0
Diphenyl Sulfide w, w. HARTX41\;, L. A. SMITH,.4ND J. B.
DICKEY
0 f
Eastman Kodak Co., Rochester, N . Y.
I
N CONSECTIOS with some studies on organic com-
pounds resistant to heat, it was desired to prepare diphenyl sulfide on a semi-commercial scale. Because of the relatively low cost of the starting materials (benzene, sulfur chloride, and aluminum chloride), and because of the apparent simplicity of the reaction, the method described below was chosen. The reactions involved in the preparation of diphenyl sulfide and thianthrene, which is a by-product, are: 2CsHe + SZC12 iA1cls)+ CaHsSCsHa + 2HC1 + s ss + 6CsHe (AIC1s)+ 2(CsH&S f (CeH4)zSz 44IIzS
(1)
(2)
Diphenyl sulfide can be prepared by treating phenylmagnesium bromide with sulfur chloride or sulfur dichloride (6) ; together with thiophenol and diphenyl disulfide by treating phenylmagnesium bromide with sulfur (24); by treating diphenyl sulfoxide nTith methylmagnesium iodide (11); from benzenesulfinic acid and phenylmagnesium bromide (21); by treating thioaniline with etJhyl nitrite (16); by the action of hydrogen sulfide on a solution of benzenediazonium chloride or sulfate (10) ; by treating benzenediazonium chloride with Rodium thiophenylate ( 2 5 ) ; and by the action of copper sulfate and sodium thiosulfate on benzenediazonium chloride (3). It is possible to prepare diphenyl sulfide by heating sulfur arith naphthalene (8),and wit,h cyclohexane (9); by heating sodium benzenesulfonate (25); by heating diphenyl disulfide in a closed tube (13); by heating bromobenzene with copper thiocyanate (21); b y treating an absolute alcohol solution of thiophenol and iodobenzene with sodium and copper (20) ; by heating lead thiophenylate alone ( I S ) , or with bromobenzene ( 4 ) ; by heating diphenyl ether, diphenyl selenide or telluride with sulfur (18); by heating diphenyl sulfone with sulfur (19); by treating thiophenol Kith aluminum chloride in boiling ligroin (6); by reducing diphenyl sulfoxide with aurous chloride (12); hy heating diphenylinercury with sulfur (1'7) ; and by treating thionyl phenylhydrazine with silver oxide or mercuric oxide (14). Diphenyl sulfide can be prepared best by treating benzene and aluminum chloride with sulfur chloride (1, da), sulfur dichloride (9,2a), and sulfur ('7). In addition to diphenyl sulfide there are found traces of thiophenol and varying amounts of thianthrene.
EXPERIMENTAL PROCEDURE The method described here is an extension and modification of the work of Boeseken (1, 2a). It is believed that the method described is applicable to quantities many times that described in this report. The reaction was carried out in a 22-liter flask fitted with a mechanical stirrer, an inverted Liebig condenser connected to a suitable means for removing the hydrogen chloride formed in the reaction, and an S-tube with dropping funnel. I n the flask were placed 7500 grams (96.02 moles) of dry benzene' and 4050 grams (30.3 moles) of aluminum chloride. The mixture was then cooled to 10" C. with an ice bath, and a solution of 3525 grams (26.1 moles) of a commercial grade of sulfur chloride dissolved in 3120 grams (40 moles) of ben1 T h e benzene was dried by distilling a commercial grade of benzene through a 1.5-foot (45.7-cm.) column until the distillate waa no longer milky. About 15 per cent of t h e benzene wa8 distilled over.
