CE 561 Lecture Notes Fall 2009

p. 1 of 13
Days 1 and 2: Introduction and Overview

Motivation for understanding chemical kinetics and reaction design:

This is what makes us chemical engineers the reactor is the central feature of most
chemical processes. Even if separation costs dominate, the reactor often determines the
separation costs.

Chemical reactions are ubiquitous in nature and industry.

In this course, we will construct mathematical descriptions of chemical reactions and chemical
reactors. These allow us to predict and understand the behavior of these reactions and reactors.

Definitions of, and Notation for, Reaction Rates:

Reaction rate: In a perfectly mixed, closed, constant volume system (or in some region of space
over which conditions are uniform) with the generic reaction

aA + bB cC + dD

The reaction rate is defined as


1 1 1 1

C A B D
dC dC dC dC
r
a dt b dt c dt d dt
= = = =

In these expressions, -a, -b, c, and d are the stoichiometric coefficients of the chemical species A,
B, C, and D, respectively. C
A
, C
B
, C
C
, and C
D
are the concentrations (number of molecules or
moles per unit volume) of the chemical species.

For a more general system of reactions, written as


1
0, 1,
N
ij j
j
A i M
=
= =

(
ij
< 0 for reactants, > 0 for products)

where N is the number of species, M is the number of reactions, and
ij
is the stoichiometric
coefficient of species j in reaction i, the rate of reaction i is defined such that the rate of change
of concentration of species j is given by


1
j
M
A
ij i
i
dC
r
dt

=
=

Note that for multiple reactions, this may not uniquely define the rates of reaction. There is
some minimum set of reactions required to describe the rates of change of species
concentrations. Any linear combination of those reactions could equally well be used to describe
the overall changes in composition.
CE 561 Lecture Notes Fall 2009
p. 2 of 13

For a homogeneous reaction (occurring in the gas, liquid, or solid phase) the rate has units of
concentration per time or moles per volume per time.

For a heterogeneous reaction (occurring at a surface or interface) the rate has units of moles per
area per time or surface concentration per time.

As presented here, the rate is an intensive quantity, which means that it is independent of the size
of the system, and is defined for a homogenous system. Sometimes, it is more appropriate to
describe systems in terms of the extensive rate, which is simply the intensive rate multiplied by
the total system volume.

In general, the reaction rate is a function of temperature, pressure, and composition. At fixed
temperature and pressure, the reaction rate is usually expressed as a function of the species
concentrations. That is


1 2
( , ,..., )
N
i A A A
r f C C C =

The most commonly used functional dependence of the rate on the concentrations is to set the
rate proportional to a product of algebraic powers of the species concentrations:


1
ij
j
N
i A
j
r C

or
1
ij
j
N
i i A
j
r k C

=
=



The constant of proportionality (k
i
) is often referred to as the rate constant. Perhaps a better term
is rate coefficient since it is only constant with respect to the species concentrations. It can still
depend on temperature, total pressure, etc.

With the above form, we refer to the
ij
as the order of the i
th
reaction with respect to the j
th

species.

The overall reaction order of reaction i is
1
N
ij
j

=

.

Note: In the above expressions, sum and product notation has been used to keep the
equations both compact and general. Make sure that you understand the notation, and
take the time to write out particular examples (put in numbers for N, M, and the
ij
's).

In your undergraduate kinetics course, you should have learned all of this, perhaps without the
sum and product notation. Be sure you know how to take a reaction mechanism and write the
kinetic equations (which are first-order ordinary differential equations) for the concentrations of
the species in a constant temperature, constant volume system. Also, become comfortable with
the sum and product notation it makes dealing with large reaction mechanisms much easier,
and is essential for doing things on the computer.

