Pre-requisites to the course Molecular Transport Phenomena (CH3151)

Author: Volkert van Steijn

Delft, April 2017

Dear students, the main goal of this document is to clarify the expected entree
level for the course Molecular Transport Phenomena. A key reason for
compiling this document for you is based on the wish expressed by students who
attended the previous edition of the course. They would have loved to know the
required entry-level way before the first day of the new academic year. I am
thankful to those students and to those who helped me compiling this document.

To test whether there are any gaps in your prior knowledge, I expect you to do
the self-assessment in section 2 of this document prior to the start of the course.
This helps you identifying which areas of your theoretical knowledge/practical
skills are up-to-speed and which ones need to be practiced and brushed-up.
Please do the assessment at least one month in advance, such that you have
sufficient time for the brush up. Study material to help you do that is provided in
section 3, while section 4 provides some additional practice material. Section 5
provides a partial list of final answers, so you can check your answers. Note that
full solutions are not provided.

Section 1. Course Pre-requisites

The course Molecular Transport Phenomena builds on courses in your
undergraduate, particularly on transport phenomena, mathematics, and physical
chemistry. Although the list below is not exhaustive, it gives you a fairly good
idea of the expected entree level for the courses on these different subjects.
Please note that some of you have not seen a single course on Transport
Phenomena in their undergraduate program, but a series of different courses on
heat transfer, mass transfer, and fluid flow, which together comprise the
area of Transport Phenomena.

1. Transport phenomena
I can explain the following terms (in words a high school student understands)
- steady state, quasi steady state, - batch reactor, plug flow reactor,
transient stirred tank reactor
- Poiseuille flow - incompressible flow
- Reynolds number - inertia
- drag force - dimensionless number
- no slip & no shear boundary - zero flux & continuity of flux
condition boundary condition
- continuum approximation - Knudsen number
- diffusive transport * - convective transport*
- Peclet number - penetration theory
* Describe them in the context of heat, mass (species), and momentum transport.

I know by heart
- Newtons second law; Ficks second law of diffusion
- Ficks first law of diffusion and Fouriers law of conduction
- Hagen-Poisseuille equation for steady laminar flow through a pipe

1
I am able to
- analyze problems involving transport of mass, momentum, and energy in
Cartesian, cylindrical, and spherical coordinates by [exercises 1-4]
o picking a relevant control volume,
o indicating the fluxes entering and leaving the control volume,
o setting up a material balance, species balance, momentum balance, or
energy balance
o simplifying the balance equation into a partial differential equation
that captures how the parameter of interest (e.g. mass, concentration,
temperature, velocity) depends on time and space
o formulating the boundary and initial conditions for the differential
equation
o solving the differential equation
- use the above strategy to derive the continuity equation myself
- analyze problems involving forces, by setting up a force balance starting
from Newtons second law of physics [exercise 5]
- explain the physical meaning of the different terms in the Navier-Stokes
equations and able to simplify the Navier-Stokes equations when analyzing a
particular problem

2. Mathematics
2.1 Differential equations [exercise 7]
I am able to
- apply the chain rule when differentiating,
- solve homogeneous first-order ordinary differential equations,
- solve non-homogeneous first-order ordinary differential equations,
- solve homogeneous second-order differential equations,
- simplify a differential equation or its solution using Taylor expansions (and
use Taylor and series expansions in a more general context)
2.2 Integration
I am able to
- integrate basic functions, for example using a relevant substitution or using
integration by parts [exercise 7]
2.3 Statistics
I am able to
- write down the law of large numbers,
- write down the formula that describes a Gaussian distribution,
- write down the general formula to calculate the average and root mean
square value (or standard deviation) of a quantity, which is distributed
according to a given distribution function, and apply this formula to a given
problem [exercise 8]

3. Physical Chemistry
I am able to
- explain the concept of mean free path
- explain the concept of equi-partition
- explain the background of Maxwell-Boltzmann distributions
- work with the ideal gas law

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Section 2. Self-assessment

Exercise 1
Consider a continuously stirred tank reactor (CSTR) with a volume V0. The tank
is filled up to a level that it contains a volume of 0.2V0 of water. At t=0, a solution
of salt in water with a concentration c0 flows into the CSTR at a flow rate v. At
the same time, a valve is opened at the bottom of the tank through which fluid
exits the CSTR at a rate of flow v/3.
a) Make a sketch of the problem, indicating all relevant variables.
b) Determine how the volume of liquid in the CSTR depends on time.
c) Write down the differential equation from which the salt concentration at
the exit of the CSTR can be computed.
d) Use the differential equation in b) to determine how the salt concentration at
the exit depends on time.

