Prof.

Swati Bhattacharya
Overview of Chemical Kinetics
Introduce:

Chemical Identity
Rate of Reaction
Mole Balance Equation
Recall: Chemical Identity
A chemical species is a chemical substance or ensemble composed of
chemically identical molecular entities.
The identity of a chemical species is determined by the kind, number
and configuration of the atoms of the species.

A chemical species is said to have reacted when it has lost its chemical
identity.
Ways by which a species may lose its identity:
• Decomposition: 𝐴𝐵 → 𝐴 + 𝐵
Examples: (i) 𝐶𝑎𝐶𝑂3 → 𝐶𝑎𝑂 + 𝐶𝑂2
(ii) 2𝐻2 𝑂 → 2𝐻2 + 𝑂2

• Combination or synthesis: 𝐴 + 𝐵 → 𝐴𝐵
Examples: (i) 𝑆 + 𝑂2 → 𝑆𝑂2 (ii) 𝑁2 + 𝑂2 → 2𝑁𝑂

• Isomerization : Example: (i) 𝐶2 𝐻5 𝐶𝐻 = 𝐶𝐻2 → 𝐶𝐻2 = 𝐶 𝐶𝐻3 2

Reaction Rate
How fast is one species being consumed (number of moles per unit
time) to form another ?

Rate Law for Species A:

• rA: the rate of formation of species A per unit volume [e.g.,

mol/m3•s]
• -rA: the rate of a consumption of species A per unit volume
Reaction Rate: The Convention
Isomerization: 𝐴 → 𝐵
𝑟𝐴 : rate of formation of species 𝐴 per unit volume
−𝑟𝐴 : rate of disappearance of species 𝐴 per unit volume
𝑟𝐵 : rate of formation of species 𝐵 per unit volume
Suppose: 𝐵 is being formed at the rate of 1 mol/dm3/s
Then,
𝑟𝐵 = 1 mol/dm3/s
𝐴 is disappearing at the same rate, i.e., −𝑟𝐴 = 1 mol/dm3/s

Rate of formation of 𝐴 is :𝑟𝐴 = −1 mol/dm3/s

Catalytic reaction
For reactions at an interface, e.g. reactions at solid catalyst surface, the
unit of the reaction rate is different (𝑚𝑜𝑙/𝑚2 𝑠). We use a different
notation for the rate of reactions at interfaces; −𝑟𝐴′′ .
How do we determine the surface area of the catalyst ?
The surface area from experimental techniques (BET) is reported as 𝑎𝑐 where
𝑚2
[𝑎𝑐 ] =
𝑘𝑔

For a catalytic reaction, a convenient method is to define −𝑟′𝐴 , the

rate of disappearance of species 𝐴 per mass of catalyst (𝑚𝑜𝑙/kg (of
catalyst)/s)
What do we know about 𝑟𝑗 ?

▪ 𝑟𝑗 can be a function of the concentration, temperature, pressure,

catalyst etc.
▪ 𝑟𝑗 is independent of type of reactor (batch, CSTR etc).
Rate Law
The rate law is an algebraic equation. Consider
𝐴→𝐵
If 𝐶𝐴 (𝑡) is the instantaneous concentration of species 𝐴
The rate law can be of the form
−𝑟𝐴 = 𝑘𝐶𝐴 , i.e. 𝑟𝐴 = −𝑘𝐶𝐴 First Order Reaction
Or −𝑟𝐴 = 𝑘𝐶𝐴2 , i.e. 𝑟𝐴 = −𝑘𝐶𝐴2 Second Order Reaction

𝑘𝐶𝐴 Q. Where does the temperature or pressure

Or maybe, −𝑟𝐴 = dependence come in ?
1+𝑘1 𝐶𝐴
Other forms of Rate Law
A + B → products
−r A = kC A CB 1st order in A, 1st order in B, 2nd order overall

