Substituting into Eq. (6.2-22) with z, — z, = 0.5 ft (0.1524 m), RT(z, — 2,)Pam 0.73528X(0.5)(0.988) = 1.175 x 107 Ib mol/h- ft? (0.250 x 107*X1,01325 x 10(2341 x 10° ~ 0) B314(293X0.1524\ 1.001 x 105) = 1,595 x 10°? kg mol/s-m? N, (Pas — Par) ™ EXAMPLE 6.2-3. Diffusion ina Tube with Change in Path Length Diffusion of water vapor in a narrow tube is occurring as in Example 6.2-2 under the same conditions. However, as shown in Fig. 6.2-2a, at a given time tthe level is z m from the top. As diffusion proceeds, the level drops slowly. Derive the equation for the time t, for the level to drop from a starting point ofzomatt = tozpatt = tsas shown. Solution: We assume a pseudo-steady-state condition since the level drops very slowly. As time progresses, the path length z increases. At any time f, Eq, (6.2-22) holds; but the path length is z and Eq. (6.2-22) becomes as follows where N, and z are now variables. DaP RT zp Assuming a cross-sectional area of 1 m, the level drops dz m in dts and paldz- YM jis the kg mol of A that have left and diffused. Then, paldz-1) My dt Na= (Pai — Par) (6.2-23) Nel (6224) Equating Eq, (6.2-24) to (6.2-23), rearranging, and integrating between the limits of = 29 when ¢ =Oand z = zp whent =p, Pa. ("gy = Das Plas — Pas) ("4 i [[oaen Date a os Solving for ty pal? — 22)RT Pass M4 Dag Par ~ Par) ae ‘The method shown in Example 6.2-3 has been used to experimentally determine the diffusivity Dy. In this experiment the starting path length z. is measured at ¢ = 0 and also the final 2p at tr. Then Eq, (6.2-26) is used to calculate Dy. 62D_ Diffusion Through a Varying Cross-Sectional Area Jn the cases so far at steady state we have considered Ng and J as constants in the integrations. In these cases the cross-sectional area A m? through which the diffusion ‘occurs has been constant with varying distance z, In some situations the area A may vary. Then it is convenient to define N , as Ne Nat (62-27) where Nis kg moles of A diffusing per second or kg mol/s. At steady state, Ng will be constant but not A for a varying area. 390 Chap.6 Principles of Mass Transfer1. Diffusion from a sphere. To illustrate the use of Eq. (6.2-27), the important case of diffusion to or from a sphere in a gas will be considered. This situation appears often in such cases as the evaporation of a drop of liquid, the evaporation of a ball of naph- thalene, and the diffusion of nutrients to a spherical-like microorganism in a liquid. In Fig. 62-3a is shown a sphere of fixed radius m in an infinite gas medium. Component (A) at partial pressure py, at the surface is diffusing into the surrounding stagnant medium (B), where pyz = 0 at some large distance away. Steady-state diffusion will be assumed, The flux N, can be represented by Eq. (6.2-27), where A is the cross-sectional area 4nr? at point r distance from the center of the sphere. Also, 1V, is a constant at steady state N= (62-28) Since this isa case of A diffusing through stagnant, nondiffusing , Eq. (6.2-18) will be used in its differential form and N4 will be equated to Eq. (6.2-28), giving x, Gar’ Pay da RT palPh dr Na (62.29) Note that dr was substituted for dz, Rearranging and integrating between r, and some point r, alarge distance away, (62-30) N, EG- a) (6231) Since, > ry Irs & 0. Substituting pyy from Eq, (62-21) into Eg (62-31), Na a (6232) This equation can be simplified further. Ifp., is small compared to P (a dilute gas a a @) () Fioure 62-3. Diffusion through a varying cross-sectional area: () from a sphere to a surrounding medium, (b) through a circular conduit that is tapered uniformally. Sec. 62 Molecular Diffusion in Gases 391Phase), pany = P. Also, setting 2r, = D,, diameter, and ¢,; = pay/RT, we obtain Das Nai =e lea — ead (62-33) ‘This equation can also be used for liquids, where D 4g isthe diffusivity of A in the liquid, EXAMPLE 6.2-4. Evaporation of a Naphthalene Sphere A sphere of naphthalene having a radius of 20 mm is suspended in a large volume of still air at 318 K and 101325 x 10° Pa (1 atm). The surface temperature of the naphthalene can be assumed to be at 318 K and its vapor pressure at 318 K is 0.555 mm Hg, The Dy of naphthalene in air at 318 K is 692 x 10-* m*/s, Caleulate the rate of evaporation of naphthalene from the surface, Solution: The flow diagram is similar to Fig. 6.2-3a. Dy = 6.92 x 1076 m/s, Pay = (0.555/760X1.01325 x 10°) 14.0 Pa, paz = 0, r, = 2/1000 m, R= 8314 m?