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Differential Equations of Mass Transfer
For constant density, constant diffusivity and no chemical production, RA = 0, we obtain v'VcA=DABV2CA
If additionally, v = 0, the equation reduces to
V CA =
Equation (25-23) is the Laplace equation in terms of molar concentration. Each of the equations (25-15) through (25-23) has been writteIl in vector form, thus each applies to any orthogonal coordinate system. By writing the Laplacian operator, V2, in the appropriate form, the transformation of the equation to the desired coordinate system is accomplished. Fick's second "law" of diffusion written in rectangular coordinates is aCA_ D [a CA+ a CA+ a CA] at - AB ax2 ay2 az2 in cylindrical coordinates is aCA_ D [a CA+! aCA+_ a CA+ a CA] at - AB a,2 r a, ao2 az2
2 2 2 2
and in spherical coordinates is
aCA=DAB[\ ~(,2aCA)+_2_1_j_(sinOaCA)+ at r ar a, r sin 0 ao ao,
21 a C1] sin 0 a</>
The general differential equation for mass transfer of component A, or the equation of continuity of A, written in rectangular coordinates is aCA [aNA. aNA.y -+ --+--+-at ax ay
in cylindrical coordinates is aCA -+ at
[1 ar (N A,. ) +---+--ao aNaz . 1 aNA.(J A --, a r r
and in spherical coordinates is aCA 1 a . -+ [1 a 2 z-(,NA')+-'-O-O(NA(JsmO)+-.---;:at r a, 'r 1 r sin
aNA tP] =RA a.,.,
COMMONLY ENCOUNTERED BOUNDARY CONDITIONS
A mass transfer process may be described by solving one of the differential equations of mass transfer, using the appropriate initial or boundary conditions,
or both, to determine the constants of integration. The initial and boundary conditions used in mass transfer are very similar to those used in section 16.3 for energy transfer. You may wish to refer to that section for discussion of initial and boundary conditions. The initial condition in mass transfer processes is the concentration of the diffusing species at the start of the time interval of interest expressed in either molar or mass concentration units. The concentration may be simply equal to a constant, at t = 0, CA= CAo molar units in at t = 0,
= PAo in mass units
or be more complex if the concentration distribution is a function of space variables at the start of the time measurement. The boundary conditions most generally encountered include: 1. The concentration of a surface may be specified. This concentration may be in terms of molar concentration, CA= CA,; of mole fractions, YA = YA, in gases or XA = XA, in liquids and solids; of mass concentration, PA = PA,; or of mass fraction, WA = WA,. When the system is a gas, the concentration is related to the partial pressure by Dalton's law; accordingly, the concentration may be in terms of partial pressure, PA = PA, = YA,P. For the specific case of diffusion from a liquid into a gas phase, the boundary condition at the liquid surface is defined for an ideal liquid solution by Raoult's law to be PA, = xAP A,where XA is the mole fraction in the liquid, and PAis the vapor pressure of species A evaluated at the temperature of the liquid. 2. The mass flux at a surface may be specified; for example, iA = iAl or NA = NA,. Cases of engineering interest include where the flux is zero due to an impermeable surface and where the mass flux is specified as, for example,
dWAI = - P DABdz
3. The rate of a chemical reaction may be specified; for example, if component A disappears at the boundary by a first-order chemical reaction, we may write NA, =k1cA" where kl is the rate constant for a first-order reaction. When the diffusing species disappears at the boundary by an instantaneous reaction, the concentration of that species is often assumed to be zero. 4. When a fluid is flowing over the phase for which the differential equation of mass is written, the species may be lost from the phase of interest by convective mass transfer. The boundary mass flux is then defined by (25-30) where CA", is the concentration in the fluid stream, CA,is the concentration in the fluid adjacent to the surface, and k; is the convection mass-transfer coefficient defined in section 24.3. We will apply these initial and boundary conditions in solving moleculardiffusion problems in Chapters 26 and 27. Examples on reducing the general differential equation for mass transfer to only the relevant terms follow.
!. oxygen diffuses through an air film to a carbon surface where it reacts according to the following equation: 3 C + 2 O2 ~ 2 CO + COz (a) With the assumption that the carbon surface is flat. aZcAjazZ = 0 and if the concentration does not vary with the angle 0. the rate of production of neutrons is proportional to the neutron concentration.=O aCo2 at . aZCA/a02 = 0. equation (25-11) stipulates V·No. the equation reduces to aCA -=D at [a cA 1 acA] + C k --+-AB arz r ar A 2 The only obvious boundary condition is aCAj ar . For component A.~O -0 which requires the concentration of the diffusing species to be finite at the center of the rod. equation (25-11) stipulates V'N A +--R at aCA A =0 Since the rate of production is proportional to the neutron concentration. For diffusion in solids. we obtain 2 aCA = DAB[aZCA +! aCA +. Upon substituting these relations into equation (25-11).+---Ro. Use one of the general differential equations for mass transfer to write the differential equation which describes the mass transfer process. reduce the general differential equation for mass transfer to write the specific differential equation that describes this steady-state process. EXAMPLE 2 In a hot combustion chamber. a CA + aZcA] + kCA z at ar r ar rZ ao2 az2 If the cylinder is relatively long compared to the radius. where the bulk motion contribution is zero. RA = kcs.516 Differential Equations of Mass Transfer EXAMPLE 1 In a cylindrical nuclear fuel rod which contains fissionable material. List any obvious boundary conditions. For oxygen.
