CHEMICAL KINETICS Mr.

Mutie Joseph

CHAPTER TWO
CHEMICAL KINETICS
• Chemical kinetics is the branch of physical chemistry which deals with the study of the rate of
chemical reactions.
• Such studies enable us to elucidate the mechanism by which a reaction occurs.
• Kinetics include:
− The rate of the reactions and rate laws
− The factors as temperature, pressure, concentration and catalyst that influence the rate of a
reaction.
− The mechanism or the sequence of steps by which a reaction occurs.
Reaction rate
• Rate, speed or velocity of a reaction has the same meaning in chemical kinetics.
• The rate of reactions is defined as the change in concentration of any of reactant or product per
unit time.
A→B
• Rate of reaction = rate of disappearance of A = rate of appearance of B
−𝑑[𝐴] 𝑑[𝐵]
Rate = =
𝑑𝑡 𝑑𝑡
In general, for the reaction of the type
aA + bB → mM + nN
−1 𝑑[𝐴] −1 𝑑[𝐵] 1 𝑑[𝑀] 1 𝑑[𝑁]
Rate = = = =
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑚 𝑑𝑡 𝑛 𝑑𝑡

Example
Butane, C4H10 burns in oxygen to give CO2 and H2O according to the following equation.
CHEMICAL KINETICS Mr. Mutie Joseph

2C4H10 (g) + 13O2 (g) → 8CO2(g) + 10H2O(g)

If at a certain moment the butane is reacting at a rate of -0.20 mol L-1S-1, calculate the rate at which
oxygen is being consumed and the rates at which the products are formed.
Solution
This is basically a simple stoichiometry problem, because the magnitude of the rates are related to
each other by the coefficients in the balanced equation.
−1 𝑑[C4H10] −1 𝑑[O2] 1 𝑑[CO2] 1 𝑑[H2O]
Rate = = = =
2 𝑑𝑡 13 𝑑𝑡 8 𝑑𝑡 10 𝑑𝑡

−1 𝑑[O2] −1 𝑑[C4H10]
=
13 𝑑𝑡 2 𝑑𝑡

−1 𝑑[O2] −1 𝑑[C4H10]
=
13 𝑑𝑡 2 𝑑𝑡
𝑑[O2] −1 𝑑[C4H10] −13 13 𝑑[C4H10]
= × =
𝑑𝑡 2 𝑑𝑡 1 2 𝑑𝑡
𝑑[C4H10]
But, = -0.20 mol L-1S-1
𝑑𝑡
𝑑[O2] 13
= (-0.20 mol L-1S-1)
𝑑𝑡 2
𝑑[O2]
= -1.3 mol L-1S-1
𝑑𝑡
−𝑑[O2]
Rate at which oxygen is being consumed, = -1.3 mol L-1S-1
𝑑𝑡
1 𝑑[CO2] −1 𝑑[C4H10]
=
8 𝑑𝑡 2 𝑑𝑡
𝑑[CO2] −1 𝑑[C4H10] 8
= ×
𝑑𝑡 2 𝑑𝑡 1
𝑑[CO2] −8 𝑑[C4H10]
=
𝑑𝑡 2 𝑑𝑡
𝑑[CO2] −8
= (-0.20 mol L-1S-1)
𝑑𝑡 2
𝑑[CO2]
= 0.8 mol L-1S-1
𝑑𝑡
CHEMICAL KINETICS Mr. Mutie Joseph

1 𝑑[H2O] −1 𝑑[C4H10]
=
10 𝑑𝑡 2 𝑑𝑡
𝑑[H2O] −10 𝑑[C4H10]
=
𝑑𝑡 2 𝑑𝑡
𝑑[H2O] −10 𝑑[C4H10]
=
𝑑𝑡 2 𝑑𝑡
𝑑[H2O] −10
= (-0.20 mol L-1S-1)
𝑑𝑡 2
𝑑[H2O]
= 1.0 mol L-1S-1
𝑑𝑡
Since the product concentrations are increasing with time, their rates are expressed as positive
quantities. Therefore, rate of formation of CO2 = +0.80 mol L-1S-1
Rate of formation of H2O = +1.0 mol L-1S-1
EXAMPLE
The following data were collected for the reaction below at a temperature of 530oC
CH3CHO → CH4 + CO
Time (s) [CH3CHO] (mol/L
0 0.2
20 0.153
40 0.124
60 0.104
80 0.09
100 0.079
120 0.07
140 0.063
160 0.058
180 0.053
200 0.049
By the means of a suitable graph, determine the rate of CH3CHO at t = 50 seconds and at t = 130
seconds
CHEMICAL KINETICS Mr. Mutie Joseph

