Sitarambhai Naranji Patel: Chemical Engineering Department

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CHEMICAL ENGINEERING DEPARTMENT
CRE-I (Assignment with Question and Answer)
Q-1. Discuss the classification of chemical reaction based on thermodynamics and
stoichiometry with suitable examples of each.
Solution: Classification of chemical reaction

1. Chemical reaction may be classified depending upon the number of phases involved as
homogenous and heterogenous reactions.
Homogenous reaction is one which takes place in only one phase, i.e., all the reactant
materials, product and catalysts (if any) will all be present within a single phase (one
phase).
Examples:
(i) Oxidation of nitrogen oxide to nitrogen dioxide with air, is a gas phase reaction.
1
NO + O → NO2
2 2
(ii) Formation of ester from organic acids and alcohols in the presence of sulphuric
acid is a liquid phase reaction.
𝐻2 𝑆𝑂4
C2 H5 OH + CH3 COOH ↔ 𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5
Heterogenous reaction is one which involves presence of more than one phase i.e., in
heterogenous reactions at least one of the reactants, catalyst or products is present in a
phase different from that of the remaining components of the reacting system.
Examples:
Oxidation of sulphur dioxide to sulphur trioxide using vanadium pentoxide catalyst is
heterogenous reaction as SO2, O2 and SO3 are gaseous while V2O5 is a solid material.
1 𝑉2 𝑂5
𝑆O2 + O2 → 𝑆𝑂3
2
2. The reaction may be classified as catalytic and non-catalytic reactions.
Catalytic reactions are those reactions which involve the use of catalyst to enhance the rate
of a reaction/speed of a reaction.
𝑁𝑖
𝐻𝑒𝑎𝑡
Example: C2 H4 + H2 ↔ 𝐶2 𝐻6
Ethylene Ethane
Hydrogenation of ethylene is a catalytic reaction which makes use of nickel catalyst.
DR. NILESH S DUMORE 1

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Non-catalytic reactions are those reactions which does not involve use of catalyst.
Oxidation of NO to NO2 is a non-catalytic reaction.
1
NO + O → NO2
2 2
3. The reaction may be classified based upon the molecularity of a reaction, i.e., based upon
the number of molecules that take part in the reaction (in the rate determining step) as
unimolecular, bimolecular and trimolecular reactions.
Examples:
(i) Decomposition of cyclobutene is a unimolecular reaction.
H2C - CH2
2C2H4
H2C - CH2
Cyclo-butane ethylene
(ii) Decomposition of hydrogen iodide is a bimolecular reaction which involves
collision of two molecules.
2HI (g) → I2 (g) + H2 (g)
(iii) Oxidation of NO to NO2 is a trimolecular/termo-molecular reaction which
involves collision of three molecules.
2NO + O2 → 2NO2
4. The reactions may be classified based upon the heat effect (i.e., according as they give off
or absorb heat to or from the surroundings) as exothermic and endothermic reactions.
An exothermic reaction is the one in which heat is evolved.
The reaction between CO and H2 to produce methanol is an exothermic reaction.
CO + 2H2 → CH3OH + Heat
An endothermic reaction is the one in which heat is absorbed (heat will be supplied to
the reacting system from the surrounding for reaction to take place).
Dehydration of ethyl alcohol to produce ethylene is an endothermic reaction.

Al2O3
C2H5OH C2H4 + H2O – Heat
Ethyl alcohol Ethylene
5. The reactions may be classified based upon the order of a reaction as first order reaction,
second order reaction, third order reaction, etc.

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A reaction of which overall order of reaction is one (i.e., sum of order with respect to
participants in the reaction is unity) is called first order reaction.
Decomposition of nitrogen pentoxide is a first order reaction.
1
𝑁2 𝑂5 → 𝑁𝑂2 + O
2 2
A reaction of which the sum of orders with respect to reactants participated in the reaction is two,
is called second order reaction.
Saponification of ester is a second order reaction.
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH
Ethyl acetate Sodium acetate
Example of third order reaction is
2NO(g) + H2 (g) → N2O (g) + H2O (g)
(6) The reactions are also classified as reversible and irreversible based upon whether they
proceed in one or both the directions.
Reversible reactions are those in which the forward and reverse reactions take place
simultaneously.
Example: Esterification reaction is a reversible reaction.
𝐻+
C2 H5 OH + CH3 COOH ⇔ CH3 COOC2 H5 + H2 O
Ethanol Acetic acid Ethyl acetate
Irreversible reactions are those which proceed only in one direction (till the reactants practically
disappear).
Example: Nitration of benzene is an irreversible reaction.
𝐻+
C6 H6 + HNO3 → C6 H5 NO2 + H2 O
Benzene Nitrobenzene
Q-2. What is rate equation? Also mention unit of rate of reaction and rate constant for first,
second and third order elementary chemical reactions.
Solution: Suppose a single-phase reaction aA + bB → rR +sS. The most useful measure of

reaction rate for reactant A is then

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rate of disappearance of A
1 𝑑𝑁𝐴 (𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐴 𝑑𝑖𝑠𝑎𝑝𝑝𝑒𝑎𝑟𝑖𝑛𝑔) 𝑚𝑜𝑙

−𝑟𝐴 = − = , [ 3 ] … . (1)
𝑉 𝑑𝑡 (𝑣𝑜𝑙𝑢𝑚𝑒)(𝑡𝑖𝑚𝑒) 𝑚 .𝑠
Note that this is an

The minus sign means
intensive measure
disappearance
In addition, the rates of reaction of all materials are related by

−𝑟𝐴 −𝑟𝐵 𝑟𝑅 𝑟𝑆
= = =
𝑎 𝑏 𝑟 𝑠
Experience shows that the rate of reaction is influenced by the composition and the energy of the
material. By energy we mean the temperature (random kinetic energy of the molecules), the light
within the system (this may affect the bond energy between atoms), the magnetic field intensity,
etc. ordinarily we only need to consider the temperature, so let us focus on this factor. Thus, we
can write
mol/m3. s
−𝑟𝐴 = 𝑓[(𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠), (𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠)]
𝑚𝑜𝑙 1−𝑎
As an example, ( 𝑚3 ) 𝑠 −1 Activation energy
𝑘𝐶𝐴𝑎 = 𝑘0 𝑒⏟−𝐸 ⁄𝑅𝑇 𝐶𝐴𝑎
reaction
temperature
order
dependent term
Here are a few words about the concentration dependent and the temperature-dependent terms of
the rate.

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Q-3. Discuss molecularity and order of reaction with suitable examples.
Solution:
1.The molecularity is defined as the number of molecules, atoms or ions participating the rate
determining step of the reaction.
2. The order of reaction is defined as the sum of the exponents of the concentrations in the rate
equation.
3. Molecularity of a reaction is a theoretical quantity to satisfy the experimental finding whereas
the order of the reaction is entirely an experimental quantity.
4. Molecularity of a reaction must be a whole number and never be zero or a fraction but the
order of a reaction may be a whole number, zero or a fraction.
Q-4. Discuss variable factor affecting the rate of reaction.
Solution:
(i) Nature of the reactants.
(ii) Concentration of the reactants
(iii) Temperature at which the reaction occurs.
(iv) Pressure of the reacting system.
(v) Pressure of catalyst in the reaction.
(vi) Physical state of the reactant (area of contact between the reactants).
(vii) Rates of heat and mass transfer.
For homogenous system, the possible factor that affect the rate of reaction are temperature, pressure
and composition of the reaction system. These are interdependent factors and the pressure is
determined given the temperature and composition of the phase. Thus, for homogenous systems,
we can write the rate of reaction as a function of the temperature and composition.
𝑚𝑜𝑙
−𝑟𝐴 = 𝑓[𝑡𝑒𝑚𝑝𝑟𝑎𝑡𝑢𝑟𝑒 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠, 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚],
(𝑙. 𝑠)
As an example, for A → R
−𝑟𝐴 = 𝑘. 𝐶𝐴𝛼
−𝑟𝐴 = 𝑘𝑜 . 𝑒 −𝐸⁄𝑅𝑇 . 𝐶𝐴𝛼
Where,
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𝑘𝑜 . 𝑒 −𝐸⁄𝑅𝑇 - Temperature dependent term

𝐶𝐴𝛼 - Concentration dependent term
E- Activation energy
α- order of reaction with respect to A.
Q-5. Define single and multiple reactions. Classify multiple reactions.
Solution: When a single stoichiometric equation and single rate equation are chosen to
represent the progress of the reaction, we have a single reaction. When more than one
stoichiometric equation is chosen to represent the observed changes, then more than one kinetic
expression is needed to follow the changing composition of all the reaction components, and
we have multiple reactions.
Multiple reactions may be classified as:
series reactions
A → R →S
parallel reactions, which are of two types
R A → R
A and
S A → S
Competitive Side by side
and more complicated schemes, an example of which is
A+B →R
R+B →S
Here, reaction proceeds in parallel with respect to B, but in series with respect to A, R, and S.
Q-6. Differentiate between Elementary and Non-Elementary reactions.

Solution:
1. Elementary reactions are single step reactions whereas nonelementary reactions are
multistep reactions i.e., such reactions occur through series of reaction steps.
2. Elementary reactions are simple in nature whereas the nonelementary reactions are
complex in nature.
3. For elementary reaction, the order agrees with the stoichiometry (i.e., order is equal to
stoichiometry co-efficient of a reacting participant) whereas for nonelementary reaction,

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the order does not agree with the stoichiometry (i.e., there is difference between order and
stoichiometry co-efficient).
4. For elementary reaction, the order of reaction must be an integer whereas for
nonelementary reaction, the order of a reaction may be an integer or have a fractional
value.
5. For elementary reaction, 2A → S, the rate law is -rA = k CA2 whereas for nonelementary
reaction 2B → S, the rate law is -rB = k CBα where α ≠ 2.
6. Example of an elementary reaction:
(i) C2H5OH + CH3COOH → CH3COOC2H5 +H2O
Example of nonelementary reaction:
(i) H2 + Br2 → 2HBr
(ii) CH3CHO → CH4 +CO
Q7. What is an autocatalytic reaction? For an autocatalytic reaction A + R → R + R show that

ln[(𝑀+𝑋𝐴)/𝑀 (1−𝑋𝐴)] =𝐶𝐴0 (𝑀+1) 𝑘𝑡
Solution: A reaction in which one of the products of reaction acts as a catalyst is called
autocatalytic reaction.
Consider the following simple autocatalytic reaction
A+R→R+R
The rate of this reaction is given by
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴 𝐶𝑅 … . (1)
𝑑𝑡
As the total number of moles of A and R at any time t during the course of reaction remain
unchanged, the stoichiometry related the concentrations of reacting components and so we
can write
𝐶𝑜 = 𝐶𝐴 + 𝐶𝑅 = 𝐶𝐴𝑜 + 𝐶𝑅𝑜 = Constant , at any time t
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 ) … . (2)
𝑑𝑡
Rearrangement, we get

