DIFFUSION In a mixture consisting of two or more components, if the concentrations of the components vary from point to point then there is a natural tendency for each component to migrate/ transport from regions of high concentration to those of low concentration. This process of transfer of mass as a result of the concentration difference of the component in a mixture is called as mass transfer. (Tho transport of a component present in a mixture from a rigion of higher concentration to a region of lower concentration within the mixture is called as mass transfer.) ‘The operations carried out for separating the components of mixtures, involving the transfer of material from one homogeneous phase to another, utilising differences in vapour prossure, solubility or diffusivity, — in which the driving force for transfor is a concentration difference are called as mass transfer operations. In case of evaporation of water from a pool of water into a stream of air flowing over the water surface, molecules of water vapour diffuse through those of the air at the surface into the main portion of air stream, as a consequence of which they are carried away with air. In this case, mass transfer is a rosult of a concentration difference, or gradient, the diffusing substance (water) moving from a region of high concentration to one of low concentration. Hence, the driving force for mass transfer is a concentration difference just as a temperature difference in heat transfer. Fractional distillation (one of the methods of separation) depends on the difference in vapour pressures of different components at the same temperature (volatility), while g absorption depends on the difference in solubility of gases in a selective solvent. Liquid-liquid extraction and leaching depend on the difference in solubility in a liquid solvent. Mass transfer operations include separation techniques such as distillation, gas absorption, liquid extraction, drying, crystallisation, etc. . In mass transfer operations, mass transfer may occur : (a) In one direction, e.g., gas absorption. (b) In opposite directions, e.g., distillation. (c) With simultaneous heat transfer, ¢.g., drying and crystallisation. (4) With a simultaneous chemical reaction, e.g., gas absorption accompanied by a chemical reaction (absorption of CO) in an aqueous solution of KOH) (e) With the exchange of one or more components. (4) Isothermally (at constant T) and non-isothermally. (7A)Unit Operations - il 14 Diffusion molecular diffusion is a slow process whereas eddy diffusion is a fast process, The molecular diffusion is the mechanism of mass transfor in a stationary fluid, i.c., a fluid at rost and fluids in laminar flow. In case of mass transfer in fluids in turbulent flow, the mechanism of mass transfer is by eddy diffusion. The transfer of material in the presence of a concentration gradient is classified as molecular transfer and eddy transfer. Molecular transfer of mass is encountered in stationary fluids or fluids in laminar flow whereas eddy transfer i encountered in the case of fluids under turbulent conditions. Role of diffusion in mass transfer : Diffusion may occur in one phase or in both phases in all the mass transfer operations. In case of distillation, the more volatile component diffuses through the liquid phase to the interface between the phases (liquid and vapour phases) and away from the interface into the vapour phase. The less volatile component diffuses in the opposite direction and passes from the vapour phase to the liquid phase. In case of gas absorption, the solute gas diffuses through the gas phase to the interface and then through the liquid phase (liquid solvent phase) from the interface between the phases. In case of crystallisation, the solid solute diffuses through the mother liquor to the erystals and deposit on tho solid surfaces. In case of drying operation, liquid water (moisture) diffuses through the solid towards the surface of the solid, evaporates and diffuses as a vapour into the gas phase (drying medium). In case of liquid-liquid extraction, the liquid solute diffuses through the raffinate phase and then into the extract phase (solvent phase) from the interface between the phases Molecular Diffusion : Concentrations, velocities and fluxes: Let us consider two chemical species A and B are placed in two compartments that aro separated by a impermeable partition. Now, assume that the partition is suddenly removed so that the species A will diffuse into B and the