Chemical Kinetics

Joshua Micole Felizarta, LPT

Overview
• Rate of Reaction
• Factors Affecting Reaction
• Rate Law for a Reaction
Chemical Kinetics
• Study of the rate of chemical reactions, including the mechanism by
which the reaction occurs and the different factors that affect it.

• Molecules or atoms of reactants must collide with each other in

chemical reactions.
• Molecules must have enough energy to initiate a reaction
Chemical reactions can be either:
• Fast:
• Combustion of gasoline and oxygen
• Vinegar and baking soda (bubble formation)
• Slow:
• Rusting of iron
• Green patina (film) on copper
Rate of reaction
• The change in the concentration of a reactant or product per change
in time.

Example: aA + bB → cC + dD (hypothetical chem eq)

Expression of chemical reaction

1 Δ[𝐴] 1 Δ[𝐵] 1 Δ[𝐶] 1 Δ[𝐷]

Rate = − ( ) = − ( ) = ( ) = ( )
𝑎 Δ𝑡 𝑏 Δ𝑡 𝑐 Δ𝑡 𝑑 Δ𝑡
Reaction Rate Defined
Reaction rate: changes in a concentration of a
product or a reactant per unit time.
[]
[ ] concentration
Reaction rate = ——
t

change [ ]

t

t
Expressing reaction rates
For a chemical reaction, there are many ways to express the reaction rate. The
relationships among expressions depend on the equation.
Note the expression and reasons for their relations for the reaction
2 NO + O2 (g) = 2 NO2 (g)
[O2] 1 [NO] 1 [NO2]
Reaction rate = – ——— = – — ———— = — ———
t 2 t 2 t
Make sure you can write expressions for any reaction and figure out the
relationships. For example, give the reaction rate expressions for
2 N2O5 = 4 NO2 + O2

7
Practice Exercise
1. 2 H₂O₂ → 2 H₂O + O₂
2. 2 N₂O → 2 N₂ + O₂
3. 2 C₄H₁₀ + 13 O₂ → 8 CO₂ + 10 H₂O
4. N₂ + 3 H₂ → 2 NH₃
5. 2 N₂O₅ → 4 NO₂ + O₂
Calculating reaction rate
The concentrations of N2O5 are 1.24e-2 and 0.93e-2 M at 600 and 1200
s after the reactants are mixed at the appropriate temperature. Evaluate
the reaction rates for
2 N2O5 = 4 NO2 + O2
Solution:

(0.93 – 1.24)e-2 – 0.31e-2 M

Decomposition rate of N2O5 = – ———————— = – ——————
1200 – 600 600 s
= 5.2e-6 M s-1.
Note however, The reaction rates
rate of formation of NO2 = 1.02e-5 M s-1. are expressed in 3
rate of formation of O2 = 2.6e-6 M s-1. forms
Factors Influencing Reaction Rates
• Concentrations
• Surface Area
• Temperature
• Catalyst
Factors
Concentration
• As the concentration of the reactant increases, the reaction rate
increases.

• More concentration, more collisions. More collisions, more reactions.

Factors
Surface area
• As the surface of the reactants increases, the reaction rate increases.

• High surface area, more reaction rates.

Factors
Temperature
• As the temperature of a system increase, the reaction rate increases.

• Temperature = measure of average kinetic energy of a particles

Factors
Catalyst
• The presence of a catalyst increases the reaction rate.
• It lowers the activation energy.

• Ways to lower AE:

• Increase the frequency of collisions
• Reduce intermolecular bonding within reactant molecules
Rate Law
• Mathematical expression that shows how the rate of reaction
depends on the concentration of reactants.

In A → product

Expression rate = k [A]ˣ

where k = rate constant
rate = M/s (molar per second)
Order of a Reaction
• Zero-order reaction (x = 0)
• First-order reaction (x = 1)
• Second-order reaction (x =2)
Zero-order reaction (x=0)
• Has a constant rate that is equal to its rate constant k regardless of
the change in the concentration of reactant

rate = k [A]⁰ = k
First-order reaction (x=1)
• The rate k doubles when the concentration of a reactant is doubled.

rate = k [A]¹ = k[A]

Second-order reaction (x=2)
• The rate k quadruples when the concentration of the reactant is
doubled.

rate = k [A]²
Rate Laws for Different Reaction
Reaction Order Rate Law Units of k
Zero rate = k [A]⁰ = k M·s-¹
First rate = k [A]¹ = k[A] s-¹
Second rate = k [A]² M-¹·s-¹
Third rate = k [A]³ M-²·s-¹
Example 1
• 2 O₃ → 3 O₂
Experiment Initial [O₃] Initial Rate
(M) (M/s)
I 2.00 0.500

II 4.00 1.000

III 6.00 1.500

Example 2
• N₂O₄ → 2 NO₂
Experiment Initial [N₂O₄] Initial Rate
(M) (M/s)
I 0.50 0.050

II 1.00 0.200

III 1.50 0.450

Example 3
Hypothetical equation A+B→C

Experiment Initial [A] Initial [B] Initial Rate of

(M) (M) Reaction (M/s)
I 0.012 0.0034 1.4 x 10-³
II 0.024 0.0034 2.8 x 10-³
III 0.012 0.0068 5.6 x 10-³
Practice Problem 1
• CHCl₃ + Cl₂ → CCl₄ + HCl
Experiment Initial [CHCl₃] Initial [Cl₂] Initial Rate
(M) (M) (M/s)
I 0.0011 0.014 2.60 x 10 -⁴

II 0.0011 0.028 5.20 x 10 -⁴

III 0.0022 0.028 2.08 x 10 -³

IV 0.0022 0.014 1.04 x 10 -³

 Assignment 1
• BrO₃- + 5 Br- + 6H → 3 Br₂ + 3 H₂O
Experiment Initial [BrO₃-] Initial [Br-] Initial [H] Initial Rate
(M) (M) (M) (M/s)
I 0.0050 0.0017 0.0042 3.80 x 10 -⁴
II 0.0050 0.0034 0.0042 7.60 x 10 -⁴
III 0.0100 0.0034 0.0042 1.52 x 10 -³

IV 0.0100 0.0034 0.0084 6.08 x 10 -³

V 0.0050 0.0017 0.0084 1.52 x 10 -³