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1980, 19, 219-221
Gaseous Diffusion Coefficients by the Stefan-Winkelmann Method Using a Polymer-Solvent Mixture as Evaporation Source
Coca," Julio L. Bueno, and Ricardo Alvarez
Department of Chemical Engineering, University of Oviedo, Oviedo, Spain
Gaseous diffusion coefficients of binary gas-vapor mixtures have been determined by the Stefan-Winkelmann evaporation tube method, using a high boiling point compound (as a polymer)-solvent mixture as evaporation source. Experimental results at 1 atm pressure have been obtained for the systems air-benzene (67 ' C ) and air-toluene (100 ' C ) and they are in good agreement with values expected when the pure solvent is used. The use of a polymer-solvent mixture as the source of vapor offers the possibility of avoiding some of the drawbacks pointed out for the Stefan-Winkelmann method.
Introduction Gas and liquid diffusion coefficients are of particular importance in considering mass transfer in gas-liquid chromatography (Szepesy, 1971) as mass transfer may affect the column efficiency considerably (Butler and Hawkes, 1972). Factors influencing mass transfer in a gas chromatographic column correspond to the different terms of the van Deemter equation (van Deemter et al., 1956) or its modified forms (Jones, 1961). In this equation the gas phase diffusion coefficient of the sample, ,BG enters in the longitudinal diffusion term and the liquid phase diffusion coefficient of the sample, ,BI,, enters in the resistance to the mass transfer process term. By using an empty tube, under appropriate conditions, Y l G can be determined (Giddings and Seager, 1962) and knowing ,BG, 2ILcan also be estimated from the dispersion of samples in columns in which the stationary phase is supported on glass beads (Butler and Hawkes, 1972). Among conventional methods for measuring gas and vapor diffusion coefficients, that of Stefan (Stefan, 1871) has been broadly used (Marrero and Mason, 1972). Some of the drawbacks pointed out for this method are the following: (a) poor precision for vapors of liquids of very high or very low pressures, (b) measurements cannot be made above the boiling temperature of the liquid, and (c) large amounts of sample and time-consuming experiments. Modifications of the Stefan-Winkelmann method (Winkelmann, 1884) have been reported in the literature (Pommersheim, 1971,1973; Mato and Bueno, 1977a), and the precision achieved is comparable with that of the chromatographic method. In this work a modified Stefan-Winkelmann technique has been used to determine gas diffusion coefficients by using a polymer or a high boiling point compound mixed with a solvent as the evaporation source. Gas-liquid chromatography stationary phases (polyphenyl ether, Carbowax 1500, and tricresyl phosphate) have been used as the second component in the mixture with a solvent (benzene or toluene). The mathematical model used in
connection with the nonsteady-state method of StefanWinkelmann has been extended for mixtures high boiling point substanc-olvent, and gas diffusion coefficients have been determined in a certain range of concentration of the evaporation liquid mixture. The use of a high boiling point compound mixed with a solvent removes several limitations of the StefanWinkelmann technique, particularly the temperature range at which the diffusion coefficient can be determined. It also allows the obtaining of some data of polymer-solvent mixtures, some of them of particular interest in mass transfer studies by gas chromatography and processes with polymers (Coca et al., 1979).
