Dr.

Mohsen El-Tahawy
Assistant Professor of Physical chemistry,
Chemistry Department,
Faculty of Science, Damanhour University
PhD, University, Italy

Contents
✓ Chemical Equilibrium
❑ Chemical kinetics → loading
❑ Principles of Thermodynamics
❑ The Colloidal State
 Chemical Kinetics
 In equilibrium reactions, the rates of the two opposing
reactions are equal and the concentrations of reactants
or products do not change with lapse of time.
 Most chemical reactions are spontaneous reactions.
i.e. the reactions occur from left to right till all the
reactants are converted to products.
❑ NaCl + AgNO3 → AgCl very fast
❑ the rusting of iron is a slow reaction that occurs over
the years.
The branch of Physical chemistry which deals with the
rate of reactions is called Chemical Kinetics.
Chemical Kinetics includes the study of:
 The rate of the reactions and rate laws.
 Thefactors as temperature, pressure,
concentration, and catalyst, that influence the
rate of a reaction.
 Themechanism or the sequence of steps by
which a reaction occurs.
Importance
✓ to understand the chemical of reactions.
✓ toselect optimum conditions for an industrial
process to occur at a rate to give maximum
yield.
REACTION RATE
 The rate of a reaction tells as to what speed the
reaction occurs.
𝐴 → 𝐵
➢ The [A] decreases, and the [B] increases as time
passes.
The rate of reactions:
the change in concentration of any of reactant or
products per unit time.
i.e. for the 𝐴 → 𝐵 , the rate of reaction may be equal
to the rate of disappearance of A which is equal to the
rate of appearance of B.
i.e. for the 𝑨 → 𝑩 ,
rate of reaction = rate of disappearance of A = rate of
appearance of B
𝑑𝐴 𝑑𝐵
𝑜𝑟 𝑟𝑎𝑡𝑒 =– = +
𝑑𝑡 𝑑𝑡
 Negative and positive signs show the decrease, and
the increase of the reactant and the product,
respectively.
REACTION RATE
 To generalize, then, for the reaction
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

𝟏𝒅 𝑨 𝟏 𝒅[𝑩] 𝟏 𝒅[𝑪] 𝟏 𝒅[𝑫]

𝑹=− =− = =
𝒂 𝒅𝒕 𝒃 𝒅𝒕 𝒄 𝒅𝒕 𝒅 𝒅𝒕
Example:
N2 (g) + 3H2 ( g)
→ 2NH3 (g)
 therate of consumption of N2 and H2 and the
rate of production of NH3 are not the same
 therate of production of ammonia is twice the
rate of consumption of nitrogen
 therate of consumption of hydrogen is three
times the rate of consumption of nitrogen.

𝒅 𝑵𝟐 𝟏 𝒅[𝑯𝟐 ] 𝟏 𝒅[𝑵𝑯𝟑 ]
𝑹=− =− =
𝒅𝒕 𝟑 𝒅𝒕 𝟐 𝒅𝒕
UNITS OF RATE
Reactions rate has the units of concentration
divided by time. As rate == d[]/dt
 Concentrationsare given in moles per litre
(mol/litre or mol/l or 𝑚𝑜𝑙 𝑙−1 )
 time may be given in any convenient unit second
(s), minutes (min), hours (h), days (d) or possible
years.
the units of reaction rates may be
 𝑚𝑜𝑙𝑒/𝑙𝑖𝑡𝑟𝑒 𝑠𝑒𝑐 𝑜𝑟 𝑚𝑜𝑙 𝑙−1 𝑠 −1
 𝑚𝑜𝑙𝑒/𝑙𝑖𝑡𝑟𝑒 𝑚𝑖𝑛 𝑜𝑟 𝑚𝑜𝑙 𝑚𝑜𝑙 𝑙−1 𝑠 𝑚𝑖𝑛−1
 𝑚𝑜𝑙𝑒/𝑙𝑖𝑡𝑟𝑒 ℎ𝑜𝑢𝑟 𝑜𝑟 𝑚𝑜𝑙 ℎ−1 𝑎𝑛𝑑, 𝑠𝑜 𝑜𝑛
Measuring Reaction Rate
 Tomeasure a reaction rate, we usually monitor
either a product or a reactant for its change.
 Anyphysical characteristic related to the
quantity or concentration of a product or
reactant can be monitored.
Some of the characteristics to be monitored are:
 change in pressure,
 change in color (spectroscopic measurement),
 temperature for exothermic or endothermic
reaction, and
 presence of certain key substance
 The change can be plotted on a graph, and from the
graph, we can get the average rate or the instantaneous
rate by either graphical method or using computer for
the data analysis.
Average Rate of Reaction is a Function of Time
 consider the reaction
𝐶𝑂(𝑔) + 𝑁𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 𝑁𝑂(𝑔)
 The average rate of reaction may be expressed as
𝑑 𝐶𝑂
𝑅=−
𝑑𝑡

