried out by N. P. Keyyer (Ref. 2), A. A. Bfibushkin and A. V.
Uvarov (Ref. 3), and V. E. Vassorberg and A. A. Balandin (Ref. 4). BY
examining the decomposition of isopropyl alcohol on the layer adsorbed on
aluminum oxide by the differential isotope method, they found that the
aluminum-oxide surface was inhomogeneous. Dehydration of isoprop.Vl
alcohol occurs on only 4-6% of the aluminum-oxide surface. The results
obtained by studying the dehydration of isopropyl alcohol on aluminum
oxide appear in Figs. I and 2. The specific activity of all reaction
Card 1/3
op

Application of the Isotopic Exchange Method for 3/195 60/001/004/006/015
the Investigation of Surface Inbomoguneity of BO17/ 055
Oxide Catalysts by Decomposition of Isopropyl
Alcohol. II, Aluminum Oxide and Zinc Oxide
products desorbed during isopropyl-alcohol dehydration was found to be
constant. Desorption and dehydration of isopropyl alcohol on Al 203 is
illustrated in Fig. 4. The kinetics of isotopic exchange between iso-
propyl alcohol adsorbed on Al 203and isopropyl alcohol in the gaseous
phase is graphically shown in Fig. 3. The decomposition of isopropyl
alcohol on zinc oxide was investigated by the differential isotope
exchange method whereby both dehydrogenation and dehydration products of
isopropyl alcohol were found to have constant but different specific
activity levels. Fig. 5 gives a graphic representation of the results
obtained at decomposition of isopropyl alcohol on ZnO. Dehydrogenation
and dehydration of isopropyl alcohol occur at different active centers of
the zinc oxide surface. Dehydration occurs mainly at active centers having
a lower activation energy. The kinetics of isotopic exchange between
isopropyl alcohol adsorbed on ZnO and isopropyl alcohol in thegaseous
phase Is shown In Fig. 6. Isotopic exchange reactions of isopropyl
alcohol adsorbed on ZnO and Al 203 are much delayed, thus indicating the
Card 2/3

Application of the Inotopic Exchange Method for S1195V601001100410061015
the Investigation of Surface Inhomogeneity of B017/"055
Oxide Catalysts by Decomposition of Isopropyl
Alcohol. II. kluminum Oxide and Zinc Oxide
inhomogeneity of the active surface of the catalyst. There are 7 figures
and 6 Soviet references.
ASSOCIATION: Institut fizicheskoy khimii AN SSSR (Institute of Physical
Chemistry of the AS USSR)
SUBMITTED: March 23, 1960
Card 3/3
'iy
S ~71~

Mco/ //90) 20617
S/063J60/005/005/006/021
1114 )153 A051/AO29
AUTHORSt Krylov, O.Y., Candidate of Chemical Sciences, Frolov, V.M.
TITLEt Chemical Reactions on the Surface of Germanium, Silicon and Their
Electronic Analogues
PERIODICALs Zhurnal Voesoyuznogo Khimicheskogo Obshchestva im. D.I. Mende-
leyeva, 1960, No. 5, Vol. 5, Pp. 535-543
TEXT: Although the chemical reactions, which take place on the surface of
semiconductors, are of great practical significance, these surface proper-
ties have not been investigatedas well as those of the bulk. The following
processes are included in chemical reactions taking lace on the surface of
a solid body: 1) chemical adsorption (chemosorption~o 2 ) catalysis, 3)
formations of new phases. The present article is dedicated to the nalysis
of chemooorption, formation of new phases connected with the aspects of
chemosorption, and to a lesser degree to the catalytic reactions. A discus-
9ion is given on the electronic processes in chemosorption on semiconductors.
Card 1"8

20617
3/063J60/005/005/006/021
k051/kO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
It is said that Soviet works (Ref.6-9) have been published on this subject.
The main aspects in this connection are listeds 1) A free electron (or free
electron "hole") of the semiconductor lattice isIthe center of chemosorp-
tion. 2) Adsorption atoms and molecules are regarded as admixtures, deatrcv-
ing the strictly periodic structure of the lattice. 3) The adsorption abil-
ity and the catalytic activity of the semiconductor surface is determined
by the mutual distribution of the local level of the adsorption particle and
by the Fermi level (level of chemical potential) on the surface. 4) The po-
sition of the Fermi level on the semiconductor surface F_ depends on the po-
sition of the Fermi level in the volume E , and on the bend of the zones at
the surface, i.e.9 the difference of potbaliale between the surface and vol-
ume ~Ae_ viz., E - F_o + dF_. 5) The position of the volume Fermi level
(e_0) at low temperatures is determined by admixtures introduced into the
semiconductor. 6) The bend of the zones on the semiconductor surface (AF-)
is determined by its charging during adsorption and also by the non-adsorp-
Card 2/18
V.

