96

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 40, No. 1

This method of evaluating kGa and b ~ a has two distinct advantages: The conditions of flow of the vapor and the liquor, on which the magnitudep of k a aud k ~ depend, are maintained , a constant during the experiment; and in a sing!c run, involving the tapping and analysis of five samples and the evaluation of four graphical integrals, sufficient data t o ctrlc:*1ate the values of k ~ a a n d kLa are obtained. The values of the film coefficients are useiul not only for design purposes but also for correlations. For instance, kca may be correlated against the characteristic dimensions and properties o the gas film as defined by Reynolds group d f i p I p and the f Bchmidt group p , / p D . This correlation could be also used to verify the Chilton and Colburn theoretical equation (2)for mass transfer. Moreover, new correlations between kLa and other dimensionless groups which define the thickness and properties of the fluid film can also be attempted.
ACKNOWLEDGMENT

K&

number of theoretical units defined by

hc, = number of theoretical units defined by

IV& = number of theoretical units defined by
?,!*

(?/* -

Y)

P R

The authors are highly grateful to Jnan Zhandra Gosh, director of Indian Institute of Science, for his constant encouragement o investigations into the principles of chemical engineering. f They are also thankful to R. L. Pigford and E. M. Schoenborn for their criticism and valuable suggestions.
NOMENCLATURE

= rate of withdrawal of product, Ib. m l:; oe/. ft. X hr. = reflux ratio L I P u = linear velocity of vapors, ft./sec. x = mole fraction of more volatile component, in liquid phase 5* = mole fraction of more volatile component in equilibrium with vapors of composition y xi = mole fraction of more volatile component at interface in equilibrium with vapor of composition y, 1 1 = mole fraction of more volatile component in vapor phase y* = mole fraction of more volatile component in equilibrium with liquid of composition z Vi = mole fraction of more volatile component a t interphase Ay = small finite change in y 2 = height of column, ft. 2 = height of column required to enrich vapors from y i to
P C c = =

PI

density, Ib./cu. ft. coefficient of viscosity of main body of fluid, lb./sec. X ft,. = average coefficient of viscosity of film, lb./sec. x ft,.
LITERATURE CITED

YD.

a = area of interphase contact, sq. ft./cu. ft.

d = equivalent diameter, ft. D = coefficient of diffusion, sq. ft./hr. G = rate of flow of vapors, lb. moles/hr. X sq. ft. H = Henrys law constant, lb. moles/cu. ft. X atm. km = gas film coefficient, lb. moles/cu. ft. X hr. X Ay k~ = liquid film coefficient, lb. moles/cu. ft. X hr. X Ax KQU= over-all gas transfer coefficient, lb. moles/cu. ft. X hr. X AII KLU = over-all liquid transfer coefficient, lb. moles/cu. ft. X hr. X A x L = rate of flow of reflux, lb. moles/sq. ft. X hr. m = sloue of eauilibrium curve

(1) Colburn, A . P., Trans. Am. Inst. Chem. Engrs., 35,211 (1939). (2) Colburn, A. P., and Chilton, T. B., IND.ENQ.CHEM., 1183 26,
(1934). (3)

Furnas, C. C., and Taylor, M. L., Trans. Am. Znst. Chem. Engre..
36, 135 (1940).

(4)

Haslam. R. T.. Rvan. fV. P.. and Weber. H. C.. Ibid.. 15. Pt. 1.
I

177 (1923). (5) Lewis, W. K., Whitman, W. G., IND. and ENG. CHEM., 1 2 1 5 16,
20 (1924).

No, = number of theoretical units defined by

LYD?,.
Y)

(6) McCabe and Thiele, Ibid., 17, 605 (1926)

RECEIVED March 3 , 1945.

Kinetics of an Esterification with Cation-Exchange Resin Catalyst

LJ
*/

CHARLES L. LEVESQUE AND ANDREW M. CRAIG

Resinous Products and Chemical Co., Philadelphia, Pa.

T h e esterification of butanol and oleic acid has been studled in the presence of an acid-form cation-exchange resin as catalyst. The reaction is essentially second-order after on initial slow period. The velocity constant for the reactbn is directly proportional to the surface area of the catalyst per unit weight of reactants.