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−𝑑𝐶𝐴
= 𝑘 𝑑𝑡 … (3)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
Braking into partial fraction, we get
𝐴 𝐵 1
+ = … . (4)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 ) 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
𝐴 (𝐶𝑜 − 𝐶𝐴 ) + 𝐵 (𝐶𝐴 ) = 1
For calculating A, put 𝐶𝐴 = 0,
1
𝐴=
𝐶𝑜
Similarity,
For calculating B, Put 𝐶𝐴 = 𝐶𝑜 ,

1
𝐵=
𝐶𝑜
So, putting values of A and B and integrating equation (4)
1 1 1
+ = … . (5)
𝐶𝑜 𝐶𝐴 𝐶𝑜 (𝐶𝑜 − 𝐶𝐴 ) 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
Rearranging equation (3)

𝐶𝐴 𝑡
1 1
−∫ [ − ] 𝑑𝐶𝐴 = 𝑘 ∫ 𝑑𝑡 … . (6)
𝐶𝐴𝑜 𝐶𝑜 𝐶𝐴 𝐶𝑜 (𝐶𝑜 − 𝐶𝐴 ) 0
1 𝐶𝐴 1 1
− ∫ [ − ] 𝑑𝐶𝐴 = 𝑘 𝑡
𝐶𝑜 𝐶𝐴𝑜 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
𝐶𝐴 𝐶𝐴
1 𝑑𝐶𝐴 𝑑𝐶𝐴
− [∫ [ ]−∫ [ ]] = 𝑘 𝑡
𝐶𝑜 𝐶𝐴𝑜 𝐶𝐴 𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 )
𝐶𝐴 𝐶𝑜 − 𝐶𝐴
−𝑙𝑛 ( ) + 𝑙𝑛 ( ) = 𝐶𝑜 𝑘 𝑡
𝐶𝐴𝑜 𝐶𝑜 − 𝐶𝐴𝑜
𝐶𝐴𝑜 𝐶𝑜 − 𝐶𝐴
𝑙𝑛 ( ) + 𝑙𝑛 ( ) = 𝐶𝑜 𝑘 𝑡
𝐶𝐴 𝐶𝑜 − 𝐶𝐴𝑜
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 )
∴ 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡 … (7)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 )
𝐶𝑜 = 𝐶𝐴 + 𝐶𝑅 = 𝐶𝐴𝑜 + 𝐶𝑅𝑜

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𝐶𝐴 = 𝐶𝑜 − 𝐶𝑅
𝐶𝐴𝑜 = 𝐶𝑜 − 𝐶𝑅𝑜
So,
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝑜 + 𝐶𝑅 )
∴ 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡 … (8)
𝐶𝐴 (𝐶𝑜 − 𝐶𝑜 + 𝐶𝑅𝑜 )
𝐶𝐴𝑜 𝐶𝑅
∴ 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡
𝐶𝐴 𝐶𝑅𝑜
𝐶𝐴𝑜 𝐶𝑅 𝐶𝑅 /𝐶𝑅𝑜
∴ 𝑙𝑛 [ ] = 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡
𝐶𝐴 𝐶𝑅𝑜 𝐶𝐴 /𝐶𝐴𝑜
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) 𝐶𝐴𝑜 𝐶𝑅 𝐶𝑅 /𝐶𝑅𝑜

∴ 𝑙𝑛 [ ] = 𝑙𝑛 [ ] = 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡 = (𝐶𝐴𝑜 + 𝐶𝑅𝑜 ) 𝑘 𝑡 … . . (9)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) 𝐶𝐴 𝐶𝑅𝑜 𝐶𝐴 /𝐶𝐴𝑜
𝐶
In terms of the initial reactant ratio 𝑀 = 𝐶𝑅𝑜 and XA is the fractional conversion of A, then
𝐴𝑜
∴ 𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴0 (1 − 𝑋𝐴 )]
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴0 + 𝐶𝐴0 𝑋𝐴 ]
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝑅𝑜 + 𝐶𝐴0 𝑋𝐴 ]
𝐶𝑅𝑜
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 . 𝐶𝐴0 [ ⁄𝐶 + 𝑋𝐴 ]
𝐴0
𝑪𝑨𝒐 (𝑪𝒐 − 𝑪𝑨 ) = 𝑪𝑨𝒐 𝟐 [𝑴 + 𝑿𝑨 ] … (𝟏𝟎)
∴ 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 (1 − 𝑋𝐴 ) [ 𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴𝑜 ]
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 (1 − 𝑋𝐴 ) 𝐶𝑅𝑜
𝐶𝑅𝑜
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 2 (1 − 𝑋𝐴 )
𝐶𝐴0
𝑪𝑨 (𝑪𝒐 − 𝑪𝑨𝒐 ) = 𝑪𝑨𝟎 𝟐 (𝟏 − 𝑿𝑨 ) 𝑴 … . . (𝟏𝟏)
∴ 𝐶𝑜 𝑘 𝑡 = (𝐶𝐴𝑜 + 𝐶𝑅𝑜 ) 𝑘 𝑡
𝐶𝑅𝑜
𝐶𝑜 𝑘 𝑡 = 𝐶𝐴𝑜 (1 + ) 𝑘𝑡
𝐶𝐴𝑜
𝑪𝒐 𝒌 𝒕 = 𝑪𝑨𝒐 (𝟏 + 𝑴) 𝒌 𝒕 … . . (𝟏𝟐)
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In term of M and XA, equation (9) becomes
𝐶𝐴𝑜 2 [𝑀 + 𝑋𝐴 ]
∴ 𝑙𝑛 [ 2 ] = 𝐶𝐴𝑜 (1 + 𝑀) 𝑘 𝑡
𝐶𝐴0 𝑀 (1 − 𝑋𝐴 )
[𝑴 + 𝑿𝑨 ]
∴ 𝒍𝒏 [ ] = 𝑪𝑨𝒐 (𝟏 + 𝑴) 𝒌 𝒕
𝑴 (𝟏 − 𝑿𝑨 )
Note that some product R (here acting as the catalyst) should be present initially if the
autocatalytic reaction is to be at all.
Q8. Discuss autocatalytic reaction with conversion-time and rate-concentration curves. (4M)
Or define autocatalytic reactions with Conversion-time and rate-concentration curves.
autocatalytic reaction. Consider the following simple autocatalytic reaction
A + R → R + R …. (1a)
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴 𝐶𝑅 … . (1𝑏)
𝑑𝑡
Fig. 1: Conversion-time and rate-concentration curves for autocatalytic reaction of Equation

1(a) & (1b). This shape is typical for this type of autocatalytic reaction.
For an autocatalytic reaction in a batch reactor some product R must be present if the reaction
is to proceed at all. Starting with a very small concentration of R, we see qualitatively that the
rate will rise as R is formed. At the other extreme, when A is just about used up the rate must
drop to zero. This result is given in Fig. 1, which shows that the rate follows a parabola, with
a maximum where the concentrations of A and R are equal.

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Q9. Write short note on autocatalytic reactions. (7M)

Solution: When a material reacts away by any nth order rate (n > 0) in a batch reactor, its rate
of disappearance is rapid at the start when the concentration of reactant is high. This rate then
slows progressively as reactant is consumed. In an autocatalytic reaction, however, the rate at
the start is low because little product is present; it increases to a maximum as product is formed
and then drops again to a low value as reactant is consumed. Figure 1 shows a typical situation.
Reactions with such rate-concentration curves lead to interesting optimization problems. In
addition, they provide a good illustration of the general design method presented in this chapter.
For these reasons let us examine these reactions in some detail. In our approach we deal
exclusively with their 1/(-rA) versus XA curves with their characteristic minima, as shown in
Figure. 1.
Figure 1: Typical rate-concentration curve for autocatalytic reactions,
for example:
A + R → R + R …. (1a)
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴𝑎 𝐶𝑅𝑟 … . (1𝑏)
𝑑𝑡
Plug Flow Versus Mixed Flow Reactor, No Recycle. For any particular rate concentration
curve a comparison of areas in Fig. 2 will show which reactor is superior (which requires a
smaller volume) for a given job. We thus find
1. At low conversion the mixed reactor is superior to the plug flow reactor.
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2. At high enough conversions the plug flow reactor is superior.

These findings differ from ordinary nth-order reactions (n > 0) where the plug flow reactor is
always more efficient than the mixed flow reactor. In addition, we should note that a plug flow
reactor will not operate at all with a feed of pure reactant. In such a situation the feed must be
continually primed with product, an ideal opportunity for using a recycle reactor.
Figure 2. For autocatalytic reactions mixed flow is more efficient at low conversions, plug
flow is more efficient at high conversions

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Q10. Empirical rate equation of nth order

Answer: For the reaction
A → Products
Rate is given by
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘𝐶𝐴𝑛
𝑑𝑡
Rearranging, we get
𝑑𝐶𝐴
−
= 𝑘. 𝑑𝑡
𝐶𝐴𝑛
Integrating above equation within the below given limits
CA = CA0 at t = 0
CA = CA at t = t
𝐶𝐴 𝑡
𝑑𝐶𝐴
−∫ 𝑛 = 𝑘 ∫ 𝑑𝑡
𝐶𝐴0 𝐶𝐴 0
𝐶
𝐶𝐴−𝑛+1 𝐴
−[ ] = 𝑘𝑡
−𝑛 + 1 𝐶
𝐴0
1 1 1
[ 𝑛−1 − 𝑛−1 ] = 𝑘𝑡
(𝑛 − 1) 𝐶𝐴 𝐶𝐴0
1 1
[ − 𝑛−1 ] = (𝑛 − 1) 𝑘𝑡, 𝑛 ≠ 1
𝐶𝐴𝑛−1 𝐶𝐴0
The dimension of the rate constant (k) for nth order are (time)-1 (concentration)1-n.
Q11. Derive the equation of overall order of irreversible reaction from the half time.
(7marks)
Answer: The half-life of a reaction t1/2, is defined as the time required for the concentration
of the reactant to fall to one half of its initial value. The reaction order and rate constant of a
reaction can be determined from the data half-life of a reaction as a function of initial
concentration obtained by performing experiments in laboratory.
For the irreversible reaction,
aA + bB + …. → Products … (1)
We may write the rate expression as
𝑑𝐶 𝛽
−𝑟𝐴 = − 𝑑𝑡𝐴 = 𝑘 𝐶𝐴𝛼 𝐶𝐵 … .. … (2)

