Engineering Chemistry

Module -1

A. Laws of thermodynamics - entropy change (selected

processes) – spontaneity of a chemical reaction and Gibbs free
energy - Carnot cycle

B. Kinetics - Order of reactions- Concept of activation energy and

energy barrier - Arrhenius equation- Homogeneous,
heterogeneous and Enzyme catalysis (Lock and Key
mechanism)

1
1st class 5th class
Thermodynamics: Basic Terminologies Chemical kinetics
0th Law of Thermodynamics Factors affecting reaction rates
1st Law of Thermodynamics Rate laws and rate constants
First order reaction
2nd class Half-life of first order reaction
Enthalpy & Heat Capacity 6th class
Application of 1st Law to the Expansion Work Second-order reactions
Numerical from 1st Law Zero-order reactions
Pseudo first order reaction
3rd class 7th class
2nd Law of Thermodynamics Temperature and rate of reactions
Entropy and Carnot Cycle Collision model and activation energy
Arrhenius equation
4th class Catalysis
Free Energy 8th class
Numerical from 2nd law of Thermodynamics Types of catalysis
Spontaneity of a Chemical Reaction Homogeneous and Heterogeneous catalysis
3rd Law of Thermodynamics Enzyme catalysis
2
 Part-A
Thermodynamics
- Laws of thermodynamics
- Entropy change (selected processes)
- Spontaneity of a chemical reaction and
- Gibbs free energy
- Carnot cycle

3
 Thermodynamics: Basic Terminologies

the quantity of matter or a Properties of a system:

Thermodynamic Systems: region in space upon which # Intensive Properties:
attention is concentrated in the
analysis of a problem
Everything
external to
the system

# Extensive
Properties

4
 Thermodynamics: Basic Terminologies

Internal energy (U)

# State function: = Kinetic energy + Potential energy
Depends on the initial state & final state;
independent of the path used to reach from. ∙ It’s a state function & an extensive property
Example: T (Temperature), P (Pressure), U of the system.
(Internal energy), H (Enthalpy) etc. ∙ Internal energy of a system changes when
energy is transferred into or outside the
system in the form of heat or work

# Path function:
Depends on the path between the initial & final
state 5
Example: W (work done), q (heat transferred) etc.
 Thermodynamics: Basic Terminologies
State of a system
⮚ The state of thermodynamic variables Work done on/by the system
such as pressure, temperature, volume, W (Work) = F (force) x w (distance moved in the direction of
composition which describes the system force)
is called state of the system.
⮚ when one/more variables undergo
change, the system is said to have
undergone a change of state
• Adiabatic – no heat transferred
• Isothermal – constant
temperature
• Isobaric – constant pressure
• Isochoric – constant volume
⮚ Gas is heated ⇒ it will expand and pushes the piston, thereby doing work on the piston.
The work done (dw) when the system expands by dV against a pressure Pex:
dw = −PexdV

 This is an example of the system doing the work on the surrounding 6

 Reversible Process in Thermodynamics
# Example 1:
❑ A thermodynamic process is
Thermal equilibrium of two systems with the same temp.
reversible if the process can be
▪ If the temperature of either system is lowered infinitesimally,
turned back such that both the
then energy flows into the system with the lower temperature.
system and the surroundings
▪ If the temperature of either system at thermal equilibrium is
return to their original states,
raised infinitesimally, then energy flows out of the hotter system
with no other change anywhere
else in the universe.
# Example 2:
❑ In reality, no such processes as Reversible expansion:
reversible processes can exist. Suppose a gas is confined by a piston.
external pressure (Pex) = pressure (P) of the confined gas.
❑ A change can be reversed by ▪ Such a system is in mechanical equilibrium with its
an infinitesimal modification of surroundings because an infinitesimal change in the
a variable. external pressure in either direction causes changes in
volume in the opposite directions.

7
 0th Law of Thermodynamics

⮚ According to 0th law:

If two systems are in thermal equilibrium with a third
system, then those two systems are in thermal
equilibrium with each other.

❑ Two physical systems are in

thermal equilibrium if there is no
net flow of heat (thermal energy)
between them when they are
connected by a path permeable to
heat.

⮚ The 0th law of thermodynamics defines thermal equilibrium

and forms a basis for the definition of temperature.

8
 1st Law of Thermodynamics

▪ It’s the law of conservation of energy

❑ The energy of an isolated system remains constant. Whenever a quantity of energy (some
form) disappears, an exactly equivalent quantity of energy (some other form) must make an
appearance.
⮚ Heat (q) and work (w) are equivalent ways of changing the internal energy of a system
→ Example:
o If a weight has been raised/lowered in the surroundings, transfer of energy happens by doing the
work.
o If ice melts in the surroundings, it indicates the transfer of energy as heat.

⮚ For a system, if w = work done on a system, q = energy transferred as heat to a system & ΔU =
resulting change in internal energy
The signs of w and q:
✔ +ve if energy is transferred to the system as work/heat
✔ -ve if energy is lost from the system.

9
 Enthalpy & Heat Capacity

⮚ If the change of a system is brought ❑ Heat capacity (C) of a system b/n any two
about at constant pressure, there will be temperatures – the quantity of heat (q) required to
change in volume. raise the temperature of the system from the lower
temperature (T1) to the higher temperature (T2) divided
by the temperature difference.