?047
S/063/60/005/005/006/021
A051/iO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
tion surface states (Umm levels, surface defects). Several conclusions are
drawn from these aepectev which were confIrmed experimentallyt The depend-
ence of the adsorption and catalytic ability on the olectroconduetivity 07
and the work of the electron escape (f of the semiconductor,and the reverse
phenomenon: a change in a and P in the adsorption process and that of cat-
alysis; the effect of admixtures introduced into the lattice of the semi-
conductor, ioes; so-called "modification" on the adsorption and catalysis,
the opposite effect of the donor and acceptor admixtures, the appearance of
kinetic anomalies in the adsorption and catalysis, etc. The authors refer
-to the question of the connection between the surface properties of semi-
conductors and the electronic structure of the atoms which constitute the
11 urface, stating that this aspect has been only slightly investigated. Com-
ments are made of Dowden's theory (Ref,14) on this subject and that of
Goryunova (Ref. 13). It is stated that moot authors, with regard to the pro-
cesses of chemooorption and catalysis, classify semiconductors according to
their ability to capture some admixtures (Bemiconductors of the n- Iand p-
Card 3/18

20617
S/063/60/005/005/006/021
A051/AO29
Chemical React;ons on the Surface of Germanium, Silicon and Their Electronic
Analogues
type). Others consider the anomalous behavior with regard to the adsorption
and catalysis of semiconductors with transition metals in their composition.
It in pointed out that if the limiting stage of the surface chemical reac-
tion is the interaction of the adsorption molecule and the free electron of
the semiconductor, semiconductors of the n-type will speed up this reaction
primarily, and then all the factors, which increase the concentration of the
free electrons in the semiconductor, will increase the rate of reaction
(Ref.15). The conclusion is drawn from data derived in Ref.15 that elec-
trons of the lattice participate in the limiting stage of the reaction.
Hauffe (Ref.16) thinks that this stage may be the desorption of hydrogeni
H2(gae) -=mt2H+ + 2e )
ads. fast
D2(gas) 2D+
ads.+ 2e
H+ + D + + 2e HD(gas) slow.
ads. ads.
Card 4/18

20617
S/063/60/005/005/006/021
A051/AO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
The interest expressed by workers in recent years in the processes taking
place on the surface of elementary semiconductors not containing d-electrons
is pointed out (Ref-17). 1t is further stressed that more research has been
carried out on the subject of germaniump since it Is widely used in semicon-
ductor electrical appliances. A brief historical review of the development
of scientific interest in ohemooorption on germanium is given mentioning the
early works of 1930 (Ref.18) on the reaction of jermanium nitride formation,
also Ref,19 on the decomposition of german (GeH4 with the formation of dis-
persed germanium. Chemists showed interest in clarifying the interconnec-
tion between the chemical surface properties of the semiconductor with its
electronic, volume and surface properties. Since Go is covered with an oxide
film in air, it is pointed out that prior to a chemosorption investigation
a thorough purification of the Ge surface must be initially undertaken. Sur-
face cleaning is based on combining the ionic bombardment with subsequent
heating in a vacuum of 10-10 mm Eg. Other methods are% crushing single
crystals in a vacuum (Ref.21), reduction with hydrogen (Ref.22021), produc-
Card 5/18

20617
S/063J60/005/005/006/021
A051/AO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
tion of Ge films by evaporation in a vacuum (Ref.23)t cathode atomizing
(Ref.24) and decomposition (Ref.25) of GGH4. The compact single crystal
samples are considered to be the most appropriate for measuring electrical
properties, but difficulties arise due to the small surfaces. Ref.26 is one
of the first works on the investigation of the changes of the electrical pro-
perties as a result of contact of the sample with some gas at various pres-
eures over a certain period of time. It was established that the contact
potential of the surface can change reversibly between two extreme values
differing by about 0.5 v with a change in the gas medium. Experimental re-
sults proved the existence of a layer of a space charge on the semiconductor
surface determined by the surfaces states. The experimental results showed
that even the most thorough purification of the surface by available methods
does not lead to the disappearance of surface states. According to Handler
(Ref.27) the existence of surface states is determined by unsaturated bonds
of the surface atoms of Ge. Fig.2 shows the surface distribution of the Ge
Card 6/18

20617
3/063/60/005/005/006/021
A051/AO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
atoms for a crystallographic plane (III). The surface Ge atom becomes in
the electrical respect similar to the atom with 5 electrons in the outer
shell. The surface Go atoms fulfill the role of acceptor levels. Any diB-
crepancies in the results of the evaluation of the density of the surface
states for the processed Ge surface by different methods is explained by the
different densities of the unsaturated chemical bonds of the surface. An
investigation of the electrical properties of the Ge surface, processed with
a CP-4, (SR-4) scouring agent, showed the presence of a more complex struc-
ture of the surface states as compared to pure surfaces (Ref.30). Several
works were published on the acceptor nature of the first layer of adsorbed
oxygen (Ref.27,32,33)- Ref.33 a towed'that the contact of a pure Ge surface V~
with oxygen at a pressure of 10- mm Bg causes an increase in the work per-
formed by the escaping electron by 0.2 ev, whereby the equilibrium value of
the work is reachedmithin a few minutes. A study of the adsorption on
single crystalline samples proved the electron-graphical methods using slow
Card 7/18
4T