zene mas added with stirring over a period of 2 hours, keeping the temperature a t about 10' C. The reaction was evidenced by the evolution of hydrogen chloride and the separation of a yellow aluminum chloride complex. When all of the sulfur chloride had been added, the reaction mixture was removed from the ice bath and stirred at room temperature for 2 hours and then warmed to 30" C. with stirring until practically no more hydrogen chloride was evolved (1 to 2 hours). The mixture was poured with care over 10 kg. of cracked ice in a 68-liter stoneware crock, and, when the hydrolysis was completed, the benzene layer mas separated and placed in a 22-liter flask. The excess benzene was distilled off on a steam bath, and the dark oily residue was cooled to 0" C. and filtered through a Buchner funnel to remove the sulfur which had crystallized out of solution. After removal of the sulfur, the residue was stirred with 5 liters of commercial methanol for 4 hours a t 0" C. and again filtered to remove the precipitated sulfur. The methanol was then removed on a steam bath, and the residue was distilled under reduced pressure from a &liter modified Claisen flask with water-cooled 3-liter receiver. After a short forerun there were obtained 4300 grams of a yellow liquid boiling a t 155-170° C. a t 18 mm. pressure and 150 grams of a material cont.aining some solid boiling between 170-200" C. a t 18 mm. pressure. There were several hundred grams of tar left in t,hedistillation flask. The first fraction was heated on a steam bath with stirring with GOO grams of zinc dust and 2100 grams of 40 per cent sodium hydroxide for one hour.2 The oily layer was separated and washed twice with 3 liters of water, dried over sodium sulfate, and distilled as before. The yield was 4050 g r a m , or 83.3 per cent of the calculated amount of diphenyl sulfide boiling a t 162-163' C. a t 18 mm. pressure. The high-boiling material on crystallization from methanol gave 80 g r a m of thianthrene melting a t 135-156" C. Thus diphenyl sulfide can be prepared on a semi-commercial scale in an 83.3 per cent yield from benzene, sulfur chloride, and aluminum chloride. A small amount of tliianthrene can be obtained from the high-boiling residues. LITERATURE CITED (1) Boeseken. Rec. t m v . chim.,24, 209 (1905); Boeseken and Watermsnn, Ihid., 29, 319 (1910); Genveresse, B u l l . SOC. chin&., [3] 15, 409 (1896). ( 2 ) Boeseken. Rec. trav. chim., 24, 217 (1905). (2a) Boeseken and Konine, [hid., 30, 116 (1911). (3) Bornstein, B e r . , 34, 3968 (1901). (4) Bourylois, Ibid., 28, 2312. 2320 (1895). (5) DeusJ. Rec. trav. chim., 27, 145 (1908). (6) Ferrario, Bull. soc. chim., I41 7, 522 (1910). (7) Friedel and Crafts, Ann. chim.phus., [6] 14, 437 (1888); Boeseken, Rec. trav. chim.. 24, 17, 219 (1905). (8) Friedmann, Petroleum, 11, 978 (1916); C h e m . Zentr., 1916, 11, 485. (9) Friedmann, German Patent 296,980 (1917) ; Friedlander, 13, 258 (1916-21). (10) Graebe and Mann, Ber., 15, 1683 (1882). (11) HeDworth and Clapham, J. C h e m . Soc., 1921, 1196. (12) He;mann, Ber., 39; 3812 (1906). (13) Hinsberg, Ihid., 43, 1874 (1910). (14) Hutchison and Smiles, I b i d . , 47, 514, 516 (1914). (15) Kekul6, 2. C h e m . , 1867, 194. (16) Krafft, Ibid., 7, 384 (1874). (17) Krafft and Lyons, Ihid., 27, 1771 (1894). (18) Krafft and Steiner, Ihid., 34, 560 (1901).
1317
2
The treatment described is necessary t o obtain a colorless produot.
1318 (19) (20) (21) (22) (23)
I N D U S T R I A L A N D E N G I N E E R I N G C H E 11.1: I S T R Y
Krafft and Vorster, I b i d . , 26, 2813 (1893). Mauthner, Ibid., 39,3593 (1906). Oddo, Gatr. chim. itnl., 41 ( l ) , 15 (1911). Rosenmund and Harms, Ber., 53, 2232 (1920). Stenhouse, Proc. Roy. Soe. (London), 14, 351 (1865); Ann., 140, 284 (1866).
Vol. 24, No. 11
(24) Wuyts and Cosyns, Bull. SOC. ehim.,[3] 29, 686 (1903); Wuyts, I b i d . , [4] 5, 405 (1909). (25) Ziegler, Be?., 23, 2469 (1890). RECEIVEDJuly 23, 1932.
A Note on the Prandtl-Taylor Equation A. E. LAWRENCE, E. I. du Pont d e Nemours & co., - ~ N DJ. J. HOGAN,Massachusetts I n s t i t u t e of Technology, Cambridge, Mass.
