NORTH CAROLINA STATE UNIVERSITY

DEPARTMENT OF CHEMICAL & BIOMOLECULAR ENGINEERING

ChE 711 PROBLEM SET 1

1. Two identical atoms of mass M having potential energy of interaction given by the Lennard-
ma f a f r
12 6
Jones formula, φ( r ) = 4 ε σ / r − σ / r , are initially at their equilibrium separation of
1/6
2 σ. Because of being momentarily disturbed by an encounter with a third particle, the
original two oscillate about their equilibrium separation. Use Newton’s law of motion, and
find the displacement as a function of time. (Hint: Use a Taylor series expansion of φ about
the equilibrium separation.)

2. The equations governing the motion of an incompressible fluid in the boundary layer
adjacent to a flat plate are:
∂u ∂u ∂ 2u
conservation of x momentum: u +ν =υ 2
∂x ∂y ∂y
∂u ∂ν
conservation of mass: + =0
∂x ∂y
no slip condition: at y = 0 for x > 0, u = 0
no mass flux condition: at y = 0 for x > 0, ν = 0

For a two-dimensional flow, a useful concept is the stream function ψ which is related to the
velocity components as follows:

∂ψ ∂ψ
u= and ν = −
∂y ∂x

Show that the equations of motion, conservation of mass and the boundary conditions are
satisfied by a stream function of the form:

1
 ψ = ( 2υUx ) f (η ) where η = (U / 2υ x )
1/ 2 1/ 2
y

i.e., show that the ordinary differential equation f ′′′ + ff ′′ = 0 is obtained after appropriate
manipulations. What are the boundary conditions for f?

3. A rotary filter is used to deposit a solid cake on the outside of a rotating porous belt by
continuously pulling a vacuum through the belt. The filter rotates at an angular velocity Ω
and has a radius R. The solution subtends an angle ψ as shown in the figure. The purpose of
this problem is to construct a model equation to predict the rate of solid product fed to the
conveyer belt as a function of the system parameters.
Assume that the bottom slurry pan of the filter contains a uniform suspension of the solid at
concentration Cs g solid/cm3. The porous belt on the filter may be assumed to be a perfect
filter, i.e., no solid is passed through the belt. The permeation velocity νp (cm/s) through the
filter cake is given by Darcy’s law.
k1
νp = Δp
δ+t
where k1 and δ are constants, Δp is the pressure drop across the filter cake which is constant
and t is the thickness of the cake. You may assume that the cake is deposited at a constant
porosity ε.
a) Derive by a shell balance the differential equation that governs the thickness of the cake as a
function of the angle θ.
b) From the solution to the model equation developed in (a) show how to calculate the amount
of solid produced as a function of operating and system parameters.

Feed Slurry
θ
ψ

=
=

ψ
0
θ

Conveyor to dryer

Solution Level

Return to
slurry tank

4. A classical fluid dynamics problem is the calculation of the velocity profile about a solid
sphere immersed in a Newtonian fluid when the velocity U far from the sphere is spatially
uniform. If the creeping flow assumption is valid, the equations of motion in spherical
coordinates with polar angle symmetry may be reduced to

2
 E 2 ( E 2ψ ) = 0

where the operator E2 is defined as

∂ 2 1 ∂ 2 cot θ ∂
E ≡ 2+ 2
2
− 2
∂r r ∂θ 2 r ∂θ
and ψ is the stream function. Very far from the sphere, the uniform velocity condition implies
the following behavior for the stream function
U 2 2
ψ ( r → ∞, θ ) = − r sin θ
2
At the solid surface, the stream function is zero, as well as, the fluid velocity.
The boundary conditions suggest a solution of the form
ψ (r ,θ ) = f (r ) sin 2θ
where f(r) is an unknown function of r to be determined. Upon substitution into E 4 ψ = 0, the
following ordinary differential equation for f(r) is obtained
D2 ( D2 f ) = 0

where D2 is the operator

d2 2
D2 = −
dr 2 r 2
The constraints on f(r) are:
Ur 2
r →∞ f (r ) → −
2
r=R f (R)=0
r =R f ′(R)=0
Find the solution to the ODE for f(r). (HINT: You may find it easier to solve the two
problems
D 2 f ≡ g (r )
D2 g ≡ 0
but this reduction is not necessary.)

5. A semi-infinite metallic rod of radius R is exposed at the z = 0 face to a heat source which
maintains the temperature at T0 across entire face. Along the length of the rod, energy is lost
to the environment at a rate given by Newton’s law of cooling h(T - Ta) (J cm-2 s) where T is
the (assumed) radially uniform temperature at position z and Ta is the constant, ambient
temperature. The heat transfer coefficient h is temperature independent, but the thermal

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 conductivity of the rod (k) linearly decreases with temperature as k(T) = k0 - αT where k0 and
α are constants.
a) Show that the steady state temperature field is governed by
d ⎡ dT ⎤ 2h
( k − α T ) = (T − Ta )
dz ⎢⎣ dz ⎥⎦ R
0

List all assumptions you make in the derivation.

b) What are the boundary conditions for the above equation?
c) Show that the differential equation can be written in a dimensionless form as
d ⎡ dΘ
⎢ (1 − βΘ ) ⎥⎤ = Θ
dZ ⎣ dZ ⎦
Identify each of the variables and parameters (Z,Θ,β) in terms of the dimensional groupings.
What are the boundary conditions on Θ?
d) What is the physical interpretation of β?
e) Solve the equation in part C to determine the dimensionless heat loss through the rod, i.e.
dΘ
find .
dZ z =0

6. A chemically active rotating disk is embedded on the face of a much larger cylinder as shown
in the figure below. A chemical species of concentration C0 far from the disk is pumped to
the surface by means of the rotation. On the surface a reaction occurs which reduces the
reactant’s concentration to CW. Boundary-layer-type arguments can be applied to reduce the
conservation of material equation to the following form
dC d 2C
vz =D 2
dz dz
dC d 2C
−az =D 2
2

dz dz
where a is a constant > 0.
Pose the boundary conditions for the above equation and solve the ODE to find C(z) and the
reaction flux on the disk’s surface.

