SCIENTIFIC ABSTRACT BORESKOV, G. K. - BORESKOV, G. K.
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B'.ORBSKOV,G.K., doktor'khimichookikh nauk
Effect of heat transfer and various substances on the ratp of
contact reactions. Khim.prom.no.9:257-263 5147. (MLRA 8:12)
(Chemical reaction, Rate of)
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Kov
G K.
"Influence CrIthe Cmdlti-& of Prepi3~atlm-on-the
Structure of Silica-Gel," G. 1. Boreskov, M. S. Boris-
*ftpld.-M. Dihigit,tY."A. Ditalko,"T. P. Drsvl4g,IA.
V. rDieliij, 10. A. "LikMobsia, "Webow auto U Imeal U.
v.'700~9sov- MW* Chis Ust Imml L. Ya. Mupov,,
Moscow, 14 pp
vzhur Iriz! Mde Vol Imn, -No 5
SOMPUM of ww1bas ty~oOW silica Sol (vitreous,
obal1q..'etc.) obtained-by differaut methods and their
absorbent propertloo'coupared. Results are tabulate&
end shown graphically. Submitted 14 A114,1947.
P.A 60-T24
Oct
Silica Gels
Temperature
*Iffect of the Ignition Temperature on the StructuM
of SiLica. Gels," G. K. Boreskor, X. S. Borisova,
&V. A.'bzielko, A. V. Kiselev, 0. A. Likhacheva, T.
&N. Morokhorets, Moscow State U imeni.N.7. L=oiiosor.
97 it is expedient; to diminish the tem-
perature in the last gas K layers to under 4400.
Card 2/2 -148-
tic it olmotras. 1. S"Ift
'kAscift, Italy Y
latlontrn -latin Rtahst5.1 V. S. 02 f,
s.--CF-Fw' --- f-M =..X o~A.
spetlfl~ rAt-LI),tic activlt~ Ve Pt 'Vitt, f4DH, old serem,
'POngy allti Pbbl'-ized SIO., gel in the SOioxidatiDns, cmved
that the sp,--ific activity of all the cajajy-~ts Wa3 al---
yj the
ante -~When rcjtrXC4 ts) a -111it of Pt surface. Anj Was affected
Only Sligbtly by 1hC:il1e of the P1 ru-mal' Qr ttC temp. of the
activity o!
platinlzed'sio~~gA at.ioileps 'at 0,031-0.5 wt. % is pro-
p"rilo'"I to tlw UlAt 1,. f Pi in tilt tat:ab..~t. The site of
Pt cr, ma-15 I)n tilt S102 Z--l 9, -here
I . JoTe independent of tim Pt
.021-11L and &Peuds lanly on tht pam5fly III Ole st) Ntrur-
The
;1[tivation raergy of the SO~osldalbn reaction oa imissive
I't md plnlink~J SzO. get is abaut 23, kcal-/mol.
stcrabcIg
TM
s
BORESKOV,3. K. (Prof.)
"Some Questions of Catalyst Selection."
report presented at Scientific Conference at the Inst. for Physical Chemaistry
imeni L. Ya. Karpcv, Acad. Sci. USSR, Nov 1957.
AVDLYEIIKO, 1-1. A., Bffli~SKOV) G. K., SLIN'KQ, M. G.
"Catalytic Activity of Metals in ReLation to the Homomolecular Isotopic Exchange
of Hyarogen,"
Probi,eW Kirwe-tics ArA C&tmklysia, v. 9, 1150topw in (~aUlyri'k,
A rs Si~ 9 5-1 404-1-
W.wt af the p5p-ro In tbla colle~,t3ov vvrli~ preaentt-tl %t tb~~
lzatcjrl~%, in VUSCh too), ra;rsve in W*00w, 1.1- Apr
BORESKOV, G.K., doktor khim.nnuk, prof.; SLOIKO, M.G., knnd.khim.nauk.
Applying the fluidized bed method to heterogeneous cRtalysis
procosses. J[him.prom. no.6:321-330 S 457. (MIRA 11:1)
1.Fiziko-khimicheskiy institut imeni L.YR. KArpova.
(Catalyeis) (Fluidization) ~
, ko t-' 6-' k-
f
_,r
AVDBYBNKO, H&Ae; BORWXOV, G.K.; SLINIKO, M.G.
Catalytic activity of metals in respect to homomolecular isotopia
excharge of hydrogen. Probl. kin. i kat. 9:61-75 157. (MIRA 110)
(Catalysis) (Radioactive tracers)
BORNSKOV, G.K. - I .
- --------
Dismission. Probl. kin. i kat. 9:92 '57. (MIRA 11:3)
(Cataly,sts)
7
~
xpbdflc-aUjjCj%-kt ty d metab. fl. K~
zf-b- of D,~ tl~r P."-d th,- NH~
kl, xm~ Nt~ isTcafipatc,!, llt
y -,va,; e-~Zzm!--ea ~n tzr---- j :1-
ard~r end chm, vDmp;i, ol Lhe mtilys', t-,:,acludr"
1-~ctn &,at &,m. the -,fi,ity L7-, the
m-strars iazl A-ts, i"I'l tl,-- a!. Lo- mzt~~Es a
-
~
l
V~
M
f
!
~m~
,c rril-ta
r
Gf-
,r !
S o
.
u
"talytif, -~uv -, 1, ~j -- t r-
mvt--
11 e~T N, wtich
Y b, nm~ energ F vl-~Ii:t-; f
mul-~cc. Tle
"
I~y
M
'*P*rl Presented at th. Ar-l )b.tivg or th& Oermn Cbdd
y 'a let1`216, 28 Octar - I S..vw&bsr 19
958
WIA"11, A. A. (AS tM,
rd
21~,'lo.."* Co"StrUCtlon of a Unified 7VAPM7 of Ct~yl. - Str-t-M and Inara
9~ ~e
x1co-Owaical hint. in Kkrmv, JL"c_)
or '--t 8"- wA catayt..-
!!AUNSIZYI. A. Ye. (Inat. of Iklologlcl " V
C.t,W 'Oftm)
Pyrld-mlensyss." 'd I Cal try. AIM.LMM, V
"arlml Q stiom of Blololeal Catalysts in the Litht of th. A~tl,jty of the
I- (IMt- ChWeal MYSICS, AS USM, Noec.)
'N~ Catalysts wA awacal Im-tion in aim Oxidstlon . Chsia p4actlon.,
a. Z.
and Kimtlcs of the Ndf.Ltf* Catalypt.-
WA YASWDW8 A. (Inst. Organic Cbealstry, As Ukrainian go)
or CatalAte Action of Awanowus to the hwtlm Of Carb.,Wl
VILUM, P. and IMM, A. ("I" I"t-, Emin" State Universit7)
'Phoueloctivele Ikatealas as the soft.. of Wr-Lift Ctalyt.,-
OMWL*~ 09to1eer 1938, owl.
