CHM101

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CHM101

CHEMICAL KINETICS
LECTURER:
DR UNEGBU S.O.
WHAT IS CHEMICAL KINETICS
• The area of chemistry that concerns reaction rates and
the various factors that affect reaction rates is known
as chemical kinetics.The application of chemistry focus
largely on chemical reactions.
• A reaction is defined by its reactants and products
,whose identity must be learned by experiment .Once
the reactants and products are known .The equation
for the reaction can be written and balanced ,and
products are known ,the equation for the reaction can
be written and balanced and stoichiometric
calculations can be carried out.
SPONTANEITY:

• Another very important characteristic of a reaction is its spontaneity. Spontaneity refers to the
inherent tendency for the process to occur however, it implies nothing about speed. Spontaneous
does mean fast .There are spontaneous reactions that are so slow that no apparent reaction
occurs over a period of weeks.
• 2H2(g) + O2 (g) → 2H2O (I)
• The two gases can coexist indefinitely at 25∙C
• Again gaseous reactions :
• H2 (g) + CL2 (g) → 2HCL (g)
• N2 (g) + 3H2 (g) → 2NH3 (g).
• In addition, the process of changing diamond to graphite is spontaneous but its so slow that it is not
detectable.

• To be useful ,reactions must occur at a reasonable rate. Apart from understanding the
stoichiometry and thermodynamics of a reaction ,we must also understand the factors that govern
the rate of reaction.
• One of the main goals of chemical kinetics is to understand the steps by which a reaction takes
place. This series of steps is called the reaction mechanism.


REACTION RATES


• The reaction rate of a chemical reaction is defined as the change in concentration of a reactant or product per
unit time.
• The speed or rate of a process is defined as the change in a given quantity over a specific period of time.
• For chemical reactions,the quantity that changes is the amount or concentration of a reactant or product.

• Rate = Concentration of A at time T2—Concentration of A at time T1
• T2-T1

Rate= ∆ (A)/∆t
• Where A is the reactant or product being considered and the square bracket indicate concentration in mol/L,
the symbol ∆ indicates a change in a given quantity.

• Note that a change can be positive ( increase) or negative (decrease) thus leading to a positive or negative
reaction rate by this definition the rate as a positive quantity.
• Example
• The decomposition of nitrogen dioxide ,a gas that causes air pollution ,Nitrogen dioxide decomposes to nitric
oxide and oxygen as follows.
• 2N02(g) → 2NO(g) +O2(g).
• Now let us calculate the average rate at which the concentration of NO2 changes over the first 50 seconds of the
reaction using the data given.
• Change in (NO2)/Time elapsed = ∆ (NO2)/∆t

• =(NO2)t=50 - (NO2)t=0/50.s-0s

• 0.0079mol/L - 0.0100mol/L|50.s
GRAPH
• If you are to plot a graph of Time(s) V
concentration (mol/L)


• Note that since the concentration of NO2
decreases with time, ∆(NO2) is a negative
quantity ,because ,it is customary to work
with positive reaction rates .
TIME(S) V CONCENTRATION (mol)
12

10

0
1 2 3 4 5 6 7 8 9 10
We define the rate of this particular reaction as

• Rate= ∆ ( NO2)/∆t
• Since the concentration of reactants always decreases
with time any rate expression involving a reactant will
include a negative sign .The average rate of this
reactions from 0 to 50 seconds is then.

• Rate = ∆ (NO2)/∆t

• = -(-42 X 10-5 mol/L-s


• =4.2 X10-5 mol/L-s
CHEMICAL REACTIONS

• C hemical reactions are those changes in which some new chemical


substances are formed.
• The substances involved which undergo the chemical changes are
known as Reactant ,while the new substances formed are called
products.
• Chemical Reactions can be grouped in the following way.
• Reversible reaction
• Combination reaction
• Displacement reaction
• Double decomposition
• Catalytic reaction
• Thermal dissociation
• Oxidation and Reduction.

Reversible Reactions

• These are those reactions in which the direction of chemical changes can be reversed. Depending on the
reaction conditions the products formed may react to form the original reactants such reactions are
known as Reversible reactions.
• To represent the reversibility of a reaction in an equation the symbol === is used.
• For instance A + B ===== C + D
• The reaction between iron filings and steam is reversible under the same conditions since red heat is
needed for both the forward and the reverse reactions.
• 3Fe(s) + 4H20 (g) ==== Fe304 (s) + 4H2 (g).