CE 561 Lecture Notes Fall 2009
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Example:
Suppose we have the set of reactions

SiH
4
SiH
2
+ H
2
with net forward rate r
1
= k
1
[SiH
4
] k
-1
[SiH
2
][H
2
]
SiH
4
+ SiH
2
Si
2
H
6
with net forward rate r
2
= k
2
[SiH
4
][SiH
2
] k
-2
[Si
2
H
6
]
Si
2
H
6
Si
2
H
4
+ H
2
with net forward rate r
3
= k
3
[Si
2
H
6
] k
-3
[Si
2
H
4
][H
2
]

In a well-mixed, constant temperature, constant volume system, the rate equations for the
species concentrations are

4
1 2 1 4 1 2 2 2 4 2 2 2 6
2
1 2 1 4 1 2 2 2 4 2 2 2 6
2
1 3 1 4 1 2 2 3 2 6 3 2 4 2
[SiH ]
[SiH ] [SiH ][H ] [SiH ][SiH ] [Si H ]
[SiH ]
[SiH ] [SiH ][H ] [SiH ][SiH ] [Si H ]
[H ]
[SiH ] [SiH ][H ] [Si H ] [Si H ][H ]
d
r r k k k k
dt
d
r r k k k k
dt
d
r r k k k k
dt



= = + +
= = +
= + = +

and so forth.

The first reaction is 1
st
order with respect to silane, in the forward direction, and is first
order overall in the forward direction. It is first order with respect to SiH
2
, first order with
respect to H
2
, and 2
nd
order overall in the reverse direction.

We can write the above reactions in matrix notation as follows. We arbitrarily put the
species into a vector in the order in which they appear. That is, our species vector will be


4
2
2
2 6
2 4
SiH
SiH
H
Si H
Si H
A
(
(
(
( =
(
(
(



The corresponding stoichiometric matrix is then


1 1 1 0 0
1 1 0 1 0
0 0 1 1 1

(
(
=
(
(



and with these definitions, the reaction system can formally be written as
0 A = or as


1
0, 1 to
N
ij j
j
A i M
=
= =

, with M = 3 and N = 5.
CE 561 Lecture Notes Fall 2009
p. 4 of 13

In your undergraduate reaction engineering course, you probably also dealt with various forms of
fractional conversion and extent of reaction. These can always be uniquely defined for a
single reaction, and can often be uniquely defined for systems of reactions. However, they are
also often used ambiguously. Always check that you understand the definition being used in a
given situation. In this course, we will sometimes work with extent of reaction variables, but
will more often work directly with species concentrations.

Solving Simple Kinetics Problems Analytically
As an undergraduate, you also should have learned how to analytically integrate the rate
equations for 1
st
order, 2
nd
order, and probably n
th
order reactions. You should memorize the
simplest of these especially the 1
st
order result:

, with , so , and exp( )
o
A
A A A A
dC
A B r kC r kC C C kt
dt
= = = =

On a test, you would be expected to be able to write this down from memory (that is, in less than
10 seconds).

You will find some other simple integrated rate equations in the text by Froment and Bischoff on
p. 7. There are many more in other kinetics texts, but of course you can always integrate the rate
equations by hand or using Mathematica or Maple. Be sure that you are proficient in this as
well.

Example:
Suppose we have the two reactions

A + B C, with r
1
= k
1
C
A
C
B
and k
1
= 10 liter mol
-1
s
-1

C + D E, with r
2
= k
2
C
C
C
D
and k
2
= 5 liter mol
-1
s
-1

and the initial concentrations of the species are
C
Ao
= 1 mol/liter
C
Bo
= 2 mol/liter
C
Co
= 1 mol/liter
C
Do
= 0.5 mol/liter
C
Eo
= 0 mol/liter.

We can write the rate equations for these reactions in terms of the concentrations as
CE 561 Lecture Notes Fall 2009
p. 5 of 13
1
1
1 2
2
2
A
A B
B
A B
C
A B C D
D
C D
E
C D
dC
k C C
dt
dC
k C C
dt
dC
k C C k C C
dt
dC
k C C
dt
dC
k C C
dt
=
=
=
=
=


Since there are only two reactions, we know that at most two of these equations are
independent. That is, we can solve for two concentrations or two extents of reaction, and
the other concentrations can then be determined from the reaction stoichiometry. There
are several possible approaches to this. One way to do this is to write the concentrations
in terms of C
A
and C
D
. Either directly from the reaction stoichiometry, or by observing
that

, ,
C B A D A E D
dC dC dC dC dC dC dC
dt dt dt dt dt dt dt
= = =

We can write

( )
( ) ( )
( )
B Bo Ao A
C Co Ao A Do D
E Eo Do D
C C C C
C C C C C C
C C C C
=
= +
= +


If we had written the reactions in matrix form, we could obtain these relationships in a
more systematic fashion by performing row operations on the stoichiometric matrix.
This will be described further below.