25.2 dY02 ~-2 N 02" or __ cD02-m. starting with the control-volume expression for the conservation of mass. applying to specific situations.4 CLOSURE The general differential equation of mass transfer has been developed in this chapter for a diffusing component in a mixture. this stipulates tN02. dz + Y02(N 02.) According to the reaction.. Fick's law for molecular diffusion stipulates N 02. two moles of oxygen enter the film and two moles of carbon monoxide leave.z' The reaction also predicts that as the two moles of oxygen enter.. accordingly. aCoziat = O. The reaction occurs at one of the boundaries and not uniformly along the diffusion path.' + Nco" + N C02. No> reduces to dN02.z = -NC02. . With diffusion in only the z direction.=O dz (b) Write Fick's law in terms of only oxygen.xture dY02 . Roz = O. were presented. Special forms of the general equation.xture dY02 - 1 +2 Y02 dz This equation can either be substituted into the differential equation that is defined in part (a) or integrated directly in order to obtain the flux of O2 in the z direction. one mole of carbon dioxide leaves../dz and the differential equation becomes dN02. O2.z' The net flux of nitrogen is zero. With these stipulations. accordingly.xture N. N02" = -Nco.1 Derive equation (25-11) for component A in terms of molar units.' = -cD Oz-m. the bulk contribution term becomes = -2No2 Y02 Y02 . V .Problems 517 Since this is a steady-state process.' + N Nz. The boundary conditions most generally encountered in mass-transfer processes have been listed.z and Fick's law reduces to Noloz = -cD02-m. PROBLEMS 25.
decomposed) H L ---r-----l-------' w/////////////////W////////////0"##/:z 0 = = 8 by the reaction H ~ 3L the light products diffuse back into the gas stream. catalytic surface.e.2 Transform equation (25-27) from rectangular coordinates -+--+--+--= aCA aNA. 25.y ay aNA.x at ax aNA. which diffuse through the gas space above the liquid pool. flows' across the mouth of the tube carrying away the vapors of A. A pool of pure liquid A is maintained at the bottom of a small Flow of gas B Z=Z2 diameter tube.3 Show that equation (25-5) may be written in the form apA . the evaporation of A is a steady-state process. (b) Repeat (a) for a spherical. A gas.4 The following sketch illustrates the gas-phase diffusion in the neighborhood of a catalytic surface.z az R A into an equivalent equation written in cylindrical coordinates. isobaric conditions. Reduce the general differential equation for mass .2 -+(V·Av)-DABV P at PA =r« 25. Hot gases of heavy hydrocarbons diffuse to the catalytic surface where they are cracked (i. Under isothermal. (a) Reduce the general differential equation for mass transfer to write the specific differential equation that will describe this steady-state transfer process if the catalyst is considered a flat surface.5 An Arnold diffusion cell is a simple device that is used to measure gas diffusion coefficients. 25. (c) Determine the Fick's law relationship in terms of only compound H. which is insoluble in the liquid.518 Differential Equations of Mass Transfer 25.
The concentration of the water vapor at the outer edge of the air layer is 0. layer of air to a beaker of sulfuric acid where it is instantaneously absorbed.9 Use the general differential equation for mass transfer to write the specific differential equation that will describe the diffusion of a microorganism that was initially placed in a stagnant fluid or gel.5 em thick surrounding the drop. Use . Reduce the general differential equation for mass transfer to write the specific differential equation for (a) the transfer of oxygen into the lake without the presence of a chemical reaction. What would be the form of the Pick's law relationship for species A that would be substituted into the differential equation? Give two boundary conditions that might be used to solve the resulting differential equation. Give two boundary conditions that might be used to solve the resulting differential equation. 25.rj.6 A hemisphere drop of water. Reduce the general differential equation for mass transfer to write the specific differential equation that will describe this steady-state masstransfer process.10 Water vapor diffuses through a O. lying on a flat surface. !. 25. What would be the form of the Pick's law relationship written in terms of only the diffusing water vapor? Give two boundary conditions that might be used to solve the resulting differential equation. Reduce the general differential equation for mass transfer to write the specific differential equation that will describe this mass-transfer process. (b) the/transfer of oxygen into the lake that occurs with the simultaneous disappearance of oxygen by a first-order biological reaction. which initially had a uniform oxygen concentration of 1 kg/rn". evaporates by molecular diffusion through an "effective film" of air 0. has its surface concentration suddenly raised and maintained at a 9 kg/rn ' concentration level.8 The moisture in the hot.15 IbmH20/Ibm dry air.l-in. ! Problems 519 transfer to write the specific differential equation that will describe this mass-transfer process. 25. humid air surrounding a cold-water pipeline continually diffuses to the cold surface where it condenses.7 A large deep lake. 25. 25. the microorganism has a cell division as it diffuses that follows the first-order reaction A ~ 2A Give two boundary conditions that could be used to solve the differential equation.
it begins to decompose B~A The rate of formation of component A is equal to RA -k - lYB moles A produced • (timejtvolume) where YB is the concentration of B expressed in mole fraction.520 Differential Equations of Mass Transfer the general differential equation for mass transfer to write the differential equation for this steady-state. having an initial moisture content of 55 wt%. Reduce the general differential equation that will describe the drying of the interior of the oak roller. unidirectional mass-transfer process. 25.13 A liquid flows over a thin. Show that the equation governing the mass transfer. where y is the distance from the plate and a is a constant. List the two boundary conditions in terms of mole fraction of water vapor. the liquid velocity may be assumed to be parallel to the plate and to be given by v = ay. List the boundary conditions that could be used in solving the differential equation. What would be the form of Fick's law for this process.12 The foIlowing sketch illustrates hood of a catalytic surface: z=o Component A diffuses through a stagnant film to the catalytic surface.11 An oak lawn-mower roIler. with certain simplifying assumptions. where it is instantaneously converted into species B by the reaction A~B When species B diffuses into the stagnant by the first-order reaction film. is placed in a drying kiln where its surface moisture content is maintained at 20 wt%. is D(iCA ax --Z +--2 aZCA) =ayaCA ay ax List the simplifying assumptions. written in terms of the diffusing water vapor? 25. Use the general differential equation for mass transfer to write the differential equation that describes this diffusion process. . Over the region in which diffusion is occurring. the gas-phase diffusion in the neighbor- 25. flat sheet of a slightly soluble solid.