species B will diffuse in A and this will continue at a constantly decreasing rate until the mixture becomes everywhere uniform in the concontration of its constituents. The process is one of molecular diffusion in which the species are diffused in one another solely as a result of the random motion of molecules. The rate of diffusion is governed by Fick's law and before dealing with this law, we will define the above mentioned terms based on the combination of such species. We make it clear that by word solution we mean a mixture of species of the same phase — gas in gas, liquid in liquid, ete., i.e., one phase - a gascous, a liquid or a solid mixture, ‘Concentration : ‘There are various ways to express the concentration of the various species in a multicomponent system/mixture. We limit our discussion to mass concentration, molar concentration, mass fraction and mole fraction. Mass concentration : It is the mass of species A per unit volume of the solution (mixture). It is equivalent to the density of A and designated as Pi, For the above binary system composed of A and B, Pata = P ve (7D) where p is the mass density of the solution. Molar concentration : It is the number of moles of species A per unit volume of the solution. A Cy = mm (7.2) where Ma is the molecular weight of component A. The units of molar concentration in SI system are kmol/m®. Hence, for a binary system of A and B, the total molar concentration of the mixture is given by C = Ca+Cp + (7.8)Unit Operations ~ It 1. Diffusion Mass fraction : The mass fraction x, of a species A may be defined as the ratio of the mass concentration of species A to the mass density of the solution. x, = 2S wu (TA) Pp Mole fraction : The mole fraction (x4) of a species A can be defined as the r: concentration of A to the molar concentration of the solution. io of the molar ¢ XA = ce we (7.5) For a binary system, we have : x+y = 1 and xetxp = 1 In the gas phase, concentrations are usually expressed in terms of partial pressures. For the ideal gasA, p,V = ngRT CG = ep os (7.8) where pq is the partial pressure of species A in the mixture, na is the number of moles of A in the mixture, V is the mglar volume of the mixture, T is the temperature (absolute), and R is the univeral gas constant. x, in terms of pg is given as : Cy __pyRT _ py = Cae *s = C “PRT =P (TD where P is the total pressure exerted by the gas mixture, _ _Pa, Pe _?P Also, we have C = ysCy =the mae (7.8) Velocities = In a diffusing mixture, various chemical species are moving at different velocities as they may have different mobilities. The bulk velocity of the mixture would be some sort of an average velocity. Let uj be the velocity of the i'® species with respect to the stationary coordinate system. Then, for a mixture of n species, the local mass average velocity u is defined by, 2 2 pin 1 : 79) Zp ia pu is the local rate at which mass passes through a unit cross-section when it is placed oorpendicular to u. In a binary system of A and B components = Pavat Pp Up wa (710) p ‘The local molar avorage velocity of the mixture U, is defined by LZ Gu (TDUnit Operations ~ Il 76 Diffusion Cu is the local rate at which moles pass through a unit cross-section which is placed perpendicular to U. In a binary system, ¢ U = Sasa Ce so (7.19) Let us define two diffusion velocities relative to/with respect to the two bulk velocities (mass and molar average velocities of the mixture). ‘The mass diffusion velocity of a species is the velocity of that species relative to the local mass average velocity of the mixture. Mai diffusion velocity of species i w.r.t. u = uj Mass diffusion velocity of species A wrt, u = U,~ u. The molar diffusion velocity of a species is the velocity of species with respect to/relative to tho local molar avorago velocity of the mixturo. Molar diffusion velocity of species i wr.t. U = uj—U va (7.19) Molar diffusion velocity of species A w.rt. U = uy-U ea (7.14) Mass flow rate : It is the quantity of material flow in mass units per unit time. Molar flow rate : It is the quantity of material flow in molar units per unit time. Flux: The mass transfer flux of a given species (vector quantity) is defined as the amount of that species, in either mass or, molar units, that crosses a unit area per unit time. We will define four types of fluxes, two with reference to fixed coordinates in space and two with respect to local mass average velocity and local molar average velocity (w.r.t. coordinates moving with mass average velocity