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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.
we obtain 2 aCA = DAB[aZCA +! aCA +. where the bulk motion contribution is zero. the rate of production of neutrons is proportional to the neutron concentration. equation (25-11) stipulates V'N A +--R at aCA A =0 Since the rate of production is proportional to the neutron concentration.~O -0 which requires the concentration of the diffusing species to be finite at the center of the rod. RA = kcs. 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 . List any obvious boundary conditions.!. For diffusion in solids. For component A. 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. For oxygen.+---Ro.=O aCo2 at . Upon substituting these relations into equation (25-11). reduce the general differential equation for mass transfer to write the specific differential equation that describes this steady-state process. aZcAjazZ = 0 and if the concentration does not vary with the angle 0. aZCA/a02 = 0.516 Differential Equations of Mass Transfer EXAMPLE 1 In a cylindrical nuclear fuel rod which contains fissionable material. EXAMPLE 2 In a hot combustion chamber. equation (25-11) stipulates V·No. a CA + aZcA] + kCA z at ar r ar rZ ao2 az2 If the cylinder is relatively long compared to the radius. Use one of the general differential equations for mass transfer to write the differential equation which describes the mass transfer process.
accordingly. .. two moles of oxygen enter the film and two moles of carbon monoxide leave.z and Fick's law reduces to Noloz = -cD02-m. accordingly. starting with the control-volume expression for the conservation of mass. one mole of carbon dioxide leaves.=O dz (b) Write Fick's law in terms of only oxygen. With these stipulations. With diffusion in only the z direction. The reaction occurs at one of the boundaries and not uniformly along the diffusion path.xture N. were presented. aCoziat = O.) According to the reaction./dz and the differential equation becomes dN02. O2. No> reduces to dN02. this stipulates tN02.' + Nco" + N C02.Problems 517 Since this is a steady-state process. dz + Y02(N 02.. the bulk contribution term becomes = -2No2 Y02 Y02 . Fick's law for molecular diffusion stipulates N 02. Special forms of the general equation. 25. applying to specific situations.z' The reaction also predicts that as the two moles of oxygen enter.z = -NC02.2 dY02 ~-2 N 02" or __ cD02-m.xture dY02 . N02" = -Nco.z' The net flux of nitrogen is zero.' = -cD Oz-m. PROBLEMS 25.1 Derive equation (25-11) for component A in terms of molar units.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.' + N Nz..4 CLOSURE The general differential equation of mass transfer has been developed in this chapter for a diffusing component in a mixture. V . Roz = O. The boundary conditions most generally encountered in mass-transfer processes have been listed.
A pool of pure liquid A is maintained at the bottom of a small Flow of gas B Z=Z2 diameter tube. (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. (c) Determine the Fick's law relationship in terms of only compound H. 25. A gas. 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. isobaric conditions.3 Show that equation (25-5) may be written in the form apA . the evaporation of A is a steady-state process. which diffuse through the gas space above the liquid pool. 25.2 -+(V·Av)-DABV P at PA =r« 25.y ay aNA. (b) Repeat (a) for a spherical.2 Transform equation (25-27) from rectangular coordinates -+--+--+--= aCA aNA.e. which is insoluble in the liquid.5 An Arnold diffusion cell is a simple device that is used to measure gas diffusion coefficients.x at ax aNA. catalytic surface. Under isothermal. Reduce the general differential equation for mass . Hot gases of heavy hydrocarbons diffuse to the catalytic surface where they are cracked (i.z az R A into an equivalent equation written in cylindrical coordinates. flows' across the mouth of the tube carrying away the vapors of A.518 Differential Equations of Mass Transfer 25.4 The following sketch illustrates the gas-phase diffusion in the neighborhood of a catalytic surface.