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If the reactants are present in the stoichiometric ratios initially, they will remain at that ratio
during the course of reaction.
For reactants A and B at any time,
𝐶𝐵 𝑏
=
𝐶𝐴 𝑎
So
𝛽
𝑑𝐶𝐴 𝛼
𝑏
−𝑟𝐴 = − = 𝑘 𝐶𝐴 ( 𝐶𝐴 )
𝑑𝑡 𝑎
𝛼+𝛽+⋯
−𝑟𝐴 = 𝑘 (𝑏⁄𝑎)𝛽 … 𝐶𝐴
−𝑟𝐴 = 𝑘 ′ 𝐶𝐴𝑛 … . (3)
Integrating with initial condition CA = CA0 at t = 0, we get
𝐶𝐴1−𝑛 − 𝐶𝐴0
1−𝑛
= 𝑘 ′ (𝑛 − 1) 𝑡, 𝑓𝑜𝑟 𝑛 ≠ 1 … (4)
The half-life is the time required for the concentration of the reactants to fall to one-half of its
initial value, i.e.,
1
𝑡 = 𝑡1/2 𝑤ℎ𝑒𝑛 𝐶𝐴 = 𝐶
2 𝐴0
1−𝑛
1 1−𝑛
( 𝐶𝐴0 ) − 𝐶𝐴0 = 𝑘 ′ (𝑛 − 1) 𝑡1/2
2
𝐶𝐴01−𝑛 1−𝑛
− 𝐶𝐴0 = 𝑘 ′ (𝑛 − 1) 𝑡1/2
21−𝑛
1
𝐶𝐴01−𝑛 [ − 1] = 𝑘 ′ (𝑛 − 1) 𝑡1/2
21−𝑛
𝐶𝐴01−𝑛 [2𝑛−1 − 1] = 𝑘 ′ (𝑛 − 1) 𝑡1/2
(2𝑛−1 − 1)
𝑡1/2 = 𝐶 1−𝑛 … . (5)
𝑘 ′ (𝑛 − 1) 𝐴0
Taking the natural log of both sides of equation (5), we get

(2𝑛−1 − 1)
ln 𝑡1/2 = 𝑙𝑛 [ ′ ] + (1 − 𝑛) ln 𝐶𝐴0 … (6)
𝑘 (𝑛 − 1)
So, the plot of ln t1/2 v/s ln CA0 yields a straight line with slope equal to 1-n.
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Fig. 1. Overall order of reaction from a series of half-life experiments (method of half-lives)
So this method requires taking a series of runs each at different initial concentrations. For
reaction involving single reacting component,
A → Products
We have to determine the half-life of reaction, each at different initial concentration of A, to

determine n and k.
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴𝛼 = 𝑘 𝐶𝐴𝑛
𝑑𝑡
Integrating with the initial condition CA = CA0 at t = 0, we get
𝐶𝐴1−𝑛 − 𝐶𝐴0
1−𝑛
= 𝑘(𝑛 − 1) 𝑡
𝑡 = 𝑡1/2 𝑎𝑡 𝐶𝐴 = 𝐶𝐴0 ⁄2
(2𝑛−1 − 1)
𝑡1/2 = 𝐶 1−𝑛
𝑘 ′ (𝑛 − 1) 𝐴0
2𝑛−1 − 1
ln 𝑡1/2 = 𝑙𝑛 [𝑘 ′ (𝑛−1)] + (1 − 𝑛) ln 𝐶𝐴0 … (7)
Here n is the order with respect to A.
Another variation of this procedure is – if the reaction involves two components, then we have
to use the method of excess (isolation method) in conjunction with the half-time method. In

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such procedure, if A and B are reacting component and if we take B in large excess so that
𝐶𝐵 ≈ 𝐶𝐵0 then.
𝑑𝐶𝐴
− = 𝑘 ′′ 𝐶𝐴𝛼
𝑑𝑡
𝛽
Where 𝑘 ′′ = 𝑘 ′ 𝐶𝐵0
Zero order reaction
A reaction is of zero order when the rate of reaction is independent of the concentration of the
reactant.
A reaction of zero order is represented as
A → Product
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘𝐶𝐴0 … (1)
𝑑𝑡
𝑑𝐶𝐴
− =𝑘
𝑑𝑡
𝐶𝐴 𝑡
− ∫ 𝑑𝐶𝐴 = 𝑘 ∫ 𝑑𝑡
𝐶𝐴0 0
𝐶𝐴0 − 𝐶𝐴 = 𝑘𝑡 … (2)
Equation (2) is the integrated rate equation for zero order reaction in terms of concentration.
We have
𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 )
𝐶𝐴0 − 𝐶𝐴 = 𝐶𝐴0 𝑋𝐴
𝐶𝐴0 𝑋𝐴 = 𝑘𝑡 … (3)
Equation (3) is the integrated rate equation in terms of conversion.
Characteristics:
Equation (2) is the integrated rate expression for zero order reaction. The dimensions
of specific rate constant are concentration/time.

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A plot of 𝐶𝐴0 − 𝐶𝐴 against t yields a straight line passing through origin with slope equal to
k.
Fig: Test for irreversible zero order reaction
The important chacteristic of zero order kinestic is the half life which is proportional to the
initial concentration of the reactant. Half life is defined as the time required to reduce the
concentration of reactant A to half to its original value.
Substituting the condition t = t1/2 when CA = CA0/2, in equation (2), we get
𝐶𝐴0 − 𝐶𝐴 = 𝑘𝑡
𝐶𝐴0
𝐶𝐴0 − = 𝑘𝑡1⁄2
2
𝐶𝐴0
= 𝑘𝑡1⁄2
2
𝐶𝐴0
𝑡1⁄2 = … (4)
2𝑘
𝑡1⁄2 𝛼 𝐶𝐴0 … (5)
Where CA0 is the initial concentration of the reactant. Hence the half-life of the zero-order
reaction is directly proportional to the initial concentration of reactant.
Q11. What is activation energy?

Answer: the minimum amount of energy which the colliding molecules must have in order to
bring about a reaction is known as activation energy (or the energy barrier that the molecules
must overcome when the reaction system passes from one state to another).

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CRE-I Question and Answer

1. Milk is pasteurized in 30 minutes if it heated at 63 0C but if it is heated 74 0C it only needs
15 seconds for the same result. Find the activation energy of this sterilization process.
(4 Marks)
Solution: To ask for the activation energy of a process means assuming an Arrhenius
temperature dependency for the process. Here we are told that
t1=30 min at a T1=336 K
t2=15 sec at a T2=347 K
Now the rate is inversely proportional to the reaction time, or rate ∝ 1/ time so Eq. 35
becomes
𝑟2 𝑡1 𝐸 1 1
𝐼𝑛 = 𝑙𝑛 = ( − )
𝑟1 𝑡2 𝑅 𝑇1 𝑇2
or
30 𝐸 1 1
𝑙𝑛 = ( − )
0.25 𝑅 336 347
4.787 * 8.314 = E * 9.4346 *10-5
from which the activation energy
E=422000 J/mol or 421885.039 J/mol
2. The pyrolysis of ethane proceeds with activation energy of about 7500 calories. How much
faster is the decomposition at 650 0C than at 500 0C? (7 marks)
Solution:
C2H6 Product
E=75000 cal/mol
Let, K1 be the rate constant at T1 and k2 be the rate constant at T2.
T1= 500 0C = 773 K,
T2= 650 0C = 923 K,
𝑘2 𝐸 1 1
𝑙𝑛 = ( − )
𝑘1 𝑅 𝑇1 𝑇2

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R=1.987 cal/mol.K
𝑘2 75000 1 1
𝑙𝑛 = ( − )
𝑘1 1.987 773 923
𝑘
𝑙𝑛 𝑘2 = 7.9354
1
𝑘2
= 2794.47
𝑘1
𝑘2 = 2794.47 𝑘1
At 650 0C, the decomposition is faster by a factor 2794.47 than at 500 0C.
3. The activation energy of chemical reaction is 17982 cal/mol in the absence of catalyst and
11980 cal/mol with a suitable catalyst. By how many times the rate of reaction will increases
in presence of catalyst if a reaction proceeds at 25 0C.
(4 marks).
Solution:
Let, E1 be the activation energy of a reaction without catalyst (17982 cal/mol)
E2 be the activation energy of a reaction with catalyst (11980 cal/mol)
We have,
k = k0. e-E/RT
k1 be the rate constant of a reaction without catalyst.
k2 be the rate constant of a reaction with catalyst.
k1= k0. e-E1/RT k2= k0. e-E2/RT
𝐸1
𝑘1 𝑒 −𝑅𝑇
= 𝐸2
𝑘2
𝑒 −𝑅𝑇
𝑘1 (𝐸1 −𝐸2 ) 𝐸1 − 𝐸2 17982 − 11980

= 𝑒 𝑅𝑇 = 𝑒𝑥𝑝. ( ) = 𝑒𝑥𝑝. ( )
𝑘2 𝑅𝑇 1.987 × 298
𝑘1
= 2.52 × 104
𝑘2
𝑘1 = 2.52 × 104 . 𝑘2
In presence of catalyst, the rate of reaction will grow by 2.52 × 104 times (the rate for
uncatalyzed reaction)

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4. Experiment shows that the homogeneous decomposition of ozone (2O3 2O2) proceeds
with a rate law – rO3 = k [O3]2 [O2]-1.
What is overall order of reaction?
Suggest a two – step mechanism consistent with the rate law and discuss how the mechanism will
be verified?
Solution: The homogenous decomposition of ozone proceeds as
2O3 2O2
And follows the rate law
– rO3 = k [O3]2 [O2]-1.
The two-step mechanism, consistent with this rate, suggested is:

K1
Step 1: O3 O2 + O (fast at equilibrium)
K2
K3
Step 2: O + O3 2O2 (Slow)
The step 2 is the slower, rate determining step and accordingly, the reaction rate is given by
−𝑑[𝑂3 ]
−𝑟𝑂3 = = 𝑘3 [𝑂3 ] [𝑂] … . (1)
𝑑𝑡
The step 1 is fast and reversible. From this equilibrium step, we have:
𝑘1 [𝑂2 ] [𝑂]
𝐾= =
𝑘2 [𝑂3 ]
[𝑂3 ]
[𝑂] = 𝐾. … . (2)
[𝑂2 ]
Putting the value of [O] from equation (2) into equation (1), we get
−𝑑[𝑂3 ]
𝑟𝑂3 = = 𝑘3 𝐾. [ 𝑂3 ]2 /[𝑂2 ]
𝑑𝑡
Let
k = k3 K
-rO3 = k [O3]2 [O2]-1

Over all order of reaction is 2-1 = 1.

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5. At 1100 K n-nonane thermally cracks 20 times as rapidly as at 1000 K. Estimate the activation
energy for this decomposition.
Solution:
T2 = 1100 K, r = r2
T1 = 1000 K, r = r1
We have,
r2 = 20 r1
r2 E 1 1
ln = ( − )
r1 R T1 T2
20. r1 E 1 1
ln = ( − )
r1 8.314 1000 1100
E
ln 20 = × (9.0909 × 10−5 )
8.314
E = 273971.97 J/mol
E = 274 KJ/mol
6. The primary reaction occurring in the homogeneous decomposition of nitrous oxide is
1
N2 O → N2 + O2
2
with rate equation as given below.
k1 [N2 O]2
−rN2O =
1 + k , [N2 O]
Derive the mechanism to explain this observed rate.

(7 marks).
Solution: The gas phase decomposition of N2O proceeds as
1
𝑁2 𝑂 → 𝑁2 + 𝑂2
2
The rate expression for this reaction is

𝑘1 [𝑁2 𝑂]2
−𝑟𝑁2𝑂 =
1 + 𝑘 , [𝑁2 𝑂]

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The propose mechanism is
K1
Step 1: N2O + N2O N2O + N2O*
K3 K2
Step 2: N2O* N2 + ½ O2
The rate of reaction is given by the rate of formation of N2.