☻ If mass of the system is 1 g, the heat capacity is

called the specific heat of the system.
☻ For 1 mol of substance, the heat capacity is
termed as ‘molar heat capacity’

❑ The quantity (U + PV) is called the

enthalpy (H) of the system ⮚ Molar heat capacity varies with temperature

❑ Molar heat capacity at constant volume

ΔU = ΔH – PΔV
or ΔH = ΔU + PΔV @ constant volume w = 0 & ΔU = q
, 10
 Heat Capacity
❑ Molar heat capacity at constant pressure (Cp )
ΔU = q - w
@ constant pressure,
there is change in As quantity (U+PV) is the ⇒
volume & some work is enthalpy (H) of the system
done
❑ Relationship between Cp & Cv ▪ For ideal gas, PV = RT (for 1 mole)
Δ(PV) = R ΔT

Heat capacity ratio,

11
Application of 1st Law to the Expansion Work

⮚ Isothermal Process (constant temperature)

▪ In an isothermal process,
the temperature stays
constant, so the pressure
and volume are
work done inversely proportional to
one another.

⇒ For an ideal gas,

The internal energy (U) ∝ Temperature (T)
if T = fixed, ΔU = 0 (according to 1st law, which deals with ΔU)

▪ If the system does work, the energy

Pressure-volume diagram
comes from heat flowing into the
system from the surrounding
# Magnitude of w depends on whether the ▪ If work is done on the system, heat
expansion is reversible or irreversible. flows out of the system to the
12
surrounding.
 Application of 1st Law to the Expansion Work

⮚ Reversible isothermal expansion:

(as PV = nRT)

▪ Work done by the n moles of gas can be

evaluated as:

in an isothermal expansion of a perfect gas)

 Irreversible Isothermal expansion ⮚ The work done by a perfect gas when it expands
reversibly and isothermally is equal to the area
under the isotherm p = nRT/V.
⮚ The work done during the irreversible
expansion against the same final pressure is
equal to the rectangular area shown slightly
darker. Note that the reversible work done is
greater than the irreversible work done.
13
 Application of 1st Law to the Expansion Work
 Adiabatic process (constant heat)  Reversible adiabatic expansion
 no heat is added/ removed from a  Relation between T, V and P
system. −1
st =
 1 law of thermodynamics: ln = −1

ΔU = w
(as no heat is allowed to enter/leave the system, q = 0)
 Example: A gas expanding so quickly that no heat 푪풑 [ , = ]
 ln = −1
can be transferred. Due to the expansion work, 푪풗
temperature drops. This is exactly what happens 푹
with a carbon dioxide fire extinguisher, with the  ln = [ , ― = R]
푪풗
gas coming out at high pressure and cooling as it
푻풊
expands at atmos. pressure  푪풗 ln
 Expansion: w = ― ve, ∆ 푼 = ― ve; 푻풇
So, T of the system falls 푽풇
 Irreversible
= 푹 풍풏 adiabatic expansion
 Work is done by the system at the expense of
푽
its internal energy  Free expansion (Pex풊 = 0) : ∆ = 0, = 0, ∆
 w = ∆ = 푪풗횫푻 (for 1 mole of gas) =0
 ∆ = 푪 횫푻 (for 1 mole of gas)  Expansion against a constant pressure:
풑
−
− 14
=
 Application of 1st Law to the Expansion Work
 Isobaric
process
(constant
pressure)  Isochoric process (constant volume

 the pressure is kept constant.  the volume is kept constant

 The work done by the system in an isobaric  The work done is zero in an isochoric
process is simply the pressure multiplied by the process
change in volume  . Example of an isochoric system: A gas in a
 Example of an isobaric system: A gas, being box with fixed walls
slowly heated or cooled, confined by a piston in a
cylinder.

15
 2nd Law of Thermodynamics
▪ Why we need for the 2nd law of thermodynamics? ⮚ The 1st law uses the internal energy to
→ The 1st law of thermodynamics does not tell us identify permissible changes
anything about the direction of change. The⮚ The 2nd law uses the entropy to identify
direction of spontaneous change of a process is which of these permissible changes are
defined by the 2nd law of thermodynamics spontaneous.
❑ 2nd law of thermodynamics → A spontaneous process points towards
the direction in which the total entropy
▪ Heat does not flow spontaneously from a cool
increases.
body to a hotter body.
⮚ Entropy (S) is a state function.
▪ The entropy (S) of an isolated system
increases in the course of a spontaneous ⮚ Thermodynamic definition of entropy
change. ΔStot > 0 → The thermodynamic definition of entropy
Where, Stot = S + Ssur concentrates on the change in entropy
S = the entropy of the system of interest, & (dS) that occurs as the result of a
Ssur = the entropy of the surroundings physical or chemical process.
nd
→ dqrev is the energy transferred as heat
# Note: when considering applications of the 2 law – it reversibly to the system at the absolute
is a statement about the total entropy of the overall temperature T.
isolated system (the ‘universe’), not just about the
entropy of the system of interest. 16
 Entropy
▪ Process that leads to an increase in entropy (ΔS > 0)
⮚ Entropy change for the system of an
isothermal expansion of a perfect gas

☻ Notice the increasing disorder in above processes 17

 Entropy
⮚ Total Entropy change in irreversible ⮚ Isothermal Reversible expansion
(spontaneous) process of a perfect gas
✔ example: Isothermal expansion of an ideal gas
at constant temperature into vacuum

⮚ Clausius inequality

⇒ All spontaneous process occurring in

Nature are irreversible and entropy of the
universe is increasing continuously. 18
 Entropy

