EFFECT OF STRUCTURE ON RATE K. KOCHLOEFL, M. KRAUS, CHOU CHIN-SHEN**, L. BERANEK and V. BAZANT Institute, of Chemical Process Fundamentals, Czechoslovak Academy of Science, Prague Received February 21st, 1961 The effect of the structure of 14 secondary alcohols on the rate of their dehydration on y-alumina has been determined. The compounds studied included some aliphatic alcohols, cyclic alcohols of various ring size and some stereoisomeric alkylcyclohexanols. Activation energies have been estimated and the reactivity of the alcohols has been compared on the basis of reaction rate constants for 200. The effects of vicinal carbon atom substi- tution, of ring size and of steric configuration of the reacting molecule are discussed. The results indicate that the geometry of the reacting molecule is of major importance in the dehydration of alcohols on solid catalysts. qne of the most fruitful approaches to the elucidation of reaction mechanisms in organic chemistry has been the study of structure effects on reactivity. This approach is extensively used for homogeneous transformations and it was to be expected that its application to heterogeneous catalytic reactions would equally contribute to a bet- ter understanding of such processes. For catalytic dehydration of alcohols some very divergent mechanisms have been proposed recently (see 1 - 3) none of which explains satisfactorily all experimental facts. Further work is therefore necessary and in this paper kinetic measurements of the dehydration of a series of secondary alcohols are described. By varying the structure of the reacting compound, the influence of carbon chain branching, of ring size and of configuration was studied. Kinetics of primary and secondary alcohol dehydration over alumina has previously been studied by Bork and Tolstopjatova 4 ; these authors have found the same activation energy values for all primary alcohols and another for aU secondary alcohols. However, from the small number of substances reported in their paper no conclusions concerning the effect of the structure of carbon skeleton on the reaction rate can be derived. Recently, Miller 5 and Laible 6 have studied dehydration of some alcohols on silica-alumina catalyst. Unfortunately, their results form no basis for consideration of structure effects on reactivity. * Part L: This Journal 25, 2513 (1960). ** On leave of absence from the Institute of Applied Chemistry, Chang-ehun, China. Vol. 27 (1962) 1199 Kochloe/l, Kraus, Chou Chin-Shen, Beranek, Balant: Experimental Boiling points and melting points values are uncorrected. The purity of all substances used was controlled by gas-liquid chromatography. Prepara tion of Cyclic Alcohols Cyclopentanol was prepared by sodium reduction of cyclopentanone in aqueous methanol- ether solutions. Yield 75%, b. p. 139-140 0 /760mm. Cyclohexanol. A commercial product was converted into cyclohexyl acetate which was frac- tionated on a column of 30 TP. The fraction boiling 1735/760 mm was hydrolysed with sodium hydroxide solution and the alcohol destilled through the same column. B. p. 160 -1605, m. p. 20, nfio 14650. Cycloheptanol and cyclooctanol were prepared by reduction of the corresponding ketones with lithium aluminium hydride 9 in 94% and 954% yield, respectively: Cyc1oheptanol boiled at 88 -90/18 mm, cyc1ooctanol at 103 -104/15 mm. For the preparation of cyc1oheptanone and cyc1ooctanone the standard ring enlargement of cyc1ohexanone by means of diazomethane was used 10 ,11. The composition of the reaction pro- ducts as determined by gas-liquid chromatography for different cyc1ohexanone-diazomethane ratios is shown in Table 1. The crude reaction mixture was fractionated on a destillation column of 30 TP and the individual ketones were purified as semicarbazones. Cyc1oheptanone, b. p. 63 -64 /12mm; semicarbazone,m.p. 1635 (methanol). Cyc1ooctanone, b.p.100 -1005 /35 mm, m. p. 34; semicarbazone, m. p. 1710 (methanol). 