8 The moisture in the hot. Give two boundary conditions that might be used to solve the resulting differential equation. 25. ! Problems 519 transfer to write the specific differential equation that will describe this mass-transfer process. layer of air to a beaker of sulfuric acid where it is instantaneously absorbed. !. Use . humid air surrounding a cold-water pipeline continually diffuses to the cold surface where it condenses. (b) the/transfer of oxygen into the lake that occurs with the simultaneous disappearance of oxygen by a first-order biological reaction. 25. has its surface concentration suddenly raised and maintained at a 9 kg/rn ' concentration level.15 IbmH20/Ibm dry air. 25. lying on a flat surface.rj. 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.7 A large deep lake. 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.l-in. Reduce the general differential equation for mass transfer to write the specific differential equation that will describe this mass-transfer process.10 Water vapor diffuses through a O. Reduce the general differential equation for mass transfer to write the specific differential equation that will describe this steady-state masstransfer process.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. The concentration of the water vapor at the outer edge of the air layer is 0.5 em thick surrounding the drop. evaporates by molecular diffusion through an "effective film" of air 0. 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. 25.6 A hemisphere drop of water. which initially had a uniform oxygen concentration of 1 kg/rn". 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. 25.
having an initial moisture content of 55 wt%. Over the region in which diffusion is occurring. flat sheet of a slightly soluble solid. List the boundary conditions that could be used in solving the differential equation.520 Differential Equations of Mass Transfer the general differential equation for mass transfer to write the differential equation for this steady-state. unidirectional mass-transfer process. the liquid velocity may be assumed to be parallel to the plate and to be given by v = ay. is D(iCA ax --Z +--2 aZCA) =ayaCA ay ax List the simplifying assumptions. Reduce the general differential equation that will describe the drying of the interior of the oak roller. . Show that the equation governing the mass transfer. 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. Use the general differential equation for mass transfer to write the differential equation that describes this diffusion process. with certain simplifying assumptions.13 A liquid flows over a thin. written in terms of the diffusing water vapor? 25.12 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. What would be the form of Fick's law for this process. where y is the distance from the plate and a is a constant. 25. the gas-phase diffusion in the neighbor- 25. List the two boundary conditions in terms of mole fraction of water vapor. 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. is placed in a drying kiln where its surface moisture content is maintained at 20 wt%.
17 Derive the equation of continuity for component A. This reaction was necessary to explain the metabolic consumption of the oxygen to produce carbon dioxide. 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. that is. (b) only carbon dioxide is produced on the carbon surface.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. there is one-dimensional interdiffusion of the two liquids. was divided into halves by a removable disk. The lower half was initially filled with water and the upper half with the alcohol. (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. The vertical cylinder. 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//. What would be the form of Fick's relationship written in terms of only the diffusing oxygen? 25. By considering a tissue cylinder surrounding each blood vessel.16 In a hot combustion chamber. using an infinitely long cylindrical control volume and cylindrical coordinates. where m is a constant. No reaction occurs in the gas film. What would be the form of Fick's law if (a) only carbon monoxide is produced on the carbon surface. The concentration of oxygen at z = 8 is 21 mole percent. Use the general differential for mass transfer to write the specific differential equation that will describe the diffusion of oxygen in the human tissue. RA = -m. When the disk is removed.Problems 521 25. 20 em long.14 The diffusivity of isopropyl alcohol in water was measured in a Loschmidt diffusion cell.15 An early mass-transfer study of oxygen transport in human tissue won a Nobel prize for August Krough. 25. he proposed the diffusion of oxygen away from the blood vessel into the annular tissue was accompanied by a zero-order reaction. .
If the reaction at the surface of the carbon particle is instantaneous. (b) only carbon dioxide. Determine the Fick's law relationship for the flux of oxygen from the surrounding air environment if (a) only carbon monoxide.522 Differential Equations of Mass Transfer 25.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. give two boundary conditions that might be used in solving the differential equation. . which produces a lower surface moisture content of PA. It is placed into a forced-air dryer. 25.18 A fluidized coal reactor has been proposed for a new power plant. 25. CO2.18. 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.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. when carbon monoxide is produced at the surface and as it diffuses away from the particle it reacts with oxygen to form carbon dioxide.20 A charcoal briquet is formed with an initial moisture content of PAO. The briquet is approximately spherical with a radius of R. If the coal can be assumed to be spherical. CO. is produced at the surface of the carbon particle.
