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Catalytic Dehydrogenation of Isopropyl Benzene S/020/60/132/02/27/067 B011/BO02 is illustrated by Fig. 2:. The points of these two dependences are lying on the same curve. Hence the authors concluded that their experiments took place within the kinetic range. From S2 and z3 the changes of the liberated snergyA F, the host content jinffl and. the entropy 68 were calculated in the adsorption dis- placement from the active centers of dehydrogenation. The degree of the dehydro- genstion of isopropyl benzene increases with rising temperature. At 5800 and 6070, the yield in 0(-methyl styrene attains 70-5~ and 83~.j respectively (Table 1). G. M. Marukyan is mentioned. There are 2 figures, 2 tables, and 8 references, 4 of which are Soviet. ASSOCIATIONs Institut organicheekoy khimil im. N. D~ Zelinskogo, Akademli nauk SSSR (Institute of Organic Chemistry imeni N. D. Zelinskiy of the Academy of Soienceaj USSR); SUBMITTEDs February 8, 1960 Card 3/3 B/020/60/i32/03/24/o66 BOII/BO08 AUTHORS: Balanding A. Aog Academician, Teteni, P. TITLE: On the Influence of the Nature of Metals on Their Catalytic Activity PIRIODICAL; Doklady Akademii nauk SSSR, 1960, Vol. 132, No. 3, PP. 577-500 TEXT: In the paper under review the authors experimentally studied the kinetics of the dehydrogtnation of the isopropyl alcohol on metallio silver, platinum, and palladium. The methods of the kinetic measurements have been described previously (Refs. 10t11). The rate constants k were calculated. in accordance with equation k w (z2 + z3)Ajln Al M - (32 + z3 - 9m. (i). This equation was Al obtained from the general kinetic equation which was derived by A. A. Balandin (Ref. 19)t with Al being the volume rate of the alcohol Card, 1/3 on the Influence of the Mature of Metals 8/02 60/132/03/24/066 on Their Catalytic Activity BOIIYBO08 passagag a the hydrogen volume separated within I min. and z2 and z the relative:adoorption coefficients of the acetone and hydrogen. TL determination Of 22 and s3 was necessary for the calculation of k. This was done by neane of the reaotion-kinetio method (Ref. 20). For the methods of the determination and calculation see Refs. 15 and. 16. The results are given In Tables 2 and 3. The authors carried out separate experimental series at different temperatures and at a constant volume rate In order to determine the activation energy Eof the dehydrogenation of the isopropyl alcohol* The values Aj, m and ( 52 + 3) were inserted informula (1) for the calculation of the Yalu of k :a 3 increases in the case of the platinum catalyst with the ri:: of t e perature (Table 3), 2 had therefore to be determined for the desired temperature with the aid of interpolation from the dependence diagram log !3 of I/T. The true activation energy was only determined on silve r and p atinum, since the relative adsorption coefficients of the reaction products were only available for these catalysts* For palladiumo the approximate activation energy was only determined from the tangent of the angle of slope of the straight line in the diagram log m, I/T. The values determined for C are Card 2/3 On the Influence of the Nature of Metals 3/020/60/132/03/24/066 on Their Catalytic Activity B0111BOOD shown in Tables 4-6 and Pigs 2* The points come to lie on the straight line by Arrhenius with sufficient accuracy (Fig* 2). Table I shown the activation energies,. also those taken from the papers (Refs. 15 and 16). In the introduction, the authors explain the multiplet, theory by A. A. Balandin (Ref. 1) and the structural# as well as energetic correspondence between the chemical compounds reacting in the substrate and In the catalyst. They state, moreover# that the results mentioned in Table 1 have a sufficiently general charsoters The authors mention A. Us Rubinshteyu* S. Z. Roginskiyj F. P. Volskenshtsyn and K. D. Zelinskiy. There are 2 figures, 6 tables, and 20 references, 11 of which are Soviet. ASSOCIATION: Moskovskiy goeudaretyennyy universitet im. H. V. Lomonosova (Moscow State University imeni M. V. Lomonosov) SUBMITTED: September 9, 1959 Card 3/3 PATRIEffW, T.Y.; BALARDIN A*A. akademik; ]aABUNOVSKIT. Te.I.; PARDASHIT, YU.S.1 MMIA5V.W. T Selectivity towards optical Isomers of adsorbents fromed in the presence of bacteria. Dokl.AN SSSR 1132 no.4o.850-852 JS ;~O (KIRA .53 1, Institut, orgknichookoy khimii I*. II.D.Zolinakogo Almdemii nauk SSSR. (Advorbouts) (Isomers) Mo AUTHORS: B/018i'?'jj(0/1 33/0t/36/070 110C Doi 1 B003 Tolatopyatova, A. A,,9 Bala, , Academician, KOz6nkOA-- 1* 1, Adini A. L TITLE: Catalytic transformations of Alcohols and CZolio ftdro- cairbontion Titaniim Dioxide PERIODICAL: Doklady Akadesii nauk SSBR, 1960, Vol. 133, No0j, pp. 130 - 135 TEXT: Although titanium dioxide is easily ayallableg It belongs to the little investigated astalyslalThe authors wanted to study its oata- lytio properties with various modes, of preparation# In reactions with *thyl-, isopropylp and a-propyl alcohol as well as with eyolohexans, oyolohox*ne# and 1P4-oy*lohex&dien*. Moreover, they wanted to inv*eti- gat* the kinetics of these reactions and the energies of the bonds of C-, H-, and O-stome with th: TiO urfaoe, The method of the difteren- tial thermocouple is used f r thl Nudy of the catalytic reactions._ Fig. i shows the position of the catalyst in relation to the thersto OK couple. The electromotive force (eaf) was uninterruptedly recorded on Card 1/3 as hYdroxide f roperties Uen r04 TICI On fo Ur 4 w1 th 8172~ 1 'Catalytic Transformation* of Alcohol* and 0/133/01/36/070 Cyclic Hydrocarbons on Titanium Dioxide ioll/BO03 waterp No. 2 - the a&&* with ammonia. No. 3 by oxidation of freshly pre- pared Ti (003 (precipitated from TiC13 with annonia) with airt and No. 4 by hydrolysis of orthoethyl titanate, It was established by X-ray struo- tural analysis that anataso resulted in No. 1. Table 2 shows the reac- tion* studied in certain temperature ranges, the activation energies 'C. as W:11,:Six, of the krrhenius equation; furthermore, the degree of do- oarb ni t on of each sample surface. It say be seen from these data and Table 4 that the nod* of preparation exerts a great Influence on the above-mentioned values and the binding energy. Table 3 shows the d9pen- depoe of the adsorption coefficient z on AV (heat *out nt) the ontro-- pjFA80, and the change in free *n:r AFO. The binding :ner6 value* were calculated for the first tie Fuble 4). Thera are i figure, 4z tables, and 11 references: 10 Soviet. ASSOCIATION: Institut organicheskoy khinii is. N, D, Zelinskogo Akademit nauk 8839 (Institute of OManic ChouistrZ i N. D. Zelinskiy of the Academy of Sciences, M OMITTED: 1pril 2, 1960 Card 3/3 S/020160/t33/03/07/013 B016/BO68 AUTHORS: Balandin, A, At.,.Academician, Bogdanova, Ot Koa, Shchogloval A. P. TITLE: Catalytic Dehydrogenatio~n of qyolohexanol~ PERIODICAL: Doklad.y Akademii nauk SSSR, 1960t Vol. 133# No. 3, pp. 578 - 580 TEXT: It was shown by the authors in earlier publications (Ref. 1) that several aliphatic alcohol@ can be dohydrogenated over a mixed oxide catalyst without any noticeable formation of by-products due to decomposition and dehydration. They showed in this publication that the same oatelyst may be alett used to dehydrogenate eyolohexanol. This meth- od cf preparing cyolohexaione is being used in the production of syn - thotio fibers in which oyclohexanone is applied an a good solvent. Ac- ooriing to To. V. Turi S. A. Anisimov, and M. S. Platonov (Bef. 2), the oyoldhexanons jiold is up to 25.3~ over finely disperse rhonium at 3500C. Bonzeae# oyclohexanep and other compounds form as by-products. The oycloho2anone, yield over a nickel-aluminum catalyst according to Card 1/3 k__100, Catalytic Dehydrogenation of Cyclohoxanol S/020160/133/03/07/013 B016/BO68 Zellnekiy and Komarevskiy is about 37A at 3800C, with larger amounts (allut 48%) of bonsenep and, in addition, phenol, eyolohex*ne, and pol,raer produats being formed. Moreover, the authors give data obtained by German and Japanese researchers* They studied the kinetic@ of the mentioned reaction, and.determined the relative absorption coefficients, the reaction rate constants together with the activation energies (Table 3), the changes in free energy, heat content, and the entropies found for the, adsorptive displacement of the alcohol molecules from the otive dehydrogenation centers by cyclohexanone (Table 2). Finally, the : uthors established the oonditionsof dehydrogenation which asours high yields of oyl)lohexanone. The continuous method was applied for theme experiments. They were carried out in an apparatue described previously (Rer. 0) and over a similar oxide catalyst,sample. The conversion degree of alcohol in oyolohexanone varies between 16 and 754 of theory (Table 1). The results of further experiments carried out with binary cyolohexanol - oyclohsx&nons mixtures (containing 24.6 mole % of the latter) are shown in Table 2. Prom these results, it follows that the relative adoorption coefficient of cyclohexanol is 3.03 at 2810C9 and drops to 0.1)1, if the temperature is raised to 3360. A logarithmic Card 2/3 Catalytic Dikhydrogenation of Cyclohexanol 8/020160/133/03/07/013 B0161BO66 dependence holds between the adsorption coefficient and reciprocal tem- perature (Fig. 1). it can be seen from Table 2 that the values of the mentioned ocefficients retain unaltered, if the temperature in kept constant and. the rates of passage are varied. From Table 4, it can be seen that the conversion degree of alcohol increases from 6T.9 to 6841 when the temperature in raised from 333 to 3600C and