i}c [al ENGINEERING Mass transfer - CH2051 Dr. Tran Tan Viét Vice Dean - Faculty of Chemical Engineering HoChiMinh City University of Technology — VNU HCM Email: [email protected] Room: 114 B2Chapter 2 Molecular Diffusion Dr. Tran Tan Viét | 4\ 5) ®& . Sa ueModes of mass transfer Mass transfer could occur by the following three ways: Q Diffusion is the net transport of substances in a stationary solid or fluid under a concentration gradient. Q Advection is the net transport of substances by the moving fluid. It cannot therefore happen in solids. It does not include transport of substances by simple diffusion. Q Convection is the net transport of substances caused by both advective transport and diffusive transport in fluids.Modes of mass transfer Spoon Water Md, Stirring the water > with a spoon if creates forced convection. Cup gi) KL That helps the sugar molecules to yey (ora) Convection (slower) (faster) transfer to the bulk water much faster.CONTENTS Molecular Convective pried] ECM Be litte Chapter 2 51. Diffusion phenomena QOFick’s law: linear relation between the rate of diffusion of chemical species and the concentration gradient of that species. QO Thermal diffusion: Diffusion due to a temperature gradient. Usually negligible unless the temperature gradient is very large. OPressure diffusion: Diffusion due to a pressure gradient. Usually negligible unless the pressure gradient is very large.1.Diffusion phenomena + Whenever there is concentration difference in a medium, nature tends to equalize things by forcing a flow from the high to the low concentration region. Water [salt Before After + The molecular transport process of mass is characterized by the general equation: Rate of transfer process = driving force resistance1. Diffusion phenomena Example of Mass Transfer Processes Consider a tank that is divided into two equal parts by a partition. Initially, the left half of the tank contains nitrogen /V, gas while the right half contains H, at the same temperature and pressure. When the partition is removed the /V, molecules will start diffusing into the air while the 4, molecules diffuse into the /V>. If we wait long enough, we will have a homogeneous mixture of /V, and H, in the tank.The temperature and pressure are such that the diffusion coefficient is 0.1 cm?/sec. Find [-—}— hydrogen the molar average velocity v’, the mass average velocity v, the volume average velocity Vv’ at the average concentration in ooo the system. ; The volume in this system does not move, so v’ = 0. If the gases are ideal, the molar concentration is constant, so v’ = 0. j=ey,= Gu ~c,)) Diffusion in the thin-film Dee) _ 0-11-90) _ j For nitrogen at an average ook ( G d= 10 05 }=0.02 cm/sec! concentration of 0.5 ¢ =-0.02 cm/sec For hydrogen at an average concentration of 0.5 c = = PSH = 0.933 Mass fraction of nitrogen M,+c,M, 0.5(28)+0.5(2) _ -__ 95) 9 967 Mass fraction of hydrogen > 0.5(28) + 0.5(2) y= v1, +; 1, = 0.933(0.02) + 0.067(20:02) = 0.017 cm/sec1. Diffusion phenomena * Liquid in open pail of water evaporates into air because of the difference in concentration of water vapor at the water surface and the surrounding air. * Adrop of blue liquid dye is added to a cup of water. The dye molecules will diffuse slowly by molecular diffusion to all parts of the water.Understanding diffusion in one dimensionSolvent B concentration of A concentration of A is high is low Mass transfer by diffusion occurs when a component in a stationary solid or fluid goes from one point to another driven by a concentration gradient of the component.Pe * SofventBe° . SoluteA « a ° ° : concentration of A is the same everywhere Diffusion is the macroscopic result of random thermal motion on a micoscopic scale (Brownian motion). It occurs even when there is no concentration gradient (but there will be no net flux).Liquids A and B are separated from each other. Separation removed. A goes from high concentration of A to low concentration of A. B goes from high concentration of B to low concentration of B. Molecules of A and B are uniformly distributed everywhere in the vessel purely due to DIFFUSION. Equilibrium is reachedA diffusion