2,2-Dimethylcyclohexanol. 2-Methylcyc1ohexanone was methylated 12 yielding 65% of 2,2- dimethylcyc1ohexanone, b. p. 1695/740 mm, which was reduced by lithium aluminium hydride to the alcohol in 90% yield. B. p. 169 -172/750 mm. Preparation of Aliphatic Alcohols 2-Methylhexanol-(3). An attempt to purify the product of the reaction of isopropylmagnesium bromide with butyraldehyde 13 (yield 46%) by distillation was unsuccessful. It was therefore converted to the corresponding ketone by potassium bichromate oxidation in dilute sulphuric acid 14 . The 2-methylhexanone-(3) obtained was then purified as the semicarbazone by crystal- lisation from methanol; m. p. 117 -118. Reduktion of the ketone by lithium aluminium hydride afforded 2-methylhexanol-(3) in 92% yield; b. p. 144/760 mm. 1200 Table I Composition of the Crude Reaction Product from the Reaction of Cyc1ohexanone with Diazomethane Molar ratio of diazomethane to cyc1ohexanone: A 116, B 232. Compound A B Cyc1ohexanone 05 0 Methylenecyc10hexane epoxide 51 06 Cyc1oheptanone 788 50 Methylenecyc10heptane epoxide 39 76 Cyc100ctan one 89 820 Cyc1ononanone 28 48 ,Collection Czechoslov. Chern. Commun. Mechanism of Dehydration of Secondary Alcohols over Alumina Catalyst. 11. Heptanol-(4). The crude product obtained by the reaction of propylmagnesium bromide with ethyl formate 15 was purified using the same method as above. Heptanone-(4), b. p. 144/760 mm; semicarbazone, m. p. 132 (methanol). Heptanol-(4), b. p. 153 -153'5/748 mm. 2,4-Dimethylpentanol-(3) was prepared from isopropylmagnesium bromide and isobutyral- dehyde 16 . Fractionation on a column of 20 TP afforded the pure alcohol, b. p. 1384 -138'8/ 744 mm, in 68% yield. Preparation of Stereoisomeric Alkylcyc1ohexanols For kinetic measurements 40 - 80 g of the pure alcohols were required and the known methods for the preparation of the stereoisomeric alkylcyclohexanols were therefore modified to make them more suitable for large scale work. In general, a crude mixture enriched in one of the stereo- isomers was transformed into the crystalline ester which was then purified by repeated crystal- lisation. Table II Sodium Reduction of the Ketones in Absolute Ethanol Ketone Alcohol Yield Alcohol Composition, % % trans I cis 2-Methy lcyclohexanone 780 880 120 4-Methylcyclohexanone 823 871 129 4-t-Butylcyclohexanone 742 927 7'3 Table III Hydrogenation of the Ketones on Platinum Black in Acetic Acid-Hydrochloric Acid Mixture Ketone Alcohol Yield Alcohol Composition, % % cis I trans 2-Methy lcyclohexanone 863 950 50 4-t-Butylcyclohexanone 812 94'5 4'5 2-t-Butylcyclohexanone 943 810 190 The crude products for the preparation of trans-comp ounds were obtained by reduction of the corresponding alkylcyclohexanones with sodium in absolute ethanol 17 (see Table II). For the preparation of cis-compounds the ketones were hydrogen ated on platinum black in acidic medium (see Table III). In the case of trans-2-methylcyclohexanol the difference in esterification rates of the stereoisomers was made use of for its isolation fro m the product of o-cresol hydrogenation. The starting alkylphenols were hydrogenated on a Raney-nickel catalyst in ethanol at 80 and 150 atm. The unreacted alkylphenol and the corresponding ketone formed as by-product were separated from the alcohol by the usual procedure. The isomer composition of the alcohols is given in Table IV. Vol. 27 (1962) 1201 Kochloe/l, Kraus, Chou Chin-Shen, Berdnek, Bazant: Table IV Hydrogenation of Alkylphenols on Raney-nickel Alkylphenol Alcohol Composition, % cis I trans o-Cresol 250 750 