and molar average velocity). Mass flux : The mass flux of a species i is defined as the mass of the species i that passes through a unit area per unit time. ‘The mass flux relative to the stationary/fixed coordinates is given by, n= Lu so (7.18) ‘The mass flux relative to the mass average velocity u is given by, i = piQy- 0) ves (7.16) Molar flux : It is defined as the moles of species i that passes through a unit area per unit time. ‘The molar flux relative to the stationary coordinates is given by, N= Oy ee (TAD) ‘The molar flux relative to the molar average velocity U is given by, J = Gj-U) ose (7.18) It is true that any one of the above mentioned notation used for the flux is adequate for all diffusion problems, but each has certain advantages. In process calculations, it is usually desirable to refer to a coordinate system fixed in an equipment so the flux Nj is used ir engineering. The fluxes jj and Jj are the usual measures of rates of diffusion and are useful ir formulating the equations of change for multicoinponent systems.Unit Operations - I! 77 Diffusion For a binary system of A and B : ‘The mass fluxes of A and B relative to stationary coordinates are : DA = Pau (7.19) Dp = pap --(7.20) ‘The mass fluxes of A and B relative to mass average velocity are Ja = Pa(ua-u) + (7.21) is = Ps(ug—u) ++ (7.22) ‘The molar fluxes of A and B with respect to stationary coordinates are : Na = Caug (7.28) Na = Opup + (7.24) ‘The molar fluxes of A and B relative to molar average velocity U are: Tn = Ca(ua~ U) (7.25) Jy = Cp(un- U) (7.26) Jaand Jp are diffusion flux of components A and B. The various fluxes can be interrelated We have, Since, Similarly, Fick's law of diffusion : mA Na IN, Na = PAMA = pa(u+ug—u) = pautpa(uy-u) = pautii = Bo 2 PARP + (7.27) = x, Ow tii = Epi ui = pv = x Lay +h = Caua = Cq(U+u-U) = C,U+Cy(uy- U) = CaUtdy = xq (CU) +d, = LG uy =CcU = xa CENj)+Jq «++ (7.28) (7.29) ++ (7.30) A relation between the flux of the diffusing substance and the concentration gradient responsible for molecular diffusion-mass transfer was first proposed by FICK in 1855 and is therefore referred to as Fick's first law of diffusion. The flux of diffusing component A (diffusion flux of A) in z direction in a binary mixture of A and B is proportional to the molar concentration gradient.Unit Operations - It 78 Diffusion So Fick's law of diffusion for a binary mixture for steady state diffusion can be expressed as Cc Jn = —Day- S28 (731) where J, is tho molar flux of A in the 2 direction relative to the molar average velocity [moles per unit area per unit time, kmol/m?.s)). Cys the concentration of A [moles of A per unit volume, kmol/m'] is the concentration gradient in the z-direction. Das is the proportionality constant, known as the molecular diffusivity or diffusion coefficient for component A diffusing through B, m%s and z is the distance in the direction of diffusion, m. The negative sign indicates/implies that diffusion occurs in the direction of a drop in concentration. Diffusivity is defined as the ratio of the flux to the corresponding concentration gradient. ‘The dimensions of the diffusivity are L7/0 and its SI units are m%/s. The diffusivity of any component is a measure of its diffusive mobility and is a function of the temperature, pressure, nature, and concentration of the other components Diffusive mobility is a function of the number of collisions. Therefore, diffusivity inereases with decrease in pressure because number of collisions are less at lower pressure However, the effect of pressure is negligible in case of liquids. Also, as the random motion of the molecules increases with increase in temperature, diffusivity increases with increase in temperature. For a binazy system in the z direction, dropping the subscript z : Jax = Ca(ug- U) we (7,82) Equating equations (7.31) and (7.32), we get Jy = Cqluy-U) = Disc Cata = ~ Dao SE +C,U ++ (7.33) Now, U according to equation (7.12) is given by 1 U = G Cam+Cy us) QU = & (Cy uy + Cp up) CaU = Xa (Ca ua +Cp up) Substituting CaU in equation (7.33), we get ac, Cau, = -DeG + x4 (Ca uy + Cy ug) Using equation (7.23), the above expression becomes Na = Daw SEB 4 xq(Ng + No) Na = Ja +x, (Na+ Neg) we (7.34) Here, J, is the contribution due to concentration gradient, diffusion flux and xy (Na + Np)is the bulk motion contribution, flux due to bulk flow.Molecular Diffusion in Liquids 1. Steady-state equimolar counter diffusion : ‘We have Na = —Np = constant ‘The flux equation for steady state equimolar