Substituting these into the rate equations for A and D, we get

( ) ( )
( ) ( ) ( )
1
2
A
A Bo Ao A
D
D Co Ao A Do D
dC
k C C C C
dt
dC
k C C C C C C
dt
=
= +


We could now integrate these equations. Alternative, we can write equations in terms of
two extents of reaction. The definition of these is somewhat arbitrary, but one reasonable
choice is

1 2
,
Ao A Do D
Ao Do
C C C C
x x
C C

= =
CE 561 Lecture Notes Fall 2009
p. 6 of 13

These are dimensionless (intensive) extents of reaction, but we could equally well choose
extensive reaction progress variables (with units of moles) or dimensional intensive
extents of reaction (with units of concentration). With these definitions, the
concentrations can be written in terms of the extents of reaction as

( )
( )
1
1
1 2
2
2
1
1
A Ao
B Bo Ao
C Co Ao Do
D Do
E Eo Do
C C x
C C C x
C C C x C x
C C x
C C C x
=
=
= +
=
= +


Substituting the above expressions into the rate equations for C
A
and C
D
gives

( ) ( ) ( )( )
( ) ( ) ( )( )
1 1 1 1
2 2 2 1 2
1 1
1 1
Ao Ao Bo Ao
Do Do Co Ao Do
d
C x k C x C C x
dt
d
C x k C x C C x C x
dt
=
= +

or

( )( )
( )( )
1
1 1 1
2
2 2 1 2
1
1
Bo Ao
Co Ao Do
dx
k x C C x
dt
dx
k x C C x C x
dt
=
= +


the first of these equations is a separable equation that we can integrate directly as

( )( )
1
1
0 0
1 1 1
1
x t
Bo Ao
dx
dt t
k x C C x
= =




integrating this equation (using Maple, Mathematica, integral tables or whatever method
is most convenient) gives

( ) ( )
1
1 1
1
ln
1
Bo Ao
Bo Ao Bo
C C x
t
k C C C x
| |

=
|
|

\ .


which we can solve for x
1
to get

( )
1
1 exp( ( ) )
1 / exp( ( ) )
Bo Ao
Bo Ao Bo Ao
C C kt
x
C C C C kt

=



substituting this into the equation for x
2
gives
( )
( )
2
2 2 2
1 exp( ( ) )
1
1 / exp( ( ) )
Bo Ao
Co Ao Do
Bo Ao Bo Ao
C C kt dx
k x C C C x
dt C C C C kt
| | | |

= + | |
| |

\ . \ .

this ODE does not have an explicit analytical solution for x
2
(or at least I couldn't readily
solve it). However, it can be integrated numerically for particular values of the rate
CE 561 Lecture Notes Fall 2009
p. 7 of 13
constants and initial concentrations. For the values given at the beginning of this
example, the extents of reaction vs. time are as plotted here:




If you are viewing this from the web page, you should be able to download a Maple
worksheet for solving this example by clicking here.

What's the point?
This example illustrates two main points:
(1) We can write kinetic equations and solve kinetics problems in terms of either
concentrations or extents of reaction
(2) Even a simple-looking problem like two consecutive second-order reactions may not
have a simple analytical solution

Some Additional Important Definitions (of words shown in italics):

Another important concept in chemical kinetics is the difference between an elementary reaction
and the overall or stoichiometric reaction. The overall reaction is what is observed
macroscopically, for example in a methane flame, the overall reaction is

CH
4
+ 2 O
2
CO
2
+ 2 H
2
O

However, this occurs in many steps. At the molecular level, two oxygen molecules do not come
together with a methane molecule and rearrange to give two water molecules and carbon dioxide.

An elementary reaction is one that occurs as a single, irreducible event. That is, the molecules
react as written. An elementary step that occurs during methane combustion is

CH
4
+ OH CH
3
+ H
2
O

Note that this reaction contains species that are not part of the overall reaction (the highly
reactive radicals OH and CH
3
). Species such as these are referred to as reactive intermediates.

CE 561 Lecture Notes Fall 2009
p. 8 of 13
Elementary reactions are often classified by their molecularity. This is simply the number of
molecules participating in the reaction. Thus,

A B and A B + C

are unimolecular reactions they each have one reactant. The first reaction is an isomerization
and the second reaction is a unimolecular decomposition reaction.

