Unit 3

Analysis of Chemical Kinetic Data

Learning Objectives

Experimental methods for measuring chemical kinetics

Integral and differential analyses of the rate data
Methods of half lives
Analysis of reversible reactions

The Need for Rate Laws

All reactor design equations require the knowledge of rate
laws:
Batch:
CSTR:
PFTR:
where

Ni dN
dN i
i
= riV t =
Ni 0 r V
dt
i
Fi Fi 0
V=
ri

dFi
= ri
dV

dFi
Fi 0 r
i

V =

Fi

(i =1,2,n)
(i =1,2,n)
(i =1,2,n)

ri = i R = f (c , T )

Rate laws are often deduced from experimental

measurements taken from a laboratory scale reactor
(usually a batch or a CSTR). A constant density system is
often used to simplify the data analysis
While it is not commonly done, rate data may be used
directly for reactor design without regression analysis. This
approach is valid only when certain specific conditions are
met (See homework/tutorial assignments)

Steps to a Rate Law

1. Rate law is a property of the chemical reaction and as
such is independent of the measurement method. Hence
chemical kinetics measured from one reactor type may be
used for the design of other types of reactors (batch,
CSTR or PFTR).
2. Rates are measured in terms of the changes in some
properties of the reaction participants or the system (e.g.
concentration, absorbance, conductivity, or system
volume or pressure) as a result of chemical reactions Choose a method fast enough to follow the progress of
the reaction.
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3. Means to control reaction progress

Batch reactor:
by the time of reaction
Flow reactor*:
by residence time or space time
(through adjustments of the feed flow rate)
* Analysis of fast reactions in a batch system is limited by the resolution of
the time-counting device. A flow system can do better because of the
translation of reaction time into distance in the flow direction. Linear flows of
high velocities (several thousand cm sec-1) can be achieved with modern
equipment, and if steady flow conditions are maintained so that the
concentration-distance profile is stable, a series of measurements may be
made along the flow direction even for reactions occurring at moderately
fast rates (rate constants of the order of 1000 s-1) if a long flow tube is used.

4. Data analysis
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Common Methods of Analysis

Integral (indirect) analysis
Make a very explicit guess of the rate law and integrate
the rate law to generate the expected experimental
response (e.g. concentration variations with time). Reject
the rate law if the agreement is poor and repeat the
exercise with an improved guess
A very trying trial and error exercise.
Suitable for simple rate laws that can lead to closed form
(analytical) solutions.

Differential (direct) analysis

Measure the reaction rates directly from experiments.
Correlate the rates with concentrations according to the
form of the proposed rate law (some guess work is
needed). Test the goodness of fit and revise the guess if
the fit is not satisfactory.
Mathematically simpler (no integration) and some
reduction in guess work
Suitable for more complex rate laws
More data are required to provide accurate
measurements of rates (rate data is nosier, i.e. more
scattered)
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Integral Analysis
A rate law is proposed and integrated to predict the time
course of concentration (or some functions of concentration),
which is then compared with the experimental response.
Any reactor type can be used but for the convenience of
analysis, a constant density system is preferred.
Example: A first order reaction in a constant volume batch
reactor
dc A

= kc A
dt
kt
c
=
c
e

A
A0
ln c A = ln c A0 kt
or
Plot of ln cA vs t will yield a straight line with slope -k
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If the same first order reaction is studied in a CSTR

FA FA0 (c A c A0 )v 0 (c A c A0 ) V
V=
=
=
( )
rA
kc A
kc A

c A0
1 + k

Rearranging

cA =

or

1
1
k
=
+
c A c A0 cA0

Plot of 1/cA vs will give a straight line with slope k/cA0

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Integral analysis of first order reactions

Batch

CSTR
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Generally for a nth order reaction (n1) in a constant volume

batch reactor:
c1An c1A0n = (n 1)kt
Ex

c A = c A0 kt

(n = 0)

1
1

= kt
c A c A0

(n = 2)

Notes:
For n > 1, the reaction can never reach completion (cA = 0)
in a finite time
For n < 1, cA=0 occurs at a finite time and cA becomes
negative thereafter. Since concentration can never fall
below zero,
Reactions with order less than one cannot prevail
over a wide concentration range
Reaction order shifts up as concentration falls
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(shifting order reaction)

 Power law kinetics is a simplification of rate laws of a

more general form
Ex

k1c A
rA =
1 + k2 c A2

which is -1st order at high concentrations and 1st order at

low concentrations
For rate laws that depend on more than one concentration,
e.g.
rA = kcA cB
the integral analysis is more involved. The integrated form
of concentration function depends not only on time, but also
on reaction stoichiometry and feed composition
B = cB 0 / c A 0
(see p. 44-45 of Levenspiels text)
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Differential Analysis
ri
) are measured and correlated with
i
the concentrations of reaction participants.
The reaction rates ( R =

How to measure reaction rates?

From a batch reactor

ri =

1 dN i
V dt

for constant density systems this simplifies to

dci
ri =
dt

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 From a CSTR

Fi Fi Fi 0
ri =
=
V
V

for constant density systems

From a PFTR

r i=

ci ci 0

dFi
ri =
dV

for constant density systems

dci
ri =
d

Example for AR
dx A
rA = c A0
(any )
d
dc A
rA =
(constant where c A = c A0 (1- x A ) applies)
d
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Differential Analysis of Power Law Kinetics

Rate depending on one concentration only
A Products
rA = kcA or ln( rA ) = ln k + ln c A

and k can be obtained graphically or by linear

regression.

