CE 561 Kinetics and Reaction Engineering

Class 02

Agenda

Chemical reaction rates

Rate expressions
Idealized models for laboratory reactors
Perfectly mixed batch

Perfectly mixed continuous flow stirred tank (CSTR)

Plug flow reactor (PFR)

Testing the ideality of flow

Chemical Reaction Rates

Recall two meanings of chemical reaction

An apparently unified process whereby a few chemical entities, in fixed proportions, are
converted into a few different chemical entities, also in fixed proportions
A molecular event wherein 2 or 3 specific reactant species undergo an encounter that results
in changes in the bonding within and among those reactant species resulting in the formation
of specific product species, different from the reactant species

The preferred definition of a reaction rate is the frequency of the molecular

encounters described in the second definition

This definition wont work with the first, more general definition of a chemical reaction above
Nonetheless, it forms the basis for any theoretical consideration of reaction rates
A few points to note, for future reference:

The rate will depend upon the positions, orientations, relative velocities, and internal states
of the reactant species

Except for the most fundamental types of studies, we are usually interested in the net
frequency of such encounters

this requires summing or averaging over all possible positions, orientations, relative
velocities and internal states

The commonly used definition (next slide) is based upon observation at a

macroscopic scale

That is, at a scale where it appears that a single, stoichiometric reaction is taking place
involving known and observable reactants and products and no other intermediate species

Chemical Reaction Rates

To define the rate of a chemical reaction

Select a region in space that is uniform in composition and where only that reaction is taking
place

In homogeneous systems this is typically a volume

In heterogeneous systems, it may be a volume within one phase or an interfacial area
between two phases

Within the selected region in space, observe the change in the number of moles, ni, of any
one reactant or product, i, of the reaction during an interval of time, t
The rate of reaction of the observed species i is defined in the limit where the interval of time
goes to zero as the ratio of the change in moles of i to the interval of time divided by the size of
the observed region in space

1
n 1 dni
lim i =
V t t V dt
1
n 1 dni
- When the observed region in space is an area, A, ri, j = lim i =
A t t A dt
- The subscript j in these definitions denotes the single reaction taking place during the

When the observed region in space is a volume, V,

ri, j =

period of observation

As defined here, the rate is an intensive quantity

It is normalized using the extent of the region in space where the reaction takes place, i. e.
volume or surface area
Caution: rates normalized in other ways (for example per mass of heterogeneous catalyst) can
lead to scaling problems

Rates and Rate Expressions

ri, j =

1 dni
V dt

ri, j =

1 dni
A dt

The rate as defined above is called the rate of generation of species i via
reaction j or the rate of reaction j with respect to species i
ri,j will be positive if i is a product and negative if i is a reactant

A generalized rate of reaction j (that is without reference to any of the

reactants or products) can also be defined
rj =

ri, j 1 d j
ri, j 1 d j
=
or rj =
=
i, j A dt
i, j V dt

rj will always be positive

rj =

ri, j
ri, j
r
= k, j
no matter which reactant or product is used as i, therefore,
i, j
i, j k, j

In either case, the rate of reaction is expected to depend upon the

composition and temperature at the location where the reaction is taking

place
A rate expression is a mathematical equation that describes how a rate
varies with the composition and temperature (the environmental variables)
It should be single valued
It should evaluate to zero when the composition and temperature correspond to
thermodynamic equilibrium

Terms in Rate Expressions that

Depend upon Temperature

Concentrations and Partial Pressures of Gases Depend upon

Temperature

e. g. if the gas is ideal

Ci =

ni
P
= i
V RT

and

Pi =

ni RT
V

Equilibrium Constants can Appear in Rate Expressions, and Equilibrium

Constants Depend upon Temperature

G j
S j
H j
H j
K j = exp
= exp
exp
= K 0, j exp

RT
R
RT
RT

Rate Constants (Rate Coefficients) Depend upon Temperature

The Arrhenius expression is the most commonly used form for rate expressions

E
k = k0 exp
RT
A plot of ln(k) vs. (1/T) is called an Arrhenius plot

When the Arrhenius expression is valid, the plot is a straight line and the parameters,
k0 and E, can be determined from the slope and intercept

A popular expression for the rate coefficient used in mechanistic combustion kinetics

E
k = k0T m exp
RT
m is an additional parameter

Procedure for Developing Rate Expressions

1. Choose a reactor for the experiments
1.1. Generate design equations for the reactor
1.2. Validate the design equations

2. Gather experimental data

2.1. Use the widest possible range of environmental variables
2.2. At minimum span region of environmental variables at which rate expression will be used