A + B C + D

is a bimolecular reaction.
A + B C

is also bimolecular, and is often referred to as a recombination reaction. Unimolecular reactions
and recombination reactions often have pressure dependent rate parameters. Termolecular
reactions (which have three reactants) are very rare. No elementary reactions of molecularity
higher than 3 are known.

A necessary, but not sufficient, condition for a reaction to be elementary is that its rate follows
the law of mass action. This simply means that the reaction order with respect to each reactant is
the absolute value of its stoichiometric coefficient. Note that reactions that are not elementary
may coincidentally obey the law of mass action especially over limited regimes of species
concentrations, temperature and pressure. Most observed reactions are not elementary, but are
the sum of multiple elementary reaction steps. Most reactions do not obey the law of mass
action over wide ranges of species concentrations.

All reactions are, in principle, reversible. We generally only consider a reaction reversible when,
under some conditions of interest, it reaches equilibrium with detectable amounts of all reactants
and products present. The equilibrium constant for reaction i is defined by

1

exp
ij
o N
j
i
i o
j j
f
G
K
RT f

=
| |
| |
= |
|
|
\ .
\ .

This is the usual thermodynamic equilibrium constant, and it can be obtained from the Gibbs
energy change (G

i
) of the reaction (relative to reference states consistent with the units used
for measuring concentrations). Above it is written in terms of the fugacities of the reactants and
products, but in the context of this course, we will almost always assume we are dealing with
ideal gas mixtures, or an ideal solution of liquids. For a reaction occurring in a mixture of ideal
gases:

( )
1
N
ij
ij j
N
j i o
j
P
y K
P

| |
=
|
\ .

Where y
j
is the mole fraction of species j, or

CE 561 Lecture Notes Fall 2009
p. 9 of 13

( ) ( )
1
N
ij ij
j
N
o
j i
j
p K P

=

Where p
j
is the partial pressure of species j, or

( )
1
N
ij
j
ij
o N
j i
j
P
C K
RT

| |
=
|
\ .

Where C
j
is the molar concentration (moles per volume) of species j. In all cases, P

is the
reference pressure the pressure of the standard state at which the Gibbs energies of the species
have been computed (almost always 1 bar or, in older literature, 1 atm).

For an ideal liquid solution,


( )
1
ij
N
j i
j
x K

=
=

Where x
j
is the mole fraction of species j or


( ) ( )
1
N
ij
ij
j
N
j i tot
j
C K C

Where C
j
is the molar concentration of species j and C
tot
is the molar density or total molar
concentration of the solution.

For elementary reactions, the law of microscopic reversibility states that the forward and reverse
rate coefficients are related by the equilibrium constant.

,
,
i f
i
i r
k
K
k
=

For example, the reversible reaction
A + B C + D

has net reaction rate

, , i i f A B i r C D
r k C C k C C = .

Noting that the net rate is zero at equilibrium shows that the above relationship between the rate
constants and equilibrium constants is true. This requires that the form of the rate expression
does not change for concentrations away from equilibrium. This is true for elementary reactions,
which obey the law of mass action at all concentrations. The above relationship can be more
rigorously derived based on the time reversibility of the laws of motion (but we will not do so
here).

CE 561 Lecture Notes Fall 2009
p. 10 of 13
At this point, it is worth noting that the concept of elementary reactions is most rigorously
applicable to gas phase and gas-surface reactions. In condensed phase reactions, solvent
molecules are always present and continuously interacting with the reactants and products.

The temperature dependence of the rate coefficient is generally expressed by the Arrhenius
equation or a generalized form of it. This is
exp
a
E
k A
RT
| |
=
|
\ .


E
a
is known as the activation energy, and A is called the pre-exponential factor. This functional
form was established on empirical grounds, but there are theoretical reasons (to be discussed in
detail in a few weeks) why a form like this should work. A more general form that is often used
when rate coefficients must be parameterized over a large temperature range is
exp
a
E
k AT
RT
| |
=
|
\ .


Note the strong temperature dependence of the rate coefficient on temperature, and note that
small uncertainties in the activation energy can lead to large uncertainties in reaction rate.