=-t ~ (26-86) 1T exp As previously shown in section 26.. Four types of solutions to mass-transfer problems ill more than one direction were discussed. film and penetration.5 CLOSURE .80 em" cross-sectional area and a diffusion path of 16 ern. One-directional systems both with and without chemical production were considered. 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.013 x 105 Pa. were introduced.7914. (c) 12 cm. If the results agree with the value reported in Appendix J. Two models of mass transfer. These methods included analytical. These models will be used in Chapter 28 to evaluate and explain convective mass-transfer coefficients. and thus enable him to decide whether they are relevant or irrelevant to any specific situation. described in problem 26.yIY~1l = CAn \j-.l. how much methanol must be supplied to the cell to maintain a constant liquid level.1 A steady-state Arnold cell is used to determine the diffusivity of methanol in air at 298 K and 1. when the diffusion was accompanied by a rapid chemical disappearance of the diffusing component. PROBLEMS 26. (b) 6 em. graphical.7 x 104 Pa and its specific gravity is 0. and the cell has a 0. is to be operated as a pseudo-steady-state cell. analogical and numerical techniques. At 298 K. the vapor pressure of methanol is 1.560 Steady-State Molecular Diffusion or NA. how long would it take for the methanol level to fall to the following levels: (a) 4 em. 26. 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. .2. If the tube was initially filled to within 3 cm of the lip of the tube.2 The Arnold cell. In this chapter we have considered solutions to molecular mass-transfer problems.1. the penetration model mass flux varies as the diffusion coefficient to the! power. 26.
a partial pressure gradient for component B must also exist. (a) If 0. P2. For a diatomic gas. respectively. If this is so. what should be the value of the diffusivity of ethanol in air? (b) Calculate the same diffusivity. CAl' in equilibrium with the applied pressure. which dissociates upon dissolving into a solid. Pb through a membrane of thickness z. Sievert's law is a variant of Henry's law for gases that dissociate upon dissolving. The length of the diffusion path was 15. using the Hirschfelder equation.4 26.0 em. The cell. 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. P2.3 The diffusivity of ethanol through air was determined in a steady-state Arnold evaporating cell.6 The permeability of solids by gases is experimentally determined by steady-state diffusion measurements.1 and 0. The results will help confirm the concept of penetration depths that were discussed in section 26. the mass flux of component A is described by equation (26-8). into a low-pressure reservoir. how can component B be considered a nondiffusing (NB = 0) gas? 26. was operated at 297 K and 1. (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.0445 em" of ethanol was evaporated in 10 hr of steady-state operation.Problems 561 26. Consider a mass transfer area of 100 em" and a water film temperature of 283 K. and compare the two diffusion coefficient values. A2. is where DA2 is the diffusivity of A2 through the membrane. 26. The diffusing solute is introduced at one side of a membrane and removed from the other side as a gas. Sievert's law relates the concentration of A atoms in the surface layer of the membrane. (a) Prove that the rate of diffusion of a diatomic gas from a high-pressure reservoir.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. and since the total pressure for a given system often remains constant. having a cross-sectional area of 0.4 In the case of diffusion through a nondiffusing medium.013 x 105 Pa pressure.0 kg moles/rn '. p i.82 ern". When standard .