counter diffusion is given by D; D, Na = PAP Cy Cy) = Pa (i) (xa — x42) (748) where X,1 — Xae is the concentration difference in terms of mole fraction. (P/MDavg. = Cavg = [oyMy + po/My/2 wu (T.A4) Cayg, is the total average concentration of A and B in kmol/m', p; and pz are the average densities of the solution in kg/m? at locations 1 and 2 respectively, and M; and M, are the average molecular weights of the solution at locations 1 and 2 respectively in ke/kmol. 2. Steady state diffusion of A through nondiffusing B: Na = constant, Np = 0 The flux is given by D, Na = zp OMDayg, (sa — xm) os (745) whero X3,m_= (ise — XpiVIn (p2/ep1) Diffusion in Solids : ‘The operations like leaching, drying, ete. involve contact of fluids with solids and involve diffusion in the solid phase. Fick's law for tho steady stato diffusion can bo written as ac, Na = -DaGe ove (7.48) where Nq is the rate of diffusion of A per unit cross-section of solid. Da is the diffusivity of A through the solid, - dC,/dz is the concentration gradient in the direction of diffusion. 1. Diffusion through a flat slab of thickness 7: ‘Taking Da constant, integration of the above equation (7.46) yields Na = Palau Gadd (TAD) 4 2-2, = thickness of the slab Ca, and Ca; are concentrations of A at the opposite sides of the slab. For other solid shapes, the rate of diffusion is given by D Aayg- (Cai— Caza) W = Ny Aayg, = SEA wo (7-48) Aayg, is the average cross-section available for diffusion. For the radial diffusion through a solid cylinder of inner and outer radii r, and rz and length L : 2 yh ay In (r2/r,) For the radial diffusion through a spherical shell of inner and outer radii r, and rs, Aavg. = 4€1ir2 and z=1—T Aavg. 2 TTUnit Operations ~ Il 7.13 Diffusion ‘The total molar concentration for the gaseous mixture is given hy C= Qty (7.53) Differentiating both the sides of equation (7.58) with respect to x, = Cs 80 ws (164) or a == —ihe ++ (7.55) Therefore, if a gradient exists in the gas A, a gradient existe in the gas B. The gradient of B is equal but opposite in sign to that of A. Fick's law for component A for constant total concentration is Ja = Day SSA (7.56) Combining equations (7.49), (7.50) and (7.51), dC, Sn = -Das Gt ac, = -Jpe -[- Dea a] (TBD, aC, | da Din GS = Daa G w= (7.58) aC _ _aCy but dx = dt w+ (7.59) Das = Dpa --- (7.60) This shows that for a binary mixture of A and B, the diffusivity cooffcient Dyn for A diffusing in B is the same as Dpa, for B diffusing in A. se We have : Ja = = Dy SCA (76D) For ideal gases, molar concentration of A is related to the partial pressure of A by N, =o4 = PA Cy=af = BR «-- (7.82) ac, 1 dp mA 5 ate va (7.68) Das dP, J, = - - (7.84) Integrating, we get — Daz @ar- Pao) Sa = RT (q— x) ~~ 1.60) Das (Pa1- Pas) = pen Pa Pa | xem vs (7,86) For species B, _ Dea (Ps1~ Pps) k= Re + (T.6DUnit Operations — II 714 Diffusion Equations (7.66) and (7.67) are the equations for steady state equimolar counter diffusion. We know that aC Fe ta «+ (7.68) ‘The gradient of B is equal but opposite in sign to that of A. Since the gradient for B exists, there.must be molar flux of B, as stated by equation (7.50). Combination of equations (7.50), (7.56) and (7.68) gives Js = -dp .. (7.69) This shows that the rates of diffusion aro oqual but in opposite diroctions. Equation (7.69) is always true in the binary mixtures, irrespective of what other mechanisms for mass transfer may be operating. The rates of transfer of the two species by molecular transport (diffusion) are always equal but in opposite directions. When molecular transport is the only mechanism, the overall transfer process is called as an equimolar counter diffusion. ‘Mass Transfer Coefficients : In most mass transfer operations, the turbulent flow is desired to increase the rate of transfer per unit area. In such cases, the mass transfer rate is expressed in terms of mass transfer coefficients. In turbulent flow there are three regions of mass transfer but as it is very difficult to know the value of distance in turbulent region through which diffusion occurs, it is considered that the entire resistance to mass transfer lies in a laminar sublayer of thickness (effective laminar film thickness). The resistance offered by the effective laminar film thickness is approximately the same as the combined resistance offered by three regions in turbulent motion. The flux equations for such situations are of the type : Flux = (Mass transfer coefficient) x (Concentration difference) ‘As the concentration