AUTHORS: Kasatkina, L. A., Boreskov, G. K., Krylova, "Ll. L.,
Popovskiy, V. V. 153-56-1-3/29
TITLE: Investigation on the Mobility of Oxygen in Vanadium-Pentoxide
by Means of the Isotope-Exchange Method (Issledovaniye
podvizhnosti kisloroda pyatiokisi vanadiya metodom izotopnogo
obmena)
PERIODICAL: Izvestiya vyqshikh uchebnykh zavedeniy. Khimiya i khimiches-
kaya tekhnologiya, 1958, Nr 1,pp. 12 - 19 (USSR)
ABSTRACT: Vanadium pentoxide forms the active component of many oxi-
dizing catalysts (vanadium contact-masses with the production
of H2so 41 catalysts of the naphlialene-,'anthracene-oxidat4.on
and of other production). It was interesting to compare the
catalytical activity of V 205 and the readiness of the ex-
change of its oxygen against the molecular-oxygen and the
steam. A survey of the publications (References 1 to 4)
dealing with this problem is given. It is followed by an ex-
perimental part with the description of the methods. The
Card 113 following conclusions were drawn from the results obtained:
Investigation on the Mobility of Oxygen in Vanadium-Pentoxide by Means
-of the Isotope-Exchange Method 153---58-1-3/29
1)After an investigation of the isotopic exchange of the
vanadium pentoxide with oxygen (at 045og5oo,53o and 5500C)
and with steam (at 2oo,385 and 450 C), it was found that
the exchange with oxygen at all above-mentioned temperatures
is accelerated very rapidly. At 2ooO. an exchange against
steam does not take place.
2~It was proved that the exchange with steam (figures 7 to
9 takes place at lower temperatures and at greater ve-
locities than with molecular oxygen (figures 1 to 6).
3) An addition of potassium-sulfate increases the exchange-
ability of pentoxide both with oxygen and with steam.
4) The exchange between the vanadium-preparations and the
molecular oxygen is determined by the exchange on the sur-
face and takes place according to the first order. In the
.case of steam the velocity of surfacf-exchange is considerab-
ly higher; the oxygen diffusion does not follow the equali-
zation of the isotopic composition in the interior of the
crystal, so that the velotity of exchange decreases more
Card 2/3 rapidly with increasing degree of exchahge, than this would
Investigation on the Mobility of Oxygen in Vanadium-Pentoxide by Means
of the Isotope-Exchange Method 153-58-1-3/29
correspond to the equation of first order.There are 9
figures and 7 references, 6 of which are Soviet.
ASSOCIATION: Moskovskiy khimiko-tekhnologicheskiy institut imeni D. I.
Mendeleyeva, Kafedra tekhnologii razdeleniya i primeneniya
izotopov (Moscow Chemical Teohnological Institute imeni
D. 1. Menedeleyev" Professorial Chair for the Technology
of the Separation and Use of Isotopes)
SUBMITTED: October 22, 1957
Card 3/3
~ORESKOV, G.K.
Certain aspects of the theory of catalyst selection.
Probl.fiz.khim. no.1:101-110 '58. (MIRA 15;11)
1. Laboratoriya tekhnicheakogo kataliza Nauohno-issledovatellskogo
tiziko-khimicheakogo instituta im, Karpova.
(catalysts)
(Ghemioal;,"aotionp Rate of)
SOV/ 64-58-4-2/20
AUTHORS: Vlasenkoj V. M., Candidate of !Chemlical Sciences,
esk9x,__Q,_, Corresponding Member, Academy of ScienceBj USSR,
- - A ~_
Braude, G. Ye.
TITLE: The Catalytic Purification of the Nitrogen-Hydrogen Mixture
of CO (Rataliticheakaya ochist1ca azoto..vxli~odnoy smesi 0t CO)
PERIODICAL: Kimicheskaya promyshlennosti, 1958, Nr 49 pp. 2oo - 2o5 (USSR)
ABSTRACT: As the premnoe of oxygen and carbon monoxide in the gas mix-
ture in the ammonia synthesis acted as a catalyst poison,*
it has often been tried to investigate and remove it; the
present work mentions results of investigations on the prob-,
lem mentioned above in the case of low temperature with nickel
catalysts being used* From the data on the conditions of
aquilibrium of tho hydration of o&tbon monoxida may b@ adon
that the equilibrium concentration of CO increases highly
with the concentration of carbon oxide in the initial mixture
and that it decreases with an increase of pressure. The
equilibrium content of CO in the gas mixture increases with
Card 1/3 the temperature as well. When the purification process is
sov/64-58-4-2/2o
The Catalytic Purification of the Nitrogen-Hydrogen Mixture of CO
carrieqout at 300 atmospheres a good effect can also be ob-
tained at higher temperatures, while below 300 0. all experi-
ments showed that the hydration is irreversible. The investi-
gations of catalysts carried out show that nickel is the
most active of the noj~j2mcicus metals; a porous catalyst with
a highly developed inner surface was used. The schematic
representation of a high-pressure plant is enclosed from
which among other things it can be seen that a constancy of
the pressure was obtained by means of a regulator according
to 1. P. Sidorov (Ref 13). It was observed that the 0hydration
takes place with sufficient velocity already at loo , the
degree of transformation changin
og with the temperature and
the pressure. Starting from 125 the velocity of the increase
of the degree of transformation is slowed down which is ex-
plained by an external aiffusion on the catalyst; this is
represented by an equation where the coefficient of the mass
transfer as well as the pressure were fixed. In case
oxygen and carbon monoxide are present together in the syn-
thesis of ammonia in the gas mixture the completeness of the
gas purification is dependent on the hydration of carbon oxide*
Card 2/3 There are 6 figures, 6 tables, and 14 references, 7 of which
are Soviet.
SOV164-58-4-2120
The Catalytic Purification of the Nitrogen-Hydrogen Mixture of CO
ASSOCIATION: Gosudarstvannyy nauahno-issledovatellskiy i proyektnyy in-
stitut azotnoy promysh'.'Lennopti
(State Scientific Research and Desigh* Institute of Nitro-
gen Industry)
1. Hydrogen mixtures-4urification 2. Carbon monoxide-Chemical
reactions 3. Nickel catalysts--Applications
Carcl 3/3
-50)
AUTHORS: Vlasenko, V. M., Candidate of Chemical SOV/64-58-8-6/19
Sciences,'BDreak9vt G. K., CorrespondinG Member, Academy of
Sciences, USSR, Braud-e-,-'G-.--Ye.