4
7. A stream with a constant reactant concentration Cs flows past a flat membrane that contains
an immobilized enzyme. The reactant diffuses into the membrane and reacts with the enzyme
with a rate given by
kC mole
r=
1 + KC cm3 ⋅ s
where C is the concentration of the reactant in the membrane. The product of this reaction
then diffuses back to the flowing stream. Assume Fickian diffusion of reactant with a
constant diffusion coefficient. For purposes of this analysis, also assume that the membrane
is of infinite extent in the direction of diffusion. What is the rate of reactant consumed in a
membrane of length L and width b?

∞ ∞

Immobilized enzyme in membrane

diffusion and reaction

Cs

8. Monsanto has developed a hollow fiber separation device that will selectively remove H2
from a gaseous stream (figure below). The wall of the fiber is permselective to H2 only, and a
99% recovery of H2 from a mixed gas stream containing CH4, CO, CO2, O2, or N2 in a single
pass has been claimed. Designate the inner bore radius of a fiber as R and the H2 pressure at
the open end of the fiber as PL. (All pressures will refer to partial pressures of H2). The
permeation velocity of H2 through the membrane has been found to be proportional to the
pressure difference of H2 across the membrane.
vw R
= K [ P0 − Pi ( x) ]

where K is the permeability of the membrane, P0 is the uniform H2 partial pressure on the
outside of the fiber and Pi(x) is the pressure within the fiber which will depend upon x.
Let us analyze this problem to determine how much H2 can be recovered from a single fiber
as a function of the operating pressure and the system parameters. You will need to make
various assumptions in your analysis: Assume that the flow is incompressible, L >> R, and
the Hagen-Poiseuille relationship is valid locally in the fiber bore.

5
 dPi 8μ
= − 2 ub
dx R
where μ is the viscosity and ub is the bulk-average velocity.
⎡ π D2 ⎤
Relate the mass flow rate of H2 at the open end ⎢ ρ ub ( L ) ⎥ of the system and operating
⎣ 4 ⎦
parameters.

H2
P0

Single
P = PL Fiber

9. A small but massive, neutrally buoyant spherical particle of radius R is suspended in a

viscous fluid. The particle is initially at rest. At time greater than zero, it becomes subject to
an external force F(t) = A sin ωt where ω is the frequency of the force and A is the amplitude
and this force is perpendicular to gravity. Find the position and velocity of the particle as a
function of time and find the amplitude and phase lag of the particle’s velocity when it
achieves a “steady-state” oscillation (i.e., the stationary state). Take the viscous resistance to
motion of the particle to be given by Stokes law
Fdrag = 6π Rμ v

where μ is the fluid viscosity and v is the particle velocity.

10. A certain chemical diffuses into a spherical porous catalyst pellet where it undergoes a first-
order chemical reaction. The concentration of this chemical at the outer surface of the pellet
is held constant at Cs by placing the catalyst in a vigorously stirred vessel so that there is
negligible resistance to mass transfer outside the particle.
Write a shell balance for the molar concentration of the reactant and assume Fickian
diffusion to show that the steady-state concentration profile within the pellet is governed by
1 d ⎛ 2 dC ⎞ ak
⎜r ⎟= C
r 2 dr ⎝ dr ⎠ D
where D is the effective diffusivity and a is the specific interfacial area of the catalyst. Find
the total rate of conversion by solving the above equation with appropriate boundary
conditions. Assume that C = V/r, and solve the resulting equation for V to determine the
concentration profile, but first nondimensionalize the problem and define and interpret all
dimensionless parameters.

6
11. In a population in which reproduction is bisexual, rather than asexual, it is realistic to
suppose that the birth rate is proportional to the number of pairs of individuals. Assuming a
birth rate of this nature and a death rate proportional to the number of individuals, set up and
solve the differential equation governing the population size N, given that the initial size of
the population is N0.

12. In a previous homework problem, you were asked to derive an expression to predict the
molar flowrate of a gaseous component at the open end of a permselective hollow fiber in
terms of system and operating parameters. You were told to assume incompressible fluid
flow to derive the result. In this problem, you shall relax this assumption, and instead,
assume ideal-gas behavior.
Consider the fiber shown below. An A/B binary, ideal-gas mixture of uniform constant
partial pressure PA0 and PB0 is exposed to the outer surface of the fiber which is permeable
only to A. The permeation velocity vw of A across the fiber wall is related to the local partial
pressure driving force as
vw R
= K ⎡⎣ PA0 − PA ( z ) ⎤⎦

where PA(z) is the local pressure of A in the fiber bore. Assume the local bulk-average
velocity in the fiber bore is related to the local pressure gradient as
R 2 dPA
ub ( z ) = −
8μ dz
where μ is the pressure-independent viscosity.
Develop, by use of a shell balance, a model differential equation the solution of which will
predict the steady-state mass flowrate of A out the open end of the fiber. Do not assume
constant density, but rather use the ideal-gas law to relate mass density to the pressure. Make
the differential equation dimensionless and give a physical interpretation for any
dimensionless parameters you generate. Be sure to define all nomenclature and clearly state
your assumptions. DO NOT attempt to solve the differential equation, but do list sufficient
boundary conditions.

H2
P0

Single
P = PL Fiber

13. A polymeric membrane of infinite depth dissolves a gaseous component A adjacent to it. At
the gas-polymer interface, the species A is at the equilibrium concentration Cs in the
membrane. Far from the surface, the concentration of A (and its flux) approach zero because
A is consumed by a first-order reaction within the membrane. The volumetric reaction rate is

7
 given by kC [=] mole/cm3s. Diffusion of A is the transport mechanism for A within the
membrane, and its diffusivity is concentration dependent. Hence, Fick’s law is written as
dC
N = − ( D0 + α C )
dx
where N is the molar flux, D0 and α are constants, C is the concentration of A in the
membrane, and x is the coordinate measured from the gas-polymer interface into the
membrane.
a) Derive by a shell balance the ordinary differential equation that governs the steady-state, one-
dimensional concentration profile in the membrane.
b) What are the boundary conditions for the above?
c) If Θ ≡ C(x)/Cs, show that the ode derived in part (a) may be written in a dimensionless format
as
2
d 2Θ dΘ
(1 + βΘ ) 2 + β ⎜⎛ ⎟⎞ = Θ
dX ⎝ dX ⎠
Identify β and X in terms of dimensional quantities.
d) Show that the flux of A into the membrane is given by
Cs kD0 ⋅ 1 + 2 β / 3

