Sept.,
1920
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
With regard t o t h e first assumption, i t appears quite probable t h a t t h e relationship mentioned ho¶ds quite accurately for ethane. If this be true, the equations t h a t have been worked out would apply t o natural gases where t h e average number of carbon atoms per molecule is less t h a n 2 , and most natural gases would be included in this class. The applicability of t h e formulas t o rich natural gases and gasoline vapor is problematical, a n d experimental proof of t h e accuracy of t h e basic assumption is needed. It will be noted t h a t t h e specific heat of t h e hydrocarbons t h a t constitute gasoline ranges from 0.426 t o 0.448. This is considerably less t h a n t h e value of 0 . 5 t h a t is generally employed for gasoline in liquid form. The assumption as t o t h e composition of t h e natural gas has been made purely for convenience. If analysis shows constituents other t h a n paraffin gases, it is a simple matter t o make the necessary corrections. SUMMARY
I-Formulas have been developed t o correlate the following characteristics of normal paraffin hydrocarbons : Calories per gram-molecule and number of carbon atoms per molecule (2) B. t. u. per lb. and number of carbon atoms per molecule (4) B. t. u. per cu. f t . and number of carbon atoms per molecule (6) B. t. u. per lb. and specific gravity in liquid form (8) B. t. u. per gal. and specific gravity in liquid form (IO) Specific gravity in liquid form and number of carbon atoms per molecule (Note) Specific heat and number of carbon atoms per molecule (IS) Specific heat and specific gravity in gaseous form (~7) Volumetric specific heat and specific gravity in gaseous form (18) 11-The relationships between specific gravity and B. t. u. per lb. and per gal. may be expressed quite accurately b y linear equations. The significance of this is t h a t t h e specific gravity of a mixture of normal paraffin hydrocarbons determines its heating value, expressed either in B. t. u. per lb. or B. t. u. per gal., regardless of what variation may take place in the number and proportions of constituents. This statement applies t o gasoline in so far as gasoline is a mixture of t h e normal paraffin hydrocarbons. 111-Probable values of t h e heating value and specific gravity of vapor, and volume of vapor per gallon have been computed for four different grades of gasoline. IV-Figures have been prepared showing the change in t h e heating value and specific gravity as a result of t h e extraction of different amounts of g o o BB. gasoline from different grades of natural gas. ALKALI FUSIONS, 11-THE FUSION OF SODIUM BENZENE ~ADISULFONATE WITH SODIUM HYDROXIDE FOR THE PRODUCTION O F RESORCINOL' By Max Phillips and H. D. Gibbs COLORI,ABORATORY, BUREAUOF CHEMISTRY,WASHINGTON, D. C.
I n a paper2 recently published from this laboratory, there ware given results of a series of experiments 1 Presented at the 59th Meeting of the Amerkan Chemical Society, St. Louis, Mo., April 12 to 16, 1920. 2 THIS JOURNAL., 12 (1920), 145.
857
ascertaining t h e proper conditions for obtaining t h e highest yield of carvacrol b y t h e fusion of sodium #-cymene sulfonate with sodium hydroxide. I n connection with these experiments an apparatus was devised especially suited t o t h e study of alkali fusion of aromatic sulfonic acids. Using this apparatus we have now completed a similar study of t h e production of resorcinol by t h e fusion of sodium benzene mdisulfonate with sodium hydroxide. Although this subject has received attention from a number of investigators, a survey of the literature shows quite conclusively t h a t , with possibly one exception, no systematic study of this problem has been made. There appears t o be no agreement among those who have contributed t o this subject as t o t h e proper method of conducting an alkali fusion of sodium benzerie m-disulfonate in order t o get t h e best yield of resorcinol. The recorded yields v a r y from about 2 0 t o IOO per cent. HISTORICAL R E V I E W
Among the earliest contributions on this subject those of Garrickl and V. MeyerZ may be mentioned. The former claimed t o have obtained an almost quantitative yield of resorcinol by the fusion of sodium benzene m-disulfonate with potassium hydroxide for V. Meyer in his paper gives no 2 t o 3 hrs. a t 230'. details as t o method or yield. Barth and Senhofer3 obtained a 90 t o 95 per cent yield of resorcinol b y fusing sodium benzene m-disulfonate with potassium hydroxide, b u t failed t o describe just how the fusion was conducted. T h e same authors in a second paper4 stated t h a t an almost theoretical yield of resorcinol was obtained by fusing the potassium salt of benzene m-disulfonic acid with potassium hydroxide, b u t again failed t o give any details as t o their method. Durands gave t h e following directions for making resorcinol: The sodium salt of benzene na-disulfonic acid is fused for from 24 t o 36 hrs. with five times its weight of sodium hydroxide (35 moles) in an iron pot provided with a mechanical stirring device and heated in an oil bath. The melt is dissolved in water, acidulated with sulfuric acid, and extracted with ether. No data are given as t o the yield or t h e temperature a t which t h e fusion is conducted. Binschedler and Buscho gave a description of t h e process of making resorcinol then commercially in use. Sixty kilos of sodium benzene m-disulfonate were added t o 1 5 0 kilos (17.6 moles) of molten sodium hydroxide, containing as little water as possible, and fused for from 8 t o g hrs. at 270'. An almost theoretical yield of resorcinol was claimed. Degener' was t h e first t o make a study of t h e various conditions affecting t h e yield of resorcinol, such as temperature and time of fusion, proportion of alkali t o be used, and t h e effect of substituting sodium I