20 em long.Problems 521 25. there is one-dimensional interdiffusion of the two liquids. When the disk is removed. The lower half was initially filled with water and the upper half with the alcohol.15 An early mass-transfer study of oxygen transport in human tissue won a Nobel prize for August Krough.14 The diffusivity of isopropyl alcohol in water was measured in a Loschmidt diffusion cell. oxygen diffuses through air to a flat carbon surface where it reacts to make CO and/or CO2• -------~ytg:------l-----------z=o co and/or CO2 W///#////$#//////////#////!/////#/////#dY//. (c) the following instantaneous reaction occurs on the surface 4C+302 ~ 2CO+2C02 25. The reaction at the surface may be assumed to occur instantaneously. What would be the form of Fick's law if (a) only carbon monoxide is produced on the carbon surface. Write the differential equation for the concentration distribution of isopropyl alcohol and state the necessary boundary conditions that would be required to solve the differential equation. using an infinitely long cylindrical control volume and cylindrical coordinates. This reaction was necessary to explain the metabolic consumption of the oxygen to produce carbon dioxide. The vertical cylinder. that is. The concentration of oxygen at z = 8 is 21 mole percent. RA = -m.16 In a hot combustion chamber. .a z=0 Reduce the general differential equation for mass transfer to write a specific differential equation for oxygen that will describe the steady-state mass transfer process.17 Derive the equation of continuity for component A. he proposed the diffusion of oxygen away from the blood vessel into the annular tissue was accompanied by a zero-order reaction. (b) only carbon dioxide is produced on the carbon surface. 25. What would be the form of Fick's relationship written in terms of only the diffusing oxygen? 25. Use the general differential for mass transfer to write the specific differential equation that will describe the diffusion of oxygen in the human tissue. was divided into halves by a removable disk. By considering a tissue cylinder surrounding each blood vessel. where m is a constant. No reaction occurs in the gas film.
reduce the general differential equation for mass transfer to obtain a specific differential equation for describing the steady-state diffusion of oxygen to the surface of the coal particle. CO.18. is produced at the surface of the carbon particle. Determine the Fick's law relationship for the flux of oxygen from the surrounding air environment if (a) only carbon monoxide. It is placed into a forced-air dryer.19 Use the general differential equation for mass transfer to write the specific differential equation for describing the steady-state diffusion of oxygen to the spherical particle of coal that is described in problem 25. The briquet is approximately spherical with a radius of R. . 25. CO2. If the coal can be assumed to be spherical. (b) only carbon dioxide. give two boundary conditions that might be used in solving the differential equation.18 A fluidized coal reactor has been proposed for a new power plant.20 A charcoal briquet is formed with an initial moisture content of PAO. 25. If the reaction at the surface of the carbon particle is instantaneous.522 Differential Equations of Mass Transfer 25. when carbon monoxide is produced at the surface and as it diffuses away from the particle it reacts with oxygen to form carbon dioxide. which produces a lower surface moisture content of PA.s' Reduce the general differential equation for mass transfer to obtain a differential equation that will describe the drying of the interior of the briquet. is produced at the surface of the carbon particle.
If the tube was initially filled to within 3 cm of the lip of the tube. how long would it take for the methanol level to fall to the following levels: (a) 4 em.1 A steady-state Arnold cell is used to determine the diffusivity of methanol in air at 298 K and 1.80 em" cross-sectional area and a diffusion path of 16 ern.013 x 105 Pa. These models will be used in Chapter 28 to evaluate and explain convective mass-transfer coefficients. PROBLEMS 26. graphical.7914.7 x 104 Pa and its specific gravity is 0. how much methanol must be supplied to the cell to maintain a constant liquid level. These methods included analytical.2 The Arnold cell. 26.2. and the cell has a 0.=-t ~ (26-86) 1T exp As previously shown in section 26. . 26. At 298 K.l. the penetration model mass flux varies as the diffusion coefficient to the! power. when the diffusion was accompanied by a rapid chemical disappearance of the diffusing component. is to be operated as a pseudo-steady-state cell.. described in problem 26. film and penetration. (c) 12 cm.560 Steady-State Molecular Diffusion or NA. analogical and numerical techniques.5 CLOSURE . were introduced. One-directional systems both with and without chemical production were considered. Four types of solutions to mass-transfer problems ill more than one direction were discussed. It is hoped that this two-pronged attack will provide the student with an insight into the various terms contained in the general differential equation. If the results agree with the value reported in Appendix J.yIY~1l = CAn \j-.1. In this chapter we have considered solutions to molecular mass-transfer problems. (b) 6 em. the vapor pressure of methanol is 1. The defining differential equations were established through the use of a control volume expression for the conservation of mass or by using the general differential equation for mass transfer. and thus enable him to decide whether they are relevant or irrelevant to any specific situation. Two models of mass transfer.