problem that occurs in the field of microelectronics is the oxidation of silicon according to the reaction Si + O,— SiO). When a slab of the material is exposed to gaseous oxygen, the oxygen undergoes a first-order reaction to produce a layer of the oxide. The task is to predict the thickness d of the very slowly- growing oxide layer as a function of time f. Oxygen hs Cao at Z=0 Silicon oxide layer Ca=CasatZ=5Mathematical modelling of steady-state one dimensional diffusive mass transfer* Molecular diffusion or molecular transport can be defined as the transfer or movement of individual molecules through a fluid by mean of the random, individual movements of the molecules. ® Figure schematic diagram of molecular difusion process (1) + if fhiensare greater number of A molecules near point (1) than at (2), then since molecules diffuse randomly in both direction, more A molecules will diffuse from (1) to (2) than from (2) to (1). * The net diffusion of Ais from high to low concentration regions.For mass transfer occurring only in z-direction Jy =- Dag —A ———— (1) Mixture Ca of A&B What is J,? Ja Cy, + dC, dzJ,=+-D ~ concentration gradient of A AB ~~» Ain z-direction Unit: mass (or moles) per volume per distance diffusion coefficient (or diffusivity) of A in B diffusion flux of A in relation to the bulk motion in z-direction Unit: mass (or moles) per area per time What is the unit of diffusivity? Chapter 2 1For dissolved matter in water: D = 10° cm/s For gases in air at 1 atm and at room temperature: D = 0.1 to 0.01 cm?/s Diffusivity depends on the type of solute, type of solvent, temperature, pressure, solution phase (gas, liquid or solid) and other characteristics.Molecular diffusion of Helium in Nitrogen: A mixture of He and Nz gas is contained in a pipe (0.2 m long) at 298 K and 1 atm total pressure which is constant throughout. The partial pressure of He is 0.60 atm at one end of the pipe, and it is 0.20 atm at the other end. Calculate the flux of He at steady state if Dag of He-N, mixture is 0.687 x 10-4 m?/s. Solution: Use Fick’s law of diffusion given by equation (1) as dc J,=-D A A AB dz Rearranging the Fick’s law and integrating gives the following: Chapter 2 a22 Cys [us dz = -[Pas ic, ———_@ 4 Cay At steady state, diffusion flux is constant. Diffusivity is taken as constant. Therefore, equation (2) gives Jq(Z2— 21) = - Dag (Ca2— Car) —— 8) Dag is given as 0.687 x 10+ m?/s (Z)—2,) is given as 0.2 m (Cag— Cas) =?Even though C, is not given at points 1 and 2, partial pressures are given. We could relate partial pressure to concentration as follows: pe Number of moles of A Cua a V~—— Total volume __» Absolute temperature Pa V=ngRT —_ “~*Gas constant Partial pressure of A Combining the above we getEquation (3) can therefore be written as dyheo- a. Das a= Pa which gives the flux as i (Pa2— Par) oe lege (0.6 — 0.2) x 1.01325 x 105 Pa (8314 J/kmol.K) x (298 K) x (0.20-0) m Ja = 5.63 x 10° kmol/m?.s Ja = - (0.687x10-4 m/s)Summary: Modelling diffusion in z-direction (Caz— Car) _ D (Pa2— Pas) J, =-D nae aaa *® RT(Z)- Z;) \ Ca, and pa, at Z, and Zp z |Caz and paz at 2, oe remain unchanged with d time (steady state). Dag is constant Longitudinal flow: Flow area perpendicular to the flow direction is a constant.Derivation of Dag = Dg, under certain conditions Dag: diffusivity of Ain B Daa: diffusivity of Bin AConsider steady-state diffusion in an ideal mixture of 2 ideal gases A & B at constant total pressure and temperature. Molar diffusive flux of Ain B: J, = - Bg (4) dz iffusi ime JG = dc Molar diffusive flux of Bin A: J, = - Dpa ~ “8 6) dz Jaand Js : molar diffusive flux of A and B, respectively (moles/area.time) C,and Cg: concentration of A and B, respectively (moles/volume) Dag and Dga: diffusivities of Ain B and of B inA, respectively z: distance in the direction of transferSince the total pressure remains constant, there is no net mass transfer. That is, Jat Jp =0 (6) For an ideal gas mixture at constant pressure, Cy + Cg = p,/RT + pp/RT = P/RT = constant (7) Substituting (6) and (7) in (4) and (5), we get Therefore, dC, + dC, =0 Dag = Dga = D (Say) Therefore, (4) & (5) give Ja=-D dC, —— (8a) dz