Conc. of CO 0.100 0.067 0.050 0.040 0.033

Time (sec) 0 10 20 30 40
Conc. of CO 0.100 0.067 0.050 0.040 0.033
Time (sec) 0 10 20 30 40
 Over the first 10 seconds, the average rate is
𝑑 𝐶𝑂 0.067 − 0.100 0.033
𝑅=− =− =
𝑑𝑡 10 − 0 10
= 0.0033 𝑚𝑜𝑙 𝑙 −1 𝑠 −1
 In the time interval between 30 and 40 seconds
0.033 − 0.040 0.007
𝑅=− = = 0.0007 𝑚𝑜𝑙 𝑙 −1 𝑠 −1
40 − 30 10
✓ The reaction in indeed slowing down with
time.
✓ average rates are not always useful.
Conc. of CO 0.100 0.067 0.050 0.040 0.033
Time (sec) 0 10 20 30 40

The average rate is equal to the slope of the curve.

 The slope of tangent at 10
seconds is equal to the
instantaneous rate

➢ at any time, the instantaneous rate is equal to the slope of the

straight-line drawn tangent to the curve at that time.
➢ For example, at 10 seconds is found to be 0.0022 𝒎𝒐𝒍 𝒍 −𝟏 𝒔−𝟏
RATE LAWS
 Ata fixed Temperature, the rate of a given
reaction depends on concentration of
reactants.
 therate of a reaction is directly proportional
to the reactant concentrations, each
concentration being raised to some power.
Thus, for a substance A undergoing reaction,
𝐴→𝑃
𝑟𝑎𝑡𝑒 ∝ [𝐴]𝑛
 or
𝑟𝑎𝑡𝑒 = 𝑘[𝐴]𝑛 … . . 1
 For a reaction
𝟐𝑨 + 𝑩 → 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔
𝒓𝒂𝒕𝒆 = 𝒌[𝑨]𝒂 [𝑩]𝒃
➢ The power (exponent) of concentration a or b
in the rate law is known as the order of
reaction
➢ it is usually a small whole number integer (1,
2, 3) or fractional.
➢k is called the rate constant for the reaction.
➢ An expression which shows how the reaction
rate is related to concentrations is called the
rate law or rate equation.
Examples of rate law:
 𝟏 𝟐𝑵𝟐 𝑶𝟓 → 𝟒 𝐍𝑶𝟐 + 𝑶𝟐 𝐫𝐚𝐭𝐞 = 𝐤 [𝑵𝟐 𝑶𝟓 ]
𝒏=𝟏
 𝟐 𝑯𝟐 + 𝑰𝟐 → 𝟐𝐇𝐈 𝐫𝐚𝐭𝐞 = 𝐤 [𝑯𝟐 ] [𝑰𝟐 ]
𝒏=𝟏+𝟏=𝟐
 (𝟑) 𝟐𝐍𝑶𝟐 → 𝟐𝐍𝐎 + 𝑶𝟐 𝐫𝐚𝐭𝐞 = 𝐤 [𝐍𝑶𝟐 ]𝟐
𝒏=𝟐
 𝟒 𝟐𝐍𝐎 + 𝟐𝑯𝟐 → 𝑵𝟐 + 𝟐𝑯𝟐 𝐎
𝐫𝐚𝐭𝐞 = 𝐤 [𝑯𝟐 ] [𝐍𝐎]𝟐