 The 1st law & the 2nd law of thermodynamics were summed up by German Physicist Rudolf Clausius as below:
The energy of the universe remains constant; the entropy of the universe tends towards a maximum
 Entropy change during different processes  Heat engine
 Its a device which transforms heat into work
 For an ideal gas (1 mole) with variable T & V  This happens in a cyclic process
∆ = ln + ln  Heat engines require a hot reservoir to supply energy
 For an ideal gas with variable P & T (QH ) and a cold reservoir to take in the excess energy (QC)
∆ = ln − ln – QH is defined as positive, QC is defined as negative
 For an ideal gas in an isothermal process  Carnot Cycle
∆ = ln = − ln
 A Carnot cycle (named after the French engineer Sadi
 For an ideal gas in an isobaric process Carnot) consists of four reversible stages in which a gas
∆ = ln (the working substance) is either expanded/compressed in
 For an ideal gas in an isochoric process various ways
∆ = ln  To demonstrate the maximum convertibility of heat into
work
 The system consists of 1 mole of an ideal gas which is
subjected to four strokes
19
  Four stages of Carnot Cycle:
A. 1st stroke: 3A Entropy 83 B. 2nd stroke:
Curve AB: AB: Isothermal expansion at Th Curve BC (B → C): Adiabatic expansion,
Work done by the gas Work done by the gas

C. 3rd stroke:
A Curve CD (C → D): Isothermal compression at TC,
4
Work done on the gas.
Pressure, p

1 Isotherm Adiabat
D. 4th stroke:
D Curve DA (D → A): Adiabatic compression
B Work done on the gas
Adiabat
2
Isotherm 3
• The thermal efficiency ( ) of a heat engine is
C 휼=
Volume, V
풘풐풓풌 풑풆풓풇풐풓풎풆풅
풉풆풂풕 풂풃풐풔풓풃풆풅 풇풓풐풎 풕풉풆 풉풐풕 풔풐풖풓풄풆
Figure 3A.9 The basic structure of a Carnot cycle. Stage 1 is the 푾Another statement of the 2nd Law:
 The “engine” statement of the 2 nd Law:
sothermal reversible expansion at the temperature Th. Stage 2 is =
– adiabatic
a reversible it is impossible for the
expansion in which any to have an 풒풉– It is impossible for any process to have as its sole result
systemfalls
temperature
efficiency
rom Th to Tc. Stage of 100%
3 is an isothermal ( =compression
reversible 1) at Tc. = ퟏthe
− transfer
풒풄 / 풒풉of =heat
ퟏ− from
푻풄a/cooler
푻풉 object to a warmer 20
Stage 4 is an adiabatic reversible compression, which restores the object
 Carnot Cycle

 Four stages of Carnot Cycle:

3A Entropy 83
A. 1st stroke:
Curve AB: AB: Isothermal expansion at Th
Work done by the gas
 The gas is placed in thermal contact with QH (at Th) and
undergoes reversible isothermal expansion from A to B.
A
 The entropy change is qh/Th ( qh = the energy supplied to
4 the system as heat from the hot source)
Pressure, p

1 Isotherm Adiabat 푽푩
풒풉 = − 풘ퟏ = 푹푻풉 풍풏
푽푨
D
B B. 2nd stroke:
Curve BC (B → C): Adiabatic expansion,
Adiabat
2 Work done by the gas
Isotherm 3
 Contact with QH is broken & the gas undergoes
C
reversible adiabatic expansion from B to C.
Volume, V  No energy leaves the system as heat, ΔS = 0
 The expansion is carried on until the temperature of
Figure 3A.9 The basic structure of a Carnot cycle. Stage 1 is the the gas falls from Th to Tc (the temperature of Qc)
isothermal reversible expansion at the temperature Th. Stage 2 is
− 풘ퟐ = − 푪풗 (푻풉 − 푻풄) 21
a reversible adiabatic expansion in which the temperature falls
 Carnot Cycle

3A Entropy 83
C. 3rd stroke:
Curve CD (C → D): Isothermal compression at TC,
Work done on the gas.
 The gas is placed in contact with the cold sink (Qc) and
undergoes a reversible isothermal compression from C to D at
A Tc .
 Energy is released as heat to the cold sink; the entropy change of
4 the system = qc/Tc, where qc is negative.
Pressure, p

1 Isotherm Adiabat
− = 3
D = ln
th
D. 4 stroke:
B
Curve DA (D → A): Adiabatic compression
Adiabat
2 Work done on the gas
Isotherm 3  Contact with Qc is broken and the gas undergoes
C reversible adiabatic compression from D to A such
that the final temperature is Th.
Volume, V
 No energy enters the system as heat, so the change
Figure 3A.9 The basic structure of a Carnot cycle. Stage 1 is the in entropy is zero.
isothermal reversible expansion at the temperature Th. Stage 2 is 4= ( h− )
22
a reversible adiabatic expansion in which the temperature falls
 3A Entropy 83
Carnot Cycle

 The area enclosed by the four curves represents the net

work done by the engine in one cycle
 The total change inHot
entropy around the cycle is the sum A
of the changes in each of these four steps:
Stage 4
Pressure, p