dc, Jp =-D Bb) dz Chapter 2 28This is known as equimolar counter diffusion. This describes the mass transfer arising solely from the random motion of the molecules (i.e., only diffusion) It is applicable to stationary medium or a fluid in streamline flow. dC, Jg=-D—A— — (6a) dc J,So[) = __ (iy) dz Chapter 2.Mathematical modelling of steady-state one dimensional convective mass transferDiffusion is the net transport of substances in a stationary solid or fluid under a concentration gradient. Advection is the net transport of substances by the moving fluid, and so cannot happen in solids. It does not include transport of substances by simple diffusion. Convection is the net transport of substances caused by both advective transport and diffusive transport in fluids. Jais the diffusive flux described by Fick’s law, and we have already studied about it. Let us use Na to denote the total flux by convection (which is diffusion plus advection.dC, dz The velocity of the above diffusive flux of Ain B can be given by Molar diffusive flux of Ain B: Ja =- Das (4) Ja (mol/m.s) (9) Vadiffusion (M/S) = Cx (mol/m3) A The velocity of the net flux of Ain B can be given by Na (mol/m?.s) (10) Vaconvection (M/S) = C, (mol/m?) The velocity of the bulk motion can be given by (Na+ Ne) (molim?.s) — ___(11) (Cy) (mol/m) =e*Total concentration Vuk (m/s) =Va.convection = Vadiffusion * Vbutk Multiplying the above by Ca, we get CaVaconvection = CaVaditusion * Ca Vbutk Using equations (9) to (11) in the above, we get (Na+ Np) Cr Na= Ja + Ca ——— (12) Substituting J, from equation (4) in (12), we get (13)Let us introduce partial pressure p, into (13) as follows: Cae A = PA (14a) Vv RT Cre aK = — (14b) tse a ~~ Total pressure Total number of moles Using (14a) and (14b), equation (13) can be written as (15) Dap dpa i Pa (Na+ Np) P RT dzLet us introduce molar fractions x, into (13) as follows: Na = Ca ____ (16) x= —_— (Nat Np) Cc, Using (16), equation (13) can be written as (17)In terms of concentration of A: Na = -Das en + fc (Nat Ne) iz Cy (13) In terms of partial pressures (using py = C,RT and P = C;RT): (15) RT dz Bi Na= - Das 8a Pa (Na+ Ne) In terms of molar fraction of A (using X, = C,/Cy): Na = -CyDag os + Xa(Na+ Ng) (17) IZLiquid Benzene (A) Evaporation of a pure liquid (A) is at the bottom of a narrow tube. Large amount of inert or non- diffusing air (B) is passed over the top. Vapour A diffuses through B in the tube. The boundary at the liquid surface (at point 1) is impermeable to B, since B is insoluble in liquid A. Hence, B cannot diffuse into or away from the surface. Therefore, Ng = 0Substituting Ng = 0 in equation (15), we get Ny=- Das Ba PA_(N,+0) RE dz Rearranging and integrating D, d 22 Paz D, d Na] dz =- AB pea RT (1 - p,/P) 2 Pat DagP in [ee (18) <”-RT(2)-2,) [P—Par pIntroduce the log mean value of inert B as follows: p = (Pp2 — Pa: ) - (P — Pao) — (P— Par) SLM" In(Pp2 /Ps1 ) In[(P - Paz! (P= Pas II = (Par — Paz) In[(P - Paz / (P - Pat )I Equation (18) is therefore written as follows: DagP Na = a AB. (Pat - Paz) (19) RT(Zp— Z;) Pam Equation (19) is the most used form.Using X, = Ca/Cz, Pa = CaRT and P = C;RT, equation (18) can be converted to the following: Ny= —Das©r tn | 1-Xa2} (20) (Z-2;) 1—Xay Introduce the log mean value of inert B as follows: Fae = (Xs — Xp) a (1 = Xa2) = (1 = Xa1) BENT Line Xe) I(T = Xa2 (= Xan] = (Xa1 = Xa2) Inf(1 - Xp2)/ (1 - Xa] Therefore, equation (20) becomes the following: N,=- — DasCr (%pa = Xa) 7 (Z)— Z4) Xp.um ieee (21)Diffusion of water through stagnant, non-diffusing air: Water in the bottom of a narrow metal tube is held at a constant temperature of 293 K. The total pressure of air (assumed to be dry) is 1 atm and the temperature is 293 K. Water evaporates and diffuses through the air in the tube, and the diffusion path is 0.1524 m long. Calculate the rate of evaporation at steady state. The diffusivity of water vapour at 1 atm and 293 K is 0.250 x 10 m?