Z. Chem., 1869, 549.
Ber., 7 (1874), 1308. A n n , 174 (1874), 235. 4 Ber., 8 (1875), 1477. 6 Mon. Sci., 18 (18761, 696. 8 Ibid., 20 (1878), 1169. 7 J . grakt. Chem., [Z]20 (1879), 300. 2
3
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hydroxide for the potassium compound. He came t o the conclusion t h a t potassium hydroxide was somewhat better t h a n sodium hydroxide and t h a t a mixture of one mole of each of these two alkalies was nearly as satisfactory as pure potassium hydroxide. The optimum temperature when potassium hydroxide was used for the fusion was from 250' t o 255', whereas with sodium hydroxide the best yields were obtained at from 270' t o 280'. The results also indicated t h a t 1 2 moles of alkali t o one of sodium benzene m-disulfonate were sufficient, and t h a t 20 min. was the most favorable fusion period. I n general, the yields were low, the best being 25.94 per cent of the theory. The fact t h a t all t h e fusions were conducted below 280' undoubtedly accounts, t o some extent, for the low yields. Mulhauserl described the commercial process for making resorcinol. Two hundred and fifty kilos of sodium hydroxide (14.1 moles), I O kilos of water (4 per cent of the weight of t h e sodium hydroxide), and 1 2 j kilos of sodium benzene m-disulfonate are fused in an open pot provided with a stirrer. The reaction is said t o be complete when t h e mixture becomes quiet. A yield of 2 0 t o 2 3 kilos of resorcinol (41t o 47.2 per cent of t h e theory) is obtained. The commercial process for making resorcinol as described by Schoop2 is essentially the same as the foregoing, t h e only difference being t h a t he prescribes 2 3 0 kilos of sodium hydroxide t o 1 2 5 kilos of sodium benzene m-disulfonate. He claims, however, t h a t from 1 2 5 kilos of sodium benzene m-disulfonate, 48 t o 50 kilos of resorcinol were obtained. Inasmuch as t h e theoretical yield is 48.7 kilos, his figures are obviously too high. MATERIALS A N D APPARATUS S O D I U M B E N Z E N E m-DISULFONATE-This Salt was prepared according t o the method of Barth and SenhoferJ3save t h a t the sodium salt was obtained through t h e barium salt instead of the lead salt. The product was dried in a vacuum oven a t 140' for 48 hrs. About 800 g. were made and used in all of our fusion experiments. An analysis gave the following results: substance gave 0 1846 g . COz and 0.0302 g. HzO substance gave 0.2228 g COz and 0 0358 g H10 substance g a v e 0 2572 g. hTa2SOa substance gave 0.2532 g NazSOa --FoundCalculated for I I1 CeH4(SOaNa)z Per cent Per cent Per cent 25.14 25.52 c . .. . . . . . . . 25.31 1.60 , 1.43 H . , . . . . . . . . . 1.69 s. . . . . . . . . . . .2 2 . 7 4 22.77 22.73 16.37 16.30 N a . . . . . . . . . . . 16.36 34.12 34.02 0 (by diff.).. 33.90
(I) 0 1989 g. (11) 0.2417 g. (I) 0 5086 g. (11) D 5005 g
.
HYDROXIDE-This was a good grade of the commercial article (not C. P.), assaying 93.j per cent NaOH. It was used in powdered form. APPARATUS-A full description of t h e apparatus used will be found in t h e earlier articlea4 SODIUM
EXPERIMENTAL METHODS
FusIoNs-The problem of determining the proper conditions for obtaining the maximum yield ALKALI
Diagler's polytech. J . , 263 (1 887), 154. 2. Chem. I n d . , 2 (1887). 1. 8 Beu., 8 (1875), 1477. 4 Lac. cit. 1
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Vol.