• When excess carbon (IV) oxide is passed through lime water a milky suspense of insoluble calcium
trioxocarbonate (IV) is formed first.
• This disappear after some time owing to the formation of soluble calcium hydrogen trioxocarbonate (IV).If
this clear solution is heated ,the reverse reaction will take place and the milkiness will reappear . In this
case the forward reaction takes place in the cold,while the reverse reaction occurs only when heat is
supplied.
• CaC03(s) + H20 (I) +C02 (g) → Ca (HCO3)2 (aq).
• Milky suspension clear solution

• Ca(HC03)2 (aq) ------heat------------- CaC03 (S) + H20 + C02(aq).
• Clear soln. milky suspension

• CaC03(s) + H20(I) +C02 (g)===== Ca(HC03)2 (aq).
• If a reaction can not reversed when they occur the reaction is said to be irreversible.


FACTORS THAT AFFECT REACTION
RATE OF A CHEMICAL REACTION

• There are some factors that influence the


reaction rate.We can measure the rate of a
chemical reaction by measuring either (1)How
quickly a reactant is consumed (2) How
quickly a product is formed ,therefore the rate
of a reaction is the change in concentration of
a reactant or a product over a certain period
of time.
CONCENTRATION OF A REACTANT OR A PRODUCT VS
TIME
7

4
concn

0
1 2 3 4 5 6 7
Time (s)
COLLISION THEORY OF CHEMICAL KINETICS

• Chemical reactions only happen when the


reactant molecules collide with one another
.This is known as the collision theory of
chemical kinetics,which states that in order for
a reaction to happen ,the reactants must
collide with sufficient energy that is greater
than the activation energy ( Ea). Factors that
affect reaction rates are as follows:
THE NATURE OF THE REACTANTS

• In an aqueous solution chemical reactions take place almost immediately.It is


because the molecular bonds in the molecules of reactants are broken down.The
attractive forces beween the ions are broken and ions become hydrated by the
water molecules .
• In addition,most ions exert attractive forces equally in all directions .Usually,no
covalent bonds need to be broken in these cases.
• In contrast reactions between molecules that require covalent bonds to be broken
tend to proceed very slowly .Therefore certain structural characteristics of the
reactant molecules ,such as bond,polarity,geometry,overall,size and orientation
influence the rate of reaction.


• Ionic bond
• Na---------------CL
• ↓
• Na+ CL-

The Concentration of the Reactants:

• For most reactants,the rate of reaction will increase as


the concentration of the reactants increases.
• For many reactions,there is a direct relationship
between the concentration and rate of reaction .
Therefore ,when the concentration doubles,the rate of
reaction also doubles.
• If we double the number of reactant molecules,there
will be twice as many collisions occurring at the same
time.
GRAPH OF HOW CONCENTRATION AFFECTS REACTION
RATE
4.5

3.5

3
Reaction Rate

2.5

1.5

0.5

0
1 3 6
Concentration
TEMPERATURE

• The rate of a reaction increases with increasing


temperature .Each time the temperature is
increased by 10’C,the rate of reaction
doubles.The collision theory explained that the
average kinetic energy of all molecules is a direct
function of the temperature.The molecules
collide with a greater energy that is,their
activation energy decreases.

GRAPH OF EFFECT OF TEMPERATURE

1.2

0.8
Reaction Ratee

0.6

0.4

0.2

0
3 6
Temperature
The Presence of a catalyst

• A catalyst is a substance that increases the rate of


reaction without actively participating in the reaction.
Catalysts work by providing an alternate pathway for
the reaction.The presence of catalyst increases the
reaction rate. It speeds up the reaction rate. For
examples catalysts
• Iron used as a catalyst for the synthesis of ammonia
from nitrogen and hydrogen through the Haber
process.
• Zeolites, commonly used as catalysts for organic
reactions such as petroleum cracking and the synthesis
of hydrocarbons.Biocatalysts like proteins and enzymes
END
• There are other factors that can influence the
reaction rates,but we have looked these major
ones.

• Thank you.

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