/s. Assume that the vapour pressure of water at 293 K is 0.0231 atm. Answer: 1.595 x 1077 kmol/m?.s Chapter 2 a"Diffusion of water through stagnant, non-diffusing air: Water in the bottom of a narrow metal tube is held at a constant temperature of 293 K. The total pressure of air (assumed to be dry) is 1 atm and the temperature is 293 K. Water evaporates and diffuses through the air in the tube, and the diffusion path is 0.1524 m long. Calculate the rate of evaporation at steady state. The diffusivity of water vapour at 1 atm and 293 K is 0.250 x 10 m?/s. Assume that the vapour pressure of water at 293 K is 0.0231 atm. Answer: 1.595 x 10-7 kmol/m2.s Chapter 2 42Solution: The set-up of Example 6.2.2 is shown in the figure. Assuming steady state, equation (19) applies. Daa P Air (B) N,= ——48-—_ - A RT(Z)— 21) Pam (Pas - Paz) as where X19} - (Pas — Paz) 7 7 a Pe.tm = In{(P - Paz / (P - Pat )] Data provided are the following: ae i Dag = 0.250 x 104 m/s; P=1atm; T=293K; Water (A) Pa; = 0.0231 atm (saturated vapour pressure); Pao = 0 atm (water vapour is carried away by air at point 2) rapt 5Substituting the data provided in the equations given, we get the following: (0.0231 -0) Pim = <= (0.988 atm , In[(1 - 0)/ (1 — 0.0231 )] (0.250x10-4 m2/s)(1x1.01325x10® Pa)(0.0231 - 0) atm (8314 J/kmol.K) (293 K) (0.1524 m) (0.988 atm) = 1.595 x 10°” kmol/m?.sDiffusion in a tube with change in path length: Diffusion of water vapour in a narrow tube is occurring as in Example 6.2.2 aa ° {2 under the same conditions. However, 7 as shown in the figure, at a given “LI time t, the level is z from the top. As diffusion proceeds the level drops slowly. Drive the equation for the time te for the level to drop from a starting point z) m att = 0 to z- att = tp s as shown. Air (B) Water (A) Chapter 2 45Solution: Since the level drops very slowly, we assume pseudo-steady-state condition. Therefore, equation (19) applies in which (z, — z,) must be replaced by z. a | Ze Dag P feat Na = ———- (Pat - Paz) RTZ Pam —— (22) haptSuppose that the level reduce by dz in dt time. Mass balance yields the following: (Na XAX dt) x Ma = Pa X (Ax dz) —— (23) where A is the cross-sectional TI area of the tube, M, is the molecular mass of water and = 2 P, is the density of water. } z dz haptCombining equations (22) and (23), we get Ma Dag P dz= MACABRE (pay-Paz)dt © —— (24) Pa RTZ Peim ae Rearranging (24), we get Zp te Mg Dag P Is it okay to take zdz= —A-AB’ (pa; - dt oa RT Pam Bs “Past Par aNd Pas as 0 constants? (252-27) _ Ma DagP t Px a =RT Pew Pat” Pag) te te= Pa RT Paum (22-20) (25) 2 Ma Dag P (Pat - Pa) This above equation is used to experimentally, determine diffusivity DagEvaporation of a Naphthalene sphere: A sphere of naphthalene having a radius of 2.0 mm is suspended in a large volume of still air at 318 K and 1.01325 x 10° Pa (1 atm). The surface temperature of the naphthalene can be assumed to be at 318 K and its vapour pressure at 318 K is 0.555 mm Hg. The Dag of naphthalene in air at 318 K is 6.92 x 10° m/s. Calculate the rate of evaporation of naphthalene from the surface. If the radius of the sphere decreases slowly with time, drive the equation for the time taken (te) for the sphere to evaporate completely. Chapter 2 PazSolution: All this time the mass transfer of Ais taken as Na (in moles/m?.s) and it is assumed to remain constant for systems at steady-state or pseudo steady-state while carrying out the integrations concerned. For the system considered here, we cannot do that since the area across which the mass transfer occurs vary as the radius changes. Paz Therefore, we use the following definition: Mass transfer Mass transfer per time per area per oad i A time Na - (26) “\. Area of mass transfer For the given system, equation (26) gives Na N,= — 2h AS 4m?Since the given system is a case of A diffusing through stagnant, non-diffusing B, we could start from equation (15). Naz -—a® SPA 4 PA (Na+ Ne) (15) RT dz P Setting Nz = 0 and rearranging the above gives: Das dpa om Na=7 RT (1-p,/P) dz Using equation (26) and replacing dz by dr, th above could be written as follows: N, = Ma Das dP A” At? RT (1-p,/P) dr which can be rearranged to giveMy or __ Das dpa ano RT (1-p,/P) Integrating the above between r, and some point r, (which is a large distance away) gives the following: Paz tn Paz Da or aa Das dpa 40 r RT (1 - p,/P) q Pat Ma | 1_ 1] _ DagP |P- Pag 4m | tp RT |P—Pay hapt (28)Since r, >> 1r,, 1/ r, is much smaller than 1/r, in equation (28), and therefore neglected. So, equation (28) gives the following: Ba DagP |P- Pas 4ur, RT [([P—Pai Using equation (27) and the definition of pai, Paz the above could be written as Ma _ _DapP_ Pat - Pao ___ (29) 4ur,? RTr, Pam A= Equation (29) gives the rate of evaporation of naphthalene from the surface at r, radius.Data provided are the following: Dag = 6.92 x 10% m?