3 The diffusivity of ethanol through air was determined in a steady-state Arnold evaporating cell. Consider a mass transfer area of 100 em" and a water film temperature of 283 K. The results will help confirm the concept of penetration depths that were discussed in section 26. Sievert's law is a variant of Henry's law for gases that dissociate upon dissolving. P2. respectively. using the Hirschfelder equation. When standard . (a) If 0.Problems 561 26. is where DA2 is the diffusivity of A2 through the membrane.6 The permeability of solids by gases is experimentally determined by steady-state diffusion measurements. If this is so. P2. A2.5 Determine the time for one mole of ethanol to diffuse through a 4-mm thick stagnant film of water if the concentrations at the leading and exiting planes are 0.0445 em" of ethanol was evaporated in 10 hr of steady-state operation. (a) How is the flux of component A influenced if the pressure on the system is doubled? (b) Since a partial pressure gradient for component A must exist if it is transferred. how can component B be considered a nondiffusing (NB = 0) gas? 26. was operated at 297 K and 1.4 26. of the diatomic gas by the relation CAl = k(Pd / l2 This same equation also holds at the other surface of the membrane for the off-gas pressure. p i. 26. CAl' in equilibrium with the applied pressure. into a low-pressure reservoir. (a) Prove that the rate of diffusion of a diatomic gas from a high-pressure reservoir.013 x 105 Pa pressure. For a diatomic gas. having a cross-sectional area of 0. The diffusing solute is introduced at one side of a membrane and removed from the other side as a gas.82 ern". a partial pressure gradient for component B must also exist. The length of the diffusion path was 15. Pb through a membrane of thickness z. the mass flux of component A is described by equation (26-8). The cell. and since the total pressure for a given system often remains constant.4 In the case of diffusion through a nondiffusing medium. and compare the two diffusion coefficient values.1 and 0. what should be the value of the diffusivity of ethanol in air? (b) Calculate the same diffusivity. which dissociates upon dissolving into a solid.0 kg moles/rn '.0 em. Sievert's law relates the concentration of A atoms in the surface layer of the membrane.
is selectively removed from an air-Nl-I.1 Determine the rate of diffusion of ammonia. . The oxide that is produced has a larger volume than the metal that is consumed. For the oxidation to proceed. The temperature of the system is 15°C and the total pressure on the system is 1 atm. an oxide film is formed on the surface of the metal. NH3. JA2.42 mole percent and the concentration at the lower boundary of the water layer is essentially zero. The concentration of ammonia at the outer boundary of the gas layer is 3.0 em" /100 g of nickel.9 15 20.8 6. and the density of nickel at 700°C is 9. The diffusivity of hydrogen through nickel at 700°C is 6 X 10-5 cm2/s. 2 mm thick.0 20 32. The solubility of hydrogen in nickel at 1 atm pressure and 700°C is approximately 7.215 cm2/s and in liquid water it is 1.7 In the oxidation of many metals. Eventually. oxygen must diffuse through the oxide film to the surface of the metal.0 g/cm3• Calculate the number of cubic centimeters of hydrogen per hour that diffuses through the nickel. is called the permeability of A2• (b) A piece of laboratory equipment operating at 700°C had hydrogen gas at 8 atm that was separated from a continuously evacuated space by a 8 cm2 nickel disk. At 15°C. oxygen concentration of the free surface of the oxide film. 26. The concentration at the interface between the gas and the liquid phases is given by' the following equilibrium data: Equilibrium Data for Ammonia in Air over Aqueous Solutions PNH3 (mmHg) 5 10 11. In this steady-state process. 26. the oxidation becomes diffusion controlled and the dissolved oxygen concentration at the oxide-metal interface becomes essentially zero.8 Ammonia. the diffusion path increases with time.77 x 10-5 cm2/s. accordingly.6 30 84.1 25 53. the diffusivity of ammonia in air is 0.562 Steady-State Molecular Diffusion pressures are employed with a membrane of standard thickness. develop an expression that tells the depth of the oxide film as a function of time. If a pseudo-steady-state condition may be assumed. ammonia is transferred by molecular diffusion through a stagnant gas layer 2 em thick and then through a stagnant water layer 1 em thick. and the diffusivity of oxygen through the oxide. mixture by absorption into water.
11 An ethanol/water vapor mixture is being rectified by contact with an alcohol/water liquid solution. when the chlorine concentration levels are 0. 26. The temperature is 368 K and the pressure is 1. 26. Both components are diffusing through a gas film 0. back through the stagnant film. The mole fraction of oxygen at z = 0 is 0. chlorine gas is bubbled through water as a disinfecting agent. The mole fraction of ethanol is 0. The alcohol is transferred from the liquid to the vapor phase and the water is transferred in the opposite direction.04 mol/rn" on the one edge of the film and 0.. Component A diffuses through a stagnant film to the catalytic surface where it is instantaneously converted to B. (b) only carbon dioxide is produced at the carbon surface. Compare the time that is required for 1 mole of chlorine to diffuse through a 5-mm thick film of (a) air at 289 K. oxygen diffuses through air to the carbon surface where it reacts to make CO and/or CO2.9 In the treatment of wastewater. The product B diffuses away from the catalytic surface.122 x 106 J/kg and 2. Calculate the rate of diffusion of ethanol and of water in kg/s through one square meter of area.1 mm thck. At that temperature. The reaction at the surface may be assumed to be instantaneous. No reaction occurs in the gas film. (c) the following instantaneous reaction occurs at the carbon surface: 4C+302 ~ 2CO+2C02 26.013 x 105 Pa.80 on one side of the gas film and 0.01 mol/m" on the other edge. respectively.10 In a hot combustion chamber. (b) liquid water at 289 K.12 The following sketch illustrates the gas-phase diffusion in the neighborhood of a catayltic surface.013 x 105 Pa. . co --------t-----------1-----Oxygen Z and/or =8 2 CO o//#/7//#//////////////P/?////?#dP##&#//Z =0 Determine the rate of oxygen diffusion per hour through one square meter of area if (a) only carbon monoxide is produced at the carbon surface.244 x 106 J/kg.Problems 563 26. The pressure on the system is 1.20 on the other side of the film.21. the latent heat of vaporization of the alcohol and water are 1.
