CHEMICAL ENGINEERING

KINETICS
LECTURE 2
September 21, 2019
OVERVIEW
• Stoichiometric relationships of rates of different
substances in a reaction.

• Determination of reaction orders, rate laws, and rate

constant by method of initial rate.

• Determination of rate laws by graphical or integration

method.
• Reactors ( Batch, Continuous and Plug Flow)
 KINETICS
how fast does a reaction proceed?
RATE OF REACTION
Can be determined by monitoring the change
in concentration of either reactants or products as a
function of time.
REACTANT A  PRODUCT B
Rate with respect to A
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 ∆𝐴
Rate = =-
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑖𝑚𝑒 ∆𝑡

Rate with respect to B

𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐵 ∆𝐵
Rate = =
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑖𝑚𝑒 ∆𝑡
FACTORS AFFECTING REACTION RATE

1. Temperature – reactants will have more kinetic energy

2. Concentration of Reactants – more molecules will collide

3. Catalyst – speeds up reaction

4. Surface Area of reactants – area of contact between reactants

increases
RATE LAW
The relationship between the rate of reaction to
the rate constant and the concentration of the
reactants.

Rate = k[𝑨] [𝑩] 𝒎 𝒏

- [A] and [B] represent the reactants

- The exponents m and n are called “reaction orders”
- The proportionality constant k is the “rate constant”
- Overall reaction is m+n
1. What is the reaction order of 2A+ B  P

a. First Order
b. Second Order
c. Third Order
d. Cannot be Determined

Answer: d. Cannot be Determined

ELEMENTARY REACTION
- Only one step reaction

- No intermediate

- Only one transition state

2. Given the rate data for the reaction between 𝑭𝟐 and
𝑪𝒍𝑶𝟐
[𝑭𝟐 ] (M) [𝑪𝒍𝑶𝟐 ] (M) Initial Rate (M/s)
1. 0.10 0.01 1.2x10−3
2. 0.10 0.04 4.8x10−3
3. 0.20 0.01 2.4x10−3

Find the reaction order of the following:

a. F2 = 1
b. [𝑪𝒍𝑶𝟐 ] = 1
c. Overall order = 2
TYPES OF RATE LAW
• Differential Rate Law
shows how the rate of a reaction depends on
concentrations.

• Integrated Rate Law

shows how the concentrations of species in
the reaction depend on time.
TYPES OF RATE LAW
• Zero Order
Rate does not depend on the concentration of the
reactant.

• First Order
Rate is proportional to the concentration of the reactant.

• Second Order
Rate is proportional to the concentration of the reactant.
Zero Order
Integrated Rate Law
[𝑨]𝒇 − 𝐴 𝑜 = −𝑘𝑡

Half- life
𝐴𝑜
2𝑘
Graph Form
[𝑨]𝒇 = −𝑘𝑡 + 𝐴 𝑜
y mx b
First Order
Integrated Rate Law
ln[𝑨]𝒇 − ln[𝑨]𝒐 = −𝑘𝑡

Half- life
𝑙𝑛2
𝑘
Graph Form
ln[𝑨]𝒇 = −kt + ln[𝑨]𝒐
y mx b
Second Order
Integrated Rate Law
1 1
− = kt
[𝑨]𝒇 𝐴𝑜
Half- life
1
𝑘𝐴𝑜
Graph Form
1 1
= kt +
[𝑨]𝒇 𝐴𝑜
y mx b
 SUMMARY
Reaction Differential Rate varies with Integrated Rate Half-Life Graph form
Order Rate Law Concentration Law 𝒕𝟏/𝟐 y = mx + b

Rate doubles 𝑙𝑛2

1 -r = k𝐴1 ln[𝑨]𝒇 − ln[𝑨]𝒐 = −𝑘𝑡 ln[𝑨]𝒇 = −kt + ln[𝑨]𝒐
when [A] doubles 𝑘

Rate quadruples 1 1 1 1 1
2 -r = k𝐴2 − = kt = kt +
as [A] doubles [𝑨]𝒇 𝐴𝑜 𝑘𝐴𝑜 [𝑨]𝒇 𝐴𝑜