and the diffusivity of oxygen through the oxide. 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. the diffusivity of ammonia in air is 0. Eventually.77 x 10-5 cm2/s.8 6.215 cm2/s and in liquid water it is 1. The oxide that is produced has a larger volume than the metal that is consumed. and the density of nickel at 700°C is 9. an oxide film is formed on the surface of the metal. The solubility of hydrogen in nickel at 1 atm pressure and 700°C is approximately 7. . The diffusivity of hydrogen through nickel at 700°C is 6 X 10-5 cm2/s. JA2.0 g/cm3• Calculate the number of cubic centimeters of hydrogen per hour that diffuses through the nickel.9 15 20. the diffusion path increases with time.8 Ammonia. In this steady-state process. 26.7 In the oxidation of many metals.1 Determine the rate of diffusion of ammonia. oxygen must diffuse through the oxide film to the surface of the metal. the oxidation becomes diffusion controlled and the dissolved oxygen concentration at the oxide-metal interface becomes essentially zero. accordingly.0 em" /100 g of nickel. develop an expression that tells the depth of the oxide film as a function of time. oxygen concentration of the free surface of the oxide film. At 15°C.0 20 32. 2 mm thick. NH3. mixture by absorption into water. ammonia is transferred by molecular diffusion through a stagnant gas layer 2 em thick and then through a stagnant water layer 1 em thick. 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. 26.6 30 84. If a pseudo-steady-state condition may be assumed.1 25 53. The temperature of the system is 15°C and the total pressure on the system is 1 atm.562 Steady-State Molecular Diffusion pressures are employed with a membrane of standard thickness. is selectively removed from an air-Nl-I. For the oxidation to proceed. The concentration of ammonia at the outer boundary of the gas layer is 3.42 mole percent and the concentration at the lower boundary of the water layer is essentially zero.
back through the stagnant film. The mole fraction of oxygen at z = 0 is 0.12 The following sketch illustrates the gas-phase diffusion in the neighborhood of a catayltic surface.01 mol/m" on the other edge. The reaction at the surface may be assumed to be instantaneous.20 on the other side of the film.244 x 106 J/kg.10 In a hot combustion chamber.Problems 563 26. Calculate the rate of diffusion of ethanol and of water in kg/s through one square meter of area.21. The product B diffuses away from the catalytic surface. oxygen diffuses through air to the carbon surface where it reacts to make CO and/or CO2. Component A diffuses through a stagnant film to the catalytic surface where it is instantaneously converted to B. . The alcohol is transferred from the liquid to the vapor phase and the water is transferred in the opposite direction.9 In the treatment of wastewater. No reaction occurs in the gas film. (b) liquid water at 289 K.013 x 105 Pa. 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. 26.013 x 105 Pa. the latent heat of vaporization of the alcohol and water are 1.1 mm thck. Both components are diffusing through a gas film 0. The temperature is 368 K and the pressure is 1.80 on one side of the gas film and 0. chlorine gas is bubbled through water as a disinfecting agent. 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. (c) the following instantaneous reaction occurs at the carbon surface: 4C+302 ~ 2CO+2C02 26.122 x 106 J/kg and 2.04 mol/rn" on the one edge of the film and 0. respectively..11 An ethanol/water vapor mixture is being rectified by contact with an alcohol/water liquid solution. (b) only carbon dioxide is produced at the carbon surface. At that temperature. The pressure on the system is 1. The mole fraction of ethanol is 0. when the chlorine concentration levels are 0. 26.
~. '&?W/?/07&////l&///#/?/w' Z =0 (a) If the reaction on the surface is A ~ B.13 A liquid mixture of A and B is being separated by a distillation operation.SO at one side of the film and 0. 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. (b) If the reaction on the surface is A ~ 3B. from the liquid surface. The tank is cylindrical with a diameter of 1 m. 26. Determine an equation that will predict the concentration in mole fraction of A at various distances.5 m t---------Il 1 1 1m m (a) (b) . determine an equation that will predict the concentration profile. The more volatile component A is transferred from the liquid phase into the vapor phase while B is transferred in the opposite direction.564 Steady-State Molecular Diffusion ---1~------1.14 A tank containing water has its top open to the air. -.3 on the other side. YA at various z levels. Both components are diffusing through a gas film 1 in. i. At the temperature of the system. thick. 26. The mole fraction of A isO. z.e. 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..