An Arrhenius plot is a plot of ln(k) vs. (1/T). This gives a straight line with a slope of -E
a
/R if
the temperature dependence of k obeys the Arrhenius equation. You should know how to make
an Arrhenius plot from a set of data and extract the activation energy and pre-exponential factor
from it.

The reaction mechanism is the set of elementary reactions that lead to an observed overall
reaction. Generally, it consists of a large number of reactions, and it is not possible to
analytically integrate the reaction rates to find the species concentrations as an explicit function
of time. A simple reaction mechanism describing the thermal decomposition of dichlorosilane is:

SiH
2
Cl
2
SiHCl + HCl (1)
SiHCl + SiH
2
Cl
2
HCl
2
SiSiH
2
Cl (2)
HCl
2
SiSiH
2
Cl HCl
2
SiSiCl + H
2
(3)
HCl
2
SiSiCl HClSiSiCl
2
(4)
HClSiSiCl
2
SiHCl + SiCl
2
(5)

(disclaimer: this is highly simplified for pedagogical purposes and should not be interpreted as a complete reaction mechanism
for dichlorosilane decomposition).

The overall process described by this mechanism is
SiH
2
Cl
2
SiCl
2
+ H
2


The other species (SiHCl, HCl
2
SiSiH
2
Cl, HCl
2
SiSiCl, and HClSiSiCl
2
) are produced in relatively
small amounts and can be considered reactive intermediates.

The complete set of rate equations for this mechanism is
CE 561 Lecture Notes Fall 2009
p. 11 of 13
2 2
2 2 2 2 2 2
2 2 2 2 2 2 2 2
2 2
1 1 2 2
1 1 2 2 5 5
1 1
SiH Cl
SiH Cl SiHCl HCl SiHCl SiH Cl HCl SiSiH Cl
SiHCl
SiH Cl SiHCl HCl SiHCl SiH Cl HCl SiSiH Cl HClSiSiCl SiHCl SiCl
HCl
SiH Cl SiHCl HC
dC
k C k C C k C C k C
dt
dC
k C k C C k C C k C k C k C C
dt
dC
k C k C C
dt

= + +
= + +
=
2 2
2 2 2 2 2 2 2 2
2
2 2 2 2 2 2
2
2 2 2
2 2 3 3 HCl SiSiCl
HCl SiSiCl
3 3 HCl SiSiCl 4 HCl SiSiCl 4 HClSiSiCl
3 3 HCl SiSiCl
l
HCl SiSiH Cl
SiHCl SiH Cl HCl SiSiH Cl HCl SiSiH Cl H
HCl SiSiH Cl H
H
HCl SiSiH Cl
dC
k C C k C k C k C C
dt
dC
k C k C C k C k C
dt
dC
k C k C C
dt

= +
= +
=
2
2
2 2 2 2
2
2 2
HClSiSiCl
4 HCl SiSiCl 4 HClSiSiCl 5 5
5 5
H
HClSiSiCl SiHCl SiCl
SiCl
HClSiSiCl SiHCl SiCl
dC
k C k C k C k C C
dt
dC
k C k C C
dt

= +
=

This is a set of coupled, nonlinear ODEs that cannot readily be integrated analytically. We will
study numerical means of integrating such systems soon. You should also note that not all of the
equations given above are independent three of them could be eliminated by taking linear
combinations of the others (try this for yourself). For now, however, we will consider some
classical approximation techniques that have often been applied in simplifying reaction
mechanisms. With the advent of modern computers it is no longer necessary to apply these to
get a solution, since we could always integrate the full equations numerically. However, their
application can still be very useful in developing physical understanding the reaction mechanism.

Classical Approximation Methods:
The first approximation that we will consider is the partial equilibrium approximation. Here we
assume that a particular reaction (or set of reactions) is so fast (in both the forward and reverse
direction) that it reaches equilibrium on a time scale much shorter than the time scale for the
overall process. In the reaction mechanism above, reaction (4) is very fast relative to the others,
and it may be a good approximation to assume that it is in equilibrium. If so,


2 2
2 2 2
4 HCl SiSiCl 4 HClSiSiCl
4
HClSiSiCl HCl SiSiCl 4 HCl SiSiCl
4
0, and k C k C
k
C C K C
k

=
= =


Thus, we can eliminate one concentration variable from the system of equations by making this
approximation.