Exercise 2
Consider dispersed plug flow in a straight tube of uniform cross-section and
length L. At the left side the tube is connected to an ideal stirred vessel
containing only water. This is flowing into the tube with a velocity v. At the other
end, the tube is connected to a big, ideally stirred tank with water container
species A in a concentration c0.
a) Make a sketch of the problem, indicating all relevant variables.
b) Consider a relevant control volume and set up a shell balance (microbalans
in Dutch) to derive the 1-dimensional mass balance for species A in the tube
for a steady state.
c) Assume diffusion can be neglected. What will the concentration profile in the
tube look like?
d) Assume the velocity is very small. What will the concentration profile look
like?
e) Solve the balance of (a) and compare the outcome with your answers to (b)
and (c). Explain the differences and observations.

Exercise 3
Consider laminar flow between two, large, vertical plates. The distance -D D
between the two plates is 2D. In the space between the two plates, a
Newtonian fluid (constant density , viscosity ) flows vertically
downwards under the influence of gravity (no pressure difference is
applied to the system). The situation is in steady state.

Set up a microbalance and show that the velocity distribution is equal

to:
g ( 2 g
vy = D x2 )
2

y
x
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Exercise 4
Consider a metal rod (length L, cylindrical shape). The rod is insulated except for its
ends.
a) The rod has a constant heat conduction coefficient, . The rod has a fixed
temperature T0 at the left end a fixed temperature T1 at the right end.
Determine the steady state temperature profile in the rod and calculate the heat
flux.
b) The rod has a heat conduction coefficient, , which is a function of the axial
1 x
=
position along the rod: 0 1 + . The rod has a fixed temperature T0 at
2 L
the left end a fixed temperature T1 at the right end. Determine the steady state
temperature profile in the rod and calculate the heat flux.

Exercise 5
Water with a viscosity flows through a cylindrical pipe. The diameter of the
pipe (d) is small enough to ensure that the flow through the pipe is laminar.
Applying a constant pressure difference p over the pipe, which has a length L,
results in a steady flow through the pipe. In this exercise, we derive the Hagen-
Poisseuille equation, which explains how the volume flow rate depends on the
pressure difference.
a) set up a microbalance, which allows you to derive the velocity profile.
b) use the microbalance to derive vx(r)
c) calculate the average velocity <v> in the pipe?
d) how does the volumetric flow rate depends on <v>?
e) show that with

which is the Hagen-Poisseuille equation for laminar flow through a pipe

with a circular cross section.
f) The parameter R is often called the hydrodynamic resistance. Can you
explain the analogy between Ohms law and the Hagen-Poisseuille equation?

Exercise 6
Consider a small sphere submersed in quiet water (density 1000 kg/m3,
viscosity = 1 mPa.s). The radius of the sphere is 10 m, its density 1 kg/m3.
a) Make a sketch of the sphere and draw the forces acting on the sphere. Then
write down Newtons second law to describe the motion of the particle.
b) Give the general expression for the steady drag force acting on a sphere
moving in a liquid.
c) Give Stokes drag law. Explain under what conditions this law is applicable.
d) Use the force balance to compute the steady rise velocity of the sphere.