can be expressed in number of ways, we have a variety of types of mass transfer coefficients. Mass transfer coefficient is thus defined as the rate of mass transfer per unit area per unit concentration difference. ‘The flux equation obtained for the steady state equimolar counter diffusion (components A and B diffusing at the same molar rates in opposite directions) for turbulent motion becomes D, Na = RT (Pat ~ Pas) = (7.10) Dye Rzo For a given situation, the term is constant and it can be termed as the mass transfer film coofficient for the gas, k, Na = kg (Pa Pa) eu (LT) The flux equation obtained for the steady state diffusion of A through non-diffusing (stationary) B for turbulent motion may be written as : Dap P Na = RTvpaw (Par Pas) so (7.72) Na = Ke (Par~Pas) + (1.73) Dap P whore, he + Etta Similar equations can be written for the liquid phase.Unit Operations - ih 7.18 Diffusion In absorption of a solute gas A in a liquid solvent from a gas mixture, as shown in Fig. 7.2, mass transfer occurs in the gas phaso from pa to pa; (at the interface) and in the liquid phase from Cx; (at the interface) to Cy. As equilibrium exists at the interface (between the phases), there is no resistance to mass transfer at the interface and pa and Ca, are related through the equilibrium relationship : pa = Hy w+. (7.88) where H is the Henry's constant for the system under consideration, Equilibrium : In mass transfer operations usually there are two phases which are brought in contact for the transfer of constituent material(s) from one phase to another or in both the phases. If two phases come to a state of equilibrium, the net transfer of material ceases. The equilibrium relationship between the phases involved is of basic importance in all the mass transfer calculations. The equilibrium relationships can be expressed by an equation or can be shown graphically. For gas absorption operation, the relationship between the equilibrium concentrations of solute in a gas phase and a liquid phase at constant temperature and pressure is the desired equilibrium relationship between the two phases. Now we will obtain the equilibrium relationship for absorption of ammonia by liquid water from an ammonia-air mixture. Consider that a definite amount of liquid water along with a gaseous mixture of ammonia and air is placed in a closed container which is maintained at constant temperature and pressure. As the ammonia is very soluble in water, some of the ammonia molecules will transfer from the gas phase to the liquid phase, crossing the interface separating the two phases. Some of the ammonia molecules return back into the gas, st a rate proportional to the ammonia concentration in the liquid. As more and more ammonia enters the liquid, its concentration in that phase increases and due to this the rate at which ammonia returns back to the gas phase inereases. This will continues and ultimately a stage will reach at which the rate with which ammonia enters the liquid phase becomes exactly equal to the rate with which it leaves the liquid phase and also at the same time ammonia concentration throughout each phase becomes uniform through the mechanism of diffusion. A dynamic equilibrium is now said to exist between the phases. In a state of equilibrium, the net transfer of ammonia ceases even though ammonia molecules continue to transfer back and forth from one phase to another. The concentrations of ammonia within each phase do not change with time. Then these concentrations of ammonia in these two phases are its equilibrium concentrations, If we further inject additional ammonia into the container, equilibrium will be disturbed, the system will try to attain the state of equilibrium and finally we get a new set of equilibrium concentrations. These equilibrium values of concentrations are higher than the previous obtained values. In this way we can obtain the complete relationship between the equilibrium concentrations in both phases at constant temperature and pressure. If we express the equilibrium concentrations of ammonia (A) in both phases in terms of its mole fractions x, and ya in the liquid and the gas phase respectively and plot the values of y, (as ordinate) against the corresponding values of x, (as abscissa), we obtain a curve as shown in Fig. 7.3. Such a curve is called an equilibrium distribution curve. This curve changes only by conditions imposed on the system such as temperature and pressure. One should note here that at equilibrium, the concentrations