the rate of passage per hour is increased. There are 2 figurest 4 tables, and 10 references: 7 Soviet and 3 American6 ASSOCIATION: Institut organicheskoy khimii im, No D. Zelinskogo Akademii nauk SSSR (Institute of 2rganio Chemistry imeni No Do Zelinskiy of the.kciaWa SUBMITTED: March 18, 1960 Card 3/3 3102 60/153/004/036/04OXX BOI 6YB054 AUTHORSs Bogdanova, 0. K., Balandin, A. A., Academician, and Belomestn1kh, I. P. ------ TITLEi The Effect of the Conjugation Energy on the Rate of Catalytic Dehydrogenntion of Alkyl-aromatio and Alkyl- hexahydro-aromatic Hydrocarbona PERIODICALs Doklady Akademii nauk SSSR, 1960, Vol. 1331 No- 41 PP- 80-842 TEXTt The authors report on their investigations of the dehydrogenation of ethyl oyclohexans, and leopropyl cyclohexane on mixed oxide catalyst. They proceeded from the results of a previous paper (Ref. 1) which showed. that ethyl benzene and isopropyl benzene are well dehydrogenated on this catalyst. The rate constant of the dehydrogenation of isopropyl benzene with a ramified alkyl radical is twice that of ethyl benzene (Table 1). Apparatus and methods used for the experiment are described in the paper mentioned (Ref. 1). The amount of catalyst used was 10 ml, the temperature Card 1/3 The Effect of the Conjugation Energy on the 8/020/60/133/004/036/04OXX Rate of Catalytic Dehydrogenation of Alkyl- B016/BO54 aromatic and Alkyl-hexahydro-aromutic Hydrocarbons was 550 - 6000C, the volume velocity of the hydrocarbon was 1000 ml/l - h (equal to a rate of travel of 0.5 ml per 3 min). Afer every experiment, the catalyst was blown through with vapor - air mixture and with air. Cyclohexane was also used for the experimentol it can, however, not be dehydrogenated under the above conditions. The dehydrogenation of ethyl cyclohexane at 5500 was poor ( 1% of vinyl cyclohexnne was formed)l the Oftme agplies to isopropyl cyclohexane (2,9 of isopropylidene cyclohexane). At 600 C, these yields were 5.8, and 6.7% respectively. At 6000C, methane# ethane, and unsaturated hydrocarbons were formed by cracking. The authors conclude from their results that the rate of catalytic dehydrogenation depends on the structure of the hydrocarbons used, on that of their alkyl radicals, and mainly on. the poseibility of formation of a conjugate bond with the aromatic ring. The dehydrogenation of the alkyl group of the hexahydro -aromatic ring is rendered diffioult. There are 1 table and 7 references' 5 Soviet, I British, and 1 German. Card 2/3 The Effect of the Conjugation Energy on the S/02Y60/133/004/036/04OXX Rate of Catalytic Dehydrogenation of Alkyl- B016 B054 aromatic and Alkyl-hexahydro-aromatic Hydrocarbons ASSOCIATIONt Inatitut organioheskoy khimii im. N. D. Zelinakogo Akademii nauk SSSR (Institute of Organic Chemistry imeni N. D. Zelinakiy of the Academy of Sciencea USSR) SUBMITTEDe April 13, 1960 Card 3/3 8/020/60/133/005/031/0-34/XX ,67 le? B016/BO60 AUTHOR: Balandin, A. A., Academician TITLEi Structural Correspondence in Catalysis PERIODICAL: Doklady Akademii nauk SSSR, 1960, Vol. 133, No. 5, pp. 1073 - 1076 TEXT: As far back as 1929 (Ref. 2) the author had already defined the principl* of structural correspondence between catalyst and reacting molecules. The evidence gathered in the course of time regarding the signi- ficance of structural factora.for catalysia~ and especially the exper imen- tal results indicating a sextet model have been collected by the author in Refs. 7 - 11. Since two years have already passed since the last-mentioned work., the author now adds further results. Table 1, compiled on the- basis of the now (Ref. 12,, 1958) detailed collection of interatomic distances, includes only metals, viz., such as crystallize in simplest systems (Al, A2, A3, and A4). This shows that the rule earlier established is also valid for the now values of interatomic distances. The elements known as catalysts of cyclohexane dehydrogenation actually belong to the metals with lattice Card 113 Structural. Correspondence in Catalysis S/020/60/133/005/031/034/XX aoWBo6o types Ai and A3. These metals including rhenium have the shortest interatomic distances do The Cyclohexane dehydrogen&tion by Re, predicted by the multiplet theory, has been.proved by the author jointly-with Te. N. K&rpoyakay& and A. A. Tolatopyatova (R#f. 13). Th& author further succeeded in establishing a case of so-called irreversible catalysis of cyclohexone on Re, which takes place more slowly than the dehydrogenation of cyclo- hexans, to benzene. This confutes the assumption contradicting the sextet scheme, uttered by some authors (Rot. 14), according to which the dehydro- ic genation of cyclohexane proceeds by way of irreversible catalysis. Accord- ing to Table 1, also technetium belongs to the category of dehydrogenation catalysts. This would have to be checked experimentally. Cu has proved to be a catalyst of benzene hydrogenation(according to B. V. Yerofeyev and N. V. Nikiforova, Ref. 15). Its weak activity Is explained by other, not structural factors. Thel low-temperature modification of manganese has a complex lattice U12) and is not Table 1. According to theory, cyclohexane, is not dehydrogenated on Kn (Rot. 16). The same holds for Fe. The author believes that the data by I. E. Anderson and C. Kemball (Ref. 17) do not contradict Table 1. The mechanism of dehydrogenation discussed here has been checked from still another angle: the dehydrogenation of 7- and Card 213 Structural CorreapoAdence in Catalysis 8/020/60/133/005/031/034/XX B016/BO60 5-membered rings (1), giving rise to non-benzoid aromatic compounds (II) (Ref. 21). The sextet model is excellently confirmed by the fact that on Pd (Ref. 22) bicyclo-(0,3,5) decane is dehydrogenated to azulene (III) only in a small amount. Table I of the article under consideration is intended to replace the table given in the author's earlier paper (Ref. 2, 1929). It is also applicable in the case of other catalytic reactions on metals as, e.g., in the hydrogenation of olefins and aldehydes. Papers by A. Ye. Agronomov and V. N. Luzikov (Ref. 16), and by the author and I. I. Brusov (Ref. 20) are mentioned. There are I table and 26 references: 15 Soviet, 3 US, I British, I Swiss, and I German. ASSOCIATION: Moskovskiy gosudarstvennyy universitet im. M. V. Lomonosova (Moscow State University imeni M. V. Lomonosov), Institut organicheskoy khimii im. N. D. Zelinskogo Akademii nauk SSSR (Institute of Organic Chemistry imeni N. D. Zelinskiy of the Academy of Sciences USSR) 6UBMII'TED: April 29, 1960 Card 3/3 S/020/60/t33/006/007/016 B016/D060 AUTHORS: Shchoglova,_A. P., Dogdanoval Oo st Dalandint A. A.11 Academician TITLE. The Problem of Dehydrogenating Butane - Butylene Mixtures -on-an Aluminum Chromium Catalyst I PERIODICAL-. Doklady Akademii nauk SSSR, 1960, Vol. 133, No. 6, pp- 1350-1353 TEXT: The present investigation was. carried~out in 1950. The catalyst was supplied by M. N. Marushkin (Ref. 6). The authors wanted to collect data concerning the kinetics and mechanism of the 4ehydrQgenation I mentioned in the title. The dehydrogenation rates of butane and it's binary mixtures with butylene (Table 2), butadiene, and hydrogen (Table 3) were measured under optimum conditions. Since butylene and butadiene are deconpooed on this catalyst, the authors measured the reaction rates in binary mixtures of these hydrocarbons with ethane in order to determine the degree of decomposition. In fact, ethane occupies, Card 1/3 The Problem of Dehydrogenating Butane - Butylene Mixtures on an Aluminum Chromium catalyst 5/020/60/133/006/007/016 B016/B060 on the active surface, a part equal to butane, but is neither dehydrogenated nor decomposed. Figs. I and 2 show the decomposition of butylene and butadienet respectively, as dependent on temperature. Experimental results confirmed the assumption previously put forward by the authors, according to which coal and resins result from the dehydrogenation mentioned in the title, due to the decomposition of butylene and, even more, butadionel(Table 3). The authors state in conclusion that the following reactions take place: 1) dehydrogenation of butane to butylene; its rate is inhibited by the butylenc that is present in the initial mixture; 2) dehydrogenation of butane and butylene to butadiene; 3) decomposition of butane; 4) decomposition of butylene into light hydrocarbons and coali 5) decomposition of butadiene into light hydrocarbons, coal, and condensation products. Butadiene develops in low ykelds at atmospheric pressure. The catalyst is soon poll-ated with coai. and requires frequent regeneration. A more selective dehydrogenation o-.r butane to butylene can be attained (Refs. !16) at lower temperatures. Lose light hydrocarbons and coal are thus formed. Card 2/3 The Problem of Dehydrogenating Butane - S/020/60/133/006/007/016 Butylene Mixtures on an Aluminum Chromium B016/Bo6o Catalyst The authors draw the conclusion that the catalyst used is specific for the dehydrogenation of saturated hydrocarbons (butane). There are 2 figures, 4 tables, and 6 Soviet references. ASSOCIATION: Institut organicheskoy khimii im. N. D. Zelinskogo Akademii nauk SSSR (institute of Organic Chemistry inani 11. D. ZelinaKi_y_of_the Academy of Sciences USsR) SUDIMITTED. March 26, 1960 Card 3/3 8h577 S/020/60/134/001/036/038/XX B004/Bo64 AUTHORS., Balandin, A. A., Academiciano RoghdeatXonakaya. Is Lot a nd _A. Blinkin"7r TITLE: Effect of the Treatment of Chromium Oxide Catalysts With Gases Under Various Conditions Upon Their Catalytic and Magnetic Properties PERIODICAL: Doklady Akademil nauk SSSR, 1960, Vol. 154, Ho. It pp. 