13 A liquid mixture of A and B is being separated by a distillation operation. '&?W/?/07&////l&///#/?/w' Z =0 (a) If the reaction on the surface is A ~ B. Determine an equation that will predict the concentration in mole fraction of A at various distances. Both components are diffusing through a gas film 1 in. z. thick. determine an equation that will predict the concentration profile. the difference in the latent heats of vaporization for the two compounds predicts that 2 mol of A will vaporize per mole of B that is condensing. YA at various z levels. from the liquid surface. i. At the temperature of the system. 26.564 Steady-State Molecular Diffusion ---1~------1.~. The tank is cylindrical with a diameter of 1 m.3 on the other side. The liquid level is maintained at a level 1 m below the top of the tank as shown in sketch (a) 0. determine an equation that will predict the concentration profile.. The mole fraction of A isO.SO at one side of the film and 0. 26.5 m t---------Il 1 1 1m m (a) (b) .e.14 A tank containing water has its top open to the air. -. (b) If the reaction on the surface is A ~ 3B. The more volatile component A is transferred from the liquid phase into the vapor phase while B is transferred in the opposite direction.
013 x 105 Pa pressure. having internal diameters of 0.005 cm. 26. where m is a constant.15-m diameter duct. which is 3 m in length. Since the tissue cylinders were believed to be arranged in a hexagonal bundle. as a function of r. that is. 26. at the duct's larger and smaller ends. 1. What will be the loss per hour in this case if dry air at 310 K is blown across the top of the tank? 26. Determine the time that is necessary to reduce the diameter to 0. are connected by a circular 0. .17 An early mass-transfer study of oxygen transport in human tissue won a Nobel prize for August Krough. determine the rate of ammonia transfer between the two tanks.Problems 565 (a) How many moles of water are lost per hour if dry air at 310 K is blown across the top of the tank? (b) It is proposed to add a tapered top to this water tank as shown in sketch (b). the following boundary conditions were suggested: at r =R1. he proposed that the diffusion of oxygen away from the blood vessel into the annular tissue was accompanied by a zero-order reaction. The process is limited by diffusion of the oxygen counterflow to the CO2 and CO that are formed at the particle surface. PA. Twice as much CO is formed as CO2• Assume that the coal is pure carbon with a density of 1280 kg/ern" and that the particle is spherical with an initial diameter of 0. PA =PA at r = R2. Determine the rate of ammonia transfer between the two tanks. and the flux of oxygen that enters the tissue cylinder. = dPA dr 0.16 If the two tanks that are described in problem 26. assuming a steady-state mass transfer.1 m. The reaction was necessary to explain the metabolic consumption of the oxygen to produce carbon dioxide. 26. maintained at the same temperature and pressure. The system is at 273 K and 1.18 A pulverized coal particle burns in air at 1145 K. the diffusivity of oxygen in the gas mixture may be assumed to be 10-4 m2/s. By considering a tissue cylinder surrounding each blood vessel. One tank contains a uniform mixture of 60 mole % ammonia and 40 mole % air and the other tank contains a uniform mixture of 20 mole % ammonia and 80 mole % air. RA = +m.015 em.15 Two large gas tanks. Assume the ammonia diffuses along the duct in the direction of decreasing diameter.15 had been connected by a truncated conical duct. the average oxygen pressure value between arterial and venous ends of the blood vessel the due to the identical oxygen fluxes from the neighboring tissue cylinders Determine the concentration profile. Air (21 mole% oxygen) exists several diameters away from the sphere.20 and 0. respectively. Under the conditions of the combustion process.
0 . At this pressure and at the average temperature of the air film.42 x 1O-31b mol/(hr)(fe) at the surface of the spherical catalyst and the atmosphere surrounding the catalyst contains 30 mole% Hand 10 mole% inert gas. and the thickness of the stagnant film surrounding the catalyst. (b) Evaluate the concentration profile. neglect the effect of the gas phase that is required to replace the evaporated liquid. 26.22 Carbon dioxide diffuses through a 0. the concentration of compound H in the bulk of the gas phase. The pressure of the system is 757 mm Hg. of the catalyst in inches at that specific instant. The gaseous atmosphere is at 1000°C and 1.22 cm2/s.20 is 1. Initially. the diameter of the catalyst particle.5 atm and the diffusivity of H in the gas mixture is 0.25 to 0. The main environment beyond the effective film can be assumed to be free of water vapor. Determine the concentration profile for this process.25 in thick. and if the concentration of carbon dioxide at the outer edge of the air layer is 4 mole%. hot gases of heavy hydrocarbons diffuse to the catalytic surface where they decompose by the following reaction: H--'» 2P The product. P. R.20 In the catalytic cracking of hydrocarbon oils. which covers the drop. How would your estimate be affected if you were to consider the bulk motion of the phase that is required to replace the evaporating liquid? 26. The water in the drop will be maintained at a temperature such that the vapor pressure of the water will always be 76 mm Hg. respectively.566 Steady-State Molecular Diffusion 26.1 in. diffuses back into the gas stream. 26. determine the radius. 0.13 cm2/s. (a) Develop an expression for the cracking reaction rate in terms of the gas-phase properties. Estimate the rate of transfer across one square foot of area if the temperature and pressure of the system are 70 P and 1 atm.19 Estimate how long it will take to reduce the diameter of a hemispherical drop of water that lies on a flat surface from 0.05 in.21 If the flux of the heavy hydrocarbon that is described in problem 26. the diffusion coefficient of water in air may be taken as 0. A kinetic investigation verified that the reaction taking place on a spherical catalyst particle occurs so rapidly that one may presume the rate of diffusion in the stagnant film surrounding the particle controls the overall reaction. expressing the mole fraction of H as a function of the distance from the particle's surface. if the water evaporates by molecular diffusion through an "effective film" of air. stagnant air film to a NaOH solution where it instantaneously disappears by a chemical reaction.
