‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬

CHEMICAL KINETICS: branch of physical chemistry which deals with the

rates of chemical reactions and the mechanisms by which they occur
Kinetics:
 The rate of the chemical reactions and rate law equations
 The reaction mechanism or the sequence of steps by which a reaction occurs
 The factors affecting the reaction rate such as nature of reactants,
temperature, concentration, catalyst, etc...
Reaction Rate: is the change in concentration of a reactant or a product per unit
time
Reactants (R) → Products (P)
𝑑[𝑅] 𝑑[𝑃]
Rate= - or + 𝑑𝑡 (mole/litre.time)
𝑑𝑡

Reaction stoichiometry refers to the number of moles of each reactant and

product appearing in the reaction equation
The rate law is an equation that expresses the relationship between the reaction
rate and the concentrations of the reactants raised to some power
‫معبدنً جعبر عه عالقً بٕه سرعً انحفبعم َ جركٕس انمحفبعالت مرفُعً الش ٔسبَْ رجبً كم مه ٌمب‬
2A+ B →products
Rate α [A]n[B]m Rate= k [A]n [B]m (n and m are the order of reaction)
Elementary reactions: )‫ تفاعالت اوليه‬Simple reactions which occur in a single step
Non-elementary reactions ‫تفاعالت غير اوليه‬: Complex reactions which occur in
two or more steps
rate = k [reactant]n (The rate law for a reaction is determined experimentally, but
NOT from the stoichiometry of the balanced chemical reaction)
Note:
• We cannot deduce the rate law from the balanced chemical equations.
• The mechanism of a reaction must be consisted with the experimental rate law
and the net balanced equation ‫رجبً انحفبعم فٓ انقبوُن جحذد عمهٕب‬
 ‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬

The rate constant (k) is the proportionality constant in the rate law equation.
‫ٌُ ثببث انحىبسب فٓ معبدنة قبوُن سرعً انحفبعم‬
It is dependent on temperature and independent of concentration.
Unit of rate constant (k):
The unit of a rate constant changes according to the overall order.
Reaction order is the sum of the powers of concentrations in the rate law
‫رجبً انحفبعم ٌٓ مجمُع انقُِ انمرفُعً نٍب انحركٕسات‬
Rate = k[A]x[B]y Reaction order: n = x + y
 x and y are the reactant orders determined experimentally.
 x and y are NOT the stoichiometric coefficients.
 The powers (orders) in the rate law can be integers, fractions, or zero
Molecularity is the number of reacting species taking part in an elementary
reaction (single step). )ً‫ٌُ عذد انمُاد انمحفبعهً فٓ انمرحهً االبحذائًٕ (انخطُي انبطٕئ‬
Unimolecular Reaction: NH 4 NO 2 → N 2 + 2H 2O
Bimolecular Reaction: 𝐍�𝐎� + 𝐎��2 → 𝐍�𝐎��2 + 𝐎��2
Trimolecular Reaction: 2NO + O 2 → 2NO 2
Comparison between molecularity and reaction order
Molecularity Reaction order
Can be integers only Can be integers, fractions, zero, or negative
The molecularity is determined by
stoichiometric coefficients The reaction order is determined experimental

It is the number of reacting species It is the power of concentration in the rate law.
 ‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬

Orders of reactions:
Zero order First order Second order Third order
the rate is independent of the rate is dependent on the the rate is dependent on the the rate is dependent
the concentration of the concentration of one reactant. concentration of the two on the concentration
reactant A → product reactants. of three reactants.
A → product D.R.L: 2A → product 3A → product
D.R.L : 𝑑[𝐴]
- 𝑑𝑡� =k[A] D.R.L: D.R.L:
𝑑[𝐴] 𝑑[𝐴] 𝑑[𝐴]
- = K[A]0=K 𝑑[𝐴] - = k[A]2 - = 𝑘[𝐴]3
𝑑𝑡 =-kdt 𝑑𝑡 𝑑𝑡
d[A]=-kdt [𝐴] 𝑑[𝐴]
= -kt
[𝐴] 𝑑[𝐴]
− ∫[𝐴] 𝑡 [𝐴]3 =k∫0 𝑑𝑡
𝑡
[𝐴]𝑡 𝑑[𝐴] 𝑡 [𝐴]2
[𝐴]𝑡
∫[𝐴]0 𝑑[𝐴]=
𝑡
−𝑘 ∫0 𝑑𝑡 ∫[𝐴]0 [𝐴] = -k ∫0 𝑑𝑡 [𝐴]𝑡 𝑑[𝐴] 𝑡
0