-Paskg mol-K, pp = P— pay = 101325 x 10° — 740 = 1.01251 x 10° Pa, ppp = P — Pua = 1.01325 » 10% — 0. Since the values of — ~ ‘Pe: and py, areclose to each other, 101 + Pog _ (1.0125 + 1.01325) x 10° : Substituting into Eq, (62-32), Dan Play — Paz) _ (6.92 x 107 °K 1.01325 x 10°K74.0 — 0) RTrypou ————_-8314(318(2/1000 1.0129 x 105) = 9.68 x 10° kg mol A/s-m? Na Ifthe sphere in Fig, 6.2-3a is evaporating, the radius r of the sphere decreases slowly with time. The equation for the time for the sphere to evaporate completely can be derived by assuming pseudo-steady state and by equating the diffusion flux equation (62-32), where ris now a variable, to the moles of solid 4 evaporated per dt time and per unit area as calculated from a material balance. (Sec Problem 6.2-9 for this case.) The material-balance method is similar to Example 6.2-3.The final equation is. Pa RT Pow © IM, Dax Plax ~ Pas) where ris the original sphere radius, p the density of the sphere, and M., the molecular weight. ty (62-34) 2. Diffusion through a conduit of nonuniform cross-sectional area. In Fig. 6.2-3b compo- nent A is diffusion at steady state through a circular conduit which is tapered uniformally as shown. At point 1 the radius is r, and at point 2it is r. At position z in the conduit, for A diffusing through stagnant, nondiffusing B, Pan __ dba RT palP) dz (6235) Using the geometry shown, the variable radius r can be related to position 2 in the path as follows: (sat pen was an Chap. 6 Principles of Mass TransferThis value of r is then substituted into Eq. (6.2-35) to eliminate r and the equation integrated. (62.37) A case similar to thisis given in Problem 6.2-10. 62E Diffusion Coefficients for Gases 1. Experimental determination of iffusion coefficients. A number of different experimen- tal methods have been used to determine the molecular diffusivity for binary gas mixtures. Several of the important methods are as follows. One method is to evaporate pure liquid in a narrow tube with a gas passed over the top as shown in Fig. 6.2-2a. The fallin liquid level is measured with time and the diffusivity calculated from Eq. (62-26). In another method, two pure gases having equal pressures are placed in separate sections of a long tube separated by a partition. The partition is slowly removed and diffusion proceeds. After a given time the partition is reinserted and the gas in each section analyzed. The diffusivities of the vapor of solids such as naphthalene, iodine, and benzoic acid in a gas have been obtained by measuring the rate of evaporation of a sphere. Equation (6.2-32) can be used. See Problem 6.2-9 for an example ofthis. ‘A useful method often used is the two-bulb method (NI). The apparatus consists of two glass bulbs with volumes ¥, and V, m? connected by a capillary of cross-sectional area A m? and length L whose volume is small compared to ¥, and V,, as shown in Fig 62-4, Pure gas A is added to ¥, and pure B to ¥, at the same pressures. The valve is opened, diffosion proceeds for a given time, and then the valve is closed and the mixed contents of each chamber are sampled separately. The equations can be derived by neglecting the capillary volume and assuming each bull is always ofa uniform concentration. Assuming quasi-steady-state diffusion in the capillary, de Dayle cy) Jaa =D Gem — (62.38) where c; is the concentration of A in V, at time ¢ and ¢, in Yj. The rate of diffusion of A going to V, is equal to the rate of accumulation in _ Dudes — end _ 5, der Ala / 4 ia dt (62-39) ‘The average value cy, at equilibrium can be calculated by a material balance from the starting compositions c9 and 2 at r = 0 Ot Wea = hel + hed (62-40) FiouRe 62-4, Diffusvity measurement of ito ‘gases by the ewo-bulb method. Ve t , Ei @ bo 4—| z-—_ bs 0 Sec.6.2 Molecular Diffusion in Gases 393