20617
3/063/60/005/005/006/021
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
electrons to be very promising (Ref.20). The authors of this work obtained
a relationship for the connection of the intensity of the beam with a coat-
ings I/Io . (1 - 0)2 (2), where I and Io are the intensities of the beam
for the partially covered and pure surfaces, respectively, 15 is the specif-
ic filling. If the kinetics of the adsorption is described by the expres-
sioni E) a 1 - e- C(Spt (3), where OL is the number of impacts of the gas
molecules on the surface per second at 1 mm Hg relative to one surface atom
of Ge, S the probability of adsorption in the impact of the gas molecule
against the pure surface, p the pressure and t the time. Combining this ex-
pression with the previous one, the authors could trace the kinetic adsorp-
tion according to the change in the intensity of the electronic beam with
time. These data correspond to the postulation of the constant activation
energy and to the rate of adsorption being proportional to the products of
the adhesion coefficient and part of the uncovered surface. Further refer-
ence is made to the work of Green (Ref.28), where equation 3 is used for the
description of the chemosorption kinetics of oxygen on germanium. A mano-
Card 8/ 18

20617
S/06 60/005/005/006/021
A051YA029
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
metric study was made of the chemo aorption kinetics of oxygen 0.1. Gowder
obtained by crushing in a high vacuum (Ref.21). Green's publicati:np(Ref. 28)
aseumea that the slow adsorption of oxygen described by the Roginakiy-Zell-
dovich equation: dN/dt a ae-bN (6 ), where N is the amount of oxygen ad-
sorbed at the time moment t, a and b are constants for the given temperature
and pressure,begine with the filling. It is stated that on the basis of the
kinetics of the slow adsorption of oxygen by Ge, it is difficult to form a
conclusion of the exact mechanism of this process, since various types of
mechanisms of interaction between a solid body and a gas may lead to the law
of logarithma. In studying the kinetics of the chemosorption of oxygen on
single crystal plates of Go by the weight method data were obtained which
coincided with Green's results (Ref-35). It was found that the drop in the
adsorption heat of the oxygen with filling according to Green was determined
byrepulsion forces between the adsorbed atoms. Other investigations under-
taken are listed as followai The adsorption of 112, H29 CO and C02, at -196,
~78 and 250C on single crystal Go rode by the spark method; the igh tem-
Card 9/ 18

3/063J60/005/005/006/021
A051/AO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
perature oxydation of Geq the chemooorption of hydrogen on Ge at high tempe-
ratures; the chemosorption of ammonia at 2780C on a Ge filml the adsorption
of H21 CO and 02 on Ge powderal the adsorption of a number of gases in the
crushing of single crystal Ge of the n-t pe results of the latter are given
in Table I (Refs.38,39,40,41,42,43,22,4T In all cases where adsor.ption
was observed, it took place ui kly before filling close to the monolayer.
The cause of gas adsorption Zexcept of pyridine and dioxane) is assumed to
be the electrostatic interaction between the dipoles of the molecules of the
adsorbate and the Go surface. The authors exclude the possibility of val-
ency bond formation in the adsorption of the investigated gases on Ge, since
the latter calls for the dissociation of the gas molecules which invariably
leads to ()< 1. An analysis is given of the chemosorption on silicon and
other electronic analogues of Ge. An investigation was made of the 02 chem-
osorption on thread-like single crystal samples of silicon by the spark
method (Ref. 46,-46). Recently in semiconductor electronics semiconductors
Card 10/18
N,

20617
3/063j60/005/005/006/021
A051/AO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
have been applied in addition to Go and Si, which also did not contain d-
electrons and were formed by elements equidistant from the fourth groupi
AIIIBV, AIIBVI. The processes of gas etching of this type of semiconductor
were Investigated (Ref-52). Ainvov (Ref-54) studied the electrical proper-
ties of the surface of the A B compounds. By measuring the effect of the
field in samples of single crystals AlSb, InSb and GaSb of the n-type, it
was shown that inversion layers are formed on the surface of these somioon-
ductors connected with the presence of surface acceptors (Fig.1). Certain
facts, such as the high value of the field effect on the AlSb in a vacuum as
compared to air, indicate a high influence of the adsorption on the elec-
trical properties of semiconductors of this type. No definite answer has as
yet been obtained on the difference in the chemosorption properties of n-
and p-semiconductors. It was shown (Ref-55,56) that additions of 11 0 and
Ga,203 to ZnO hardly affect the rate and energy of activation of the 12 chem-
osorption. Similar results were obtained for the catalytic activity of the
latter in the dehydration of 04118 Reference is also made to the works of
Card 11/18
N