p-Cresol 320 680 p-t-Butylphenol 295 705 o-t-Butylphenol 300 700 trans-2-Methylcyclohexanol trans-2-Methylcyclohexanol p-nitrobenzoate. To a mixture of dry pyridine (145 ml) and 2- methylcyclohexanol (114 g, 1 mole, 75% trans-isomer) a solution of p-nitrobenzoyl chloride (120 g, 0649 mole) in dry benzene (500 ml) was added dropwise under cooling and mixing. Mter standing for 20 minutes, the reaction product was poured on a mixture of hydrochloric acid (180 ml) and ice. The benzene layer was separated, washed with sodium hydrogen carbonate solution and the unreacted alcohol and benzene were removed by steam distillation. The p-nitro- benzoate was :filtered off; yield 137 g (521 %). Analysis of a hydrolysed sample indicated a content of 93% of trans-isomer in the ester. Four crystallisations from methanol afforded pure trans-2- methylcyclohexyl p-nitrobenzoate (80 g), m. p. 635 -'- 64. trans-2-Methylcyclohexanol. The p-nitrobenzoate (256 g, 0973 mole) was refluxed \\,'ith a solution of potassium hydroxide (112 g, 2 mole) in water (900 ml) and methanol (400 ml). After two hours, the methanol was distilled off through a column; the remaining mixture was diluted with water and the trans-2-methylcyclohexanol taken up in ether. The pure product was obtained by destillation in 55% yield (615 g); b. p. 165/750 mm, r;25 = 372 cPo cis-2-Methylcyclohexanol .2-Methylcyclohexanone was prepared by potassium bichromate oxidation of crude 2-methyl- cyclohexanol in dilute sulphuric acid 14 in 812% yield. The ketone was purified as the semicar- bazone, m. p. 1915 (methanol). The yield of the pure 2-methylcyclohexanone was 664%, b. p. 160 -161/746 mm. Hydrogenation of 2-methylcyclohexanone. The ketone (130 g, 116 mole) was hydrogenated on platinum black catalyst (14 g) at atmospheric pressure and room temperature in glacial acetic acid (600 ml) to which 80 ml of pure hydrochloric acid was added. When the hydrogen uptake has ceased the catalyst was :filtered off and the solution diluted with water (600 ml). The oily layer was separated, the aqueous layer was neutralised with sodium hydroxide solution and extracted with ether. The combined products were washed and dried. Ether was distilled off and the residue which contained some 2-methylcyclohexyl acetate was hydrolysed with potassium hydroxide in a water- methanol solution. Working up of the crude product yielded 114 g (853%) of 2-methyl- . cyclohexanol (95% cis-isomer). cis-2-Methylcyclohexyl 3,5-dinitrobenzoate. To a mixture of the above alcohol (1472 g, 129 mole) and pyridine (300 ml) a solution of 3,5-dinitrobenzoyl chloride (300 g, 13 mole) in benzene (1000 ml) was a::lded under cooling. After standing for 3 hours, the reaction product was worked up in the same manner as in the case of trans-2-methylcyclohexyl p-nitrobenzoate. Five-fold re- crystallisation from methanol yielded 267 g (672%) of the pure cis-ester, m. p. 975 - 980. 1202 Collection Czechoslov. Chern. Cornrnun. Mechanism of Dehydration of Secondary Alcohols over Alumina Catalyst. II. cis-2-MethylcyclohexatlOl. The 3,5-dinitrobenzoate (267 g, 0868 mole), potassium hydroxide (112 g, 2 mole), water (900 ml) and methanol (3400 ml) were refluxed for two hours. The yield of the pure alcohol was 743 g (75%), b. p. 162/740 mm, r;25 = 172 cPo ' trans-4- Me thylcyclohexanol 4-Methylcyclohexanone was prepared from the crude alcohol in the same way as 2-methyl- cyc1ohexanone; yield 730%. An alternative preparation by oxidation with chromium trioxide in acetic acid afforded only 442% of the ketone. trans-4-Methylcyclohexyl hydrogen phthalate was obtained from 4-methylcyc1ohexanol (com- position see Table II) and phtalic anhydride in pyridine by the standard method 2o . The crude product was purified by four-fold