Mikhail Temkin

16.09.1908-1.10.1991

Family

With sister Roza

Parents: Isaak (1881-1938) and Gitel (1879-1947)

Father

Isaak Temkin was rector of Moscow State University of Geodesy and Cartography

Family

Wife Liya

Daughter Elena

Beginning

1932

Karpov Institute, architect B. Iofan

Teachers
N. Kobozev (Moscow State University) N.N. Semenov and A.N. Bach

Kobozev, N. I.; Temkin, M.; Fraiberg, S. Oxidation of nitric oxide to nitrogen pentoxide by means of ozone in the silent electric discharge. Zhurnal Obshchei Khimii (1933), 3, 534

Temkin, M. I.; Bakh, A. N. Adsorption of hydrogen by palladium in the presence and absence of water. J. Phys. Chem. (USSR) (1934), 5, 809

Teachers

Frdric and Irne Joliot-Curie

Fuks Frumkin Petryanov

Bach

Temkin, M. I.; Frumkin, A. N. Activation energy of the discharge of hydrogen ions. Zhurnal Fizicheskoi Khimii (1955), 29 1513

Teachers

Michael Polanyi

Transition State Theory

Temkin, M. Transition state in surface reactions. Acta Physicochimica URSS (1938), 8, 141 Temkin, M. I. The Arrhenius equation and the active complex method. Acta Physicochimica URSS (1940), 13 733

each molecule one elementary space random distribution of molecules activated complexes occupy several adjacent elementary sites several possible positions of activated complexes number of activated complexes is small in comparison with total number of sites

Surface Reactions
Reaction : 11+ ...+ 11+...= 11+ ...+ 1 1+...
r+=(kT/h)gLqt/(qA1v1...qB11) A1v1...os-v1cB11exp(-o/kT)

where qt - modified partition function L - total number of sites

Surface Reactions
r+=(kT/h)gLqt/(qA1v1...qB11)A1v1...os-v1cB11exp(-o/kT)

Consequences
1. 2.

Rate is proportional to the number of sites Rate depends on the surface structure and configuration of activated complexes.

Lab of Chemical Kinetics

Pyzhev

Temkin

Temkin, M.; Pyzhev, V. Kinetics of the synthesis of ammonia on promoted iron catalysts. J. Phys. Chem. (USSR) (1939), 13, 851 Theory applied to practical problems

Hugh Taylor

Temkin, M. Fugacities in gas mixtures. Acta Physicochimica URSS (1944), 19, 163

Gas mixtures
Temkin, M. The Krichevskii - Kazarnovskii equation of state for gaseous mixtures. J. Phys. Chem. (U. S. S. R.) (1943), 17 Temkin, M. Volatility in gaseous mixtures. J. Phys. Chem. (U. S. S. R.) (1943), 17, 414 Temkin, M. Partial pressures in real gaseous mixtures. Acta Physicochimica URSS (1945), 20 713

Prof. I. Kazarnovskii Father-in-law of M. Temkin

Surfaces are not uniform

Surfaces are not uniform

Temkin, M. I. Kinetics of heterogeneous catalysis. J. Phys. Chem. (U. S. S. R.) (1940), 14, 1153 Temkin, M.; Levich, V. Adsorption equilibrium on heterogeneous surfaces. J. Phys. Chem. (U.S.S.R.) (1946), 20, 1441

as p = s 1 + as p
Levich

as p ds 1 + as p 0

1 1 + a0 p ln f 1 + a1 p

Quasi-logarithmic isotherm

1 1 + a0 p = ln f 1 + a1 p
a0=a at s=0 (highest a) where a1=a at s=1 (lowest a)
The number of sites with the same adsorption strength

Strongly nonuniform surfaces

=
1 1 + a0 p ln f 1 + a1 p

a0>> a1

a0p>>1, a1p<<1,

For the most strongly adsorbing sites the probability of being occupied is almost 1 and for the weakly adsorbing sites almost 0 (medium coverage)

Logarithmic (Temkin) isotherm

uniform

1 ln(a 0 p) f

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Temkin isotherm
=
1 ln(a 0 p) f

Explaining to I. Langmuir and A. Frumkin that surfaces are nonuniform Frumkin-Shlygin isotherm was in fact derived by Temkin in a footnote of Frumkin, A.N. and Shlygin, A.I., On Platinum Electrode, Dokl Akad. Nauk SSSR, 1934, 2, 173.

