VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY

UNIVERSITY OF TECHNOLOGY
FACULTY OF CHEMICAL ENGINEERING

Chapter 2
Interpretation of Batch Reactor Data
from rate data => rate equation

FCE – HCMC University of Technology Chemical Reaction Engineering

 Rate data analysis
Có note trong tập
-rA = f (C) = k CA or kCA ^2 or CA/1+kCA
A rate equation characterizes the rate of reaction
Form of rate equation may either be suggested by
• theoretical considerations
• simply be the result of an empirical curve-fitting procedure.
• The value of the constants of the equation can only be found by experiment;
predictive methods are inadequate at present.
The determination of the rate equation is usually a two-step procedure:
1. the concentration dependency is found at fixed temperature
2. the temperature dependence of the rate constants is found, yielding the
complete rate equation.
temperature unchange => The rate depend on concentration
 Rate data analysis

Equipment by which empirical information is obtained can be: batch and

flow reactors.
In batch reactor, the extent of reaction at various times, and this can be
followed
• the concentration of a given component.
• the change in some physical property of the fluid, such as the electrical
conductivity or refractive index.
• the change in total pressure of a constant-volume system.
• the change in volume of a constant-pressure system.
The experimental batch reactor is usually operated isothermally and at
constant volume because it is easy to interpret the results of such runs.
The flow reactor is used primarily in the study of the kinetics of
heterogeneous reactions.
 Rate data analysis
Equipment by which empirical information is obtained can be: batch and flow reactors.
In batch reactor, the extent of reaction at various times, and this can be followed
• the concentration of a given component.
• the change in some physical property of the fluid, such as the electrical
conductivity or refractive index.
• the change in total pressure of a constant-volume system.
• the change in volume of a constant-pressure system.
The experimental batch reactor is usually operated isothermally and at constant
volume because it is easy to interpret the results of such runs.
The flow reactor is used primarily in the study of the kinetics of heterogeneous
reactions.
There are two procedures for analyzing kinetic data:
• the integral
• the differential methods
In the integral method of analysis, we guess a particular form of rate equation and,
after appropriate integration and mathematical manipulation, predict that the plot of a
certain concentration function versus time.
 Types of reaction

❖ Single and Multiple Reactions:

• Single reaction: When a single stoichiometric equation and single rate equation
are chosen to represent the progress of the reaction.
• Multiple reactions: When more than one stoichiometric equation is chosen to
represent the observed changes, then more than one kinetic expression is
needed to follow the changing composition of all the reaction components

– Series reactions:

– Parallel reactions:
 Types of reaction

❖ Elementary and Nonelementary Reactions:

Elementary reactions: the rate equation corresponds to a stoichiometric equation

are called.

Phản ứng cơ bản: phương trình tốc độ tương ứng với phương trình cân bằng hóa họcđược gọi là.

Nonelementary reactions: there is no direct correspondence between

stoichiometry and rate.

Phản ứng không cơ bản: không có sự tương ứng trực tiếp giữa cân bằng hóa học và tỷ lệ.
 Order of Reaction

❖ Order of the reaction:

• powers to which the concentrations are raised the order of the reaction.

• have a fractional value and need not be an integer.

• Whatever measure we use leaves the order unchanged;

• For rate expressions not of the above form, it makes no sense to use the term
reaction order.
 Conversion

• The fraction of any reactant, say A, converted to something else

Batch operation

A +B
Continuous operation A là limited component khi A complete
but B not complete, B: remaining

Constant volume
 Integral Method of Analysis of Data

General procedure:
• Puts a particular rate equation to the test by integrating and comparing the
predicted C versus t curve with the experimental C versus t data.
• If the fit is unsatisfactory, another rate equation is guessed and tested.
• The integral method is especially useful for fitting simple reaction types
corresponding to elementary reactions.
• Linear regression is often used

A linear regression line has an

equation of the form Y = a + bX, where
X is the explanatory variable and Y is
the dependent variable.
The slope of the line is b, and a is the
intercept (the value of y when x = 0).
 Chapter 2. Interpretation of Batch Reactor Data

The measured data can be inllustrated in a ln(CA/CA0) vs. T diagram. The slope
of the straight line leads to the reaction rate constant (Figure 2.3).