crystallisation from a light petroleum-ethyl acetate mixture (5: 1). Yield 436% m. p. 1105 -1195. trans-4-Methylcyclohexanol was prepared from the above ester by hydrolysis with alkali in 841% yield. B. p. 172-173/760 mm. trans-4-t-Butylcyclohexanol 4-t-Butylcyclohexanone was obtained from crude 4-t-butylcyc1ohexanol by chromium trioxide oxidation in acetic acid 21 in 80% yield and purified as the semicarbazone, m. p. 212 (methanol). The pure ketone has b. p. 92/ 10 mm, m. p. 495. trans-4-t-Butylcyclohexyl hydrogen phthalate was prepared from the alcohol (see Table II) by the standard method. Five-fold crystallisation from light petroleum-ethyl acetate (5 : 1) afforded 560% of the pure trans-isomer, m. p. 146. trans-4-t-ButylcyclohexanoI 21 . The ester was hydrolysed with alkali and the alcohol isolated by the same method as trans-2-methylcyc1ohexanol. Yield 950%, m. p. 815 -820 (light petro- leum). cis-4-t-Butylcyclohexanol The crude alcohol (Table III) was converted to the hydrogen phtalate, purified and hydrolysed in the same way as the trans-isomer. Hydrogen phtalate, m. p. 141 -142; cis-4-t-butylcyc10- hexanol, overall yield 838%, m. p. 81 - 82. cis-2-t-Butylcyc lohexanol 2-t-Butylcyclohexanone was obtained from the alcohol by oxidation with chromium trioxide in acetic acid 17 . The crude product (yield 803%) was converted to the semicarbazone, m. p. 181 -182 (methanol). Hydrolysis of the semicarbazone gave the pure ketone in 640% yield; b. p. 105 -106/38 mm. cis-2-t-Butylcyclohexyl p-nitrobenzoate. The same method as for cis-2-methylcyc1ohexanol 3,5-dinitrobenzoate was used. Yield 384%, m. p. 885 - 890 (ethanol). cis-2-t-Buty!cyc!ohexanoI 17 . Alkali hydrolysis of the p-nitro benzoate afforded the pure alcohol in 897% yield; m. p. 560 - 570 (light petroleum). Catalyst The same lot of a y-alumina catalyst as in our previous work 7 was used. Analytical Methods The course of the preparation of all compounds and of their purification was control1ed after each step or operation by gas chromatographic analysis of the products. Glycerol was used as. the stationary phase, celite as the support, and nitrogen as the carrier gas (see 22 ); the temperature Vol. 27 (1962) 1203 Kochloe/l, Kraus, Chou Chin-Shen, Beranek, Bazant: of the column and the gas velocity was waried according to the boiling point of the particular alcohol or ketone. Conversion in kinetic measurements was calculated from determinations of the unreacted alcohol by the acetylation method 23 . For the aliphatic and simple cyclic alcohols 25 -27 fold molar excess of acetic anhydride and one hours reaction time gave satisfactory results. For the substituted cyclohexanols the acetylation time had to be 15 hour. In the case of cis-2-t-butyl- cyclohexanol a 13 fold molar excess of acetic anhydride and 5 hours of reaction time were neces- sary for complete reaction. Procedure The apparatus used for kinetic measurement is described in our previous paper 7 The partial pressure of the reacting alcohol was adjusted by addition of a suitable amount of toluene. As a sample for analysis the middle fraction of the reaction products (corresponding to steady state conditions) was separated and pyridine added until the aqueous and toluene layers disappeared . . With this homogenised sample two or three parallel determinations were performed. At different temperatures kinetic measurement included usually 4 different parcial pressures for which two to four separate conversion determinations were made. An example of experimental values for trans-2-methylcyclo- hexanol is presented in Fig. 1. The points represent averages from two to four conver- Q 6 . - - - - - - - - . - - - - - - - - - - - - - - - - - ~ x sion measurements. 