In general, −r A = kC A n nth order in A

k1C A
− rA = Michaelis-Menton: common in enzymatic reactions
1 + k 2C A

 −Ea 
 RT 
-rA = A e C
A Arrhenius dependence on temperature
A: pre-exponential factor E A : activation energy
R : ideal gas constant T:temperature
Rate constants and Equilibrium constants
Consider a single step reaction
𝐶𝑙𝑁𝑂2 𝑔 + 𝑁𝑂 𝑔 ⇌ 𝑁𝑂2 𝑔 + 𝐶𝑙𝑁𝑂 𝑔

Rate of forward reaction is 𝑅𝑎𝑡𝑒𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑘𝑓 𝐶𝐶𝑙𝑁𝑂2 𝐶𝑁𝑂

Rate of reverse reaction is 𝑅𝑎𝑡𝑒𝑟𝑒𝑣𝑒𝑟𝑠𝑒 = 𝑘𝑟 𝐶𝑁𝑂2 𝐶𝐶𝑙𝑁𝑂

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In equilibrium the rate of the forward reaction equals the rate of the
reverse reaction
𝑘𝑓 𝐶𝐶𝑙𝑁𝑂2 𝐶𝑁𝑂 = 𝑘𝑟 𝐶𝑁𝑂2 𝐶𝐶𝑙𝑁𝑂

Rearranging, we define
𝑘𝑓 𝐶𝑁𝑂2 𝐶𝐶𝑙𝑁𝑂
𝐾𝑐 = =
𝑘𝑟 𝐶𝐶𝑙𝑁𝑂2 𝐶𝑁𝑂

This is called the equilibrium constant of the reversible reaction

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Mechanisms of reactions
Some reactions can have multiple-steps.
2𝑁𝑂 𝑔 + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)

Step 1.
2𝑁𝑂 ⇌ N2 O2 Fast step
Step 2.
𝑁2 𝑂2 + 𝑂2 ⇌ 2𝑁𝑂2 Slow step 2𝑁𝑂 ⇌ N2 O2
𝑁2 𝑂2 + 𝑂2 ⇌ 2𝑁𝑂2
----------------------------
Combine the two gives: 2𝑁𝑂 + 𝑂2 ⇌ 2𝑁𝑂2

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The second step is called the rate limiting step. The reaction cannot proceed
faster than the rate limiting step.

Rate of the second step is 𝑅𝑎𝑡𝑒2𝑛𝑑 = 𝑘𝐶𝑁2 𝑂2 𝐶𝑂2

Rate of the “total” reaction is also almost the same

𝑅𝑎𝑡𝑒 ≈ 𝑘𝐶𝑁2 𝑂2 𝐶𝑂2

But how do we measure the concentrations of intermediates ?

Here 𝑁2 𝑂2 is an intermediate

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• Look at the first step which is reversible:
2𝑁𝑂 ⇌ N2 O2
Rate of the forward reaction is 𝑅𝑎𝑡𝑒𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑘𝑓1 𝐶𝑁𝑂 2

Rate of the reverse reaction is 𝑅𝑎𝑡𝑒𝑟𝑒𝑣𝑒𝑟𝑠𝑒 = 𝑘𝑟1 𝐶𝑁2 𝑂2

Since it is a fast reaction, it will quickly equilibrate, so that the rates of the
forward and reverse reactions will be equal.
In Equilibrium: 𝑘𝑓1 𝐶𝑁𝑂 2 = 𝑘𝑟1 𝐶𝑁2 𝑂2

This gives:
𝑘𝑓1 2
𝐶𝑁2 𝑂2 = 𝐶𝑁𝑂
𝑘𝑟1

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• Substitute it back to the rate of the overall reaction:
𝑘𝑓1
𝑅𝑎𝑡𝑒 ≈ 𝑘𝐶𝑁2 𝑂2 𝐶𝑂2 = 𝑘 𝐶𝑁𝑂 2 𝐶𝑂2
𝑘𝑟1
Combine all the constants into one:
𝑅𝑎𝑡𝑒𝑜𝑣𝑒𝑟𝑎𝑙𝑙 ≈ 𝑘𝑒𝑓𝑓 𝐶𝑁𝑂 2 𝐶𝑂2

𝑘𝑓1
Where 𝑘𝑒𝑓𝑓 = 𝑘
𝑘𝑟1

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How to get Order of a Reaction from Reaction
Data ?
The rate law for a reaction can be determined by studying what
happens to the initial instantaneous rate of reaction when we start
with different initial concentrations of the reactants.