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Temkin Kiperman Romanushkina

Kulkova

Romanushkina, A. E.; Kiperman, S. L.; Temkin, M. I. Equilibrium in the reaction of hydrogen with nitrogen adsorbed on iron. J. Phys. Chem. USSR (1953), 27, 1181 Kul'kova, N. V.; Temkin, M. I. Kinetics of the reaction of conversion of carbon monoxide by water vapor. Zhurnal Fizicheskoi Khimii (1949), 23, 695

Temkin, M. I.; Shvartsman, L. A. Auxiliary table for chemical-thermodynamic calculations. Uspekhi Khimii (1948), 17, 259
0 0 H 298 S 298 I ln K = + + RT R R 0

I =

C p 1 C p dT + 298 T dT T 298
T T

I = aM 0 + bM 1 + cM 2 + c' M 2
298 T 1 + ln 298 T

M0 =
Mn =

298n+1 298n Tn + (n + 1)T nT n(n + 1)

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Temkin, M. Mixtures of fused salts as ionic solutions. Acta Physicochimica URSS (1945), 20, 411

Temkin, M. I.; Kiperman, S. L.; Luk'yanova, L. I. Flow-circulation method of investigation of the kinetics of heterogeneous catalytic reactions. Doklady Akademii Nauk SSSR (1950), 74, 763 The pressure in the system is constant Gas (liquid) composition does not change with time or in space Each single pass of reactants through the bed results in very small conversion as the circulation rate is very high. The system is free from concentration gradients along the catalyst bed, concentration gradients due to axial dispersion and temperature gradients. The treatment of data is simplified as the rate is extracted directly in the differential form
Buss Berty Carberry

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Temkin, M. I. Calculation of surface area from data of vapor adsorption. Zhurnal Fizicheskoi Khimii (1955), 29 1610 Cherednichenko, V. M.; Temkin, M. I. The effect of internal diffusion on the course of a heterogeneous catalytic reaction retarded by the reaction product. Zhurnal Fizicheskoi Khimii (1957), 31, 157. Cherednichenko, V. M.; Temkin, M. I. Kinetics of catalytic synthesis of methanol. Zhurnal Fizicheskoi Khimii (1957), 31, 107

Cherednichenko, Slinko, Boreskov, Kulkova, Lukyanova

Temkin, M. I. Reaction kinetics on the surface of solids and the problems of the highest catalyst activity. Zhurnal Fizicheskoi Khimii (1957), 31 3 Kurilenko, A. I.; Kul'kova, N. V.; Rybakova, N. A.; Temkin, M. I.. Oxidation of ethylene to ethylene oxide on a silver catalyst. II. The reaction kinetics. Zhurnal Fizicheskoi Khimii (1958), 32, 1043

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Temkin, M. I. Conditions that determine the coexistence of gas phases. Zhurnal Fizicheskoi Khimii (1959), 33, 2040 Gel'bshtein, A. I.; Temkin, M. I., Determination of the reaction order from the acidity. Proc. Akad. Sci. Phys. Chem. Sect. (1958), 118, 57

Temkin

Temkin, M. I. Kinetics of stationary reactions. Doklady Akademii Nauk SSSR (1963), 152, 156

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Ostrovskii, V. E.; Karpovich, I. R.; Kul'kova, N. V.; Temkin, M. I. Calorimeter for the determination of heats of chemisorption at elevated temperatures. Zhurnal Fizicheskoi Khimii (1963), 37, 2596

Temkin, M. I.; Apel'baum, L. O. Application of a semipermeable membrane to the study of chain characteristics of surface reactions. Problemy Kinetiki i Kataliza, Akad. Nauk U.S.S.R. (1960), 392. Temkin, M. I. Double stage kinetics on a heterogeneous surface. Doklady Akademii Nauk SSSR (1965), 161, 160. Temkin, M. I. Kinetics of stationary reactions. Journal of the Research Institute for Catalysis, Hokkaido University (1968), 16, 355

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Theory of complex reactions

N 1. 2. 3. 4. 5. O2 + 2* 2O* H2 + 2* 2H* H* + O* OH* + * OH* + H* H2O + 2* H2 + O* H2O + * 2H2 + O2 2H2O
(1)