TITLE: The Catalytic Purification of a llitro~~en-Hydrogen Mixture
From Carbon Dioxide (Katalitichoskaya ochistka azoto-vodorod-
noy smesi ot dvuokisi ugleroda)
PERIODICAL: Khimicheskaya promyshlennost', 1958, Nr 8,
PP 473 - 475 (USOR)
ABSTRACT: In the prodaction of ammonia the nitrogen-hydropen mixture
is carefully purified from substances containing oxyc-len prior
to the synthesis. The purification process can be simplified
'
by hydrogenating CO and CO simultaneously, which requires
sults of tests carried out
highly active catalysts, Th re
with a porous nickel catalyst are given, The properties of the
catalyst as viell as the investigation technique have already
been described (Ref 1). It is known that the hydrogenation
of CO in the gas purifying apparatus is practically irrevers:i-
ble (Ref 1). A diagram (Fig 2) shows the dependence on
Card 1/3 temperatura of the equilibrium concentration of CO 2 at varying
The Catalytic Purification of a flitrogron-Hydrogen I.Iixture SOV/64-50-8-6/19
From Carbon Dioxide
pressures and concentrations of the admixtures in the nitrogen-
hydrogen mixture. This shows that at temperatures below
3000 the formation of methane is just as irreversible as that
of CO. The process of purifying the nitrogen-hydrogen mixture
from CO2 was studied at 1, 10,and 300 atmospheres, while the
simultaneous hydrogenation of CO and C02 ras carried out
at 1 and 300 atmospheres. At atmospheric pressure the hydro-
genation of CO2 takes place at a temperature of 125 0, and
at 300 atmospheres at 800 (Table 1). The hydrogenation of
CO is accomplished more easily (Table 4). The hydrogenation
of CO2 takes place at 300 atm' a CO2 concentration of
0.02%, a linear velocity of the gas of up to 0.02 cm per
sec, and a temperature of more than 1250 in the area of ex-
ternal diffusion. For these conditions an equation (3) is
given by which the mass transfer coefficient can be calculated.
The degree of purification of the nitrogen-hydrogen mixture
is determined by the hydrogenation of the CO 2' There are
3 figures, 6 tables, and 2 references, 1 of which is Soviet.
Card 2/3
-The Catalytic Purification of a 11itro-en-Hydrogen Mixture SOV/64-58-8-6/119
From Carbon Dioxide
ASSOCIATION: Gosudarstvennyy nauchn-issledovatel'skiy i proyektnyy institiit
azotnoy promyshlennosti (State Scientific Research and
Planning Institute for the Nitrogen Indiistry)
Card 3/3
5 ( 4 )'
AUTHOR: Boreskov, G. K. SOV//76-32-12-13/32
TITLE: The Interaction Between Catnlyst and Reacting System (Vzai-
modeystviye katalizatora i reaktsionnoy sistemy)
PERIODIC4L: Zhurnal fizicheskoy khimii, 1958, Vol 32, fir 12,
pp 2739 - 2747 (USSR)
ABSTRACT: In the course of the reaction the catalyst may undergo
the following changes: 1) a transforiation of the active
component of the catalyst; 2) a change in the inner com-
position of the catalyst; and 3) a change in its surface
layer. The transformation of the catalytic component is
easily discernible and can be avoided by selecting appro-
priate catalysts. Changes within the catalyst body are
less obvions but always to be found. They can extend to
the entire volume but very often confine themselves to
the surface. In connection with the for-lation of monomo-
lecular liyers of oxy,5en on platinum, silver, and nickel
references 8, 9 and 10 are !-ientioned. The influence of the
composition of solids on catalytic properties is given
Card 112 by the fact that atoms of solids are connected i7ith each
The Interaction Between Catalyst and Reacting Systenn SOV/-6-32-12-13/32
other. If an emission or admiosion of electrons takes
place on the surface, this has an effect on the structure
of the entire solid. The stationary state of the cata-
lyst depends on the speed Qf partial reactions -.-,hich
cause a state of equilibrium. If the equilibrium is
reached slowly, the previous treatment of the catalyst
is decisive for its activity. References 11-14 and 20 are
mentioned in connection with the various catalytic
properties of zinc ox'de, nickel - I - oxide, and vanadium
pentoxide treated in different ways. If the equilibrium
is reached quickly, the activity is predoninantly de-
termined by the composition of the reaction mixture. This
means, in practice, that it is possible to re,,-,ulate the
properties of a catalyst by changing the reaction mixture.
There are 4 figures and 20 references, 11 of which are Soviet.
ASSOCIATION: Fiziko-khimicheakiy institiat im. L. Ya. Karpova, Moskva
(Physico-Chemical Institute ineni L. Ya. Karpov, Moscow)
SUBMITTED: December 13, 1957
Card 2/2
AUTHORS: Bbreskov.,, G, K., Kuchayevp Ve L. 20-11-1-2-31/6o
TITLE: The Catalytic Activity of germanium in Relation to the
Isotopic Exchange Reaction Between Hydrogen and Deuterium
(Kataliticheakaya aktivnost' germaniya. v otnoshenii
reaktaii izotopnogo obmena vodoroda s deyteriyem)
PERIODICAL: Do lady Akademii Nauk SSSR, 1958, Vol
119, Nr 2,
,
Pp) 302-304 (USSR)
ABSTRACT: The present paper compares the specific catalytic activity
of a germanium semiconductor element with the activity
of the transition metals having incompletely filled
d-zones' This comparison is here made with respect to the
reaction of isotopic exchange of hydrogen with deuterium.
The authors investigated the catalytic activity of
germanium by means of the static method with circulation.
The content of HD in the hydrogen-deuterium mixture was
determined by means of the method of thermal conductivity.
The reactiozatook vlace in~a reaction vessel of quartz
Card 1/4 within the temperature interval 3300 - 5500C. the equimolar,
The-Catalytic Activity of Germanium in Relation 20-119-2-31/60
to the Isotopic Exchange Reaction Between Hydrogen and Deuterium
mixture of hydrogeniwith deuterium having had a
pressure of 90 - 190 mnL torr. Mbnoorystalline germanium
with an electronic line of the resistance 6 Ohm.am
served as catalyst. The gases hydrogen and deuterium
used for reaction were produced electrolytically.
The formula used for the calculation of the specific
catalytic activity of germanium is given; it is valid
for random mechanisms of the exchange of hydrogen and
deuterium. A diagram shows the dependence of the catalytic
activity of the two investigated germanium samples on
the inverse temperature. The activation energy of the
reaotion'amounted to 17 kcal/9-mol. The specific-
catalytic activity of the2two germanium samples amounted
to 3300,3*10-10 9-mol/cm sec. The catalytic activity
of the samples determined'at 6500C was a little greater.
The reaction or&er-was investigated with one of the two
germanium samples at 4800c. The same degree of'transformation
Card 2/4 at various pressures shows that the reaction takes place
The Catalytic Activity of Germanium in Relation 20-119-2-31/6o
to the Isotopic Exchange Reaction Between Hydrogen and Deuterium
according to the first order. A table contains the
specific catalytic activities of germanium and of some
metals in relation to the reaction of the oxygen-deuterium
exchange at 3000C and at a pressure of the mixture of
40 torr. Inithe"experiments aiscussea.here the exchange
ta4es place according to the absorption-aesorption.:
mechanism whenithe surface of germanium is only little
filTled and when the absorption is the limiting stage of
reaction. Ira the transition to a stronger filling of the
germanium surface the activation energy of the reaction
must obviously increase and approach the desorption
energy of hydrogen (about 41 kcal/9-mol). The catalytic
activity of the metals of period IV increases with
growing atomic number and reaches a maximum with nickel.