Theoretical Development The Stefan-Winkelmann method for measuring diffusivities of vapors is based on determining the rate of evaporation of a volatile liquid that can be followed by the rate of descent of the liquid surface in a glass tube or diffusion cell. The diffusion cell shown in Figure 1contains a liquid mixture of a volatile solvent A and a high boiling point compound, I, that does not diffuse into the gas phase. At the top of the cell there is a flow of gas B insoluble with the liquid at the bottom of the cell. Diffusion of A takes place through a stagnant film of A + B and for each time ti the interface depth is ti. By measuring these variables the mass flux NA*12=o be can determined and also the diffusion coefficient a)AB. By a quasi-steady-state analysis, the interface depth as a function of time can be obtained by the following equation (Pommersheim, 1971; Mato and Bueno, 1977a)
0 1980 American Chemical Society
Figure 1. Coordinates scheme and concentration profile. Interface vapor pressures data are needed to determine experimental diffusivities.b). and 20 cm length) fiied with the polymersolvent mixture is immersed in a n adiabatic still in which the vapors of a boiling liquid act as a thermostatic fluid. Alvarez. Eng. adiabatic still. flow chamber. when the bulk concentration of the liquid phase is c A ~ .18 cm i. Values of pAi as a function of cAi were determined from mixtures of A and I by vapor pressure osmometry using a Knauer unit (Burge. The evaporation tube (0. after flowing through filtering and drying stages. The liquid interface level was followed by a cathetometer to the nearest 0. Experimental Equipment The experimental Stefan-Winkelmann technique was similar to that described earlier (Mato and Bueno. and tricresyl phosphate with benzene and toluene as solvents. Adiabatic still and flow chamber. 1976. diffusion cell.001 mm. Chern. Simplified diagram of the experimental technique: A.tl). B. l "C. The gas. 1977a. (arn) be determined can by performing the experiment in a small range of cAiso as to fulfill the assumptions of the quasi-steady-state regime. which is essentially true in most experimental conditions in an open system and for a pure solvent A. This kind of arrangement allows the obtaining of good thermostatic conditions and minimizes convective effects. but the concentration potential in the gas phase. mixing can be provoked by using a polymer or a high boiling point substance of higher density than the solvent the homogeneity of the liquid phase was verified by holographic interferometry (SBnchez et al. but data on vapor pressures at the interface. Then it flows through a small nozzle directed toward the top of the evaporation tube. Vol. As shown in Figures 4 to 7.. The temperature in the diffusion chamber was measured by a mercury thermometer and could be read f O . T. Pressure in the system was controlled to f 2 mm H20 for all runs by means of an electronic relay connected with a pump. The vapors are condensed and recirculated to the still. Equation 1has to be written in the following form The right-hand side of eq 3 can be written as where (aAB) average value of the diffusion coeffiis the cient determined from the concentrations in the stagnant gas film in the interval ( t 2. steel tube placed inside the adiabatic still.220 Ind. most of the assumptions implicit in eq 1still hold. 2. assuming saturation conditions. cathetometer. F. responsible for the diffusion process. will be a function of time as the solvent concentration in the liquid phase decreases with time. No. By changing the liquid in the still different temperatures can be obtained.p k is the vapor pressure at the interface. Carbowax 1500. By graphic integration of eq 3. Figure 3 shows a diagram of the adiabatic still and flow chamber. 1963. In Table I experimental results at several temperatures are compared with calculated coefficients by the Chen- . 1980 /bo B (aas) I +B I I Figure 2. 1977). the diffusion coefficient of the solvent-air systems are constant for the range of composition shown in the gas phase. thermocouple probe. is preheated by passing it through a coiled stainless Figure 3.. C. 19. Equation 1 assumes that P and pAi are independent of time. A simplified diagram of the experimental technique is shown in Figure 2. Results and Discussion Measurements were performed using the three aforementioned liquid phases: polyphenyl ether. as a function of the liquid phase composition. The temperature in the adiabatic still can be maintained to h0.05 "C.d. If the vapor source is a homogeneous mixture of A with a high boiling compound I as a polymer. 1977a). Fundam. heater. D. To avoid concentration gradients in the liquid phase. are required to obtain the diffusion coefficients.
