August, 1934
I N D U S T R I A L A N D E NG I N E E R I N G C H E M I ST R Y LITERSTERE CITED
Beatty, H. A , and Calingaert, G., IND.ENG. (?HEM., 26, 504 (1934). Beckmann, E , and Faust, O., Z. physik. Chem., 89, 235 (1914). Bredig, G., and Bayer, R., Ibid., 130, 1 (1927). Bromiley, E. C., and Quiggle, D., IXD.ESG. C I i E h f . , 25, 1136 (1933). Cummines, L. ST’. T., Stones, F. W.,and Volante, M. ii., Ibid., 25, 728 (1933). Jackson, D. H., and Young, S., J . Chem. Soc , 73, 922 (1898). EXG.CHEM.,25, 569 (1933). Keyes, D. B., IND. Lee, S. C., J . Phvs. Chem., 35,3558 (1931). Lewis, G. S . ,and Randall, M., “Thermodynamics and the Free Energy of Chemical Substances,” 1st ed., p. 210, McGraw-Hill Book Co.. N. Y.,1923. (IO) Ibid., p. 256.
909
Ibid., p. 268. Lewis, W. K., and Luke, C. D., ISD.ENG.CHEM., 25, 725 (1933); Trans. 9 m . SOC.Jfech. Engr.s., 54, 55 (1932). Lewis, W. K., and Murphree, E. V., J . Am. Chem. S o c . , 46, 1 (1924). Marshall, A,, J . Chem. SOC.,89, 1350 (1906). Montonna, R. E., and Cornell, L. W., IND. ENG.C“En1.. 25, 1331 (1933). Ostwald, W., quoted by Marshall (14). Rosanoff, M. A , , Bacon, C. R., and Schulze, J . F. W . , J . Am. Chem. SOC., 36, 1933 (1914). Rosanoff, XI. A,, and Easley, C. W., Ibid., 31,953 (1909). Tongherg, C. W., and Johnston, F., IND. ESG. (?HEY., 25, 733 (1933). Zawidski, J. Y., 2. phgsilz. Chenk., 35, 129 (1900). RECEIVED .ipril 9, 1934
Preparation of Anhydrous Metallic Soaps Titanium Soaps L. W. I ~ Y L NAND ~ W-.R. PLECHNER, Titanium Pigment Company, Inc., New York, I S.Y.
T
HE term “metallic soaps” is applied to the salts of the fatty, resin, or naphthenic acids, and the metals other than the alkali metals or the ammonium radical. These metallic soaps have many useful applications in the arts. They are used in waterproofing material,, as thickening agent5 in oils and greases, as stabilizers for suspensions and emulsions, as netting agents, and to give many special properties to paints and varnishes. Soaps of cobalt, manganese, and lead form the commonly used driers for paints. There are tx-o types of metallic soaps which are usually referred to as precipitsted and fused soaps, respectively. The precipitated soaps are prepared by the double decomposition of aqueous or alcoholic solutions of alkali metal or ammonium soaps with aqueous solutions of salts of the other metals. The reaction results in the replacement of the alkali metal or ammonium in the water-soluble soap with the other metal, thua producing a water-insoluble or relatively insoluble metallic soap. The precipitated soaps are, when properly made, chemical compounds containing a definite percentage of metal which completely saturates the acid used. The fused metallic soaps are made by heating free fatty fir resin acids with a suitable metallic compound, usually the oxide or hydrate and less frequently the acetate. The ease of preparation of the fused soaps and their suitability for many purposes gives them preference in some instances over the precipitated soaps ( 2 ) . For certain purposes trivalent metallic soaps are preferable to divalent soaps. For example, a small amount of aluminum stearate in a paint is more efficient in preventing hard-settling of the pigment than is zinc stearate. The preparation of metallic soaps of titanium and other tetravalent elements was therefore undertaken in this laboratory in order to determine if metallic soaps of tetravalent elements posaess any advantages over the metallic soaps of di- and trivalent elements. Titanium oxide is an extremely inert pigment, and therefore no reaction could be expected between a free fatty acid and titanium oxide to form a titanium soap. However, hydrous titanium oxide, and more particularly the orthotitanic form which is precipitated by the addition of an alkali to a titanium solution in the cold, is readily soluble in dilute mineral acids and the strong organic acids. Therefore it was attempted to form a titanium soap by mixing hydrous titanium oxide with a free fatty acid and heating under varying conditions. In n o case waq there any indication of the formation of any tit anium-fatty acid compound. 1
Present address, United Color & Pigment Company. Uewark,
N. J
I t was then found that titanium tetrachloride reacted with fatty acids a t moderate temperatures with the elimination of hydrogen chloride. This reaction is very rapid and is accompanied by the evolution of considerable heat. It is therefore necessary to add the titanium tetrachloride in small portions with rapid agitation to prevent marked charring ot the organic acid. The presence of substances capable of reacting with hydrochloric acid, such as calcium carbonate or aniline, was also found to be helptul in decreasing the violence of the reaction.