The catalytic activity decreases strongly in the
transition from nickel to copper. There are 1 figure,
2 tableq'j,-..,'t"d 2 referencesp 1 of which i$ Soviet.
Card 3/4
Th Catalytic Activity of Germanium in Relation 20-115-~-zi/6o
P .1
to the Isotopic Exchange Reaction Between Hydrogen and Deuterium
ASSOCIATICN: klauchno-issledovatellskiy fiziko-khimichesk-*,~ inS+i~,-~
,1- - U~
im, L. Ya. Karpova (Physico-Chemical Scient-if-io, Resear,--,h
Institute imeni L. Ya. Karpov)
PRESENTED: October 9, 1957, by A. A. Balandin, Member, Academy of
Sciences USSR
SUBI-~=TED: October 1, lIP57
Card 4/4
5(2)
AE TH 02 S Boreskov G K Corres-.0nd in& 1:0":.ber, SCV/12 o - 12 --1 - 2 3 /5 6
lt__nret~ ~of Foi el-d-es- , USSR , Gorbunov, A. 1 0. L.
TITLE: Isotopic E--chan;-e in 1~oleculaar 11itrof-en on Iron Catalysts
Used in the Synthesis of Ammonia (Isotopnyy obmen
v molekulyarnom _-zote na zheleznylrh 1catalizatorakh sinteza
amni i aka )
PERIODICAL: Dolclady Akademii nauk SSSR, 1955, Vol 123, N" 1,
pp 90 - 92 (USSR)
ABSTRACT: It Yas proved (Refs 1-3) that the addition of K 20
and Al203 to the iron catzllysts increases their specific
activity (related to unit surface) with re~;ard
to the synthesis of ammonia at high pressure. Once or
twice activated samples have proved to be much more
active than a non-activated iron catalyst. The acti-
vating effect of K 20 was more marked than that of Al 203'
The published views regarding the effect of these
additions at atmospheric pressure are rather at
Card 1/4 variance (Refs 4,5). Thirefore an additional, more
Isotopic Exchange in Molecular Nitrogen on Iron SOV/2o-123-1-23/56
Catalysts Used in the Synthesis of Annonia
comprehensive investigation of the problem under
review with various contents of activator became
necessary. The method of the experiment was already
previously described in detail (Ref 5). Table I gives
the values of the activation energy, of the order of
reaction and of the specific catalytic activity K(P't)
at corresponding pressure and temperature for the
samples investigated: It can be concluded from this
that the activated catalysts, as far as their specific
activity is concerned, considerably surpass the Armko
iron (without activator) (in accord rith reference 5).
There is quite a definite parallelism in the accelerating
effect of the mentioned additions exerted on the
processes of the ammonia synthesis and of the isotopic
nitrogen exchange. This fact is difficult to under-
stand if it is taken for proved (Refs 7-9) that, the
limiting stage in the --mmonia synthesis is dfe to the
hydrogenation of the adsorbed nitrogen. If it is
assumed that the isotopic exchange and the synthesis
Card 2/4 of a.=onia pass a common staGe, nitrogen adsorption,
Isotopic Exchange in Molecular Nitrogen on Iron SOV/2o-123-1-23/56
Catalysts Used in the Synthesis of Ammonia
the rates of both reactions may be quantitatively
compared with each other. Here, tile filling of the
surface of the catalyst by the adsorbed nitro6en
must be coGidered (Ref 5). The calculation shows that
t'ne absolute rat,~s of reaction of the ammonia synthesis
and of the isotopic excl-hange proved to be similar in
samples once activated and in Arnko-iron, at equal
covering by adsorbed nitrogen (the data of N.M.Morozov
from the laboratory of Professor M.J.Temkin were uti-
lized). Thus, the evidence presented in this paper con-
firmed the mechanism of Temkin-Pyzhev (Ref 10) regarding
the isotopic exchange on iron-ammonia catalysts. There
are I table and 10 references, 7 of which are Soviet.
ASSOCIATION: Fiziko-khimicheskiy institut im.L.Ya.Karpova (Physico-
Chemical Institute imeni L.Ya.Karpov) 11001-ovskiy
khimiko-tekhnoloi;icheskiy institut im. D.I.Mendeleyeva
(11oscow Institute of Chemical TechnoloC;y imeni D.I.
Qard 3/4 Mendeleyev) I
24(8),25(5)
-AUTHORSi nen4rik, M. N., Boreakov, 0. K. SOV,/04-579-5-1121'21
TITLEj Calculation of an Adiabatic Reactor for Endathermir, Processes
(Raschet adiabaticheskogo reaktora dlya endotermicheskikh
protsessov)
PERIODICAL: Xhimicheskaya promyshlennost', 1959, 11r 3, P.P 55-57 (USSR)
ABSTRACT: Since a number of endothermic processes recently has been
carried out in industry by means of adiabatic reactors (fcr
instance producing divinyl of butylene, styrene of ethyl
benzene and alcohols of esters), the development of a method
for calculating those reactors is of special interest.
A graphic method was developedp based upon the general method
for the computation of the catalyst volume with which exo-
thermicl reversible reactions take place. It was found that the
task lies mainly in the definition of the quantity-r
(v - fictitious contact time) in seconds, acccrdinu to the
equation (1). Isotherms are given for the dehydration of
isopropylbenzene which represent the function of the degree of
transformation oL of T (Fig 1), carried out in the Giprokauchuk.
The temperature function t ofoc- for the process mentioned above,
Card 1/2 computed according to an equation (4), is also represented
Calculation of an Adiabatic Reactor for SOV/64-59-3-12/24
.Endothermic Processes
graphically (Fig 2). The graphio method of definition in also
represented in the same example (dehydration of isopropyl-
benzene) by means of a diagram dv (ng 3). It is
d oL
pointed out that the change of the catalyst activity has to be
considered, and therefore the value computed for -v has to be
multiplied by the coefficient 1-15 . The dehydration of iso-
propylbenzene wasalso exdmined on a large scale Olef 4)-
Conditions and some results are given (Table). There are
3 figures, I table, and 4 references, 3 of which are Soviet.
Card 2/2
50)
AUTHOR: Zlotin, L.