Pressure, p
1
∮ Stage
= h1
Isotherm Adiabat
h D
+ B
Cold
 For an ideal gas, ∮
Stage 3
= 0 and h
=
Stage 2
Adiabat
2
Isotherm 3
−Efficiency
h of a heat engine
C
• The thermal efficiency of a heat engine is
Volume, V Volume, V
= ==1− / h =
h h h
Figure 3A.8 The four stages which make up the Carnot cycle.
h Figure 3A.9 The basic structure of a Carnot cycle. Stage 1 is the
1− / h
In stage 1 the gas (the working substance) is in thermal contact isothermal
• Another reversible expansion
statement of the 2ndatLaw:
the temperature Th. Stage 2 is
 The “engine” statement of the 2 Law: nd
with –theithot reservoir, andfor
in stage 3 contact –a reversible adiabatic for
It is impossible expansion in whichtothe
any process temperature
have falls
as its sole
is impossible any system toishave
with an
the cold
fromresult
Th to Tthe transfer of heat from a cooler object to
c. Stage 3 is an isothermal reversible compression at Tc.
reservoir;efficiency
both stages
of are isothermal.
100% ( = 1) Stages 2 and
[Kelvin’s 4 are
statement] a warmer
Stage object reversible
4 is an adiabatic compression,
[Clausius’s which23restores the
statement]
adiabatic, with the gas isolated from both reservoirs.
 These
Application of the appliances
Carnot Cycle can be thought of as heat
engines operating in reverse.
By doing work, heat is extracted from the cold
 Energy efficiency of the
reservoir and exhausted to the hot reservoir.
Carnot cycle is independent
of its working substance.
 Any cyclic process that
absorbs heat at one
temperature and rejects
heat at another
temperature and is
reversible has the energy
efficiency of a Carnot cycle.

 Thermal devices or thermal machines are one of

the applications of this cycle.
 Refrigeration, Air conditioners & Heat pumps
 The heat pumps to produce heating,
● These appliances are heat engines operating
 the refrigerators to produce cooling,
in reverse.
 the steam turbines used in the ships,
● By doing work, heat is extracted from the cold
 the combustion engines of the combustion vehicles
reservoir & exhausted to the hot reservoir
 the reaction turbines of the aircraft 24
 Temperature & Free Energy

 Thermodynamic Temperature  Free energy and the spontaneity

 Suppose an engine works reversibly  As, Δ = +
between a hot source at a temperature and Δ is a criterion for the spontaneity/feasibility of a process.
Th and a cold sink at a temperature Tc,
then it follows that  It is not always easy to know the entropy change of
both system and the surrounding
Tc = (1 − η)Th
 We can express this in terms of G (the free energy
 Kelvin used this expression to define the function) and thus can device a criterion of spontaneity
thermodynamic temperature scale in in terms of the state function of the system.
terms of the efficiency of a heat engine in  There are few assumptions:
which the hot source is at a known  Assumption no 1:
temperature and the cold sink is the object The system is in thermal equilibrium with its surroundings at
of interest. a temperature T.
 The Kelvin scale (which is a special case of  Assumption no 2:
the thermodynamic temperature scale) is Heat transfer between the system and the surrounding
currently defined by using water at its happens at constant volume
triple point as the notional hot source and  Assumption no 3:
defining that temperature as 273.16 K Heat transfer between the system and the surrounding
exactly. happens at constant pressure. 25
 Free Energy

 Under the Assumption 1 & Assumption 2  The criterion of spontaneity in terms of Gibbs Free
energy change (dG) and Helmholtz energy (dA)
Clausius inequality becomes: dS − ≥0
≤0& ≤0
[we get this by applying the1stlaw &
the = ]  In an endothermic reaction:
dH > 0
 TdS ≥ dU but if such a reaction is to be spontaneous at constant
dA=dU−TdS [A = Helmholtz free energy] temperature and pressure, G must decrease.

 A=U−TS  as dG = dH − TdS
it is possible for dG to be
negative provided that
 Under the Assumption 1 & Assumption 3 the entropy of the system
Clausius inequality becomes: dS − ≥ 0 increases so much that
[constant P, no additional work] TdS outweighs dH.
 TdS ≥ dH  Endothermic
reactions are
dG=dH−TdS [G = Gibbs free energy] therefore driven by
 G=H−TS the increase of
entropy of the system
26
 Free Energy

 In an exothermic reactions

 Commonly spontaneous because dH < 0 & then  At chemical equilibrium

dG < 0 provided TdS which is not so negative
that it outweighs the decrease in enthalpy.  dG = 0
 Free energy change with
temperature and pressure:

∆ = ln 2
1
= ln 1
2

27
 Spontaneity of a Chemical Reaction
• A spontaneous reaction is a reaction that favors the formation of products at the conditions
under which the reaction is occurring. Spontaneous processes may be fast or slow, but they occur
without outside intervention.
Ex. i) Conversion of graphite to diamond is slow;
ii) A burning fire is relatively a fast reaction.
• "In any spontaneous process there is always an increase in the entropy of the universe“
• For a given change to be spontaneous, ΔSuniverse must be positive.

Gibbs Free Energy

• Free energy is energy that is available to do work. The free energy change of a reaction is a
mathematical combination of the enthalpy change and the entropy change.

• The change in enthalpy, change in entropy and change in free energy of a reaction are the
driving forces behind all chemical reactions.
28
 Conditions for Spontaneity of a Chemical Reaction
(Changes in Enthalpy (ΔH), Entropy (ΔS), and Free Energy (ΔG))
• A spontaneous reaction is one that releases free energy, and so the sign of ΔG must be negative.
Since both ΔH and ΔS can be either positive or negative, depending on the characteristics of the
particular reaction, there are four different possible combinations as shown in the table below.