METHODOF PREPARATION In general, a method of preparation of a titanium compound of a fatty acid is to suspend calcium carbonate in amount equivalent to the chloride of the titanium tetrachloride to be used in the fatty acid a t a temperature a t which the fatty acid is completely liquid. Titanium tetrachloride, in somewhat more than the theoretical amount for the reaction, 4HR TIC14 +TiRd t 4HC1
+
+
is added in small portions with vigorous stirring. The reaction mass is then heated on a water bath until the evolution of hydrogen chloride ceases. The bulk of the hydrogen chloride formed by the reaction escapes as the gas, the remainder reacting with the calcium carbonate to form calcium chloride. The cooled reaction mass is dissolved in a suitable volatile solvent, preferably benzene, and filtered or centrifugalized to remove the calcium carbonate and any calcium chloride or titanium oxide or oxychlorides formed in the course of the reaction. The solvent is removed and recovered by distillation. However, solution of the reaction mass in a volatile solvent in order to permit removal of solids is not necessary, as the i n a s may be clarified by filtering a t a high enough temperature t o maintain fluidity. A product of higher titanium oxide content is obtained by triturating the above material with alcohol, or by precipitation from the solvent by the addition of alcohol. While the primary product is quite soluble in most organic liquids, the alcoholprecipitated product is very nearly insoluble in most. For example, 600 grams of stearic acid were heated to 90” C., and 100 grams of calcium carbonate were suspended in the melt. To this were added 85 grams of titanium tetrachloride in small portions and n i t h vigorous stirring. The reaction mass was heated on a water bath until the odor of hydrogen chloride had practically disappeared, then cooled, dissolved in 1800 gram. of ether, and filtered on a Buchner funnel im-
I N D U S T R I h L A N D E N G I N E E R I N G C H E M IS T R Y
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mersed in ice water to prevent loss of ether. The ether was then distilled off and the residue heated under vacuum on a water bath. The product so obtained contained 6.5 per cent titanium oxide (theoretical for titanium stearate, 6.6 per cent) and 0.2 per cent chlorine. It melted between 63.5" and 66" C. without giving a sharp melting point. The melt appeared to be perfectly clear. This product was triturated with alcohol, filtered, and air-dried, and then contained 13.1 per cent titanium oxide. Inasmuch as the titanium oxide content of the alcohol-treated material was almost twice that of the untreated material, this may indicate that the alcohol treatment does not merely remove free fatty acid but also brings about some decomposition of the primary product, similar to hydrolysis in a n aqueous system, to form a basic titanium salt. Titanium linoleates and resinates were similarly prepared. The tung acids combine with titanium in much the same way as stearic, linseed, and rosin acids, except that the resulting 2.5 compounds have quite a low titanium content-about per cent titanium oxide-which may be due to polymerization of the tung acids. Gardner and Bielouss ( I ) found that small amounts of titanium tetrachloride polymerized linseed and tung oils. Since one of the principal uses for metallic soaps in paints is to prevent hard-settling, some titanium soaps were ground into a number of Titanox-B flat wall paints by the Paint,
Vol. 26, No. 8
Varnish, and Lacquer Laboratory of this company and stored for 30 days. Comparisons were then made with similar paints to which aluminum stearate, which is considered to be the most efficient antisettler of the common metallic soaps, had been added. Titanium linoleate had very poor antisettling properties; titanium resinate was only a shade better. On the other hand, titanium stearate suspended the pigment more efficiently than the best grade of aluminum stearate. X-ray examination of a titanium stearate did not show t h e presence of titanium oxide in either crystalline or amorphous form, which indicates that the formation of a titanium stearate compound had taken place. Inasmuch as the reaction of titanium tetrachloride with free fatty or rosin acids was successfully used for the formation of titanium soaps, it was thought that the anhydrous chlorides of other metals might react similarly. I n fact this was found to be true, and cerium, thorium, zirconium, and aluminum stearates were prep&ed by the reaction of their anhydrous chlorides with stearic acid. LITERATURE CITED (1) Gardner, H. A., and Biolouss, E., Am. Paint Varnish Mfrs.' Assoc.. Sci. Sect.. Circ. 365 (1930). (2) Gardnor, H. A., and Coleman, R . E:,Paint Mfrs.' Assoc. U. S., Circ. 120 (1921). RECEIVED June 4, 1934.
A Chart for the Rapid Calculation of .Mixtures J. S. BAKER,E. R. Squibb & Sons, Brooklyn, N. Y.
T
HE calculation of the amounts of two or more sub-
stances of known concentration, which when mixed will produce a mixture of an intermediate desired concentration, is a problem often encountered in chemical plants and laboratories. By 'concentration" of an ingredient, as used here, is meant the number of units of that ingredient, solid, liquid, or gas, dissolved in or uniformily mixed with another substance or mixture of substances to form one hundred units of mixture. The chief difficulty with the usual graphical presentations for the rapid solution of problems of this type is that one or more irregular scales, such as logarithmic or reciprocal scales, are employed in their construction, resulting in poor accuracy over a t least pant of the range. It is the aim of the chart here presented to overcome this
PERCMT OF MIXTURE MADE U P OF STRONGER COKSTITUENT
objection. Since the scales are all regular and straight, this chart may be constructed on regular coordinate paper in a few minutes. This chart is based on the relation: C - B A - B where A = concn. of stronger constituent B = concn. of weaker constituent C = intermediate desired concn. X = fraction of final mixture made up of stronger constituent To construct this chart, draw perpendicular identical scales a t the ends of a base line having one hundred equal divisions. Let the perpendicular scales represent the concentrations involved, B and C on the left and A on the right, and the baseline scale, as measured from the left end, equal the percentage of the final mixture consisting of the stronger constituent. To use this chart, draw a horizontal straight line a t the elevation above the base line representing the desired concentration, C. Connect another straight line from the point representing the weaker concentration B, on the left scale with the point representing the stronger concentration, A , on the right scale, The horizontal distance, as measured on the base line, from the left perpendicular to the point of intersection of these two lines gives the percentage (100 X) of the final mixture made up of the stronger constituent. A simple geometric consideration of the similar triangles involved in the above construction establishes the validity of this method. A similar chart may be made for the mixture of liquids of different gravities, A and B , to obtain a desired gravity, C. The units on the base line in such a chart will represent volume per cent. Obviously such a chart cannot be used for mixtures of liquids such as alcohol and water, in which there is an over-all volume change, without the introduction of a correction factor.
x=-
RECEIVED April 7 , 1934.