0.25

0.2
Concentration

0.15

0.1

0.05

0
0 50 100 150 200 250
Time (s)

Rate = -slope

Reaction Order and rate constant

• The rate of a reaction depends on concentration of reactants.
• For the general reaction: aA + bB → cC + dD,
Rate α [A]x [B]y

Rate law = k[A]x [B]y

• Where [A] and [B] are the concentration of reactants remaining after time t.
• The reaction order is;
x - with respect to reactant A.
y -with respect to reactant B
x+y – overall order is the sum of the powers
• The order of a reaction tells us the exact dependence of rate on concentration. It is a constant which
can only be determined experimentally.
• From the above relationship we obtain the rate equation
Rate law = k[A]x [B]y
CHEMICAL KINETICS Mr. Mutie Joseph

Where k is a constant of proportionality called the rate constant. This is also known as the velocity
constant.
The rate constant, k is a number which depends on the temperature only and not on the
concentration.
Examples
1. The following data were obtained for the reaction of (CH3)3CBr with hydroxide ion at 55oC.
(CH3)3CBr + OH− → (CH3)3COOH + Br−

Initial concentration (mol L-1) Initial rate of formation of

[(CH3)3CBr] [OH ]− (CH3)3COOH (mol L-1S-1)
0.10 0.10 1.0×10-3
0.20 0.10 2.0×10-3
0.30 0.10 3.0×10-3
0.10 0.20 1.0×10-3
0.10 0.30 1.0×10-3
What is the rate law for this reaction and what is the value of the rate constant?
Solution
Rate = k[(CH3)3CBr]x[OH−]y
1.0×10-3 = k (0.1)x (0.1)y
2.0×10-3 = k (0.2)x (0.1)y
2.0×10−3 𝑘(0.2)𝑥 (0.1)𝑦
=
1.0×10−3 𝑘(0.1)𝑥 (0.1)𝑦
0.2 𝑥
2=( )
0.1
2x = 2
x=1

1.0×10-3 = k (0.1)x (0.3)y

1.0×10-3 = k (0.1)x (0.2)y
1.0×10−3 𝑘(0.1)𝑥 (0.3)𝑦
=
1.0×10−3 𝑘(0.1)𝑥 (0.2)𝑦
0.3 𝑦
1=( )
0.2
3 𝑦
1=( )
2
3
Log101 = y Log10( )
2
log 1
y= 3 =0
log(2)
CHEMICAL KINETICS Mr. Mutie Joseph

Rate = k[(CH3)3CBr]1 [OH−]0

Rate = k[(CH3)3CBr]
k = Rate / [(CH3)3CBr]
1.0×10−3
k=
0.1
k = 10×10-3 S-1
k = 1.0×10-2 S-1
Rate = 0.01 [(CH3)3CBr]
Where k = rate constant

2. The following data were measured for the reduction of nitric oxide with hydrogen
2NO (g)+ 2H2 (g) → N2 (g) + 2H2O (g)
Initial concentration (mol L-1) Initial rate of formation of
[NO] [H2] (CH3)3COOH (mol L-1S-1)
0.10 0.10 1.23×10-3
0.10 0.20 2.46×10-3
0.20 0.10 4.92×10-3
Solution
Rate = k [NO]x [H2]y
1.23×10-3 = k(0.10)x (0.10)y
2.46×10-3 = k(0.10)x (0.20)y

2.46×10−3 k(0.10)x (0.20)y

=
1.23×10−3 k(0.10)x (0.10)y
y
2=2
y=1

1.23×10-3 = k(0.10)x (0.10)y

4.92×10-3 = k(0.20)x (0.10)y
4.92×10−3 k(0.20)x (0.10)y
=
1.23×10−3 k(0.10)x (0.10)y
4 = 2x
x=2

3. A series of experiments was carried out to determine the initial rate of reaction for various
concentrations of compound A. The following data were obtained.