5OV/64-59-5-25/28
TITLE: Conference of Workers of the Synthetic EtIlyl Alcohol Industry
Branch
N~11100D I ','A L Ii-h a' i~iOh66kqYa pro_t!~ 1~hl S nnIs 1, 959 , lir P t~--~ `-,Is,
ABSTRACT: The regular branch conference took place this year in !%Tovo-
kuybyshevsk fror. July 14th to 17th, to discuss problems of the
industry of synthetic ethanol. The conference was convened by
Upravleniye komiteta. Soveta Ministrov SSSR po khimii (Admini-
stration of the Committee for Chemistry of the Council of Mini-
sters of the USSR) and by the Kuybyshev sovnarkhoz. Delegates
from all plants of synthetic alcohol, of the Gosplan program
SSSR and of the Gosplan program RSFSR and of the Goskhirkomitat
as well as leading workers of the Novokaybyshevsk and of a
number of research institutes (Fiziko-khimicheskiy institut
it,.ioni Karpova (Inqtituto of Phy,;ieal and Cho.;iieal Scir-~lnct~o)l
VXIIneftekhim, NIISS and others), of the Kuybyshevskiy indastrd-
allnyy institut (Kuybyshev Institute of Industry), of the
Planning Instituteu (Giprokauchuk, Giprogaztopprom), of tile P(!-
Card 1/3 troleum refineries, etcparticipated in this con'ference, which
- Q V
Conference of Workers of the Synthetic Ethyl Alcohol /64-3r)-=-2=/2B
Industry Branch
was attended bY 300 persons. it was oDened by Comrade I. M.
Barov, Secretary of the Kuybyshavskiy oblast-nyy komitet KFSS
(Kuybyshev oblast' Committee of the VSU). Lectures were 'r.old
in the plenary sessions concerning tne tasks of the industry
ot synthetic ethanol (L. i. 'i.lotin (Goskhimkomitet)), and
reports were made on the i.ork of the plants during the year
1958 and during the first quarter of 1959 (1. A. Valushko -
Kuybyshevskiy zavod sinteticheskc.-o spirta (Kuybyshev Plant of
Synthetic Alcohol)), A. P. Litvin - Groznenskiy khimicheskJ.y
zavod (Groznyy Chemical Plant), I. A. Anisimov - Saratovskiy
zavod sinteticheskogo spirta ~Saratov Plant of Synthetic Alcc-
hol), A. V. Likhachev - Orskiy zavod sinteticheskogo spirtua
(Orsk Plant of Synthetic Alcohol), M. M. Ryabova - Ufimskiy
zavod sinteticheskogo spirta (Ufa Plant of Synthetic Alcohol)i
14. Ya. Klimenko - MISS). Lectures were also held on the follo-x.-
ing subjects; On the aecrease of the prime cost of alcohol
(Ye. P. Shchukin - NIISS), on the optimum conditions of ethylEne
j
hydration (Corresponding Member of AS USSR G. K. Boresk2y', 0-1
foreign investigations concerning the produ(~Zion of synthetic
Card 2/3 alcohol and their analysis in the USSR (Doctor of Technical Scienca.,
Conference of Workers of the Synthetic Ethyl Alcohol SOV/64-59-c-25/28
Indus try Branch
M. A. Dalin), on the utilization of by-products of the pro-
duction of synthetic ethanol (Director of TsZL Orskogo zavoda
S. D. Razumovskiy (Central Plant Laboratory of the Orsk Plant
N, on further automation of alcohol produc-
S. D. Razumovskiy)j
tion (V. V. Aranovich - Giprokauchuk), on rust protection (A. B~
Neyman - MISS), on production of ethylene (T. I. Bogolepova -
Giprokauchuk). During the conference 5 study groups discussed
the following problems: Preps.'ring of raw material, ethylene
production, alcohol production, the economic, automatic and pro-
duction control-30 lectares were held. it was decided, among
others, to disregard the building of 2-3 new plants and the
workers were appealed to accomplish the new 7-Ye" Plan in 6
ye4Ts.
Car d 3/3
5W SOV/76-33-9-13/37
AUTHOR: Boreokov, G~ K.
TITLE., Effect of,the Interaction Between the Reaction System and the
Catalyst on the Kinetics of Catalytic Reactions
PERIODICAL: Zhurnal fizicheskoy khimii, 1959, Vol 33, Fr 9, pp 1969-1975
(USSR)
ABSTRACT: If, in an interaction between a reaction mixture and the catalyse
the stable composition of the latter is obtained fairly soon,
this change in the catalyst (caused by a change in composition
of the reaction mixture) will exert a noticeable influence on
the kinetics of the catalyzed reaction. The influence of the
concentration of the reaction mixture components on the reaction
rate-will be thus exerted,in two directions: by the collision
number of reacting part401089 considering the surface con-
centration of chemisorbed particles on the catalyst, and by
the effect of the reaction mixture on the properties of the
catalyst, i.e. on the "constant" of the reaction rate. Many
phenomena that were explained by the,heterogenei'vy of the
catalyst surface, are actually due to the said effect of the
reaction mixture on.the catalyst properties. On the st'l-eng-t-h
Card 1/2 of examples with the reaction kinetics of an oxidation occuz-
SOV/76-33-9-13/37
Effect of the Interaction Between the Reaction System and the Catalyst on the
Kinetics of Catalytic Reactions
ring on an arbitrary oxidation catalyst by the passage of
oxygen atoms between the reacting components, it is shown that
the form of the kinetic curves of some oxidation reactions can
be explained by the affect of the reaction mixture on the
catalyst properties, whereas it had been formerly explained by
the assumption of a heterogeneous chemisorption energy on the
catalyst surface. The following names are quoted in the paper:
N. V. Kullkova, M. I. Temkin, T. i. Sokolova, S. Z. Roginskiy.
There are 9 references, 8 of which are Soviet.
SUBMITTED: Pebruary 22, 1958
Card 2/2
5(4) BOV/20-127-1-391'65
AUTHORS: Kharfkovskaya, Ye. N.,_Bore8kov.-Ge K., Corresponding Member
AS USSR, Slin1ko, M. G.
TITLE: The Kinetics of Interaction Between Hydrogen and Oxygen on
Platinum (Kinetika reaktaii vzaimodeystviya vodoroda a
kislorodom na platine)
PERIODICALi Doklady Akademii naulc SSSR, 1959, Vol 127, Nr 11 PP 145-140
(USSR)
ABSTRACT: The measuring results hitherto supplied by publications
concerning the interaction mentioned in the title are contra-
diotory (Refs 1-5)- Experiments were made within too narrow
conoentration ranges or under oonditions that did not allow
aGourate measurements. The mentioned interaction was therefore
carried out at temperatures of from 20 to 1800, pressure of
from 50 to 750 torr and different compositions of the reaction
mixtures in a circulation system, Investigations were made on
hydrogen, nitrogen-hydrogen mixtures, nitrogen-oxygen mixtures
and oxygen. Flatifium was used in the form of 0.1 mm gauge wire.