14. In the preparation of printed circuit boards, it is often required to coat the wall of a hole
which passes through the board to connect electronically the circuit lines on the opposite
faces. A procedure used is electrodeposition. Hazlebeck and Talbot published a paper in the
AIChE journal (AIChE J., 35, 1145, 1990) which presented a mathematical model to
calculate the metal-deposit distribution on the inner surface of a cylindrical tube. The authors
argued under certain circumstances the concentration distribution of the metal ion in the pore
during the electrodeposition is governed by
d 2C
2
= βCs
dx
where C is the metal ion molar concentration, x is the axial coordinate in the hole, β is a
constant, and s is the known reaction order. If the hole is sufficiently long, we may consider
it to be semi-infinite and the two boundary conditions for the above equation are
x = 0, C = C0
x → ∞, C (= C ′) = 0
a) Suppose s = 1, determine C(x).
b) Suppose s ≠ 1, determine C(x).
c) Show that your solution to C(x) from part (b) reduces to that for C(x) from part (a) in the
limit of s → 1. (Hint: Note xα = eα ln x)

8
15. Microscopically small (diameter < 1 μm) contaminant particles may be deposited from de-
ionized water onto the surface of a silicon wafer. The particles are dilute in number
concentration (C < 106 particles/ml) and, depending upon the nature of the particle, may
carry either a negative or positive charge.
A expression is proposed to relate the number flux of particles j (number/cm2 s) impinging
on the wafer surface to the driving force for particle transport as
dC CD dVT
j = −D −
dx kT dx
where D is the particle diffusivity (cm2 s-1) k is Boltzmann’s constant (J K-1), T is the
absolute temperature (K), and VT(x), is the total interaction energy (J) between the particle
and wafer. The first term on the right side accounts for the diffusion flux and the second
accounts for the migration flux in the energy field. The coordinate x is measured from the
wafer surface at which x = 0. The particle number concentration increases outward and
reaches the bulk value C0 at x = δ, the edge of a mass-transfer boundary layer.
a) Show that a conservation-of-particles principle applied in the boundary layer yields dj/dx = 0
at the steady state; hence, integration demonstrates that j is a constant, although it is not a
priori known.
b) The interaction energy VT(x) may be found by accounting for electrostatic and van der Waals
energies. Assume that an analytical formula for VT(x) is available for 0 ≤ x ≤ δ, with VT(δ) =
0.
Show that the maximum flux of particles, given by solving the above equation subject to
C(0) = 0 and C(δ) = C0, is
− DC0
j= δ
∫ exp [VT ( x) / kT ] dx
0

16. The following dimensionless equation was derived in a previous homework problem to
govern the pressure distribution of an ideal gas within a hollow fiber with a permeable wall
2
d 2 P ⎛ dP ⎞
P 2 +⎜ ⎟ + β (1 − P ) P = 0
dZ ⎝ dZ ⎠
dP
=0
dZ Z =0

P(1) = γ
a) Solve the differential equation to show that
P (0)

∫
6 P dP
=Z
β { }
1/ 2
P(Z ) 3⎡⎣ P 4 − P (0) 4 ⎤⎦ − 4 ⎡⎣ P 3 − P (0)3 ⎤⎦

where P(0) is the (unknown) pressure at the closed end of the fiber.

9
b) Show that the pressure gradient at the open end of the fiber may be written as
β /6
dP
{ }
1/ 2
=− 3 ⎡⎣γ 4 − P(0) 4 ⎤⎦ − 4 ⎡⎣γ 3 − P(0)3 ⎤⎦
dZ Z =1 γ
Hence, the mass flux can be calculated once P(0) is determined.
dP
c) Suppose γ = 0.1, calculate P(0) and for β = 0.1, 1 or 10 using the Matlab m-file
dZ Z =1
provide on the course web site.

17. A liquid stream in turbulent flow passes between two planar electrodes of width W which are
separated by a distance h(x) which depends upon the streamwise position x. The fluid enters
at x = 0 and exits at x = L. Because the flowrate is constant, the bulk-average velocity ub(x)
also varies with the streamwise position such that the product h(x)ub(x) ≡ Γ remains constant
(Γ = flowrate per unit electrode width). An ionic current flows between the two electrodes
and, because of joule heating, effects a temperature increase in the fluid. Such a device is
called an ohmic heater and is used by the food industry to sterilize liquids. A significant
advantage over more conventional heaters is that heat-transfer surfaces are not used with an
ohmic heater: organic materials tend to degrade on and foul these surfaces, which decreases
the heat-transfer efficiency and product quality.
a) If we assume that (1) the cell is well insulated, (2) convective heat transfer dominates over
conduction, and (3) the temperature profile between the electrodes is flat at any position x,
the following enthalpy balance can be derived
dT
ρC pΓ = QJ h( x) (1)
dx
where ρ and Cp are the density and heat capacity of the stream. The volumetric production
rate of enthalpy by joule heating is QJ and is related to the cell voltage V, electrode
separation h(x), and temperature-dependent ionic conductivity κ(T) by
2
⎡ V ⎤
QJ ( x) = κ (T ) ⎢ ⎥ (2)
⎣ h( x ) ⎦
where
κ (T ) = κ 0 + a (T − T0 ) (3)

with κ0 being the conductivity at inlet temperature T0 and a ≥ 0 is a known constant. Solve
the above to determine T(x) as

κ0 ⎡ ⎛ aV 2 ⎞ ⎤
T ( x) − T0 = ⎢exp ⎜⎜ I 2 ( x) ⎟ − 1⎥ (4)
⎟
a ⎢⎣ ⎝ ρC pΓ ⎠ ⎥⎦
where