Concentration of compound A (mol dm-3) Initial rate (mol dm-3s-1)

0.060 3.12 × 10-4
0.120 6.23 × 10-4
0.180 9.38 × 10-4
0.240 12.5 × 10-4
CHEMICAL KINETICS Mr. Mutie Joseph

From the data in the table, deduce the order of reaction with respect to compound A.
Explain your reasoning
Solution
Doubling the concentration of A, the rate also doubled hence the order of the reaction with
2
respect to A is one i.e =1
2
4. In an investigation of the recombination of X atoms to give X2 molecules in the gas phase in the
presence of argon, that is the reaction X + X + Ar → X2 + Ar the following data were obtained.
With the concentration of argon fixed at 1.0×10-3 mol dm-3
Concentration [X] (mol dm-3) 𝑑[𝑋2 ]
Initial rate (mol dm-3s-1)
𝑑𝑡
1.0×10-5 8.70 × 10-4
2.0×10-5 3.48 × 10-3
4.0×10-5 1.39 × 10-2

With the concentration of X fixed at 1.0×10-5 mol dm-3

Initial concentration [Ar] (mol dm-3) 𝑑[𝑋2 ]
Initial rate (mol dm-3s-1)
𝑑𝑡
1.0×10-3 8.70 × 10-4
5.0×10-3 4.35 × 10-3
-2
1.0×10 8.69 × 10-3
Find the order of reaction with respect to [X] and [Ar], hence determine the overall velocity
constant for the formation of X2 molecules
Solution
Keeping the concentration of argon constant; doubling the concentration of X, the rate
4
increases four times hence the order of reaction with respect to X is 2= 2.
Keeping the concentration of X atoms constant; increasing concentration of Ar 5 times, the
5
rate also increases five times hence the order of reaction with respect to Ar is 5= 1.
Rate equation is given by; Rate = k [X]2 [Ar]
8.70 ×10-4 = k (1.0×10-5)2 (1.0×10-3)
8.70 ×10−4 mol dm−3 s−1
K= −3
(1.0×10−5 moldm−3 )2 (1.0×10−3 moldm )

K = 8.7×109 dm6mol-2s-1

Factors Affecting Rate of a Reaction

(i) Concentration
• A reaction may go faster when the concentration of one or more of the reactants increases. Such
an increase in concentration increases the number of reactants per unit volume.
• Because molecules are closer together, the number of collisions per unit time increases.
CHEMICAL KINETICS Mr. Mutie Joseph

• As total collisions increase, the number of molecules that have the orientation and energy required
for the reaction also increases.
• However, the fraction of effective collisions remains the same, because the temperature and kinetic
energy are constant.
• As reaction proceeds, the concentration of the reactants must inevitably decrease and hence its rate
must also progressively decrease.
• Thus, rate of a reaction will depend on the stage of progress of the reaction. The nearer it is to the
end stage, the slower its rate will be.
(ii) Intimacy of reactants
• The rate of a reaction is increased by bringing the reactants into more intimate contact.
• This is particularly marked in reaction between solids where the state of subdivision and
thoroughness of mixing are important.
• When metals are finely powdered, they are often much more reactive owing to their greatly
increased surface area.
• Liquids of different densities often react together only slowly, especially when they are
immiscible, unless continually stirred or shaken.
• Similarly it is found worth in some industrial processes to use elaborate devices to ensure thorough
mixing of gases with liquids,e.g in the solvay process for making sodium carbonate.
• The catalysts used in heterogeneous reactions, such as hydrogenation are often prepared by
chemical means in a special condition of extreme sub-division, so that the largest possible surface
area of the metal is exposed to the reacting gases.
• Similarly, it is the large surface area of metals in the colloidal condition which accounts for their
efficiency as catalysts.