/s; P=1 atm; T= 318K; 1, = 2mm = 2/1000 m; Pas = 0.555/760 atm (saturated vapour pressure); Paz = 0 atm (no naphthalene vapour far away from the sphere) Substituting the data provided, we get the following: (0.555/760 — 0) = aie ei piagagrat Pam In{(4 - 0 )/ (1 — 0.555/760 )] an (6.92x10 m?/s)(1.01325x105 Pa)(0.555/760 - 0) atm (8314 J/kmol.K) (318 K) (2/1000 m) (0.9996 atm) = 9.686 x 10° kmol/m?.sNow, we need to drive the equation for the time taken (t-) for the sphere to evaporate completely. That is, the radius of the sphere is r, att = 0 and it is zero at t = te. Since the radius of the sphere is said to decrease slowly, we assume pseudo-steady- state condition. Therefore, equation (29) applies in which r, is replaced by a as follows: Paz __ tx _ _DagP’ Pat > Par 30 N.-anc? “Kin fam Sphere is enlarged.Suppose that the surface reduce by da in dt time. Mass balance yields the following: (Ng xAx dt) x My = pa x (Ax (-dax)). —— (31) where A is the surface area of the sphere at radius a, M, is the molecular mass of the Paz sphere and py, is the density of the sphere. : Par ss OF) ry Sphere is enlarged.Combining equations (30) and (31), we get Mg Dag P r AE (Pai - Paz) dt ~—, da = —A—ABT RA RTo Pam Rearranging and integrating, we get 0 is oPa2 = MaDasP ip. -p. fat pa fade = RT Pays PA Pao) eee q 0 toes Is it okay to assume that py; and paz : ci ‘ remain constants as the radius of the ; sphere (a) reduces from r, to 0? / a Sphere is enlarged. haptIntegration gives the following results: i (y7=0) 2 Ma Dag P (Pat - Paz) te PA 2 RT Pg.im Paty? RT p, Cr) Pro 2 Ma Dag P (Pat - Paz) The above gives the time taken for py, Ta Al 7 the sphere to vanish completely at a slow rate of evaporation. { RQ) do. ‘ ry Sphere is enlarged. haptEstimating diffusivitiesDiffusivities for different systems could be estimated using the empirical equations provided in the following slides as well as those provided in other reference texts available in the library and other sources.An example at 1 atm and 298 K: System Diffusivity (cm/s) H.-NH3 0.783 H,-CH, 0.726 Ar-CH, 0.202 He-CH, 0.675 He-N, 0.687 Air-H,0 0.260 Air-C,H;OH 0.135 Air-benzene 0.0962(4) Diffusivities of gases in the case of absence of experimental data Holman gives a semiempirical equation by T — Absolute temp, K: P— Absolute reese atm Mg, Msg - molar weights of A, B, g/mol Va, Vg_- molecular volumes of gases A, B , define by sum of molecular volumes of all elements . In case of benzene, naphtalene or anthracen exist, the molecular volumes must be minus structure constance (benzene = 15; Naphtalen 30; anthracen 47,5) Dag is proportional to 1/P and T'.’5 Chapter 2 62Atomic volume, ible 24.5 Atomic volumes for complex molecular volumes for iple substances? Atomic volume, Element in cm*/g mol Element in cm*/gmol Bromine 210 Oxygen, except as noted below 74 Carbon 148 Oxygen, in methyl esters 91 Chlorine 21.6 Oxygen, in methyl ethers 99 Hydrogen 37 Oxygen, in higher ethers Iodine 37.0 and other esters 11.0 Nitrogen, double bond 15.6 Oxygen, in acids 120 Nitrogen, in primary amines 10.5 Sulfur 25.6 Nitrogen, in secondary amines 120 1G. Le Bas, The Molecular Volumes of Liquid Chemical Compounds, Longmans, Green & Company, Ltd., London, 1915. si corrections are recommended: for three-membered ring, as ethylene oxide for four-membered ring, as cyclobutane for five-membered ring, as furan for pyridine for benzene ring for naphthalene ring for anthracene ring Chapter 2 deduct 6 deduct 8.5 deduct 11.5 deduct 15 deduct 15 deduct 30 deduct 47.5 63Table 24.4 Molecular volumes at normal boiling point for some commonly encountered compounds Molecular volume, Molecular volume, Compound in cm3/g mol Compound in cm3/g mol Hydrogen, Hz 143 Nitric oxide, NO 23.6 Oxygen, O. 25.6 Nitrous oxide, N20 36.4 Nitrogen, Nz 312 Ammonia, NH3 25.8 Air 29.9 Water, HO 18.9 Carbon monoxide, CO 30.7 Hydrogen sulfide, H2S 32.9 Carbon dioxide, CO. 34.0 Bromine, Br2 53.2 Carbonyl sulfide, COS Sis Chlorine, Cl, 48.4 Sulfur dioxide, SO. 448 Iodine, In WS: Chapter 2 6410371% (t+t} D.