10
 x dx′
I 2 ( x) = ∫ (5)
0 h( x′)
b) Suppose a = 0, use equation 4 to find T(x).
c) Consider a fluid element which enters the heater at x = 0. At some time t later, the particle
z
has traveled a length x where time is defined at t = 0 dx / ub ( x ). By change of variable, show
x

that equation 1 can be written as

dT Q
= J (6)
dt ρ C p
d) Suppose a constant heating rate dT/dt is a design target where
dT QJ (0) V 2κ 0
= = = constant (7)
dt ρC p ρ C p h 2 (0)
Based upon the result from part c, derive a differential equation that governs h(x) to obtain
this goal. Integrate to show
aV 2
h( x) = h(0) + x (8)
2 ρC pΓ

18. In problem 1-17, a mathematical model for an ohmic heater was derived. Specifically, for a
parallel-plate ohmic heater we determined that the fluid was heated at a constant rate dT/dt
dT QJ ( 0 ) V 2κ 0
= = = constant (1)
dt ρC p ρ C p h 2 (0)
if the interplate spacing h(x) as a function of the streamwise position x is given by
aV 2
h( x) = h(0) + x (2)
2 ρC pΓ
where time t is measured by a fluid particle moving through the heater at the local bulk-
z
average velocity ub(x), i.e., t = 0 dx ′ / ub ( x ′), and all notation is defined in the homework
x

problem.
Now, suppose that neutrally buoyant solid food particles are dispersed in the liquid feed.
Your goal is to determine the heating rate of the solid dTs/dt, where Ts is the assumed
spatially uniform temperature of a particle.
a) If the solids are spherical with radius R, show that the temperature of any sphere may be
described by the solution to the following
dTs 3h f / R
= (T − Ts )
dt ( ρ C p ) (3)
s

t = 0, Ts = T0

11
 where T0 is the entering temperature of the solid (which is identical to that of the fluid), hf is
the fluid-to-solid heat-transfer coefficient (J cm-2 s-1 K-1), and ρCp is the volume specific heat
capacity of the solid (J K-1 cm-3). List all assumptions made to derive equation 3 to receive
full credit.
b) Given h(x) from equation 2, the integration of equation 1 yields
V 2κ 0
T (t ) = T0 + t (4)
ρ C p h 2 (0)
Use the above result to solve equation 3 and determine the time dependence of the solid
heating rate dTs /dt.

19. A polymer film of thickness h is coated onto a metal substrate. The film at the x = 0 surface
is in contact with air. At the same surface an ultraviolet source irradiates the film such that
the monomer is photochemically cleaved from the polymer at a local volumetric production
rate of the monomer rD (mol cm-3 s-1); that is,
( M )n ⎯⎯
hv
→ ( M )n −1 +M

where (M)n is the polymer, M is the monomer, and (M)n-1 is also the polymer, but with one
less monomer unit. The monomer is soluble in the polymer and, since the substrate is
impermeable, leaves the film only at the x = 0 surface. The depolymerization kinetics are
zero-order in the dissolved monomer concentration, but the rate is attenuated in distance by
absorption of the radiation according to
rD = r0e − λ x
where r0 and λ are known constants.
Assume Fickian diffusion describes the transport of the dissolved monomer and that a
pseudo-steady state exists.
a) Derive by the shell-balance approach the governing differential equation for the monomer
concentration. Let D represent the constant diffusivity and C the molar concentration of the
dissolved monomer.
b) Assume that the concentration of the dissolved monomer at x = 0 is 0. What is the
appropriate boundary condition at x = h?
c) Make the equation in Part A and boundary conditions in part B nondimensional.
d) Derive a formula for the molar rate per unit area of the film (mol cm-2 s-1) at which the
monomer leaves the polymer?

20. When an insoluble bubble rises in a deep pool of liquid, its volume increases; however, there
is a competing action of dissolution that tends to reduce its size. Under practical conditions, it
has been shown that the mass-transfer coefficient (kc) for spherical particles (or bubbles) in
free-fall (or free-rise) is substantially constant. Thus, for sparingly soluble bubbles released
from rest, the following material balance is applicable

12
 ⎛ 4 ⎞
d ⎜ C ⋅ π R3 ⎟
⎝ 3 ⎠ = −k ⋅ C * ⋅4π R 2 t
c ()
dt
where C = P/RgT is the (ideal) molar density of gas, C* is the molar solubility of gas in
liquid, and R(t) is the changing bubble radius. The pressure at a distance z from the top liquid
surface is P = PA + ρLgz and the rise velocity is assumed to be quasi-steady and to follow a
linear relation between speed and size given by
2/3
dz ⎛ 2g ⎞
=U = ⎜ 1/ 2 ⎟
⋅ 2 R(t ) = β ⋅ R(t )
dt ⎝ 15υ ⎠
where υ is the liquid kinematic viscosity.
a) Show that a change of variables allows the material balance to be written as
dR 1 R2 λ
R + =−
dP 3 P P
where
kc Rg TC *
λ=
ρL g β
b) Solve the equation in part (a) subject to the initial condition R(0) = R0, P(0) = P0 =
PA + ρ L gz0 and prove that
3/ 2
P ⎛ r02 + 3λ ⎞
=⎜ ⎟
P0 ⎝ R 2 + 3λ ⎠
This expression could be used, for example, to find the time required for a bubble to reach
the surface (z = 0) after release at z0.

21. Solid, cylindrical metal rods may be used as heat promoters on the exterior of a hot surface.
The ambient air flowing around the rod-promoters has a temperature TA. The metal
conductivity (k) and the heat-transfer coefficient (h) around the surface of the promoters are
constant.
a) Consider a single rod of diameter 2R and length L. Show that a steady-state differential
energy balance yields
d 2T ⎛ 2h ⎞
−⎜ ⎟ (T − TA ) = 0
dx 2 ⎝ Rk ⎠
for the case when the metal temperature changes mainly in the x direction (x is directed
outward from the hot surface).
a) Given the following boundary conditions,

13
 x = 0, T = TH (hot surface)
dT
x = L, −k = h (T − TA ) (exposed flat tip)
dx
define dimensionless groups and write a nondimensional form of the differential equation
and boundary conditions.
b) Give a physical interpretation to dimensionless parameters generated in step (b).
c) Find the solution for the nondimensional temperature profile.
d) Derive a formula to calculate the total heat-transfer rate Q (watts) through the x = 0 face of
the promoter.