110-113 TEXT; The authors wanted to find a relation between the magnetic sus- ceptibility X and the catalytic. properties in the Cr 0 catalyst treated 2 3 by various methods. The chromium hydroxide prepared from chromium nitrate, degree of purity "pro analysill, was treated as follows: Card 1/5 8h577 Effect of the Treatment of Chromium Oxide S/020/60/134/001/036 /038 /XX Catalysts With Gases Under Various Condi- B004/B064 tions Upon Their Catalytic and Magnetic Properties Cr2 03(VII) H2t5000C It h 10 h Cr 203(1) H Cr2 03(VIII) h 0 h H, 20 h ir,500 C H, 20 h/ ~i 10 h Cr20 3(IX) Cr 203(V) Cr(OH)3 N 2,5000C air, 500 0C' 10 h 10 h C r 2 03(n) Cr 203(111) OOG H2,5000C air 600 0C Ir I 1 h h rh C ~r_ Cr 2 03(iv) Cr 2 3 (VI) Cr 0 was treated with atomic hydrogen in aspectal apparatus (Fig. 2 3 H formed in vacuum at a voltage of 10,000 - 12,000 v and 1 2 mm Hg, and was sucked through the Cr 203sample. Sabsequently, catalysis was made in the sum* apparatus under the exclusion of air. Table 1 shows the tempera- ture dependence of X for the various C 20, preparations. Card 2/5 8h577 Effeet of the Treatment of Chromium Oxide S/020/60/134/001/036/038/xx Catalysts With gases Under Various Condi- B004/Bo64 tions Upon Their Catalytic and Magnetic Properties No. of sample )(010 200 C1 500C 800C I 1600CI ff,K1 PB N of sample X 010() 200cl 50'C1 800CI 1600C 1 24.0 25-3 24-4 23.3 VI 24.4 25.2 23.4 23.0 11 23.0 25.0 23.6 22.9 VII 92.0 - - - 111 340.0 - - - Is 96..o - IV 28.0 - 25.8 24.0 500 3.7 Ila 21.8 - 2291 20.8 V 22.8 24.3 23.3 22.8 The samples Is. and Ila were prepared from impure Cr 0 The ferromagnetism of sample Is is caused by impurities. The ferromagniti;m of III is-, hew. ever, not due to impurities and occurs only when Cr 0 is treated with 2 3 air at 6000C. The nuthors assume that CrO 2' forms in low yields. This now phase could, however, not be confirmed by X-ray- and electron diffraction pictures. Table 2 gives the results of the catalytic decomposition of isopropanol and the dehydrogenation of cyclohexane by means of the samples. Card 3/5 8h577- Effect of the Treatment of Chromium Oxide S/020160/134/001/036/038/XX Catalysts With Gases Under Various B004/BO64 Conditions Upon Their Catalytic and Magnetic Properties Different activity, selectivity, and activation energy were found to exist The dehydrogenation of C 6H12 was reduced both in the ferromagnetie sample III and the antiferromagnetio sample IX, and the dehydration of I-C 3 H7 OR increased. Herefrom, the authors infer the presence of hydroxyl groups on the catalyst surface. Their origin Is, for IX, explained by the chemo- sorption of atomic H, for III by the interaction of CrO. with H. forming at the beginning of the reaction. The inactivation of sample I bg treat- men% with water vapor and subsequent regeneration with H2 at 500 C con- firmed the inhibiting effect. of the OR group upon the dehydrogenation of C6Hi2# The authors came to the result that it is not possible to draw conclusions from the magnetic and electrical properties upon the surface structure that determines the catalytical properties only. There are I figure, 2 tables, and 13 references: 5 Soviet, 5 US, 3 British, and 2 German. Card 4/5 84577 Effect of the Treatment of Chromium Oxide S/020/6O/t34/OO1/O36/O36/XX Catalysts With Gases Under Various B004/BO64 Conditions Upon Their Catalytic and Magnetic Properties ASSOCIATION: Institut organicheakoy kh1m1i im. N. D. Zelinskogo kkademil nauk SSSR (Institute of Organic Chemistry imeni N. D. Zelinskiy of the Academy of ScieRces, USSR) SUBMITTED: May 17, 1960 Card 5/5 S/020/60/134/002/039/041XX B0000611 AUTHORS: Vasserberg, V. E., BAlp_ndin, A. As, Academician, and Georgiyevakaya, Tb V. TITLE: Conjugate Dehydration of Alcohols in an Adsorbed Layer 3n Aluminum Oxide Catalysts PERIODICLLI Doklady kkademii nauk SSSR, 1960, Vol- 134, NO* 2, PP. 371-373 TEXT; In studying the dehydration of alcohols In A1203 (Refs- 1-3) the authors observed different reaction rates in catalysts which had been prepared in different ways. In the present paper, they examined such catalysts. No. 1: A1203 precipitated by moans of WaOR at pH - 6031 No. 2: A1203 obtained by hydrolysis of aluminum isopropylatel No. 3: precipitated from aluminate solution by means Of C02 at OOC. First, the different activities of the catalysts in the dehydration Of C2Hr)OH and 'GO-C3H7OH were confirmed. Furthermore, the dehydration of Isopropanol in the presence of ethanol. was studied. Since the dehydration of isopropancl Card 1/5 Conjugate Dehydration of Alcohols in an S/020J60/134/002/039/041XX Adsorbed Layer on Aluminum Oxide Catalysts B004/BO67 proceeds rapidly already at 120 - 1500C, whereas ethanol d',es not yet react at this temperature, the dehydration of isopropyl alcohol was studied on a catalyst whose surface was covered with ethanol which wa* considered an inert subritance. Furthermore, water and methanol were used as inert substances. The effects of these Inert substances were fcund tG be different. Water, methanol, or ethanol adsorbed in equal quantities reduced the dehydration of isopropanol to a difforont degree) this reduction depending also on the method of catallyst preparation. Sinco this could not be explained by a blocking of the catalyst surface, the authors thoroughly studied the kinetics of ':he joint decomposition of isopropanol and ethanol. First, ethanol was adsorbed at 120 - 1500C, thon isopropanol, and the pressure rise of the olefin formed was measured. It was found that the pressure p oetheor a 0.6 - 0.7 mm Hg calculated fcr a 100% decomposition of isopropanol was mu.,h higher (p 00~'Xp -i.i - i.6mm 11~) and increased in the course of reaction. H-nce, the authors con~~Iude that when ethanol and ioopropanol are jointly adsorbed on the catalyst, a conjugate dehydration occurs. The dekydratlon of ethanol wan strongly Card 2/3 Conjugate Dehydration of Alcohols in an Adenrbed Layer on Aluminum Oxide Catalysts S/020/60/134/002/039/041XX MOW accelerated (compared with that of pure ethanol), while that of isopropanol was delayed. The authors therefore conclude that the complexes adsorbed on the catalyst surface are not isolated but react with neighboring molecules, and are capable of forming combinod voml4oxotv (ethanol-iuopropanol and mothanol-toopropanol aomploxva) which decompose moro alowly than tho ioopropanol complexes. There are 3 figures and 3 references: 2 Soviet and 1 German. ASSOQIATION: Inatitut or-anichookoy khimii im. H. D. Zelinskogo A.kadem"i nauk SSSR ~Inetitute of Organic Chemistry imeni N. D. I "elinskiy of the Academy of Sciences USSR) SUBMITTED: May 17, 1960 Card 3/3 20 S /0: /60/134/003/030/033/XX B004/B064 AUTHORS% BalanAin_L_A. A., Academician, ToletopyatoyalA.A., and __U_8~9 S~ve TITLE: The Catalytic Activitylof Tungsten Pentoxide 7-1 PERIODICAL: Doklady kkademii nauk SSSR, 19609 Vol. 1~41 No. )I pp. 625 - 628 TEXT: The authors investigated the dehydration of ethanoll isopropanol, t-butanol, oyclohexanol, , and Tetralin th W 0 under iso- .1 m~~anol 1 7w'. 2 5 thermal conditions. Blue W 205 was obtained from tungetic acid at 350 - 4000C in an air current. First, WO was formed and then reduced to 3 W20 5 during the reaction with the alcohols at 200 - 3000C. The reaction apparatus operated continuously, and the liquid substances were auto- matically added. The gaseous products were oollected in an automatic Patrikeyev gasometer, and analyzed with a BTA (VTI) apparatus or ohroma- tographically, In the liquid produot of catalysis, the amount of Card 1/4 The Catalytic Activity of Tungsten S/02q6O/134/003/C30/033/XX Pentoxide B004/BO64 unsaturated hydrocarbons was determined by the method of Kaufman-Gall- porn. Since the ondothermia effect of reaction affected the results of measurement,, the catalyst was diluted in a ratio of 2 : 3 with quartz of the same grain size, the alcohol with water orwith the corresponding unsaturated hydrocarbon. Under these oonditlona, the process was Iso- thermal. By determining the apparent activation energy (Table 1) it was found that the primary alcohols were dehydrated with the same energies (approximately 30 ktal/mole), that the activation energy of the second- ary alcohols was about 6 kcal/sole lower than that of the primary onset and that the activation energy of the tertiary alcohol was approximately 6 kcal/mole lower than that of the secondary ones. The reaction constant and the relative adsorption coefficients z 2 and z5 of water and the un- saturated hydrocarbon were computed (Table 2) by Balandin's method (Rof. 3) with reference to the adsorption coefficient of alcohol. Check- ing by introduction of the experimental. data into Balandinla equation confirmed the validity of this equation (Table 31. Table 4 gives the actual activation coefficients for isopropanol and n-butanol; which are approximately 3 koal/mole higher than the apparent ones. For the binding Card 2/4 The Catalytic Activity of Tungsten e/020/60/1 34/003/0 30/C 33/XX Pentoxide B004/Bo64 "C-C I(CH they affect the binding energy betwein the C, H, and 0 H11 I[H(CH 3) ' atoms and the catalyst. The authors mention a paper by IH OfH 1. Yo. Adadurov and P. Ta. Krayniy. There are 5 tables and 8 Soviet references. ASSOCIATION: Mookovskiy gosudarstvennyy universitet im. H.V. Lomonosova, (Moscow state University iment X. gonoftay) SUBMITTED: May 17, 1960 Card 4/4 S/062/60/000/03/02/007 BOOS/B000 AUTHORS: Proydlin, L. Kh., Balandin, A. As, Nazarova, N. Me kylation of Isobutaae'~~ TITLE: Catalytic Al y Ethylene at High Ttoporaturis and Under Fr-essure ' PERIODIC-kL-. lavestiya Akademil nauk SBSR* Otdelenlys khimicbeekikh