= Ma Mz ag = lerien)] Das - diffusivity in cm?/s P - absolute pressure in atm M; - molecular weight T - temperature in K V; - sum of the diffusion volume for component i Dag is proportional to 1/P and T'.75Table 24.3 Atomic diffusion volumes for use in estimating D4g by method of Fuller, Schettler, and Giddings Atomic and structure diffusion-volume increments, v c 16.5 cl 19.5 H 1.98 Ss 17.0 oO 5.48 Aromatic ring —20.2 N 5.69 Heterocyclic ring —20.2 Diffusion volumes for simple molecules, v Hy 7.07 Ar 16.1 H,O 12.7 D, 6.70 Kr 22.8 CCIF, 114.8 He 2.88 co 18.9 SF, 69.7 Nz 17.9 co, 26.9 Ch S77 02 16.6 N20 35.9 Bry 67.2 Air 20.1 NH3 149 SO, 41.1 Chapter 2.Normal butanol (A) is diffusing through air (B) at 1 atm abs. Using the Fuller et al. method, estimate the diffusivity Dag for the following temperatures with the experimental data: (a) For 0 °C. (b) For 25.9 °C. (c) For 0 °C and 2.0 atm abs.Solution For part (a), P= 1.00 atm, T = 273 + 0 = 273 K, M, (butanol) = 74.1, Ms (air) = 29. From Table 6.2-2, >) v4 = 4(16.5) + 10(1.98) + 1(5.48) = 91.28 (butanol) > ve = 20.1 (air) Substituting into Eq. (6.2-45), _ 1.0 x 10°7(273)!(1/74.1 + 1/29)!2 oe 1.0[(91.28)"? + (20.1) "8? = 7.73 X 10°° m/s This values deviates +10% from the experimental values of 7.03 x 10-° m?/s from Table 6.2-1Solution * For part (b), T= 273 + 25.9 = 298.9. Substituting into Eq. (6.2-45), Dag= 9.05 x 10° m2/s. This values deviates by +4% from the experimental value of 8.70 x 10-6 m2/s ¢ For part (c), the total pressure P = 2.0 atm. Using the value predicted in part (a) and correcting for pressure, Dag = 7.73 x 10°°(1.0/2.0) = 3.865x10% m2/sFor very large spherical molecules (A) of 1000 molecular weight or greater diffusing in a liquid solvent (B) of small molecules: 9.96 x 10°12 T Dag = ————————_ __ applicable pV," for biological Das _ - diffusivity in cm2/s solutes such fi] - temperature in K as proteins y - viscosity of solution in kg/m s Va - solute molar volume at its normal boiling point in m3/kmol Dag is proportional to 1/y and TFor smaller molecules (A) diffusing in a dilute liquid solution of solvent (B): 1.173 x 10-2 (® Mg)"2 T Dag = eT Up Va” applicable Dap - diffusivity in cm/s for biological Mg - molecular weight of solvent B solutes T - temperature in K H - viscosity of solvent B in kg/m s Va, - solute molar volume at its normal boiling point in m?/kmol ® - association parameter of the solvent, which 2.6 for water, 1.9 for methanol, 1.5 for ethanol, and so on Dag is proportional to 1/uUg and TFor smaller molecules (A) diffusing in a dilute liquid solution of solvent (B): 8.928 x 101° T (1/n, + 1/n.) D°x5 = a (1A, + 14) D°ag is diffusivity in cm?/s n, is the valence of cation n_ is the valence of anion A, and A_are the limiting ionic conductances in very dilute solutions T is 298.2 when using the above at 25°C Dag is proportional to TEXAMPLE 5 Estimate the liquid diffusion coefficient of ethanol, C2HsOH, in a dilute solution of water at 10°C. ‘The molecular volume of ethanol may be evaluated by using values from Table 24.5 as follows: Vesuon = 2Vc + 6Vi + Vo Veuon = 214.8) + 63.7) + 7.4 = 59.2cm3/mol At 10°C, the viscosity of a solution containing 0.05 mol of alcohol/liter of water is 1.45 centipoises; the remaining parameters to be used are T= 283K @p for water = 2.26 and Mp for water = 18 Substituting these values into equation (24-52), we obtain 7.4 x 10-8(2.26 x 18)!