A more widely applicable approximation is the pseudo-steady-state approximation. This is also
called the steady state approximation or the Bodenstein steady state approximation. Here, we
CE 561 Lecture Notes Fall 2009
p. 12 of 13
assume that the reactive intermediates are produced and consumed at rates much faster than the
stable species. Their concentrations therefore adjust very rapidly to the concentrations of the
stable species, and they behave as if they are in steady state on the time scale of the
concentration changes of the stable species. We therefore assume that the rates of change of the
concentrations of the reactive intermediates are zero. Mathematically, this allows us to replace
ordinary differential equations with algebraic equations. If we apply the pseudo-steady-state
approximation to the reactive species in the mechanism above (without applying any partial
equilibrium approximations) we obtain


2 2
2 2 2 2 2 2
2 2 2 2 2 2 2 2
2 2
1 1 2 2
1 1 2 2 5 5
1 1
2
0
0
SiH Cl
SiH Cl SiHCl HCl SiHCl SiH Cl HCl SiSiH Cl
SiH Cl SiHCl HCl SiHCl SiH Cl HCl SiSiH Cl HClSiSiCl SiHCl SiCl
HCl
SiH Cl SiHCl HCl
Si
dC
k C k C C k C C k C
dt
k C k C C k C C k C k C k C C
dC
k C k C C
dt
k C

= + +
= + +
=
=
2 2 2 2 2 2 2 2
2 2 2 2 2 2
2
2 2 2 2
2 2
2 3 3 HCl SiSiCl
3 3 HCl SiSiCl 4 HCl SiSiCl 4 HClSiSiCl
3 3 HCl SiSiCl
4 HCl SiSiCl 4 HClSiSiCl 5
0
0
HCl SiH Cl HCl SiSiH Cl HCl SiSiH Cl H
HCl SiSiH Cl H
H
HCl SiSiH Cl H
C k C k C k C C
k C k C C k C k C
dC
k C k C C
dt
k C k C k C

+
= +
=
=
2 2
2
2 2
5
5 5
HClSiSiCl SiHCl SiCl
SiCl
HClSiSiCl SiHCl SiCl
k C C
dC
k C k C C
dt

+
=


In principle, this allows us to eliminate all of the reactive intermediates concentrations from the
system of equations. In practice, this still may not be easy.

For the above system, it allows us to write

This illustrates that the overall reaction is in fact
SiH
2
Cl
2
SiCl
2
+ H
2


and that HCl inhibits the overall reaction, even though it is neither a reactant nor a product in the
overall reaction. However, it is still not simple to obtain an analytical expression for the rate of
change of SiH
2
Cl
2
concentration with time.

Important things to know from this set of lecture notes:
Definitions of:
reaction rate, stoichiometric coefficient, homogeneous reaction, heterogeneous reaction,
intensive rate, extensive rate, rate constant, rate coefficient, reaction order, fractional
conversion, extent of reaction, elementary reaction, overall reaction, stoichiometric
reaction, reactive intermediate, molecularity, unimolecular reaction, bimolecular reaction,
termolecular reaction, recombination reaction, law of mass action, reversibility of
reactions, equilibrium, equilibrium constant, law of microscopic reversibility, Arrhenius
2 2 2 2 2 2
2 2
2
1 2
2
1
0
SiH Cl H SiCl SiH Cl
HCl SiSiH Cl
HCl
HCl
dC dC dC C
k k
k C
dt dt dt k C
dC
dt

= = = +
=
CE 561 Lecture Notes Fall 2009
p. 13 of 13
equation, Arrhenius plot, reaction mechanism, partial equilibrium approximation, pseudo-
steady-state approximation, Bodenstein steady state approximation.

How to write reactions in vector-matrix notation and in sum-product notation.

How to write rate equations based on a set of reactions.

How to analytically integrate simple rate expressions (0
th
order, 1
st
order, 2
nd
order), both in
terms of concentrations and in terms of extents of reaction.

How to use the principle of microscopic reversibility to relate forward and reverse rate
constants to the equilibrium constant for an elementary reaction.

How to make an Arrhenius plot and extract rate parameters from it.

How and when to apply the partial equilibrium approximation.

How and when to apply the pseudo-steady-state approximation.