ΔH◦ ΔS◦ ΔG◦

Negative Positive Always negative

Negative at higher temperatures, positive at

Positive Positive
lower temperatures

Negative at lower temperatures, positive at

Negative Negative
higher temperatures

Positive Negative Always positive

29
 3rd Law of Thermodynamics
▪ At T = 0, all energy of thermal motion has
been quenched and in a perfect crystal all
the atoms/ions are in a regular, uniform
array.
▪ The localization of matter and the absence
of thermal motion suggest that such
materials also have zero entropy.
▪ Statistical or microscopic definition of entropy:
S = k ln W
→ When T = 0, W = 1
where, S = the entropy, ∴ S = k lnW
k = Boltzmann constant, =0
W = the number of microstates ⇒ if the value zero is ascribed to the entropies of elements
or the total number of ways a in their perfect crystalline form at T = 0, then all perfect
molecular state can be crystalline compounds also have zero entropy at T = 0
distributed over the energy
states for a specific value of total
energy. ⮚ Third law of thermodynamics:
The entropy of all perfect crystalline substances is zero at T = 0. 30
 Part-B
Chemical Kinetics
- Order of reactions
- Concept of activation energy and energy barrier
- Arrhenius equation
- Homogeneous catalysis
- Heterogeneous catalysis
- Enzyme catalysis (Lock and Key mechanism)
31
• The chemistry that deals with the reaction rates is known as chemical
kinetics.
• It plays an important role in the production of chemicals on an industrial scale
and the decay of radioactive isotopes used in medicine.
• Chemical kinetics is also useful in providing information about how reactions
occur—the order in which chemical bonds are broken and formed during the
course of a reaction.
• Experimental information on the rate of a given reaction provides important
evidence that helps us formulate a reaction mechanism, which is a step-by-
step, molecular-level view of the pathway from reactants to products.
It is to be contrasted with thermodynamics, which deals with the direction in
which a process occurs but in itself tells nothing about its rate
Factors That Affect Reaction Rates
1. Physical state of the reactants- homogeneous, involving either all gases or all
liquids, or as heterogeneous, in which reactants are in different phases.
2. Reactant concentrations.
3. Reaction temperature.
4. The presence of a catalyst.
 Reaction Rates
On a molecular level, reaction rates depend on the frequency
of collisions between molecules. The greater the frequency of
collisions, the higher the reaction rate.
 The change in concentration of reactants or products per
unit time.
 Here, the instantaneous rate of disappearance of one of
the reactants (A or B) at a given time, t (at constant
volume) is −d[R]/dt.
 Similarly, the rate of formation of one of the products is
d[P]/dt. (Note the change in the sign)
 The negative sign indicates that the concentration is
decreasing with time.
Concentration and the rates of reactions
Consider a general reaction, A + B → C
• The rate of this reaction can be expressed either as the rate of disappearance of reactant
‘A’ and ‘B’ or as the rate of appearance of product ‘C’.
• The rate of reaction will be:
• Average rate of appearance /disappearance of A, B or C = change in concentration of
A, B or C
change in time
d A d B  d C 
  
dt dt dt
Now, consider another general reaction: aA + bB → cC + dD
where a, b, c & d are stoichiometric coefficients
The rate of reaction will be:

1 d A 1 d B  1 d C  1 d D 
  
a dt b dt c dt d dt
The rates of reactions

Sample Questions:
Write rate expressions for the following reactions:
1. NO2 (g) + CO (g) → NO (g) + CO2 (g)
2. 2HI (g) → H2 (g) + I2 (g)

Solution:
d NO2  d CO  d NO  d CO2 
1.    
dt dt dt dt

2. 1 d HI   d H 2   d I 2 
2 dt dt dt

35
Rate laws and rate constants

 The rate law is the relationship between the rate and the concentration, which
are related by a proportionality constant ‘k’, known as rate constant.
For the general reaction:
aA + bB → cC + dD
the rate law generally has the form
rate = k [A]m [B]n
where exponents ‘m’ and ‘n’ are order of reaction in ‘A’ and ‘B’, respectively and
‘k’ is the rate constant.
This above equation is called the rate law of the reaction.
Exponents m and n are typically small whole numbers, whose values are not necessarily
equal to the coefficients a and b from the balanced equation.

36
Rate laws and rate constants…
Important points about rate laws and rate constant:

 Rate law is a result of experimental observation. You CANNOT look

at the stoichiometry of the reaction and predict the rate law (unless
the reaction is an elementary reaction).

 The rate law is not limited to reactants. It can have a product term,
For example: rate = k[A]m [B]n [C]c

 The rate constant is independent of the concentrations but depends

on the temperature.

 The units for k vary. Determine units for k by considering units for
rate and for concentration.

37
Order of a reaction
• It is the sum of the exponents of the concentrations in the rate law equation
• It can be integers, fractions, negative or positive.
• It can be determined only experimentally
• It may not be equal to the number of molecules of reactants
Ex. For the reaction: A+B→C
rate = k [A]m [B]n
• where, m is the order of reaction with respect to A, n is the order of reaction with respect to
B.
• The overall reaction order is the sum of the exponents in the rate law = m + n
 m = 0 (Zero order k [A]0)
 m = 1 (First order k [A]1)
 m = 2 (Second order k [A]2)
Examples:
H2 + Cl2 → 2HCl. Rate = k [H2]0 [Cl2]0 (Zero order)
SO2Cl2(g) → SO2(g) + Cl2(g) Rate = k [SO2Cl2]1 (First order)
2NO2 → 2 NO + O2 Rate = k [NO2]2 (Second order)
2NO(g) + 2H2(g) → 2N2 (g) + 2H2O (g) Rate = k [NO]2 [H2]1 (Third order)
CH3COOC2H5 + H2O  CH3COOH + C2H5OH Rate = k [CH3COOC2H5]1[H2O]0 (pseudo-first-order)