22. A membrane of thickness 2d is contacted at each face with a gas that contains component A
which absorbs in the membrane and reacts with a zero-order reaction rate k0 mol cm-3 s-1. For
time t < 0 the membrane is covered with an impermeable barrier and does not contain
component A. For t > 0 the barrier is removed, and A diffuses into and reacts within the
membrane. Equilibrium is instantaneously established at the membrane-gas interface, so the
concentration of A is known to be Cs at each face. The membrane length L and width W are
such that L/d >> 1 and W/d >> 1. Component A diffuses into the membrane with a flux (mol
cm-2 s-1) given by Fick’s law, but with a concentration-dependent diffusivity D(C) (cm2 s-1).

a. Use the shell-balance technique to derive the partial differential equation that governs
the transient concentration profile C(x,t), where x is the coordinate measured from the
midplane (where x = 0) and x = ± d are the membrane-gas interfaces. Do not non-
dimensionalize your result. State any assumption you make in the analysis.

b. State sufficient initial/boundary conditions on C(x,t).

c. Assume that the diffusivity is given as D = D0emC where D0 (cm2 s-1) and m (cm3 mol-
1
) are known constants. Show that the steady-state concentration profile is

C ( x) 1 ⎛ β 1 ⎞
= ln ⎜ e − β r (1 − X 2 ) ⎟
Cs β ⎝ 2 ⎠

where X = x/d, β = mCs, and r = k0d2D0-1Cs-1.

d. Derive a formula for the total molar consumption rate (mol s-1) of A in the membrane
at steady state.

23. A polymer electrolyte membrane has an electrode adjacent each face and separates an aque-
ous solution of methanol (MeOH) from humidified nitrogen (figure below). Initially, there is
no current flow and the membrane is uniformly saturated with MeOH at molar concentration

14
Cm in equilibrium with the solution adjacent the left side. For t > 0, a voltage is applied
across the two electrodes such that MeOH is oxidized at a mass-transport limited rate at the
right electrode (anode) at x = 0 according to CH 3OH+H 2 O → CO 2 +6H + +6e- and simultane-
ously proton is reduced at the left electrode (cathode) at x = A according to
6H + + 6e- → 3H 2 . The proton generated at the anode migrates through the membrane to the
cathode and sustains the ionic current. Each proton in this transit carries along ξ solvent
molecules (in this case, MeOH + water); this phenomenon is called electroosmotic transport,
and here the flow from right-to-left opposes the diffusive transport rate of methanol from
left-to-right. If the partial molar volume of MeOH is constant, it can be shown that the net
molar flux N (mol cm-2 s-1) of MeOH through the membrane may be written as the sum of a
diffusive and electroosmotic term as

∂C ∂C C
N = −D + 6ξ x f D

∂x ∂x x =0 Cm

diffusive
 

electroosmotic
flux flux

where D is the diffusivity of MeOH, xf is the mole fraction of MeOH in the membrane phase
that is in equilibrium with the feed solution, and ξ is the electroosmotic drag coefficient. All
three parameters (D, xf, ξ) are known constants, but the concentration gradient (∂C / ∂x) x =0 is
an unknown that must be determined in the course of the analysis.

x=A x=0

Polymer Electrolyte
Membrane
methanol N2
+ +
water (liquid) H+ water (vapor)

methanol

porous cathode porous anode

a) Given the above expression for the molar flux N of methanol, use the shell-balance
technique to show that the MeOH concentration profile C(x,t) is governed by

15
 ∂C ∂ 2C ∂C ∂ ( C / Cm )
= D 2 − 6ξ x f D
∂t ∂x ∂x x =0 ∂x

The boundary conditions are the known MeOH concentration at each side of the
membrane

i) C ( t, 0 ) = 0
ii ) C ( t , A ) = Cm

and the initial condition is

C ( 0, x ) = Cm

b) Show that a nondimensionalization of the result from part a yields

∂θ ∂ 2θ ∂θ ∂θ
= 2 − 6ξ x f
∂τ ∂z ∂z z = 0 ∂z

θ ( 0, z ) = 1; θ (τ , 0 ) = 0; θ (τ ,1) = 1

Define all nondimensional variables in terms of dimensional quantities.

c) Consider the steady-state condition in which the left side of the above equation is zero,
i.e., θ = θ(z). Solve the resulting mass balance to show that the flux of methanol at x = 0
is given as
dC
N ( x = 0) = −D (since C (0) = 0)
dx x =0
- DCm dθ
=
A dz z =0

- DCm ln (1 + 6ξ x f )
=
A 6ξ x f

d) The term (-DCm/ A ) in the above result is the steady-state diffusive molar flux in the
absence of electroosmotic transport. Show that in the limit of ξ → 0 (i.e., if
electroosmotic transport is unimportant), the purely diffusive transport rate is obtained
using the result from part c.

24. A polymeric membrane of thickness d separates two compartments (figure below).

The compartment on the left, at the x = d face of the membrane, contains methanol
that permeates through the membrane to the x = 0 face at which it is swept away by a

16
 gas flow. The concentration of methanol in the membrane is known at x = d, C = Cs,
and at x = 0, C = 0. Uniformly dispersed throughout the membrane is a catalyst that
effects the irreversible reaction of methanol to carbon dioxide:
CH 3OH+ 1.5 O 2 → CO 2 +2H 2 O . You may assume that the membrane is saturated
with dioxygen, and that the reaction is first-order in methanol and irreversible. Under
these conditions, the local volumetric reaction rate of methanol is given by kC (mol
cm-3 s-1), where k is a pseudo first-order rate constant, and C is the molar
concentration of methanol in the membrane.

a) Suppose the membrane at t = 0 does not contain methanol, but for t > 0, the
boundary conditions described above are applicable. Furthermore, assume that the
molar flux N of methanol is described by Fick’s law with a constant diffusivity;
that is,
∂C
N = −D
∂x
Use the shell-balance technique to derive the pointwise conservation equation that
governs C(x,t). Do not attempt to solve.

b) Make the equation from part (a) non-dimensional. Define all terms. Provide a
physical interpretation to any dimensionless parameters that are generated.

c) Consider the steady state. Derive a formula that predicts the molar flux of
methanol leaving the membrane at the x = 0 face; that is, find –N(0) =
D(dC/dx)|x=0.