the concentration of the sulfur dioxide in the surrounding environment and on the surface of the calcium oxide. 26. and the diameter of the calcium oxide spherical pellets. it has been proposed to fluidize crushed limestone simultaneously with the coal.05. 26. The specific gravity of uranium is 19.25 A fluidized coal combustion tower has been proposed for a new power plant. In an effort to help eliminate this hazardous pollutant. Develop an expression for the sulfur dioxide adsorption rate in terms of the gas-phase properties. The UF6 is to be prepared by exposing pure uranium pellets. which will. Due to the high sulfur content in most coals. to fluorine gas at 1000 K and 1 atm pressure.24 Determine the time that is required to reduce the diameter of the uranium pellet that is described in problem 26. The molecular diffusion of fluorine to the pellet surface is thought to be the controlling step. UF6. If the reaction occurs irreversibly and instantaneously on the pellet surface and the diffusivity of fluorine through uranium hexafluoride is 0. is to be used as a fuel in an experimental nuclear power reactor.23 from 0. the limestone will decompose to calcium oxide. At the combustion temperatures. in turn.23 Uranium hexafluoride.273 cm2/s at 1000 K and 1 atm. . spherical in shape. adsorb sulfur dioxide from its immediate surrounding environment. 26.2 em. determine the moles of UF6 that is produced when the pellet's diameter is 0.Problems 567 26. sulfur dioxide will often be one of the combustion products.4 to 0.4 em.26 The decomposition of An to form A occurs on a catalytic surface according to the reaction This reaction is so rapid that diffusion through the stagnant film surrounding the catalyst controls the rate of the decomposition. The rate of production of UF6 is required for the reactor design.
30 In a cylindrical nuclear rod that contains fissionable material. Upon reaching the catalytic surface. When Y$#/ff/lff#$##_l~. 26.28 A 20-cm long. Component A diffuses through a stagnant film containing only A and B.26 with the reaction involving the isomerization of A to form An according to nA ~ An. (b) What would be the composition of oxygen 1. (c) a cylindrical rod of radius R and length L. (b) a flat plate of length L and width W.5 em when the sphere infinite amount of air at 165°P and 1 atm molecular weight of 128 g/rnol. the diameter of a naphthalene is suspended in an effectively pressure. ---------------------z=o . and a vapor 26. the concentrations of A and An in the bulk of the fluid phase.1Ibm/fe.0-cm radial distance from the center of the rod.0-cm radial distance from the rod is 40 mole%.0 cm and the oxygen concentration that is 1. 26. a density pressure of 5 mm Hg at 165°P.013 x 105 Pa pressure.27 Reconsider problem 26. and the thickness of the stagnant film if the catalyst is (a) spherical radius of R .0 to 0. Naphthalene has a of 71.29 Estimate the time that is required to reduce sphere from 1. Under the conditions of the combustion process.568 Steady-State Molecular Diffusion Develop an expression for the decomposition rate in terms of the fluid properties.~. the rate of production of neutrons is proportional to the neutron concentration. Assume a steady-state process. (a) Determine the moles of CO that are produced at the surface of the rod per second at the time when the diameter of the rod is 1.0 x 10-5 m2 Is. 26.31 The following sketch illustrates the gas-phase diffusion in the neighborhood of a catalytic surface. cylindrical graphite (pure carbon) rod is inserted into an oxidizing atmosphere at 1145 K and 1. 26. determine the neutron concentration profile in a fuel rod of radius R. The oxidizing process is limited by the diffusion of oxygen counterflow to the carbon monoxide that is formed on the cylindrical surface. Assuming that only thermal neutrons are produced. it is instantaneously converted into species B by the reaction A ~ B. the diffusivity of oxygen in the gas mixture may be assumed to be 1.
the surface area of the edge of the disks are small in comparison with that of the two circular faces.34 Reconsider problem 26. 8 em in diameter. a liquid film is formed on the exterior of the tube. Under steady-state conditions. its thickness is equivalent .31 and determine the concentration profile of compound A in the stagnant film if in the film B decomposes to form A and if A reacts to form B. and one half the thickness of the disks L. A is instantaneously reacting to form B on the catalytic surface. is used as a condenser for removing water from a water vapor-air mixture. 26. develop an expression for (a) the concentration profile within the catalyst.33 Compound A is converted to compound B on the "active sites" within a porous catalytic particle manufactured in the shape of thin disks.elh the concentration of A on the surface CAs> the reaction rate constant ka.32 Reconsider problem 26. (b) the molar flux at the surface z = ±L.Problems 569 B diffuses back into the stagnant film. 26. where a is the available catalytic surface area per unit volume of catalyst. where YB is the concentration of B expressed in mole fraction. Determine the rate at which A enters the gas film if this is a steadystate process. 26. 26. it begins to decompose by the first-order reaction The rate of formation of component A within the film is equal to RA = k1YB. In terms of an "effective diffusion coefficient" D A. The rate of disappearance of A is related to the concentration of A within the catalyst by RA =kac.35 A cooled metal tube.33 for a spherical catalyst of radius R. both by first-order reactions Simultaneously.. moles A produced/(time)(volume).