(iii) Ionic strength of solutions

• Presence of non-reactive ions in a reaction mixture increases its ionic strength.
• Such increase in ionic strength of a solution restricts freedom of movement of all ions in the
solution including the reacting ions.
• As a consequence, the rate of reaction decreases on increasing ionic strength of a solution.

(iv) Isotopic composition of a reactant

• Some isotopes of an element are considerably heavier than others.
• Thus, replacement of ordinary hydrogen atoms by deuterium in a low molecular weight substance
like CH4 considerably reduces mobility of a molecule.
• Its reactivity also decreases proportionately.
• Heavy water reacts slower than ordinary water.

(v) Reaction aids

• Many reactions proceed faster in presence of a catalyst.
CHEMICAL KINETICS Mr. Mutie Joseph

• Some may take place faster under the influence of light or electricity or any other energy providing
aid.

EFFECT OF TEMPERATURE ON REACTION RATE

The rate of a chemical reaction is increased by raising the temperature and the rate constant for a
reaction is only a constant at a fixed temperature.
According to kinetic theory, an increase in temperature will increase molecular motion and raise
the rate of intermolecular collisions.
The variation of rate or rate constant of a reaction with temperature belongs to one of the five
forms shown below.

• Type I curve is obtained for most of the reactions.

• Type II curve is obtained for explosion. In this curve, a sudden rise in the rate of the reaction is
shown. This happens at the ignition temperature.
• Type III of curve is obtained in catalytic hydrogenations and in enzyme reactions.
• Type IV is obtained when carbon is oxidized.
• Type V is obtained only for the reaction:
2NO + O2 → 2NO2
− This is the only reaction which exhibits a negative temperature coefficient.

Type I corresponds to the curves as given by Arrhenius relating variation of rate constant with
temperature. Hence this is known as Arrhenius temperature dependence while type II to V are
referred to as anti-Arrhenius curves.
According to Arrhenius, a molecule would only react on collision if it had higher energy than
the average energy i.e if it was activated with the necessary energy for reaction to occur, being
known as the activation energy. Hence the activation energy (Ea), is the factor which links rate
constant with temperature.
CHEMICAL KINETICS Mr. Mutie Joseph

Arrhenius proposed the equation given below which relates temperature and rate constants.
−𝐸𝑎
k = A𝑒 𝑅𝑇 …………………(i)
k denotes the rate constant of the reaction
A denotes the pre-exponential factor or frequency factor which in terms of collision theory is the
frequency of correctly oriented collisions between the molecules that have sufficient energy to
spark a chemical reaction. The value of A must be determined experimentally since it assumes
different values for different reactions.
e is the base of the natural logarithm (Euler’s number).
Ea denotes the energy of activation or threshold energy for the reaction. It is the energy which the
reacting molecules must possess above the average molecular energy, per mole of molecules.
R denotes the universal gas constant.
T denotes the reaction temperature on Kelvin scale (K).
−𝑬𝒂
𝒆 𝑹𝑻 denotes the exponential or the activation energy factor. This counts for the fraction of the
molecules present in a gas which have energies equal to or excess of activation energy at a
particular temperature.
RT denotes the average kinetic energy

The equation (i) can also be written as;

𝐸𝑎 1
In k = In A - ………………….(ii)
𝑅 𝑇
−𝐸𝑎 1
Graphical form In k = ( ) (𝑇) + In A
𝑅
y= mx + c

𝐸𝑎 1
Log k = Log A -
2.303𝑅 𝑇
CHEMICAL KINETICS Mr. Mutie Joseph

THE ENERGY OF ACTIVATION

The molecules must acquire a certain amount of energy before they could undergo chemical
reaction. This means that for a chemical reaction to occur the molecules must be activated i.e they
must be raised to a higher energy state. The minimum energy that the reacting molecules must
possess before a reaction can occur is known as the energy of activation.
The reacting molecules must acquire sufficient energy to cross an activation energy barrier.