M
Methanol E
vapor in air M
B air
R
A
N
E

x=d x=0

25. A plate of width W of solid surfactant is immersed in water such that the plate is
normal to the air-water interface and extends into the air, as shown in cross section in
the figure below. The surfactant dissolves only onto the air-water interface since it is
not soluble in water. The surfactant is transported away from the plate by one-
dimensional surface diffusion along the air-water interface. The local surfactant
surface concentration is Γ ( x) (mol cm-2), where x is the surface coordinate measured
from the plate. The local surface diffusion flux Ns(x) (mol cm-1 s-1) of the surfactant is

17
 described by Fick’s law N s = − Ds (d Γ / dx), where Ds (cm2 s-1) is the surface diffusion
coefficient. The surfactant reacts with O2 from air and the reaction product is soluble
in water and immediately dissolves into the bulk liquid. The local surfactant reaction
rate (mol cm-2 s-1) is given by kΓ, where k (s-1) is a pseudo first-order rate constant.
The surfactant concentration at x = 0 is known from equilibrium considerations as Γ0,
and the surfactant concentration is zero far from the plate (x → ∞).

a. Use the shell-balance technique to derive the ordinary differential equation that
describes the steady-state surfactant concentration Γ ( x ) .

b. Show that the result from part a may be rewritten in a nondimensional manner as
d 2θ
=θ
dz 2
Define z and θ in terms of dimensional parameters, and state the appropriate
boundary conditions.

c. Derive a formula for the rate n (mol s-1) at which the surfactant dissolves from
the plate onto the water surface.

surfactant
air

O2

solid surfactant

x
soluble reaction product

water

26. A zeolite membrane of thickness d separates two compartments in which the partial
pressure of methane is P0 and Pd, with P0 > Pd. (Zeolite membranes are
polycrystalline aluminosilicates with pore sizes typically between 0.3 and 1.3 nm.)
Diffusion of methane through the zeolite is assumed to follow a five-step process: (1)

18
adsorption onto the membrane surface at z = 0; (2) migration into the micropore
network; (3) diffusion through the micropores; (4) migration out of the micropores
onto the opposite surface of the membrane at z = d; and (5) desorption from the
surface. Based upon single-file diffusion of methane through the zeolite pores, the
fraction of available adsorption sites θ is governed by

∂θ ∂⎛ ∂θ ⎞
= ⎜ D(θ ) ⎟ (1)
∂t ∂z ⎝ ∂z ⎠

where θ = q / qsat , q is the local coverage of methane (mol/ kg zeolite), and qsat is the
saturation coverage of the methane adsorbate. The fractional coverage of methane is
related to its partial pressure P (Pa) according to a Langmuir isotherm as

q bP
θ= = (2)
q sat 1 + bP

where b (Pa-1) is a known constant. The diffusivity D (m2 s-1) is a function of the
methane surface coverage θ as

D0
D(θ ) = (3)
1−θ

where D0 (m2 s-1) is a known constant. [Mass transport through zeolite membranes, as
described above, is discussed by Gardner et al., AIChE J, 48, 1155, 2002.]

a) Consider the steady-state transport of methane from the z = 0 to the z = d face.

Find a formula for molar flux of methane N (mol m-2 s-1) through the membrane
given that

dθ
N = − ρ qsat D (θ )
dz

where ρ is the density (kg m-3) of the zeolite.

b) Using the result from part a, show in the limit of b → 0 (i.e., linear adsorption
isotherm) that the steady-state molar flux of methane is proportional to the
pressure difference P0 - Pd.

c) Using the result from part a, show that in the limit of b → ∞ (i.e., saturation
coverage) that the steady-state molar flux of methane is proportional to ln( P0 / Pd ) .

19
27. The figure below is a cross-section of a rectangular-channel heat exchanger of width
W and thickness tf through which an incompressible fluid flows at steady state. The
channel is constructed such that W>>tf. The fluid enters the channel at x=0 with
known temperature T0 and flows with a flat velocity profile v throughout. The surface
at y=tf of the channel is thermally insulated and the surface at y=0 is defined by a thin
metal plate of thickness tm, with tm<< tf. At the opposite side of the metal plate (i.e.,
the non-wetted surface), a uniform heat flux qw (W m −2 ) is imposed. Because the
metal plate is thin, the temperature is uniform across it in the y direction, however, the
metal temperature Tm(x) depends upon the x coordinate. The metal plate is insulated
at the x=0 and x=L ends. The fluid is heated by the plate at a local rate (W m −2 ) given
by h (Tm ( x) − T f ( x) ) , where h is the known heat-transfer coefficient and Tf (x) is the
fluid temperature at position x. It is assumed that the fluid is well mixed in the y
coordinate, which is consistent with the flat velocity profile.

You may assume that all material properties of the plate and fluid are constant. Heat
transfer in the plate is by conduction and described by Fourier’s law. Conductive
energy transport in the fluid is negligible in comparison to convective transport.

T0

a. Given the above description and assumptions (and any others that you feel
necessary), show using a shell-balance that the temperature in the metal and
fluid phases are governed, respectively, by
d 2Tm
tm km = h(Tm − T f ) − q w (1)
dx 2
dT f
t f ρ vC p = h (Tm − T f ) (2)
dx
b. What are the boundary conditions for equations 1 and 2?

c. The two equations from part a can be made non-dimensional as

d 2 ym
= β1 (y m − y f ) − β 2 (3)
dz 2

20
 dy f
= α (y m − y f ) (4)
dz
where y m (z ) and y f ( z ) are the non-dimensional metal and fluid temperatures,
respectively. Derive the above two equations from results in part a making
certain to define all terms.

d. Solve the equations from part c, subject to boundary conditions from part b, to
find the expression for Tm(z).