The circulation rate varied between 400 and 1100 1/h. The
Card 1/4 reaction rate proved to be independent of the circulation rate
and of the nitrogen partial pressure; it depended only on the
The Kinetics of Interaction Between Hydrogen SOV120-127-1-39165
and Oxygen on Platinum
partial preaeure of hydrogen and oxygen, Pigs 1-3 allow the
miasuiing results for the different concentrations and
temperatures as roll as the influence of the pre-treatment pf
platinum with hydrogen at increased temperatures, figure 4 the
dependence of the reaction rate on the H2- and 02 concentration
at 1800. Experimental data are indicative of a complicated
catalytic process. In mixtures with hydrogen excess, the
reaction of the first order (referred to 0 2) and its being
little dependant on the pressure of H2 , permit the conclusion
to be drawn that here the interaction between chemically sorbed
atomic hydrogen, which covers the platinum durfacet and
molecular oxygen, forms the limiting stage. The oxygen reaction
is made easier by interaction with the d-electrons of the
catalyst (adsorption type C according to Dowden, Ref 11).
If the oxygen is not altogether removed from the platinum
surfacep 0-atoms remain adsorbed to the surface by means of the
d-electrons of the metal (type B), and the activity of platinum
Card 2/4 drops. When passing over to stoichiometric R 2-0 2-mixtureB,
The Kinetics of Interaction Between Hydrogen SOV/20-127-1_319/65
and Oxygen on Platinum
the platinum surface is freed from hydrogen, and a chemical
83rption of the oxygen with dissociation into atoms is made
possible. (Type A). in this range the reaction proceeds by
interaction of the atomically adsorbed oxygen with H21 this
requires less activating ene�,77, and causes an increased
reaction rate. In the case of oxygen excess, two stationary
conditions are possible, which differ by the reaction rate and
dependence on concentration of the components. The readily
occurring reaction is likely to be related with a chain
process, in which high-energy endothermal products participate,
which are regenerated in the course of reaction. On lowering
the temperature and temporarily evacuating the system, these
unstable products vanish, and there only remains a relatively
tightly platinum-adsorbed oxygen which reacts with hydrogen
slowly and with increased energy demand. The decreased
Card 3/4
The Kinetics of Interaction Between Hydrogen
and Oxygen on Platinum
SOV/20-127-1-39/65
reaction rate at increased oxygen pressure is probably due to
a partial blocking of the platinum surface by tightly adsorbed
oxygen. There are 4 figures and 11 references, 8 of which are
Soviet.
ASSOCIATION: Nauchno-6iscledovatel.'skiy fiziko-khimicheskiy institut im.
L. Ya. Karpova (Scientific Research Institute of Physical
Chemistry imeni L. Ya. Karpov)
SUBMITTED: Maroh 30, 1959
Card 4/4
5 (4)
AUTHOR: Boreskov,,G~.-X.,, Corresponding Member, SOV/20-127-3-32/71
--A-S~U~-S~
TITLE; The Influence of the Displacement of the Level of the Chemical
Potential of Electrons Upon the Activity of Semiconductor
Catalysts
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 127, Nr 3, PP 591-594 (USSR)
.ABSTRACT. The IPvel of the chemical potential of a catalytic reaction is,
by its immediate connection with the formation energy of the
surface intermediate bond, in connection with the catalytic
activity of semiconductors. For the purpose of investigating this
6onnection the simple example of the chemisorption of a particle A
with formation of a charged particle At on the catalyst
surface is aealt with. The adsorption heat Q of the process is
then Q -'I - IA+ WA+K ; T is the work function for the electron,
which immediately determines the level of the chemical potential.
It depends on the electron structure of'the semiconductor and on
the concentration of the adsorbed substwnce (the surface charge
formed influences q). IA - the ionization energy is determined
Card 1A only by the properties of the adsorbed molecule. WA+K is -the
The Influence of the Displacement of the Level of the SOV20-127-3-32/71
Chemical Potential of Electrons Upon the Activity of Semiconductor Catalysts
interaction energy of the ion A+ with the catalyst, it is
dependent on the position of the adsorbed particle on the catalyst
surface. The influence of a slight variation of tp or the influence
produced by additions upon the sorption rate is investigated. By
way of simplification it is assumed that in this connection a
variation Of WA+K may be neglectedp as also the variation of tf
is neglected with occupation of the surface. It then holds that
0 QO +,A y, and the degree of surface occupation
bpA (2) vrith b-adsorption coefficient and p pressure of
1+bpA A-
the substance A. For sorption equilibrium, when adsorption and
desorption rate, &j I cog , are equal, the expression
pAbQe QO/RTe vAT/RT is foun
W, W K -0 d (3). It increases
2 = o2 1 + PAboe QO/RTe'6qj"T
with the increase of q at small 6, and decreases again at large
The maximum corresponds to the value ~, for which a = m 1 which
Card 2/4 is in agreement with the general results obtained by M. I. Temk~-r.
The Influence of the Displacement of the Level of the SOV/20-127-3-32/71
Chemical Potential of Electrons Upon the Activity of Semiconductor Catalysts
When the variation of T with the occurrence of surface charge
is taken into accountq this maximum is not displaced, but the
state 0 = ac is attained at a chemical potential at which it is
reduced by S40 compared to q if the influence of the resultant
surface charge is neglected. In the case of an inhomogeneous
surface, the rules continue to hold only within the homogeneity
ranges. The conclusions are applied to oxide catalysts.
Figuxe 2 shows the variatiou of the activation energy of the
reaction of the isotopic exchange in moleadlar hydrogen in the
case of reduction of the chemical potentialp and figure 3 shows
the special influence in the case of interaction on the surface
with transition of an electron from the reacting substance to the
catalyst. If the chemical potential is reduced, the activation
energy of adsorption decreases, and that of desorption rises. The
process, which may also develop with the transfer of an electron
to the adsorbed substance, leads, with an increase of the chemical
potential, to a decrease of the activation energy, and the latter
Card 3A again increases with transformation of Un intermediate product.
T~e"Influence of the Displacement of the Level oT the SOV/20-127-3-32/71
Chemical Potential of Electrons Upon the Activity of Semiconductor Catalysts
The connection between catalytic activity and the free energy of
oxide dissociation is briefly discussed. There are 3 figures
and 5 Soviet references.
ASSOCIATION: Nauchno-issledovatellskiy fiziko-khimicheskiy institut im. L. Ya.
Karpova (Scientific Research Physi o o- chemical Institute imeni'
L. Ya. Karpov)
SUBMITTED: may 13, 1959
Card 4/4
4) SOV/20--127-5-28/58
AUTHORS: Boreskov, G. K., Corresponding Member AS USSR, Vasilevich,A. 0.