0,4 Fig. 1 Q2 Dehydration of trans-2-Methylcyclohexanol Conversion (x) dependence on reciprocal space velocity (W/F). 1 193C, 2 204C, 32145C. 0,3 Kinetic Equation It was ascertained by preliminary experiments that a linear relationship exists between reci- procal space velocity (contact time) and conversion of the reacting alcohol approximately to a value of the latter quantity of 04. At constant temperature a single line in conversion against reciprocal space velocity graphs was obtained for different parcial pressures of the alcohol in the feed. It was therefore possible to calculate the rate constant k by means of the integral equation k = xF/W (1) where x is the conversion of the alcohol, F the feed rate of the alcohol [mole/h] and W the volume of the catalyst bed [1]. On the basis of Langmuir-Hinshelwood kinetics of catalytic reactions an equation of this type can be obtained in two cases: 1. For a irreversible reaction if the rate determining step is desorption of the products from the surface of the catalyst. In this case, the x- W/ F plot should be linear in the whole range of conversions; however, this condition is not fulfilled here. 2. For a irreversible reaction if a) the rate determining step is a surface reaction, b) the alcohol is adsorbed on a single center, c) the adsorption coefficient of the alcohol is high in general and higher than 1204 . Collection Czechoslov. Chem. Commun. Mechanism of Dehydration of Secondary Alcohols over Alumina Catalyst. II. the adsorption coefficient of water, and d) the olefin formed is practically not adsorbed. In such case it is possible to 'Omit the terms 1, KRPR and KsPs in the basic rate equation (2) where K A , KR and Ks denote adsorption coefficients of the alcohol, water and the olefin, respec- tively, and P A' PR and Ps the corresponding partial pressures. Equation (2) simplifies to r=k (3) which on integration gives Equation (1). For higher water contents, i. e. for higher conversions, it is not possible to omit the term KRPR; this gives (4a) After rearrangement we get (4b) For confirmation ofthis hypothesis the experimental data of 4-methylcyclohexanol dehydration from our previous paper 7 were used. The reaction conditions in these experiments were: temper- ature 215C, partial pressure of the alcohol PA = 0095 atm, dilution with toluene and nitrogen. In the x- WI F plot the tangent was found for wi F = 0 which practically coincided with a curve drawn through experimental points up to x = 03. This gave with the help of equation (1) the value of the k. Additional tangents were measured at points of x = 04 and 0'6, respectively, and from their values and equation (4b) an estimate of KRIKA ratio was obtained (approximately 0'5). Using this value and the rate constant, the dependence of the x on the wlF was calculated and good agreement with all experimental points was obtained. From this we conclude that dehydration of secondary alcohols over our y-alumina catalyst is governed by a surface reaction as the rate-determining step. This confirms that our kinetic data described the rate of a chemical reaction and not the rate of adsorption or of any other process. Results and Discussion A comparison of the appropriate values for the aliphatic alcohols (Table V and Fig. 2) shows no substantial influence of chain branching in the neighbourhood of the hydroxyl group on the rate and activa- tion energy. This indicates that electronic effects, which usually play an important role in liquid phase reactions, have little influence under our conditions. Fig. 2 Arrhenius Plots of Rate Constants for Ali- phatic and Simple Cyclic Alcohols 1 Heptanol-(4), 2 2-methylhexanol-(3), 32,4- dimethylpentanol-(3), 4 cyclopentanol, 5 cyc- lohexanol, 6 cycloheptanol, 7 cyclooctanol, 8 2,2-dimethylcyclohexa?ol. Vol. 27 (1962) -1,0...