RA = +m.015 em. respectively. = dPA dr 0. PA.18 A pulverized coal particle burns in air at 1145 K. Assume the ammonia diffuses along the duct in the direction of decreasing diameter. he proposed that the diffusion of oxygen away from the blood vessel into the annular tissue was accompanied by a zero-order reaction. the diffusivity of oxygen in the gas mixture may be assumed to be 10-4 m2/s. where m is a constant. the following boundary conditions were suggested: at r =R1.15 Two large gas tanks. assuming a steady-state mass transfer.013 x 105 Pa pressure. which is 3 m in length.16 If the two tanks that are described in problem 26. are connected by a circular 0. Since the tissue cylinders were believed to be arranged in a hexagonal bundle. 26. 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. The process is limited by diffusion of the oxygen counterflow to the CO2 and CO that are formed at the particle surface. The system is at 273 K and 1. 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. maintained at the same temperature and pressure.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). Air (21 mole% oxygen) exists several diameters away from the sphere. as a function of r.005 cm. . 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. 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. that is. and the flux of oxygen that enters the tissue cylinder. Determine the time that is necessary to reduce the diameter to 0.15-m diameter duct.15 had been connected by a truncated conical duct.20 and 0. 1. PA =PA at r = R2. at the duct's larger and smaller ends. The reaction was necessary to explain the metabolic consumption of the oxygen to produce carbon dioxide. By considering a tissue cylinder surrounding each blood vessel.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. determine the rate of ammonia transfer between the two tanks. having internal diameters of 0. 26. 26.1 m. Under the conditions of the combustion process.
stagnant air film to a NaOH solution where it instantaneously disappears by a chemical reaction.21 If the flux of the heavy hydrocarbon that is described in problem 26. 26. of the catalyst in inches at that specific instant.20 In the catalytic cracking of hydrocarbon oils.20 is 1. The pressure of the system is 757 mm Hg. At this pressure and at the average temperature of the air film.13 cm2/s.25 to 0. Initially. if the water evaporates by molecular diffusion through an "effective film" of air.05 in. 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. 0. hot gases of heavy hydrocarbons diffuse to the catalytic surface where they decompose by the following reaction: H--'» 2P The product. R. 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. the diameter of the catalyst particle.5 atm and the diffusivity of H in the gas mixture is 0. respectively.22 cm2/s. expressing the mole fraction of H as a function of the distance from the particle's surface. and the thickness of the stagnant film surrounding the catalyst. (a) Develop an expression for the cracking reaction rate in terms of the gas-phase properties. 0 . diffuses back into the gas stream. 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.22 Carbon dioxide diffuses through a 0.19 Estimate how long it will take to reduce the diameter of a hemispherical drop of water that lies on a flat surface from 0.566 Steady-State Molecular Diffusion 26. Determine the concentration profile for this process. The main environment beyond the effective film can be assumed to be free of water vapor. P. determine the radius. The gaseous atmosphere is at 1000°C and 1.25 in thick. neglect the effect of the gas phase that is required to replace the evaporated liquid. the diffusion coefficient of water in air may be taken as 0. the concentration of compound H in the bulk of the gas phase. 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. 26. (b) Evaluate the concentration profile. which covers the drop.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.1 in. and if the concentration of carbon dioxide at the outer edge of the air layer is 4 mole%.
. the limestone will decompose to calcium oxide. sulfur dioxide will often be one of the combustion products. UF6. 26. the concentration of the sulfur dioxide in the surrounding environment and on the surface of the calcium oxide. is to be used as a fuel in an experimental nuclear power reactor. The specific gravity of uranium is 19.26 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. determine the moles of UF6 that is produced when the pellet's diameter is 0. it has been proposed to fluidize crushed limestone simultaneously with the coal.Problems 567 26. 26. spherical in shape.23 from 0. to fluorine gas at 1000 K and 1 atm pressure. At the combustion temperatures.2 em. 26.4 em. Develop an expression for the sulfur dioxide adsorption rate in terms of the gas-phase properties.05.4 to 0.23 Uranium hexafluoride. in turn. which will.25 A fluidized coal combustion tower has been proposed for a new power plant. adsorb sulfur dioxide from its immediate surrounding environment.24 Determine the time that is required to reduce the diameter of the uranium pellet that is described in problem 26. Due to the high sulfur content in most coals. In an effort to help eliminate this hazardous pollutant. The molecular diffusion of fluorine to the pellet surface is thought to be the controlling step. and the diameter of the calcium oxide spherical pellets.273 cm2/s at 1000 K and 1 atm. The UF6 is to be prepared by exposing pure uranium pellets. The rate of production of UF6 is required for the reactor design. If the reaction occurs irreversibly and instantaneously on the pellet surface and the diffusivity of fluorine through uranium hexafluoride is 0.