2.6 of 2.3

Figure 2.3. Determination of the reaction rate constant k using the

integrated method in a linearised formulation
 Chapter 2. Interpretation of Batch Reactor Data

1. Rates of reaction
1.1. Description of reaction rates
Reaction rates depend usually in a complex manner on the concentrations, the
temperature and often on the effect introduced by catalysts:
r = f ( ci ,T, catalyst)

The order of a reaction is related to the concentration dependence. Typical

examples are:
Irreversible Reactions:

• First order:
A → Products: r = k(T)CA k in [s-1]

• Second order:
A + B → Products: r = k(T)CACB k in [m3 mol-1s-1]
2A → Products: r = k(T)CA2 k in [m3 mol-1s-1]
 Chapter 2. Interpretation of Batch Reactor Data

Reversible Reactions:

• First order:
A  R: r = k1CA – k2CR k in [s-1]

• Second order:
A + B  R + S: r = k1CACB – k2CRCS k in [m3 mol-1s-1]
2A  2R: r = k1CA2 – k2CR2 k in [m3 mol-1s-1]
2A  R + S: r = k1CA2 – k2CRCS k in [m3 mol-1s-1]
A + B  2R: r = k1CACB – k2CR2 k in [m3 mol-1s-1]

The dependency of the reaction rate on the temperature can be described using
Arrhenius law:
• EA is the activation energy of the reaction.
 EA 
k (T ) = k0 exp −  • ko is the pre-exponential factor (not dependent on
 RT  the reaction temperature
 Chapter 2. Interpretation of Batch Reactor Data

1.2. Rate laws of simple reactions

In this section, rate equations of simple reactions and the corresponding
temporal change of concentration are analyzed. A closed system (isothermic,
batch reactor) and aconstant volume are assumed.
1.2.1. Irreversible first-order reactions (Decomposition reactions)
A → Products
1 dCi
The rate equation is: r= = kCi (2.1)
 i dt
dC A
With i is A and vi = -1, then: r = − = kC A (2.2)
dt
CA t
dC A CA
The integration form: − 
C Ao
CA
= k  dt or − ln
0
CCA0
= kt (2.3)

− ln A = kt
C A0
 Chapter 2. Interpretation of Batch Reactor Data

The eq. (2.3) leads to the temporal course of concentration cA.

C A = C A0 e − kt (2.4)

C A0 − C A
With XA = , the eq. (2.3) leads to: (2.5)
C A0

Y= − ln(1 − X A ) = kt or X A = 1 − e − kt (2.6)

1.2.2. Irreversible bimolecular-type second-order reactions

Consider the reaction (A + B → Products) with corresponding rate equation

should convert conversion of limiting
component
r= stoichiometric number: 1A+1B (2.7)
If 1A+2B => B comple bf A => convert all
CA = CAo (1-XA) M= CAo/CBo
parameter to XB, XB is main variable to
CB = CBo (1-XB)
calculation
 Chapter 2. Interpretation of Batch Reactor Data

Noting that the amounts of A and B that have reacted at any time t are equal and
given by CA0XA, eq. (2.7) can be written in terms of XA as

r= (2.8)

(2.9)

(2.10)
 Chapter 2. Interpretation of Batch Reactor Data

After breakdown into partial fractions, integration, and rearrangement, the final
result in a number of different forms is

(2.11)