Exercise 7

a) Given that x is a function of t, show that

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Solve the following differential equations, where b is a function of time (t) and C
is a constant:
b) db/dt = C
c) db/dt = Cb
d) db/dt = Cb + 2Ct
e) d2b/dt2 = b

Exercise 8

Given that , solve the following integrals. (hint: use integration

by parts)
a) b) c)

d) e) f)

Exercise 9
A group of dancers is waltzing on a one-dimensional dance floor of length L.
Since the dancers avoid the walls, the probability of finding a dancer at a position
x between the walls at x=0 and x=L is proportional to sin2(pi*x/L).
a) Determine the normalized distribution function for the position of the
waltzers.
b) Make a sketch of the normalized distribution function.
c) Calculate the most probable position of the waltzers from the distribution
function.
d) Give the general equation to calculate the average position.
e) Calculate the average position of the waltzers from the distribution function.
f) Give the general equation to calculate the root mean square position.
g) Calculate the root mean square position of the waltzers from the distribution
function.
h) Consider part of the dance floor between L/2 s + L/2 +s. Calculate the value
of s to find 70% of the people in this part of the dance floor.

Useful relations: sin2(x) = 0.5*(1-cos(2x));

Exercise 10
A toxic compound is spilled on a layer of soil. The concentration in the polluted
layer can be treated as a constant, with a value of 5 kg/m3. The compound will
over time diffuse into the soil, with an effective diffusion coefficient D = 2 10-10 in
SI-units.
a) What are the SI units of D?
b) Estimate how long it takes for the pollution to reach a depth of 30 cm in the
soil layer.

5
Section 3. Recommended literature

Having made the exercises in the self-assessment section, you - by now - should
have a fairly good idea which pre-required knowledge/skills are well-developed
and which ones need to be further brushed up. This section points you to the
right resources to do this by recommendation of books. If you have other
relevant resources (for instance the ones used in your undergraduate program
such as Bird, Stewart & Lightfoot), of course use those, as you are most familiar
to them and will be able to quickly navigate to the relevant parts. Please note
that the books recommended below will not be used in the Molecular Transport
Phenomena course itself.

1. Transport phenomena (highly recommended as mass transport, heat

transport and fluid flow are all integrated in this book)
Transport Phenomena the art of Balancing by van den Akker and Mudde,
ISBN: 9065623582 (see e.g. amazon.com)

Please note that an online version of a transport phenomena course is

available:
https://www.edx.org/course/basics-transport-phenomena-delftx-
tp101x-0
https://www.edx.org/course/advanced-transport-phenomena-delftx-
tp201x
While the first one is more a primer, the second one corresponds to the level
of the undergrad course, and hence to the required entree level.

Below, you find a list of topics from this book, including the section, which are
seen as pre-requisites for the course MTP.

Topic Section
General concept of balances 1.1 and 1.2.1
Different types of chemical reactors 1.2.2
Diffusion and diffusive transport 2.1,
mechanisms
Dimensional analysis and importance of 2.2
for example the Reynolds and Peclet
number
Drag force 2.3
Setting up shell balances for problems Heat transport: 3.1, 3.4
in Cartesian, cylindrical and spherical Mass/species transport: 4.1, 4.2, 4.4, 4.6
geometries Momentum transport: 5.6
Penetration theory 3.3, 4.2.5
Hagen-Poisseuille flow 5.3, 5.6

Useful to have seen

Winkelmans experiment 4.3
Navier-Stokes equations 5.8

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2. Mathematics
Calculus: Early Transcendentals, 7th edition by Edwards & Penny
ISBN:9781292022178

Online lectures are for example available at the website of MIT, see
for example
http://ocw.mit.edu/courses/mathematics/18-01sc-single-variable-
calculus-fall-2010
http://ocw.mit.edu/courses/mathematics/18-02sc-multivariable-
calculus-fall-2010
http://ocw.mit.edu/courses/mathematics/18-06sc-linear-algebra-fall-
2011
http://ocw.mit.edu/courses/mathematics/18-03sc-differential-
equations-fall-2011

3. Physical Chemistry
Physical Chemistry by Engel and Reid, ISBN: 032181200X

Topic Chapter
Kinetic theory of gases 33

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Section 4. Additional exercises on Transport Phenomena

Based on my experience, students find it difficult to set up a problem involving

transport of mass, species, heat/energy and momentum. Once the strategy to
solve the problem is determined (based on a proper sketch and identification
which control volume to consider, which balances to set up, and which
mechanisms are involved), further working out the problem is then rather
straightforward. The exercises below help you further practice setting up
balances to solve Transport Phenomena problems. Most of them are in the area
of fluid flow, as students typically find such problems more challenges than the
ones involving mass/species/heat transport.