W617
S/063J60/005/005/006/021
A051/AO29
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
Chizhikova (Ref- 57)9 Kutseva (Ref-58), on the study of the chemosorption of
CO and 02 on ZnO and NiO. Several examples are listed when the limiting
11 tage of the ohomosorption in catalysis in not the electronic interaction of
the adsorbed molecule with the semiconductor. Some authors assume that the
limiting stage is the movement of the active centers - structural defects -
from the volume to the ZnO surface. Finally, the author discusses the oat-
alytio reactions of the Ge surface and that of its an&logues. The catalyt-
ic properties of Go are mentioned quoting Refs.25, 59. Conclusions were
formed that the rate of reaction of the auto-catalytic decomposition of GeH 4
on a Ge film is controlled either by the dissociation of adsorbed radicals
of GeHx (x w 2 or 3) or by the desorption of oxygen when the surface is com-
pletely covered by the GeRx radicals and hydrogen. The kinetics of the re-
action H2 - D2 exchange on Go powders obtained by crushing of single crys-
tals in air with subsequent reduction by hydrogen were studied (Ref.60,61).
The ortho-para conversion of hydrogen and H2 D2 exchange on Go films pro-
duced by the cathode atomization in an interv;l of 77 1750C was investi-
Card 121"
0--

20617
3/06 60/005/005/006/021
A051YA029
Chemical Reactions on the Surface of Germanium, Silicon and Their Electronic
Analogues
gated (Ref.24)- A comparison of the rates of these two reactions led the
authors to the conclusion that the first one is of a magnetic or chemical
nature. The authors of this article and Roginskiy investigated the oatalyt-
ic properties of Ge on an example of dehydration of alcohols, cyolohexane,
decomposition of hydrazine reactions on powders and films. The results
showed that Go is an active catalyst in the respective reactions. A study
was also made of the kinetics of the catalytic reactions on n- and p- Ge
with various admixture contents (Sb or Ga). Fig-3 shows the relationship of
the apparent activation energy of dehydration of C2H OH to the concentration
of the main charge carriers. From Refs.65, 66 regaraing the hydration reac-
tion of ethylene and formic acid decomposition, it was also found that the
hole samples were more active in the catalytic sense and were characterized
by a lower activation enargy than 'the electronic -ones. A study was made of
the decomposition of HCOOR on AM and InSb. The hole sample had a lower
activation energy than the electronic ones. Fig-4 shows the relationship of
the catalytic activity at 2000C relative to a unit of surface for the decom-
Card 13/18

Z-11- F
S106 60/005/005/006/021
A051YA029
Chemical Reactionson the Surface of Germanium, Silicon and Their Electronic
Analogues
position of C H 09 to the width of the forbidden zone. Data obtained from
J17
chemical reao one on the surface of Ge and its electronic analogues point
to the faulty deductions presented in Refs,14, 16, maintaining the all-im-
portant role of transition elements in chemosorption and catalysis. There
are 3 tables, 2 diagrams, 2 figures and 73 references; 24 are Soviet, 42 are
English, 7 are German.
Card 14/18

Ir. M 0 68617
5~~
AUTHOR: Xryloy, O.V. S/020/60/130/05/030/061
B004/BO14
TITLE: A Case of Homogeneous Continuation of a Heterogeneous
Catalytic Reaotionq
PERIODICAL: DoklaAv Akad*mii nauk SSSRI 1960, Vol 130, Nr 5, pp 1063-1066
(USSRT
ABSTRACT: In reference 1 the author had studied the decomposition of
hydrazine on metallic, semiconductor, saltlike, acid, and
'basic catalysts. N2H4 + L--+NH2-L + ("Yadaorb (L- free radical
on the catalyst surface, NH.-L - solid, bielectronic bond on
the catalyst surface) was assumed to be the primary reaction
on the catalyst surface on the basis of thermochemical caloula-
tions carried out in analogy to the calculation of R.N. Semenov
(Ref 2) and V.V. Voyevodskiy (Ref 3). Next, chain and radical
reactions follow on the catalyst surface the scheme of which
ie given. In order togive a direct proof of the chain reaction,
the author studied the problem as to whether the reaction passes
from the catalyst surface into the volume of the reaction vessel
Card 1/3 at temperatures at which the radicals NHi, y3, and H* are no

66617
1 Case of Homogeneous Continuation of a
Heterogeneous Catalytic Reaction
Card 2/3
3/020/60/130/05/030/061
B000014
longer bound to the surface by adsorptive forces. Tno inv6sti-
gation was carried out by separate calorimetration according
to X.L. Bogoyavlenekaya and A.A. lovallakiy (Ref 5) In a
molybdonum-glass apparatus designed by PoYu. Butyngin and
L.Ya. Margolis (Ref 6). Iron, ammonia catalyst of the type
KATZ-55 (Fe promoted with alkali), ZnO, 3Geks.G 2Se 3P CaO, and
a cracking aluminosilioate catalyst served as catalysts. A
t;mperature rise in the volume was found for the Fe catalyst
( ig 1) and 30els.Ga2go3 (Fig 4), which proved the course of
reaction in the volume. This effect was distinctly marked in
the case of Fe, whereas in the case of the semiconductor and
ZnO it could be observed only at high temperatures. The thermo-
couple located in the reaction space showed no temperature
rise for KATZ-55 (Fig 2), CaO, and the aluminosilicate catalyst
(Fig 3), so that the reaction did not pass over into the
volume when using these catalysts. The author thanks S.Z.
-Roginskiy, Corresponding Member of the ASUSSR, for his help-
f'u1__ad_v1_ce, and X.Ya. Kushneroy for his assistance In
experiments. There are 4 figures and 6 references, 5 of which