28. Two rectangular-shaped materials are placed adjacent to one another, as indicated in
the drawing below. The width of the slabs is much greater than their thickness (i.e., W
>> t1 and W >> t2). Heat is injected at a known uniform flux (W m-2) at the x=0 face
of material 2, whereas material 1 is insulated at the same surface. At the x=L surface,
material 2 is insulated and material 1 is maintained at a known uniform temperature,
which for convenience sake is defined as zero. Heat is transported across the slab-slab
interface at a local flux (W m-2) given by h(T2-T1), where h is a known constant and Ti
is the local temperature of material i, which is assumed to depend only upon the x
coordinate.
Q
insulation The objective of this problem is to determine
x=0
the relationship between the total heat-
mat’l 1 mat’l 2 transport rate per width of the slabs Q (W m-
1
) and the overall temperature driving force,
t1 t2
T2(0) - T1(L).

h(T2 – T1) You may assume: steady-state heat transport;

Fourier’s Law is applicable; constant
physical properties; and one-dimensional
x=L
temperature distribution in each slab [i.e.,
T=0
T1=T1(x) and T2=T2(x), but T1(x) ≠ T2(x)]. If
you feel it necessary to make other
assumptions, then list these in your analysis.

a. Use a shell-balance procedure to show that the temperature profiles in the two
materials are governed by
d 2T
t1k1 21 = − h(T2 − T1 )
dx
d 2T2
t2 k2 = h(T2 − T1 )
dx 2
s.t.
dT1 dT
x = 0, = 0 and − t2 k2 2 = Q
dx dx

21
 dT2
x = L, T1 = 0 and = 0
dx
where ki is the thermal conductivity of material i.

b. Show that the above equations and boundary conditions can be made
nondimensional as

d 2θ1
= −αβ (θ 2 − θ1 )
dz 2
d 2θ 2
= β (θ 2 − θ1 )
dz 2
s.t.

z = 0, θ1′ = 0 and θ 2′ = −1
z = 1, θ1 = 0 and θ 2′ = 0

Define all nondimensional terms. Hint: α ≡ k2t2/ (k1t1).

c. Show that the two differential equations from part b can be combined and
solved to yield

θ 2 ( z ) − θ1 ( z ) = C1 sinh γ z + C2 cosh γ z

where C1 and C2 are integration constants to be determined in part d

and γ ≡ β (1 + α ) .

d. Substituting the result from part c into the differential equation that governs θ2
yields

d 2θ 2
= β C1 sinh γ z + β C2 cosh γ z
dz 2

Solve the above equation to find an expression for θ2(z). With θ2(z) now
available, a formula for the overall temperature driving force can be found to
arrive at the objective given in the problem description. (NOTE: Do not
derive the formula below; it is provided for closure only.)

T2 (0) − T1 ( L) k2t2 α ⎡ 2 + (α + α −1 ) cosh β (1 + α ) ⎤

= ⎢1 + ⎥
Q L 1 + α ⎣⎢ β (1 + α ) sinh β (1 + α ) ⎦⎥

22
29. The figure below shows a sketch of a regeneration unit for a bioreactor. A stream
containing a low concentration C B0 (g m-3) of bacteria and a concentration C N0 (g m-3)
of a nutrient are fed to the unit at a known flowrate Q (m3 s-1). The regenerator can be
modeled as a plug-flow reactor of length L (m) and radius R (m). In the reactor, the
bacteria multiply and the nutrient is consumed with volumetric rates (g s-1 m-3) given
by:

rB = k B CB ( ε C N − CB )
rN = −k N CN CB

where CB and C N are the concentrations of the bacteria and nutrient, k B (m3 g-1 s-1)
and k R (m3 g-1 s-1) are rate constants, and ε is a nondimensional parameter that
measures the maximum steady concentration of bacteria that can survive at a given
concentration of the nutrient.

C B = C B0
C B (L ), C N (L )

C N = C N0
L

It can be shown that the equations governing the concentration profiles of the
bacteria and the nutrient along the regenerator are:

Q dCB
= k BCB ( ε CN − CB )
π R 2 dx
Q dCN
= −k N C N CB
π R 2 dx

with the initial conditions:

CB ( 0 ) = CB0 , C N ( 0 ) = C N0

(You are not required to derive the above equations).

(a) Show that the differential equations for the concentrations of the bacteria and the
nutrient can be made dimensionless as:

23
 dθ B
= αθ B ( εθ N − θ B )
dξ
dθ N
= −αβθ Nθ B
dξ

with the initial conditions:

θ B ( 0 ) = 1, θ N ( 0 ) = γ

Define all variables and parameters. What is the physical meaning of the
parameters α , β and γ ?

(b) Show that the two first-order differential equations from part (a) can be combined
to eliminate θ B and yield the second-order equation for θ N :

2
d 2θ N ⎛ dθ ⎞ dθ N
θN ( )
− 1 + β −1 ⎜ N ⎟ − αεθ N2 =0
dξ ⎝ dξ ⎠ dξ
2

with the initial conditions:

dθ N
θ N (0) = γ , = −αβγ
dξ ξ =0

(c) Solve the equation from part (b) to show that the concentration of the nutrient
along the regenerator is given by the expression:
θ N (ξ )
yκ − 2 αε
∫γ κ
y −λ
dy =
κ
ξ

where κ ≡ 1 − β −1 , β ≠ 1 , and:

⎛ β −1
−1 ⎞
λ ≡ γ −β ⎜ +γ ⎟
⎝ ε ⎠

(d) Derive the expression equivalent to that of part (c) for the case β = 1 .

(e) Derive an expression for the position within the reactor where the concentration
of the bacteria reaches a maximum (for β ≠ 1 ). Find the nondimensional
concentration of the bacteria and the nutrient at this point.

