NEW BOOKS Catalysis in Industrial Chemistry. By G. G. Henderson. 22 X 15 cm; pp.. New York: Longmans, Greeizand Co ,1919, Price: $3.00. Thefirst chapter begins with generalities in regard to catalysis and catalytic agents, including a discussion of autocatalysis, negative catalysis, catalyst poisons, and promoters. The latter part of the chapter deals with the preparation of active materials. The second chapter is devoted to hydrogen; chlorine and chlorine compounds; graphite; carbon tetrachloride and phosgene; removal of carbon disulphide from coal gas; sulphur, sulphuric acid, sulphuryl chloride, persulphates; regeneration of chromic acid. The third chapter deals with ammonia, nitric acid and other compounds of nitrogen, while the fourth chapter has to do with hydrogenation. Dehydrogenation itnd oxidation are the subjects of the fifth chapter, while hydration and hydrolysis, dehydration, polymerization and condensation are discussed’ in chapter six. The last chapter includes such things as: preparation of hydrocarbons, halogen derivatives, amine derivatives, diazo compounds, aldehydes and ketones, and sulphur compounds; intramolecular rearrangement; enzymes ; surface combustion. In an appendix is a list or catalysts. There is only a slight attempt made to consider the theoretical side of the subject. On p. 3 the author says: “The theories which have been advanced t o explain the mechanism of catalysis fall into two classes, the chemical and the physical. The former asserts that the effect of the catalyst is to be attributed t o the continuous formation and decomposition of unstable intermediate products; while the physical theory explains the phenomena as heing due t o the condensation, ob increase in concentration, of the reacting substances a t the surface of the catalyst, such increase in concentration being brought about by capillary forces. Here it must suffice t o state that beyond doubt many catalytic reactions, and probably all which take place in homogeneous systems, depend upon the formation of unstable intermediate compounds, and that it is difficult to understand how the physical theory can afford an explanation of the specific action of catalysts and of the diversity of the effects which they produce. In many cases of heterogeneous catalysis the possibility of the formation of intermediate products is by no means excluded. The effect of metals as catalysts of hydrogenation may be explained on the assumption that metallic hydrides are formed, which under the conditions of the experiment give up their hydrogen to the substance undergoing hydrogenation. The catalytic action of metals in promoting the combination of nitrogen and hydrogen to form ammonia may b e attributed to the formation of metallic nitrides which interact with the hydrogen; and in fact nitrides, such as uranium nitride, are excellent catalysts of the reaction. The dehydrating action of alumina on alcohols may be the result of the formation and subsequent decomposition of aluminum alkyl oxides, which, i n fact, are known t o exist and to break down under the influence of heat; for example, the formation of ethylene from ethyl alcohol may be represented by t h e following equations: ( I ) A1203 2CzHs.OH = Hz0 A120z(OCzH5)2’ (2) AlzO?(OCzHb)z= HnO AlzOa 2C2H4
ix
+ 202.
+
+
+
+
New Books
23 9
M a n y other examples might be quoted, but a t the same time i t must be admitted t h a t in a t least some cases of heterogeneous catalysis the physical theory appears t o offer the only explanation of the action of the catalyst.” It is interesting t o read, p. 9, t h a t “the behavior of a nickel catalyst toward poisons is said t o differ considerably according t o its method of preparation, A catalyst prepared by distributing basic nickel carbonate on an inorganic carrier and reducing it a t a temperature of 450’ was found to be remarkably resistant to poisoning by anticatalysts such as hydrocyanic acid, sulphuretted hydrogen, and carbon disulphide, and, for hydrogenation a t the ordinary temperature, to have an activity much greater than that of nickel prepared by reduction a t much lower temperatures.” Under hydrogenation, p. 93, there are a couple of paragraphs which certainly call for more study. “In discharging a number of dyes employed in pattern printing on textile fabrics, the addition of a catalyst to the reducing agent has been found to increase its efficiency in a very marked manner Naphthylamine Bordeaux, Paranitraniline Red, Chloroanisidine Orange, @Nitrotoluidine Yellow, Dianisidine Black, Chrysoidine Bistre and analogous compounds are discharged by means of neutral or slightly alkaline pastes containing sodium formaldehyde sulphoxylate along with a metal, metallic oxide, or metallic salt, which either itself is a reducing agent or is capable of acting as a carrier of the reducing power of the sulphoxylate; the salts of iron, e. g., ferrous sulphate or ferric chloride, are preferred as catalysts. “Somewhat later the remarkable discovery was made t h a t the effect of the color-discharging agent is much intensified by the addition