and the gas mixture is at 370 K and 1. If the water vapor diffuses by molecular diffusion through a path length that is 10% of the tube radius. The gas and liquid phases are in equilibrium at the surface of the water film. determine the rate of water condensation as kg/s per meter of tube length. The gas contains 65 mole% water vapor.013 x 105 Pa. the temperature of the metal surface is 310 K.570 Steady-State Molecular Diffusion to a heat-transfer coefficient of 2500 J/m2 • s : K. . At one point in the condenser.
508 3. having constant thickness.540 4.080 1.z> at any time in terms of the concentration unit WA'. After an appropriate time. are analyzed for the concentration of the solute.96 z '.05 1.10 0.3 Estimate the depth below the surface of a plate of mild steel at which the concentration of carbon may be expected to decrease to 40% of its .67 1.41 0. a thin layer of the particular solute is applied to the end of a bar and allowed to diffuse into the bar.096 2.1 Develop equations that are equivalent to equations (27-6) through (2710) that would permit the evaluation of the mass flux. CA = M -/4'ITDAt e -z2/4D. and z is the distance in the direction normal to the initial solute film. nA. 27. distance at start of section x 104 m % Nickel 0. Arbitrarily setting the last section in which there was no nickel at zero distance.048 4.032 4. since the concentration of the tracer can be determined with higher accuracy than is possible by using chemical analysis.31 1.82 6. t is time.604 3. thin sections are removed parallel to the initial interface. 27. A short length of copper-5% nickel alloy was joined to a bar of pure copper.02 5.69 4.2 The evaluation of diffusion rates within metals is an important metallurgical problem.016 4. This technique is now used with a radioactive tracer as the diffusing solute. A where CA is the concentration of the diffusing solute.064 0.112 (a) Show that the following expression satisfies Fick's second law and the boundary conditions of the diffusion process. M is the quantity of solute that is applied to the end of the bar.524 2. To measure the diffusion coefficient. the following average compositions were obtained for the particular section: % Nickel 0.92 7. These sections.05 4. sections were taken parallel to the plane of joining with the aid of a lathe. After 100000 s.584 Unsteady-State Molecular Diffusion be used for obtaining a solution of an unidirectional transient mass transfer by use of a digital computer or a modified Schmidt plot.63 6. Each section was analyzed for its nickel content. PROBLEMS 27.21 0.000 3.572 1.
CA. the time that is necessary to reduce the center moisture content to 6 wt%. the drying was controlled by the internal diffusion of liquid water to the surface. 27.5 A slab of clay.1 m in diameter.8 A large semideep lake. If the relative resistance to mass transfer at the surface was essentially zero. as a function of the depth. z.4 A porous sphere with a !-in. has its surface concentration suddently raised and maintained at a 9 kg/rrr' concentration level. The surface moisture was constant throughout the process at 4 wt%.1 m long and 0. what would be the concentration at the center of the sphere after 37. Sketch a concentration profile.4h? 27. well-agitated reservoir of pure water. Under the specified drying conditions. The initial moisture content was 18 wt% and the four thin edges were sealed to prevent evaporation. 27. If the concentration of the ethanol at the center of the sphere is lowered to 27% of its initial concentration in 30 h. the center moisture content had fallen to 10 wt%.5 after 36000 s of drying. 27. was dried from both flat surfaces by being exposed to a drying air stream. which initially had a uniform oxygen concentration of 2 kg/rrr'. (d) repeat (c) for a cylinder that is 0.Problems 585 initial value as a result of exposure to strongly decarburizing conditions at 1700°F for (a) 1 h and (b) for 10 h if the diffusivity of carbon in steel at 1700°F is 1 x 10-7 cm2/s. The sphere is dropped into a large.6 Plot the moisture in problem concentration profile in the clay slab that is described 27. 27. .7 Determine the time that is necessary to reduce the center moisture content to 10 wt% if a 5-cm-thick slab of clay is placed on a belt passing through a continuous drier.3 x 10-4 cm2/s.1 m in diameter from 18 to 10 wt% if the cylinder is made from the same clay as in part (a) and dried under the same drying conditions. 5 ern thick.5 m long and 0. calculate: (a) the effective diffusivity. for the period of (a) 3600 s. In 20 000 s. (c) the time that is necessary to lower the center moisture content of a cylinder 0. diameter is saturated with ethanol. The void space in the solid provides sufficient pores so that molecular diffusion can take place through the liquid in the passage. thus restricting the drying to only one of the flat surfaces. The effective diffusivity of water through clay is 1. The initial moisture content will be 15 wt% and the surface moisture content under the constant drying conditions will be maintained at 4 wt%. (b) under the same drying conditions.