naukt 1960# No. 3t PPw 409-412 TEET: The alkylation of isobutans in the presence of aluminum oxide at high temperatures was investigated. The experiments were carried out in the oontinuous-flow unit described in Ref. 5. The reaction conditions, degree of ethylene transfornationp and alkylate yields are given in Table 1. The characteristics of the various alkylats fractions obtained in experiments No. 2 and 4 are shown In Table 2. The fractionation curve of the catalyzate obtained In experiment No- 4 is represented In Fig. 1. Experimental results show that, ethylene and propylene react mainly with the tertiary carbon atom of isobutane, and only to a lesser extent with its primary carbon atoms, In these reactions, 2#2-dimethyl butane and Card 1/2 Catalytic Alkylation of Isobutans, by 8/062j6o/OOO/O3/02/007 Ethylene at High Temperatures and Under BOOS/BOO6 Pressure 2-methyl pentanst respectively, are formed.. An octane fraction was also obtained, which was identified to consist mainly of an alkylation product of 2#2-dinothyl butane. Alkylation at this stage, however# proceeds via the primary carbon atom at the unbranched end of the carbon chain. This fact confirms the stopwise character of the alkylation process established previous ly (Ref. 6), It was found that in the presence of aluminum oxide an olefin (ethylene, propylene) in added to the tertiary carbon atom of isobutane less easily than to the secondary carbon atom of n-butane. Yu. Pe Yegorov and K, 0. Gayyoronska analyzed the: fractions by means of their Haman spectra. There are I figure, 2 tables, and 11 references, 6 of which are Soviet. ASSOCIATION: Inet1tut organichookoy khisti in. N, D. Zelinskogo Akademii nauk SSSR (Institute of Organic Chemistry imeni N9 D.--- Zelinskiy of the Academy, of Sciences# USSR) SUBMITTED: July 16f 1958 Card 2/2 5 13000 05 SO'1/62-60- 1 -51/37 AUTHORS: SteFner, G., Balandin, A. A., Iludenko, A P. TITALE: Influence of Different Stages of Polycondensation of the Products of Gataly'.Ilo Deccmposition of Ethyl Alcohol on the Rate of Carbonizatlon PERiODICAL: Izvestiya Akademil nauk SSSR. Otdelenlye khtmicheskikh nauk, ig6o, Nr 1, pp 24-30 (USSR) ABSTRACT: This Is a contInti3tion of' the author's previous work (Izv. AN SSSR, Chem. Ed., 1959, 1896) on the mechanism of carbonization in the dec-omposition of ethyl alcohol over copper-allIca. Experimental data presented In thIs paper confIvm previous concluslons (see above refevence) concerning the mechanism of carbonization which accompanies catalyt.,Ic decomposition of ethyl alcohol. Carbon.1,zatlon is considered to be a multi- stage polycondensation of ethyl alcohol and the pro- ducts of its catalytic decomposition. The so-called Card 1/2 low temperature carbonization (below 6000) proceeds Influence of DIVIerent Stages of Polycondensat-lon or the Products of' Catalytic Decomposition of Ethy'A Alcohol on the Rate of Carbonization ASSOCIATION: SUBMITTED: Y8059 S07/6'2-60- 1 -5/37 through dehydrogenation of ethyl alcohol. Accele- ratlon or slowing down of' ethy, alcohol decompos',tion (dehydrogenation and dehydratlon) causes a change In the rate of carboillzation. There are 4 f,-gure3; and 11 references, 1 German, 10 Soviet. M. V. Lomonooov Moscow State Uri versity (Ywkovski gosudav-stvennyy unIversitet Imer! M. V. Lomonosova May 4. Card 2_12 5 SoV/6-2-60- & -4/3'7 AUTPORS.- Ft-eylilin. L. Kh., BalandIrl, A. A., BorUnova, N. V., Agronomov, A. Ye. TITLE: Concei-ning Connections Between the Microstructure of' Aluminum Oxide and Activity of Mckel-Alumina Catalysts of Various Nickel Content PERIODICAL: Izvestlya Akademil. nauk SSSR. Otdelenlye khlm'.cheskikh nauk, 1960, Nr 1, pp 21-2,~ (USSR) ABSTRACT: This paper presents the results of Investigations of the connection between the microstructure of aluminum oxide and activity of nickel-alumlna catalysts of various Ni content. Th~ catalysts were prepared: by impregnation of alumina with Nl.(NO,);,, and reduction 0 with Hn at 350 . The alumina for the catalysts 1 and 2 Isee Table) was prepated by Ignition of com- 0 rrercial aluminum oxide at 500 . Alumina for catalyst I w4th ammonia. 3 was prepared by treatment of klk'NO-,,, 3 Card 1/4 . Activity of the catalysts was determined by the degree Concerning ConneCLIOtls Between me Microstructure of Aluminum Oxide and Act',vity of Nickel-Alumina Catalysts of Various Nickel Content c)-A SOV/62-60-1-4/37 of' cyclohexane del-,ydrogenation. The results are shown in T,:_ble 1. The following conclusions were made! Propertles of' nIckel-alumina catalysts of various Nt content depend on the character of microstructure of alumina. Catalyst3 prepared with large-pore alumina, conta-Ining 5-10% Ni, are of high 'Irld practically the 3ame activity. Activity of the L catalyst. containing 50% N1. in considerabl,y lower. Catalysts prepared with fine-pore alumina, and containing 5, 10, and 30% Ni are of a low activity and unstable. There are I table; and 9 references, I U.S., and 8 Soviet. The U.S. reference Is: S. Brunauev, P. Emmet, A. Teller, J. Am. Chem. Soc., 62, 1723 (1940). ASSOCIATION: N. D, Zelin.ukiy Institute of Organic Chemistry Academy of Sciences USSR and M. V, Lorronosov voscow State University T Anstitut organicheskoy khtmi! Imen'. N. D. Zelinskogo Akademil nauk SSSR., Moskovskly gosudarstvennyy universitet iment M. V. Lomonosova) SUBMITTED: May 5. 1953 Card 2/4 concel,111111, callnect-jolm the m1crostmictuve of Almninum OxI(le and Activity of Nlelwl-Ahnfltm Citnlyst..-, of Vat,loiju Nickel Conteut Table 1 sov/62-6o-i-4/37 175 1 oil i tAlk 17 .5 211 -It w I t,2 -f.3 4,8 typ'll lo W1,2 1.01 2rw too 41, 3. 3 1 .5 U'll rl-, i v zx 4,7 3M Il- %1 4 20 3711 11 - - it 1 22 3 7 1 48,1 fit? 10 21 X,l V I I -X) 21) 3 211 *_'70 (Key to Table on Cavd Concerultir, Connections Bet"weet) the 7.5058 Mict-0-11tructure of Aluminum Oxide and sov/62-6o-i-11/37 Activity of' Nickel -A lumina Catnlynts of Varlou,", Nickel Content Key to Table 1: (a) numl,er; (b) experiment; (c) sample of aluminum oxide; (d)-N1 content In % by weight; (e) duration of reduction with H2 in hr; (f) specific SUrfACe iU.M2/,,; W range of pore size in A; (h) maxlrnum distribution of volxunea of pores along the radlus In A; (1) total amount of benzene absorbed on saturation, in millimoles/g; (J) degree of cyclohexane dehydvogenation In % of theoretical, Card 4/4 5 - -.5200 AUTHORSt Brimov, 1. 1., Polkovulkov, 13. D. TITLE i Kineticn of' 2-YAnylpyvidine Ilydvoir(,mation Over Raney's Catalynt PERIODICAL: Izventlya Akademill nauk SASS11. Otdolonlye Ichimi- cheakikh nauk, 1960, Ni, 1, PI) 15-20 (IJSSR) ABSTRACT: Thin paper prenentu experimental data on kinetics of 2-vIny1pyr1dIne hydi-ogenittlon over Rimey nickel In 96% ethyl al(!Ohol at te-tweratures from 5 to 400, under atmosphertc pressure. 'I'le esultil obtained are nhown In the figuves, where Aj 0 (a) In the total. volume t 6V t of hydrogen absorbed and (b) the volmne 2 Of' 112 absovbed, mid re(hwe-l to ntandard conditions. Erfect, of rtyvene concentrallon on the vate of lt:i hYdVOj'Cnn1,IOn Wa9 11,10 -Itlldled; L-110 reSUltS ShOWn Card 1p In FIF, 6. Kineticu of 2-Vinylpyvidine Ilydvogena t ton 78057 0-ier Rancylto CntAyst la 6 Fig . I . Effect of 2-vIn IPYvIdIne concen trat toll oil the rate or hytivogentat ~- 0.398,1 g; (2) 0.79,16 g; (3) 1.1949 g (a and b given it) text). Fig. 2. Effect of the producta of reaction on the rate of 2-vinylp vidine hydrogenation. 11) without addition of tile Product s; ~21~ on repeated hydilogenation; 3 with ndditioti of 2 rill I'll X V j# Av IV Alv Card VI of 2-ethylpyi-Iditio (a and 1) alto explained In text). Killet-1co of* -'-Vtliy.lpyv1,11,tw Ovel. Ralley's cat-aly.A. Fig. 5. ErVect of' inolvent on hydrogenation of' 2-vitlylpyridine: (1) in 96% 0211 5011; (2) '11 CO(J); (A. and b given in tcxt~- v v fit a in w of w rv /a OR Flg. 4 6 C, 1A I'd 3/ 7 (captlall for loig'. I; oil Cant lilt Kinet-Ilog of' C-.1-Vinylpyridine Hydvoi-,cuntion Over Raney's Catilytit SOV;~i), -60-1-3/37 Fig. 4. Kinetica cut-ves of' 2-vinylpyridine hydro- genatJon at various t~cmpevatuves: (1) 5.40; (2) 100; (3) 15'; (14 ) 20'; (t . 0 0 .5) 25 (6) 500; (7) 550; (8) 40 (a and b.given itt text). j4 a j Fig. 5. Dependence of the log of rate constant on temperature. Card ell N N ,V . . . . . . . J71 rs IV am In ja jul w JR ju ju I T o Kinetic-11 Or ','-VII'Yl PYPI tilOo 11Y(lV(Wf!W'l 1 11 Ovel. Ratley"I Cat"llyst'181- .01 SOVA2-6o-i-3/37 u lu Fi P. 6. Hydro enation or stTrene. (1) 0-3875 V; L J2~ O:p7r- 0-7750 9; 4) 0-4155 C,; (5) 0.111 5 gi 6 0 ~5" in this case another cataiyat was ui3edl a and b given In text). Card 5P Kinetics of ~2-Vinylpyrldine Hydrogenation '(8057 Over Raney',; Catalyst SOV/62-6o-1-3/37 The following conclusions were made: Hydrogenation of 2-vinylpyrid1ne proceedo rapidly In 04 ethyl alcohol; In benzene the reaction is about 1.6 times slower. The rate of reaction increases about 3 times with in- 0 creasing temperature from 5 to 40 . At these tempera- turen the reacl.