REACTION

KINETICS
Why reaction between element occur

⚫ Why Reaction
AB + C → D Take place.
The chemical reaction take
place inorder the system AB + C

Eenergy Level
becomes: ---------
1. More order …. ? ΔH reaction

2. More stable …. ? AC + B

---------------
Reaction Coordinate
Stability of molecule system compared to atom

Non-Bonding

Atom at distance
ΔEnergy
Lowest Energy
? Most stable
Atom Bonded In Molecule
 How does the reaction occur?

A +A → B (H + H → H2)
AB + C → A–C + B (H2 + ½ O2 → H2O)

1. Sharing electron among the elements ( covalent )

2. Give/received the electron(s) ⇒ ions
3. Attraction between different ions ( ionic )
4. Restructuring the electronic configuration in the
molecules, by:
Breaking down the bonds = (required energy)
Rearrangement the pair(s) of electron(s)/Bonding
Formation of new bonds (released energy)
Rate of reaction

E.g; aA + bB cC + dD

⚫ Rate of consumption of reactant A =

 
⚫ Rate of consumption of reactant B =

⚫ Rate of formation of product C =

 
⚫ Rate of formation of product D =
 
⚫ The sign (+) and (-) 🢡 the formation of
product and the consumption of reactant.

C and D
Concentration

A and B

Time
⚫ The differential rate equation, υ

⚫ Example:
A + 2B 3C + D
 [N2O5],M

Time (t), hours

Can you explain how to determine the rate of reaction from the graph?
⚫ Example 1.
The radical of CH3 reaction below occur at
certain condition. Find the rate of reaction
and the rate of formation of CH3CH3
where the rate of formation of CH3 radical
is,
= - 1.2molL-1s-1

2CH3 (g) CH3CH3

Rate law and rate constant

◦Consider a general equation

⚫  aA + bB cC + dD
  υ = k[A]x [B]y
⚫   Where : k = rate constant.
⚫  In mathematical function, the rate of
reaction;
⚫ υ = f([A],[B],…..)

 
⚫ For gases reaction – concentration of species
replace by partial pressure
υ = f(pA, pB, ……)
⚫ The rate law is determined by an experiment
not by chemical reaction equation.
⚫  E.g: A reaction between hydrogen and
Bromine
⚫  H2 (g) + Br2 (g) 2HBr (g)
⚫ The rate law is given:
Order of reaction

⚫  Consider a general reaction below;

⚫   aA + bB cC + dD
⚫   Rate law, υ = k[A]x [B]y
Where, x and y = partial order of reaction
x + y = overall order of reaction
Determination of rate law, order of
reaction and rate constant
1. Differential method
⚫ The rate of reaction can be determined by the gradient of
graph concentration vs times.
C

ΔC1
C1
Δt
ΔC2

Δt C2

ΔC3
C3
Δt

time,t
⚫ The rate law equation given by:-
  υ = kCn
⚫  Where; k = rate constant
C = concentration of reactant
n = Order of reaction
υ = rate of reaction
⚫ In logarithme,
ln υ = ln k + n ln C
⚫ Plot of ln υ vs ln C gives a straight line
ln υ = n ln C + ln k

y = mx + c
ln υ

Slope = Δ ln υ = n
Δ ln C

the intercept of ln υ = ln k

ln C
2. Integrated method

(a) Zero order

⚫ Consider the following reaction;
 
A Z
time, t [A] [Z]
t=0 a0 0
t=t a0 - x x

⚫ The rate of formation of Z,

 
 
⚫ Rearrange;

⚫ And
⚫ Integrate the equation;

⚫ A plot of x against t will give a straight line graph

 x = kt 0
y = mx + c

Slope, m = k

t
(b) 1st order
A Z
⚫ Rate of formation of Z :-

⚫ Rearrange:

⚫ And integrate the equation:

-ln (a0 – x) = kt + C
⚫ At t = 0, value of x = 0 , therefore C = -ln a0

⚫ So that equation become;

-ln (a0 – x) = kt + (-ln a0)

⚫ Simplified the equation where;

a0 = A0 and a0 – x = At

ln At = -kt + ln A0
⚫ Plot of graph ln At vs t gives a straight line

ln At
Intercept = ln A0

Slope = k

t
(c) 2nd order – identical molecule
2A Z

Slope=k

Intercept =

t
2nd order –non identical molecules
A+B Z

Plot of against t gives a

straight line
The summary of order of reaction, integrated equation and
differential equation

Order of Differential equation Integrated equation

reaction
0 x = kt

1 ln

3
3. Half-life method, t1/2

⚫ In logarithme,

ln t1/2 = ln k – (n-1) ln a0

⚫ where; ao= initial concentration

n = overall order of reaction
k = rate constant
plot of ln t1/2 vs ln a0

ln t ½
Intercept = ln k

Slope = n - 1

ln ao
4. Isolation method
⚫ Requires that all the reactant except one are arranged to
be in large excess.
⚫ The dependence of the reaction rate on the one reactant
present in small concentration.
⚫ Consider the following reaction,
2I - + S2O82- I2 + 2SO42-
⚫ The rate of reaction;
υ = k2[S2O82-][I-]

⚫  If [I-] is in excess and its concentration remain essentially

constant during the course of reaction, the reaction will
appear to follow first order and is said to be pseudo-first
order reaction.
υ = k’[S2O82-] where; k’ = k2[I-]
5. Method of Initial Rates

Experiments
⚫ Method of Initial Rates
⚫ If reaction is sufficiently slow
◦ or have very fast technique
⚫ Can measure [A] vs. time at very beginning of reaction
◦ before it curves up very much, then

◦ Set up series of experiments, where initial

concentrations vary
Example 6
3A + 2 B ⎯→ products
Rate = k[A]m[B]n

Expt. [A]0, M [B]0, M Initial Rate, M/s

1 0.10 0.10 1.2 × 10−4
2 0.20 0.10 4.8 × 10−4
3 0.20 0.20 4.8 × 10−4

▪ Convenient to set up experiments so

▪ [X] of one species is doubled or tripled
▪ while [X] of all other species are held constant
▪ Tells us effect of [varied species] on initial rate
Answer
Expt. # [A]0, M [B]0, M Initial Rate, M/s
1 0.10 0.10 1.2 × 10−4
2 0.20 0.10 4.8 × 10−4
3 0.20 0.20 4.8 × 10−4

▪ Comparing 1 and 2

2m = 4 or m=2 30
▪ Comparing 2 and 3

2n = 1 or n=0

⚫ Conclusion: rate = k[A]2

⚫ Can use data from any experiment to determine k
⚫ Let’s choose experiment 1

31
The relationship of order of
reaction and half life
⚫ From the integral equation for zero order,
x = kt
⚫ When t = t1/2 and x =
⚫ therefore;

⇒ t1/2 =
•The summary of order of reaction and half life

Order of reaction t1/2

0 t1/2 =

1 t1/2 =

2 t1/2 =

3 t1/2 =