of ammonia in the two phases are not equal but it is the chemical potential of ammonia that is the same in both phases and it is this equality of chemical potentials and not of concentrations, which causes the net transfer of solute (ammonia) to cease,Unit Operations — I 7.19 Diffusion yn) ‘Mole fraction of A in gas —» ‘Mole fraction of A in liquid. ——> &) Fig. 7.3 :Equilibrium-distribution curve at constant temperature Mechanism of Mass Transfer : ‘The mechanism of mass transfer across a phase boundary (an interface) can be explained by the various theories such as : G) Whitman's two-film theory (ii) Higbie's penetration theory (ii) Danckwert's surface renewal theory Civ) Toor and Marchello's film penetration theory. The Two-film Theory : Salient features of Whitman's two film theory are: (i) Resistance to transfer in each phase is regarded as lying in a thin film close to the interface (i.c., in two fictitious films one on each side close to the interface). (ii) The transfer in these films is by a steady state process of molecular diffusion. (iti) The concentration gradient is assumed to be linear in these films and it is zero outside the films, i.e., zero in the bulk fluid. Concentration of diffusing solute A Distance Fig. 7.4 (iv) The theory assumes that the turbulence in the bulk fluid die out at the interface of the films. (v) The film capacity is negligible ie. time taken for concentration gradient to establish is small compared to time of transfer. Consider a case of a solute gas (A) diffusing from a gas phase into a liquid phase. There must be a concentration gradient in the direction of mass transfer within each phase. This is shown in Fig, 7.4 graphically in terms of distance through the phases.Unit Operations - I! 721 Diffusion * A YAN YA __ Yanai) + Vai-yy) K-N, * Na 41 _ yazya YSWA KON 7 ON ad _1 Yai-Yp K, * k, * kr Gai- xa) 1 1 m toi ym +++ (7.98) K ~ kt where, m =slope = (a- ya) = x4) VK, is the overall resistance to mass transfer and 1/k, and m/k, are the resistances in the liquid and gas films. The resistances in two phases are added to get an overall resistance and hence it is also called as two resistance theory. On a similar line, x, is a measure of y, and it can be readily shown that i 1 w+ (7.94) ‘The Penetration Theory : ‘The penetration theory was proposed by Higbie, The main features of this theory are : 1. As the time of exposure of fluid for mass transfer generally being short, development/establishment of the concentration gradient of film theory (characteristic of steady state) is not possible. 2. The transfer is largly because of fresh material brought to the interface by the eddies. 3. A process of unsteady state transfer occurs for a fixed period at the freshly exposed surface. 4, Each fluid element (eddy) resides for the same length of time period at the surface. According to this theory, the mass transfer coefficient is proportional to the square root of the diffusivity. Surface Renewal Theory : According to this theory proposed by Danckwerts 1. The eddies of the fluid at the surface aro exposed to varying lengths of time. 2. On the basis of exposure-time histories, an age distribution for the surface elements is calculated. 8. The mass transfer coefficient is proportional. to the square root of the diffusivity regardless of the nature of the surface renewal rate Counter current and Cocurrent Mass Transfer : Mass transfer processes that involve two fluid streams are frequently carried out continuously by passing the fluid streams either in a counter current or a cocurrent fashion in a column device. The average driving force for a given situation will be larger in the countercurrent operation than in the cocurrent operation and because of which smaller size equipment is needed for a given set of flow conditions for countercurrent operation. The counter current flow is more common. ‘The examples of counter current mass transfer processes are : (Distillation in packed column : In this caso, a vapour stream (thermally created) is moving up against the downward flow of a liquid reflux. At steady state, a state of dynamic equilibrium is set up. The more volatile component under the action of aUnit Operations — Il Z. iftusion concentration gradient is transferred from the liquid phase to the interface and then from the interface into the'vapour phase. The less volatile component is transferred in the opposite direction and passes through the vapour into the liquid. Here equimolar counter diffusion takes place