-.Ion follows first order kinetics. The true energy of' :,:7tivation In equal to 5.6 kcal/mole. Hydrogenation ol" styrene under similar conditiono is also a first ordev reaction. Substitution of one hydrogen atom In ethylene by an CL-pyrldyl radical has the same effect on the rate of hydrogenation over Raney nickel as substitution by a phenyl radical. There are 5 tables; 6 figures; and 7 references., I U.S., 1 Polish, 5 Soviet. The U.S. reference is: E. C. D. Craig, J. Am. Chem. Soc., 70, 3138 (1948). card. 6p GregF Kinetics of 2-Vinylpyridine Hydrogenation 78057 Over Raney's Catalyst sov/62-6o-i-3/37 ASSOCIATION: N. D. ZelInskly Institute of Organic Chemistry Academy of Sciences USSR (Inatitut organicheskoy khtmit Imeni N. D. Zelinskogo Alcademil nauk SSSR) SUMMED: April 25, 195B Card 7/7 S/595/6o/ooo/(,)(- c/oi.o/oi Ii E075/0435 '101,110t?j: Bogdanova, O.K., 11alandin. A.A., VX-Iryshnil,ova, T.11. TIT LE: Dohydrogenation kinetics of othyl bonzene to styrone and isopropyl benzene to a-methylstyrono SOURCE: Vaesoyuz;oyo noveshchaniye po Ichi-miclicskoy percrabotke neftyanykh uglevodorodov v poluprodulcty dlYa sintozn volokon i plastichoshild, Tlakui 1957. Baku, Izd-vo Ali, Azorb. SSR, 1960, 241-247 TZ*,%T: The object of the work is a study of the kinctics of dchydrogonation of othyl and isopropyl benzene; it is a continuation or the authors.' investigations on the orract or molecular structure on dehydrogenation hinotics. The experimental work was carried out by passage through an electrically heated glass tube conta:hing an oxide catalyst on a screen, at atmospheric pressure. Dilution ratios of 1:3 to 5 and 1:2 were used for ethyl and propyl benzene respectively; the steam was superheated to 3000C. Liquid and gaseous product fractions were analysed and good agreement between hydrogen and unsaturated hydrocarbons was found. The kinetics of isopropyl benzene dohydrogonation were studied at three food rates in the Card 1/ 4 Dehydrogenation kinetics'... temperature range of 500 to 5500C, rate hydrogen produced. A table of reaction given.. Under identical conditions the binary mixtures of isopropyl benzene nndits a-methylstyrono, were studied to obtain the catalyst from S/595/60/000/000/010/014 E075/E435 being measured by the product analysis in dehydrogenation rate of reaction product, adsorption coefficients an where mo = number of moles reaction product for food of pure starting material; in w number of moles reaction product for fece, of mixture; p = % of starting material in mixture. The relative adsorption coefficient of hydrogen was found to W, 0.7 and was independent of temperature. The relative adsorption coefficient of a-methylstyrono falls with tomperature, a table and graph are given. Plotting the log of the adsorption coefficient against the reciprocal of the absolute temperature gives-a straight line. The reaction rate was calculated by using the general equation for catalytic reactions derived by A.A.Balandin Olef.2: Card 2/4 S/595/60/000/00o/olo/o14 Dehydrogenation kinetics ... E075/E435 ZhOKh, 19420 12, 156) j2,403(z,+r4)AjjIg- (2) Al-m The calculated reaction rate has been plotted against the reciprocal of the absolute temp .erature and the points lie on a straight line. The activation energy has been calculated as 30.3 Kcals/mol. A series of experiments with catalyst particles varying in size from 1*5 to 5 mm was carried out; particle size had no effect on reaction rAtt. The dehydrogenation of ethyl benzene was studied in the range or 520 to 5600C. The results were similar to those obtained with iaopropyl benzene but the adsorption costricientx and reaction rates were considerably lower. Figures for picluct analysist adsorption coefficients and reaction rates are give-t. The higher rates for isopropyl benzene are considered to ja due to the introduction of a mothyl group into the alpha position. At higher temperatures there is a considerable increase in conversion; in,the 58o to 6oo*C range at rates. of 800 to 1000 ml/litre catalyst/hour, yield of' styrene Card 3/11 I S/595/60/000/000/010/014 Dehydrogenation kinetics ... E075/E435 and methyletyrone reached 70 to 83%, which is near to equilibrium. This in of considerable practical interest. Increase of feed rate towards 1400 to 2000 ml/litro catalyst/hour led to a slow decrease in yield. At these higher temperatures the reAction rate~plot changes but the plot of Log K against the reciprocal of the-absolute temperature still falls on a straight line of a different slope. The activation energies become 18.8 and'19.5 Kcals for isopropyl and ethyl benzene respectively. (Abstractor's notes St::m.ldsorption was neglected in all reaction rate calculati a The dehydrogenation of ethyl cyclohoxane was investigated. The low rate of reaction sliows that in tho absonce of conjugation, the dehydrogenation of the side chain is slowed down, There are 5 figures, Is t.%bles and 5 raferencest 2 Soviet-bloc and 3 non-Soviet-bloc. Tho reference to an English language publication reads as follows: ner.4s Gilliland E.K. Chem. Eng. News. 23, 129 (1945). Card-4/4 s/595/60/000/000/009/014 E134/E485 AUTHORS: JDAjAndin, A.A., nogdanova, O.K., Shcheglova, A.P. TITLEs Catalytic dehydrogonation of isopentenes to isoprens SOURCE: Vaesoyuznoye soveshchanlye po khimichaskoy pererabotke neftyanykh uglevodorodov v poluprodukty dlya sinteza volokon i plasticheakikh mass. Baku, 1957. Baku, Izd-vo AN A.zerb. SSR, 1960. 233-239 TEXT: The paper in concerned with the catalytic dehydrogenation of isopentenes and the conversion of isopentant-isopentenes inixtures to isoprene as part of the general problem of ituAnuracture of isoprene rubber from the isopentane fraction in petroleum. The authors studied dehydrogenation of isopentene and isopentans-isopentenes mixtures in the presence of steam at atmospheric pressure. Artificial inixttires eta well as mixtures obtained by dehydrogenation of isopentane on an Al-Cr- catalyst were used. The experiments were carried out by continuous flow over a mixed oxide catalyst. Work on isopentone was concerned with the effect of temperature, flow rate and steam dilution ratio on isoprene yield. Yield based on isopentene feed increased from 14-5 to 36% as temperature rose from 540 to 620"C but dropped from Card I/ I S/595/60/000/000/009/014 Catalytic dehydrogenation E134/E485 92 to 85% of'the reacted isopentene, Curves showing the effect of temperature and flow rate on isoprene yield are given (Fig,I and Beat dilution ratios are It2 or 113 by weight. ;% complete tilass balance for operation with a 113 ratio at 600'C at a rate of 4500 g/litre ca.taly:it/hour is given. Under these cir:uttistan[-4.%-~ yield is 28 to 30% on feed and 88 to. 92% on reacted Loopentene. The removal of carbon from the catalyst in the form of carbon dioxide makes prolonged reaction without regeneration possiblt-- The results show that the catalyst acts selectively. InvestIgatIons of mixtures 55% isopentarke-45% Isopentene welle carried out under identizal tonditions to study the effe:t of flo- rate and temperature. Conversion of mixtur-m and yield of -1joprert increased with rising temperature but yield of isoprene ba,'-ed -Yi reacted Isopentene dropped from 94 to 86.5%, A full analyiia is given, At 600"C, a flow rate of 4400 g/litye cataly&t/hour ard 1;3 dilution ratio yield of isoprene on iaopentent present wa6 38 to 40% and was more than 90% of the rea-ted isopentene. Undt~?- identical conditions dehydrogenation of isopentana ro iscptnten,, only took plac--* tc~ the extent of q to ~.I',ere is no dire,,t Card 2/4 ~ Catalytic dehydrogenation ... conversion to laoprene. Results with mixtures obtained by dehydrogonation of isopentane over an Al-Cr catalyst wex-1, to those with synthetic mixtures. Full analysis sooving efrect of now rate and toml)orature is given. Tho degree of convc:r!,-.1o,I decreases with increasing flow rate. The killotica of Uic reaction were investigated in the 530 to 5300C range with a stoam dilution ratio of 122 and hourly flow rates of 51.c,,(-;- to 7000 g/litre catalyst/hour. Reaction rate in given by aquation of the following type djc d.v EA,Itz:j A+23 V: The adsorption coefficients z were deternined axpori?-,entally by measuring the rato of dehydrogenation of binary mixtures of the starting material and the reaction products and were calculatcd Card E134/L485 Catalytic dehydrogenatio6 ... where me - nwnbor of mola of reaction prodtict for feed of pure starting material; m - numbor of mols of reactioli product for food of mixture; p - percent of reacting material in initial mixture, The hydrogen adsorption coafficients rcmaincd cn-.i3tant at 0.83. The isoprene adsorption coefficients droppe(l fro;~, ',^.7 to 2-8 (z2) between 530 and.580-C. The reaction rates were calculated using tho adsorption coefficients and the plot of log N against the reciprocal of the absolute temperature gave a str,iight line. The activation energy was calculated as 23300 calories/ raolecule. The mixtures used in the tests were produced in tl,.c laboratory of Academician B.A.Kazanalciy and Corresponding N.I.Shuykin. There are 3 figures, 4 tables and 6 reforences: 2,Soviet-bloc and 4 non-Soviet-bloc. The four references to English language publications read as follows: Ref.3: U3 Patent 2440471, 1948; C.A.42, 54 4, 1948; Raf.h: US Patent 2442319, C.A.42, 61o6, 1948; Ref.5: Grosse A., Morell J.C., Navity J.."