Take decomposition of hydrogen peroxide

𝐼−
2𝐻2 𝑂2 𝑎𝑞 → 2𝐻2 𝑂 𝑎𝑞 + 𝑂2 (𝑔)

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 Initial Initial [𝑰− ] (M) Initial
𝑯𝟐 𝑶𝟐 (M) Instantaneous Rate
𝑴
( )
𝒔
Trial 1 1.0 × 10−2 2.0 × 10−3 2.3 × 107
Trial 2 2.0 × 10−2 2.0 × 10−3 4.6 × 107
Trial 3 3.0 × 10−2 2.0 × 10−3 6.9 × 107
Trial 4 1.0 × 10−2 4.0 × 10−3 4.6 × 107
Trial 5 1.0 × 10−2 6.0 × 10−3 6.9 × 107

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What is the Rate law for the reaction
𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙1 1
Consider =
𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙2 2

𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙1 1
And =
𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙3 3

So, if we do a power law fit 𝑅𝑎𝑡𝑒 ∝ 𝐶𝐻𝑛2𝑂2

clearly, 𝑛 = 1

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Now compare, Trial 1 with Trials 4 and 5.

𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙1 1
=
𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙4 2

𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙1 1
And = .
𝑅𝑎𝑡𝑒𝑇𝑟𝑖𝑎𝑙5 3

Here the initial concentrations of 𝐻2 𝑂2 was same but the concentration of

𝐼 − was different. We see that
𝑅𝑎𝑡𝑒 ∝ 𝐶𝐼−

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Combining the two

𝑅𝑎𝑡𝑒 = 𝑘𝐶𝐻2𝑂2 𝐶𝐼−

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Integrated for of Rate Laws
The rate law for a reaction is a useful way of probing the mechanism of a
chemical reaction but it isn't very useful for predicting how much reactant
remains in solution or how much product has been formed in a given
amount of time.
For these calculations, we use the integrated form of the rate law.
Let 𝐶𝑋 be the molar concentration of a species 𝑋. Consider first order
kinetics.
𝑑 𝐶𝑋
− = 𝑘𝐶𝑋
𝑑𝑡
𝐶𝑋
Integrating, ln = −𝑘𝑡
𝐶𝑋 0

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Finding the order of a reaction from
integrated rate laws
Consider a first order reaction.
𝑑𝐶𝑋
= −𝑘𝐶𝑋
𝑑𝑡

Integrating, ln 𝐶𝑋 𝑡 = ln 𝐶𝑋 0 − 𝑘𝑡
There are two parameters, ln(𝐶𝑋 (0)) and the rate constant 𝑘.
So, the plot of the natural logarithm of instantaneous concentration
vs. time is a straight line.

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 The signature of a first order
reaction is a straight line
ln(𝐶𝑋 0 )
ln(𝐶𝑋 𝑡 ) plot of ln 𝐶𝑋 𝑡 𝑣𝑠. 𝑡.
Slope −𝑘

What happens for a second

order reaction ?
What about a reaction that is
Time → first order in two reactants but
second order overall ?

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Calculation of Activation Energy

k(s-1 ) T(K) ln(k) 1/T

0.00043 312.5 -7.75173 0.0032
0.00103 318.47 -6.8782 0.00314
0.0018 322.58 -6.31997 0.0031
0.00355 327.87 -5.64081 0.00305
0.00717 333.33 -4.93785 0.003

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 0
0.00295 0.003 0.00305 ln(k) vs (1/T)
0.0031 0.00315 0.0032 0.00325

-1

-2

-3

-4
ln(k)

-5
y = -14018x + 37.123
R² = 0.9998
-6

-7

-8

-9
1/T

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Example: Calculation of 𝐸𝐴
𝑦 = −14017𝑥 + 37.2
1
ln 𝑘 = 37.2 − 14017 × ( )
𝑇
ln 𝐴 = 37.2
𝐸𝐴
− = 14017
𝑅

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