to i t of small quantities OF certain dyes themselves. For example, sodium hydrosulphite employed in a neutral medium, e. g., in the presence of dextrin and glycerol, gives an imperfect discharge on tissues dyed with @Naphthylamine Claret, but complete discharge takes place readily when certain basic dyes, for instance, Thionine Blue, Auramine, or Rhodamine 6 G, are added to the mixture. With sodium formaldehyde sulphoxylate also some dyes appear to have a c9talytic effect in promoting the discharge of colors; those which have been found to act most powerfully in this direction are Setopaline and Nitroalizarine. Rhodamine G and Ayridine Yellow act in a similar manner but their effect is not so marked.” On p. 160 the author says: “The rubbers obtained synthetically from isoprene and other similar hydrocarbons correspond not only to the supposed constitution of Para rubber but also to various analogues of that substance, and exhibit differences in properties which depend upon the constitution of the hydrocarbon from which they are prepared by polymerization and the method by which this change is brought about. Harries classifies synthetic rubbers in one or other of two groups: The first comprising the ‘normal’ rubbers which are obtained by the polymerization of the unsaturated hydrocarbons brought about by heating them alone or along with acetic acid, the second including the ‘sodium’ rubbers obtained by the action of the alkali metals, especially sodium, o n the hydrocarbons. The two series are not identical, but exhibit various differences. Ostromisslenski, in the course of a discussion of the different synthetic rubbers, claims that the product obtained by the polymerization of pmprcene differs from all previous synthetic caoutchoucs, being perfectly identical with natural Para rubber.”
240
New Books
When discussing the organic accelerators of the vulcanization of rubber, p. 187, the author says: “The organic accelerators differ from such substances as magnesia or oxide of lead in so far that exceedingly small quantities are effective; their action is apparently catalytic in character. In this connection i t should be noted that certain organic compounds possess the property of retarding vulcanization, that is t o say, appear t o act as anticatalysts; among such are phenylhydrazine, methylene blue and glucose. “As already indicated, most of the effective organic catalysts are basic in character, and their activity is roughly proportional to their alkalinity, a relativelyfeeble base like aniline having little influence on the rate of vulcanization. The inorganic accelerators in common use are also basic in character. Bearing these facts in mind Twiss was led to attribute the relative advantage attaching t o the use of organic bases chiefly to the fact that these substances are soluble in rubber, whereas the inorganic catalysts, being sparingly soluble, are not so uniformly distributed through the mass. He therefore concluded that the alkali hydroxides would prove to be excellent accelerators if a solvent for these compounds could be found which would itself dissolve in rubber. He finally patented the use of glycerol which dissolves approximately 25 percent of potassium hydroxide and a smaller proportion of sodium hydroxide. If from I to z percent of this solution is added to a rubber-sulphur mixture the vulcanization process is strongly accelerated, the effect being comparable with that of the Wilder D . Bancroft strongest organic accelerator.” Chemical Engineering Cataloz. By Franczs M . Twner, J r . Fourth edition. 31 X 25 cm; p p . 1200 The Chemical Catalog Company, Inc., 1919. Price: $5 .oo.-The fourth annual edition is an improvement over the preceding three. I t presents an enormous mass of information in a n easily accessible form and is consequently of great value t o all who purchase equipment and materials in the various industries using chemical processes of manufacture. As the publishers point out, the field of the Chemical Industries is a broad and vital one, embracing such lines of manufacture as sugar making and refining, fertilizer, cement, paints and varnishes, prepared foods, leather, textile bleaching and dyeing, paper and pulp, rubber, metals, oils, soaps, extracts, glass and many others in addition to chemicals and acids. It is worth noting how many on this list involve colloid chemistrv. The techiiical and scientific books section has been expanded very much, 1061 books being listed as against 325 in the 1918edition. The increase in space from twenty-two to sixty pages has made i t possible t o include a subject index which simplifies the problem of finding references in regard to a particular topic. In most cases the date of publication of the book is given. This is distinctly valuable because the individual publishers of scientific books are very apt t o omit that information from their catalogs. The fact that the number of firms using space has increased from 132 in 1916 to 604 in 1919 shows that the catalog was needed and that consumers Wilder D . Bancroft are making use of it.