∴ 𝑟𝑁2 = 𝑘3 [𝑁2 𝑂∗ ] … . . (1)
As per the steady state approximation, the net rate of formation of the active intermediate
[N2O*] is zero
𝑑[𝑁2 𝑂∗ ] 2
∴ 𝑟𝑁2𝑂∗ = = 𝑘1 [[𝑁2 𝑂] − 𝑘2 [[𝑁2 𝑂] [𝑁2 𝑂∗ ] − 𝑘3 [𝑁2 𝑂∗ ] = 0
𝑑𝑡
2
𝑘1 [[𝑁2 𝑂] − 𝑘2 [[𝑁2 𝑂] [𝑁2 𝑂∗ ] − 𝑘3 [𝑁2 𝑂∗ ] = 0
2
𝑘2 [[𝑁2 𝑂] [𝑁2 𝑂∗ ] + 𝑘3 [𝑁2 𝑂∗ ] = 𝑘1 [[𝑁2 𝑂]
2
∗]
𝑘1 [[𝑁2 𝑂]
[𝑁2 𝑂 = … . . (2)
𝑘3 + 𝑘2 [[𝑁2 𝑂]
Putting the value of [𝑁2 𝑂∗ ] from equation (2) in equation (1), we get
2
𝑘3 . 𝑘1 [[𝑁2 𝑂]
𝑟𝑁2 =
𝑘3 + 𝑘2 [[𝑁2 𝑂]
We have
𝑟𝑁2 = −𝑟𝑁2𝑂
2
𝑘1 [[𝑁2 𝑂]
−𝑟𝑁2𝑂 = 𝑟𝑁2 =
𝑘
1 + 2 [[𝑁2 𝑂]
𝑘3
Let
𝑘2
𝑘, =
𝑘3
2
𝑘1 [[𝑁2 𝑂]
−𝑟𝑁2𝑂 = 𝑟𝑁2 = … … … … … . . 𝑨𝒏𝒔𝒘𝒆𝒓
1 + 𝑘 , [𝑁2 𝑂]
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So, the suggested mechanism is consistent with the observed rate

At low concentration of N2O
𝑘 , ([𝑁2 𝑂) ≪ 1
2
−𝑟𝑁2𝑂 = 𝑘1 [[𝑁2 𝑂]
The rate follows second order kinetics i.e., the rate is second order with respected to N2O.
At high N2O concentrations:
𝑘 , ([𝑁2 𝑂) ≫ 1
−𝑟𝑁2𝑂 = 𝑟𝑁2 = 𝑘. [𝑁2 𝑂]
𝑘1
Where 𝑘= 𝑘,
∴ The rate is first order with respect to N2O.
7. A rocket engine burns a stoichiometric mixture of fuel (liquid hydrogen) in oxidant (liquid
oxygen). The combustion chamber is cylindrical, 75 cm long and 60 cm in diameter, and the
combustion process produces 108 kg/s of exhaust gases. If combustion is complete, find the
rate of reaction of hydrogen and of oxygen.
1
𝐻2 + 𝑂 → 𝐻2 𝑂
2 2
Figure: Rocket engine
Solution:
We want to evaluate
1 𝑑𝑁𝐻2
−𝑟𝐻2 = −
𝑉 𝑑𝑡
And
1 𝑑𝑁𝑂2
−𝑟𝑂2 = −
𝑉 𝑑𝑡
Let us evaluate terms. The reactor volume and the volume in which reaction takes place are
identical. Thus,
𝜋
𝑉 = − (𝑑)2 (𝑙)
4
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𝜋
𝑉= − (0.6)2 (0.75)
4
𝑉 = 0.2121 𝑚3
Next, let us look at the reaction occurring.
1
𝐻2 + 𝑂 → 𝐻2 𝑂 … … (𝑖)
2 2
molecular weight: 2 gm 16 gm 18 gm
Therefore,
𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 𝑘𝑔 1𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙

𝐻2 𝑂 = 108 ×( )=6
𝑠 𝑠 18 𝑘𝑔 𝑠
So, from Eq. (i)
H2 used = 6 kmol/s
O2 used = 3 kmol/s
and the rate of reaction is

1 𝑘𝑚𝑜𝑙
−𝑟𝐻2 = − ×6 ( )
0.2121 𝑠
𝑘𝑚𝑜𝑙
−𝑟𝐻2 = 28.288 ( 3 )
𝑚 .𝑠
𝒎𝒐𝒍 𝒖𝒔𝒆𝒅
−𝒓𝑯𝟐 = 𝟐. 𝟖𝟐𝟗 × 𝟏𝟎𝟒 ( 𝟑 )
(𝒎 𝒐𝒇 𝒓𝒐𝒄𝒌𝒆𝒕) . 𝒔
1 𝑘𝑚𝑜𝑙
−𝑟𝑂2 = − ×3 ( )
0.2121 𝑠
𝑘𝑚𝑜𝑙
−𝑟𝑂2 = 14.144 ( 3 )
𝑚 .𝑠
𝒎𝒐𝒍 𝒖𝒔𝒆𝒅
−𝒓𝑶𝟐 = 𝟏. 𝟒𝟏𝟓 × 𝟏𝟎𝟒 ( 𝟑 )
(𝒎 𝒐𝒇 𝒓𝒐𝒄𝒌𝒆𝒕) . 𝒔
Rate of reaction for hydrogen is 2.83×104 mol⋅s−1per m3 of chamber.
Rate of reaction for oxygen is 1.42×104 mol⋅s−1 per m3 of chamber.

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8. Liquid A decomposes by first-order kinetics, and in a batch reactor 50% of A is converted

in a 5-minute run. How much longer would it take to reach 75% conversion?
(3 Marks)
Solution: A → Product
For a first order reaction, the rate of equation is
−𝑟𝐴 = 𝑘. 𝐶𝐴
In terms of conversion, the integrated rate expression for first order reaction is
1
𝑙𝑛 ( ) = 𝑘𝑡
1 − 𝑋𝐴
Case I: XA = 0.5 when t = 5 min
1
𝑙𝑛 ( )=𝑘 ×5
1 − 0.5
∴ 𝑘 = 0.1386 (𝑚𝑖𝑛−1 )
Case II: XA = 0.75 when t =
1
𝑙𝑛 ( ) = 0.1386 × 𝑡
1 − 0.75
∴ 𝑡 = 10 𝑚𝑖𝑛
9. The rate constant k at 27°C is 1.3×10-3 sec-1 and its frequency factor is 2.785*10-6 sec-1.
Determine its Entropy of activation and Enthalpy of activation.
Solution: We have
𝑘𝐵 𝑇 ∆𝑆∗ −∆𝐻∗
𝑘= . 𝑒 𝑅 . 𝑒 𝑅𝑇
ℎ
𝑘𝐵 𝑇 ∆𝑆∗⁄
𝑘𝑜 = .𝑒 𝑅
ℎ
𝑘𝐵 𝑇 ∆𝑆 ∗
𝑙𝑜𝑔𝑘𝑜 = 𝑙𝑜𝑔 +
ℎ 2.303 𝑅
ko = 2.785×106 (s)-1, k = 1.3×10-3 (s)-1, T=273+27=300 K
h = 6.62× 10-27 erg.s, R=1.987 cal/(mol.K)
1.38 × 10−3 × 300 ∆𝑆 ∗

log 2.785 × 106 = log −27
+
6.62 × 10 1.987 × 2.303
∆𝑆 ∗
6.448 = 12.7963 +
1.987 × 2.303
∆𝑆 ∗= −29.06 𝑒. 𝑢.

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Now,
𝐾𝐵 . 𝑇 ∆𝑆∗ −∆𝐻∗
𝑘= . 𝑒 𝑅 . 𝑒 𝑅𝑇
ℎ
−∆𝐻∗
𝑘 = 𝑘0 . 𝑒 𝑅𝑇
−∆𝐻 ∗
𝑙𝑜𝑔 𝑘 = 𝑙𝑜𝑔 𝑘0 +
2.303 × 𝑅𝑇
−∆𝐻 ∗
log 1.3 × 10−3 = log 2.785 × 106 +
2.303 × 1.987 × 300
Solving we get,
∆𝐻 ∗= 12.8 𝑘𝑐𝑎𝑙/𝑚𝑜𝑙
10. Experimental studies of a specific decomposition of A in a batch reactor using pressure

units show exactly the same rate at two different temperatures:
At 400K −𝑟𝐴=2.3 𝑃A2
At 500K −𝑟𝐴=2.3 𝑃A2
Where unit of –rA is mol/m3.sec and unit of PA is atm.
(a) Evaluate the activation using these units
(b) Transform the rate expression into concentration units and then evaluate the activation
energy.
The pressure is not excessive, so the ideal gas law can be used. (7 Marks)
Solution:
(a) Using pressure units: We see right away that a change in temperature does not affect
the rate of reaction. This means that
E=0
Alternatively, we can find E by going through the calculations. Thus
𝑘2 2.3
𝐼𝑛 = 𝑙𝑛 =0
𝑘1 2.3
Hence replace in following equation
𝑘2 𝐸 1 1
𝐼𝑛 = [ − ]
𝑘1 𝑅 𝑇1 𝑇2
𝑅𝑇1 𝑇2 𝑘2
𝐸= . 𝐼𝑛
𝑇2 − 𝑇1 𝑘1
𝐸=0

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(b) Transform pA in CA, then find E. First write the rate equation with all units shown
𝑚𝑜𝑙 𝑚𝑜𝑙
−𝑟𝐴 , 3
= (2.3, 3 ) (𝑝𝐴2 , 𝑎𝑡𝑚3 )
𝑚 .𝑠 𝑚 . 𝑠. 𝑎𝑡𝑚2
Next change pA to CA. From ideal gas law

𝑛𝐴
𝑝𝐴 = 𝑅𝑇 = 𝐶𝐴 𝑅𝑇
𝑉
Combining the two preceding equations
−𝑟𝐴 = 2.3𝐶𝐴 2 𝑅 2 𝑇 2
At 400 K
𝑚𝑜𝑙 2 −6
𝑚3 . 𝑎𝑡𝑚 2
−𝑟𝐴 = 2.3 𝐶 × (82.06 × 10 ) (400 𝐾)2
𝑚3 . 𝑠. 𝑎𝑡𝑚2 𝐴 𝑚𝑜𝑙. 𝐾
𝑚3
−𝑟𝐴1 = 0.0025 𝐶𝐴 2 , where 𝑘1 = 0.0025
𝑚𝑜𝑙.𝑠
At 500 K, Similarly
𝑚𝑜𝑙 2 −6
𝑚3 . 𝑎𝑡𝑚 2
−𝑟𝐴 = 2.3 𝐶 × (82.06 × 10 ) (500 𝐾)2
𝑚3 . 𝑠. 𝑎𝑡𝑚2 𝐴 𝑚𝑜𝑙. 𝐾
𝑚3
−𝑟𝐴1 = 0.0039 𝐶𝐴 2 , where 𝑘1 = 0.0039 𝑚𝑜𝑙.𝑠
Here, we see that in concentration units the rate constants are not independent of temperature.
Evaluating the activation energy and replacing number gives as follows
𝑅𝑇1 𝑇2 𝑘2
𝐸= . 𝐼𝑛
𝑇2 − 𝑇1 𝑘1
(8.314)(400)(500) 0.0039
𝐸= . 𝐼𝑛
500 − 400 0.0025
𝑱
𝑬 = 𝟕𝟑𝟗𝟒
𝒎𝒐𝒍
This example shows that E values from differ when either p or C used to measure
concentrations of materials.