/2)\ (283 Pesssor-tso = (a Tas, = 7.96 x 10-% cm/s (7:96 x 107" m/s) Chapter 2 3Diffusion in solids Diffusion in solids are occurring at a very slow rate. However, mass transfer in solids are very important. Examples: Leaching of metal ores Drying of timber, and foods Diffusion and catalytic reaction in solid catalysts Separation of fluids by membranes Treatment of metal at high temperature by gases.Diffusion in solids Diffusion in solids occur in two different ways: - Diffusion following Fick’s law (does not depend on the structure of the solid) - Diffusion in porous solids where the actual structure and void channels are importantDiffusion in solids following Fick’s Law Start with equation (13) from Set 1: Na= -Dag Ca 4 Sa (Ny +N) dz Cy we Bulk term is set to zero in solids (13) Therefore, the following equation will be used to describe the process: Na= -Dag CA (33) dzDiffusion in solids following Fick’s Law Pure molecular Pure knudsen diffusion diffusion D ge=€7 Day Figure 24.3 Types of porous diffusion. Shaded areas represent nonporous solids. Chapter 2Diffusion in solids following Fick’s Law The Knudsen number, Kn, given by 2__ mean free path length of the diffusing species Kn . pore diameter pore d, dj 8KNT Dy = Se atm 8 g-cm molecules\ [T fi FS - 19°62 6.023 - 023 Ata (I 38-10 IK )( = mol ) Ma hapter 2Diffusion through a slab Applying equation (33) for steady-state diffusion through a solid slab, we get — Dag (Cay - Caz) N, = _7AB Yat” Va2 34 A a (34) where Na and Dag are taken as constants. Drive (34) and compare it with heat conduction equivalent. Cas Cag Zye,Relating the concentration and solubility The solubility of a solute gas in a solid is usually expressed by the notation S. Unit used in general is the following: m3 solute at STP m? solid . atm partial pressure of solute Relationship between concentration and solubility: S Pa 22.414 Cc. kmol solute /m° solid where pa is in atm STP of 0°C and 1 atmRelating the concentration and permeability The permeability of a solute gas (A) in a solid is usually expressed by the notation Py. in m* solute at STP (0°C and 1 atm) diffusing per second per m? cross-sectional area through a solid 1 m thick under a pressure difference of 1 atm. Unit used in general is the following: m? solute at STP . 1 m thick solid s . m? cross-sectional area . atm pressure difference Relationship between concentration and permeability: Py = Dag S where Dag is in m?/s and S is in m3/m3.atmDiffusion of H, through Neoprene membrane: The gas hydrogen at 17°C and 0.010 atm partial pressure is diffusing through a membrane on vulcanized neoprene rubber 0.5 mm thick. The pressure of H2 on the other side of neoprene is zero. Calculate the steady-state flux, assuming that the only resistance to diffusion is in the membrane. The solubility S of Hz gas in neoprene at 17°C is 0.051 m3 (at STP of 0°C and 1 atm)/mé solid. atm and the diffusivity Dag is 1.03 x 101° m2/s at 17°C. Answer: 4.69 x 10-12 kmol H2/m2.s Chapter 2 82Diffusion through a packging film using permeability: A polythene film 0.00015 m (0.15 mm) thick is being considered for use in packaging a pharmaceutical product at 30°C. If the partial pressure of O2 outside the package is 0.21 atm and inside it is 0.01 atm, calculate the diffusion flux of O2 at steady state. Assume that the resistances to diffusion outside the film and inside are negligible compared to the resistance of the film. Permeability of O, in polythene at 303 K is 4.17 x 10-12 m? solute (STP)/(s.m2.atm.m). Answer: 2.480 x 10-12 kmol O2/m2.s Would you prefer nylon to polythene? Permeability of O2 in nylon at 303 K is 0.029 x 10-12 m% solute (STP)/(s.m?.atm.m). Support your answer. Chapter 2 83Diffusion through a cylinder wall Applying equation (33) for steady-state diffusion through a cylinder wall of inner radius r, and outer radius r, and length L in the radial direction outward, we get Mass transfer _Mass transfer per time per area per fh < an time pace eo ‘A 35 Na= oar Das dr (35) Area of mass transfer Na= 2mL Das(Cai _ Caz) (36) ((< In(ro/ 14) wes t Drive (36) and compare it with \. y heat conduction equivalent.Diffusion through a spherical shell Applying equation (33) for steady-state diffusion through a spherical shell of inner radius r, and outer radius r, in the radial direction outward, we get Mass transfer _Mass transfer per time per area per fh < an j A time Na= iw = -Das ‘A (37) Area of mass transfer nya Atte Daa(Car- Caz) y= 2 ash at AR) (t2- 4) Drive (38) and compare it with heat conduction equivalent. ____ (38)Fick’s First Law of Diffusion