R. University of Valladolid. 33.. Budapest.. M. Chen. Chem. 114 (1977b). Chem. H. g-mol/cm3 BG. Fundam. I Bueno..1101 ChenOthmer (1962) 0. 318 (1977). B. Ann. 73. Wien. V. C. Oftadeh. 1973. Durou. An. Anal.l o -? 013 0-~-0-0-0- "C T. l(1971). Jones. well within the precision limits of the technique... 1980 221 Table I.1193 009 545 Figure 4. cm2/s hi = total interface depth. I d ..(mm Hg 1 I Nomenclature A = solvent B = gas cAi = concentration of A at the interface. g/cmg Literature Cited Burge. 22. Benzene + Carbowax 1500-air system. in the operation range used in this work. A. Bird. Eng. No. Chem. J.. 18. J. 123 Figure 7. Pommersheim.. R . 7 . l(1884). Data. D. 1977a. Mato.D. R. Sci... 3 (1972). Bueno. 100 toluene-PFE ( 6 rings)-air toluene-TCPair toluene-air 0. 10.. 1. . Chem. L. C. W. 87. 829 (1961).1199 0. Fundam. Fundam. M. Bull. 1979 . Ind. 22. 2590 (1963).1149 ChenOthmer (1962) 0. H. Sci..1289 0.. T. Data. cm ~ ~ ( x ~ ~ 1 ( = molar fraction of the liquid phase for t = 0 and .. Eng. Ser..246 (1973). 4.. Clifton. Giddings. 63 (1871). M.. dimensionless MA = molecular weight of solvent A P = pressure. Eng. Phys. Coca. University of Oviedo. 1. Eng. Zulderwerg. calcd ref this work this work 67 benzene-PFE (6 rings)-air benzene-CW1500air benzene-air 550 pAl(mmW 0. Chem.. 12. deviations being lower than 1. Chem. SBnchez. 73. J. J. 1093 (1976). 137 (1958). Chem. Ind. An..... 19.. SBnchez. C . J. M. I . 1979 Accepted December 18. N. J... J. Fundam. SBnchez. Chem..... Data. Ind. Wis. Butler. 459 (1979). J. L. Bueno. L. L. E.l ) at 1 a t m Pressure 2 __ .. B.. This fact increases the possibilities of the StefanWinkelmann technique. Ph.. Othmer and Slattery-Bird equations. Quim.5%.. Ref.. Bueno. Phys.. mean value. E.1196 0. Marrero. 518 (1972). Diffusivities of Benzene and Toluene (cm' s .1288 0. 1977). Fundam. . J. Pommersheim. S. cm I = polymer or high boiling compound K = constant defined by eq 2.. Chem. Received for review March 30. D. R. van Deemter. Hawkes. atm R = gas constant. Phys. cm2/s a)AB = molecular diffusion coefficient. Eng. Chem.Akadgmiai Kiad6. Alvarez. 108 (1977a). one of the most severe limitations of the conventional technique. J. A. 2. "Gas chromatography". I I I Figure 6. A. 10.. J . J . Slattery. Seager. Chem. dimensionless Y A ( ~ ) yA(v = molar fraction in the gas phase for t = 0 and t . Oo9 490 495 PA. Szepesy.. V. 1971. Eng. Toluene V 01' Alvarez.Ind.1284 Bueno (1973) 0. the polymer or high boiling point substance does not affect the diffusivity values in the gas phase. F.D.. 277 (1962). dimensionless Greek Letters P A = density of the solvent A.. F. 271 (1956). 1977. J. Experimental runs with the same apparatus but using pure solvents instead of polymer-solvent mixtures as the evaporation source show good agreement (Mato and Bueno. J. C.. Quim. Akad. Vol. (atrn) (cm3) (K)-l (g-mol)-' T = absolute temperature. Toluene + polyphenyl ether (6 rings)-air system. (1977). Acad. Therefore. 63.. J . S. Ranck. particularly for measuring diffusivities in a wider range of temperatures and near the boiling point of the solvent. Eng. L. J.. h 2 O" I+ tricresyl phosphate-air system. L. Eng.b. L. F. J. Polym. Klinkenberg. Hot..~ ) t = t... P. atm p A i = vapor pressure at the interface. J. 282. Ph.. s z. Mason. Mato.BL = gas and liquid diffusion coefficients.. Thesis. J.. K ti = time. F. ( BAB). Sci.. J . Alvarez.1255 Slattery-Bird (1958) * 011 a 1 Figure 5. R. = t . C. L. Chromatogr.. = interface depth. V.1158 Slattery-Bird (1958) this work - I I this work Bueno (197 3) 0. Clifton. Stefan. 5 . cm zo = initial interface depth. A. Benzene + polyphenyl ether (6 rings)-air system. system aAB* exptl aAB.p 63. Winkelmann.. Othmer.. J. Thesis. 37 (1962). AIChE J..