Sussmans experiments. This paper reports the results of the application of kinetic theory to these data. It is unfortunate that the study of the kinetics was not the primary purpose of the R-ork. Had it been, refinements in experimental conditions could have yielded data better suited to kinetics analysis. However, the results obtained seem of considerable interest from b?th a theoretical and practical point of view.
CATALYST PREPARATION

URING the war years, German chemists discovered the usefulness of acid-form cation-exchange resins as catalysts for esterification reactions, and apparently developed the process to the point of large-scale continuous operation (1, 5). Recently Bussman (6) reported data on the use of such resins in a number of reactions susceptible to acid catalysis. In the course of work in this laboratory, considerable data have been obtained on the butanol-oleic acid system used in most of

The cation exchanger used was a phenol-formaldehyde-sulfonic acid resin (Q), with an exchange capacity of 2.7 milliequivalents per gram of dry weight. (A similar resin is commercially available, sold under the name Amberlite IR-100.) Two samples were prepared:

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INDUSTRIAL AND ENGINEERING CHEMISTRY

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washed upflow between char es. The product was then washed with deionized water until t f e effluent gave no test for sulfate with barium chloride, and air-dried. The resin contaiped 20.9% water, 8.517sulfur, and 6.34% ash. 11. A 1000-gram sample of finely ground (through 50-mesh) resin was agitated with 5 liters of 5% sulfuric acid for 0.5 hour. The acid was decanted and the slurry was washed upflow with deionized water until the effluent gave no test for sulfate. The resin was sucked dry on a Bijchner funnel; it contained 40.590 water.
ESTERlFlCATlON TRIALS

I. A 400-gram sample of 16- to 20-mesh resin was stirred for 0.75 hour with each of four %liter charges of 10% sulfuric acid

1.6

/ I

Four moles of butanol and 1 mole of oleic acid (double distilled white olein) were placed in a 1-liter flask fitted with stirrer, thermometer, and reflux condenser with water separator. The catalyst was added, and the mixture rapidly heated t o refluxing (less than 15 minutes). Heat input was duplicated for each run by using a Variac on the electric heater unit; reflux temperatures were 114 to 116 C. Zero time was taken as the time when refluxing commenced, always within 15 minutes. At the end of the run, the catalyst was filtered off and air-dried. In experiments B, C, D, E, I, and J, the portion of catalyst I1 used in each run was that filtered off from the preceding runs. Manipulative losses 0% catalyst were very small. The same portion of catalyst I was used for experiments F and G. Samples were removed at 4, 8, and 12 hours (except in run A in which samples were removed at 0.7 and 6.1 hours) and analyzed for acid number. The values given for run K are corrected for the acidity of the added sulfuric acid, assuming that i t was half esterified. The data are given in Table I.

g 1

TABLE ESTSRIFICATION I.
Run

A H B

G K A

I E J F

C D

Variable No catalyst No catalyst 3.5%H 0 z 4 . 9 % I1 (1st run) 4.97 I1 (2nd run) 4 . 9 d I1 (3rd run) 4 . 9 % I1 plus 3 . 5 % Hz0 9.257 I1 9.25% bone-dry I1 9.25% I ( 1 s t run) 9.257 I (2nd run) 0 . 1 3 4 HaSOi No catalyst

Acid Number 4 hours 8 hours 12 hours 69.5 56.1 46.5 79.2 62.8 51.3 46.9 11 8 3.3 53.4 23.6 9,o 53.3 23.0 8.4 52.4 20.7 7.6 44.2 9.8 1.8 51.4 6.2 1.6 73.3 46.4 34.8 71.2 48.8 29.1 2.1 1.5 1.3 1/a hour = 90.4, 6 . 1 hour = 6 1 . 1
1.6

HOURS

I2 -

Figure 1. Effect of Weight of Catalyst

Rune A, A, uncntalyzed u D let 8 R u nn K, 9.2;s2ndt a3rdrune with 4.95 catalyst 1 R nE : d l y s t I1 Ru O.lS% HrSO,

CALCULATIONS

A number of the usual equations for esterification reactions of a kimilar sort (2) were applied to the data; none gave a straight line over the whole 12 hours. However, in all cases the data for the last 8 hours fitted the bimolecular equation
kt =
1

1.4

In

(z

1.2

: : e )

fairly well. Figures 1,2, and 3 show the plots of log against t for the various runs. The slopes, k1, of the straight lines drawn are proportional to k , times the specific gravity of the mixture a t the reaction temperature. Since ttbe latter was not determined, k1 was used for the succeeding plot. In Figure 4,the values for IC1 for runs A, C and D, E, and F and G arc plotted against square centimeters of catalyst surface per 100 grams of reactants. The surface areas were calculated by assuming that the catalyst particles were either cubes or spheres. If 1 gram of material is divided into spheres of diameter D, or into cubes of side D, the resulting surface in both cases is equal to

02

Figure 2. Effect of Pardcle Size of Catalyst 0 R u n A, uncatalyzed

(D R u n F 0 R u n G , l e t a n d 2nd runs w i t h 9.25% oatalyst I (coarse) 0 R u n E, 9.25% catalyst I1 (fine)

rf
I

P /
6 HOURS

(>

le

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INDUSTRIAL AND ENGINEERING CHEMISTRY