Exercise 11
Consider a long cylindrical tube with diameter d and length L. Water flows
through this tube as a plug flow with velocity v. This flow contains species A and
B, which react with each other according to A + B C. The reaction is first order
in the concentration of both species, i.e. r = kcAcB, with k the reaction rate
constant. The tube receives the reactive water stream from a mixing unit, in
which separate streams of A (concentration cA0, flow rate QA) and B
(concentration cB0, flow rate QB) are quickly and thoroughly mixed before the
resulting stream enters the tube. Assume no reaction has occurred yet in the
mixing unit. In this exercise, you analyze the concentration profile in the tube.
Consider the transport of species in the tube to be one-dimensional.
Furthermore, assume that the reaction does not change the density of the fluid
involved (neither due to change in composition, nor due to temperature effects).
Similarly, other fluid properties like the diffusion coefficients (use DA for species
A, and DB for species B) remain constant during the process.
a) Make a sketch of the tube, draw a control volume between x and x+dx, and
indicate all fluxes of A entering and leaving this control volume. Then set up a
shell balance (microbalans in Dutch) for species A. Translate this balance
into a differential equation that describes how cA depends on time and
location. Important: do not solve the partial differential equation.
b) Now consider species B. Give the partial differential equation that describes
the transport of species B (no need to start from a microbalance).
For (c) and (d): Consider the system at steady state and neglect diffusion.
c) Write down the simplified differential equations for species A and B and
provide the corresponding boundary conditions. Briefly explain the boundary
conditions.
d) Determine the concentration profile of species A and show that it is equal to
. Give expressions for the positive constants C1 and C2.

Given the general equation:

8
Exercise 12
Two immiscible Newtonian liquids flow side by side between two parallel plates
(separated by a distance 2d) as shown in the sketch. The two liquids have
viscosities Aand B. The inlet and exit are a distance L apart, with the pressure
being equal to pin at the inlet and to pout at the exit.

The following assumptions/simplifications can be made:

the system is two dimensional, with the coordinate system as indicated in
the sketch;
the system is at steady state;
the flow is laminar and fully developed;
gravity can be neglected.

a) We are interested in the velocity profile in the two fluids. We start by

considering the flow in fluid A. To derive the differential equation that
describes the flow profile, take the following 5 steps: (1) Copy the sketch on
your exam paper with the coordinate system as indicated, (2) indicate the
control volume you need to consider when you want to derive the velocity
profile in fluid A, (3) indicate the relevant forces acting on the control
volume, (4) use the sketch you made to set up the microbalance, and (5)
simplify the microbalance such that you yield a differential equation that
describes how the velocity in fluid A depends on the y-position. It is not
needed to solve the differential equation.

b) Repeat question (a) for fluid B.

c) Write down all the boundary conditions that need to be taken into account
when you want to solve the two differential equations in (a) and (b). You may
assume that the position of the interface (at y=w) is known.
d) In question (b), the position of the interface was assumed to be known. In
reality, it depends on the flow rates QA and QB in the two phases. Explain in
detail how the interface position could be obtained when the ratio QA/QB is
known, but do not actually carry the calculations through to completion.

9
Exercise 13
The figure below shows a solid wire of radius r1 that is being pulled at a constant
velocity V through a horizontal die of length L and internal radius r2. The space
between the wire and the die is filled with a Newtonian liquid with a viscosity .
The pressure at both ends of the die is atmospheric. When the wire leaves the
die, it is coated with a liquid film that has a uniform thickness . Ignore gravity in
this problem. Furthermore, assume that the velocity is one-dimensional (in the z-
direction).

To solve question (a), use the following general strategy: set up the appropriate
(micro)balance(s), sketch the control volume(s) that you consider and identify
the relevant fluxes (mass, species, energy, and/or momentum), translate the
balance(s) into differential equation(s), state the boundary conditions, and solve
the differential equation(s).

a) Show that the velocity profile vz in the annular space in the die equals

b) Derive an expression for the total volumetric flow rate v through the
annular space. Subsequently use this expression to show what the value is for
the limit that r1 approaches to zero.
c) Now consider the liquid film on the wire after the wire is pulled out of the
die. Give the boundary conditions needed to find the velocity profile in the
film. Use them to explain why the velocity profile inside the film is flat and is
described as vz(r) = V.
d) Express the final thickness of the coating in terms of the variables given in
the sketch.
e) Derive an expression for the force F required to pull the wire through the die.
Discuss whether the expression you obtained makes sense.