TITLE: The Mechanism of Isotopic Exchange in Molecular Hydrogen in
Platinum Films
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 127, Nr 5, pp 1035-1036
(USSR)
ABSTRACT: This investigation was carried out for the purpose of finding
out whether the exchange mentioned in the title takes place
according to the mechanism of an adsorption-desorption or by
chain reaction (Refs 1-3). By using tritium adsorbed on platinum
foils, the exchange rate at various points of the film and the
variable activation energies caused by inhomogeneity of the
platinum surface could be measured. The apparatus is shown by
figure 1. The platinum film was produced by the atomization of
a platinum wire in a vacuum. Figure 2 shows the exchange rate
tritium-hydrogen at 900K, figure 3 - the exchange rate H 2-D2
at 780K and 900K. Figure 4 shows the dependence of the exchange
rate and of the activation energy on the degree of the exchange.
Card 1/2 The conclusion is drawn that exchange takes pla-.e according to
SOV/20-127-5-28/98
Tk~e'Meohanism of Isotopic Exchange in Molecular Hydrogen in Platinum Films
an adsorption-desorption mechanism. The great difference in
iactivation energies (about 7-5 kcal/mol at temperatures of more
than 2730K, 1-0.5 kcal/mol at lower temperatures) could be ex-
plained by the fact that at low temperatures only small parts.
of the surfaoe are active, whereas on the major part of the
surface the reaction is smaller by 1.10-9. The active sections
may be caused by impurities, adsorption of other gases, in-
homogeneous distribution of the adsorbed atoms, etc. At higher
temperatures the difference in the activation energies of the
individual sections are smaller, so that the film reacts prac-
tically homogeneously. Although.the adsorption-deeorption
mechanism may be looked upon as probablep the production of
complicated active complexes is not to be excluded. There are
4 figures and 7 references, 3 of which are Soviet.
ASSOCIATION: Nauchno-issledovatellskiy fiziko-khimicheskiy institut im. L. Ya.
Karpova (Scientific Physico-chemiQal Research Institute imeni
L. Ya. Karpov)
SUBMITTED: May 23, 1959
Card 2/2
0
-o
0
-d 10 .91
g :.
~o
1; o
All lill.
I I IVY
S/064/60/000/03/03/022
B010/BO08
AUTHORBs Boreskoy_p_G. K. Slinlko, MO G.
i -
TITLEz Computation of Catalytic Processesl in Industrial Reaction
Apparatus
PERIODICALs Khimicheskaya promyshlennost', 1960, No- 39 Pp- 193-201
TEM Problems and examples regarding the application of electronic com-
puters for the computation of catalytic contact processes are given and
discussed here. A classification of contact apparatus is given intro-
ductorily (Fig. 1). Computations of the optimam temperature distribution
and the degree of conversion in the individual stages are illustrated by
the contact sulfuric acid production, and computation results obtained
with the,4-20 (M-20) electronic computer at the 1nstitut matematiki
Sibirskogo otdeleniya AN SSSR (Institute of Mathematics of the Siberian
Debartment of the AS USSR) are listed (Table). Exothermic processes in
apparatus with internal heat exchange are explained next, and computations
of the oxidation of ethylene to ethylene oxide, carried out by P. V. Kopay-
Gora. G. M. Ostrovskiyv and Ya. 1. Grinya at the Institut schetnogo mashino-
Card 1/2
Computation of Catalytic Processes in
Industrial Reaction Apparatus
s106416010001031031022
BOIO/BOOB
stroyeniya (Institute of Computer Construction), as well as corresponding
diagrams applying the data by M. I-.-Te-mkiW--et-al. (Ref- 3) are shown
(Figs- 7,8)- Computatic-'as for the application of apparatus with pseudo-
liquid layer in exothermic processes are also mentioned. Computations of
the limit of stable working conditions of contact apparatus are explained
for heterog6neous catalyses by means of pseudoliquid catalyst layers, the
method by Ao No Lyapunov (Ref. 5) applied in mechanics as well as a paper
by Do A. Frank-Kamenetskiy (Ref. 8) are mentioned, andan explanation of the
critical conditions is given. It is finally pointed out that electronic
computers permit the solution of complicated computations of the course
of catalytic processes, such as multi-btage processes with reactions
developing parallel and successively, catalyses in which the activity of
the catalyst drops quickly, etc. There are 10 figures, 1 table, and
6 Ireferencest 7 Soviet and 1 American.
Card 2/2
s/o64/6o/ooo/006/005/011
B020/BO54
AUTHORS: Boreskov, G. K. and Chesalova, V. S.
ysts
TITLE: Production of Industrial CaLaL I
PERIODICAM Khimicheskaya promyshlennost', 1960, No. 6, Pp, 38-44
TEXT: Catalysts which were initially prepared under laboratory conditions
with primitive equipment in small workshops are now produced on a large
industrial scale, The essential factor is the quality of the catalyst,
the consumption of material being of no, or only inferiory importance,.
This factor primarily depends on the chemical composition of the catalyst.
Fig. 1 shows the use of the individual elements of the periodic system as
catalysts in the industry, all natural elements being used except for the
rare gases. The"blank spots" in the table are mainly due to an insufficient
investigation of the respective elements as catalysts; rhenium has
recently gained importance as a catalyst, In the industrial practice,
complicated mixtures are mostly used, the strict observance of the formulBs
being of great importance in many cases.. As an example, Pig.. 2 shows the
change in catalytic activity of aluminum oxide on introduction of NaOE.
Card 1/3
Production of Industrial Catalysts S/064/60/000/006/005/011
B020/BO54
Fig. 3 gives data on the catalytic activity of Si-Zr catalysts of the same
gross composition, one of them being a mechanical mixture, the other a
chemical compound. The catalytic activity depends., however, also on the
extent of the inner surface. Fig. 4 schematically shows the optimum
porosity of catalysts for various reactions; it is stated that the
properties of the catalyst can be altered by a change in the porous
structure at constant specific activity only.. Fig. 1, shows the dependence
of the pore volume of active aluminum oxide on the pH of the solution
during the precipitation of aluminum hydroxide, and on the amount of
nitric acid added during the peptization. Table 2 gives the characteris-
tics of typical carrier materials for catalysts. Fig. 6 shows a cross
section of granules of a palladium catalyst, Fig. 7 the granules of
porous corundum in the form of microspheres (Laboratoriya tekhnicheskogo
kataliza (Laboratory of Technical Catalysis) of the Fiziko-khimicheskiy
institut im. L,. Ya. Karpova (Physicochemical Institute imeni L. Ya.
Karpov)), Fig. 8 the variation of the required catalyst amount and of
the hydraulic drag of the catalyst layer with increasing dimensions of
the catalyst granules of unchanged form, and Fig. 9 some special forms of
catalysts and carriers used to form a uniform catalyst layer.
Card 2/3
Production of Industrial Catalysts
S/064/60/000/006/005/011
B020/BO54
1. Ye. Neymark (Ref. 5) is mentioned. There are 9 figures, 2 tables, and
9 references: 6 Soviet, 2 US, and I British.
Card 3/3
CHNSALOVA, V.s.
Manufacture of industrial catalysts. Ihim. prom. no. 6:476-482
3 16o. (Catalysts) (MIU 13:11)
POPOVSKIY) V.V.;__BORESKOV, G.K.