if the molar latent heats of the components are of the same magnitude (ii) Absorption in packed column : In this case, a solute gas together with a carrier gas moves up against the downward flow of a liquid (solvent). ‘The solute gas diffuses through the gas phase to the intorface where it dissolves and is then transferred into the bulk of the liquid. Gil) Liquid-liquid extraction in packed/spray column : In this ease, both the streams are Tiguid. The lighter liquid rises through the denser one. ‘The solute diffuses from the raffinate phase to the interface and away from the interface into the extract phase. Examples of Cocurrent Flow : The cocurrent flow of gas and liquid streams usually in the downward direction through a packed column is used for - catalytic chemical reaction between components of fluids, diffusional operation when 2 gas to be dissolved in a liquid is a pure substance and for diffusional operation accompanying a chemical reaction, e.g., in absorption of hydrogen sulfide in sodium hydroxide solution. The cocurrent flow produces a separation effect equivalent to that obtained with only one theoretical stage so used for such cases only. With cocurrent flow there is no flooding and there is no upper limit for permissible phase flow rates, The cocurrent flow is rarely used in the absence of a chemical reaction. Analogies among Heat, Mass and Momentum Transfer : Depending upon the fluid flow conditions, the mechanism of the transfer process can be classified a8 molecular transport (characteristic of stream line flow) and combined molecular and eddy transfer (characteristic of total flow regime). There are similarities in governing equations for molecular transport as well as for turbulent transport and we can say that we have analogies among these transport processes. A great deal of effort has been devoted in the literature in developing analogies among those three transport processes for turbulent transfer. General Molecular Transport Equation : ‘The molecular transport of momentum, heat and mass is characterised by the same general equation of the type Driving force Rate of a transfer process =F tance (7.95) Molecular transport or molecular diffusion equations for momentum, heat and mass transfer : ‘These equations are applicable to laminar Now as molecular transport is a characteristic of laminar/stream line flow. Newton's law for momentum transport, i.e., Newton's equation for molecular diffusion of momentum for constant density is Te = (7.96) Tax (79D where t,, is the momentum transferred per unit time per unit area, where momentum has units of (kg.mYs. [It is aleo called as the momentum flux], is viscosity and p is the density of fluid. v is the kinematic viscosity and also called as the diffusivity of momentum having units of m%/s.Unit Operations — 11 1.23 Diffusion Fourior's law for heat transport, i.c., Four for constant p and C, is equation for molecular diffusion of heat B . 91 2GD (7.98) where # is the heat transferred per unit time per unit area and is called as heat flux having units of Wim? [Jm?.s)). o is the thermal diffusjvity or diffusivity of heat in m%s. Fick's law of molecular mass transport or Fick's equation for molecular diffusion of mass for constant total concentration in a fluid is ac, Jn = — Dap i - — Dy and : wu. (7.99) where Ja, is the molar flux of component A in the z direction due to molecular diffusion in kmol A(m?.s), Day is the molecular diffusivity of molecule A in B or mass diffusivity in m%s, Ca is the molar concentration of A in kmol/m®. ‘These equations state, respectively, that (a) momentum transport occurs because of a gradient in momentum concentration, (b) energy transport occurs because of a gradient in energy concentration, and (c) the mass transport occurs because of a gradient in mass concentration. ‘Turbulent diffusion equations for momentum, heat and mass transfer : For combined molecular and eddy transfer, the relations for momentum, heat and mass are: For turbulent momentum transfer for constant density, te = — up +e) SP vs (7.100) tax = -(+Ey) Aeun (7.101) For turbulent heat transfer for constant p and C,, a. ap C,T) & = -+en =» (7.102) For turbulent mass transfer for constant total molar concentration, ac, Tn = ~ Din + om) GS +++ (7.108) In the above equations, ¢,, is the turbulent or eddy diffusivity of momentum in m%s, ty is the turbulent or eddy diffusivity of heat or eddy thermal diffusivity in m%s and ey is the turbulent or eddy diffusivity of mass in m%s. Again, these