-*,. Industr. Engng. Chem. 32, 309, 1940; Ref.6: ',,,avity JJII.. Zetterholm E.E. Trans. Am. Inst. Chem. Engn., 40, 1944, 1;73. Card" 4/0 11 41 U V6 v I# f WANDINs A. A. *Sow Problams of Use of Catalysis in Chemical Technology* report presented at the 09neral Conference of the Division of Chemical Sciences of the Academy of Sciences, USSR; 27-28 October 1960 Sat Izvestiya Akadexii nauk SSSRp otdoloni" khimicbeskikh nauk,,Noe 29 1, MOSCOW, Pages 378-3M' 9p 31 Sol ;Iq Ral It is -tF f gig P. 3 8/062/61/000/001/004/016 B101/B220 AUTHORS: Tolstopyatovaj As Att Konenko, I* R., and Balandin# A. A* TITLE: Kinetics of dehydrogenation and dehydration of isopropyl alcohol on titanium dioxid* (anatise) PERIODICAL: livestiya Akademii nauk SSSR. Otdel*niy* khimiohtskikh naukt noo 1, 1961t 38-44 TEM By way of introduction the author& offer a survey of reports dealing with the catalytic efficacy of T102t and then report on the dehydrogenation and dehydration of leopropyl alcohol on anatass. Regarding the production of the catalyst they refer to another report published by then* For the verification of the kinetics of monomolecular hottrogensous-oat lytic raactionT)mthey roce*d from the equation k N A1 (Z2-Z3)InA,7(A,,-m)-(Z2+Z,- (13. Al is the volume of alcohol converted per minute, which is Introduced at the rate vi m is the volume of propylene (or hydrogen) formed per minutel Z2t Z3 are the relative adsorption coefficients of the reaction products (hydrogen and acetone Card 1/3 8/062/61/000/001/004/016 Kinetics of dehydrogenation and dehydration... B101/B220 in the cast of dehydrogonationi propylens and water in the case of dehydration)l Z2 and Z~. were calculated from Z - (mo/m-')/(Ioo/p-') (2), where mo, m are the amounts of the reaction products resulting on the passage of pure alcohol (mo) and on the passage of a p molar mixture with the reaction product, Sinc# Z is the equilibrium constant of the displacement of the isopropyl alcohol from the catalytic centers by the reaction products, it was possible to calculate also A? of the free energyj 63 of entropy, and AH of the heat content. The adsorption coefficient Z,, of acetone was found to be highly dependent on temperature and much less so on the degree to which the catalyst was covered with carbon. The following is indicated for not carbonized T1021 Za - 2.4 at 2620C1 1.7 at 2940Ct 1o2 at 3100C. For carbonized TiO2 these values amounted to 2.7, 1.8 and 0,9. The adsorption coefficient Zff, of the hydrogen remains, constantly 0.9 In the range of 276-3060C. Moreover, it was found that ZR20 " 1.9 at 2820C, 1.4 at 2940C, and 0.9 at 3100C. whereas Zpropylene remains a constant 0.2 in the temperature range of 300-33000. A. M. Rubinshteyn and S. 0. Kulikov are mentioned. Card 2/3 S10621611000100110041016 Kinetics of dehydrogenation and dehydration*.. B101/B220 There are I figurej 6 tables, and 24.r9feroncost 8 Soviet-bloo and 13 non-Soviet-blooo ASSOCIATIONt Institut organioheskoy khimii im. N'. D. Zelinskogo Akadsmii nauk SSSR (Institute of Organic Chemistry imeni N. D. Zelinekiy, Academy of Sciences USSR) SUBMITTED: June 29t 1959 Card 3/3 S/062/61/000/001/005/016 B101/B220 AUTHORSt Balandin, A. A., Konenko, Is R., and Tolstopyatovat A. A. TITLE: Effect of the method of production on the catalytic proper- ties of titanium dioxide In the reaction with ethyl alcohol, isopropyl alcohol# and. oyclohoxane PERIODICAL: Isvestlys, Akademli nauk SSSR. Otdoleniye khIm1ch9skIkh nauk, no. 1, 19611 45-50 TEXT: The authors were concerned with the investigation of the catalytic properties of titanium dioxide. Here, they studied the dependence of those properties on the method of TiO 2 synthesis. Four specimens were used. Catalyst 1 (anatalle), whom# produotion is desorib*d in Refs 1, a previous report of the authoral catalyst 2, obtained by hydrolysis of TiC14 by mans of ammonia solution in a weakly &aid medium at room tesperaturel catalyst 3, obtained by precipitation of Ti(OH) 5 from TiCl3 by- means of ammonia at room temperature and conversion to Ti(OH) 4 which occurred automatically Cord 1/5 Effoot of the method of productions... 8/062JO/000/001/005M6 B101/B220 while washing the prooipitatel catalyst 4t obtained by kydmjrsisaf ethyl ortho. tits.nate by means of distilled water at room temperature. The further treatment of the hydroxides for the purpose of obtaining TIO2 was per- formed according to Ref. 1. Ethanol reacted with these catalzats accord- ing to three reactions: a) dehydrogenation, b) dehydration, c) hydrogena- tion of the, resulting ethylene. Moreover, up to 2A ethyl acetate was formed on all four catalysts. The reaction of isoprepanol corresponded to data mentioned in Refs 1. Due to the growing accumulation of carbon on the catalyst, the rate of dehydration increasest whereas that of do- hydrogenation deofeases. Cyclohexane is dehydrogenated on all four catalysts. The differences between the catalysts regarding the activation energy E and the factor k0 of the Arrhenius equation are listed in Table 8. The linear function log ko W as + b (a, b - constants) is conserved for all reactions. A. M. Rubinshtsyn and S. G. Kulikov are mentioned. There are 2 figures, 8 tables, and 6 referencest 4 Soviet-bloc and 2 non-Soviet- bloc. Card 2/5 Effect of the method of production*,. S/062/6i/000/001/005/016 3101/A220 ASSOCIATION: Institut organichookoy khImii im. N. D. Zelinskogo Akademli nauk SSSR (Institute of Organic Chemistry imetit X. D. Zelinskiyj Academy of Sciences USSR) SMITTED: July 9t 1959 Card 3/5 Effeot of the method of produetion... S/06 61/000/001/005/016 BlOIYB220 Bananas two" Spufoloutnut 1100 as staxqRSM sulprok allassuou 4 f, f. ones/ N A. cw" I"" j X.TvA 9MY" ta "MAN. ,at". 1 1 2 LS N. 0. tfNAPMHNSAUXI OTHRODOM OMPTS 22,8 20,4 014 4, 0. MAPATAUR IT"Osom c""PTA 25,0 23,4 0,0 n.0 ericAparaut nionponuowiv cnopTs. 22.0 9.1 26.2 1 4, 0: 1# 11APOremitu"A STMe"s r 21,2 24.2 13,0 14 M.0 f( erHAPMR11MUIR ttHKAOMCANA In t9,O H.7 21.0 0: 1 truApommmsaamn ff3onponmaotom ka emp" 911 t0.4 - Vit 0 OeMAPATAtUtit "MPORKAOSOM Cn*PT& 24.4 i5.8 - 411: 0: kAel'"Aporemouitun msonponnikogoro cnllpT4 11.9 - it. 0. If Acrupor"onaxt tututomKcau 25,2 - 14. 0* IjJlerAAPOrtwuus npowowo enpra 10.4 - ,y W. 0. AentAP&TSURA M.nPon"09" CIMPTS 12,1 - Card 4/5 12,4 t.0 - 100 t,040t 1.4-101 1.2-104 t2,5 t,5401 5,6401 3.7-101 4,4. up 17 2 3 7-tO* 9,1-1(P 1.0-1010 2.8-101 10:8 1:8.101 t,0. 101 t 3, 104 2,7.10% t5,0 8,7. W$ 5340' t,3. tOl 3,5404 - 1.04104 2.2404 - 4,5409 6.240% I 4',9401 - 2.3. t0l - 4,5. 10t - Effect of.the method of 4 8/062J61/000/001/005/016 B101IB220 2.84 2,8t 3.01 3.05 2.73 2 90 2 70 2,70 -2.39 2:29 2:54 2.3t 2,9t 301 301 3.10 3,2D 3:12 3:53 3,3.0 2 24 2,40 - 2:53 2.52 - 2,25 3.27 - 271 - 3:05 2,73 2,98 2,80 2,OU Legend to Table 8t Effect of'tl%e method of preparing the TiO catalyst on the amounts of activation energies. 1) Condition of catalyst urface, 2~ reaction; 3) catalYstl 4) partially carbonizedl ~) completely carbonizedl 6 not carbonizedl 7) dehydrogenation, of ethanoll 8) dehydration of etbanoll, 9 dehydration of isopropanoll 10) hydrogens tion of ethylene; 11) dehydro- genation of cyclohexanel 12) dehydrogenation-of isopropanoll 13) dehydro- genation of propanol; 14) dehydration of n-propanol. Card 5/5 AAq_.CI[L.Yi;VAt G.Yu. AcUra maing a chango in tho rochanisms ol' curbon form4tion during tho eocomposition of hydrocarbons. Izve QT 535ris Otd. kldm. nauk ro. ItI64-166 Ja 161, (laNA 1412) 1, Mloskovekiy Cosud&rt;tvennyy universitat im. EN. Lomononovi.. (HydroeLrbons) ' (Cubon) a/603Y61/001/000/050/056 BI 25 104 AUTHORS: Balandin ,-A., Spitsyn, V. I., Duzhenkov, V. I.# !t~~ Barsovap L. 1. TITLE: Radioohemical method of preparing metallic catalysts SOURCE: Tashkentakaya konferentsiya po mirnomy ispolltovaniyu atomnoy energii. Tashkent, 1959. Trudy. v. 1. Tashkent, 1961, 289-295 TEXT: Platinum and palladium catalyst& are reduced by radiochemical reac- tions from aqueous solutions of suitable compounds. Cyclohexene is hydro- genated for a catalytic check reaction. Chloroplatinic acid samples in Pyrax, glass calla, kept by a thermostat at a con tant temp ratureo were a Ole :V/cm3 irradiated by means of a lineaa(maximum dose rate 3-1 .400) and a Co6o source of 400 g-oqu. Re. At integral doses of 2-10 ev/CM3, solid YtClOH20 and its aqueous solution (0.1-1.0 M) are not reduced to metal owing to the stability of the PtCl;- ion. in saturated solutions of N&2[Pt(OH) xC16-,] and.K2[Pt(OH)xC1 6-.1" which were examined because of the Card 1/i 33120 .s/63ej61/oo1/000/05o/o56 Radiochemioal method of ... B125/B104 lower stability of the hydrocomplexes, irradiation acted indirectly upon the addends in the inner sphere. The least radiution-resistant Na2lkco~4 decomposes completely at 4-1 el ev/CM3 to form metallic platinum. The third group of compounds presented in the figure exhibits the least radiochemical resistance which drops in the sequence Cl-Pt-Cl> ON-Pt-OE>OH- Pt-Cl. The resulting palladium sharply retards the decomposition of the compounds produced, The optical density of a K 2PdCl4 solution also depends largely on the dose rate. Zelinekiy's method was used to compare the catalytic activities of the metal samples, measured in low-temperature hydrogenation of cyclohexens in 96% ethanol and in an ethanol solution in 0.1 N H2SOV with the activity of metals obtained by reducing the corresponding salts with formaldehyde. The platinum catalyst produced by radiolybis in 4-5 times more active than platinum black produced by Zelinskiy's method (Table 2). In the radiolysis ofaqueous PdC12 and X2PdCl4 solution, Pd2+ is completely reduced to metal, the reduction process being noticeably retarded by metallic palladiums The apparent activation energies of a platinum catalyst and platinum black, calculated Card 2/P 33120 5/63ej6i/001/000/050/056 Radiochemical method of ... B125/B104 from the rate constants, of zeroth order, amountto 4.0 and 6.6 kcal/mole, respectively, and their surfaces, determined from cyclohexane adsorption, amount to 23 and IS 22/g at OOC. The catalysts produced by the radiation method are lose active than the platinum black obtained by Zelinskiy's method. The catalytic action of radiolytic precipitates of PdC12 solution of different concentrations differs in intensity. The activation energy of the catalysts in question satiefies the Arrhenius equation . K;Koe' E/RT . The activity of the resulting metal *&a reduced by adding H 1 to the irradiated PdC12 solution. Both irradiated and nonirradiated palladium black samples produced by reduction according to Zelinakly's method exhibited the same activity. Previous studies did not reveal the causes underlying the change of catalytic activity in radio- lytically prepared metal blacks. It is, however, hoped that very active catalysts can be produced radiolytically. There are 4 figures, 2 tables, and 12 references: T Soviet and 5 non-Soviet. The four most recent refer- ences to English-language publications read as follows: Taylor E. H., Wethington J. A. J. Am. Chem. S00., 76, 971, 19541 Gibson E. J-9 Clarke R. W., Dorling T. A.