Engineering Chemistry

Module -1
According to the revised syllabus for Winter Semester 2023-2024

A. Laws of thermodynamics - entropy change (selected

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

B. Kinetics - Order of reactions (excluding the derivations and

half-life calculations) - Concept of activation energy and
energy barrier - Arrhenius equation- Homogeneous,
heterogeneous and Enzyme catalysis (Lock and Key
mechanism)

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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
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 Part-A
Thermodynamics
- Laws of thermodynamics
- Entropy change (selected processes)
- Spontaneity of a chemical reaction and
- Gibbs free energy
- Carnot cycle

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Thermodynamics

4
 Thermodynamics

“Thermodynamics is a science that describes how thermal energy is

converted from one form to the other and how it affects the
matter.”

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 To simplify Thermodynamics

Example systems
• Gas in a container
• Magnetization and demagnetization
• Charging & discharging a battery
• Chemical reactions
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• Thermocouple operation
System

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Open system
“The system in which heat transfer as well as mass transfer takes
place with the surroundings is known as open system.”

Closed system
“The system in which only heat energy is exchanged with the
surroundings is known as closed system.”

Isolated system

“The system in which neither mass transfer nor heat transfer takes
place
is exchanged with the surroundings is known as isolated system.” 8
 What is a temperature?

We have seen in the above example that, if kinetic energy is more, then the
body is warm (or hot) and if kinetic energy is less, then the body will be cold.
Temperature is a measurement of the average kinetic energy of the
molecules in any object.

Temperature can also be defined as a degree of hotness or coldness

of an object.

The value of temperature is indicated using temperature scales like

• Fahrenheit scale (°F)
• Celsius scale (°C) and
• Kelvin scale (K) 9
Heat

Heat always flows from higher temperature to lower

temperature
Heat is defined as a flow of thermal energy due to differences in
temperatures.

10
1 calorie = 4.18 Joules

11
What is heat transfer? How heat transfer occurs?

Conduction: Energy is transferred by direct contact.

Convection: The energy is transferred due to motion of
molecules.
Radiation: The energy is transferred by electromagnetic
radiation. 12
What is Thermal Equilibrium?

“The condition under which two objects in physical contact with each other
exchanges no heat energy is termed as thermal equilibrium. During this
condition, the temperature of both the bodies remains the same”

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Mechanical equilibrium:

“A system is said to be in mechanical

equilibrium if the net force acting on the
system is zero”

Chemical equilibrium:
“A system is said to be in chemical equilibrium if
it’s chemical composition does not change with
time and no chemical reaction takes place in the
system”
“A reaction is said to be in chemical
equilibrium if the rate of forward reaction and
rate of the reverse reaction is equal” 14
Phase equilibrium:

The triple point of water is obtained at the

pressure of 4.58 mm Hg and 273.16 K
temperature.
Triple point: The temperature and pressure at which all the three
phases of matter i.e solid, liquid and gas exist in equilibrium with
each other is known as triple point of that matter. 15
Zeroth law of thermodynamics

“If two bodies A and B are in thermal equilibrium with third body
C, then body A and B are also in thermal equilibrium with each
other.”

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Applications/examples of Zeroth law of
thermodynamics

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First law of thermodynamics | Heat, Internal Energy and Work

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First law of thermodynamics or law of conservation of energy
“Energy can neither be created nor can be destroyed but
transformation of one form into another form can be possible.”
There are two more classification of energy.
• Kinetic energy
• Potential energy
Kinetic energy: Kinetic energy is the energy which an object
possesses due to its motion.
Potential energy: Potential energy is the energy stored in a body
due to its position with respect to some other body.

Potential energy = Kinetic energy

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Equation for first law of thermodynamics
But in terms of heat, internal energy and work, the definition/statement of
first law of thermodynamics can be stated as;
“First law of thermodynamics: The net change in total energy
of a system (∆E) is equal to the heat added to the system (Q)
minus work done by the system (W).”

∆E = Q – W. Here, if Q
E2 – E1 = Q – W increases, then ∆E also
increases and
if W increases, then ∆E
decreases)
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You can’t win (1st law)
• The first law of thermodynamics is an extension of the law of
conservation of energy

• The change in internal energy of a system is equal to the heat

added to the system minus the work done by the system
ΔU = Q - W
Slide courtesy of NASA
Sign convention of heat in first law of thermodynamics

When the equation of 1st law of thermodynamics is used in calculations, it

is necessary to know the sign of the heat(Q) and work(W).

The sign of heat (+ve or -ve).

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What is Internal energy in first law of
thermodynamics?

If the temperature is higher, then the

internal energy is more.

If the temperature is lower, then the

internal energy is less.

Remember: A system does not

contain heat. But it contains interna
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What is work? How is it related to the 1st law of
thermodynamics?