Rate does not 𝐴𝑜

0 -r = k𝐴0 [𝑨]𝒇 − 𝐴 𝑜 = −𝑘𝑡 [𝑨]𝒇 = −𝑘𝑡 + 𝐴 𝑜
change with A 2𝑘
3. The decomposition of 𝑵𝑶𝟐 at 300˚C is described by
the equation
𝑵𝑶𝟐(𝒈)  𝑵𝑶(𝒈) + ½ 𝑶𝟐(𝒈)
And yields this data:
Time (s) [𝑵𝑶𝟐 ] (M)
0 0.01000
50 0.00787
100 0.00649
200 0.00481
300 0.00380

Determine the order of the reaction:

a. First Order c. Third Order
b. Second Order d. Zeroth Order

ANSWER: b. Second Order

ACTIVATION ENERGY
The minimum energy required to initiate a
chemical reaction.

ARRHENIUS EQUATION
A mathematical relationship between rate
constant (k) and Activation Energy (Ea).
Ea
−
k= Ae 𝑅𝑇

where A is the frequency factor, a number that

represents the likelihood that collisions would occur
with the proper orientation for reaction.
4. With increases in temperature, the rate
constant obeying Arrhenius equation

a. increases
b. decreases
c. decreases exponentially with temperature
d. can either increase or decrease, depends
on the frequency factor

ANSWER: a. increase
Temperature Dependence of the Rate Constant

y = mx + b

When k is determined experimentally at several

temperatures, Ea can be calculated from the slope of a
plot of ln k vs. 1/T.
5. Milk is pasteurized if it is heated to 63˚C for
30min, but if it is heated to 74 ˚C it only needs 15s
for the same result. Find the activation energy of
this sterilization process.

a. 500 kJ/mol
b. 422 kJ/mol
c. 455 kJ/mol
d. 658 kJ/mol

Answer: b. 422 kJ/mol

SYMBOLS AND RELATIONSHIPS BETWEEN
CA and XA
SPECIAL CASE 1. Constant Density Batch and Flow Systems.
𝐶𝐴
𝑋𝐴 = 1 −
𝐶𝐴0
εa = 0
SPECIAL CASE 2. Batch and Flow Systems of Gases Changing
Density with T and π Constant.
𝐶𝐴0 − 𝐶𝐴
𝑋𝐴 =
𝐶𝐴0 + ε𝐴 (𝐶𝐴 )
εa ≠0
SYMBOLS AND RELATIONSHIPS BETWEEN
CA and XA
SPECIAL CASE 3. Batch and Flow Systems for Gases in General (Varying
Density, Temperature and Pressure.
SYMBOLS AND RELATIONSHIPS BETWEEN
DIFFERENT REACTANTS

𝑎ε𝐴 𝑏ε𝐵
=
𝐶𝐴0 𝐶𝐵0

𝐶𝐴0 𝑋𝐴 𝐶𝐵0 𝑋𝐵
=
𝑎 𝑏
PROBLEM 6

Answer: CB=40, XA=0.50, XB=0.75

General Mole Balances
System
Volume, V

F0 G Ff

 Molar Flow  Molar Flow  Molar Rate  Molar Rate 

 Rate IN    Rate OUT   Generation    Accumulation 
       
dN
F0  Ff  G 
dt
 mole   mole   mole   mole 
          
 time   time   time   time 
GENERAL MOLE BALANCES
System
Volume, V

F0 G Ff

General Mole Balance on System Volume V

In  Out  Generation  Accumulation

dN A
FA 0  FA   rA dV 
dt
SYMBOLS AND RELATIONSHIPS BETWEEN
CA and XA
𝐶𝐴 = 𝐶𝐴𝑜 (1 − 𝑋𝐴 )
For εa = 0
𝐶𝐴𝑜 − 𝐶𝐴 = 𝐶𝐴𝑜 𝑋𝐴

𝐶𝐴𝑜 (1 − 𝑋𝐴 )
𝐶𝐴𝑜 =
(1 + ε𝐴 𝑋𝐴 ) For εa ≠ 0
BATCH REACTOR

𝐶𝐴0 𝑑𝑋𝐴
−𝑟𝐴 =
𝑑𝑡
WORKING PRINCIPLE

• A batch reactor has neither inflow nor

outflow of reactants or products while the
reaction is being carried out.