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Vol. 40, No. 1

0.15

0.13

0.1 I

0.09
K'

0.07

0.05

0.03

-4

400
I
I

000
AREA (CM~IIOOG

1200 1600 OF REACTANTS)

2000

0 HOURS

12

Figure 3.
fi

Effect of Initial Water Content

Figure 1. Variation of k with Catalyst Area per ' 100 Grams of Reactants

R u n H, A plus 3.5% water Run C. 4.9% catnlvst I1 R;L I;'C 3 . 5 4 water 0 Run E 9 25% catalyst 1 1 0 R u n J,'E; with catalyat dehydrated a t 125' C. prior to u s e

0 Run A, uncatalyzed

6 md, d is the density of the material, where

Density for both

catalysts I and I1 was found to be 1.39. To determine D, the catalyst samples, after use, were subjected to screen analysis. For each fraction, the average of the distances between the wires of the passed screen and those of the retaining screen was taken as the value of D. The summation of the values of weight fraction/D for each fraction, multiplied by 6 / d , gave the surface per gram (Table 11).
DISCUSSION

Thomas and Davies ( 7 ) found Xmberlite IR-100, a commercial sulfonic acid type exchange resin, to be even more efficient than hydrochloric acid in the hydrolysis of low molecular weight esters. These data suggest that for a system comprising large, slowdiffusing molecules such as oleic acid, only those acid groups a t or near the surface of an exchange resin particle can be effective catalysts; for systems involving only relatively small molecules or ions, ail acid groups in the particle are catalysts. The dependence of rate on surface area poses a problem for column operation of resin-catalyzed esterifications. From density determinations it was found that a column of base-exchange resin (sample 11)filled with the butanol-oleic acid mixture would contain about 489;b resin. Extrapolating from the points for 0, 4.9, and 9.25% of this catalyst, one obtains a value of 0.776 for k ' . If the value for IC1 held over the whole reaction, this would mean a contact time of only about 2 hours to bring the acid number

The most interesting result obtained in this research is the straight line shown in Figure 1 for the relationship of k1 and the surface of catalyst resin per 100 g r a m of reactants. In spite of the numerous assumptions involved, the data appear to be too uniform for $he relationship to be illusory. The fact that they were obtained by varying both the size and the amount of catalyst lends added validity. When a run (K) was made using 0.13% sulfuric acid (equivalent to only 0.1 the amount of total exchangeable acidity in the catalyst used for run E), esterification was essentially complete before the Phour sample was taken. Sussman (6) had previously noted this lack of concordance between total exchangeable acidity and catalytic effect. He found that Zoo-Karb H and his synthetic resin I had equal catalytic effect, while his resin I1 was substantially less effective, although all three catalysts had essentially equal exchangeable acidity (6). However, he also found that sulfuric acid and Zeo-Karb H in equivalent amounts gave identical rates of alcoholysis of amyl acetate, while

TABLE I1
I
Mesh On12 12-16 16-20 20-30 Through 30 Total

Weight Weight Fraction Av. D , Cm. Fraction/D 0,180 0.66 0.1194 0,143 3.71 0,5302 0.101 3.28 0.3318 0,0091 0.072 0.13 0.0001 0.050 0.00 0.9906 7.78 Area per gram = 33.6 sq. cm.

I1 On 50

50-60 60-70 70-100 100-200 200-325 Through 325 Total

0.032 0.269 8.4 9.3 0.027 0.250 0.024 0.173 7.2 10.0 0.018 0.181 0,0112 9.8 0.110 0.0059 0.8 0.005 0.0030 3.7 0.011 49.2 0.999 Area per gram 212 sq. cm.

January 1948

INDUSTRIAL A N D ENGINEERING CHEMISTRY

99

down to a value of 2 0 However, a bed o such finely divided .. f material would offer great resistance to flow of liquid; increasing the particle size would permit better flow rates but decrease the reaction rate. The Germans evidently encountered a similar problem, since there are statements (I) that they found the best catalyst to be large porous particles prepared by sintering finely ground base-exchange resin, lightly coated with a thermosetting phenolic. The authors have no data to support any explanation of the failure of the bimolecular equation to hold over the first 4 hours of the reaction. There appears to be some inhibiting process or induction period involved when the base-exchange resin is present. This is borne out by the fact that the 4-hour acid values for the runs with coarse catalyst (F and G) are actually higher than that for the run with no catalyst (A), although the 8- and 12hour values are lower. It was thought that this might be due to adsorbed water on the surface of the catalyst. However, a check of several runs in which either added water or bone-dry catalyst was employed (Figure 3) did not bear this out. This matter is of considerable practical importance for continuous column operation. I it is due to an integfal part o the reaction mechanism, f f the 2 hours' contact time mentioned above would need to be considerably increased to obtain a product with an acid number of 2 or lower. The phenol-formaldehyde-ulfonic acid resins are similar to Zeo-Karb H (6) in maintaining catalytic activity over a series of