* Pope D. II Intern. Conf. Peaceful Uses of atomic Energy, alconf), 15 P/63, 19581 Taylor E. H~ J. Chem. Education, 36, 396, Card 3/Y,/ " 120 8/638 61/boi/ooo/o5o/o56 Radioohemical method of B104 19591 Raldarw B. C., J. Am. Chem. Boo., 4229, 1954, ASSOCIATION; Institut fizicheakoy khimii AN SSSR (Institute of Physical Chemistry AS USSR), Moskovskiy gosuniversitat. im. M. V. Lomonosova (Moscow State University imeni M. V. Lomonosov) Table 2. Comparison.between activities of Pt black and Pd black, prepared by chemical reduction using Zelinakiy's method, and by radiolysis of salts. Legend: (1) production procesal (2) teat temperature, OCI (3) weighed portion of oatalystj (4) rate (5) specific activity of catalystj (6) ratio of specific activitioal (7) platinuml (8) palladiuml (9)cbemloaW preparedi (10) radiolytically preparedl Fig. Structural formulas of the compounds investigated. Card 4/,61/ - - -TOLSTOPUTOVA --A.-A-. -j -- -- ---- ---- - - KONLNXOp IIH, Energies of the bonds betveen reacting organio compounds and the catalytio aotive aentorcof titanim *dioxide. Ity. AN SUL Otd. khiso rAuk noW14-217 F 161. (MIRA 14t2) 19 Inatitut organlohaskoy kb W i lm.N.D.Zolinakogo AN SSSR, (Titaniua oxide) (Chemioal boade) 20937 12og 8/062J61/000/003/003/013 B117/B208 AUTHORSa Balandin, A. A., Sokolovs., N. P., and Simanov, Yu. P. TITLEt Nioblum and tantalum pen'toxidea as dehydration catalysts PERIODICALs Izvestiya Akademii nauk SSSR, Otdolonlys khimicheaklkh nauk, no. 3, 1961, 415-424 TEXT: The authors studied the dehydration kinetics of Isopropyl alcohol on niobium and tantalum pentoxides. Ihe experiments with Nb 205 samples were carried out in a catalytic contiriuous-flow device (Ref. 3s A. A. Balandin and A. A. Tolatopyatovs., Zh. fis. khimli 30, 1367, 1956) in a t mperature range of 3600-40000 and at a flow rate of the alcohol of 0.1; MI/min. The volume of the ca':alyat was 2 ml, and the volume rate of the alcohol 4.5 hr-1. The activity of Nb2o 5 was found to depend on temperature and calcination time of the oxide during its formation from metal, Experiments disclosed that the most active NbjOk samples are obtained by calcination of metallic niobium at 5300 w t in 1-2 hr. Although the formation rate of the oxide depends on the form (powder, Card 1/4 20937 S/06 61/000/003/003/013 Niobium and tantalum pentoxides ... B117YB208 filings, larger parts) of the metal used, and the individual experiments with Nb205 provide no comparable results, the oatalyBt is active in a.V case. Activity is maintained for some timej esgs, for ton hours without regeneration. X-ray phase analyses carried out with a 'OsHHKC' (FenikB) tube of the SC8 (BSV) type with an iron anode at a voltage of 25 kv and a charge of e me disclosed that the catalytically most active form of Nb205 is a low-tomperaturZir-modification. The high-temperature modification of Nb205 is 1088 &c vs. The Nb205 modification remains unchanged during catalytic dehydration of alcohol. To study the dehydration kinetics of isopropyl alcohol on T&205, the same continuous-flow system was used, The experiments were conducted in the temperature range of 3360-3820C at a flow rate of the alcohol of 0.2 ml/min. The volume of the catalyst was 2 ml, and thavolume rate of the alcohol 6.0 hr- 1. A comparison of the catalytic activity of Nb205 and Ta2051 prepared at equal temperatures, suggests that Ta20 is more active than Nb205 under otherwise equal experimental condizions, particularly in the same temperature range. A lower activation energy corresponds to the higher activity of Ta 205' as Card 2/4 209)? S10621611000100310031013 Riobium and tantalum pentoxides... B117/B206 compared with Nb205- Nb205, on the other hand, remains active for a longer time and is better regenerable. The catalysts obtained from pure NbgO5 and T&2C2 May be regenerated by air. The conditions of such a regeneration were studied. At present, the investigations of the effects, of temperature and calcination time of Ta205 on its catalytic activity, and of the effect of these factors on the activity of Nb2o5 and Ta205 with respect to other reactions, especially condensation, are continued. A. Yo. Agronomov is thanked for determining the catalyst surface by the BET method, and V. M. Akimov-for X-ray analysis of Ta 0 The laboratory 2 5* assistant Z. M. Skullskaya took par'. in the exp6rimental work. R. A. Zvinohuk and A. V. Topchiyev are mentioned. There are 3 figures, 9 tables, and 10 referenoest 8 Soviet-bloc and 2 non-Soviet-bloo. ASSOCIATIONi Institut organicheekoy khi/m'i'i im. N. D. Zelinskogo kkademii nauk SSSR (Ina titut"f I- Organic Chemistry Iment N.D. Zelinskiy, Academy of Scisnc~p,USSR)- Moskovskiy gosudarstvennyy universitet im. M. V. Lomunosova (Moscow State University Card 3/4 imeni M. V. Lomonosov) ----BOGDA.NOVA-- O.K.;I-8AIW;gj._k.Aj SHCHE=VA,, A.P. Rogularities in the catalytic dehydroganation of primary aW meanndary alcohols, Isv*AX SSSR Otd,Irh4m,nAjs no,38423-4n W 161* (ORIA Ut4) I* Inatitut organichookqy Irbiali Imni N.D.Zolinakogo AN SWR. (Dehyd"gonation) (Alcohols) 225U S/062/61/000/004/003/008 jo 22,o9, 1114,1297 B118/B20e AUTHORSo jalarLdAi_&__A. k., Spitsyn, Vikt. I., Dobrosellskayat N. P.* Mikhaylenko, I. Ye., Vereshchinakiy, 1. V., and Glazunov, P. Ya. TITLEs Effect of radioactive radiation of a solid body on its catalytic, properties PERIODICALt Izvestiya Akademii nauk SSSR. Otdoloniye khimichookikh nauk, no. 4, 1961, 565-571 TEXTs There are no data available on the effect of the proper radio- active radiation of solids on their catalytic properties. The authors of the present paper investigated the change of catalytic activity as a result of decay of the radioactive isotope, furthermore whether also the A-radiation of a foreign element affects the reaction to be studied, and the effect of irradiating the catalyst by a fast electron beam. The effect of the radioactive catalysts CaCl2' X9S04' and Na2so 41 containing the P-emitters S55 and Ca45j on the dehydration of cyclohexanol was studied. The increased catalytic activity of radioactive catalysts, contrary to Card 1/3 225U 8/062/61/000/004/003/008 Effect of radioactive ... B118/B208 non-labeled catalysts, which had been previously observed by the authors, was confirmed in many cases. The catalytic activity decreases with decreasing radioactivity of the catalyst owing to decay of the isotopes B35 and C&45. Bombardment of the surface of the non-labeled catalyst with 800-kev electrons has no pronounced effect, contrary to the effect of P-particles of labeled B35 and Ca45 which are constituents of the catalyst. Thus not only the labeled S35, but also the labeled Ca45 increases the catalytic activity of magnesium sulfate in the dehydration of cyclohexanol. The radioactive isotope need not be a component of the acting catalyst. It must be concluded that the increased activity of the radioactive cata.lyste studied is due to a continuous bombardment of the active centers of the catalyst with P-partioles. The latter tranefer their energy to the adsorbed cyclohexanol molecules and reduce the activation energy of the chemical reaction. It may be concluded from the decrease of the catalytic activity due to the decay of the isotope in the catalyst that the new elements resulting in the radioactive conversion do not increase the activity. Apparently, the activation of the catalyst surface takes place Card 0 22M Effect of radioactive ... S/062/61/000/004/003/008 B116/B208 at the expense of the proper radioactive radiation. There are 8 figures, 2 tables, and 4 Soviet-bloo references. ASSOCIATIONt Institut fizicheskoy khimii Akademii nauk SSSR (Institute of Physical Chemistry of the Academy of Sciences USSR). Moskovskiy gosudaretvennyy universitst im. M. V. Lomonosova (Moscow State University iment. M. V. Lomonosov) SUBMITTEDe January 16p 1960 Card 3/3 BOGDANOVA, O.K.; SHCIiEGWVAO A.P.1 BALANDINj A.A. VOZNESFMKAYA, I.I. catal,vtio dehydrogenation of ri-pentenes, Izv.AN SSSR Otd khilL nauk n0*057&-582 Ap 161. 1414) I* Inatitut organiche k0 khimii in. N.DZeliwkogo AN SSSR. (Pent:ns~ (Dehydrogenatior-) TOI.STOPrATOVA, A.A.; ~DIN, Ak.-j-HATYUSHMOV Kinetics of the dohydrogenation arA dehydration of alcoholes and of the debydrogenation of:hydrocarbons over WS2 and MOS2 O&talYbts, IST, AN SSSR Otd.khimenauk to.4083-590 Ap t6l. (KUU 3A W 1. Institut organiohookoy khinii im. N.D.Zelirwkego AN SSSR, (Dehydrogenation) (Dehydration (Cheaistry)) (Molybdenum sultide) (Tungsten sulfide) BAIANDINi--AQ-A*-;-RUDENXOj- A* Pq STEGNER,--G,- ---- ---- - -- -- - -- - -- -- - Formtion of coal dendrites in the course of'decomposition of alcohols on nickel, OsT-AN SSSRoOtdAhissnauk uoo5s762-770 )v 161. (KMA 1435) I* Moskovskiy~ gosudarstyenm urAversitst in, MV. Lomonosovs, Wcohols) (coal) RUDUKO.. A.P.1 B&LUMINO A.A.; ZAWWTXAXA. MA Mechanism of coal formation during the decomposition of methe oths j ethylene, wad acetylene on silica gole Izv#AN SSSR,Otd.khiao nauk no.6&98%-995 A 161. (KMA WO I* Hookovskiy gosudaret"nnyy univ*rsitet is* M,Lomonosovas (Hydrocarbons) (coal) RAIANDIN, A,A.; SOKOLOVA* N.P. Catalytic properties of niobium pentoxide in the vapor phase aminatian of ethyl alcohol with aniline. Izv. AN SSSR. Otd.khim.nauk n-7.911543-1548 3 161. (MIRA 14:9) 1. Institut, or anlohnrkoykbimli In. N.D.Zelinskogo AN SSSR. Moblum oxide) (Ethyl alcobol) (Aniline) BAIANDIN# A4A*j ISAGULYANTSj O.V.; SMOLOVA# NP.; ZAKITARTGNIEVA, 14. Mechanism of propane formation in thn decomposition of isopropyl alcohol on vanadium trioxide. Izv. All SSSR. Otd.khim.nauk no.9tlYO-1551 S 461. (MIRA 14%9) 1. Institut organicheskoy khimii im. N.D.Zelin akogo AN SSSR. (Isopropyl alcohol) (Propane) BALANDINP A.A.1 KLAMNOVSKII, Yo.1.1 LITV1Np Yet?