𝒏=𝟏+𝟐=𝟑
 Itis apparent that the rate law for a reaction must
be determined by experiment.
 Itcannot be written by merely looking at the
equation with a background of our knowledge of
Law of Mass Action.
 usually, the powers of concentration in the rate law
are different from coefficients.
ORDER OF A REACTION, n
 The order of a reaction is defined as the sum of
the powers of concentrations in the rate law.
n = 1, it is first order reaction
n = 2, it is second order reaction
n = 3, it is third order reaction
 Itis apparent that the rate law for a reaction must
be determined by experiment.
 Itcannot be written by looking at the equation with a
background of our knowledge of Law of Mass Action.
 usually,the powers of concentration in the rate law
are different from coefficients.
ORDER OF A REACTION, n
 Theorder of a reaction is defined as the sum of the
powers of concentrations in the rate law.
✓ n = 1, it is first order reaction
✓ n = 2, it is second order reaction
✓ n = 3, it is third order reaction
The half-life time of a reaction, 𝒕𝟏 ,
𝟐

 The time needed for a reactant concentration to

decrease by half compared to its initial
concentration.
 Its application in chemistry and medicine to
predict the concentration of a substance over
time.
 to determine how quickly a drug decrease in the
target after it has been absorbed in the unit of
time (sec, minute, day, etc.)
 the half-life is varied between according to the
type of reaction.
Molecularity of a Reaction
The molecularity is the number of reactant
molecules involved in a reaction.
Chemical reactions may be classed into two types:
(a) Elementary reactions
(b) Complex reactions
 Anelementary reaction is a simple reaction which
occurs in a single step.
Acomplex reaction is that which occurs in two or
more steps.
Molecularity of an Elementary Reaction
 The molecularity is defined as: the number of reactant
molecules involved in a reaction.
Type of molecularity
Unimolecular → one reactant molecule is participating
in the reaction.
Bimolecular → Two reactant molecules are participating
in the reaction.
Termolecular → Tree reactant molecules is participating
in the reaction.
Why High Molecularity Reactions are Rare?
 Thereactions involving four or more molecules
are very rare.
 Accordingto kinetic molecular theory, the rate
of a chemical reaction is proportional to the
number of collisions taking place between the
reacting molecules.
 Thechances of simultaneous collision of reacting
molecules will go on decreasing with increase in
number of molecules.
Molecularity of a Complex Reaction
 Most
chemical reactions are complex reactions.
These occur in a series of steps.
 Each step is an elementary reaction.
 The stepwise sequence is called the mechanism
of the reaction
 some of the steps will be fast, others will be
slow.
A reaction can proceed no faster than its slowest
step. i.e rate determining step (RDS) of the
reaction.
 Step 1 2N2O5 → 2NO2 + 2NO3 (fast)
Step 2 NO2 + NO3 → NO + NO2 + O2 (slow)
Step 3 NO + NO3 → 2NO2 (fast)
Overall reaction 2N2O5 → 4NO2 + O2
 Each elementary reaction has its own molecularity.
 It is meaningless to give the molecularity of the
overall
 At best could be thought of as: the number of
molecules or atoms taking part in the RDS.
 Thus step 2 in the above mechanism is RDS and has
molecularity ‘2’ which could be considered as the
molecularity of the decomposition reaction of N2O5.
Order of a Reaction Molecularity of a Reaction
 Order of a Reaction Molecularity of a Reaction
sum of powers of the number of reacting
concentration terms in species undergoing
the rate law simultaneous collision in
expression. the elementary or simple
reaction.
 Order of a Reaction Molecularity of a Reaction
It is the sum of powers of the 1. It is number of reacting species
concentration terms in the rate undergoing simultaneous collision
law expression. in the elementary or simple
reaction.

