Chemical Engineering Department

CEB2043
REACTION ENGINEERING I

Chapter 2: Kinetics of Homogeneous Reactions (part 2)

RECAP…
After completing previous lecture, students are now should be able to:
1. Define reaction rate
2. Explain how reaction occurs
3. Explain factors affecting reaction rate
Learning Outcomes

By the end of this lecture, students should be able to

1. Define conversion
2. Define rate law, relative rate of reaction , and reaction order
3. Determine activation energy
What is conversion?

• Consider the general equation (irreversible eqn)

aA + bB → cC + dD
• We will choose A as our basis of calculation

b c d
A+ B → C + D
a a a How do we define
conversion?
Conversion
moles of A reacted
XA =
moles of A feed

MAXIMUM CONVERSION?

Irreversible Reaction Reversible Reaction

X=1 X = Xe
 Relating conversion, X, with moles
of reactant, NA (Batch reactor)

Mole of A at any time t = Mole of A fed - Mole of A reacted

NA0
NA = N A0 - N A0 X

NA0X NA

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Relating conversion, X, with molar flow
rate of reactant, FA (Flow reactor)

FA = FA0 - FA0 X FA0

FA0X FA

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Consider the reaction:
where,
aA + bB → cC + dD A, B, C, D = species involved in reaction
a, b, c, d = stoichiometric coefficient of the species

𝛼 𝛽
1. Rate law is given by: −𝑟𝐴 = 𝑘𝐴 𝐶𝐴 𝐶𝐵

2. Relative rate of reaction is given by: −𝑟𝐴 −𝑟𝐵 𝑟𝐶 𝑟𝐷

= = =
𝑎 𝑏 𝑐 𝑑

b
∴ the rate of reaction of species B
in terms of species A is:
−rB = ( −rA )
a
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 Elementary vs. Non-elementary rate law
• Non-elementary rate law
• Elementary Rate Law ✓ Overall order of reaction is not an integer
✓ stoichiometric coefficient = individual Eg: CO + Cl2 → COCl2
reaction order of each reactant rCO = kCCO CCl
3/ 2
2

• Example: ✓ Free radicals

1
Eg: H2 + Br2 → 2HBr k1C H 2 C Br2
A+B→C+D rHBr =
C HBr
2

k2 +
C Br2
Rate law: -rA = kCACB
✓ Solid catalysed reaction
Eg: C → B + P k (PC − PB PP / K P )
− r'C =
1 + K C PC + K B PB
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Example 1: Relative rate of reaction
For an elementary reaction, 3A + B ➔ 2C the rate law, −rA, is given as

where,
−rA = kACA3CB kA = rate constant with respect to A, dm9.mol−3.s−1
CA = concentration with respect to species A, mol.dm−3
CB = concentration with respect to species B, mol.dm−3

If the value of kA is 30 dm3.mol−1.s−1, determine the rate constant value with respect to species B,
kB and species C, kC, respectively.

[4 marks]
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Given,
3A + B ➔ 2C What is kB ? What is kC ?

−rA = kACA3CB − rA − rB rC rD −𝑟𝐴 −𝑟𝐵 𝑟𝐶

= = = 3
=
1
=
2
a b c d
kA = 30 dm3.mol−1.s−1
−𝑟𝐴 kACA3CB 30
So, −𝑟𝐵 = kBCA3CB = = = 10 dm3.mol−1.s−1
3 3 3
−rB = kBCA3CB

rC = kCCA3CB kC = 20 dm3.mol−1.s−1
CHECKPOINT
Consider the elementary reaction: B + 2D → 3T
Which of the following rate law expression is correct?

a. − rB = kBCBCD2 c. rT = kT CBCD2

b. − rD = kDCBCD2 d . rT = 3kBCBC 2
D

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Rate constant, k
➢ Strongly dependent on temperature.
➢ Independent of concentration of species involved.
➢ Units of k depends on reaction order.
Reaction Rate Law CA -rA k
Order
0th -rA = k (mol/dm3) (mol/dm3*s) (mol/dm3*s)

1st -rA = kCA (mol/dm3) (mol/dm3*s) s-1

2nd -rA = kCA2 (mol/dm3) (mol/dm3*s) (dm3/mol*s)

Rate Constant, k, & Activation Energy, E
➢ Rate Constant, k, depends strongly on temperature (Arrhenius’ Law)

k = specific rate constant

−𝐸ൗ
𝑘= 𝐴𝑒 𝑅𝑇 T = absolute temperature, K
A = pre-exponential factor or frequency factor or Arrhenius constant
−r = k[reactants] E = activation energy, J/mol
R = gas constant, 8.314 J/mol.K
Activation Energy, E
• Minimum energy requirement for a reaction to occur

• Larger E means a reaction is more sensitive to temperature change

• Determine experimentally
Activation Energy, E
• Determine from experimental data of the same reaction carried out at different
temperature
−𝐸ൗ
𝑘= 𝐴𝑒 𝑅𝑇

𝐸 1
ln 𝑘 = ln 𝐴 − Steeper slope indicates
𝑅 𝑇 higher E, i.e. reaction is
more temperature
sensitive
Example 2: Activation Energy, E

Determine the activation energy for the decomposition of benzene

diazonium chloride given the following data:

k (s-1) 0.00043 0.00103 0.0018 0.00355 0.00717

T (K) 313 319 323 328 333

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Activation Energy, E : Example - Solution
−𝐸ൗ
𝑘= 𝐴𝑒 𝑅𝑇
k (s-1) 0.00043 0.00103 0.0018 0.00355 0.00717

𝐸 1 T (K) 313 319 323 328 333

ln 𝑘 = ln 𝐴 −
𝑅 𝑇
ln k -7.75173 -6.8782 -6.32 -5.64081 -4.93785

1/T 0.00319 0.00313 0.0031 0.00305 0.003

What is the value of E?

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Reversible reaction
• The net rate of formation of any species is:
ratenet = rateforward + ratereverse

• At equilibrium, ratenet = 0 and the rate law must reduce to an equation that is
thermodynamically consistent with the equilibrium constant for the reaction.

• Concentration of species at equilibrium is related to the equilibrium constant

through: c d
CCe C De
KC = a b
C AeC Be
Summary of Part 2…

By now, students should be able to

1. Define conversion
2. Define rate law, relative rate of reaction , and reaction order
3. Determine activation energy