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11. The rate constant of a zero-order reaction is 0.2 mol/(l.h). what will be the initial
concentration of the reactant if, after half an hour, its concentration is 0.05 mol/l?
Solution: The concentration of the reactant (CA) after time t for zero order reaction is given by
CA = CA0 -kt
CA=0.05, k = 0.2 mol/(l.h), t = 0.5 h
The initial concentration, CA0 is given by
CA0 = CA + kt
CA0 = 0.05 + 0.2 × 0.5
CA0 = 0.15 mol/l
12. The half life period of a first order reaction is 240 seconds. Calculate its rate constant in
seconds and minutes.
Solution: For a first order reaction:
0.693
𝑡1/2 =
𝑘
0.693
𝑘=
𝑡1/2
𝑡1/2 = 240 𝑠
0.693
𝑘= = 2.89 × 10−3 (𝑠)−1
240
𝑘 = 2.89 × 10−3 × 60
𝑘 = 0.1732 (𝑚𝑖𝑛)−1
13. The half-life period for a certain first order reaction is 2.5×103 s. How long will it take for
¼ of the reactant to be left behind?
Solution: For a first order reaction:
0.693
𝑡1/2 =
𝑘
0.693
𝑘=
𝑡1/2
(∴ 𝑡1/2 = 2.5 × 103 𝑠)

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0.693
𝑘=
2.5 × 103
k = 2.77 × 10−4 𝑠
Let the time required to decrease (drop) the concentration of reactant to 1/4th of its original
concentration be t, then
CA0 = 1 mol/l, CA = 1/4×[CA0] = 1/4 × 1=1/4 mol/l
The integrated rate equation for the first order reaction is
1 𝐶𝐴0
𝑡 = ln [ ]
𝑘 𝐶𝐴
1 1
𝑡= −4
ln [ ]
2.77 × 10 1/4
𝒕 = 𝟓𝟎𝟎𝟓. 𝟓 𝒔
14. Show that the decomposition of N2O5 at 67 0C is a first order reaction. Calculate the value
of the rate constant.
Data:
Time, min 0 1 2 3 4
CN2O5 , mol/l 0.16 0.113 0.08 0.056 0.040
1
Solution: 𝑁2 𝑂5 → 𝑁2 𝑂4 + 𝑂2
2
𝑁2 𝑂5 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Let, N2O5=A. Therefore, this reaction can be written as
𝐴 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
For a first order reaction, we have
𝐶𝐴
− ln [ ] = 𝑘. 𝑡
𝐶𝐴0
(1) CA = 0.113 mol/l at CA0 = 0.16; t = 1 min.
1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 0.113
𝑘 = − ln [ ]
1 0.160
𝒌 = 𝟎. 𝟑𝟒𝟕𝟖 𝒎𝒊𝒏−𝟏

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(2) CA = 0.08 mol/l at t = 2 min.

1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 0.08
𝑘 = − ln [ ]
2 0.160
𝑘 = 0.3466 𝑚𝑖𝑛−1
(3) CA = 0.056 mol/l at t = 3 min.

1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 0.056
𝑘 = − ln [ ]
3 0.160
𝑘 = 0.3499 𝑚𝑖𝑛−1
(4) CA = 0.04 mol/l at t = 4 min.

1 𝐶𝐴
𝑘 = − ln [ ]
4 𝐶𝐴0
1 0.04
𝑘 = − ln [ ]
2 0.160
𝑘 = 0.3466 𝑚𝑖𝑛−1
The constancy of the rate constant k, indicates that the decomposition of N2O5 is a first order
reaction.
0.3478 + 0.3466 + 0.3499 + 0.3466
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑘) =
4
𝑨𝒗𝒆𝒓𝒂𝒈𝒆 𝒗𝒂𝒍𝒖𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒓𝒂𝒕𝒆 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 (𝒌) = 𝟎. 𝟑𝟒𝟕𝟕 𝒎𝒊𝒏−𝟏
15. From the following data, show that the decomposition of hydrogen peroxide in aqueous is
a first order reaction. What is the value of rate constant?
Time, min 0 10 20 30 40
N 25.0 20.0 15.7 12.5 9.6
Where N is the number of ml of KMnO4 required to decompose a definite volume of H2O2
solution.

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Solution: The initial volume of KMnO4, V0 (i.e., when t = 0) corresponds to the initial
concentration of H2O2 (i.e., CA0) and the volume of KMnO4 at any time t corresponds to the
undecomposed H2O2 at that time (i.e., CA).
As the decomposition is a first order reaction, for the first order reaction, we have
1 𝐶𝐴0
𝑘 = ln [ ]
𝑡 𝐶𝐴
CA0 = 25 ml
For t = 10 min, CA = 20 ml
1 𝐶𝐴0
𝑘= ln [ ]
𝑡 𝐶𝐴
1 25
𝑘= ln [ ]
10 20
𝑘 = 0.0223 𝑚𝑖𝑛−1
For t = 20 min, CA = 15.7 ml

1 𝐶𝐴0
𝑘= ln [ ]
𝑡 𝐶𝐴
1 25
𝑘= ln [ ]
20 15.7
𝑘 = 0.02326 𝑚𝑖𝑛−1
For t = 30 min, CA = 12.5 ml
1 𝐶𝐴0
𝑘= ln [ ]
𝑡 𝐶𝐴
1 25
𝑘= ln [ ]
20 12.5
𝑘 = 0.0231 𝑚𝑖𝑛−1
For t = 40 min, CA = 9.8 ml

1 𝐶𝐴0
𝑘=
ln [ ]
𝑡 𝐶𝐴
1 25
𝑘= ln [ ]
20 9.8
𝑘 = 0.0239 𝑚𝑖𝑛−1
0.0223 + 0.02326 + 0.0231 + 0.0239
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑘) =
4
𝑨𝒗𝒆𝒓𝒂𝒈𝒆 𝒗𝒂𝒍𝒖𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒓𝒂𝒕𝒆 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 (𝒌) = 𝟎. 𝟎𝟐𝟑𝟏𝟒 𝒎𝒊𝒏−𝟏
Since the value of k (avg. = 0.02314 min-1) is almost constant. The decomposition is first order.

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16. In case of a first order reaction, show that the time required for 75% conversion is double
the time required for 50% conversion.
Solution: The integrated rate equation for first order reaction in terms of conversion is
1
𝑙𝑛 ( ) = 𝑘𝑡
1 − 𝑋𝐴
1 1
𝑡 = 𝑙𝑛 ( )
𝑘 1 − 𝑋𝐴
Let us first find time t for 50% conversion
XA = 0.75
1 1
𝑡′ = 𝑙𝑛 ( )
𝑘 1 − 𝑋𝐴
1 1
𝑡′ = 𝑙𝑛 ( )
𝑘 1 − 0.5
𝟎. 𝟔𝟗𝟑
𝒕′ = … … (𝟏)
𝒌
Let us first find time t for 75% conversion,
XA = 0.75
1 1
𝑡′′ = 𝑙𝑛 ( )
𝑘 1 − 𝑋𝐴
1 1
𝑡′′ = 𝑙𝑛 ( )
𝑘 1 − 0.75
𝟏. 𝟑𝟖𝟔
𝒕′′ = … … (𝟐)
𝒌
Comparing equation (1) and (2),
𝟏. 𝟑𝟖𝟔
𝒕′′ = = 𝟐𝒕′
𝒌
Thus, the time required for 75% conversion is double that required for 50% conversion.
17. Liquid A decomposes by first order kinetics. In a batch reactor, 50% of A is converted in 5
minutes. How long it would take to reach 75% conversion?
Solution: A------>Products
For a first order reaction, the rate equation is
−𝑟𝐴 = 𝑘 𝐶𝐴
In terms of conversion, the integrated rate expression for first order reaction is
1
𝑙𝑛 ( ) = 𝑘𝑡
1 − 𝑋𝐴
Case I: XA = 0.5 when t = 5 min
1
𝑙𝑛 ( )=𝑘×5
1 − 0.5

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𝒌 = 𝟎. 𝟏𝟑𝟖𝟔 𝒎𝒊𝒏−𝟏
Case I: XA = 0.75 when t =?
1
𝑙𝑛 ( ) = 0.1386 × 𝑡
1 − 0.75
𝒕 = 𝟏𝟎 𝒎𝒊𝒏
18. At certain temperature, the half-life periods and initial concentration for a reaction are
t1/2 = 420 s, CA0 =0.405 mol/l
t1/2 = 275 s, CA0 =0.64 mol/l
Find the rate constant of a reaction. (4 Marks)
Solution:
′ ′′
𝑙𝑛 𝑡1/2 ⁄𝑡1/2
𝑛 =1+ ′ ⁄ ′′
𝑙𝑛 𝐶𝐴0 𝐶𝐴0
′ ′
where 𝑡1/2 = 420 s, 𝐶𝐴0 = 0.405 mol/l
′′ ′′
𝑡1/2 = 275 s, 𝐶𝐴0 = 0.64 mol/l
𝑙𝑛 420⁄275
𝑛 =1+
𝑙𝑛 0.405⁄0.64
𝑛 = 1 + 0.925
𝒏 = 𝟏. 𝟗𝟐𝟓 ≈ 𝟐
th
The half-life for n order reaction is given by
2𝑛−1 − 1
𝑡1/2 = 𝑛−1
(𝑛 − 1)𝑘 𝐶𝐴0
Rearranging gives
2𝑛−1 − 1
𝑘= 𝑛−1
𝑡1/2 𝐶𝐴0
Putting n=2, we get
2−1
𝑘=
𝑡1/2 𝐶𝐴0
1
𝑘=
420 × 0.405
𝒌 = 𝟓. 𝟖𝟖 × 𝟏𝟎−𝟑 (𝒍⁄𝒎𝒐𝒍)(𝒎𝒊𝒏−𝟏 )

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19. Reactant A decomposes in a batch reactor. A Product.