2. It is an 2. It is a theoretical
experimentally concept.
determined value.
 Order of a Reaction Molecularity of a Reaction
1.It is the sum of powers of the 1. It is number of reacting species
concentration terms in the rate undergoing simultaneous
law expression. collision in the elementary or
simple reaction.
2.It is an experimentally
determined value. 2. It is a theoretical concept.

3.It can have 3.It is always a whole

fractional value. number.
 Order of a Reaction Molecularity of a Reaction
1.It is the sum of powers of the 1. It is number of reacting species
concentration terms in the rate undergoing simultaneous collision
law expression. in the elementary or simple
reaction.
2.It is an experimentally
determined value. 2. It is a theoretical concept.
3.It can have fractional value. 3. It is always a whole number.

4.It can assume zero 4.It cannot have zero

value. value.
 Order of a Reaction Molecularity of a Reaction
1.It is the sum of powers of the 1. It is number of reacting species
concentration terms in the undergoing simultaneous collision in
rate law expression. the elementary or simple reaction.
2.It is an experimentally 2. It is a theoretical concept.
determined value.
3. It is always a whole number.
3.It can have fractional value.
4.It can assume zero value.
4. It cannot have zero value.
5.Order of a reaction
5.Molecularity is
can change with the
invariant for a
conditions such as
pressure, chemical equation
temperature, and
concentration.
Pseudo–Order Reactions
 Let us consider a reaction. A + B → products
rate = k [A] [B]
 If B is present in large excess, its concentration
remains practically constant during reaction.
 Thus, the rate law can be written as rate = k′[A]
where k′ = k [B].
➢ Thus, the actual order of the reaction is second order
but in practice it will be first order. Therefore, the
reaction is said to have a pseudo-first order
➢ Any reaction shows an experimental order different
from the actual order is referred to as the pseudo-
order Or pseudo molecular reactions.
Examples of Pseudo-order Reactions
 (1)Hydrolysis of an ester. The reaction is
second order
CH3COOC2H5 + H2O → CH3COOH + C2H5OH
ethyl acetate excess acetic acid ethyl alcohol
Here a large excess of water is used, and the rate
law can be written as
rate = k [CH3COOC2H5] [H2 O]
= k′[CH3COOC2H5]
Thus, it is a pseudo-first order reaction.
(2) Hydrolysis of sucrose. The reaction though of second
order
C12H22O11 + H2O → C6H12O6 + C6H12O6
sucrose (excess) glucose fructose
 If a large excess of water is present, [H2O] is practically
constant
𝑟𝑎𝑡𝑒 = 𝑘 [𝐶12 𝐻22 𝑂11 ] [𝐻2 𝑂]
= 𝑘′[𝐶12 𝐻22 𝑂11 ]
 is experimentally found to be first order. Thus, it is a
pseudo first order reaction.
Types of chemical kinetics reactions
Zero Order reactions
➢A zero-order reaction is one whose rate is
independent of concentration
➢A reactant whose concentration does not affect
the reaction rate is not included in the rate law.
Thus [A]0 = 1
For example, the rate law for the reaction at 200°
C is
NO2 + CO → NO + CO2
rate = k [NO2 ]2
 Here the rate does not depend on [CO],
 the power of [CO] is zero.
 The reaction is zeroth order with respect to CO.
 The reaction is second order with respect to
[NO2].
 The overall reaction order is 2 + 0 = 2.
 𝐀 ⟶𝐏
𝐴𝑡 𝑡𝑖𝑚𝑒 = 0 𝑎 0
𝐴𝑡 𝑡𝑖𝑚𝑒 = 𝑡 𝑎−𝑥 𝑥
𝑎 is the initial concentration of the reactant
𝑎𝑛𝑑 𝑥 is the concentration of the product at
time 𝑡.
R=kA 0
= k (rate constant)
dA 𝑑𝑥
R=− =
𝑑𝑡 𝑑𝑡
𝑑𝑥
=𝑘
𝑑𝑡
 This is known as Zero-order differential law.
 𝑑𝑥
=𝑘
𝑑𝑡
 This is known as Zero-order differential law.
𝑑𝑥 = 𝑘𝑑𝑡
𝑥 = 𝑘𝑡 + 𝑐
𝐴𝑡 𝑡𝑖𝑚𝑒 = 0 , 𝑥 = 0 ⟹ 𝐶 = 0
𝑥 = 𝑘𝑡
➢ Thisis known as Zero-order integral law where
the units of k are M/s,
➢ therate constant is equal to the rate of
reaction at all concentrations.
𝑑𝑥
=𝑘 𝑥 = 𝑘𝑡
𝑑𝑡
Relationship Between Half-life and Zero-order
Reactions
𝑎𝑡 𝑡 = 𝑡1 ,
2
𝑎
𝑥=
2
Substitute in 𝑥 = 𝑘𝑡 So
𝒂
= 𝒌𝒕𝟏
𝟐 𝟐
𝒂
𝒕𝟏 =
𝟐 𝟐𝒌
 thehalf-life depends on the initial concentration
of reactant and the rate constant.
First Order Reactions
 ratedepends on the concentration of a single
reactant raised to one
A ⟶. P
𝐴𝑡 𝑡𝑖𝑚𝑒 = 0 𝑎 0
𝐴𝑡 𝑡𝑖𝑚𝑒 = 𝑡 𝑎−𝑥 𝑥
dA 𝑑𝑥
R=− = = 𝑘(𝑎 − 𝑥)
𝑑𝑡 𝑑𝑡
This is known as the differential equation
describing first-order kinetics.
𝑎
𝑙𝑛 = 𝑘𝑡
𝑎−𝑥
 𝑎
𝑙𝑛 = 𝑘𝑡
𝑎−𝑥
 This is known as first-order integral law

