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Factors affecting rate of reaction

• CONCENTRATIONS OF REACTANTS:
Reaction rates generally increase as the
concentrations of the reactants are increased.

• TEMPERATURE:
Reaction rates generally increase rapidly as
the temperature is increased.

• CATALYSTS:
Catalysts speed up reactions.

• PARTICLE SIZE:
The rate increases as the smaller the size of
reacting particles .
A) CONCENTRATIONS OF REACTANTS

Reaction rate ∝ collision


time
• The frequency of collision increases increases with the
concentration

4 particle system
(2 and 2)  4 collision
A) CONCENTRATIONS OF REACTANTS
• A concentration of reactants increases, the frequency
of collision increases.
• This would also result in the increase in the quantity of
effective collision. Thus the reaction rate increases.
5 particle system
(3 and 2)  6 collision
A) CONCENTRATIONS OF REACTANTS
• This observation correlates with the RATE LAW that has
been previously discussed…
x y
Reaction rate = k [ A ] [ B ] …
(A & B = reactants)
(x & y = rate order)

• Based on this equation,


Reaction rate ∝ concentration of reactants
(depending on its rate order)
• REMINDER!
Only in zero order reactions, the rate of reaction is not
dependant upon the concentration of the reactants.
Reaction rate = k [ A ]0 = k (constant)
B) TEMPERATURE

• As temperature increases, kinetic energy, of


molecules increases
• So, more collisions occur in a given time
• Furthermore, the higher the kinetic energy, the
higher the energy of the effective collisions.
• So more molecules will have energy greater
than activation energy, Ea
• Thus, the rate of reaction increases
Distribution of Kinetic Energies of Molecules

Represent total number of molecules


with kinetic energy greater than Ea
B) TEMPERATURE
ARRHENIUS EQUATION
• In 1889, Svante Arrhenius proposed the following
mathematical expression for the effect of temperature on
the rate constant, k:

-E a∕
k = Ae RT
Where…
k = rate constant
A = constant known as the collision frequency factor
e = natural log exponent
Ea = activation energy for the reaction
R = universal gas constant (8.314 J mol-1 K-1 )
T = absolute temperature
B) TEMPERATURE
ARRHENIUS EQUATION
• The relation ship between the rate constant, k and
temperature can be seen in the k vs T graph:

-E a∕
k = Ae RT

1/T (K-1 )
B) TEMPERATURE

ARRHENIUS EQUATION - DERIVATION


• The relationship between k and T is clearer when
we further derive the Arrhenius Equation…

−E a
k = Ae RT
−E a
Natural log both ends…
ln k = ln( A.e RT
)
−Ea
ln k = ln A + ln( e RT )
− Ea
ln k = ln e + ln A (But ln e = 1)
RT
− Ea 1
Thus… ln k = ( ) + ln A
R T
See the linear relationship…? y = m x+ C
B) TEMPERATURE
Graph Representation Of The Arrhenius Equation
• Plotting a ln k vs 1/T graph would show a clearer
relationship between k (Rate constant) and temperature

− Ea 1
ln k = ( ) + ln A
R T

Where,
Ea = Activation Energy
R = 8.314 Jmol-1 K-1
T = Absolute Temp
A = Collision freq. factor
B) TEMPERATURE
• If the value of A (collision frequency factor) is not known and the same reaction
conducted at two different temperatures.The Arrhenius equation at each temperature
can be written and combined to formed the equation shown in the box.

− Ea 1 − Ea 1
ln k1 = ( ) + ln A ln k 2 = ( ) + ln A
and R T2
R T1
Rearranging the equations would give…
Ea 1 Ea 1
ln k1 + ( ) = ln A ln k 2 + ( ) = ln A
R T1 R T2
Since “A” is a constant…
E 1 E 1
ln k1 + a ( ) = ln k 2 + a ( )
R T1 R T2 k1 Ea 1 1
ln = ( − )
Ea 1 Ea 1 k2 R T2 T1
ln k1 − ln k2 = ( )− ( )
R T2 R T1
Exercise: the Activation energy
The decomposition of hydrogen iodide,
2 HI (g)  H2(g) + I2(g)
has rate constants of 9.51 x 10-9 L mol-1 s-1 at 500 K and
1.10x10-5 L mol-1 s-1 at 600 K. Find Ea.

DATA: k1 = 9.51 x 10-9 L mol-1 s-1 T1 = 500K


k2 = 1.10 x 10-5 L mol-1 s-1 T1 = 600K
SOLUTION:
k1 Ea 1 1
ln = ( − ) 1.10 × 10 −5 1 1 −1
k2 R T2 T1 Ea = −(8.314) ln( −9
)( − )
9.51× 10 600 500
k1 1 1
Ea = −R ln( )( − ) −1
k 2 T2 T1
Ea = 1.76 x 105 J/mol = 176 kJ/mol
C) CATALYST

• A catalyst is a substance that increases the rate of a


chemical reaction without itself being consumed.
• Addition of a catalyst increases the reaction rate by
increasing the frequency of effective collision. That is by
– Decreasing the Ea, and
– Correct orientation
C) CATALYST
• Addition of a catalyst changes the value of k (rate
constant) .

x y
Reaction rate = k [ A ] [ B ]
(A & B = reactants)
(x & y = rate order)

• The catalyst reacts by reducing the Ea and increasing A,


thus increasing the k.

− Ea 1
ln k = ( ) + ln A
R T
C) CATALYST
• When Ea decreases, k increases,
REACTION RATE increases

rateuncatalyzed < ratecatalyzed

uncatalyzed catalyzed

Ea > E’a
Reaction pathway
D) PARTICLE SIZE

The smaller the size of reacting particles, the greater is


the total surface area exposed for reaction and
consequently the faster the reaction. In the case of
heterogeneous systems, in which the reactants are in
different phases, the area of contact between the reacting
substances will influence the reaction rate considerably.

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