The composition of A in the reactor is measured at various times. Find a rate equation to
represent the data using integral method of analysis.
Time, t sec 0 20 40 60 120 180 300
Conc. CA mol/ litre 11 9 7.2 6.5 4.3 3 2
(7 marks)
Solution: 𝐴 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
For a first order reaction, we have
𝐶𝐴
− ln [ ] = 𝑘. 𝑡
𝐶𝐴0
(1) CA = 9 mol/l at CA0 = 11; t = 20 s.
1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 9
𝑘=− ln [ ]
20 11
𝒌 = 𝟎. 𝟎𝟏𝟎 𝒔𝒆𝒄−𝟏
(2) CA = 7.2 mol/l at t = 40 s.
1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 7.2
𝑘=− ln [ ]
40 11
𝒌 = 𝟎. 𝟎𝟏𝟎 𝒔𝒆𝒄−𝟏
(3) CA = 6.5 mol/l at t = 60 s.
1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 6.5
𝑘=− ln [ ]
60 11
𝒌 = 𝟎. 𝟎𝟎𝟖𝟕𝟔 𝒔𝒆𝒄−𝟏
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(4) CA = 4.3 mol/l at t = 120 s.

1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 4.3
𝑘=− ln [ ]
120 11
𝒌 = 𝟎. 𝟎𝟎𝟕𝟖𝟐 𝒔𝒆𝒄−𝟏
(5) CA = 3 mol/l at t = 180 s.
1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 3
𝑘=− ln [ ]
180 11
𝒌 = 𝟎. 𝟎𝟎𝟕𝟐𝟏 𝒔𝒆𝒄−𝟏
(6) CA = 2 mol/l at t = 300 s.
1 𝐶𝐴
𝑘 = − ln [ ]
𝑡 𝐶𝐴0
1 2
𝑘=− ln [ ]
300 11
𝒌 = 𝟎. 𝟎𝟎𝟓𝟔𝟖 𝒔𝒆𝒄−𝟏
Time, t sec 0 20 40 60 120 180 300

Conc. CA 11 9 7.2 6.5 4.3 3 2
mol/ litre
K 1.010*10^-3 1.199*10^-3 1.048*10^-3 1.1804 1.3468 1.3636
*10^-3 *10^-3 *10^6

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20. In a gaseous reaction, the time for half change (t1/2) for the various initial partial pressures
(p) of the reactant was given as follows:
PA0 (torr) 200 300 400

t1/2 (min) 150 99.8 75.3
Find the order of the reaction.

Solution: We have
1−𝑛
𝑡1/2 𝛼 𝐶𝐴0
′ ⁄ ′′ )1−𝑛
𝑡1/2 ′ ⁄𝑡1/2 ′′ = ( 𝐶𝐴0 𝐶𝐴0
′ ⁄ ′′ )
ln(𝑡1/2 ′ ⁄𝑡1/2 ′′ ) = (1 − 𝑛) ln( 𝐶𝐴0 𝐶𝐴0
′′ ⁄ ′ )
ln(𝑡1/2 ′ ⁄𝑡1/2 ′′ ) = (𝑛 − 1) ln( 𝐶𝐴0 𝐶𝐴0
ln(𝑡1/2 ′ ⁄𝑡1/2 ′′ )
𝑛 =1+ ′′ ⁄ ′ )
ln( 𝐶𝐴0 𝐶𝐴0
We have
𝐶𝐴0 𝛼 𝑝𝐴0
ln(𝑡1/2 ′ ⁄𝑡1/2 ′′ )
𝑛 =1+ ′′ ⁄ ′ )
ln( 𝑝𝐴0 𝑝𝐴0
′ ′′
For 𝑡1/2 ′ = 150, 𝑝𝐴0 = 200 𝑎𝑛𝑑 for 𝑡1/2 ′′ = 99.8, 𝑝𝐴0 = 300
ln(150⁄99.8)
𝑛 =1+
ln( 300⁄200)
0.4074
𝑛 =1+
0.4054
𝑛 = 1 + 1.003
𝑛=2
′ ′′
Similarly, For 𝑡1/2 ′ = 99.8, 𝑝𝐴0 = 300 𝑎𝑛𝑑 for 𝑡1/2 ′′ = 75.3, 𝑝𝐴0 = 400

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ln(99.8⁄75.3)
𝑛 = 1+
ln( 400⁄300)
0.281
𝑛 =1+
0.287
𝑛 = 1 + 0.976
𝑛 = 1.987 ≈ 2
Thus, the order of the reaction is two.
21. Show that the time required for 99% conversion is double the time required for 90%
conversion for the first order irreversible unimolecular reaction. (S-22 for 7 marks)
Solution: The integrated rate equation for first order reaction in terms of conversion is
1
𝑙𝑛 ( ) = 𝑘𝑡
1 − 𝑋𝐴
1 1
𝑡 = 𝑙𝑛 ( )
𝑘 1 − 𝑋𝐴
Let us first find time t for 99% conversion
XA = 0.99
1 1
𝑡′ = 𝑙𝑛 ( )
𝑘 1 − 𝑋𝐴
1 1
𝑡′ = 𝑙𝑛 ( )
𝑘 1 − 0.99
𝟒. 𝟔𝟎𝟓
𝒕′ = … … (𝟏)
𝒌
Let us first find time t for 90% conversion,
XA = 0.9
1 1
𝑡′′ = 𝑙𝑛 ( )
𝑘 1 − 𝑋𝐴
1 1
𝑡′′ = 𝑙𝑛 ( )
𝑘 1 − 0.9
𝟐. 𝟑𝟎𝟐
𝒕′′ = … … (𝟐)
𝒌
Comparing equation (1) and (2),
𝟐. 𝟑𝟎𝟐
𝒕′′ = = 𝟐𝒕′
𝒌

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Q22. dipsersed non coalesing droplets [ Cao = 2 mol/liter ] react as per the reaction A-->R with
rate equation -rA=kCA2, k=0.5 lit/(mol.min) as they pass through the contactor. find the average
concentration of A remaining in the dropletets leaving the contactor (use E=0.50 for 1<t<3).
Solution: G-7.26
Q23. The first order reversible liquid reaction

A R, CAO = 0.5 mol/liter, CRO=0
takes place in a batch reactor. After 9 minutes, conversion of A is 30 % while equilibrium
conversion is 70%. Find the rate equation for this reaction.
Solution:
A ↔ R … first order reaction
Here we have to evaluate k1 and k2

Given , CAO = 0.5 mol/liter, CRO=0
t = 9 min, XA = 0.30 XAe= 0.7, Rate equation?
M=CR0/ CA0 = 0/0.5 = 0
The integrated rate equation for the first order reversible reaction is
𝑋𝐴 𝑀+1
∴ −𝑙𝑛 [1 − ]=( )𝑘 𝑡
𝑋𝐴𝑒 𝑀 + 𝑋𝐴𝑒 1
0.30 1
∴ −𝑙𝑛 [1 − ]=( ) 𝑘 ×9
0.70 0.70 1
−𝟏
𝒌𝟏 = 𝟎. 𝟎𝟒𝟑𝟓𝟏 (𝒎𝒊𝒏)
𝑘𝑐 𝑖𝑠 𝑔𝑖𝑣𝑒𝑛 𝑏𝑦
𝐶𝑅𝑒 𝑀 + 𝑋𝐴𝑒 𝐾1
𝑘𝑐 = = =
𝐶𝐴𝑒 1 − 𝑋𝐴𝑒 𝐾2
𝐾1 0 + 0.70
=
𝐾2 1 − 0.70
1 − 0.70
𝑘2 = 𝑘1
0.70

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𝒌𝟐 = 𝟎. 𝟎𝟏𝟖𝟔𝟒 (𝒎𝒊𝒏)−𝟏
Rate equation is
𝑑𝐶𝐴
−𝑟𝐴 = = 𝑘1 𝐶𝐴 − 𝑘2 𝐶𝑅
𝑑𝑡
−𝒓𝑨 = (𝟎. 𝟎𝟒𝟑𝟓𝟏 (𝒎𝒊𝒏)−𝟏 )𝑪𝑨 − (𝟎. 𝟎𝟏𝟖𝟔𝟒 (𝒎𝒊𝒏)−𝟏 )𝑪𝑹 , 𝒎𝒐𝒍/(𝒍. 𝒎𝒊𝒏)
The first order reversible liquid reaction (page no 2.75)

A → R, CAO = 0.5 mol/liter, CRO=0
takes place in a batch reactor. After 8 minutes, conversion of A is 33.3% while equilibrium
conversion is 66.7%. Find the rate equation for this reaction.
10. A homogeneous gas reaction A 3R has a reported rate at 215 0C

-rA = 10-2 CA 1/2, [mol/liter sec]
Find the space-time needed for 80% conversion of a 50% A, 50% inert feed to a plug flow
reactor operating at 215 0C and 5 atm (CAo = 0.0625 mol/liter).
9. The aqueous reactions A R + S proceeds as follows, (page no 2.78)
Time, Min 0 36 65 100 160 ∞

CA, mol/lit 0.1823 0.1453 0.1216 0.1025 0.0795 0.0494
With CA0 = 0.1823 mol/lt, CR0 = 0, CS0 = 55 mol/lit. Find a rate equation for this reaction.
12. The first order reversible liquid reaction A R, C A0 = 0.5 mol/lit, CR0 = 0 takes place
in a batch reactor. After 8 minutes, conversion of A is 33.3% while equilibrium conversion is
66.7%. Find the rate equation for this reaction.
(7 marks)

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Q-1. Discuss the classification of chemical reaction based on thermodynamics and
stoichiometry with suitable examples of each.
Solution: Classification of chemical reaction

1. Chemical reaction may be classified depending upon the number of phases involved as
homogenous and heterogenous reactions.
Homogenous reaction is one which takes place in only one phase, i.e., all the reactant
materials, product and catalysts (if any) will all be present within a single phase (one
phase).
Examples:
(i) Oxidation of nitrogen oxide to nitrogen dioxide with air, is a gas phase reaction.
1
NO + O → NO2
2 2
(ii) Formation of ester from organic acids and alcohols in the presence of sulphuric
acid is a liquid phase reaction.
𝐻2 𝑆𝑂4
C2 H5 OH + CH3 COOH ↔ 𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5
Heterogenous reaction is one which involves presence of more than one phase i.e., in
heterogenous reactions at least one of the reactants, catalyst or products is present in a
phase different from that of the remaining components of the reacting system.
Examples:
Oxidation of sulfur dioxide to sulfur trioxide using vanadium pentoxide catalyst is
heterogenous reaction as SO2, O2 and SO3 are gaseous while V2O5 is a solid material.
1 𝑉2 𝑂5
𝑆O2 + O2 → 𝑆𝑂3
2
2. The reaction may be classified as catalytic and non-catalytic reactions.