2.203 𝑎
𝑘= 𝑙𝑜𝑔
𝑡 𝑎−𝑥
 Sometimes the integrated rate law in the following
form is also used:
2.203 𝑎 − 𝑥1
𝑘= 𝑙𝑜𝑔
𝑡2 − 𝑡1 𝑎 − 𝑥2
 where x1 and x2 are the amounts decomposed at times
t1 and t2 from the start.
Relationship Between Half-life and first order
reactions
At t1/2 x=a/2
𝑎
𝑙𝑛 = 𝑘𝑡
𝑎−𝑥

𝑙𝑛2 0.693
𝑡1 = =
2 𝑘 𝑘
This indicates that the half-life of a first-order
reaction is a constant and it is independent of
initial concentration.
 𝐝𝑨 𝒅𝒙
𝐑=− = =𝒌 𝒂−𝒙
𝒅𝒕 𝒅𝒕
𝑎
𝑙𝑛 = 𝑘𝑡
𝑎−𝑥

𝒂−𝒙
 Collision Theory of Reaction Rates
➢a chemical reaction takes place only by collisions
between the reacting molecules.
➢not all collisions are effective.
➢Only a small fraction of the collisions produces a
reaction.

The main conditions for a productive collision

(1)The colliding molecules must possess sufficient kinetic
energy greater than the activation energy, Ea, to cause
a reaction,
➢ Ea is the minimum energy necessary to cause a
reaction between the colliding molecules.
(2) The reacting molecules must collide with proper
orientation.
➢ The correct orientation is that which ensure direct
contact between the atoms involved in the breaking
and forming of bonds.
Accordingly, the reaction rate for the elementary process
is given by the expression.
𝑟𝑎𝑡𝑒 = 𝑓 × 𝑝 × 𝑧
where
✓ f = fraction of molecules which possess sufficient
energy to react;
✓ p = probable fraction of collisions with effective
orientations, and
✓ z = collision frequency
Effect of Increase of Temperature on Reaction Rate
➢Generally, an increase of temperature increases the rate
of reaction.
➢As a rule, an increase of temperature by 10°C doubles
the reaction rate.
Temperature Dependence of Reaction Rate and
Arrhenius Equation
➢We know that the kinetic energy of a gas is directly
proportional to its T.
➢as the T of a system is increased, more and more
molecules will acquire necessary energy greater that Ea
to cause productive collisions. This increases the rate of
the reaction.
➢In 1889, Arrhenius suggested as simple relationship
between the rate constant, k, for a reaction and the T of
the system.
𝑬𝒂
− 𝑬𝒂
𝒌 = 𝑨𝒆𝑹𝑻 or 𝒍𝒏 𝒌 = 𝒍𝒏 𝑨 −
𝑹𝑻
This is called the Arrhenius equation
✓A is an experimentally determined quantity,
✓T is the absolute temperature (in K), and
J
✓R is the ideal gas constant [R = 8.314 ].
K·mol
➢we can use the Arrhenius equation to calculate the
activation energy.
𝑘2 𝐸𝑎 𝑇2 − 𝑇1
ln =
𝑘1 𝑅 𝑇2 𝑇1
Limitations of the Collision Theory
➢The collision theory of reaction rates is logical and
correct.
It has been oversimplified and suffers from the following
weaknesses.