When Y$#/ff/lff#$##_l~. Component A diffuses through a stagnant film containing only A and B. Naphthalene has a of 71. The oxidizing process is limited by the diffusion of oxygen counterflow to the carbon monoxide that is formed on the cylindrical surface.26 with the reaction involving the isomerization of A to form An according to nA ~ An. and a vapor 26.1Ibm/fe.0-cm radial distance from the center of the rod. (c) a cylindrical rod of radius R and length L.~.568 Steady-State Molecular Diffusion Develop an expression for the decomposition rate in terms of the fluid properties. and the thickness of the stagnant film if the catalyst is (a) spherical radius of R .0 x 10-5 m2 Is.0 to 0. the concentrations of A and An in the bulk of the fluid phase.28 A 20-cm long. the diameter of a naphthalene is suspended in an effectively pressure. the diffusivity of oxygen in the gas mixture may be assumed to be 1.29 Estimate the time that is required to reduce sphere from 1. 26. Assuming that only thermal neutrons are produced. Under the conditions of the combustion process.013 x 105 Pa pressure. the rate of production of neutrons is proportional to the neutron concentration.0 cm and the oxygen concentration that is 1. a density pressure of 5 mm Hg at 165°P.30 In a cylindrical nuclear rod that contains fissionable material. it is instantaneously converted into species B by the reaction A ~ B. Assume a steady-state process. 26. ---------------------z=o . (b) What would be the composition of oxygen 1.31 The following sketch illustrates the gas-phase diffusion in the neighborhood of a catalytic surface.0-cm radial distance from the rod is 40 mole%.5 em when the sphere infinite amount of air at 165°P and 1 atm molecular weight of 128 g/rnol. determine the neutron concentration profile in a fuel rod of radius R. (b) a flat plate of length L and width W.27 Reconsider problem 26. Upon reaching the catalytic surface. 26. 26. (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. cylindrical graphite (pure carbon) rod is inserted into an oxidizing atmosphere at 1145 K and 1.
(b) the molar flux at the surface z = ±L.33 Compound A is converted to compound B on the "active sites" within a porous catalytic particle manufactured in the shape of thin disks. develop an expression for (a) the concentration profile within the catalyst.33 for a spherical catalyst of radius R. 26.35 A cooled metal tube. where a is the available catalytic surface area per unit volume of catalyst. is used as a condenser for removing water from a water vapor-air mixture. the surface area of the edge of the disks are small in comparison with that of the two circular faces. both by first-order reactions Simultaneously.34 Reconsider problem 26. 26. its thickness is equivalent . moles A produced/(time)(volume). 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. and one half the thickness of the disks L.32 Reconsider problem 26.Problems 569 B diffuses back into the stagnant film. The rate of disappearance of A is related to the concentration of A within the catalyst by RA =kac. a liquid film is formed on the exterior of the tube. Under steady-state conditions. where YB is the concentration of B expressed in mole fraction.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. Determine the rate at which A enters the gas film if this is a steadystate process. In terms of an "effective diffusion coefficient" D A.. 26. A is instantaneously reacting to form B on the catalytic surface. 8 em in diameter.elh the concentration of A on the surface CAs> the reaction rate constant ka.
At one point in the condenser. . determine the rate of water condensation as kg/s per meter of tube length. The gas and liquid phases are in equilibrium at the surface of the water film. and the gas mixture is at 370 K and 1.570 Steady-State Molecular Diffusion to a heat-transfer coefficient of 2500 J/m2 • s : K. If the water vapor diffuses by molecular diffusion through a path length that is 10% of the tube radius. The gas contains 65 mole% water vapor.013 x 105 Pa. the temperature of the metal surface is 310 K.