6~1617
A Case of Homogeneous Continuation of a S/020/60/130/05/030/061
Heterogeneous Catalytic Reaction BO04/BO14
are Soviet.
ASSOCIATION: Institut fizicheskoy khimii Akademii nauk SSSR (Inf3titute of
Physioal Chemistry of the Academy of Sciences,_USSR)
PRESENTED: October 21, 1959, by P.A. Rebinder, Academician
SUBMITTED: October 8p 1959
Card 3/3

KRYLOV, O.V., YANOVSKIYj M.L(DECEASED)
"Utersuchun g akivierter Oberflachen einger Katalysatoren mit Hilfe von Isotpen-
methoden."
Report presented at the 2nd Conf. on Stable Isotopes
Eaot German Academy of Sciences, Inst. of Appl6ed Physical Material
Leipzig, GIB 30 Oct 4 Nov 1961

KMLOVI O.V.
Possible causes of the nonhomogeneity of acid and basic catalyot4l--
dielectrics, UnA kat. 2 no.5:674,-678 S-0 161. (MIRA 14:10)
1, Institut khimichookoy fiziki AN MR.
(Catalpts)

aU!
N
VN
i
,
..

Ik-
KRYIOGVP O.S.; SINUK, lu.Ya.
Now catalysts for the polymerization of ethylene oxide, Vyookom,,
aced. 3 no*6:898-9W To 161* (MERL 14:6) 1
I* Institut fizichesko khImil AN WSR.
(Ethylene oxideT (Polyurisation) (Catalysts)

115o
AUTHORSt
TITLEt
PERIODICALt
05, 12-)',.
Krjlov# 0. V. and Fokinal Ye. A.
Catalytic properties of new oomiconductura with the structure
of zinoblende
Zhuimal fizioheekoy khimii, v. 55, no. 3, 1961, 651-659
3/076j6l/O35/003/019/023
B121/B2o6
TEXTs The decomposition of IDopropyl alcohol and hydrazine in tho adsorption
laye'r of the catalysts GaAs, Ga2Se 3, GaAs,Ga 2S63 , 3GaAs-Ga2Se,,Ga2Te3, and
CuBr was studied. These aompounds of the types A IIIBV and A IIIBVI were
2 3
prepared by N. A. Goryunova and placed at the authors' disposal. According
to X. A. Goryunova, V. S. Grigor'yeva et al- Oef- 131 Zh. tekhn. fiziki,
25, 1675, 1955), compounds of the AIIIBVI type form solid solutions with
III V 2 3
compounds of the A B type. The kinetic curves of the decomposition of
ioopropyl alcohol and hydrazine on these catalysts were recorded. From their
course it may 'be seen that the decomposition of isopropyl alcohol at
130-2700C mainly proceeds in the form of dehydrogenation. The main decom-
Card 114

S/076J61/035/003/019/023
Catnlytic properties B121/-B206
position pro(lu(;ta of hydrazine (90-25000 are ammonia and nitrogen. 'The
cattilyst Gnki i!j not poinonod during the decomp8sition of isopropyl alcohol.
The activation energy at temperatures below 220 C In a15-15 kcal/rIole, and
at temperaturtifi above 22500, ft20-25 kcal/mole. The activation energy of the
decumpoiltion of N If on GaAs at 100-2001C Is approximately 16 .5 kcal/mole.
4
Beuidi?:~ dehydrog-eriation, othor reactiona occur on Ga,)Se , The a:tivation
I ~ 3
criergy of dehydrogenation amounts here to 14-19-5 kcal/mole. At 125-200'Co
the decomposition of hydrazine on Ga 2So3 proceeds at a satisfactory rate.
The decomposition Of 13opropyl alcohol on Ga 2To 3 proceeds Plowly at low
tem-pert-tture.9, and 100~ dehydgogenation sets in at elevated, temperatures. A
transition point lies at 145 C. At temperaturea below 145 C, the activation
energy of the decompos~tlon of isopropyl alcohol is kcal/mole, and at
temperatures libove 145 Ct it is 11-19 kual/mole. The decomposition of
hydrazine on Go 2 To3taken place at temperatures of 100-200 0C. The ofitalytic
activity of the compounds Gaka-Ga.2 So3 und 3GnAo-Ga 2Be3 woo only studitad from
the hydrazine depomponition, and it was establiubed that the rate of reaction
Card 2/4