➢The theory applies to simple gaseous reactions only. It
is also valid for solutions in which the reacting species
exist as simple molecules.
➢The values of k calculated from the collision theory
expression (Arrhenius equation) agree with the
experimental values only for simple bimolecular
reactions. For reactions involving complex molecules,
the experimental ks are quite different from the
calculated values.
➢There is no method for determining the steric
effect (p) for a reaction whose rate constant has
not been determined experimentally.
➢Only the kinetic energy of the colliding molecules
contributes to the energy required for
surmounting the energy barrier. There is no
reason why the rotational and vibrational energies
of molecules should be ignored.
➢The collision theory doesnot account for the
cleavage and formation of bonds involved in the
reaction.
Transition State Theory
It overcomes the drawbacks of the simple collision
theory.
➢The transition state or activated complex theory
was developed by Henry Erying (1935).
➢The transition state theory assumes that simply a
collision between the reactant molecules does not
really causes a reaction.
➢During the collision, the reactant molecules form
a transition state or activated complex which
decomposes to give the products. Thus,
➢The potential energy of the
system undergoing reaction is
plotted against the reaction
coordinate (the progress of the
reaction).
➢The difference in the potential
energy between the reactants
and the activated complex is the
activation energy, Ea.
➢The reactants must have this
minimum energy to undergo the
reaction through the transition
state.
Exothermic reaction
Endothermic reaction
‫توزيع درجات مقرر الكيمياء العامة (‪)2‬‬
‫المقرر‪ 3 :‬ساعات معتمد‬
‫الدرجة الكلية‪ 100 :‬درجة‬
‫موزعين كالتالي‬
‫‪ 50‬درجة‬ ‫امتحان نهائي نظري‪:‬‬
‫‪ 18‬درجة‬ ‫امتحان مد ترم‪:‬‬
‫‪ 15‬درجة‬ ‫كويز منصة‪:‬‬
‫‪ 5‬درجات‬ ‫امتحان مدترم نظري العملي‪:‬‬
‫‪ 5‬درجات‬ ‫امتحان نهائي نظري العملي‪:‬‬
‫‪ 10‬درجات‬ ‫امتحاني نهائي عملي واعمال سنة‪:‬‬
 ‫قناة‬
‫التلجرام‬
 ‫جروب‬
‫التلجرام‬
‫لمتابعة‬
‫االمتحانات‬
‫وإعالن‬
‫النتجة‬
Second Order reaction
In a second-order reaction, the sum of the power in the rate law is equal to two.

 Two of the same reactants (A) combine in a single elementary step

2A ⟶ P
𝐴𝑡 𝑡𝑖𝑚𝑒 = 0 𝑎 0
𝐴𝑡 𝑡𝑖𝑚𝑒 = 𝑡 𝑎−𝑥 𝑥
𝑑𝑥 2
𝑅= =𝑘 𝑎−𝑥
𝑑𝑡
𝑥
= 𝑘𝑡
𝑎(𝑎 − 𝑥)
Relationship Between Half-life and second order reactions
1
t1 =
2 𝑘𝑎
 This inverse relationship suggests that as the initial concentration of reactant is
increased, there is a higher probability of the two reactant molecules
interacting to form product