For the reaction: 2A → Products, the defining second-order differential

equation becomes

r= (2.12)

which on integration yields

(2.13)
 Chapter 2. Interpretation of Batch Reactor Data

1.2.3. Empirical rate equations of nth order

When the mechanism of reaction is not known, we often attempt to fit the data
with an nth-order rate equation of the form
n can be 1.2 1.5 we can not find the ans by integral
(2.14)
method => apply Differential method, the 3 other
method is suitable
which on separation and integration yields
(2.15)
you can not go far with n order, bc n is unknown
assume CA = 0 => reaction is zero-order
1.2.4. Zero-order reactions If it is not fit with experiment data
so we can assume CA=1 => first order
If it is not fit with experiment data
so we can assume CA=2 => second order
Integrating and noting that CA
can never become negative, (2.16)
we obtain directly:
 Chapter 2. Interpretation of Batch Reactor Data

1.2.5. Irreversible Reactions in Parallel

Consider the simplest case, A decomposing by two competing paths

The rates of change of the three components are given by

(2.17)

(2.18)

(2.19)
 Chapter 2. Interpretation of Batch Reactor Data

The k values are found using all three differential rate equations. First of all,
eq. (2.17), which is of simple first order, is integrated to give

(2.20)

Then dividing eq. (2.18) by eq. (2.19) we obtain the following

(2.21)

which integrated gives simply

(2.22)
 Chapter 2. Interpretation of Batch Reactor Data

1.2.6. Irreversible Reactions in Series

Consider the reaction

Rate eqautions for the three components are

(2.23)

(2.24)

(2.25)
 Chapter 2. Interpretation of Batch Reactor Data

Assuming that at t = 0, concentration of A is CA0, and no R or S present, integration

of eq. (2.23) gives

(2.26)

To find the changing concentration of R, substitute the concentration of A from

eq. (2.26) into the differential equation governing the rate of change of R, eq.
(2.24); thus
(2.27)

Solving the above differential equation gives

(2.28)
 Chapter 2. Interpretation of Batch Reactor Data

Noting that

which eqs (2.26) and (2.28) gives

(2.29)

If k2 is much larger than k1, Eq. (2.29) reduces to

(2.30)

If k1 is much larger than k2, then

(2.31)

Thus, in general, for any number of reactions in series it is the slowest step that has
the greatest influence on the overall reaction rate.
 Chapter 2. Interpretation of Batch Reactor Data

By differentiating Eq. (2.28) and setting dCRldt = 0, the maximum concentration of

R and the time at which it occours can be found:

(2.32)

(2.33)
 Chapter 2. Interpretation of Batch Reactor Data

Figure 2.1 shows the general

characteristics of the
concentration-time curves Eq. (2.26)
for the three components:
• A decreases exponentially, Eq. (2.29)
• R rises to a maximum and
then falls,
• and S rises continuously, the
greatest rate of increase of S Eq. (2.33) Eq. (2.28)
occurring where R is a
maximum.

Eq. (2.30)

Figure 2.1. Typical concentration-time

curves for consecutive first-order reactions.
 Chapter 2. Interpretation of Batch Reactor Data

1.2.7. First-Order Reversible Reactions

The simplest case is the opposed unimolecular-type reaction

(2.34a)

Starting with a concentration ratio M = CR0/CA0 th e rate equation is

(2.34b)

At equilibrium dCA/dt = 0. Hence from Eq. (2.34) we find the fractional

conversion of A at equilibrium conditions to be

(2.35)
 Chapter 2. Interpretation of Batch Reactor Data

and the equilibrium constant to be

(2.36)

Combining the above three equations we obtain, in terms of the equilibrium

conversion gives

(2.37)

Taking integration of the above equation, the following relation can be found:

(2.38)
 Chapter 2. Interpretation of Batch Reactor Data

1.2.8. Second-Order Reversible Reactions

For the bimolecular-type second-order reactions
(2.39a)

(2.39b)

(2.39c)

(2.39d)

with the restrictions that CA0 = CB0, and CR0 = CS0 = 0, the integrated rate
equations for A and B are all identical, as follows

(2.40)
 Integral Method of Analysis of Data
linear requestion method
assume the rate equation
2. Determination of kinetic parameters -rA = kCA =-dCA/dt volume is
2.1. Integral method rate equation: unchange