24
30. A population of bacteria co-exists with a population of fungus in a well-mixed batch
reactor. Population A (bacteria) is at initial number density n0A (m-3) and population B
(fungus) is at initial number density n0B (m-3). The two populations compete for the
same resources and, as a means to assure species survival, each population produces a
toxin that kills the other. A simple model for this deadly competition between the
populations may be written as

dnA
= − k B nB nA (0) = nA0
dt
dnB
= −k A nA nB (0) = nB0
dt

where kA (s-1) and kB (s-1) are first-order rate constants that capture the efficiency of
the toxin produced by one population to eliminate the other.

a) The population balances can be made nondimensional as:

dYA
= −αYB YA ( 0 ) = 1
dτ
dYB
= −β YA YB ( 0 ) = 1
dτ

where τ ≡ k B t , α = nB0 / nA0 , β = k A nA0 /( k B nB0 ), YA = nA / nA0 , and YB = nB / nB0 . (No

need to derive this result.) Solve the above equations to find YA(τ) and YB(τ).

b) Using the solutions from part (a), show that given sufficient time:

i) population A eliminates population B if β > α

ii) population B eliminates population A if α > β
iii) populations A and B mutually annihilate one another if α = β.

c) Discuss limitations of the proposed model and how it might be improved.

31. A spherical annulus of material Α is surrounded by air at temperature Tair and is

concentric with and abuts a sphere of material B (figure below). Both materials are
initially at a uniform temperature Tair. The volume of material A is VA and its outer
surface area is AA. The volume of material B is VB and its outer surface area is AB,
which is equal to the inner surface area of material A. A thin layer of a heat-transfer
resistant material coats the AA and AB surfaces, as indicated in the drawing. For time
greater than zero, a constant radiative heat flux qs is imposed on AA while heat is also
lost to the air from AA at a rate given by a Newton’s law of cooling; that is, the net
heat input rate at AA is

AA[qs – ho (TA – Tair)]

25
where ho is the outer-surface heat-transfer coefficient and TA is the temperature of
material A, which is assumed to be uniform throughout VA. At area AB, heat flows
into the sphere at a rate again given by a Newton’s law of cooling

ABhi(TA – TB)

where hi is the inner-surface heat-transfer coefficient, and TB is the temperature of

material B, which is assumed to be uniform throughout VB.

The density (ρA, ρB) and heat capacity (CPA, CPB) of materials A and B are different
but constant.

a) Use a lumped-parameter model to write the transient energy balance for

materials A and B and non-dimensionalize to show that the governing
balances for the non-dimensional temperatures θA and θB are

dθ A
= 1 − γ 1θ A − γ 2 (θ A − θ B )
dτ
dθ B
= γ 2γ 3 (θ A − θ B )
dτ
hΤ A hΤ ρ C V
where γ 1 = o air , γ 2 = B i air , γ 3 = A PA A . Define θA, θB, and τ in your
qs AA qs ρ BCPBVB
derivation.

b) What is the physical interpretation of the three γi ?

c) State the initial conditions and solve the equations from part a to find θA(τ).

26
 d) What is the steady-state temperature of materials A and B ?

32. A metallic slab is used to collect solar energy. The dimensions of the slab are:L (length,
m) ×W (width, m) × H (height, m), as shown in Fig. 1. Note that W/H and L/H are >> 1.

Fig. 1.
Consider the steady-state. Due to solar radiation, there is a uniform and constant energy
flux, qw (W m-2), on the top face. The bottom face of the slab is in contact with air at
constant temperature, Tair, which is lower than the slab’s temperature, T(x), that depends
on the x-coordinate only. Thus, at the bottom face, heat flows out of the slab into air by a
Newton’s law of cooling:
qout = h(T ( x) − Tair ) (W m-2)
where qout is the heat flux out, and h (W m-2 K-1) is the heat-transfer coefficient.

Within the slab, heat is transported by Fourier conduction along the x-direction:
dT
qx = − k (W m-2)
dx
where qx is the conductive heat flux in the x-direction, and k (W m-1 K-1) is the thermal
conductivity.

At both ends (x = ± L/2), the temperature is fixed at a constant T0. The solar energy is
collected at both ends in form of heat flow E (W).

a) Use a shell balance to derive the ordinary differential equation governing the
temperature profile, T(x). List all assumptions in the analysis.
b) What are the two boundary conditions for the ODE derived in Part (a).
c) Non-dimensionalize the ODE and BCs and show that the resulting dimensionless
ODE becomes:
d 2θ
= Aθ − B
dX 2
where θ and X are the nondimensional temperature and spatial coordinate,
respectively, and A and B are nondimensional parameters. Define θ, X, A, and B in
terms of the dimensional quantities that are relevant to the problem.
d) Provide physical interpretations of the dimensionless parameters A and B?
e) Solve for θ(X).

27
 f) Calculate the solar energy collection efficiency η; that is, find a formula for the
fraction of energy impinging on the top face that is collected at the two edges (x = ±
L/2).

33. A section of length L (cm) of an infinite transparent glass tube is shown below. A liquid
flows at steady state and constant velocity v (cm s-1) into this section of the tube that is
irradiated uniformly with UV light. The other sections of the tube are not exposed. The
flow is turbulent and plug flow is a good assumption. The liquid contains a reagent at
concentration C0 (mol cm-3) far upstream (x << 0) from the irradiated section (0 < x <
L). A photochemical reaction consumes the reagent in the irradiated section with a first-
order homogeneous reaction rate given by kC (mol cm-3 s-1), where C (mol cm-3) is the
local reagent concentration and k (s-1) is the rate constant. The turbulent flow provides
good radial mixing of the reagent, but its concentration is a function of axial position x,
i.e., C = C(x).

The local molar flux N (mol cm-2 s-1) of the reagent is given by
dC
N = Cv − E
dx
where E (cm2 s-1) is a so-called dispersion coefficient, a known constant. At x = 0, the
boundary condition on the reagent concentration is
⎡ dC ⎤
C0 v = ⎢Cv − E
⎣ dx ⎥⎦ x =0
At the end of the irradiated section of the tube, the boundary condition on the reagent
concentration is
dC
=0
dx x = L

a) Use the shell-balance technique to derive the ordinary differential equation (ODE)

28
 that governs the local reagent concentration, C(x).

b) Nondimensionalize the ODE from Part a to find

d 2θ dθ
2
−α − βθ = 0
dX dX
Define the dimensionless groupings θ, X, α, and β (α, β > 0) in terms of
dimensional variables.

c) What are physical interpretations of parameters α and β?

d) Solve the ODE from Part b (with use of appropriately defined nondimensional
boundary conditions) to find θ(X). To receive full credit, you must calculate all
integration constants.

8/13/10

29