Effect of temperature on the number of activated molecules

Rise in temperature increases the number of activated molecules much more than the number of
molecules with average energy
The temperature change which doubles the number of molecules with average energy will increase
the fraction of activated molecules by more than hundreds. That is why increase in temperature
has such a marked effect on reaction rate.

THE POTENTIAL ENERGY DIAGRAM

CHEMICAL KINETICS Mr. Mutie Joseph

How Arrhenius equation account for catalysts

The function of a catalyst is to lower the activation energy required by a reaction.

Therefore, the lowered activation energy (accounted for by the catalyst) can be substituted into the
Arrhenius equation in order to obtain the rate constant for the catalyzed reaction.
−𝐸𝑎
The exponential part of the equation ( 𝑅𝑇 ) accounts for an exponential increase in the value of the
rate constant for any decrease in the activation energy. Since the rate of a chemical reaction is
directly proportional to the rate constant of that reaction, the decrease in activation energy results
in an exponential increase in the reaction rate.
The rates of uncatalyzed reactions are more severely affected by temperature than the rates of
catalyzed reactions. This is because the activation energy is in the numerator of the exponential
−𝐸𝑎
term 𝑅𝑇 and the absolute temperature in the denominator. Since the activation energy of the
catalyzed reaction is relatively low, the effect of temperature on the rate constant is more visible
in the corresponding uncatalyzed.

Eliminating the A factor from the Arrhenius equation

The activation energy can also be calculated directly given two known temperatures and a rate
constant at each temperature. Using Equation (ii), suppose that at two different temperatures
T1 and T2, reaction rate constants k1 and k2:
𝐸𝑎 1
In 𝑘1 = In A - ………………….(iii)
𝑅 𝑇1
𝐸𝑎 1
In 𝑘2 = In A - …………………..(iv)
𝑅 𝑇2
Subtracting equation (iii) from (iv)
𝐸𝑎 1 𝐸𝑎 1
In 𝑘2 - In 𝑘1 = (In A − 𝑅 𝑇 ) - (In A − 𝑅 𝑇 )
2 1
𝐸𝑎 1 𝐸𝑎 1
In 𝑘2 - In 𝑘1 = In A - - In A +
𝑅 𝑇2 𝑅 𝑇1
CHEMICAL KINETICS Mr. Mutie Joseph

𝐸𝑎 1 𝐸𝑎 1
In 𝑘2 - In 𝑘1 = -
𝑅 𝑇1 𝑅 𝑇2
K2 Ea 1 1
In(
K1
)= R
(T − T )
1 2
Similarly
𝐸𝑎 1
Log 𝑘1 = Log A -
2.303𝑅 𝑇1
𝐸𝑎 1
Log 𝑘2 = Log A -
2.303𝑅 𝑇2
𝐸𝑎 1 𝐸𝑎 1
Log 𝑘2 - Log 𝑘1 = (Log A − 2.303𝑅 𝑇 ) - (Log A − 2.303𝑅 𝑇 )
2 1
𝐸𝑎 1 𝐸𝑎 1
Log 𝑘2 - Log 𝑘1 = -
2.303𝑅 𝑇1 2.303𝑅 𝑇2
K2 Ea 1 1
Log(
K1
) = 2.303R (T − T )
1 2

EXAMPLES
1. For the decomposition of acetone dicarboxylic acid k = 2.46×10-5 s-1 at 273 K and 1.63×10-3 s-1 at
303K. Calculate the energy of activation of the reaction (R = 8.314 JK-1mol-1)
Solution
K2 Ea 1 1
Log(
K1
) = 2.303R (T − T )
1 2
K2 Ea 𝑇2 −𝑇1
Log( )= (𝑇𝑇 )
K1 2.303R 1 2
1.63×10−3 Ea 𝑇 −𝑇
Log(
2.46×10−5
) = 2.303R ( 𝑇2 𝑇 1 )
1 2
1.63×10−3 Ea 303−273
Log( ) = 2.303×8.314 (273×303)
2.46×10−5
1.63×10−3 Ea 30
Log( ) = 2.303×8.314 (273×303)
2.46×10−5
1.63×10−3 273×303
Log( ) × (2.303)(8.314)× ( ) = Ea
2.46×10−5 30
Ea = 96151.96Jmol-1 or 96.15 KJmol-1