--.------.-------.-------.-----, logk 0,5 o -0,5 1205 Kochloejl, Kraus, Chou Chin-Shen, Beranek, Baiant: Table V Rate Constants and Activation Energies of Secondary Alcohol Dehydration over y-Alumina k k re1 Alcohol for 200 0 E mole/ h I for 200 0 kcal / mole , Heptanol-(4) 049 10 33 2-Methylhexanol-(3) 051 10 34 2,4-Dimethylpentanol-(3) 065 13 32 Cyclopentanol 095 19 36 Cyclohexanol 051 10 35 Cycloheptanol 119 23 35 Cyclooctanol 437 86 - 2,2-Dimethylcyclohexanol 047 09 34 trans-2- Methylcyclohexanol 092 18 44 trans-4- Methylcyclohexanol 096 19 38 trans-4-t-Buty 1cyclohexanol 105 21 38 cis-2-Methylcyclohexanol 617 121 21 cis-2-t-Buty1cyclohexanol 202 403 19 cis-4-t-ButyIcyclohexanol 692 136 27 A more marked dependence may be observed on the ring size of simple secondary cyclic alcohols. However, the values of activation energy are practically the same for all members of this group and differ only slightly from those for the aliphatic alcohols. The order of reactivity for the cyclic alcohols is in agreement with observ- ations of ring size influence on some related reactions in solution reported by various authors 25 - 28. Quantitative treatment of our findings is not yet possible, not even for the liqujd phase reactions a satisfactory explanation has been presented although some hypotheses have been proposed 25 ,26. From the similarity between the activation energy values for both aliphatic and simple cyclic alcohols we assume that the mechanism of the dehydration of this two groups of substances is identical or, if more mechanisms are in operation, the degrees of their participation are of the same magnitude. In studying the dehydration of 2,2-dimethylcyclohexanol we intended to determine whether a decrease in the number of hydrogen atoms in the neighbourhood of the hydroxyl group will influence the reaction rate. From comparison of the values i.t;l Table V for cyclohexanol and its 2,2-dimethyl derivative is evident that the presence of a quaternary carbon atom diminishes the reactivity only slightly. It appeared further important to study the dehydration of those alcohols which have a fixed position of the hydroxyl group in respect to other atoms in the molecule. This condition is not fulfilled in the case of the aliphatic alcohols where there is no 1206 Collection Czechoslov. Chern. Cornrnun. Mechanism of Dehydration of Secondary Alcohols over Alumina Catalyst. II. powerfull restriction to an arbitrary arrangement of the molecule on the surface of the catalyst; Even in 'the case of unsubstituted cyclic alcohols the position of the hydroxyl group is not strictly defined because of ready interconversion of different conform at- ions 29 The same is true for 2,2-dimethylcyclohexanol. For these reasons we studied the dehydration of some stereoisomeric 2- and 4-alkyl- cyclohexanols (Table V and Fig. 3). The t-butylcyclohexanols were most suitable because of their conformational homogeneity: the cis-isomers have the hydroxyl group in the axial and the t-butyl group in the equatorial positions whereas both substituents of-the trans-isomers are equatorial. Since the bulky t-butyl group could exert specific effect on the reaction rate we also examined the dehydration of the cor- responding 2- and 4-methyl derivates. With these compounds steric conditions are not so clear-cut; however, deviations from conformational homogeneity are small enough not to be taken in account in the present study. Fig. 3 Arrhenius Plots of Rate Constants for Ste- reoisomeric Alky lcyc1ohexanols 1 trans-2-Methyicyc1ohexanol, 2 cis-2-me- thylcyc1ohexanol, 3 trans-4-t-butylcyc1ohe- xanol, , 4 cis-4-t-butylcyc1ohexanol, 5 cis- 2-t-butylcyc1ohexanol, 6 trans-4-methy1cyc1o- hexanol, 7 cyc1ohexanol. 