Gat-alytjd activity of oxides of fourth-operiod metals with respect
to the oxidation of hydrpgane 'Probl, kin, i kat,,, 10:67-72 160.
(MIRA 14:5)
1. Moskovskiy khimiko-tekhnologicheskiy institut imeni D.I.
Mendeleyevao
(Metallic oxides) (Catalysts)
KUCHAYEV, V.L.;
Relationship between the catalytic activity and semiconductor .,
properties of germanium. Probl. kin. i kat. 10:108-110 160. -
.. (MIRA 14:5)
1. Fiziko-khimicheskiy institut imebi 1.,Yao Karpova.
(Permanium)
I
BORE
ZKOVy-G.-K,
Catalysis on metals* Probl. kin. i kat. 10:128-140 160o
(MIM 14:5)
1. Fiziko-khimicheskiy inatitut imeni L.Ya. Xarpova.
(Catalysts)
-
1, - .
QORBUNOV, A.I.; (BORMKOV, G.K.
Catalysis ofisotopic exchange in molecular nitrogen induced by
transition metals of the fourth period. Probl. kin. i kat. 10:192-
198 160. (MIRA 14:5)
1e Moskovakiy khimiko-tekhnologicheskiy institut imeni D.I.
Mendeleyeva,
(Nitrogen-Isotopes) (Catalrts)
(Transition metals
BOREWOV, G.K., VASILEVICH, A-A,
Mechanism of the isotopic exchange of hydrogen. on platinum
films. Kin. i kat. 1 no.1:69-82 Ny-je 16o. WR& 13:8)
1. Fiziko-khimicheakiy institut im. L.Ta. larpova.
(Hydrogen) (Deuterium) (Platinum)
BO~~T M.1_XASATKINA, L.A.; POPOVSKIY, V.V.;-BALOVN3V, Yu.A.
Oxygen mobility and the catalytic activity of vanadium pentoxide
promoted vith potassium sulfate. Kin.i kat. I no.2:229-236
Jl-Ag 160. (MIU 13:8)
1. Fizlko-khimichaskiy institut im. L.Ta.Karpova.
(Vanadium oxide)
(Potassium sulfate)
(Oxygen--Isotopes)
S/19 60/001/003/004/013
BOI 3YS058
AUTHORS; Kuchayev, V.- L.., Boreskov~ G K
TITLE: Isotopic Exchange of Hydrogen on Germanium Samples of
the n- and p-Type
PERIODICAL: Kinetika i katalizi 1960, Vol. 1, No- 3, PP- 356 -- 364
TEXT: In this paper the authors studied the effect of semiconductor pro.-
perties of crystalline germanium on its catalytic activity with respect
to the isotopic exchange of hydrogen with deuterium and the chemosorption
of hydrogen, on germanium samples. Hydrogen and deuterium were produced
by electrolysis.. Germanium monocrystals crushed in vacuum, from which 5
samples with various resistivity and various type of conductivity were
prepared, served as catalysts. The catalyst surfaces were megsured direcoy
in the reaction vessel after the adsorption of spectrally pure krypton at
the temperature of liquid nitrogen. The calculation was made according to
the BET method. The relative measuring accuracy amounted to about 5%.
Card 'tl#,l
Isotopic Exchange of Hydrogen on Germanium S/195/60/00"J/003/004/013
Samples of the n- and p-Type B013[BO58
Table 2 shows the change of the germanium-sample surfaces under the
Influence of various temperatures... The catalytic activity of germanium
with respect to isotopic exchange in homomolecular hydrogen was studied
by the static method at pressures of the equimolecular hydrogen-deuterium
mixture of 0-7 and 0.1 mm Eg at from 180 to 2800C~ The calculation method
was described in the paper by M. A~ Avdeyenko, G~ K,. Boreskov, and M. G.
Slinlko (Ref. 9). No noticeable difference in the catalytic activity was
ascertained between samples of different type of conductivity.. The rate
of adsorption of hydrogen was studied at room temperature (Table 3) and
at 1000C before testing the catalytic activity, It was determined that
rates of adsorption, energy of activation, and the adsorption as a func-
tion of the surface occupation are almost similar for all 4 samples. The
adsorption isotherms of hydrogen were recorded at 2100, 2440. and 2740C
and don't show any noticeable differences. With an occupation of up to
0 - 0.15, they correspond to Langmuir's equation for adsorption with
dissociation. The heat of adsorption is 25 kcal/mole, A deviation from
Langmuir's equation and a lower heat of adsorption are to be observed at
C.aTd 2/6
Isotopic Exchange of Hydrogen on Germanium S/195/60/001/003/004/013
Samples of the n- and p-Type B013/B058
a higher degree of occupation. The solubility of hydrogen in germanium-is
small and of no effect on the measuring results. As can be seen from the
dependence of the rate of desorption on the surface occupation at 1800C
(Fig. 10), it drops to one third after removal of about 201j"o' of the ad-
sorbed hydrogen from the germanium surface. It w4s established that the
rate of desorption.of the hydrogen-deuterium mixture is about 1-5 times
greater than the rate of isotopic exchange, and about 1-5 times smaller
than the rate of desorption of hydrogen, under equal conditions. The
studies gave the following conclusive results: The rates of hydrogen ad-
sorption and isotopic exchange were almost equal for all samples studied
inspite of a chbmge of the concentration of free electrons and holes by
7 to 9 orders of magnitude..This permits the conclusion that the adsorp-
tion of hydrogen on germanium proceeds without participation of free
electrons or holes, i. e. without surface charge. Similar rates of desorp-
tion and isotopic exchange point towards an adSDrption-desorption
mechanism of the reaction. Vw M. Prolov, 0. V. Krylov, and S. Z. Roginskjy
are mentioned. There are 10 figures, 3 tables, and 18 references: 5 Sovie~
10-US, 1 Dutch, and 3 German.
Card 316-
Isotopic Exchange of Hydrogen on Germanium S/195!6o/ool/003/004/013
Samples of the n- and p-lype B0137BO58
ASSOCIATION. Fiziko-khimicheskiy institut im. L. Ya. Karpova
(Physicochemical Institute imeni L. Ya. Xarpov)
SUB14ITTED: June 27, 1960
Card 4/6
Ta6a.mua 2
nonepmfoc-rb o6pa3t%oa repmaums, CAO
LL npeAsapimAbilan Tem-PaTypilan
4
M
HOMCP ) . PH
06P
ZaWA&
10D-
5w
2,3 1.9 1,4 1.3s
.2 2,0 1,6* - -
3 1,8 1,50 Ili* -
4 2,10 1,8*' - -
5 0,05 -
BORESKOV. G.K.; SLINIKO, M.G.
.Second European Symposium on Ghemical Technological Processee.
Kin. i kat.,l no. 3:483-487 s-o 160. (MMA 13:11)
(Europe--Chemistr7, Teohnical--Congresses)
i.,