For the integral method, the concentration-time-course of one commponent is

measured. data t
A typical measurement is depicted in CA CA
Figure 2.2.
After this measured data are compared CA0 * y= -ln CA/CAo
with theoretical integrated reaction rate => k: the slope of this
* curve
equation, for example: * check R2: If it approach
− kt
*
C A = C A0 e * 1 it is linear
curve * => the model is fit
the unknown parameters can be calculated *
* R2>0.95 => fitting
by non-linear regression or using the If
* smaller => check
* *
linearised form of the integrated rate other model
* * to
equation: y experiment data confirm t
CA Figure 2.2. Typical experimental
− ln = kt concentration-time-course
C A0 If all the data lie on linear line
y is linear with t t => the data is fit with rate equation
 Chapter 2. Interpretation of Batch Reactor Data

2.2. Differential method

For the differential method, also measurements of concentration-time courses are
necessary.
By means numerical and/or graphic differentiation of all measuring data of
concentration CA(t) the derivative dCA/dt can be determined. The measured data
can be approximated as a straight line in the reaction rate-concentration-diagram.
The procedure is as follows:
1. Plot the CA vs. t data, and then by eye carefully draw a smooth curve to
represent the data.
2. Determine the slope of this curve at suitably selected concentration values.
These slopes dCA/dt = r, are the rates of reaction at these compositions.
3. Search for a rate expression to represent this rA vs. CA data, either by
(a) picking and testing a particular rate form, rA = kf (CA), see Fig. 2.4, or
(b) testing an nth-order form rA = kCAn by taking logarithms of the rate equation
(see Fig. 2.5).
 Chapter 2. Interpretation of Batch Reactor Data

log(rA)
Figure 2.4. Test for the particular rate Figure 2.5. Test for an nth-order rate
form rA = kf(CA) by the differential method by the differential method.
form.
 Chapter 2. Interpretation of Batch Reactor Data

Problems
1. Aqueous A at a concentration CA0 = 1 mol/liter is introduced into a batch reactor
where it reacts away to form product R according to stoichiometry A → R. The
concentration of A in the reactor is monitored at various times, as shown below:

a)Find the rate equation for the reaction

b) For CA0 = 500 mol/m3 find the conversion of reactant after 5 hours in the batch
reactor.

2. For the elementary reactions in series

find the maximum concentration of R and when it is reached.

 Chapter 2. Interpretation of Batch Reactor Data

3. In the presence of a homogeneous catalyst of given concentration, aqueous

reactant A is converted to product at the following rates, and CA alone determines
this rate:

We plan to run this reaction in a batch reactor at the same catalyst concentration
as used in getting the above data. Find the time needed to lower the concentration
of A from CA0 = 10 mollliter to CAf = 2 mol/liter.
 Pressure dependence

aA+ bB +.. = rR + sS +..

At t=0 NAo NBo +.. = NRo + NSo +.. Ntr

At t NA= NAo -ax NB= Nbo -bx NR =NRo + rx

NS =NSo + sx, Ntr
Initial total moles: No= NAo+ NBo+ …+NRo+ NSo+ NAo+.. Ntr

At t : N = No + x (r+ s+ … – a –b – …) = No- xn

with n = r+ s+ … – a –b – …

33 2/24/2022 Chương 2. Xử lý dữ kiện động học

Pressure dependence

pA N A N A0 − a. x N A0 a N − N0
CA = = = = −
RT V V V n V

a
hay p A = C A RT = p A0 − (P − P0 ) (2.3)
n

r
cho R p R = C R RT = p R0 + (P − P0 ) (2.4)
n
In which Po: Initial total pressure
P: Total pressure at t
pAo: Initial partial pressure of A
pRo: Initial partial pressure of R
34 2/24/2022 Chương 2. Xử lý dữ kiện động học
 Varying-volume Batch Reactor