3. Pick a mathematical function to be evaluated as a rate expression*

3.1. Empirical
3.2. Theory-based

4. Put the function (from step 3) into the design equations (from step 1) and fit the
design equations to the experimental data (from step 2)
4.1. Averaging (single parameter design equation)
4.2. Least squares fitting

5. Decide whether the fit is adequate

5.1. Correlation coefficient
5.2. Rectifying (parity) plot
5.3. Residuals plots

6. If the fit is adequate, estimate the uncertainty in the parameters and you are finished
6.1. If the fit is not adequate, return to step 3

* Note that the rate expression is only related to the stoichiometry of the reaction under
special circumstances

Choosing a Reactor for Kinetics Experiments

Most laboratory reactors are designed to behave according to one of three

idealized types of reactor

Perfectly mixed batch reactor

No flow in or out during reaction

The fluid within the reactor is perfectly mixed leading to a completely uniform composition
and temperature

Perfectly mixed continuous flow stirred tank reactor

Same as the batch reactor except fluid is continually flowing in and out of the reactor

Plug flow tubular reactor

Basically fluid flowing through a cylindrical pipe in the axial direction only

No variation in the axial velocity as a function of radial position, i. e. flat velocity profile
with complete slip at the wall of the tube

Also called piston flow or slug flow

No mixing in the axial direction

Perfect mixing in the radial direction

composition and temperature are completely uniform across the tube cross-section

Before use, the reactor must be tested to ensure these assumptions are
true

For example, if data are analyzed assuming the reactor was perfectly mixed, but in actuality it
was not perfectly mixed, the resulting rate expression would not be accurate or valid

Modeling the Laboratory Reactor

(Generating Design Equations)

Mole balance on any one reactant or product, i, in a perfectly mixed

batch reactor

dni
= V fluid ri, j ; ni ( 0 ) = ni0
dt
- This assumes the reactor is perfectly mixed and the rate should be normalized using the
volume of the fluid phase

For a gas phase system, the volume of the fluid phase equals the volume of the
reactor

For a liquid phase system, there could be headspace above the liquid phase so that
the fluid volume is less than the volume of the reactor

If the reactor is operated isothermally (that is, the temperature does not change during the time
of the reaction), this is the only equation needed in order to model the reactor and analyze the
data

If the reactor is non-isothermal, an energy balance is additionally needed

That makes the analysis of the data much more difficult

Mole balance on any one reactant or product, i, in a perfectly mixed,

steady state continuous flow stirred tank reactor

n!i n!i0 = Vri, j

- Same assumptions as batch reactor for mixing and normalization
- Additionally assumes steady state operation

This is the only equation needed in order to model the reactor and analyze the data

 Mole balance on any one reactant or product, i, in a plug flow tubular

reactor with a homogeneous reaction taking place
dn!i D 2
0

=
r ; n!i ( 0 ) = n!i
dz
4 i, j
- This assumes that the rate should be normalized using the volume of the fluid phase
- It additionally assumes steady state operation

If the reactor is operated isothermally, this is the only equation needed in order to model the
reactor and analyze the data

If the reactor is non-isothermal, an energy balance is additionally needed

That makes the analysis of the data much more difficult

Mole balance on any one reactant or product, i, in a plug flow packed

bed tubular reactor with a heterogeneous catalytic reaction taking place

on the surface of a porous solid catalyst
dn!i D 2

=
bed Scat ri, j ; n!i ( 0 ) = n!i0
dz
4
- As for the plug flow tubular reactor above, this equation assumes steady state operation,
and if the reactor is operated isothermally, this is the only equation needed in order to
model the reactor and analyze the data

It additionally assumes that the rate should be normalized using the surface area of the
solid (there are a few other accepted ways of normalizing heterogeneous catalytic rates)

bed is the apparent density of the packed catalyst bed (mass per bed volume)
Scat is the specific surface area of the solid catalyst (area per mass)

IMPORTANT: this equation retains the plug flow reactor assumption that the fluid phase is
perfectly mixed (i. e. completely uniform in composition and temperature) in the radial direction

Laboratory Reactor Model Assumptions that

Must be Verified
reactor
Batch
dn

= V fluid ri, j ;

ni ( 0 ) = ni0

dt
- Reactor is perfectly mixed (uniform composition and temperature throughout the reactor)
- Reactor operates isothermally

Perfectly mixed continuous flow stirred tank reactor

n!i n!i0 = Vri, j

- Reactor is perfectly mixed (uniform composition and temperature throughout the reactor)
- Reactor operates at steady state