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Catalytic reactions are those reactions which involve the use of catalyst to enhance the rate
of a reaction/speed of a reaction.
𝑁𝑖
𝐻𝑒𝑎𝑡
Example: C2 H4 + H2 ↔ 𝐶2 𝐻6
Ethylene Ethane
Hydrogenation of ethylene is a catalytic reaction which makes use of nickel catalyst.
Non-catalytic reactions are those reactions which does not involve use of catalyst.
Oxidation of NO to NO2 is a non-catalytic reaction.
1
NO + O → NO2
2 2
3. The reaction may be classified based upon the molecularity of a reaction, i.e., based upon
the number of molecules that take part in the reaction (in the rate determining step) as
unimolecular, bimolecular and trimolecular reactions.
Examples:
(i) Decomposition of cyclobutene is a unimolecular reaction.
H2C - CH2
2C2H4
H2C - CH2
Cyclo-butane ethylene
(ii) Decomposition of hydrogen iodide is a bimolecular reaction which involves
collision of two molecules.
2HI (g) → I2 (g) + H2 (g)
(iii) Oxidation of NO to NO2 is a trimolecular/termo-molecular reaction which
involves collision of three molecules.
2NO + O2 → 2NO2
4. The reactions may be classified based upon the heat effect (i.e., according as they give off
or absorb heat to or from the surroundings) as exothermic and endothermic reactions.
An exothermic reaction is the one in which heat is evolved.
The reaction between CO and H2 to produce methanol is an exothermic reaction.
CO + 2H2 → CH3OH + Heat
An endothermic reaction is the one in which heat is absorbed (heat will be supplied to
the reacting system from the surrounding for reaction to take place).

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Dehydration of ethyl alcohol to produce ethylene is an endothermic reaction.

Al2O3
C2H5OH C2H4 + H2O – Heat
Ethyl alcohol Ethylene
5. The reactions may be classified based upon the order of a reaction as first order reaction,
second order reaction, third order reaction, etc.
A reaction of which overall order of reaction is one (i.e., sum of order with respect to
participants in the reaction is unity) is called first order reaction.
Decomposition of nitrogen pentoxide is a first order reaction.
1
𝑁2 𝑂5 → 𝑁𝑂2 + O
2 2
A reaction of which the sum of orders with respect to reactants participated in the reaction is two,
is called second order reaction.
Saponification of ester is a second order reaction.
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH
Ethyl acetate Sodium acetate
Example of third order reaction is
2NO(g) + H2 (g) → N2O (g) + H2O (g)
(6) The reactions are also classified as reversible and irreversible based upon whether they
proceed in one or both the directions.
Reversible reactions are those in which the forward and reverse reactions take place
simultaneously.
Example: Esterification reaction is a reversible reaction.
𝐻+
C2 H5 OH + CH3 COOH ⇔ CH3 COOC2 H5 + H2 O
Ethanol Acetic acid Ethyl acetate
Irreversible reactions are those which proceed only in one direction (till the reactants practically
disappear).
Example: Nitration of benzene is an irreversible reaction.
𝐻+
C6 H6 + HNO3 → C6 H5 NO2 + H2 O
Benzene Nitrobenzene

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Q-2. What is rate equation? Also mention unit of rate of reaction and rate constant for first,
second and third order elementary chemical reactions.
Solution: Suppose a single-phase reaction aA + bB → rR +sS. The most useful measure of

reaction rate for reactant A is then
rate of disappearance of A
1 𝑑𝑁𝐴 (𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐴 𝑑𝑖𝑠𝑎𝑝𝑝𝑒𝑎𝑟𝑖𝑛𝑔) 𝑚𝑜𝑙

−𝑟𝐴 = − = , [ 3 ] … . (1)
𝑉 𝑑𝑡 (𝑣𝑜𝑙𝑢𝑚𝑒)(𝑡𝑖𝑚𝑒) 𝑚 .𝑠
Note that this is an

The minus sign means
intensive measure
disappearance
In addition, the rates of reaction of all materials are related by

−𝑟𝐴 −𝑟𝐵 𝑟𝑅 𝑟𝑆
= = =
𝑎 𝑏 𝑟 𝑠
Experience shows that the rate of reaction is influenced by the composition and the energy of the
material. By energy we mean the temperature (random kinetic energy of the molecules), the light
within the system (this may affect the bond energy between atoms), the magnetic field intensity,
etc. ordinarily we only need to consider the temperature, so let us focus on this factor. Thus, we
can write
mol/m3. s
−𝑟𝐴 = 𝑓[(𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠), (𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑜𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠)]
𝑚𝑜𝑙 1−𝑎
As an example, ( 𝑚3 ) 𝑠 −1 Activation energy
𝑒 −𝐸 ⁄𝑅𝑇 𝐶𝐴𝑎
𝑘𝐶𝐴𝑎 = 𝑘0 ⏟

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reaction temperature
order dependent term
Here are a few words about the concentration dependent and the temperature-dependent terms of
the rate.
Q-3. Discuss molecularity and order of reaction with suitable examples.
Solution:
1.The molecularity is defined as the number of molecules, atoms or ions participating the rate
determining step of the reaction.
2. The order of reaction is defined as the sum of the exponents of the concentrations in the rate
equation.
3. Molecularity of a reaction is a theoretical quantity to satisfy the experimental finding whereas
the order of the reaction is entirely an experimental quantity.
4. Molecularity of a reaction must be a whole number and never be zero or a fraction but the
order of a reaction may be a whole number, zero or a fraction.
Q-4. Discuss variable factor affecting the rate of reaction.
Solution:
(i) Nature of the reactants.
(ii) Concentration of the reactants
(iii) Temperature at which the reaction occurs
(iv) Pressure of the reacting system.
(v) Pressure of catalyst in the reaction
(vi) Physical state of the reactant (area of contact between the reactants)
(vii) Rates of heat and mass transfer.
For homogenous system, the possible factor that affect the rate of reaction are temperature,
pressure and composition of the reaction system. These are interdependent factors and the
pressure is determined given the temperature and composition of the phase. Thus, for

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homogenous systems, we can write the rate of reaction as a function of the temperature and
composition.
𝑚𝑜𝑙
−𝑟𝐴 = 𝑓[𝑡𝑒𝑚𝑝𝑟𝑎𝑡𝑢𝑟𝑒 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠, 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚],
(𝑙. 𝑠)
As an example, for A -→ R
−𝑟𝐴 = 𝑘. 𝐶𝐴𝛼
−𝑟𝐴 = 𝑘𝑜 . 𝑒 −𝐸⁄𝑅𝑇 . 𝐶𝐴𝛼
Where,
𝑘𝑜 . 𝑒 −𝐸⁄𝑅𝑇 - Temperature dependent term
𝐶𝐴𝛼 - Concentration dependent term
E- Activation energy
α- order of reaction with respect to A.
Q-5. Define single and multiple reactions. Classify multiple reactions.
Solution: When a single stoichiometric equation and single rate equation are chosen to
represent the progress of the reaction, we have a single reaction. When more than one
stoichiometric equation is chosen to represent the observed changes, then more than one kinetic
expression is needed to follow the changing composition of all the reaction components, and
we have multiple reactions.
Multiple reactions may be classified as:
series reactions
A → R →S
parallel reactions, which are of two types
R A → R
A and
S A → S
Competitive Side by side
and more complicated schemes, an example of which is
A+B →R
R+B →S
Here, reaction proceeds in parallel with respect to B, but in series with respect to A, R, and S.

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Q-6. Differentiate between Elementary and Non-Elementary reactions.

Solution:
1. Elementary reactions are single step reactions whereas nonelementary reactions are
multistep reactions i.e., such reactions occur through series of reaction steps.
2. Elementary reactions are simple in nature whereas the nonelementary reactions are
complex in nature.
3. For elementary reaction, the order agrees with the stoichiometry (i.e., order is equal to
stoichiometry co-efficient of a reacting participant) whereas for nonelementary reaction,
the order does not agree with the stoichiometry (i.e., there is difference between order and
stoichiometry co-efficient).
4. For elementary reaction, the order of reaction must be an integer whereas for
nonelementary reaction, the order of a reaction may be an integer or have a fractional
value.
5. For elementary reaction, 2A → S, the rate law is -rA = k CA2 whereas for nonelementary
reaction 2B → S, the rate law is -rB = k CBα where α ≠ 2.
6. Example of an elementary reaction:
(i) C2H5OH + CH3COOH → CH3COOC2H5 +H2O
Example of nonelementary reaction:
(i) H2 + Br2 → 2HBr
(ii) CH3CHO → CH4 +CO

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Q7. What is an autocatalytic reaction? For an autocatalytic reaction A + R → R + R show that

ln[(𝑀+𝑋𝐴)/𝑀 (1−𝑋𝐴)] =𝐶𝐴0 (𝑀+1) 𝑘𝑡
autocatalytic reaction.
Consider the following simple autocatalytic reaction
A+R→R+R
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴 𝐶𝑅 … . (1)
𝑑𝑡
As the total number of moles of A and R at any time t during the course of reaction remain
unchanged, the stoichiometry related the concentrations of reacting components and so we
can write
𝐶𝑜 = 𝐶𝐴 + 𝐶𝑅 = 𝐶𝐴𝑜 + 𝐶𝑅𝑜 = Constant , at any time t
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 ) … . (2)
𝑑𝑡
Rearrangement, we get
−𝑑𝐶𝐴
= 𝑘 𝑑𝑡 … (3)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
Braking into partial fraction, we get
𝐴 𝐵 1
+ = … . (4)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 ) 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
𝐴 (𝐶𝑜 − 𝐶𝐴 ) + 𝐵 (𝐶𝐴 ) = 1

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For calculating A, put 𝐶𝐴 = 0,
1
𝐴=
𝐶𝑜
Similarity,
For calculating B, Put 𝐶𝐴 = 𝐶𝑜 ,

1
𝐵=
𝐶𝑜
So, putting values of A and B and integrating equation (4)
1 1 1
+ = … . (5)
𝐶𝑜 𝐶𝐴 𝐶𝑜 (𝐶𝑜 − 𝐶𝐴 ) 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
Rearranging equation (3)

𝐶𝐴 𝑡
1 1
−∫ [ − ] 𝑑𝐶𝐴 = 𝑘 ∫ 𝑑𝑡 … . (6)
𝐶𝐴𝑜 𝐶𝑜 𝐶𝐴 𝐶𝑜 (𝐶𝑜 − 𝐶𝐴 ) 0
1 𝐶𝐴 1 1
− ∫ [ − ] 𝑑𝐶𝐴 = 𝑘 𝑡
𝐶𝑜 𝐶𝐴𝑜 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴 )
𝐶𝐴 𝐶𝐴
1 𝑑𝐶𝐴 𝑑𝐶𝐴
− [∫ [ ]−∫ [ ]] = 𝑘 𝑡
𝐶𝑜 𝐶𝐴𝑜 𝐶𝐴 𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 )
𝐶𝐴 𝐶𝑜 − 𝐶𝐴
−𝑙𝑛 ( ) + 𝑙𝑛 ( ) = 𝐶𝑜 𝑘 𝑡
𝐶𝐴𝑜 𝐶𝑜 − 𝐶𝐴𝑜
𝐶𝐴𝑜 𝐶𝑜 − 𝐶𝐴
𝑙𝑛 ( ) + 𝑙𝑛 ( ) = 𝐶𝑜 𝑘 𝑡
𝐶𝐴 𝐶𝑜 − 𝐶𝐴𝑜
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 )
∴ 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡 … (7)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 )
𝐶𝑜 = 𝐶𝐴 + 𝐶𝑅 = 𝐶𝐴𝑜 + 𝐶𝑅𝑜
𝐶𝐴 = 𝐶𝑜 − 𝐶𝑅
𝐶𝐴𝑜 = 𝐶𝑜 − 𝐶𝑅𝑜
So,
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝑜 + 𝐶𝑅 )
∴ 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡 … (8)
𝐶𝐴 (𝐶𝑜 − 𝐶𝑜 + 𝐶𝑅𝑜 )