2. The gas-phase reaction methane (CH4) and diatomic Sulphur (S2) is given by the equation
CH4 (g) + 2S2 (g) → CS2 (g) + 2H2S (g)
At 550oC the rate constant for this reaction is 1.1 Lmol-1 s-1 and at 625oC the rate constant is 6.4
Lmol-1 s-1. Calculate Ea for the reaction.
Solution
K2 Ea 1 1
In(
K1
)= R
(T − T )
1 2
T1 = 550 + 273 = 823 K
T2 = 625 +273 = 898 K
CHEMICAL KINETICS Mr. Mutie Joseph

6.4 Ea 1 1
In(
1.1
) = 8.314 (823 − 898)
6.4
8.314 × In(1.1)
Ea = 1 1 = 144271.7 J/mol or 1.44×105 J/mol
(823 − 898)
3. For the isomerization of cyclopropane to propene

The following data were obtained

T,oC 477 523 577 623
k, s-1 0.00018 0.0027 0.030 0.26
Calculate the activation energy and comment on the answer obtained
Solution
T (K) 750 796 850 896
1 -1 -3 1.33 1.26 1.18 1.12
(k ×10 )
𝑇
In k, s -8.62 -5.91 -3.51 -1.35

Comment: This activation energy is high, which is not surprising because a carbon-carbon bond
must be broken in order to open cyclopropane ring. (C-C bond energies are typically around 350
KJ/mol). This is why reaction must be carried out at high temperature.
CHEMICAL KINETICS Mr. Mutie Joseph

4. The table below gives values for the velocity constant k, of the reaction between potassium
hydroxide and bromoethane in ethanol at a series of temperature, T
K (dm3mol-1s-1) T (k)
0.182 305.0
0.466 313.0
1.35 323.1
3.31 332.7
10.2 343.6
22.6 353.0
Calculate the value for the activation energy of the reaction (R = 8.31 JK-1mol-1)
1
𝑥 = (k-1×10-3) 3.28 3.19 3.10 3.01 2.91 2.83
𝑇
y= In k, s -1.70 -0.76 0.30 1.20 2.32 3.12

5. The rate constant for the reaction H2 (g) + I2 (g) → 2HI (g) is 5.4 ×10-4 m-1s-1 at 326oC. At 410oC
the rate constant was found to be 2.8 ×10-2 m-1s-1 calculate the
a) Activation energy (R = 8.314 JK-1mol-1)
b) High temperature limiting rate constant for this reaction.
Solution
CHEMICAL KINETICS Mr. Mutie Joseph

K2 Ea 1 1
a) In(
K1
)= R
(T − T )
1 2
T1 = 326 + 273 = 599 K
T2 = 410 +273 = 683 K
2.8 ×10−2 Ea 1 1
In(
5.4 ×10−4
) = 8.314 (599 − 683)
2.8 ×10−2
8.314 × In( )
5.4 ×10−4
Ea = 1 1 = 159881.5592 J/mol
(599 − 683)
b) Now that we know Ea, the pre-exponential factor A (which is the largest rate constant that the
reaction can possibly have) can be evaluated from any measure of the absolute rate constant of the
reaction.
𝐸𝑎 1
In k = In A -
𝑅 𝑇
-4 159881.5592
In 5.4 ×10 = In A -
8.314 𝑥 599
-7.523941418 = In A – 32.10417635
In A = 24.58023493
A = 4.732170618 x 1010
The infinite temperature rate constant is 4.732170618 x 1010 M-1S-1