VOLUME IS CHANGED (GASEOUS PHASE)

𝑁𝐴0 −𝑁𝐴 𝑉0 𝐶𝐴0 −𝑉𝐶𝐴 𝐶𝐴0 −(1+𝜀𝐴 𝑋𝐴 )𝐶𝐴
𝑋𝐴 = = =
𝑁𝐴0 𝑉0 𝐶𝐴0 𝐶𝐴0

1 − 𝑋𝐴
𝐶𝐴 = 𝐶𝐴0
(1 + 𝜀𝐴 𝑋𝐴 )
 Varying-volume Batch Reactor

1 dN i 1 d(Ci V) 1 VdCi + Ci dV
ri = = =
V dt V dt V dt
dCi Ci dV ∆𝑉
 ri = + 𝑋𝐴 =
𝑉0 𝜀𝐴
dt V dt
V = V0 (1 +  A X A )
VX A = 1 − VX A = 0
A = → expansion factor
VX A = 0
36 2/24/2022 Chương 2. Xử lý dữ kiện động học
 Varying-volume Batch Reactor

a. 2A + B -> R
Feed mixture: 40%A, 40%B, 20% inert gas
Assume Vo = 1
2A + B -> R inert gas
t=0 0.4 0.4 0 0.2
reacted 0.4 0.2 0.2 0.2
Remain 0 0.2 0.2 0.2 (XA = 1)
0.2+0.2+0.2 −1
𝜀𝐴 = = -0.4
1
B .A + B -> 2R + S
Feed: 20%A, 60%B, 20% inert gas
0.4+0.4+0.2+0.2 −1
𝜀𝐴 = = 0.2
1

37 2/24/2022 Chương 2. Xử lý dữ kiện động học

Varying-volume Batch Reactor
N A N A0 (1 − X A ) 1 − XA
CA = = = C A0
V V0 (1 +  A X A ) 1 +  AXA

N A0d(1 − X A )
(− rA ) = − 1 dN A
=−
1
V dt V0 (1 +  A X A ) dt

C A0 dX A
=
1 +  A X A dt

38 2/24/2022 Chương 2. Xử lý dữ kiện động học

Varying-volume Batch Reactor
N A N A0 (1 − X A ) 1 − XA
CA = = = C A0
V V0 (1 +  A X A ) 1 +  AXA

N A0d(1 − X A )
(− rA ) = − 1 dN A
=−
1
V dt V0 (1 +  A X A ) dt

C A0 dX A
=
1 +  A X A dt

39 2/24/2022 Chương 2. Xử lý dữ kiện động học

 Varying-volume Batch Reactor

𝑑𝑁𝐴 𝐶𝐴0 𝑑𝑋𝐴

• Zero order: − = =𝑘
𝑉𝑑𝑡 1+𝜀𝐴 𝑋𝐴 𝑑𝑡
𝑋𝐴 𝑑𝑋𝐴 𝐶𝐴0 𝐶𝐴0 𝑉
𝐶𝐴0 ‫׬‬0 = ln(1 + 𝜀𝐴 𝑋𝐴 ) = 𝑙𝑛 = 𝑘t
1+𝜀𝐴 𝑋𝐴 𝜀𝐴 𝜀𝐴 𝑉0
𝑑𝑁𝐴
• First order: − = 𝑘CA
𝑉𝑑𝑡

𝐶𝐴0 𝑑𝑋𝐴 𝑘𝐶𝐴0 (1 − 𝑋𝐴 )