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𝐶𝐴𝑜 𝐶𝑅
∴ 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡
𝐶𝐴 𝐶𝑅𝑜
𝐶𝐴𝑜 𝐶𝑅 𝐶𝑅 /𝐶𝑅𝑜
∴ 𝑙𝑛 [ ] = 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡
𝐶𝐴 𝐶𝑅𝑜 𝐶𝐴 /𝐶𝐴𝑜
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) 𝐶𝐴𝑜 𝐶𝑅 𝐶𝑅 /𝐶𝑅𝑜

∴ 𝑙𝑛 [ ] = 𝑙𝑛 [ ] = 𝑙𝑛 [ ] = 𝐶𝑜 𝑘 𝑡 = (𝐶𝐴𝑜 + 𝐶𝑅𝑜 ) 𝑘 𝑡 … . . (9)
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) 𝐶𝐴 𝐶𝑅𝑜 𝐶𝐴 /𝐶𝐴𝑜
𝐶
In terms of the initial reactant ratio 𝑀 = 𝐶𝑅𝑜 and XA is the fractional conversion of A, then
𝐴𝑜
∴ 𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴0 (1 − 𝑋𝐴 )]
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴0 + 𝐶𝐴0 𝑋𝐴 ]
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝑅𝑜 + 𝐶𝐴0 𝑋𝐴 ]
𝐶𝑅𝑜
𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 . 𝐶𝐴0 [ ⁄𝐶 + 𝑋𝐴 ]
𝐴0
𝑪𝑨𝒐 (𝑪𝒐 − 𝑪𝑨 ) = 𝑪𝑨𝒐 𝟐 [𝑴 + 𝑿𝑨 ] … (𝟏𝟎)
∴ 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 (1 − 𝑋𝐴 ) [ 𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴𝑜 ]
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 (1 − 𝑋𝐴 ) 𝐶𝑅𝑜
𝐶𝑅𝑜
𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 2 (1 − 𝑋𝐴 )
𝐶𝐴0
𝑪𝑨 (𝑪𝒐 − 𝑪𝑨𝒐 ) = 𝑪𝑨𝟎 𝟐 (𝟏 − 𝑿𝑨 ) 𝑴 … . . (𝟏𝟏)
∴ 𝐶𝑜 𝑘 𝑡 = (𝐶𝐴𝑜 + 𝐶𝑅𝑜 ) 𝑘 𝑡
𝐶𝑅𝑜
𝐶𝑜 𝑘 𝑡 = 𝐶𝐴𝑜 (1 + ) 𝑘𝑡
𝐶𝐴𝑜
𝑪𝒐 𝒌 𝒕 = 𝑪𝑨𝒐 (𝟏 + 𝑴) 𝒌 𝒕 … . . (𝟏𝟐)
In term of M and XA, equation (9) becomes
𝐶𝐴𝑜 2 [𝑀 + 𝑋𝐴 ]
∴ 𝑙𝑛 [ 2 ] = 𝐶𝐴𝑜 (1 + 𝑀) 𝑘 𝑡
𝐶𝐴0 𝑀 (1 − 𝑋𝐴 )

Ph.02622-224581, 220581 Fax : 02622-227481,225458
[𝑴 + 𝑿𝑨 ]
∴ 𝒍𝒏 [ ] = 𝑪𝑨𝒐 (𝟏 + 𝑴) 𝒌 𝒕
𝑴 (𝟏 − 𝑿𝑨 )
Note that some product R (here acting as the catalyst) should be present initially if the
autocatalytic reaction is to be at all.
Q8. Discuss autocatalytic reaction with conversion-time and rate-concentration curves. (4M)
Or define autocatalytic reactions with Conversion-time and rate-concentration curves.
autocatalytic reaction. Consider the following simple autocatalytic reaction
A + R → R + R …. (1a)
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴 𝐶𝑅 … . (1𝑏)
𝑑𝑡
Fig. 1: Conversion-time and rate-concentration curves for autocatalytic reaction of Equation

1(a) & (1b). This shape is typical for this type of autocatalytic reaction.
For an autocatalytic reaction in a batch reactor some product R must be present if the reaction
is to proceed at all. Starting with a very small concentration of R, we see qualitatively that the
rate will rise as R is formed. At the other extreme, when A is just about used up the rate must
drop to zero. This result is given in Fig. 1, which shows that the rate follows a parabola, with
a maximum where the concentrations of A and R are equal.
Q9. Write short note on autocatalytic reactions. (7M)

Solution: When a material reacts away by any nth order rate (n > 0) in a batch reactor, its rate
of disappearance is rapid at the start when the concentration of reactant is high. This rate then

Ph.02622-224581, 220581 Fax : 02622-227481,225458
slows progressively as reactant is consumed. In an autocatalytic reaction, however, the rate at

the start is low because little product is present; it increases to a maximum as product is formed
and then drops again to a low value as reactant is consumed. Figure 1 shows a typical situation.
Reactions with such rate-concentration curves lead to interesting optimization problems. In
addition, they provide a good illustration of the general design method presented in this chapter.
For these reasons let us examine these reactions in some detail. In our approach we deal
exclusively with their 1/(-rA) versus XA curves with their characteristic minima, as shown in
Figure. 1.
Figure 1: Typical rate-concentration curve for autocatalytic reactions,
for example:
A + R → R + R …. (1a)
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘 𝐶𝐴𝑎 𝐶𝑅𝑟 … . (1𝑏)
𝑑𝑡
Plug Flow Versus Mixed Flow Reactor, No Recycle. For any particular rate concentration
curve a comparison of areas in Fig. 2 will show which reactor is superior (which requires a
smaller volume) for a given job. We thus find
1. At low conversion the mixed reactor is superior to the plug flow reactor.
2. At high enough conversions the plug flow reactor is superior.
These findings differ from ordinary nth-order reactions (n > 0) where the plug flow reactor is
always more efficient than the mixed flow reactor. In addition, we should note that a plug flow
Ph.02622-224581, 220581 Fax : 02622-227481,225458
reactor will not operate at all with a feed of pure reactant. In such a situation the feed must be
continually primed with product, an ideal opportunity for using a recycle reactor.
Figure 2. For autocatalytic reactions mixed flow is more efficient at low conversions, plug
flow is more efficient at high conversions

Sitarambhai Naranji Patel: Chemical Engineering Department

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A Vidyabharti Trust Institution

CHEMICAL ENGINEERING DEPARTMENT

CRE-I (Assignment with Question and Answer)

Q-1. Discuss the classification of chemical reaction based on thermodynamics and

stoichiometry with suitable examples of each.

Solution: Classification of chemical reaction

DR. NILESH S DUMORE 1

CHEMICAL ENGINEERING DEPARTMENT

Dehydration of ethyl alcohol to produce ethylene is an endothermic reaction.

DR. NILESH S DUMORE 2

CHEMICAL ENGINEERING DEPARTMENT

second and third order elementary chemical reactions.

Solution: Suppose a single-phase reaction aA + bB → rR +sS. The most useful measure of

DR. NILESH S DUMORE 3

CHEMICAL ENGINEERING DEPARTMENT

1 𝑑𝑁𝐴 (𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐴 𝑑𝑖𝑠𝑎𝑝𝑝𝑒𝑎𝑟𝑖𝑛𝑔) 𝑚𝑜𝑙

Note that this is an

In addition, the rates of reaction of all materials are related by

−𝑟𝐴 = 𝑓[(𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠), (𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑡𝑒𝑟𝑚𝑠)]

𝑘𝐶𝐴𝑎 = 𝑘0 𝑒⏟−𝐸 ⁄𝑅𝑇 𝐶𝐴𝑎

DR. NILESH S DUMORE 4

CHEMICAL ENGINEERING DEPARTMENT

Q-3. Discuss molecularity and order of reaction with suitable examples.

Q-4. Discuss variable factor affecting the rate of reaction.

CHEMICAL ENGINEERING DEPARTMENT

𝑘𝑜 . 𝑒 −𝐸⁄𝑅𝑇 - Temperature dependent term

Q-5. Define single and multiple reactions. Classify multiple reactions.

Multiple reactions may be classified as:

parallel reactions, which are of two types

Competitive Side by side

and more complicated schemes, an example of which is

Q-6. Differentiate between Elementary and Non-Elementary reactions.

DR. NILESH S DUMORE 6

CHEMICAL ENGINEERING DEPARTMENT

6. Example of an elementary reaction:

(i) C2H5OH + CH3COOH → CH3COOC2H5 +H2O

Example of nonelementary reaction:

(i) H2 + Br2 → 2HBr

(ii) CH3CHO → CH4 +CO

Q7. What is an autocatalytic reaction? For an autocatalytic reaction A + R → R + R show that

Consider the following simple autocatalytic reaction

𝐶𝑜 = 𝐶𝐴 + 𝐶𝑅 = 𝐶𝐴𝑜 + 𝐶𝑅𝑜 = Constant , at any time t

DR. NILESH S DUMORE 7

CHEMICAL ENGINEERING DEPARTMENT

For calculating B, Put 𝐶𝐴 = 𝐶𝑜 ,

Rearranging equation (3)

DR. NILESH S DUMORE 8

CHEMICAL ENGINEERING DEPARTMENT

𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) 𝐶𝐴𝑜 𝐶𝑅 𝐶𝑅 /𝐶𝑅𝑜

𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴0 + 𝐶𝐴0 𝑋𝐴 ]

𝐶𝐴𝑜 (𝐶𝑜 − 𝐶𝐴 ) = 𝐶𝐴𝑜 [𝐶𝑅𝑜 + 𝐶𝐴0 𝑋𝐴 ]

𝑪𝑨𝒐 (𝑪𝒐 − 𝑪𝑨 ) = 𝑪𝑨𝒐 𝟐 [𝑴 + 𝑿𝑨 ] … (𝟏𝟎)

∴ 𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 (1 − 𝑋𝐴 ) [ 𝐶𝐴𝑜 + 𝐶𝑅𝑜 − 𝐶𝐴𝑜 ]

𝐶𝐴 (𝐶𝑜 − 𝐶𝐴𝑜 ) = 𝐶𝐴0 (1 − 𝑋𝐴 ) 𝐶𝑅𝑜

𝑪𝑨 (𝑪𝒐 − 𝑪𝑨𝒐 ) = 𝑪𝑨𝟎 𝟐 (𝟏 − 𝑿𝑨 ) 𝑴 … . . (𝟏𝟏)

CHEMICAL ENGINEERING DEPARTMENT

In term of M and XA, equation (9) becomes

Fig. 1: Conversion-time and rate-concentration curves for autocatalytic reaction of Equation

DR. NILESH S DUMORE 10

CHEMICAL ENGINEERING DEPARTMENT

Q9. Write short note on autocatalytic reactions. (7M)

Figure 1: Typical rate-concentration curve for autocatalytic reactions,