1,0 logk 2 a ' 0,5 2,05 Largest differences in reaction rates and activation energies were found among stereoisomeric alkylcyclohexanols. Table V shows that on the average the activation energy of the cis-isomers is substantially lower than that of the trans-isomers. For the aliphatic and simple cyclic alcohols this quantity has values between those for the alkylcyclohexanol stereoisomers. Such distinct dissimilarity in activation energies of individual conformations is clearly connected with a different geometry of reacting molecules and we regard it as evidence for different mechanisms of dehydration. One can suppose that for the formation of the activated complex on the surface of the catalyst a specific steric arrangement of a reacting molecule is necessary. A low activation energy can then be expected in the case of substances in which a suitable geometry is largely preformed in their free state. However, a precise picture of the form of the activated complex is hardly possible to propose on the basis of the pre- sent data since chemisorbed species and not free molecules are involved in its format- ion; however, this does not mean than the form of the molecule is totally changed by chemisorption. Vol. 27 (1962) 1207 Koc;hloe/l, Kraus, Chou Chin-Shen, Beranek, Bazant: In the series of trans-alkylcyclohexanols our results shows no effect of alkyl struc- ture on the rate whereas the opposite has been observed for the cis-compounds. To explain this fact we assume a different behaviour of the hydrogen atoms vicinal to the OH group which mayor may not take part in the formation of the activated complex. The first possibiljty probably holds for the cis-alcohols while no participat- ion of these hydrogen atoms has to be expected for the trans-isomers. Then for this second group of alcohols some type of non-synchronous mechanism must be valid; for example, it may involve the formation of a surface alkoxide like that proposed by Topcijeva 3o ,31 or the formation of a bridged carbonium ion 17 However, on the basis of our previous results 7 we exclude the possibility of a classical carbonium ion mechanism which has been proposed by Brey and Krieger32 to explain dehydra- tion over solid catalysts. In the case of the dehydration of cis-alkylcyclohexanols a synchronous mechanism is probable, for example of the type that has been proposed by Eucken 3 3, or quite recently by Pines 3
High reaction rate of the cis-2-t-butylcyclohexanol dehydration cannot be explained solely by suitable geometry of the molecule but steric effects of the bulky alkyl group have evidently also to be considered. In this Laboratory a similar phenomenon was observed in the case of the catalytic dealkyla60n of 2-t-butylphenoI 34 . Unfortunately, a comparison of our results with corresponding measurements of dehydration in the liquid phase is not possible as no equivalent study has been pub- lished until now, although a number of papers has been devoted to the mechanism of the homogeneous dehydration of alcohols 2 ,17,3s-38. Growing evidence from our and other authors' kinetic studies indicates (see 34 ,39-42) that specific structure effects having no direct analogy to reactions in solution may playa decisive role in hetero- geneous catalytic reactions. We wish to thank Dr J. Sicher Institute of Organic Chemistry and Biochemistry, Prague, for helpful discussions in the course of our work and in interpretation of results. We are further indebted to Dr R. Komers for gas-chromatographic analysis and to Miss V. Miko- to va for technical assistance. References 1. Winfield M. E.: Catalysis, Vol. VII (P. H. Emmet ed.) p. 93. Reinhold, New York 1960. 2. Naro P. A., Dixon J. A.: J. Am. Chern. Soc. 81, 1681 (1959). 3. Pines H.: J. Am. Chern. Soc. 82, 2401 (1960). 