=
1 + 𝜀𝐴 𝑋𝐴 𝑑𝑡 1 + 𝜀𝐴 𝑋𝐴

Integrating gives : -ln(1-XA) = kt

40 2/24/2022 Chương 2. Xử lý dữ kiện động học

 Varying-volume Batch Reactor

• Second order: 2A -> sản phẩm

A + B -> sản phẩm, CA0 = CB0
2
𝐶𝐴0 𝑑𝑋𝐴 2
1 − 𝑋𝐴
= 𝑘𝐶𝐴0
1 + 𝜀𝐴 𝑋𝐴 𝑑𝑡 1 + 𝜀𝐴 𝑋𝐴
𝑋𝐴 (1+𝜀𝐴 𝑋𝐴 )𝑑𝑋𝐴 1+𝜀𝐴 𝑋𝐴
‫׬‬0 = + 𝜀𝐴 ln(1 − 𝑋𝐴 ) = 𝑘CA0t
(1−𝑋𝐴 )2 1−𝑋𝐴
𝑑𝑁𝐴 1−𝑋𝐴 𝑛
• nth- order: − = 𝑘𝐶𝐴𝑛 = 𝑛
𝑘𝐶𝐴0
𝑉𝑑𝑡 1+𝜀𝐴 𝑋𝐴

𝑋𝐴
(1 + 𝜀𝐴 𝑋𝐴 )𝑛−1 𝑛−1
න 𝑛
𝑑𝑋𝐴 = 𝑘𝐶𝐴0 t
0 (1 − 𝑋𝐴 )

For all rate forms other than zero-, first-, and second-order the integral
method of analysis is not useful.

41 2/24/2022 Chương 2. Xử lý dữ kiện động học

 Example

The first order homogeneous gaseous reaction A→2.5 R, is carried out

in an isothermal batch reactor at 2 atm pressure with 20 mole % inerts
present, and the volume increases by 60% in 20 minutes.
In case of constant volume reactor, determine the time required for the
pressure to reach 8 atm if the initial pressure is 5 atm, 2 atm of which
consists of inerts
====
0.8∗2.5+0.2 −1
𝜀𝐴 = =1.2 =>XA =0.5, t =20 phut.
1
- ln(1-XA) = kt => k= 0.0346 (1/ph)
Po = 5atm, Pkt0 = 2 atm => PA0 = 3 atm (60% A, 40% inert gas)
XA = (PA0-PA)/P0 = 0.67
P = 8atm = PA + PR + Pkt = PA + 2.5*(PA0-PA) + Pi
PA = 1 atm
-ln(1-0.67) = kt => t = 31.75 min

42 2/24/2022 Chương 2. Xử lý dữ kiện động học

 Example

The first order homogeneous gaseous reaction A→2.5 R, is

carried out in an isothermal batch reactor at 2 atm pressure
with 20 mole % inerts
present, and the volume increases by 60% in 20 minutes.
In case of constant volume reactor, determine the time
required for the pressure to reach 8 atm if the initial pressure
is 5 atm, 2 atm of which
consists of inerts
====

43 2/24/2022 Chương 2. Xử lý dữ kiện động học

 Example

A liquid phase second order reversible reaction A+B =R+S is

carried out with equimolar concentration of A and B in the
reaction mixture (CAo=CBo=0.052 mol/l). The equilibrium
constant of the reaction is K= 1.45.
From the following data, find the rate equation for this reaction
Time,h 0.187 0.45 0.6
Fraction of A converted 0.18 0.34 0.4
Analysis Methods

• Differential method
• Integral method
• Half-lives method
• Initial rate method
• Differential reactor
• More complex kinetics
 2.1.2. Differential Method of
Analysis of Data
Procedure:
1. Plot the CA vs. t data, and then by eye
carefully draw a smooth curve to
represent the data. This curve most likely will
not pass through all the
experimental points.
2. Determine the slope of this curve at
suitably selected concentration values.
These slopes dC/dt = rA are the rates of
reaction at these compositions.
 Differential Method
dC j
( )
d d
Fj0 − Fj + rj V = N j → rj V = C j V → rj V = V
dt dt dt
0 0
dC j −dC A
= rj Where –rA = kCAa = kC Aa
dt dt
Average slope
a) Plot CA/t as a function of t
b) Determine dCA/dt from plot by graphical or numerical methods
c) Plot ln(-dCA/dt) vs ln CA