10
Exercise 14
Consider the two dimensional system shown in the figure below, where a
circular solid disc (radius R) rotates around its axis. The disc is separated from
the solid support by a very small distance d (<<R). The gap between the disc and
the support is filled with water (density , viscosity ). The disc rotates at a fixed
annular velocity (such that the surface of the disc rotates at a velocity R). Due
to the rotation, the water level at the left side is higher than the water level at the
right side by an amount h. The length over which the water wets the surface is
L. Consider the flow in the gap to be laminar and consider the system as steady
state.

In part (a), you are asked to derive the velocity profile in the gap. In doing so,
ignore the fact that the disc is curved and assume that the velocity profile is the
same along the entire length L of the wetted area (so ignore end effects). In this
way, the velocity profile only depends on the distance y (see sketch) from the
surface of the disc

a) Derive the velocity profile in the gap and show that it equals

As always, start your derivation with a sketch, draw the control

volume that you consider, set up the microbalances, etc.

b) What is the average velocity in the gap?

c) Show that the height difference equals

11
Exercise 15
Consider a microchannel with a rectangular cross section. The width of the
channel w is much larger than the height h of the channel. The length of the
channel is L. Applying a pressure difference p between the inlet and the outlet
of the channel results in a steady flow of water. We are interested in the velocity
profile in this channel.

a) Bob argues that we can calculate the velocity profile by considering the much
simpler 1-dimensional case of flow between two infinitely large parallel
plates. What is/are the argument(s) used by Bob?
b) Set up a microbalance and derive the velocity profile for the much simpler
case discussed by Bob. Proof that

c) Use the velocity profile to find an expression for the average velocity in the
channel.
d) Write down the relation between the volumetric flow rate v and the
pressure difference.
e) Bobs colleague took an advanced course on fluid dynamics and derived the
velocity profile for laminar flow in a microfluidic channel of height h and
width w. He then used it to derive the relation between the flow rate and the
pressure difference and found the following approximation for small aspect
ratios h/w

Does the relation found in d) indeed closely match this relation such that the
approach by Bob is indeed justified?

12
Section 5. List of partial/final answers

Exercise 1
a) Setting up the total mass balance yields

b) Setting up the component balance for species A yields

c) The eq in (b) can be solved using the expression of V derived under (a)
yielding

The integration constant follows from c(t=0)=0 yielding

Exercise 2
a) Full microbalance

Dividing by dx and taking the limit dx0 we find

In case the diffusion coefficient does not depend on the x-position, and the
system is at steady this, this simplifies to

b)
Logical? Yes, diffusion is the only means for A to enter the tube. If there is no
diffusion, there is not way for A to enter the tube so the concentration is zero
(except at the exit of the tube, where the concentration is c0.

c) with c(x=0)=0 and c(x=L)=c0 gives

d) Solving second order ODE in (a) with boundary conditions stated in (c) yields

Logical: if v/D is very large, this indeed yields c(x) = 0 as found in (b). If v/D is
very small (but non-zero), use a Taylor series to demonstrate that the answer in
(c) is found.

13
Exercise 3
Consider the control volume in the sketch.

Setting up the microbalance yields

Important: since there is no externally applied pressure

difference, those terms are not included.
For Newtonian fluids:

Substitution and integrating twice with respect to x yields

The integration constants follow from the no-slip boundary conditions at the walls
vy(x=-D)=0 and vy(x=D)=0. Alternatively, we can use the fact that the profile is
symmetric around x=0. This immediately tells us that C1=0. For the second
integration constant, we find

Hence,

Exercise 4
a) The full microbalance becomes:

with A the cross sectional area of the rod; fluxes are based on Fouriers law.
Turn this into a differential equation yourself. Then, show yourself that the
steady-state profile is linear.

b) Final answer:

Hint: use separation of variables to solve the resulting differential equation.