∫[𝐴] [𝐴]2 = -K∫0 𝑑𝑡 1 1 1

[A]t-[A]0=-kt Ln[A]t-ln[A]0=-kt 0 * 2− + = 𝑘𝑡
[𝐴]𝑡 1 1 2 [𝐴]𝑡 [𝐴]20
[A]t=-kt+[A]0 ln[𝐴]0=-kt -[[𝐴] − [𝐴] ]=-kt 1 1
𝑡 0
Unit (k ≡ mol.L-1.s-1) 1 1 2 − [𝐴]2 = 2𝑘𝑡
[A]t=[A]0�𝑒 −𝑘𝑡 − = 𝑘𝑡 [𝐴]𝑡 0
Ln[A]t=-kt+ln[A]0 [𝐴]𝑡 [𝐴]0 Unit k=mol-2.L2.s-1
Unit�k=S-1 Unit k= mol-1.L.s-1

Half-time (half-life):It is Half-life for first-order Half-time for second order Half-time:
the time required for the reactions: reactions: 1 1
concentration of a reactant [𝐴]𝑡 1 1 − = 2𝑘𝑡1
ln[𝐴]0=-kt − [𝐴] =kt [𝐴]𝑡 [𝐴]20
2
2
[𝐴]
to decrease to half its [𝐴]0 2
𝑡
1
0
4 1
initial value. ln2[𝐴]0=-kt1/2 − =kt1/2 − = 2𝑘𝑡1/2
1
[𝐴]0 [𝐴]0 [𝐴]20 [𝐴]20
1
t =t1\2 , [A]t=2[A]0 1
t1/2= -𝑘 ln 2
1
t1/2 =𝑘[𝐴]
0
[A]t-[A]0=-kt 𝑙𝑛2 0,963 3
1 t1/2= =
[A]0-[A]0=-kt1/2 𝑘 𝑘
2K[A]
2
[𝐴]
t ½ = 2𝑘
 ‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬

Higher order reaction:

nA product
𝑑[𝐴] 𝑑[𝐴] [𝐴] 𝑑[𝐴] 𝑡 1 1 1
− = 𝑘[𝐴]𝑛 , − [𝐴]𝑛 = 𝑘𝑑𝑡 , − ∫[𝐴] 𝑡 = 𝑘 ∫0 𝑑𝑡 , [[𝐴]𝑛−1 − [𝐴]𝑛−1] = 𝑘𝑡�
𝑑𝑡 0 [𝐴]𝑛 𝑛−1 𝑡 0

Half-time for nth order t1/2 is related to

1 2𝑛−1 −1
t1/2 α [𝐴 𝑛−1
t1/2 =(𝑛−1)𝑘 𝑛−1
0] 𝑛 [𝐴0 ]
 ‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬

FRACTIONAL-ORDER REACTIONS In fractional order reactions, the order is

a non-integer, which often indicates a chemical chain reaction or other complex
reaction mechanism. rate = k [A]0.77 [B]1.41
PSEUDO-ORDER REACTIONS Chemical reactions which appear to be of lower
order but actually are of higher order are called pseudo-order reactions or the
method of isolation.
A + B → product
𝑟�𝑎�𝑡�𝑒� = [ ] [𝐵�] large excess
𝑟�𝑎�𝑡�𝑒� = 𝑘� 𝑜�𝑏�𝑠�[𝐴�] pseudo-first order
DETERMINING RATE LAWS FROM EXPERIMENTAL DATA methods that
allow us to use experimental data to determine reaction order with respect to each
reactant, and then the rate law.

1. Differential method:
When we have a rate law that depends only on the concentration of one reactant,
there are two ways to determine the reaction order:
(a) Numerically-(Initial rate method): if there are two initial rates (R 1 & R2),
then divide the two differential rate laws to get the order n of reactant A.