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. sections were taken parallel to the plane of joining with the aid of a lathe.032 4.69 4. having constant thickness. After 100000 s.z> at any time in terms of the concentration unit WA'. 27.540 4.2 The evaluation of diffusion rates within metals is an important metallurgical problem.31 1. t is time.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 . PROBLEMS 27.1 Develop equations that are equivalent to equations (27-6) through (2710) that would permit the evaluation of the mass flux. a thin layer of the particular solute is applied to the end of a bar and allowed to diffuse into the bar.016 4. These sections.000 3.82 6. Each section was analyzed for its nickel content.064 0.080 1.67 1.63 6. A where CA is the concentration of the diffusing solute.048 4. Arbitrarily setting the last section in which there was no nickel at zero distance.92 7.10 0. distance at start of section x 104 m % Nickel 0.05 1.02 5. This technique is now used with a radioactive tracer as the diffusing solute. thin sections are removed parallel to the initial interface. M is the quantity of solute that is applied to the end of the bar. the following average compositions were obtained for the particular section: % Nickel 0.096 2.604 3.05 4.96 z '.21 0. and z is the distance in the direction normal to the initial solute film. nA.41 0. are analyzed for the concentration of the solute. 27. After an appropriate time. To measure the diffusion coefficient.508 3.524 2. A short length of copper-5% nickel alloy was joined to a bar of pure copper.112 (a) Show that the following expression satisfies Fick's second law and the boundary conditions of the diffusion process. CA = M -/4'ITDAt e -z2/4D.572 1. since the concentration of the tracer can be determined with higher accuracy than is possible by using chemical analysis.
8 A large semideep lake. the time that is necessary to reduce the center moisture content to 6 wt%. Under the specified drying conditions.3 x 10-4 cm2/s. 5 ern thick. as a function of the depth. for the period of (a) 3600 s.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. thus restricting the drying to only one of the flat surfaces. was dried from both flat surfaces by being exposed to a drying air stream.5 A slab of clay. The void space in the solid provides sufficient pores so that molecular diffusion can take place through the liquid in the passage. (b) under the same drying conditions. Sketch a concentration profile. which initially had a uniform oxygen concentration of 2 kg/rrr'. If the relative resistance to mass transfer at the surface was essentially zero. the drying was controlled by the internal diffusion of liquid water to the surface.4 A porous sphere with a !-in. The initial moisture content was 18 wt% and the four thin edges were sealed to prevent evaporation.4h? 27. In 20 000 s. calculate: (a) the effective diffusivity. 27.1 m in diameter. The initial moisture content will be 15 wt% and the surface moisture content under the constant drying conditions will be maintained at 4 wt%. 27. the center moisture content had fallen to 10 wt%. (c) the time that is necessary to lower the center moisture content of a cylinder 0. well-agitated reservoir of pure water. z. CA. The effective diffusivity of water through clay is 1. .5 m long and 0. 27. has its surface concentration suddently raised and maintained at a 9 kg/rrr' concentration level. If the concentration of the ethanol at the center of the sphere is lowered to 27% of its initial concentration in 30 h. diameter is saturated with ethanol.5 after 36000 s of drying.1 m long and 0. The surface moisture was constant throughout the process at 4 wt%. The sphere is dropped into a large.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. what would be the concentration at the center of the sphere after 37.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. 27. (d) repeat (c) for a cylinder that is 0.6 Plot the moisture in problem concentration profile in the clay slab that is described 27.
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. where T is in degrees K and R = 1.12 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. thick. Determine the time of drying for each of the described processes. low airflow rates were used. The diffusivity of water through the white pine may be assumed to be 1 x 10-9 m2/s. The ends and edges will be covered with a sealant to prevent evaporation.98. determine the depth at which plant and insect life is likely to be destroyed if a concentration of 0. 2 in. The ends and edges are covered with a moisture-resistant coating to prevent evaporation. as a function of distance as it diffuses into a sheet of mild steel that is 6 mm thick. 27. (b) 1 hr. If the drying .586 Unsteady-State Molecular Diffusion (b) 36000 s. in 2. has a moisture content of 45 wt% at the start of the drying process. 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. has the following initial moisture content at the start of the drying process: Z. Accordingly. (c) 360000 s if the lake is at a temperature of 283 K. (c) 10 h. 27.25.9 A slab of white pine.11 A large tanker truck overturns and spills a herbicide over a field.6 x 10-2 e-9200/RT 2/s.1 % by weight will destroy most life.0 wt% where z is the distance from one of the large flat surfaces. The diffusivity of hydrogen is equal to 1. the drying wind velocity was increased until the ratio of the resistances approached zero. 27.10 Plot a curve showing the concentration ratio for hydrogen. This produced a drying process in which the ratio of the surface resistance to the internal resistance to diffusion was equal to 0. Initially. 27. 5 em thick. The equilibrium moisture content is 14 wt% for the humidity conditions in the drying air.0 46.