 −dCA  − dCA dt
ln   = lnk + a lnCA Slope = a k=
 dt  C Aa
To find k, find the value of –dCA,p/dt that corresponds to a specific
concentration CA,p. Raise CA,p to the a power and divide into –dCA/dt)p
Hey, we just jumped from step a to step c. How do we get dCA/dt?
 Graphical Method
C A
−
1. Plot CA/t vs t t
2. Draw rectangles on the −
dC A 

dt  t
(−CA/t)t=0
graph. Then draw a curve so
(−CA/t)t=1
0
that the area above the curve
that is cut off of each dC A 
rectangle approximately fills − 
dt  t
(−CA/t)t
1
the unfilled area under the dC A 
− 
curve dt  t
2
3. dCA/dt is read using the value 0 t1 t2
where the curve crosses a
specified time
 Graphical Method Example

CA t t CA −CA/t -dCA/dt

8 0
4 1
2 2
1 3
 Graphical Method Example
CC
AA tt t t
CA −C
CAA/t −CA/t -dCA/dt
88 00 1 1 -4 -44 4 4.5
44 11 1 1 -2 -22 2 2.55
22 22 1 1 -1 -11 1 1.35
11 33 0.5

-
 Graphical Method Example
CA t t CA −CA/t -dCA/dt
8 0 1 -4 4 4.5
4 1 1 -2 2 2.55
2 2 1 -1 1 1.35
1 3 0.5

−dC A
= kC Aa
dt
 −dCA 
ln   = lnk + a lnCA
 dt 
Plot ln(-dCA/dt) vs ln CA
-

Slope = a
− dCA dt
k=
C Aa
 Graphical Method Example
CA t t CA −CA/t -dCA/dt ln(-dCA/dt) ln(CA)
8 0 1 -4 4 4.5 1.5 2.1
4 1 1 -2 2 2.55 0.9 1.4
2 2 1 -1 1 1.35 0.3 0.7
1 3 0.5 -0.7 0

Plot ln(-dCA/dt) vs ln CA
 −dCA 
ln   = lnk + a lnCA
 dt 
Slope = a = 1.0

− dCA dt
k=
C Aa
4 .5
→k = = 0 .6 -rA= (0.6/time)CA
81
 Graphical Method Example
CA t t CA −CA/t -dCA/dt  −dCA 
ln   = lnk + a lnCA
8 0 1 -4 4 4.5  dt 
4 1 1 -2 2 2.55 Slope = a
2 2 1 -1 1 1.35 − dCA dt
k=
1 3 0.5 C Aa

Differential Method
Only for irreversible reactions

Advantages: 1 experiment
-

Disadvantages: can only handle

simple kinetics
Analysis Methods

✓ Differential method
✓ Integral method
• Half-lives method
• Initial rate method
• Differential reactor
• More complex kinetics
 Method of Half-lives

• The half-life of a reaction, t1/2, is defined as the

time it takes for the concentration of the reactant
to fall to half of its initial value
• By determining the half-life of a reaction as a
function of the initial concentration, the reaction
order and specific reaction rate can be
determined
 Method of Half-lives

• The half-life of a reaction, t1/2, is defined as the

time it takes for the concentration of the reactant
to fall to half of its initial value
• By determining the half-life of a reaction as a
function of the initial concentration, the reaction
order and specific reaction rate can be
determined
 Method of Half-lives

dC 1  1 1 
A → products − A = kCAa t=  a −1 − 
dt k (a − 1)  CA CA0a −1


−rA = kCAa
1
ln (t1/2) CA = CA0 at t = t1 2
2

Slope = 1- a
2a −1 − 1  1 
t1 2 =  
k (a − 1)  CA0a −1 

ln CA0
2a −1 − 1
Plot ln(t1/2) vs ln CA0. Get a straight ( )
ln t1 2 = ln
k (a − 1)
+ (1 − a ) lnCA0
line with a slope of 1-α