Plugdn!flow Dtubular reactor (homogeneous reaction)

ri, j ;

n!i ( 0 ) = n!i0

dz
4
- Reactor operates isothermally and at steady state
- Plug flow (no mixing axially, perfect mixing radially, no gradients of axial velocity in the
radial direction)

Plugdn!flow Dpacked bed tubular reactor (heterogeneous catalytic reaction)

bed Scat ri, j ;

n!i ( 0 ) = n!i0

dz
4
- Reactor operates isothermally and at steady state
- Plug flow (as for plug flow tubular reactor)

Testing Flow Assumptions

Flow visualization for testing mixing

Requires ability to see into the reactor
Reaction need not be taking place
Inject smoke (gas system) or dye (liquid system) into a batch reactor or into the feed to a
CSTR

Observe whether the smoke/dye appears uniformly through the reactor volume
Observe how quickly the smoke/dye concentration becomes uniform throughout the
reactor

Variation of the impeller speed to test mixing

Again applied to batch reactors and CSTR where perfect mixing is assumed
Test is performed while reaction is taking place
Measure the conversion in a set of experiments where a different agitator speed is used in
each experiment in the set

For an isothermal, steady state CSTR every experiment should use the same fluid volume
in the reactor, temperature, feed composition and feed flow rate

For an isothermal batch reactor every experiment should use the same temperature, initial
composition and duration of reaction

A plot of the conversion versus the agitator speed should be a horizontal line

At agitator speeds where the slope of the plot is positive, the reactor is not perfectly mixed
During kinetics experiments, the agitator speed should be well within the horizontal region
of the plot

Using the Age Function to Test

Reactor Flow Assumptions

An age function, F, can be defined for flow reactors and used to assess

how well they conform to the assumptions of a perfectly mixed CSTR or a

PFR
Define F() as fraction of the fluid leaving a steady state flow system that has been inside the
system for a period of time (i. e. has an age) <
- If fluid is leaving the reactor, it had to be inside the reactor for some amount of time (it
cant leave if it never was inside) so F(0) = 0
- The reactor has not been operating since the beginning of time, so all of the fluid leaving it
has a finite age, i. e. F() = 1
A related function, known as the residence time distribution function or the age distribution
function, dF(), is equal to the fraction of the fluid leaving a steady state flow system that has
been inside that system for a period of time between and d
dF() = F( + d) - F()

age function depends upon how the fluid flows within the reactor
The
In an ideal CSTR, the flow is perfectly mixed throughout the reactor volume, and knowing this,
the age function for an ideal CSTR can be derived mathematically
In an ideal PFR, the flow is perfectly mixed in the radial direction and completely unmixed in
the axial direction; knowing this, the age function for an ideal PFR can be derived
mathematically
The age function for a real reactor can be measured experimentally

A comparison of the experimental F() for a real reactor to the derived

F() for one of the ideal reactors can be used to determine if the real
reactor violates the flow assumptions of the ideal reactor

Measuring the Age Function of a Reactor

There does not need to be a reaction taking place in order to measure the
age function (or equivalently, the residence time distribution)

It should be measured at the same feed flow rate, viscosity and temperature as will be used in
kinetics experiments
For a CSTR, the steady state fluid volume and the agitation rate should be the same as will be
used in kinetics experiments

The experimental procedure consists of applying a stimulus at the inlet

to the system and measuring the subsequent response at the outlet
from the system
Typical stimuli are a step change or an impulse in the concentration of a tracer
A tracer is something that becomes intimately mixed with the fluid and flows exactly the same
as the rest of the fluid, but that can be detected easily at the outlet

Dye or radioisotope

Fluid Element a very small amount of fluid that stays together as a unit
for the whole time its inside the reactor

Not a physical reality, but conceptually convenient

One fluid element may stay inside the reactor longer than another fluid element, but all the fluid
inside any one fluid element stays in the reactor for the same amount of time

Step Change and Impulse Stimuli

Inlet Tracer
Mass Fraction

Step Change

wf

w0

Impulse

w0

Time
t0

Measuring the Age Function

Using a Step Change Stimulus

Suppose that for a long time prior to t , the inlet contained tracer at a
0

weight fraction of w0

The weight fraction throughout the reactor is steady and equal to w0

Therefore, the weight fraction at the outlet is equal to w0

At t = t , increase the inlet tracer weight fraction to w using a step change

Take samples at the outlet at different times, t and measure the weight
0

fraction of tracer, w, in those samples

Letting = t t0, a mass balance on the tracer shows that F() can be
calculated for corresponding to each sampling time as follows