38
 Molecularity of a reaction
• It is the number of molecules or ions that participate in the rate determining step
• It is a theoretical concept and it can be determined from rate determining step
(slowest step).
• It is always an integer between 1 to 3, as it is not possible to colliding of four or
more molecules simultaneously.
• For elementary reactions (single step reactions):
– It is the sum of stoichiometry coefficients of the reactants
Ex. H2 + I2  2HI
Molecularity = 1 + 1 = 2
• For complex reactions:
– The sum of the number of reactant in the rate determining steps gives the
molecularity
 First-Order Reactions
A first-order reaction is one whose rate depends on the concentration of a single reactant raised to
the first power.
If a reaction of the type A  products is first order, the rate law is:
Straight line equation (y = mx + c)
d A
Rate =   k A
dt
Separate concentration and time terms
d A y = mx + c
 kdt
A
If we plot ln [A]t versus time, then we ln[A]0
Integrating over the limits [A]0 to [A]t and 0 to will get a straight line having negative
t, d A
slope (-k).

 A  k  dt Rate constants can be determined

from experiment by plotting data in this
manner. -k
[ A ]t
d A
t

  k  dt
[ A ]0
A 0

lnAt lnA0  kt

Half-Life of First Order Reaction
The half-life of a reaction (t1/2)
• It is the time required for the concentration of a reactant to reach half its initial value, [A]t1/2 = ½
[A]0.
• Half-life is a convenient way to describe how fast a reaction occurs, especially if it is a first-order
process.
• A fast reaction has a short half-life.
• We can determine the half-life of a first-order reaction by substituting
[A]t1/2 = ½ [A]0 for [A]t and t1/2 for t in Equation :
lnAt lnA0  kt

ln ½ [A]0 = -k t1/2
[A] 0
ln ½ = -k t1/2
t1/2 = - ln ½ = 0.693
k k
Ex. The conversion of methyl isonitrile (CH3NC) to its isomer
acetonitrile (CH3CN) at 199 °C.
ln[CH3NC]t = -kt + ln[CH3NC]0

Figure (a) shows how the pressure of this gas varies with time.
Figure (b) shows that a plot of the natural logarithm of the pressure versus time is a straight line.
The slope of this line is -5.1 X 10-5 s-1.k = 5.1 X 10-5 s-1
 Second-Order Reactions
A second-order reaction is one for which the rate depends either on a reactant concentration raised
to the second power or on the concentrations of two reactants each raised to the first power.
For Ex: in reactions A  products or A + B  products that are second order with respect to only
one reactant, A:
d A
 k A
2
Rate = 
dt • This equation, has four variables, k, t, [A]0, and [A]t,
d A and any one of these can be calculated knowing the
 kdt other three.
A 2
• This Equation also has the form of a straight line (y =
With the use of calculus, this differential rate mx + c).
law can be used to derive the integrated rate • If the reaction is second order, a plot of ‘1/ [A]t’
law for second-order reactions: versus ‘t’ yields a straight line with slope k and y-
1 1 intercept 1/ [A]0.
  kt
At A0 • One way to distinguish between first and second-
order rate laws is to graph both ln[A]t and 1/ [A]t
against t.
• If the ln[A]t plot is linear, the reaction is first order;
• if the 1/ [A]t plot is linear, the reaction is second order.
 Half-Life of Second-Order Reactions

The half-life of a chemical reaction is the time taken for half of the initial amount of reactant to
undergo the reaction.
Therefore, while attempting to calculate the half life of a reaction, the following substitutions must
be made:
[A]0
[A]t = and, t = t1/2
ퟐ
Now, substituting these values in the integral form of the rate equation of second order
reactions, we get:
1 1
  kt 1 1
At A0 ≫ –
[A]0 [A]0
= k t1/2

Therefore, the required equation for the half life of second order reactions can be written as
follows.
ퟏ
t1/2 =
k [A]0
This equation for the half life implies that the half life is inversely proportional to the
 Zero-Order Reactions
• We have seen that in a first-order reaction the concentration of a reactant ‘A’ decreases
nonlinearly, as shown by the red curve in Figure.
• As [A] declines, the rate at which it disappears declines in
proportion.
• A zero-order reaction is one in which the rate of
disappearance of A is independent of [A].
• The rate law for a zero-order reaction is
d A
 k A
0
Rate =
dt
At A0  kt
The integrated rate law for a zero-order reaction is Figure. Comparison of first-order and zeroorder
reactions for the disappearance of reactant A with time

where [A]t is the concentration of A at time t and [A]0 Ex. The most common type of zero-order reaction occurs
when a gas undergoes decomposition on the surface of
is the initial concentration.
a solid.
This is the equation for a straight line with vertical 2N2O Pt(hot) 2N2+O2
intercept [A]0 and slope -kt, as shown in the blue Photochemical reaction:
curve in Figure. H2 (g) + Cl2 (g) hv 2HCl(g)
Half-Life of a Zero Order Reaction
The timescale in which there is a 50% reduction in the initial population is referred to as half-
life. Half-life is denoted by the symbol ‘t1/2’.