3/076/61/035/00V019/023
Catalytic properties ... B121/B206
is slightly higher than on the catalysts GaAs and Ga2se 3' On CuBrt leoproWl
alcohol decomposes at 4100-270 OC at a consig erable rate. At 2000C,a 61~
dehydrogenation takes place, and up to 270 C this proportion decreases to
36~. The activation energy of the reaotionovarien from 26 to 31 koal/mole.
Hydrazine on CuBr starts decomposing at 250 C, accompanied by side reactions
and simultaneous chemical change of the catalyst under the formation of
metallic copper. It was further established that in the series Ge, GeAs,
ZnSe, CuDr and during the conversion of ZnTe to ZnSe and ZnS, and of Ga2Te 3
to Ga2se 3' which groups of compounds show identical crystalline structure
and similar lattice parameters$ a decrease of the catalytic action sets in
with simultaneous increase of the activation energy of the catalytic reac-
tion, with an Increase of the width of' 'the forbidden band 0. e., with in-
creasing ionic character of the bond). Semiconductors with bonds of highly
ionic character have therefore poor catalytic properties. The authors thank
S. Z. Roginnkiy, Corresponding Member AS USSR, for advice. V. M. Frolov and
Yu. N. Rufov are mentioned in connection with the study of the catalytic
properties of pure germanium. There are 8 figures, 2 tables, and 19 refer-
encest 12 Soviet-bloc and 7 non-Boviet-bloc. The four moot recent refer-
Card 3/4
7.~
M..

Catalytic propartiv:) ...
8/07 61/035/005/019/023
B121YB206
encea to English-language publications read as followat G. -M. Schwab#
Semiconductoi-i surface phleics, Philadelphia, p. 283, 19571 G. -M. Schwab,
Advanceu in Catalynis, N. Y., 9, 229, 19571 G- -M. Schwab, G. Greger, S.
Krawczynaki, J. Penzkofer, Z. phys. Chem. - F.), 15, 363, 1958; W. E.
1 ~H
Garner, Advances in Catalysis, N. Y 9, 9, 1957.
ASSOCIATION: Inatitut fizioheskoy khimii Akademiya nauk BSSR (Inatitute of
Physical Chemistry of the Academy of Scienceo USSR)
PRESENTEDt May 19, 1959
SUBMITTEDt July 15, 1959
Card 4/4

GAZIM, G.A.; KRYLOV, O.V.-. ROGIM.SKIY, S.Z.; SAMSONOV, G.V.; FOXINA, YF-.A.;
YANOVSKIY-,-W.I-. --
Dehydrorenation of cyclobexane on certain carbides, borides, and
sl3icides. WK. AN SSSIt 140 no.4:803-866 0 161. O-Ul%,~ 14:9)
1, Chlen-korrespondent AN 5551t (for Roginskiy).
(Cyclohexane) (Dehydrogenation) (02t2lyStS)

02/005/DDZ/o07
,/62/0
sol 5 tdO
and Sinjaws ,U of e
eril'atJ01% or
Iov 1 0 the 90110 66b-b9b tjov, It'SIA rth
1.962, - - A I
IVY to f or oeroa
'r alwa
the Po 'V6 cats of
0b t,
tad jd6s off 6c, e
f t ewil it" jy a I jeettget mdroll of rbOllat
'r -IT lie %%0r$ jfAV . And Ie C, t tort and CA Car-ZI
ejut I o%jd0s Ise dro.Xides
fri3a sevefrb f or tt%e 1hy ) 2: It 20~ it'
01% ru Ie a i'de a Ca ('A 21?0 it
'ry 0% 000111
,ILT 0%tdc blish 'Were C5501%, .1tca
ethl Ione sets mined r1co 8 4 CO and
Is to e Y. Is 01A) 2%
motS, Ir 1.0 Is 138 k ),Z9 f
'rhe mate and 'Be I ZM01K
149 Olt* Cr t C11 urpo,-
Cal Sir 1 1 i3as 31 erti, of 140 1650
135C03 Co k 010 Os ed k75- .410
ed
I . prop 'esti at rat gaip &tea
SrCI 00 jov C 6 e 1par
of
2 41cata IIt te were Z were 11 art to ted
,(Ola) etc* 11 5 &1 J~ e 0 It t or
14 2 j"ft. he t Z-O. U1.0
ertz
-Alum 7 GS to (0. AMP
is i1tca tors 'nos 1-ye tn an 0 t in 0
cat& led
tconduc otho sea Xide (5 ittolft.
gem rjeoirl. d then no 0 art
CO a 00 1A 0 etuyl-e
Iotg d Wtt1% St bY &
Co.'s t a v/
Was t%% 0 CA
froo
C'eird
Catalysts for the polymerization.*$ S/204/62/002/005/002/007
E075/E136
by breaking the pnrtition. The most active hydroxide was Be(OH)2
and BeD produced in the ampule by heating Be(OH)2 under vacuum.
At 90 0 C Beo and Be(0102 gave polymers having the molecular weight
of 100 000 - 175 000o the rate of polymerization ranging from 1-3
to 6.2 millilnoles/m2. hours. 1-19C03-~-'9(0102-1120, M&O formed from
Mg(OH);, SrCO5 and Cao formed from CaC03 also had high activity
at.90 C, giving polymers having the molecular weight of 25o 000,
350 000, 1 000 000, and 600 000 respectively, the rates of
polymerization being 5.7, 1.45, 6.1 and 2.6 millimoles/m2.hour
respectively. Certain salts and hydroxides of Fe and Al also have
high catalytic activity. In general the active compounds of
transition metals have electronic configuration do and do
'(Fe 3+ Th4+ Zr4+ Ti 4+ The acidic cata Ilysts (e.g. silica-
alumina) were not active. The molecular weight M 'of the
polymer increases an followas
C C
M a aV - 0 0 (7)
1
Card 2/3