F ( t t0 ) = F ( ) =

wt w0
w f w0

If desired, dF()/d can be determined by differentiation

dF ( )
dF ( ) =
d

Measuring the Age Function

Using an Impulse Stimulus

Let the steady-state weight fraction of tracer in the inlet to the process be

w0
At time t0, apply an impulse to the inlet tracer concentration
Let denote the steady mass flow rate and let mtot denote the total mass
of tracer used in the impulse
Take samples at the outlet at different times, t, and measure the outlet
weight fraction of tracer, wout, in those samples
Letting = t t0, a mass balance on the tracer shows that F() can be
calculated at each sampling:
t

F ( t t0 ) = F ( ) =

M! wout ( t ) w0 dt
t0

mtot

( w (t ) w ) dt
out

t0

( w (t ) w ) dt
out

t0

Note that w

out(t)

will only be known at the times when the outlet was

sampled, not as a continuous function
Therefore the integrals above cannot be evaluated analytically, they will have to be evaluated
numerically, e. g. using the trapezoid rule

 Differentiating F() gives

M! ( w ( t ) w )
dF ( )
=
out

=t t0

mtot

mtot = M! wout ( t ) w0 dt

where

t0

and the residence time (or age) distribution function can be computed:
dF ( )
dF ( ) =
d
d

Either experimental procedure (step change stimulus or impulse stimulus)

leads to a table of values of and F(), not an analytical expression for

F()
If the fluid density, , is constant it is trivial to convert the preceding
equations to use volumetric flow rates and concentrations of tracer instead
of mass flow rates and mass fractions

M! = V!
wout

MW )
(
=

tracer

Cout

Age Function for an Ideal CSTR

Note that it can be derived using either a step change or an impulse

stimulus; the age function is the same in either case

Easy to derive by writing a mass balance on the tracer following a step
change at the inlet from w0 to wf
Tracer flow in = Tracer flow out + Tracer accumulation within the reactor

! = Mw
!
Mw
t + fluidV fluid
f
out ( )

dwout ( t )
dt

wout ( t ) = w0

tM!
wout ( t ) = w f w f w0 exp

fluid fluid

fluidV fluid
t =
M!
t
wout ( t ) = w f w f w0 exp
t

Introducing the average residence time,

Substituting into the expression for measuring the age function using a step change stimulus,

t
w f w f w0 exp w0
wout w0
t
F ( ) =
=
w f w0
w f w0

F ( ) = 1 exp
t

To Test Whether a Stirred Tank

Behaves as an Ideal CSTR

Plot the CSTR age function using t equal to that of the experimental
reactor

F ( ) = 1 exp
t

Measure the age function for the experimental reactor

Plot the resulting pairs of (,F()) values calculated for each outlet sample

If the plotted points deviate significantly from the plotted age function, the
stirred tank does not obey the ideal CSTR flow assumptions
Do not use this reactor to generate kinetics data
Kinetics data generated using this reactor cannot be analyzed using the ideal CSTR model

If the plotted points fall exactly on the plotted age function, it is still

possible that the stirred tank violates the ideal CSTR flow assumptions
When a CSTR passes this test, it signifies that the time constant for completely mixing the
reactor contents is very small compared to the residence time of the fluid in the reactor

It is still possible that the time constant for substantial reaction to occur is comparable to
(or smaller than) the time for mixing

Some reaction then will take place before the reactor contents are perfectly mixed
In other words, if the reaction being studied is extremely fast, a reactor could pass this test
but still violate the assumptions of the ideal CSTR model

Age Function for an Ideal PFR

A mathematical derivation is possible, but not necessary

Consider application of an impulse stimulus
t0

t0 < t1 <

t t0

t0 < t1 <

t t0

n!i

F(t0) = 0

n!i

F(t1) = 0

n!i

F(t2) = 0

n!i

t t0
F ( ) = 0 for < t
F ( ) = 1 for t

F( t ) = 1

To Test Whether a Tube or Pipe

Behaves as an Ideal PFR

You could go through the same routine as was employed for a CSTR
Plot the expected age function if the reactor is an ideal PFR
Plot the experimentally measured age function
Compare

However, it is easier to simply examine the response directly

If the stimulus is a step change, the response should be an identical step
change

How rounded are the corners of the step?

How long does it take for the middle 95% of the response to elute?

If the stimulus is an impulse, the response should be an identical impulse

What is the width (in time) of the eluted peak at one-half of its maximum intensity?
How long does it take for the upper 95% of the peak to elute?

Using the answers to the above questions about times

What percentage of the bed length does this time correspond to at the prevailing linear flow
velocity?

This is a measure of the axial mixing distance, which should equal zero in an ideal PFR