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SBORNE REYNOLDS ( I S ) was apparently the first to use an a n a l o g y between heat transfer and friction to d e r i v e a f o r m u l a for heat transfer between a moving f l u i d a n d a solid in c o n t a c t with it. He assumed that the r a t i o of heat a c t u a l l y transferred to that amount of heat which would have been transf e r r e d had the fluid r e a c h e d the t e m p e r a t u r e of the wall w a s e q u a l to t h e ratio of the energy lost in fluid friction to the e n e r g y which would have been lost had the fluid reached the velocity of the wall-that is, if the fluid had come to rest. From this c o n s i d e r a t i o n , the following simple equation was obtained: h = fcG/2
The
Prandtl-Taylor
h
=
is to the precise experimental data of Stender on heat transfer to water flowing in turbulent flow in a aertical pipe. The calculations on these data are made in a manner in f u l l accordance with the deriflation of the equation. It is found that the value of p is a complicated function of inlet water aelocify, inlet water temperature, and average temperature difference between pipe wall and water. It is also found that, eaen under the most favorable conditions, the Prandtl-Taylor equation does not correlate the data as well as the equation of the dimensionless form:
The value of such equations lies in the p o s s i b i l i t y of the prediction of heat transfer or diffusion rates for a given condition of t e m p e r a t u r e , pressure, velocity, and material, in an a p p a r a t u s for w h i c h the f r i c t i o n is known under the s a m e conditions. Ordinarily, friction factors can be obtained e x p e r i m e n t a l l y more easily and accurately than can coefficients of heat transfer. For this reason and because of the wide i n t e r e s t in the PrandtlTaylor equation in this country and in Europe, the f o l l o w i n g study was made of the applicability of the relation.
k
in which the physical properties of the jluid are taken at main-body temperature.
(1)
As stated by McAdams (9) this equation agrees well with the experimental data on fluids of low viscosity flowing inside a horizontal pipe; however, with fluids of high viscosity the values of h predicted by this equation are much higher than those actually obtained. A fluid in turbulent flow within a pipe was later conceived to be divided into two parts; one, next the wall, a thin layer in which the particles move in a straight-line flow parallel to the wall; the other, the main body of the fluid wherein the particles move in all directions. The first section has been designated as the laminar layer, and the second as the turbulent core. Prandtl (IO) in 1910, and Taylor (16) in 1916 stated that, to be in accordance with this concept, the momentum loss-heat transfer analogy should be applied only to the turbulent core. On this basis, they derived, independently, the following equation cfcGl2)
(2) + T[(CP/k) - 11 ratio of fluid velocity at boundary b e h e e n turbulent
h=
equation,
few2 1 + r [ ( c p / k )- 11,
1
where t = core and laminar layer t o average velocity of fluid.
Equation 2 is known as the Prandtl Or Prandtl-Taylor equation. By a similar consideration of the analogy between momentum loss and mass transfer (diffusion), together with considerations introduced by a previous study of diffusion, Colburn (dl derived an equation for ,.he rate of diffusion of a soluble gas from an inert carrier gas to 8. Stationary absorbent. In this equation also the ratio r occurs.
PREVIOUS REPORTS
S e v e r a1 investigators h a v e reported a v e r a g e values of r which they found best to correlate certain experimental data on heat transfer to liquids flowing in pipes. Stanton (14) gave values of 0.29 and 0.34 for r for water, and ten Bosch (1-3), 0.35. Shemood and Petrie ( I d ) obtained individual values of T for each run and gave arithmetic averages of 0.59 for water, 0.48 for acetone, 0.43 for benzene, 0.31 for kerosene, and 0.38 for n-butyl alcohol; they also showed that the individual values of r varied from 50 to 200 per cent of the averages. It is therefore reasonable to assume that the value of r would vary with the nature of the flow and with the fluid considered. Prandtl (11), from an empirical equation for the velocity distribution in the core, the assumption of undisturbed laminar motion in the boundary layer, and the Blasius equation for pressure drop, derived the equation: r = 1.75 (dG/p)-lIa
(3)
However, Prandtl(I.2) stated that the data require that the value of the proportionality coefficient should range from 1 1 to 1.2 instead of being 1.75; he attributes the discrepancy to the lack of a sharp boundary between the turbulent core and the laminar layer. Also, according to ten Bosch ( I ) , the data of Stender (16) indicate that the coefficient ranges from 1.1 to 1.5, and furthermore that the use of a mean value of 1 Colburn (4) gave this equation as r = l.g(dG/p) -1'9. Prandtl ( 1 ) gave T = l.G(Re)-'/s, where Re is the Reynolds number containing t h e radius rather than t h e diameter. T o substitute diameter for radius, the coefficient must be divided b y 2-1'8 which gives 1.75. Using t h e equation f o . o ~ ( ~ G- I/ /~~ ,) and the incorrect value of 1.6, Colburn obtained r = t h e correct expression would be r = 5 9 f i . 53 E