6. The variation of the rate constant with temperature for the first order reaction
2N2O5 (g) → 2N2O4 (g) + O2 (g) is given in the table below
T (k) K (s-1)
298 1.74 × 10-5
308 6.61 × 10-5
318 2.51 × 10-4
328 7.59 × 10-4
338 1.40 10-3
a) Determine graphically the activation energy of the reaction
b) pre-exponential frequency factor
c) activation energy factor (exponential factor) at 298K
d) the average kinetic energy at 298 K
Solution
a)
1
𝑥 = (k-1×10-3) 3.36 3.25 3.14 3.05 2.96
𝑇
y= In k, s -10.96 -9.62 -8.29 -7.18 -6.03

−𝐸𝑎
= slope
𝑅

−𝐸𝑎
= -12.995×103
8.314
CHEMICAL KINETICS Mr. Mutie Joseph

Ea = 108040.43 J/mol or 108.04043 × 103

𝐸𝑎 1
b) In k = In A -
𝑅 𝑇
108.04043×103
-10.96 = In A - × 3.36×10-3
8.314

-10.96 = In A -43.6632
In A = 32.7032
A = 1.595215279×1014

c)
−Ea
Activation energy factor = e RT

−108.04043×103
=e 8.314 x 298
= e-43.60738255
= 1.15227x 10-19
d)
The average kinetic energy = RT
= 8.314 x 298
=2477.572 J/mol

7. The values of (log10 k)×1000 for the reaction 2NO2 → 2N2 +O2 are 4.064 and 3.575 at 1125 K and
1085 K respectively. Calculate the energy of activation for the reaction (R = 8.314 Jmol-1K-1.
Solution
log10 k1 × 1000 = 4.064
4.064
log10 k1 = 1000
𝐾1 = 1.0094 at 1125K (𝑇1 )
log10 k2 × 1000 = 3.575
3.575
log10 k2 = 1000
𝐾2 = 1.0083 at 1085K (𝑇2 )
K2 Ea 1 1
Log(
K1
) = 2.303R (T − T )
1 2
K2 Ea 𝑇2 −𝑇1
Log( )= (𝑇𝑇 )
K1 2.303R 1 2
1.0083 Ea 1085−1125
Log( ) = 2.303 x 8.314 (1085 𝑥 1125)
1.0094

Ea −40
-4.7353 × 10-4 = (
19.147142 1220625
)
Ea = 276.6774 J/mol
CHEMICAL KINETICS Mr. Mutie Joseph

Importance of studies of the effect of temperature on rates

• Temperature has pronounced effect on the complex biological and chemical processes that take
place in plants and animals. For example, the influence of temperature on rate of respiration is
important in medicine. During some surgical operations, patients are cooled to slow down
metabolic rate, the rate of blood circulation and the rate of respiration.
• Temperature also has a pronounced effect on the biochemical processes that take in food when it
is stored or cooked. The rate of food decomposition can be slowed down by various methods,
including freezing, the use of preservatives such as sorbic, sulphur dioxide and nitrite and by
suitable storage. For example, the freshness and flavour of tea depends on a number of chemicals
including a group called the theaflavins on storage. The theaflavin content steadily decreases. The
rate of loss of theaflavins is affected about equally by moisture and temperature.
(Theaflavins are a group of molecules that are found in black tea that are said to be the bio actives
of black tea)
• The optimum efficiency of many industrial chemical processes depends on temperature. The
second stage of the contact process for the manufacture of sulphuric acid is one example.
2SO2 (g) + O2 (g) → 2SO3 (g) ∆Ho = -192 KJ mol-1
Since the reaction is exothermic the yield of sulphur trioxide can be increased by lowering the
temperature.

Applications of Chemical Kinetics to Deterioration of Foods

1. Deterioration of foods
Prediction of the change in quality of a particular food as a function of both time and environmental
conditions. This information is needed by those in the food industry so that they can;
(i) Evaluate the effect of the condition of new ingredients or additives on shelf life.
(ii) Set an open date for the food on the package so that consumers are better informed in the
handling of products.
2. Chemical kinetics help us understand the human body (enzymes & catalysts)
3. Chemical kinetics has wide applications in heterogeneous catalysis
4. The optimization of practical processes such as combustion, catalysis, battery technology,
polymerization and nanoparticle production can profit from a sound knowledge of the underlying
fundamental chemical kinetics.