* Compooition of butenes formed in the catalytic dehydration of 2-butanol, IsvAH =R.,Otd.khim.nauk no.lOsl863-1870 0 161, (Mnk 14 93-0) I# Inatitut organichookoy khisil im. N.D.Zelinskogo AN MR. (Butane) (Dutawl) BALANDIN, A,A.,- ROUDESTUNSKAYA, 14D# --------------- Mechanism of cyclohexane dehydroeenation on a crystalline chromium -oxide. Izv.AN SSSR.Otd.khim.nouk no.11:1955-1961 N 461. (MIRA 14ill) 1. Institut organicheakoy khImit im. N.D.Zelinskogo AN SSSR. (Cyclohexane) (Dehydrogenation) P BALAINDIN, A.A!; KLABUNOVSKIY, YO.L; ANTIK, L.V-.--- Synthesis and transformations of dihydroxyanthrylene-naphtbohy- droquinone (stereochomistry of catalysis). Izv. AN SSSR Otd.- khim.nauk no.l2t2l89-2192 D 161. (MIRA 14.-11) 1. Inatitut organichaskoy khimil Im. N.D.Zolinskogo AN SSSR. (Anthracene) (Naphthoquinone) KIABUNOVSKIY, Ye.I.; ULANDIN, A.A.; GOVJNOVA, L.F. Chromatographie separation of menthol. Izv. AN SSSR Otd.khim.nauk no.l2t2243-2244 D 061. (MIRA 14:11) lo Institut organicheakoy khimli im. N.D.Zelinskogo AN SSSR. (Menthol) BOGDANOVA,, O.K.; SW.JMGLOVAp A.P.; BAIANDIN, A.A.j BSLDWTNM, I.?. Cata3jvtIc dehydrogenation of ethyl benzene into otyrene, NeftekUmiia 1 noo2sl95-200 Hr,-4p- 161. (MIRA 15:2) 1. Inatitut organichookoy khimli AN SSSR im. N.D. Zeliwkogo. (Benzene) (Styrene) (Dehydrogenation) 8/195/61/002/001/001/006 BiOl/B2i6 AUTHORS: Balandin, A, A.j Klabunovskiy, Ye. 1. TITLE: Steric position of atoms, and catalysis on the occasion of the 100th birthdayof N. D. Zelinskiy~ PERIODICAL: Kinetika i katalit, vs 2l no. 1, 1961, 3-8 TEXT: On the occasion of the 100th anniversary of N. D. Zelinekiyls birthday, the authors give a survey of problems of catalysis and stereoohemistry, which had been studied by Zelinekiy and further investigated by his suocessora. Zelinakly made detailed investigations of the stereoisomeriam of derivatives of di- and tribasic organic acidep and studied the optical activation of crystallization of dimethyl dihydroxy glutaric acid. Basing on stereochemical considerations,. Zelinskiy arrived at the following concept of heterogeneous ca'-lysis: "The deformation of molecules occurs under the influence of th., orce field present on the active surface of the catalyst, this force -'ield influencing the configuration of particles and rendering them rea-',, to interact ... 11. From this concept, A. A. Balandin developed his multil~lot Card 1/5 S/195/61/002/'001/001/006 Sterio position of atoms~ and B101 B216 theory of catalysis (Ref- 5: Dim. nauka i promyshlennost', A, 6559 1959), which assumes the highest possible agreement between the structure of the reacting molecules and the surface structure of the catalyst. A multiplet complex is formed between the reacting atom group and the catalyst without deformation of valency angles. It is mentioned that K. D. Zelinskiy discovered the metallic dehydrogenation catalysts with face-centerod crystal lattices in 1911. The principles of atereochemical influencing of catalytic processes are illuctratedo using the hydrogenation of cis- and trans-olefins and the conversion of maleic acid to fumario acid on palladium as examples. The multiplet theory enables claseifica.tion of all known catalytic reactions. About 2000 types of catalytic reactions were laid down, many of which have not been realized so far. The equations of the multiplet theory permitted advance calculation as to which out of the 15 possible modes of decomposition of cyolohexanol would be most likely on activated carbon, the prediction being confirmed experimentally (nef- 15: A. A. Balandin. et &I. Izv. AN SSSR, Otd. khim. nauk., 1960, 614). The steric specificity of enzyme catalysis is also explained by the multiplet theory. It is mentioned that Zelinskiy verified the organic origin of petroleum postulated by reason of the optically active Card 2/3 S/19 61/002/001/001/006 Steric position of atomep and ... BlOlyv2i6 substances contained in it, by experimentally preparing similar products by dry distillation of organic substances of vegetable and animal origin. The authors stress the versatility of Zelinskiy's scientific activity, the results of which may be utilized for further development up to the present day. There are 1 figure and 18 reference&: 17 Soviet-bloc and I non-Soviet-bloo. The reference to the English-language publication reads as follows: R. L.Burwellt Jr., Chem. Rev. 51, 895, 1957. SUBMITTED: December 8, 196o Card 3/3 --- Pladiochemical ltudy of the mechanism of dehydration catalpis. ?&A 1t Reactions of CA4 -dinathyl other vith hydrocarbons* Kin. i Jmt, 2 no.116i.65 A-F 161. (MITOlAs3) 1. Inatitut orpniobe k WWI imeni N.D. Zolinsk AN SSSR. " Oji=.arbon.) (J~ohydratl ' (Ether) 04(chemintry)) ----7OISMMT%WA. Aek.;-KONEKOp -- --- Catalytio properties of yttriua oxide. Conversions of alcobols and hydrocarbons. M. i kat. 2 no.ItI35-143 J&-JF 161. (HM U:3) 1, Institut organicheekoy khimii imed N.D. Islinskogo IN SSSR. (Ittrium oxide) (Alcohols) (Hydrocarbons) DIN I-TiDMi-OPYATv-VA---A-.A.-I--DUD;ixI -BAIAN -,-" I - t *,- Catalytic properties of thorium dioxide in the dehydrogenation and dehydration of alcohols,, and in the dehydrogenation of cyclic hydrocarbons, Kinoi kat. 2 no.2t273-284 Mr-Ap 161. (MIM 14W 1, Moskovskiy gosudarstvennyy universitet, kafedra organicheskogo kataliza. Thorium oxide) Dehydrogenation) ~Dehydration (Chemistry) ---RUDENKO---". p 0; . A. Dehydrocondensation of methane vith the formation of a coal- yielding cubstance. Kin.i kat, 2 no*4:52,9--533 JI-Aq 161. 'JKURA 14:10) 1. Moskovskiy gosudarstvennyy universitat imeni M.Lomonosova. (Met.11aale) (Condensation products (Chemiatry)) MUMINS ksk.j SPITSIN, V.I.; RUDMOO L.P.; DOUROSELISKATA, N.P.1 X.Mor 1,19s; PPMOVA, G.1.1 GLAZUNOVp P.Ta. Apparatus for studylag heterogenooux catalysit at high temperaturo using radioactive eatalpts and ionizing radiations* Kinei kate 2 no*0626-632 Jl-Ag t6l. (KLU 14,10) I* ;~wtltut ilsichosimy Irbiall AN SSSR i lbskovskiy goeudantv*MW uniftraltat imeni M.Momonosova. (catalyals) 33491 S/195/61/002/005/016/027 S71190 E030/El85 AUTHORSt Isagulyants, G.V., and Balandin, A_A. TITLEs The use of radiocarbon (in) In studying the mechanism of parallel.-consecutivo catalytic processes PERIODICALi Kinetika i kataliz, v.2, no.51 ig6i, 737-740 TEXTt The use of radiocarbon is proposed to determine the stages and process of forming products in parallel-consecutive reactions, the general scheme of which is represented bys W A B W W1 C where A is the initial product, 8 and C the products formed during the process. Three typical cases aris*i for a reaction rate W2#:-! 0, C is formed consecutively from A with B as inter- mediatel for W3 "2'eol B and C are formed from A in parallel but Card 1/ 5 33491 The use of radiocarbon (C14) S/195/61/002/005/016/027 E030/E185 independent of each otherl and when all the rates are commensurable, C is a produot of a consecutive-parallel reaction. The formulae for the rates Vi ares W do C2 W I' dot Cl Tr CL Tz a 7 7 W C3(dy/di) + (y - m)(dC3/dv) dC3 3 P - a --- ; W2 -d-t W3; where QL, 0, y are the specific activities and Cl, C2 Cz the concentrations of At 81 C, respectivelyt. T Is the con~ac time. The authors were able to observe the above discussed cases in many processes by adding to the initial product A a small quantity of B or C marked with CA and determining the changes in concentration and specific radioactivity in relation to contact time. One of these processes was that of the decompo- sition of ethyl alcohol investigated by the authors together with Ye.l. Popov and YU-1. Derbentsev (Ref.3, Izv. AN SSSR, Otd.kh1m. n., 1958, 233). The decomposition was ctrried out in the Card 2/ 5 3301 The use of radiocarbon (C14) ... s/m/61/oWoovoi6/027 E030/F.185 temperature range 275 - 400 OC with aluminium oxide as catalyst. It occurs in two directionsi Into ethylene and into ethyl ether. At the lower temperatures, dooompovition into ethylene was much slower than the dehydration reaction (reversible) into ethyl other. As the temperature rose, the decomposition rate of ethyl alcohol into ethylene rose until at 400 OC it became comparable with that of the other reaction. Thus, the concentrations of both alcohol and other show maxima. As the temperature rises the other maximum is produced not only by the direct alcohol-ethylene reaction, but also by decomposition of the ether to ethylene. At 400 OC where there is 100% conversion to ethylene, 80% of the ethylene ih produced from the alcohol and 20% from the other. The dehydrogenation of cyclohexane to cyclohexane and to benzene is another similar process (Ref.5t Yu.I. Derbentsev, A.A. Balandin, G.V. Isagulyants, Kinetika I kataliz, v.2, 741, 1961). K pure consecutive process occurs in the dehydrogenation of butane-butane mixtures on chromium catalysts. Both the butane and butenes are converted directly to butadiano, the conversion rate from butane boins about 3 times faster than from butane. Card 3/5