Catalysts for the polymerization... B/204/62/002/005/002/007
E075/E136
whores V volume of ethylene oxide, mf ; a - constant;
co and c initial and final concentration of ethylene oxide
respectively; SO - catalyst surface occupied by the active
1 1,
centres at t = 0. For c 0 - C a constf R varies linearly with
0
SI. The apparent mean activation energies for the polymerization
on various samples of WOW?
.# BeO and BOO'COVM20 ranged
from 8-7 to 17 kcal. The reaction was most ptiabably not diffusion
controlled. The authors conclude that for the alkali-earth
hydroxides at 90 *C the proportion of active centres decreases with
the increasing atomic weight of the metal, but the activity of the
individual centres tends to increase with'the atomic weight.
At 20 #C the order of the activities ii reversed, since the energy
of activation increases with the atomic weight of the metal.
There are 3 figures and 6 tables.
ASSOCIATIONj Institut khimicheskoy fiziki AN SSSR
(Institute of Chemical Physics, AS USSR)
SUBMITTED: May 51 1962
Card-3/3

S/204/62/002/005/003/007
E075/E136
Aumovs: Krylovg O.V.* Kushnerev, M~Yn., ant] Fokina, Ye.A.
TITLE: Formation of active surface in the catalysts for
the polymerization of ethylene oxide
PERIUDICALs NeftekIiiinlyaq v.2, no-5, .1962, 697-7011
TEXT: In view of the low activity of technical Beo and ?Igoe
the authors studied the preparation of-the active oxide catalysts
by decomposing Be and ~,'g hydroxides and carbonates. The action of
cnta.lytic poisotis (IlLjo and C02) was &180 investigated. A MacHain
balance was u.-srd to follow the decomposition and the adsorption
kinetics of ethylene oxide (related to polymerization kinetics),
C02 and 1120- Adsorption of ethylene oxide occurs before
polymerization, the rate of admorption~ being proportional to log t
(t = time). Subsequent polymerization takes place at a constant
rate which depends on the number of active polymerization centres
on the catalyst surface# The catalytic activity grows with the
degree of decompgaition of the hydroxides. The most active j4gO
has 30-We of its surface covered by water. For Be(011)2 the most
active catalyst results after its complete dehydration.
Card 1/2

Formation of active 8urface in the ... 5/204/62/U02/005/003/007
E075/EI36
Freshly prepared MgO and Beo reduce their high activity on
exposure to air, whil8t t1iAir surface areas decrease by only
10-20%, This is explaiiied'by the preferential adsorption fit water
on the active centres, which lowers the adsorption and
polymerization of ethylene oxide. Initial adsorption ot' C02 leads
to the incroarju of* ethylene oxide adsorption, but decreases the
polymerizntion rate by a factor of 4-5. Further C02 adsorption
has no effect. it is inferred from the adsorption kinetics that
the active centres are ~jg2+ or Be2+ ions interacting with the
oxygen in ethylene oxide molecules.
There are 9 figures and I table.
ASSOCIATION; Iiistitut khimicheskoy fiziki AN SSSR
(Institute of Chemical Physics, AS USSR)
SUBMITTED: May 5, 1962
Card 2/2

KRYWVP O.V.
Data from the literature used for the selection of catalysts.
Kin.i kat. 3 no-0502-508 JI-Ag '62. (KLRA 15:8)
1. Institut khimiaheskoy fisiki AN SSSR.
(Catalysts)

KRYLOvt O.V.; SINYAK, Yu.Ye.
Catnlysts for ethylene oxide polymerization. Haftekhimila 2 no.5j
68M96 3-0 162. (MIRA 16tA)
1. Institut khinicheakoy fisiki AN SSSR.
(Ethylene oxide)' (Polymerization)
(Catalysts)
A,

KRYLOVA.-O.V.; KUSHNEREV, M.1a.1 FOKINAO Ye.A.
Formation of the active awface of ethylene oxide polymerization
catalysts* Neftekbimila 2 no.5:697-704 S-0 162. WRA 16:1)
1. Inatitut khimichookoy fisiki'AN SSSR.
(Ethylene oxide) (Polymerization) (Catalysts)

m LOV p 0. v -HAW'VA~J- S A. -j FO KI NA, Ye,A.; TRETYAKOV, I.I.
IOUntersuchlng des Mechanisms der Adsorption und des Isotopensustauschas Von M2 an
MgO und Mg(OH)2o*
Third Working conference on Stable Isotopes, 28 October to 2 Novembor 1963, Leipzig,
777---

-PV n Ira. M.0
lswvr, Aj. T I- off -~L-Ya.;-FOKINA,-Ye.-A,
"Elementary mechanism of heterogeneous catalytic polymerization of ethylene
oxide."
report submitted to 3rd Intl Cong on Catalysis, Amsterdam, 20-25 jul 64.