• This is an unsteady state operation where

composition changes with time; however, at
any instant the composition through out the
reactor is uniform
ADVANTAGES
• Simple in construction and require little/ no
auxiliary equipment
• High conversion
• Data can be collected easily if isothermal
reactions are carried out under constant volume
condition

DISADVANTAGES
• Preferred homogeneous reactions only
• High labor cost per batch
• Difficult in large scale production
• Poor product quality (since no instrumentation)
• Long idle time (leading to downtime)
APPLICATION
• Typically for liquid phase reactions that
require long reaction times

• Used only when small amount of product is

required.

• Favored when a process is in developmental

stage or if to produce expensive product

• Used to make variety of products at different

times
PROBLEM 7
A first order and elementary liquid phase reaction
A  2B is to be carried out in an isothermal and well
mixed batch reactor. At first, the initial concentration of A
is 10 mol/L. If the rate of destruction of A is given by
–rA= kCa, with k=1/hr. Calculate the concentration of A
(mol/L) after 90 mins.
a. 3.123 mol/L
b. 3.221 mol/L
c. 2.231 mol/L
d. 2.133 mol/L
Answer: c. 2.231 mol/L
PROBLEM 8
The reaction A + 2B  Product in a constant volume
batch reactor is first order with respect to each reactant.
If equimolar amounts of A and B are introduced into the
reactor and 20% of A is converted after one hour, how
much of A will remain after 2 hours?

a. 30.44%
b. 69.60%
c. 70.51%
d. 29.47%
Answer: b. 69.60%
SPACE TIME AND SPACE VELOCITY
CSTR REACTOR
Run at steady state with continuous flow of reactants and
products; the feed assumes a uniform composition through out the
reactor, the exit stream has the same composition as in the tank

ADVANTAGES
• Good temperature control
• Easily adapts to two phase runs
• Simplicity of construction
• Low operating cost
• Easy to clean

DISADVANTAGES
• Lowest conversion per unit volume
• By-passing and channeling possible with poor agitation
 CSTR REACTOR

dN A
FA 0  FA   rA dV 
dt

Steady State dN A  0
For ε≠0
dt

PROBLEM 9
An aqueous feed of A and B (400 L/min,
100 mmol A/ L, 200 mmol B/ L is converted to
product in a backmix reactor. The kinetics of the
reaction is represented by: A + B  2R, -rA= 200CACB
mmol/ Lmin. Find the reactor size needed for 99.99%
conversion:
a. 100 L
b. 200 L
c. 300 L
d. 400 L

Answer: b. 200L
PLUG FLOW REACTOR
Arranged as one long reactor or many short reactors in a
tube bank; no radial variation in reaction rate (concentration);
concentration changes with length down the reactor.

ADVANTAGES
• High conversion per unit time
• Low Operating cost
• Continuous Operation
• Good Heat Transfer

DISADVANTAGES
• Undesired thermal gradients may exist
• Poor Temperature control
• Shutdown and cleaning may be expensive
APPLICATION

• Large Scale
• Fast Reactions
• Homogeneous Reactions
• Heterogeneous Reactions
• Continuous Production
• High Temperature
PLUG FLOW REACTOR
V

FA FA


V V  V
 

 In  Out  Generation
at V   at V  V   in V 0 dFA
       rA
FA V  FA V  V  rA V 0 dV
PLUG FLOW REACTOR
PROBLEM 10

Answer: 148L
ACTIVITY PROBLEM
Gaseous reactant A decomposes as follows:
A  3R, -rA = 0.6/min * CA. Find the volumetric flow
rate into and out of a 50L mixed flow reactor which
would lower the concentration of A in a pure feed
from CAo = 600mmol/L to CA = 60mmol.

a. In: 3, Out: 7
b. In: 4, Out: 10
c. In: 5, Out: 12
d. In: 6, Out: 14

Answer: b. In: 4, Out: 10

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