4. Bork A., Tolstopjatova A. A.: Acta Physicochim. URSS 8, 603 (1938). 5. Miller D. N.: Thesis. University of Wisconsin 1955. 6. Laible J. R.: ThesiS. University of Wisconsin 1958. 7. Beranek L., Kraus M., Kochloefl K., Bazant V.: This Journal 25, 2513 (1960). 8. Nenitcescu c., Ionescu C. N.: Bull. soc. chim. Romania 14, 65 (1932). 9. Smith P., Bauer D. R.: J. Am. Chem. Soc. 74, 6135 (1952). 10. De Boer J. Th., Backer J. H.: Org. Syntheses 34, 24 (1954). 11. Kohler E. P., Tishler M., Potter H., Thomson H. T.: J. Am. Chern. Soc. 61, 1057 (1939). 12. Bailey W., Medoff M.: J. Am. Chern. Soc. 76, 2708 (1954). 1208 Collection Czechoslov. Chern. Cornrnun. Mechanism 0/ Dehydration 0/ Secondary Alcohols over Alumina Catalyst. II. 13. Whitmore F. C., Johnston F.: J. Am. Chern. Soc. 60, 2265 (1938). 14. Bachmann W. F., Rauno E. K.: J. Am. Chern. Soc. 72,2530 (1950). 15. Dillon R. T.: J . Am. Chern. Soc. 50, 1712 (1928). 16. Conant J. B., Blatt A. H.: J. Am. Chern. Soc. 51, 1227 (1929). 17. Goering H. L., Reeves R., Espy H. H.: J. Am. Chern. Soc. 78, 4926 (1956). 18. Huckel W., Hubelle A.: Ann. 613, 137 (1958). 19. Houben-Weyl: Methoden der Organischen Chemie 4/2, p. 165, IV. Ed. Thieme, Stutt- gart 1955. 20. Stork G., White W. N.: J. Am. Chern. Soc. 78, 4604 (1965). 21. Winstein S., Holness N. J.: J. Am. Chern. Soc. 77, 5562 (1955). 22. Komers R., Kochloefi K., Bazant Y.: Chern. & Ind. (London) 1958, 1405. 23. Siggia S.: Quantitative Organic Analysis via Functional Groups, p. 4. Wiley, New York 1949. 24. Hougen .O. A., Watson K. H.: Chemical Process Principles, Part III. Wiley, New York 1947. 25. Brown H. c., Fletcher R. S., Johannesen R. B.: J. Am. Chern. Soc. 73, 212 (1951). 26. Brown H. c., Ham G.: J. Am. Chern. Soc. 78, 2738 (1956). 27. Kuivila H. G., Becker W. J.: J. Am. Chern. Soc. 74, 5329 (1952). 28. Mares F., Rocek J., Sieher J.: This Journal 26, 2355 (1961). 29. Eliel E. L.: J. Chern. Educ. 32, 126 (1960). 30. Topcieva K. V., Jun-Pin K.: Z. fiz. chim. 29, 1854 (1955). 31. Topcieva K. V., Jun-Pin K.: Z. fiz. chim. 29, 2076 (1955). 32. Brey W. S., Krieger K. A.: J. Am. Chern. Soc. 71, 3637 (1949). 33. Eucken A., Wicke E.: Naturwiss. 32, 165 (1945). 34. Schneider P., Kraus M., Bazant V.: This Journal, 27, 9 (1962). 35. Chiurdoglu G.: Bull. soc. chirn. Belges 47, 241 (1938). 36. Vavon G.: Bull. soc. chirn. [4] 49, 937 (1933). 37. Price Ch. C., Karabinos J. V.: J. Am. Chern. Soc. 62, 1159 (1940). 38. Schaeffer H. J., Collins C. J.: J. Am. Chern. Soc. 78, 124 (1956). 39. Schneider P., Kraus M., Bazant V.: This Journal 26, 1636 (1961). 40. Kadlec J . , Jost F., Bazant V.: This Journal 26, 818 (1961). 41. Kadlec J., Bazant V.: This Journal 26, 1201 (1961). 42. Rase H. F., Kirk R. S.: Chern. Eng. Progr. 50, 35 (1954). Translated by the Author (M. K.). PellOMe K. KoxJIe<pJIb, M. Kpayc, "Ioy "IHH-illeH, JI. EepaHeK H B. Ea)KaHT: 0 MeXaltU3Me oe- zuOpamaquu 6mOpUllltblX cnupm06 Ita ZilUlt03eMltOM KamallU3amope. II. Bllulllt.ue cmpoeltUIl Ita CKO- pocmb oezuopamaquu. Onpe.n;eJIeHO BJlIDIHlIe CTpoeHmr 14 BTOPH'iHbIX CllHPTOB Ha CKOPOCTb HX .n;e- rH.n;paTa:l(HH Ha y-rJIHH03eMe. HCCJIe.n;oBaHHlO no.n;BepraJIHCb HeKOTopble aJIH<paTH'ieCme CllHPTbI, IUiKJIH'ieCKHe cnHpTbI c pa3JIH'iHOH BeJIH':IHHOH KOJIen; H HeKOTopbIe CTepeOH30MepHbIe aJIKHJII.J;HKJIO- reKCaHOJIbI. On;eHeHbI 3HeprHH aKTHBaI.J;HH H peaKI.J;HOHHaH cnoco6HoCTb cnHpTOB cpaBHeHa Ha OCHO- Bamm KOHCTaHT CKOPOCTH peaKn;HH npH 200C. 06cY)K.n;eHbI BJIHHHHe 3aMemeHHH Ha coce.n;HeM aTO- Me ymepo.n;a, BeJIH':IHHbI KOJIbIn;a H npOCTpaHCTBeHHOH KOH<pHrypaI.J;HH pearHPYIOmeH MOJIeKYJIbI. Pe3YJIbTaTbI CBH,l1;eTeJIbCTBYIOT 0 TOM, 'ITO reOMeTpHH pearHpyromeH MOJIeKYJIbI HMeeT BecbMa Ba)l(HOe 3Ha'IeHHe npH .n;erH.n;paTan;HH cnHpTOB Ha TBep.n;bIX KaTaJIH3aTopax. Vol. 27 (1962) 1209