From the integral form, we have the following equation

[A] = [A0] – k t
Replacing t with half-life t1/2 we get:
1
[A0] = [A0] – k t1/2
2
Therefore, t1/2 can be written as:
1 ퟏ
k t1/2 = [A0] ≫ t1/2 = [A0]
2 ퟐ풌
Pseudo First Order Reaction
A pseudo first-order reaction can be defined as a second-order or bimolecular reaction
that is made to behave like a first-order reaction.
⮚ This reaction occurs when one reacting material is present in great excess or is maintained at
a constant concentration compared with the other substance.

A+B→C
So, if component B is in large excess and the concentration of B is very high as compared to that
of A, the reaction is considered to be a pseudo-first-order reaction with respect to A.
If component A is in large excess and the concentration of A is very high as compared to that of B,
the reaction is considered to be pseudo-first order with respect to B.
For example: CH3COOC2H5 + H2O → CH3COOH + C2H5OH

Rate = k [CH3COOC2H5]

**The concentration of water is very high and thus does not change much during the
course of the reaction.
47
 Temperature and Rate
• The rates of most chemical reactions increase as the
temperature rises.
• The faster rate at higher temperature is due to an increase
in the rate constant with increasing temperature.
• For example, CH3NC  CH3CN
The rate constant and, hence, the rate of the reaction increase
rapidly with temperature, approximately doubling for each 10
°C rise. Temperature dependence of the rate constant
for methyl isonitrile conversion to acetonitrile
The Collision Model
• The greater the number of collisions per second, the greater the reaction rate.
• As reactant concentration increases, therefore, the number of collisions increases, leading
to an increase in reaction rate.
• According to the kinetic-molecular theory of gases, increasing the temperature increases
molecular speeds. As molecules move faster, they collide more forcefully (with more
energy) and more frequently, both of which increase the reaction rate.
The Orientation Factor:
• In most reactions, collisions between molecules result in a chemical reaction only if the
molecules are oriented in a certain way when they collide.
• The relative orientations of the molecules during collision determine whether the atoms are
suitably positioned to form new bonds.
For example,
Cl + NOCl  NO + Cl2
• Molecular collisions may or may not lead to a chemical reaction between Cl and NOCl.
Activation Energy:
• In 1888 the Swedish chemist Svante Arrhenius suggested that molecules must possess a
certain minimum amount of energy to react.
• According to the collision model, this energy comes from the kinetic energies of the colliding
molecules.
• Upon collision, the kinetic energy of the molecules can be used to stretch, bend, and ultimately
break bonds, leading to chemical reactions.
• The minimum energy required to initiate a chemical reaction is called the activation
energy, Ea, and its value varies from reaction to reaction.

Energy is needed to overcome a barrier between initial and final states.

For example, • The difference between the energy of the starting molecule and the highest energy
along the reaction pathway is the activation energy, Ea.
• The molecule having the arrangement of atoms shown at the top of the barrier is
called either the activated complex or the transition state.
• The rate constant depends on the magnitude of Ea
• Generally, the lower the value of Ea is, the larger the rate constant and the faster the
reaction.
Energy profile for conversion of methyl isonitrile
(H3CNC) to its isomer acetonitrile (H3CCN).
The effect of temperature on the distribution of kinetic energies of
molecules in a sample.

• Figure shows the distribution of kinetic energies for two temperatures, comparing
them with the minimum energy needed for reaction, Ea.
• At the higher temperature a much greater fraction of the molecules have kinetic
energy greater than Ea, which leads to a greater rate of reaction.
Arrhenius equation
Arrhenius noted that for most reactions the increase in rate with increasing temperature is nonlinear.
The Arrhenius equation gives the dependence of the rate constant of a chemical reaction on
푬풂
−
the absolute temperature as k = A 풆 푹푻.
where, k is rate constant, Ea is the activation
Arrhenius equation (non exponential form)
energy,
푬풂
−
ln k = ln 풆 푹푻 A is the pre-exponential (frequecy) factor is
+ 퐥퐧 푨 constant, and RT is the average kinetic energy i.e.,
푬풂 R is the gas constant (8.314 J/mol-K), and T is the
ln k =  + 퐥퐧 푨 absolute temperature.
❖ A graph of lnk versus
푹푻 1/T is a straight line • value of from intercept at infinite T
(i.e.; 1/T=0)
when the reaction follows the behavior • value of Ea from the slope.
described by the Arrhenius equation.
❖ The higher the activation energy, the
stronger the temperature dependence of the
rate constant (i.e., the steeper the slope).
❖ If a reaction has zero activation energy, its
rate is independent of temperature.

53
Consider a series of reactions having these energy profiles:
Rank the forward rate constants from smallest to largest assuming all three reactions have
nearly the same value for the frequency factor A.

SOLUTION
• The lower the activation energy, the larger the rate constant and the faster the reaction.
• The value of ΔE does not affect the value of the rate constant.
• Hence, the order of the rate constants is 2 < 3 < 1.
 Catalysis
• A catalyst is a substance that changes the speed of a chemical reaction without undergoing a
permanent chemical change itself.
• Most reactions in the body, the atmosphere, and the oceans occur with the help of catalysts.
• Much industrial chemical research is devoted to the search for more effective catalysts for
reactions of commercial importance.
• The phenomenon of alteration of the rate of a reaction by a catalyst is known catalysis.
• The science and technology of catalysis is of great significance as it affects our daily life.
• The catalytic processes contribute greater than 30-40% of global GDP
• Four major sectors of the world economy involve catalytic processes.
 Petroleum and Energy Production,
 Chemicals and Polymer Production,
 Food industry and
 Pollution control.
 Catalytic reactions Types of catalysis
• Catalysts work by providing alternative mechanism involving a
different transition state of lower energy.
• Thereby, the activation energy* of the catalytic reaction is lowered
compared to the uncatalyzed reaction . Following are the main types of catalysis:

1. Homogeneous catalysis

2. Heterogeneous catalysis

3. Enzyme catalysis

Figure: Schematic diagram to illustrate the

effect of catalyst on activation energy of
reactions.
 1. Homogeneous catalysis
In a reaction, if the catalyst is present in the same phase as the
reactants, it is called a homogeneous catalyst and the phenomenon is
homogeneous catalysis. Such catalysis can take place in gaseous
reaction or reactions in solution.