(b) Graphically: if there are various (more than two) runs, then
 ‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬
(b) Graphically: if there are various (more than two) runs, then

A plot of log rate against log[A] will then be a straight line with a slope equal to
the reaction order, n, and an intercept equal to log k.
2. Integral method:
Numerically: In this method, we test the data with the different integrated rate
laws.
By plugging in different concentrations after regular time intervals and solving
for k, the integrated rate law which yields a constant value of k corresponds to the
correct order of the reaction.

3.Graphical integral method:

‫دْ مه خالل انرسم انىٍبئٓ نهحركٕس مع انسمه وقذر وحذد انرجبً فببنحبنٓ وحفظ االشكبل َمه خالنٍب وقذر‬
‫وسحىحج انرجبً انفرق بٕه انرجبً االَنّ َانسٔرَ اوً انرسم فحبنة االَنّ نم‬
ln[A]t
‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬

4.Half-life method:
If we have two initial concentrations ([Ao]1 , [Ao]2) and two half-lives (t1/2)1,
(t1/2)2,then divide the two half-lives equations to get the reaction order:
1 (𝑡1𝑙2 )1 [𝐴0 ]𝑛−1 (𝑡1/2 )1 [𝐴 ]2
t1/2𝛼 𝛼� 2
log [ = (𝑛 − 1)log�[[𝐴0]1]
[𝐴𝑜 ]𝑛−1 (𝑡1/2 )�2 [𝐴0 ]𝑛−1
1 (𝑡1/2 )2 1

log[(𝑡1 )1/(𝑡1 )2]

n=1+ 2 2
log�[[𝐴0 ]2 /(𝐴0 )1 ]

5. Isolation method:
This method is useful when there is more than one reactant.
A + B → product
Rate = k [A]x [B]y
To simplify the rate and to determine the order easily, the effect of the other
reactant can be isolated by taking a large excess of it.

NATURE OF REACTANTS
Physical nature:
The rate depends on the physical state of the reactants.
Reaction rates are limited by the contact surface areas between the different
phases of reactant molecules.
➢ Solid matter volume and surface area:
The smaller the reactant particles, the faster the reaction rate.
The larger the surface area of reactants, the faster the reaction rate.
Chemical nature of the reactants:
 ‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬
Chemical nature of the reactants:
Consider three pieces of minerals: sodium, zinc, and tin that have same size
and shape. Put each piece in a solution of HCl acid with the same concentration.
Which will react the fastest and why?
CONCENTRATION
The rate of a chemical reaction increases as the concentration of reactants
increases ‫ٔسداد معذل انحفبعم بسٔبدي جركٕس انمحفبعالت‬.
rate = k [reactant]n
The figure shows three tangents drawn. The magnitudes of the gradients lie in
the order AB >CD > EF at time (t1), (t2) and (t3) respectively.
As [reactant] decreases so does the rate.

PRESENCE OF A CATALYST ‫َجُد عبمم حفبز‬

A catalyst is a substance which increases the rate of a reaction without itself
undergoing any permanent chemical change.
‫انعبمم انحفبز ٌُ مبدي جسٔذ مه سرعً انحفبعم دَن حذَخ جغٕٕر فٓ انمبدي وفسٍب‬
The action of the catalyst can be explained by intermediate complex theory.
According to this theory, a catalyst participates in a chemical reaction by
forming an intermediate complex with the reactant. This complex decomposes
to yield the products and the catalyst
 ‫ملخص الكيمياء الحركية الجزء االول‬ 0540926539 ‫حمدي سلمان‬/‫د‬

TEMPERATURE
The rate of a chemical reaction increases as temperature increases.
‫ٔسداد سرعة انحفبعم انكٕمٕبئٓ بسٔبدي درجً انحراري‬
As the temperature of reaction is increased, more and more molecules will
acquire activation energy (Ea) to cause productive collisions. This increases the
rate of the reaction.
‫بسٔبدي درجً انحراري جساد طبقً جىشٕط انجسٔئبت َببنحبنٓ جسداد عذد انحصبدمبت ممب ٔسٔذ سرعً انحفبعم‬
As a rough approximation, raising the temperature by 10 degrees may double or
triple the rate constant (k).