runs. The one exception to this is the sharp drop between rum B and C, the first and second runs with the fine catalyst. This drop could be due either to the elution of a small amount of adsorbed strong acid or to the loss of a very finely divided fraction during the atration of the catalyst from run B. Data for the uncatalyzed run (A) are a t variance with Sussman's findings of no "indication of esterification" for the same system under similar conditions (6). The close conformity of the rate found for this run with those for the catalyzed runs (Figure 4) leads to the belief that tlie authors' results are correct,
ACKNOWLEDGMENT

The samples of base-exchange reain were prepared by B. Coe and G. Bodamer. The authors are indebted t o R. J. Myers, W. S. Niederhauser, and L..P. Hammett for advice and criticism.
LITERATURE CITED

(1) Diericks, FIAT Report PB866, O5ce of Technical Services, Dept. of Commerce, Washington, 1947. (2) Leyer and Othmer, Im. ENQ. CBEM., 37,968(1945). (3) Myers, F. J., FIAT Report PB42,802,Office o Technical Servf ices, Dept. of Commerce, Washington, 1947. (4) Myers, Eastes, and Myers, Im. ENQ. CEEM., 697-706 (1941). 38, (5) Sussman, Ibid., 38,1228 (1946). (6) Sussman, private communication. (7) Thomas and Davies, Nature, 159,372(1947).

RECBIVED February 11, 1947.

Thermochemistry of Sodium Carbonate and Its Solutions

KENNETH A. KOBE1 AND THOMAS M. SHEEHY2
University of Washington, Seattle, Wash.
T h e solubility and thermochemical data for sodium carbonate, its hydrates, and its concentrated solutions have been reviewed and collated. New data are: Specijic heat of saturated solution 20-32' C. is 64.0 calories per gram NaCz03.10H20dissolving during heating; mean specitic heat from 33' to boiling point is 0.851 calorie per ' per is gram of solution? heat of melting for Na2C02.10H~0 21,400 calories per gram mole.

c.

was exceeded only by sulfuric acid as a manufactured chemicat utilized for chemical purposes. The physical and chemical properties of such an industrial compound are of the utmost importance. It is the purpose of this paper to review and collate the thermochemical properties of sodium carbonate, its hydrates and its concentrated solutions. New data are given on the specific heat of the saturated solution and heat of transition.
SOLUBILITY

N 1944 the production of sodium carbonate, 4,693,000 tons,

The solubility data, solid phases, transition temperatures, and vapor pressures of saturated solutions are of fundamental importance. The solubility data given in the International Critical Tables (II) were derived mainly from three sources (8, 84, 40). During the elapsed time several investigators have given new data from the cryohydric t o the critical temperature.
1

Present address, University of Texas, Austin, Tex. Present address, Standard Oil Company (California). E Segund6 Calif. L

Caspari (4, and Bacon (IO), and Kobe and Leipper (92) Hill investigated ranges from the cryohydric to the boiling point. Seyer and Todd (36)investigated the range 17' to 173' C., and Ervin, Giorgi, and McCarthy (9) made determinations a t 100' to 150' C. The high temperature range was investigated from 50' t o 348' by Waldeck, Lynn, and Hill (B), from 1 0 and 5' to 350' by Schroeder, Beck, and Gabriel (34). These newer data have been plobted on a large scale and compared with the data from which the I.C.T. (International Critical Tables) curve was drawn. The best curve was drawn through the points, giving due weight to the reliability the data were believed to have. From this curve were taken solubility values a t regular temperature intervals. These are given in Table I. Below 50' the data of the more recent workers (6,10,@) correspond to those of the earlier workers (8, 84, 90); the data of Wells and McAdam (40) from 28' to 44" are highly accurate. Above 50" the data of Caspari (6) are definitely high, whereas those of are Kobe and Leipper (82) lower than I.C.T. values but not so low as those of Waldeck, Lynn, and Hill (38), whose data are about 1.5% lower. These latter workers used glass below 100' and a steel bomb up to 348", and report their solubility values accurate to 0.1% from 50' to 150', 0.2% from 150" to 250, and 0.3% above 250" C. Schroeder, Beck, and Gabriel (34) checked the data of Waldeck, Lynn, and Hill a t four temperatures from 150' to 350' and obtained satisfactory agreement except at 350, at whieh temperature the latter workers reported a zero solubility which is refuted by the former. Waldeck, Lynn, and Hill also report determinations a t 112.5' 'and 113.0