14
Exercise 5
In case of trouble, look up the derivation of the Hagen-Poisseuille equation (with
a shell balance as a starting point; note that looking up a derivation of the Hagen-
Poisseuille equation based on a simplification of the full set of Navier-Stokes
equations, though very instructive and useful, is not the answer to the exercise).

Exercise 6
a) Make sketch yourself.
b) F = Cd(Re) A v2/2, with Cd(Re) a drag coefficient depending on the Reynolds
number (Re=vD/) and A the cross sectional area of the object
perpendicular to the flow direction. For a sphere, this area is R2.
c) F = 6 Rv; this law follows from the general law using Cd(Re) = 24/Re,
which is valid for a spherical small object moving slowly; or more precisely,
for a spherical object with a low Reynolds number (Re<1).
d) 0.2 mm/s

Exercise 7
In case of trouble, consult your calculus books.

Exercise 8
Answers can be verified yourself, for example using the computer program
maple.

Exercise 9
A group of dancers is waltzing on a one-dimensional dance floor or length L. Since
the dancers avoid the walls, the probability of find a dancer at a position x between
the walls at x=0 and x=L is proportional to sin2(pi*x/L).

a) The probability density function equals with A the

proportionality constant. For a normalized probability density function, this

constant is such that . Working this out gives the expression

for A.
b) Do yourself.

15
c) Most probable position xmp is found for . Working it out gives xmp

= L/2.
d) General equation for the average of a distributed parameter

; since the probability density function is normalized, we

immediately know that the denominator equals 1.

e) Working it out gives xavg = L/2 (which is logical as the system is symmetric).

f) The root mean square position xrms follows from

g) Do yourself.

h) Follows from ; work out yourself.

Exercise 10
a) m2/s
b) Penetration depth can be estimated using . So, the time it takes to
reach a depth of 30 cm equals .

Exercise 11
(a)

(b)

(c)

Boundary conditions:

16
(d)

Hint: As a starting point, take the two diff. equations together to proof
that cA-cb = constant. Once you know this, it is possible to eliminate cb
from the first diff. equation and solve it. The value of the constant later
follows from the boundary conditions.

Exercise 12
(a) Setting up the shell balance and working it out yields

(integrating twice yields the velocity profile)

(b) Similarly:

(c)
No slip boundary condition at both walls:

Velocity continuous at the interface

Shear stress continuous at the interface

(d) General approach:

1. Integrate the differential equations for the velocity fields found in
question (a) and (b). This yields four unknown constants of integration.
2. Use the four boundary conditions found in question (c) to find
expressions for the four constants of integration.
3. Find an expression for the flow rates QA and QB using

So for the ratio, we can write

17
 with the position of the interface, w, the only unknown.
4. Solve the equation for l.

Exercise 13
(a)
Force balance in the z-direction

Reworking this gives (including integration in z-direction and considering a

Newtonian fluid) yields

Integrating twice, taking into account the following boundary conditions

finally yields

(b)

The volumetric flow rate is found from

Filling in the velocity profile and solving it (e.g. using the substitution z = r/r2)
yields

18
Final answer:

Interpretation of limit: If r1 approaches zero, the flow rate approaches zero

(which is sensible)

(c)
Boundary conditions

(no shear)
Since there is no shear at the interface, the velocity profile is flat.
Showing this mathematically is straightforward and leads to integration
constants C1 = 0 and C2 = V.

[correction: should be +r1 ]

(d) [2 points]
The volumetric flow rate in the film is now

Setting it equal to the flow rate found in (b) and rewriting it in terms of gives
the expression for the film thickness.

[correction: should be +r1 ]

(e) [4 points]

The force on the wire in the die equals the shear stress acting on its surface times
the surface area

From (a), we know

Hence, .

Makes sense? Indeed expected that force increases with , L, V, r1/r2.

19
Exercise 14
(a)
Final answer

(b) It is steady state, so the height difference does not change. This means that
the net flow from left to right should be zero, hence the average velocity is
zero.

(c) Integrating the velocity field over the gap gives

Solving for h gives the relation.

Exercise 15
Answer not provided. Do yourself.

20