is written as follows when C, is only a function of z: dC, Jn =- Dag aaa —_—— 11) Fick’s First Law is written as follows when C, is a function of z as well as of some other variables such as time: aC, oz Jn =~ Dap (39) Observe the use of ordinary and partial derivatives as appropriate.y Ja, in Ja, out — ac, zi iz+Az A: cross-sectional area M,: molecular weight of species A Mass flow of species A into the control volume = Jp, in XAX Ma where ES oC Ja, in = - Dap a az atz Mass flow of species A out of the control volume = Ja, out XAX Ma where 0Ca Ja, out = - Dag oz at z+AzJa, in ye a AC, Ja, out Z+Az A: cross-sectional area M,: molecular weight of species A Accumulation of species A in the control volume at x (AX Az) X My Mass balance for species A in the control volume gives, Ja, in A Ma = Ja, out A Ma aCp + at (A Az) MaMass balance can be simplified to “Den oCp oz = - Dap eC aCy = Az oz atz at z+Az at The above can be rearranged to give BCn _ Das (AC p/OZ) 247 - (OCy/OZ), | at Az (40)In the limit as Az goes to 0, equation (40) is reduced to ar _p, PCa EES ee = Das (41) which is known as the Fick’s Second Law. Fick’s second law in the above form is applicable strictly for constant Dag and for diffusion in solids, and also in stagnant liquids and gases when the medium is dilute in A.Fick’s second law, applies to one-dimensional unsteady-state diffusion, is given below: a, _ p,, PC, at ez? Fick’s second law for one-dimensional diffusion in radial direction only for cylindrical coordinates: aCy _ Dap 9 i Cy a “or. —— (43) Fick’s second law for one-dimensional diffusion in radial direction only for spherical coordinates: ax Dag 2t fi ay (42) at r or at Ee Pr or or (44)Fick’s second law, applies to three-dimensional unsteady-state diffusion, is given below: ay #Cy , PCy | Cp at ax? dy? oz? Fick’s second law for three-dimensional diffusion in cylindrical coordinates: Cy - Dag | 2 , 2a i 8 | aC, z é , 2a (45b) at r or| or 06|rd8} az| a Fick’s second law for three-dimensional diffusion in spherical coordinates: ay _ Dap 2 f “|, 1 8 si aCy Hida — (45a) a © |lar| é | sine a 20 1 Bey sin?@ ab —— (45c)—— a2) Initial condition: Cy = Cao att 3.23, error function is unity up to five decimal places. - For x > 4, the following approximation could be used: exp(-x?) rf(x) = 1- — =~ V1xXExample 3.11 : Determine how long it will take for the dimensionless concentration change (Y) to reach 0.01 ata depth 1 m in a semi-infinite medium. Assume Dag = 0.1 cm/s. Solution: 7 Starting from (46) and (47), we get Y=1- erf 21 Dast Using Y = 0.01, z = 1 m (= 100 cm) and Dag = 0.1 cm/s, we get et | —1% | =1-0.01=0.99 2V0.1xt 100 gata 2V0.1xt wter2 t=2.09hGet back to (46), and determine the equation for the mass flux from it. aCy oz Ja = - Dap atz Jn= VDag/tt exp(-z2/4Dagt) (Cag-Cao) (48) Flux across the interface at z = 0 is Ja = VDag/tIt — (Cas-Cao) (49) latz=0Exercise: Determine how the dimensionless concentration change (Y) profile changes with time in a semi-infinite medium. Assume Dag = 0.1 cm?/s. Work up to 1 m depth of the medium. Solution: Starting from (46) and (47), we get Zz Y=1- ef | —— 2NiDagtLet us get the complete profile using MATLAB which has a built- in error function. clear all DAB =0.1; %em2/s t=0; for i= 1:1:180 %in min t(i) = i*60; z= [0:1:100]; %em x =z/(2 * sqrt(DAB*t(i))); Y(:,i) = 1 - erf(x); end plot(z.Y) xlabel('z (cm)') ylabel('Non-dimensional concentration, Y') grid pause plot(t/3600,Y(100,:)) xlabel('t (h)') ylabel("Y at_ z= 100 cm') grid Chapter 2t=1min to3h 2 2 s © OH So 8 SF oO oS Oo OG A ‘eBueyo uonequeouos jeuolsuewuiIp-uoN z(cm) 103 Chapter 20.035 0.03 0.025 0.02 Yat z=100cm 001 0.005 0.015}- 05 x 15 t(h) Chapter 2 25 104Diffusion in semi-infinite medium: In gas: Dag = 0.1 cm2/s Time taken for the dimensionless concentration change (Y) to reach 0.01 at a depth 1 mis 2.09 h. In liquid: Dag = 10° cm2/s Time taken for the dimensionless concentration change (Y) to reach 0.01 at a depth 1 mis 2.39 year. In solid: Dag = 10° cm2/s Time taken for the dimensionless concentration change (Y) to reach 0.01 at a depth 1 mis 239 centuries.Chapter 2 Molecular Diffusion Dr. Tran TAn Viét AE s\ 5) & ar, Sa ue