equations are quite similar or analogous to each other. Equations (7.97), (7.98) and (7.99) for momentum, heat and mass transfer are similar to each other and to the general molecular transport equation (7.95). All these equations have a flux on the left hand side having the units of a quantity of momentum, heat or mass transferred per unit time per unit arcs; a diffusivity of momentum, heat and mass (ic.,Unit Operations — it 227 fusion Solution: 1. The flux equation for diffusion of A through non-diffusing B is D, = DP Na = Btzppw Pa-Pa) where, Dag = 2.30%10°% m/s P = 1.103x10°Pa Pa = 15x 10*Pa Pa = 5x10°Pa Pa = Ppa = 1.108x10° - 15x10" = 8.63x10'Pa Pao =:P—pa = 1.103x 10° - 5x10" = 9.63x10'Pa = Pp Pa_ Pam = Tn (pp / py) (9.63 x 10* - 8.63 x 10*) In (9.63 x 1078.63 x 10) = 9.121«10* Pa T = 208K, z= 015m R = 8.81451 m®. kPal(kmol.K) = 8314.51 m*.Pa / (kmol.K) Ny = 2:80%10°5 x 1.103 x 10° (1.5 x 10-5 x 10°) a” 8914.51 x 298 x 0.15 x 9.121 x 10° = 7.484107 kmol(m?.s) + Ans. 2. The flux equation for equimolar counter-diffusion is Na = RAE (para) 2.30 x 10° (1.5 x 10* - 5 x 10 . 8314.51 x 298 x 0.15 = 6.19 x 10" kmol(m*.s) ws Ans. Ex. 7.5 : Hydrochloric acid (A) at 283 K diffuses through a thin film of water (B) 4 mm thick. The concentration of A at location 1 on one boundary of the film is 12 weight % (density pi = 1060.7 kg/m?) and on other boundary, at location 2, is 4 weight % (density Pz = 1020.15 kg/m’). Tho diffusivity of HCl in water is 2.5 x 10~° m*/s. Calculate the flux of diffusion of A assuming water to be stagnant (i.e. non-diffusing). Solution : Molecular weight of HCI = 36.5, Molecular weight of HzO = 18 At location 1: Mole fraction of HCl (A) 12/86. . *al = 79/865 + (100 - 12/18 - = 0.063 xp, = 1-0.063 = 0.937 Average molecular weight at location-1 is 100 Mi = 39/96.5 + (100 - 12v18 19.166 kg/kmolUnit Operations ~ it 7.28 Diffusion In 100 kg of HCl — water mixture, there are 12 kg of HCI and 100 - 12 = 88 kg of H,O at location-1 (as at location—1, HCI concentration is 12 weight %). moles of HC] = a = 0.8287 kmol, moles of HO = 8 = 4.8888 kmol Total moles of mixture of HC] = 0.3287 + 4.8888 = 5.2175 kmol Moles of HCl Xa = Total moles M, = kg of mixture / kmol of mixture = Fgq7g = 19-100 ky/kmol At location-2, the molefraction of HCl is 4136.5 Xa: = (736.5) + (100 - 418 _ 0.1096 * 0.1096 + 5.3333 Xa. = 1-0.0201 0.9799 Average molecular weight at location-2 is M, = = 4/36.5 + 96/18 18.3728 kg/kmol PaM, + pp/My Cry = MLE eae (1060.7/19.166) + (1020.15/18.3728) 2 55.4336 kmol/m? (Xpo — aa) / In (po / Xp1) (0.9799 — 0.937) / In (0.9799/0.937) 0.958 2 = 4mm ‘The diffusional flux for HC with non- = 0.0201 XB, Me 0.004 m fusing water is given by Na = aes (a3 = Xan) 2.5 x 10 x 55.4336 (0.063 — 0.0201) 0.958 x 0.004 1.55 x 10% kmol(m?.s) Ans. Ex. 7.6 : Calculate the rate of diffusion of acetic acid (A) across a film of non-diffusing water (B) 1 mm thick at 290 K if the concentrations of acetic acid on the opposite sides of the film are 9% and 3% respectively. The densities of 9% and 3% solutions are 1012 kg/m? and 1003.2 kg/m? respectively. The diffusivity of acetic acid in water is 0.95 x 10° m%/s, Solution: Dag = 0.95x 10° m%s, z= 1mm =1x10%m At location 1, on one side of film : r= 1012 kg/m, Acetic acid = 9% by weight ‘Mol. Wt. of acetic acid (CH,COOH) = 60, Mol. Wt. of water (H,0) = 18 0Unit u 7.29 Diffusion = 00 _ ar = 9760 + (100 - 918 O15, * 0.16 + 5.05 = Average molecular weight of solution = 5 = 19.21 ke/kmol xpi = 1-0.0288 = cons At location-2, on other / opposite side of film : Weight % of acetic acid = 3%, py = 100.3 kg/m? 3/60 *a2 = 360+ (100- ayie = 00082 Xp2 = 1~0,0092 = 0.9908 100 Mz = ¥60+@00-syi8 ~ 184 Px/My + po/Ma Cave = z __ (1019/19.21) + (1008.2/18.40) = 2 = 53.6 kmol/m® p,m = (pz ~ xpi) In (xpe /xp1) (0.9908 — 0.9712) In (0.9908/0.9712) 0.980 - The flux of acetic acid is given by : Dap -C, Na = pan Oat %As) 0.95 x 10° = Taio x 0.98 (0088-00082) = 1.018 x 10 kmol/(m?.s) + Ans, Ex. 7.7 : Hydrogen gas at 202.6 kPa (2 atm) and 298 K (25°C) flows through a pipe made of unvuleanised neoprene rubber with id. and o.d. 25 and 50 mm respectively. The diffusivity of hydrogen through rubber is 1.8 x 10 ems. Calculate the rate of loss of hydrogen by diffusion per meter length of pipe. The solubility of hydrogen is 0.053 em’ (NTP)/em$-atm. Solution : 1 m length of pipe, gen-r = sas id. ers = 125mm =0.0125 m Da = 18x10 cem%s = 1810-10 m%/s L=im A QnL (ry— ry) __2x (1) (0.0125) ave. = “Tn (re/ty) in (0.025/0.0125) 0.1133 m?