Figure: Schematic diagram to illustrate the homogeneous catalysis.

These chemicals help in attaining the equilibrium more quickly by

increasing the rates of both the forward and reverse reactions to an
extent. 57
 Examples of homogeneous catalysis in the gas phase
(1) Oxidation of sulphur dioxide, SO2, by oxygen to sulphur trioxide, SO3, in
presence of nitric oxide, NO, in the Chamber Process for sulphuric acid manufacture.
2SO2 (g) + O2 (g) → 2SO3 (g)
here, NO acts as a catalyst.
(2) The following reaction in the gas phase is catalyzed by traces of chlorine gas,
particularly in presence of light.
2N2O (g) → 2N2 (g) + O2 (g)
In presence of light chlorine forms chlorine radicals, which react with N2O forming
the intermediate radical ClO*.
The proposed mechanism is:
Step 1: N2O (g) + Cl* (g) → N2 (g) + ClO*(g)
Step 2: 2ClO*(g) → Cl2 (g) + O2 (g)

58
Examples of homogeneous catalysis in the solution phase

(3) Hydrolysis of ester in the presence of acid and alkali:

CH3COOC2H5 (l) + H2O (l) → CH3COOH (aq) + C2H5OH (aq)

(4) Hydrolysis of sucrose (cane sugar) into glucose and fructose in

presence of minerals acids acting as catalysts:

C12H22O11 (aq) + H2O (l) → C6H12O6 (aq) + C6H12O6 (aq)

(cane sugar) (glucose) (fructose)

59
The decomposition of aqueous hydrogen peroxide, H2O2(aq) , into water and
oxygen:
2 H2O2 (aq)  H2O(l) + O2 (g) 
In presence of catalyst:
2Br  (aq) + H2O2 (aq) + 2H+ (aq)  Br2 (aq) +
2H2O(l)
Br2 (aq) + H2O2 (aq)  2Br  (aq) + 2H+ (aq) + O2 (g)


60
 2. Heterogeneous catalysis
If the catalyst is present in a different phase than the reactants is called
heterogeneous catalyst and the phenomenon is known heterogeneous
catalysis.

In heterogeneous catalysis the reactions take place at the interface of two

phases. The catalyst is, often a solid and adsorbs a liquid or a gas. This type
of catalysis is of great importance in many industrial processes.

Figure: Schematic diagram to illustrate the heterogeneous catalysis.

61
 Examples of Heterogeneous catalyst
(a) Manufacture of ammonia by the Haber process. Iron (Fe) acts as catalyst.
N2 (g) + 3H3 (g) → 2NH3 (g)
(b) Manufacture of sulphuric acid by the Contact process. Vanadium pentoxide (V2O5)
or platinum are catalysts for the production of SO3 (g) from SO2 (g) and O2 (g).
2SO2 (g) + O2 (g) → 2SO3 (g)
(c) Catalysts used in many reactions in the petroleum and polymer industries. There
are cases of heterogeneous catalysis where a reaction in the liquid phase is
catalysed by a substance in the solid state. An example is the decomposition of
H2O2 (aqueous) by MnO2 (s).
2H2O2 (aq) → 2 H2O (l) + O2 (g)
(d) Examples of reactions in which both the reactant and the catalyst are in the
solid phase. The decomposition of KClO3 is catalysed by solid MnO2.
2 KClO3 (s) → 2KCl (s) + 3O2 (g)
62
 Enzyme catalysis
• Biological catalysts known as enzymes are necessary for many of the chemical reactions occur
in an extremely complex system of the human body.
• Enzymes are protein-based molecules that can
process certain chemical reactions
• These reactions occur at a localized site, called
the active site, at the rate much faster than a
normal chemical reaction.
• Substrate is the molecule that fits into the active
site of the enzyme and undergoes transformation
to a product.
• Example of an enzyme catalysed reaction is catalase that converts
hydrogen peroxide to water and oxygen.
• It is an important enzyme protecting the cell from oxidative damage by
reactive oxygen species (ROS)

Reaction catalysed by the

enzyme, catalase
H2O2 → H2O + O2
Enzymes speed up reactions.
 Mechanism of enzyme-catalyzed reactions
❑ Enzyme-catalyzed reactions work in a lock
and key fashion.
❑ The substrate uniquely fits like a key into
the active site of the enzyme, forming a
lock-key complex.
❑ The substrate is converted into the product
by the enzyme at the active site.
❑ The product is then released from the active
Enzymes’ effect on the activation energy site.
❑ Enzymes lower the activation energy for reactions. The
lower the activation energy, the faster the rate of the
reactions.
❑ For example: the enzyme catalase reduces the
activation energy for the decomposition of hydrogen
peroxide to 8 kJ mol-1, corresponding to an acceleration
of the reaction by a factor of 1015 at 298 K.
❑ A generic equation for the complex formation is as
follows:
E+S ES P+E