0 in.14 A large semideep lake. the drying only takes place from the large flat faces.5 kg/rn''. CA. (CA -CA. The equilibrium moisture content is 14 wt% for the humidity conditions in the drying air. 27. evaluate and plot the dimensionless average concentration profile. thick. (b) a modified Schmidt plot with incremental Ilz equal to 3 mm. 2 in. z. 27. 27. 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.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).13 The slab of white pine that is described in problem 27.3 x 10-6 m2/s and the surface resistance is negligible. CA. (b) a modified Schmidt plot. as a function of depth. The lake is at 283 K. XD• 27. has an initial moisture content of 400 kg/rrr'. If the diffusivity of water in the charcoal is 1. 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.18 A lawn-mower oak roller. Use this equation to develop an equation for predicting the average concentration. estimate the time that is required to dry the center of the briquet to a moisture concentration of 50 kg/ m". having an initial moisture content of 55 wt%.3600 s by using (a) equation (27-12).12 is to be dried in another dryer that maintains the moisture content at z = 0 in.s)/(CAO-CA. is placed in a drying kiln where its surface moisture is maintained at . Determine the time that is necessary to lower the moisture content at the centerline to 30 wt%.17 A slab of Douglas fir. approximately spherical in shape with a 2-cm radius. determine the time that is necessary to lower the moisture content at the centerline to 35wt%. It is placed in a forced air dryer. which produces a surface moisture concentration of 10 kg/rrr'.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. has a moisture content of 45 wt% at the start of the drying process. 27. for the period of . at 15 wt%. has its surface concentration suddenly raised to and maintained at a 8 kg/rn" concentration level. which initially had a uniform oxygen concentration of 1.15 A charcoal briquet.s) as a function of the dimensionless relative time ratio. Due to the size of the slab. 27. at 13 wt% and the moisture content at z = 2. Sketch a concentration profile.
(c) the drying occurs from the entire surface. 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. in diameter by 18 in. in length roller be dried when (a) the ends of the roller are sealed with a vapor barrier.23 Resolve problem 27. Determine the time that is necessary to lower the moisture content at the centerline to 25 wt%.588 Unsteady-State Molecular Diffusion 20 wt%.20 A porous cylinder. Present a plot showing the concentrations within the slab for the final drying time. The cylinder is dropped into a large well-agitated reservoir of pure water. is saturated with an alcohol. The void space in the solid provides sufficient pores so that the molecular diffusion can take place through the liquid in the passage. If the concentration at the center of the cylinder drops from 30 wt% alcohol to 18 wt% in 10 h. The diffusivity of water through pine at thedrying temperature is 4 x 10-5 fe /hr. determine the moisture content at the centerline. thick. 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.21 A slab of white pine. If the maximum moisture content of the dried roller is set at 30 wt%. 27. determine the concentration wt% at the center after 15 h. 1 in.1 in. 27. The surface resistance may be assumed as negligible and the diffusivity of moisture through the oak is 4 x 10-5 fe/hr.19 For the conditions that are specified in problem 27.21 is dried for 40 h. using a Az = 0. 27.22 If the slab of white pine that is described in problem 27.21 with the use of a computer program. 2 in. The agitation maintains a concentration of 1 wt% alcohol at the surface of the cylinder. Write the program using Az = 0.1 in. 27. . Plot the concentration profile at the final drying time.17. (b) the cylinder surface is sealed with a vapor barrier. how long must the 4 in. in diameter and 3 ft long. 27. write a computer program that will explicitly solve the transient mass transfer.
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