12,
No. g
of resorginol resolved itself into a study of t h e four following factors: (I) Ratio of sodium hydroxide t o sodium benzene m-disulfonate. ( 2 ) The proper fusion period. (3) The proper fusion temperature. (4) Effect of the addition of water t o the sodium hydroxide upon the yield of resorcinol. Temporarily adopting 310' and 2 hrs. as t h e proper fusion temperature and period, respectively, and keeping these constant , experiments were conducted in which t h e ratio of sulfonate t o alkali was varied in each tube. At the end of t h e fusion t h e tubes were suddenly cooled and analyzed for resorcinol and unused sodium benzene m-disulfonate. To determine t h e proper fusion period, all six tubes were filled with the same amount of alkali and sodium benzene mdisulfonate, the two constituents being in t h e proportion found in the previous experiment t o give t h e best yield of resorcinol, and t h e fusion again conducted a t 310'. At certain intervals of time a tube was removed, suddenly cooled, and analyzed as before. Using the optimum conditions as t o period of fusion and ratio of alkali t o benzene m-disulfonate, experiments were then conducted a t different temperatures. T h e effect of t h e addition of water t o t h e fusion mixture upon the yield of resorcinol was determined in a similar manner by adding a known amount of water t o each tube, under the optimum conditions of t h e other factors as previously determined. R E S O R C I K O L DETERMINATION-The cold fused mass was removed from the tube with hot water, filtered, and the filtrate concentrated on the steam bath. I t was made up t o 2 0 0 cc. in a volumetric flask (Solution A), and 5 0 cc. were measured out with a pipet and transferred t o a separatory funnel. It was made distinctly acid with hydrochloric acid, and extracted with five so-cc. portions of ether, shaking vigorously with each portion for about one minute. The ether was evaporated o f f a t room temperature, with the aid of a small blast of air, t h e residue dissolved in 2 0 0 cc. of water, and an aliquot part analyzedfor resorcinol, according t o t h e method of Penceel I t was found preferable t o standardize the bromine solution against specially purified resorcinol instead of making the standard solution as recommended by the author. The weight of resorcinol was expressed as per cent of t h e theory. DETERMIXATION
O F THE
UNUSED
SODIUM BENZENE
m-msuLFoNATE-An aliquot part of Solution A ( 5 0 cc.) was acidified with hydrochloric acid, diluted with water, boiled until all of the sulfur dioxide had been expelled, neutralized with sodium hydroxide, filtered, and made up t o 2 0 0 cc. in a volumetric flask (Solution B). An aliquot part ( j o cc.) of this solution was transferred t o a weighed beaker, evaporated t o dryness, dried for 48 hrs. in a vacuum oven a t 140°, and weighed. A sample of the residue was analyzed for sulfur, using the Parr fusion bomb for carrying out the sodium peroxide fusion. Another measured, portion of Solution B was analyzed for sulfate sulfur by precipitating as barium sulfate with barium chloride in t h e usual 1
THISJOURNAL, S (1911), 820.
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manner. T h e total sulfur in Solution B found by this determination was deducted from t h a t found b y t h e sodium peroxide fusion, and t h e result calculated as CsH4(S03Na)2. The weight of salt t h u s found was expressed as per cent of t h e weight of sodium benzene m-disulfonate t a k e n for t h e experiment.
However, it is also evident t h a t almost as good yields were obtained with 14 t o 16 moles of sodium hydroxide, and in subsequent fusion experiments t h e ratio of I mole of sodium benzene m-disulfonate t o 16 of sodium hydroxide was used.
E X P E R I M E N T A L DATA
T h e results obtained with fusion periods of I , 2, 3, 4, 6, and 7 hrs. are shown in Table 11, and graphically in Fig. 2 , Curve c .
EFFECT YIELD
OF
OF
AMOUXT
OB
RESORCINOL-The
SODIUM
HYDROXIDE
results of
UPON
the experi-
E F F E C T OF T I M E OF E U S I O N ON RESORCINOL YIELD-
TABLE11-EFFECT OF VARYING FUSION PERIOD1 Time of CsHi S0aNa)z Fusion Yield of Resorcinol dound No. Hrs. Grams Per cent Grams Per cent 1 2114 8.6 59.4 1 1 3.2674 1.1675 8.5 63.5 3.4950 2 2 7.2 1 0099 3.4143 62.0 3 3 8.1 1.1497 3.4462 62.6 4 4 1.0914 7.7 62.0 3.4137 5 6 7.5 1.0511 3.3162 60.3 6 7 1 Ratio CeHi(S0sNa)a : NaOH = 1 : 16 (0.05 ' mole : 0.8 mole). Fusion temperature 310' C.
This table indicates t h a t t h e maximum yield of resorcinol was obtained when t h e fusion was conducted for 2 hrs. A longer fusion period seems not only unnecessary but also quite undesirable. FIG. 1-CONCENTRATION,YIELD CURVE
ments in which t h e amount of sodium hydroxide was made t h e only variable are shown in Table I a n d graphically in Fig. I . TABLE I-EFFECT OF VARYING AMOUNTO F
S O D I U M HYDROXIDE^ Ratio CeH4(SOaNa)z CaH