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Rate depending on more than one concentration

A + B Products
rA = kcA cB
l n( rA ) = ln k + ln c A + ln cB

This is best solved by multiple linear regression. A

procedure known as the method of excess (flooding) was
used in the older days

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Differential Analysis of Non-Power Laws

For rate laws such as the Michaelis-Menton (MM) kinetics
Vm [ S ]
R=
K M + [S ]
The model parameters Vm and KM may be obtained from
non-linear regression analysis or through some smart
graphical plots:
1
1 KM 1
=
+
R Vm Vm [ S ]
A plot of 1/R vs 1/[S] (the Lineweaver-Burk plot) is a straight
line with slope KM/Vm and intercept 1/Vm if the enzyme
reaction follows the MM kinetics. Can you suggest another
appropriate linear plot?
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Methods of Half Life and Fractional Life

The half life of a reaction, t1/2, is the time required to halve
the reactant concentration from its initial value.
Consider
A Products
n

r
=
kc
where
A
A
dc A
= kc An
In a constant volume batch reactor rA =
dt
Integration from cA=cA0 at t=0
c A0 n1
1
t = n1
[( ) 1]; n 1
kc A0 (n 1) c A
t=t1/2 when cA=cA0

2n1 1
t1/ 2 =

k (n 1)c An01
which is a function of cA0

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For any n, plot of ln t1/2 vs ln cA0 will produce a straight line with
slope (1-n)
For first order reactions, the above expression may be
differentiated with respect to n using the LHopitals rule
ln 2
t1/ 2 =
k
t1/2 in this case is independent of cA0
Half-life measurements need not be conducted using different
initial concentrations if the reaction is irreversible. Any point
on a concentration-time curve can be used as the starting
concentration
Other fractional life expressions can be derived likewise
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Are the half life for cA = 0.5 the same in both cases?
1.2

A R

1.0

CA

0.8

cA0 = 1M

0.6

Composition of reaction mixture at cA

= 0.5M:

0.4

0.2

0.0
0

Time

1.2

1.0

Composition of reaction mixture at

cA = 0.5M:

cA

0.8

0.6

cA0 = 0.5M

0.4

0.2

0.0
0

Time

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Analysis of Reversible Reactions

Integral analysis
Consider the special example of a first order reversible reaction
with stoichiometry A R
rA = k1c A k2 cR
Assuming
At equilibrium

cR e
c Ae

k1c Ae = k2 cR e
k1
= = K (equilibrium constant)
k2

(the relation K=k1/k2 is fortuitous)

dc A
rA =
= k1 (c A c Ae ) + k2 (cR e cR )

dt
From reaction stoichiometry cA + cR = constant

c A + cR = c Ae + cR e or c A c Ae = cR e cR
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Substitution gives
dc A
rA =
= k1 (c A c Ae ) + k2 (c A c Ae )
dt
1
= k1 (1 + )(c A c Ae )
K
c A c Ae
1
= k1 (1 + )t
Integration yields ln
c A0 c Ae
K
The equation collapses to (irreversible) first order kinetics if
we let K and cAe 0
For reversible reactions of higher orders, the integral
analysis is similar but the mathematics becomes more
involved. Some results are shown on p.58 of Levenspiel
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Analysis of More Complex Reversible Reactions

A R+S

r
=
k
c

k
c
with a proposed rate law of A
1 A
2 R cS (here , , and
are subject to thermodynamic consistency compliance)

Differential analysis by the method of initial rate:

Measurements are taken under conditions where either the
forward rate law or the reverse rate law predominates
For the analysis of only the forward reaction, a series of
experiments is carried out using A as the only reactant and
different initial concentrations cA0 to obtain different initial
rates of reaction, -rA0:
dc A
rA0 = (
) t =0
dt

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At the beginning of the reaction where R, S are not present,

rA0 k1cA0
k1 and can be determined by differential analysis using
different cA0.
Similarly, if the reaction is run with only R and S, the initial
rate will be predominated by the reverse rate law only:
rA' 0 k2 cR 0 cS 0
The orders and and the rate constant k2 can be
determined from differential analysis using either multiple
linear regression or the method of excess

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Appendix: Method of Excess (Flooding)

Consider
A + B Products

r
=
kc
where
A
A cB
ln( rA ) = ln k + ln c A + ln cB
or
Run the reaction once in excess of B such that cB is practically
unchanged.
rA (kcB 0 )cA = k 'cA
The reaction behaves like a pseudo- order reaction

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Run the reaction now in excess of A such that cA is practically

unchanged and the reaction order is pseudo-.
rA (k1cA0 )cB = k "cB

Find k from either k or k

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Appendix: Finding Chemical Kinetics Information

NIST (US National Institute of Standards and Technology) Chemical
Kinetics Database (http://kinetics.nist.gov/kinetics/ )
Kirk-Othmer Encyclopaedia of Chemical Technology
Encyclopaedia of Chemical Processing and Design (see vol. 46, p. 247
for Table of 100 chemical reactors)
Tables of Chemical Kinetics: Homogeneous Reactions (1951)
Tables of Chemical Kinetics: Homogeneous Reactions, Supp. 1 (1956)
Tables of Chemical Kinetics: Homogeneous Reactions, Supp. 2 (1960)
Liquid-phase Reaction Rate Constants
Kinetic Data for Atmospheric Chemistry (http://iupac.pole-ether.fr/)
Beilstein (organic compounds) and Gmelin (inorganic compound)
Database via Reaxys (http://www.elsevier.com/online-tools/reaxys)
Patent Databases
Source: http://library.queensu.ca/research/guide/chemical-engineering/reaction-data

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