L1 F
IACWZMCK NR:-'AM3W4---- 8/01"/&j005/W2/02%jM2
AUMORi Kry*lov,, 0* Vo; Foldna,, Yeo A*
TITM: Relationship between tb4 catelytio activity of some andoonductors Aad the
forbidden zone width
SWIM Kinotika i kataUz,, To 5p no., 2j, 1964j, 284-M
TOPIC TAGSt acalconductor catalynta,, forbidden zone, forbidden zone vidthp
Icata.1yoin, gadolinita acmiconductor, GarmAnium acmiconductorj Indim acaltonductor,,1
Izinc semiconductor
copper acmiconductor
ATIC
MIACII'; Having romid car-Uar tbar, the entalyUc activity of the inoclectroni
C.
("t-'rien or gemwium flemiconflue Lora (Go.. GaAa, ZnSe, CuDr) in the decompocition of
leopropyl alcohol and Wrazin#3 decreauca f rm Cc to GuDr, tho autLors carried
out a st',Ay to correlate the catr4tic activity witli the width of the forbidden
zone. They atudied decomponition of inopropyl alcohol iu tho adijorptioa laYer'(La
atearly-atato comlitionf3) At low presourio on the ourraco of Qa following acmicon-
Ii duatorti: Map I(P., GoAnp GaAn*GvL2Se-A GaAs43Ga2Sa . C;aSbv p GaSoj GaTo., Iw1s; InSbj
.L
%T03 'n tho teq~aratura interval of 50-320C* aver moot of thoue comiconductorsp
-71
~Cczrj
7~7 ~T,

[ACCESSICII ZIR: AP4035152
alcohol io dchydroGo.-aated* The above data vere compared urith those obtained by
r P
the authors when decompocing alcohol over GdS, Cul3r, ja , op G T Gel znQj ZnSR
CCL wije~,
..!ZnSe and ZnToo It in ahown that catalytic activity d ea b! increasing
1! 1,1vidth of the forbidden zone. With that., the decline of the rate conatant may be
caused by the decline of ko rather than the increase in Be This fact may be ex-
I plained by catalysis near the transition point from the impurity band to the coa-
ductivity band. Xt Is shown in vhich cases the compensation effect is observed:
~aymbatic change of E and log k
00 $Gratitude is expressed to S. Z, Roginakiy and
!IV. Mo Froloy for Yauable discuosious." Or1g6 art* hast 10 figurea., formulas,$
111 table.
ASSOW=CK; Iuatitut khimidwakoy MAI, AN WSR (Institute of Chemical Pbyslas
(AN SSSR)
iSM11MM 25jul62 DATE ACQ: Maya ENCL: 00
SUB CME: 08# 00 NO Mw NVI 020 01MM: 002
Card ,2/;__

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KRYLOV, O.V.; MARKOVA, Z.A.; TRETIYAKOV, I.I.; FOKINA, Ye.A.
Mechanism of adsorption and Isotope exchange Of C02 on 1-4g0
and Mg(011) 2* Kin. I kat. 6 no.1:128-136 Ja-F 165. (MIPA 18:6)
1. Institut khimicheskoy fiziki AN SSSR.

7.1 , A
Mochwilom :~f tie t~si 17 I~i c j~,:.3yrrev17-"ticn ~,f cthylene cxide.
Vysukim. sood. 7 no.6!,c,84-,~491 Je 165. (MIRA 18:9)
1. Institut khim!,-beBVay f lztKL AN SSSR.

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77-
i:6

BA.RTAN, 0.0.1 KRYLCV# O.V'.
Now hatsrogensous catalysts for polymerizaLlon of athylvaimime
Isy. A$ S.SSR, Sor. khlno no.11s2053-20g 165.
(MIRA 18;12)
I* Inatitut khimicb6skoy fiziki AN SSSR.

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IM
LIVSHITS, V.S.; Kfpt~qy,_W.; KLABUNOVSKIY, Ye.l.
Heterogeneous catalytic polymerization of the optical isomers of
propylene oxide. Dokl. AN SSSR 161 no.3:633-636 Mr 165.
(YT
,.RA 18:4)
1. Inatitut khImichookoy fizlki All SSSR. Submitted Soptember 5,
1964.
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WILOV, 0. V.
Mechanism of dohydration of alcohols. Zhur.fiz.khim. 39
no.lls2656-2663 11 165* Y, IRA 18.-12)
1. Inatitut khimicbeskoy fiziki )VI SS.SR.