(b) 1 hr.6 x 10-2 e-9200/RT 2/s. 27.12 A slab of white pine. has the following initial moisture content at the start of the drying process: Z. 27. the drying wind velocity was increased until the ratio of the resistances approached zero. 27. The diffusivity of hydrogen is equal to 1. The diffusivity of water through the white pine may be assumed to be 1 x 10-9 m2/s.9 A slab of white pine. Samples of cm the sheet of steel are exposed to hydrogen at 1 atm pressure and 500°C for periods of (a) 10min.25. Determine the time of drying for each of the described processes. as a function of distance as it diffuses into a sheet of mild steel that is 6 mm thick. 5 em thick. If the drying . where T is in degrees K and R = 1. The ends and edges will be covered with a sealant to prevent evaporation.98. (c) 10 h. has a moisture content of 45 wt% at the start of the drying process. It was found that the length of time that is necessary to reduce the moisture content at the centerline to 25 wt% was too long.1 % by weight will destroy most life. (c) 360000 s if the lake is at a temperature of 283 K. Initially. This produced a drying process in which the ratio of the surface resistance to the internal resistance to diffusion was equal to 0. 2 in. in 2. If the mass diffusivity of the fluid in the soil is 1 x 10-8 m2/s and the fluid remains on the soil for 1800 s before evaporating into the air. 27. low airflow rates were used. determine the depth at which plant and insect life is likely to be destroyed if a concentration of 0.0 46.11 A large tanker truck overturns and spills a herbicide over a field.586 Unsteady-State Molecular Diffusion (b) 36000 s.0 wt% where z is the distance from one of the large flat surfaces.10 Plot a curve showing the concentration ratio for hydrogen. thick. Accordingly. The ends and edges are covered with a moisture-resistant coating to prevent evaporation. The equilibrium moisture content is 14 wt% for the humidity conditions in the drying air.
having an initial moisture content of 55 wt%. has its surface concentration suddenly raised to and maintained at a 8 kg/rn" concentration level. (b) a modified Schmidt plot with incremental Ilz equal to 3 mm. which produces a surface moisture concentration of 10 kg/rrr'. 27. for the period of . 2 in. determine the drying time that is required to reduce the moisture content at the centerline to 25 wt% by using (a) the unsteady-state charts. at 15 wt%.s) as a function of the dimensionless relative time ratio. XD• 27.15 A charcoal briquet. (CA -CA.17 A slab of Douglas fir. (b) a modified Schmidt plot. 27. 27. has a moisture content of 45 wt% at the start of the drying process. evaluate and plot the dimensionless average concentration profile. at 13 wt% and the moisture content at z = 2. Use this equation to develop an equation for predicting the average concentration. determine the time that is necessary to lower the moisture content at the centerline to 35wt%. The equilibrium moisture content is 14 wt% for the humidity conditions in the drying air. 27. is placed in a drying kiln where its surface moisture is maintained at .16 The concentration profile resulting from transient diffusion from a large sheet of wood under conditions of negligible surface resistance is described by equation (27 -8). CA.13 The slab of white pine that is described in problem 27. 27. thick. Determine the time that is necessary to lower the moisture content at the centerline to 30 wt%.ProbJems 587 conditions maintain a constant 13 wt% surface moisture at both surfaces and the diffusivity of water through the pine is 4 x 10-5 fe /hr.5 kg/rn''. estimate the time that is required to dry the center of the briquet to a moisture concentration of 50 kg/ m". the drying only takes place from the large flat faces. which initially had a uniform oxygen concentration of 1. If the diffusivity of water in the charcoal is 1.18 A lawn-mower oak roller.12 is to be dried in another dryer that maintains the moisture content at z = 0 in. If the relative resistance to mass transfer at the surface is negligible and the diffusivity of water through the fir is 4 x 10-5 fe /hr.14 A large semideep lake. Due to the size of the slab. Sketch a concentration profile.3600 s by using (a) equation (27-12). has an initial moisture content of 400 kg/rrr'. approximately spherical in shape with a 2-cm radius. z. as a function of depth. It is placed in a forced air dryer. CA.s)/(CAO-CA.0 in. The lake is at 283 K.3 x 10-6 m2/s and the surface resistance is negligible.
21 is dried for 40 h. was initially stored in a lumber yard where evaporation from the one exposed surface to the surrounding atmosphere produced a moisture content profile of wt% = 5z +30 where z is the depth above the bottom surface in inches. Present a plot showing the concentrations within the slab for the final drying time. 27. in length roller be dried when (a) the ends of the roller are sealed with a vapor barrier. determine the moisture content at the centerline. in diameter by 18 in. The slab is to be dried in a drier in which the drying medium will maintain a constant 13 wt% surface moisture content at both surfaces. 2 in. (c) the drying occurs from the entire surface.22 If the slab of white pine that is described in problem 27.21 A slab of white pine.1 in.1 in.588 Unsteady-State Molecular Diffusion 20 wt%. 27. If the concentration at the center of the cylinder drops from 30 wt% alcohol to 18 wt% in 10 h. how long must the 4 in.20 A porous cylinder. Write the program using Az = 0. The agitation maintains a concentration of 1 wt% alcohol at the surface of the cylinder.23 Resolve problem 27. thick. Determine the time that is necessary to lower the moisture content at the centerline to 25 wt%. Plot the concentration profile at the final drying time. The surface resistance may be assumed as negligible and the diffusivity of moisture through the oak is 4 x 10-5 fe/hr. is saturated with an alcohol. If the maximum moisture content of the dried roller is set at 30 wt%. 27.19 For the conditions that are specified in problem 27.17. in diameter and 3 ft long. 27. The cylinder is dropped into a large well-agitated reservoir of pure water. determine the concentration wt% at the center after 15 h. The void space in the solid provides sufficient pores so that the molecular diffusion can take place through the liquid in the passage. using a Az = 0. The diffusivity of water through pine at thedrying temperature is 4 x 10-5 fe /hr. . 27. 1 in. write a computer program that will explicitly solve the transient mass transfer.21 with the use of a computer program. (b) the cylinder surface is sealed with a vapor barrier.
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