N(2) 1 0 0 0 2

1 2 2 2 0

N(i): routes *: active center

: stoichiometric number : stoichiometric coefficient

Horiuti - Temkin equation

P=S+W-J
P number of routes, W number of balance equations, J number of intermediates, S number of steps

r=

r+ i r i 1r+ 2 ...r+ s + r1 2 r+ 3 ...r+ s + r1r 2 ... s

i =1 i =1

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Two-step sequence

1. Z+A1ZI +B1 2. ZI+A2Z +B2 A1+A2 B1+B2

r=

k1 PA1 k 2 PA2 k 1 PB1 k 2 PB2 k1 PA1 + k 2 PA2 + k 1 PB1 + k 2 PB2

Gel'bshtein, A. I.; Airapetova, R. P.; Shcheglova, G. G.; Temkin, M. I. Acidity function in the P2O5-H2O system. Zhurnal Neorganicheskoi Khimii (1964), 9, 1502 Ostrovskii, V. E.; Temkin, M. I. Heats of oxygen chemisorption on silver. Kinetika i Kataliz (1966), 7, 529 Gel'bshtein, A. I.; Kul'kova, N. V.; Temkin, M. I.; Yukhtin, N. N.; Bakshi, Yu. M.; Bobkov, S. S.; Shcherbatykh, Yu. I. Catalyst for acrylonitrile production. U.S.S.R. (1967), SU 192760 Shub, F. S.; Apel'baum, L. O.; Temkin, M. I. Simple gradientless reactor for studying the kinetics of homogeneous gas reactions. Kinetika i Kataliz (1969), 10, 464

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Temkin, M. I. A graphic method for the deduction of kinetic equations of complex reactions. Doklady Akademii Nauk SSSR (1965), 165, 615

Graph with an empty circle

1. N2+Z=ZN2 2. ZN2+H2= ZN2H2 3. ZN2H2+Z= 2ZNH 4. ZNH+H2 =NH3+Z 5. Z+H2O=ZO+H2

Hanging vertex

1 1 1 2 0

Graph for the Langmuir-Hinshelwood CO oxidation mechanism with dissociative oxygen adsorption

Temkin, M. I.; Kul'kova, N. V. Ideal-displacement laboratory reactor. Kinetika i Kataliz (1969), 10, 461

Catalyst granules or pellets are placed into the tubes, divided with an inert material Tablet Tablet Tablet Inert material Inert material

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Temkin

Kuchaev, V. L.; Temkin, M. I. Secondary ion-ion emission study of the mechanism of the reaction of hydrogen with oxygen on platinum. II. Kinetika i Kataliz (1972), 13, 1024 Novikov, I. I.; Portnoi, V. K.; Kosikhin, Yu. P.; Sinitsyna, N. A.; Temkin, M. I.; Luzenberg, A. A. Superplastic zinc-aluminum alloy sheet by hardening and hot rolling. Patent U.S.S.R. (1974), SU 435304

Temkin, M. I. Rate relaxation in a twostep catalytic reaction. Kinetika i Kataliz (1976), 17, 1095 Meshenko, N. T.; Veselov, V. V.; Shub, F. S.; Temkin, M. I. Kinetics of the low-temperature steam reforming of ethane on a nickel-chromium catalyst. Kinetika i Kataliz (1977), 18, 962 Shapatina, E. N.; Kuchaev, V. L.; Temkin, M. I. Kinetics of the catalytic synthesis of phosgene. Kinetika i Kataliz (1977), 18(4), 968 Temkin, M. I. Transfer of dissolved matter between a turbulently moving liquid and particles suspended in it. Kinetika i Kataliz (1977), 18 493

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Mass transfer
Temkin, M. I. Transfer of dissolved matter between a turbulently moving liquid and particles suspended in it. Kinetika i Kataliz (1977), 18 493.

d
D

Vd

Sh Re
Sherwood Number Reynolds Number

1/ 2

Sc

1/ 3

Schmidt Number

Kolmogorov theory of turbulence

Critical eddies responsible for energy dissipation 1 3

Re =

V ( )

Kolmogorov equation can be applied to bubbles / solid particles with characteristic length d (Temkin, 1977; Baldi et.al., 1978)

d 1 Red ( 3 ) 3 power input per kg of liquid; energy dissipation

diameter of bubbles / solid particles

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Remember

Sh Red

0.5

Sc0.33

Analysis of experimental data:

Temkin, 1977

Sh = 1.0 Red

0.5

Sc0.33

Mass transfer coefficient

Gas-liquid

Temkin, 1990
1/ 6

gL

D 4 = 1.0 vd 2 b

Liquid-solid

diameter of bubbles
1/ 6

D 4 Ls = 1.0 vd 2 cat
diameter of particles

Temkin, 1977

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Temkin, M. I. The kinetics of some industrial heterogeneous catalytic reactions. Advances in Catalysis (1979), 28, 173-281

Temkin, M. I. Gas diffusion in porous catalysts. Kinetika i Kataliz (1981), 22, 1365 Temkin, M. I. Catalyst efficiency factor in a zero order reaction in a spherical porous grain. Kinetika i Kataliz (1983), 24, 1270

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. Kuznetsov, V. D.; Shub, F. S.; Temkin, M. I. Role of carbon dioxide in the synthesis of methanol in the presence of the SNM-1 copper catalyst. Kinetika i Kataliz (1982), 23, 932 Temkin, M. I. Simple method for the approximate calculation of the efficiency factor of a porous catalyst. Kinetika i Kataliz (1984), 25, 478 Boreskova, E. G.; Kuchaev, V. L.; Temkin, M. I. Isotope exchange and adsorption of nitrogen on a catalyst for ammonia synthesis poisoned by oxygen. Kinetika i Kataliz (1984), 25, 116 Temkin, M. I. Principles of A.A. Balandin multiplet theory of heterogeneous catalysis. Kinetika i Kataliz (1986), 27, 533

Temkin

Temkin, M. I. Equations of state of gases and liquids closely described by van der Waals models. Zhurnal Fizicheskoi Khimii (1988), 62, 2577

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Kulkova

Kuchaev

Temkin

Shub

Temkin, M. I.; Murzin, D. Yu.; Kul'kova, N. V. Kinetics and mechanism of liquidphase hydrogenation. Doklady Akademii Nauk SSSR (1988), 303, 659 Kuchaev, V. L.; Shapatina, E. N.; Temkin, M. I. Kinetics of ammonia synthesis at low temperatures. II. Sources of divergences. Kinetika i Kataliz (1988), 29, 610

Temkin, M. I. Kinetics and mechanism of ammonia synthesis. Khimicheskaya Promyshlennost (1990), 292 Murzin, D. Yu.; Kul'kova, N. V.; Temkin, M. I. Kinetics and mechanism of liquid-phase hydrogenation of benzene with formation both of cyclohexene and cyclohexane. Kinetika i Kataliz (1990), 31, 983 Temkin, M. I.; Kul'kova, N. V. Synthesis of hydroxylamine sulfate at high pressure. Khimicheskaya Promyshlennost (1991), 530

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Temkin, M. I. Application of the Guggenheim equation of state to gas equilibriums at high pressures. Khimicheskaya Promyshlennost (1991), 610 Murzin, D. Yu.; Konyukhov, V. Yu.; Kul'kova, N. V.; Temkin, M. I. Diffusion from the surface of suspended particles and specific power of mixing in vibrating reactors, Kinetika i Kataliz (1992), 33, 728

Specific mixing power in a shaked reactor : measuring of heat release

1.8 1.6

y=1/3

Specific mixing power, W/kg

1.4 1.2 1.0 0.8 0.6 0.4 0.2 120 140 160 180 200 220 240

y=1/2

y=2/3

Number of double movements

Blumenfeld

Blumenfeld L A; Temkin M I. On the possible mechanism of formation of adenosine triphosphate in the course of oxidative phosphorylation. Biofizika (1962), 7, 731

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Throughout the years: Science

...and not only

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..and not only

Reading Shakespeare

..and not only

Mountain climbing

Hiking

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 .. ( .) , : , , .

More personal memories

http://temkin-76.ucoz.ru/ D. Yu. Murzin, The man behind the name: Mikhail Temkin, Journal of Molecular Catalysis .A. Chemical (accepted)

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Jean-Paul Sartre is reported to have said I shall die twice, the first time physically and the second time when no one shall read my works. Mikhail Temkin will live a long, long second life, as his name will remain known by new generation of kineticists, who will not even need to read the original writings, since the main ideas of Temkin are already in all textbooks and monographs on heterogeneous catalysis M. Boudart

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