V1 = initial volume of the system

V2 = final volume of the system
P = constant pressure of the system

The work done by the system can be obtained from

following formula;
W = P (V2 – V1)
= P ∆V 26
At one bar pressure, the volume of gas is 0.6 litre. If the gas
receives 122 Joules of heat at one atmosphere pressure, the
volume becomes 2 litres, then calculate it’s internal energy. (1
litre bar = 101.32 Joule).
Pressure P = 1 bar
Initial volume of gas V1 = 0.6 litre
Final volume of gas V2 = 2 litre
∆V = V2 – V1
= 2 – 0.6
= 1.4 litre
Now, W = P ∆V
W = 1 × 1.4 = 1.4 litre bar
But 1 litre bar = 101.32 joule
So, W = 1.4 × 101.32
= 141.85 joule
Here, the work is done by the system
So, W = +141.85 joule
The heat obtained by the system
Q = 122 Joule
According to thermodynamics first law;
∆U = Q – W
= 122 – 141.85
= -19.85 joule 27
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Lets do some practice

A system receives 224 Joule heat and does work of 156 joule.
Calculate the change in the internal energy.

System receives heat

So, Q = 224 joule

Work is done by the system

So, W = 156 joule

Now according to first law of

thermodynamics;
∆U = Q – W
= 224 – 156
= 68 joules
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Lets do some practice

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Lets do some practice

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Process Terminology

• Adiabatic – no heat transferred

• Isothermal – constant temperature
• Isobaric – constant pressure
• Isochoric – constant volume
Adiabatic Process Remember ΔU = Q - W
• An adiabatic process transfers no heat
• therefore Q = 0
• ΔU = Q – W
• When a system expands adiabatically, W is positive (the
system does work) so ΔU is negative.
• When a system compresses adiabatically, W is negative (work
is done on the system) so ΔU is positive.
Isothermal Process
• An isothermal process is a constant temperature process. Any heat flow
into or out of the system must be slow enough to maintain thermal
equilibrium
• For ideal gases, if ΔT is zero, ΔU = 0 ΔU = Q - W
• Therefore, Q = W
• Any energy entering the system (Q) must leave as work (W)
Isobaric Process
• An isobaric process is a constant pressure process. ΔU, W, and Q are
generally non-zero, but calculating the work done by an ideal gas is
straightforward
W = P·ΔV
• Water boiling in a saucepan is an example of an isobar process

ΔU = Q - W
Isochoric Process
• An isochoric process is a constant volume process. When the volume of
a system doesn’t change, it will do no work on its surroundings. W = 0
ΔU = Q - W ΔU = Q
• Heating gas in a closed container is an isochoric process
40
Summary of Thermodynamic Processes

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Summary of Thermal Processes

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 Two more thermodynamic processes are:
• Reversible process
• Irreversible process

Reversible process:
The thermodynamics process which can be reversed back to its
original state is known as reversible process.

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Irreversible process

The thermodynamic process which can not be reversed back

to its original state is known as irreversible process.

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 Two more thermodynamic processes are:
• Reversible process
• Irreversible process

# Magnitude of w depends on whether the

expansion is reversible or irreversible.
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Expression for Work (on the system)
Reversible expansion of work
Work (W) = force x distance
W = - F Z
Change equation to relate
pressure and volume

Force F
P= =
Area A
F = P A

W = - P A ΔZ
Volume change (ΔV) = A ΔZ
W = - P ΔV
True expression for Work

Vf
dW = - Pex dV W= -
V
Pex dV
i
49
Thermodynamic Approach
There are two thermodynamics approaches to study the behaviour of
matters:
• Macroscopic approach,
• Microscopic approach,

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 Heat and work are state
function
Internal energy (U)
= Kinetic energy + Potential energy
∙ It’s a state function & an extensive property of the system.
∙ Internal energy of a system changes when energy is transferred into or outside
the system in the form of heat or work

The change in the internal energy in a chemical reaction is given

by
ΔU=Uproducts–Ureactants
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Internal Energy: Energy that exist internal to
the system
First Law: The internal energy of an isolated system is a
constant; Energy cannot be created or destroyed.

U total = U system  U surroundings 0 ΔU= change in internal energy

q = heat (released or absorbed)
U system = q +- w w = work done on or by the system

Internal energy can have different forms:

Translational Kinetic Energy
Rotational Kinetic energy
Vibrational Kinetic energy
*Energy within the atom
 Internal Energy: Energy that exist internal to the system

𝑛 is the number of moles of the gas.

Δ𝑈=1/2𝑛𝑓𝑅Δ𝑇

𝑓 is the total number of degrees of freedom.

𝑅 is the universal gas constant.
𝑇 is the absolute temperature.
Therefore, we can infer that the change in internal
energy is a state function i.e., it only depends on the 57
Heat and work are path
function

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Lets do some practice

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60
Expression for Work
Work (W) = force x distance
W = - F Z
Change equation to relate
pressure and volume

Force F
P= =
Area A
F = P A

W = - P A ΔZ
Volume change (ΔV) = A ΔZ
W = - P ΔV
True expression for Work

Vf
dW = - Pex dV W= -
V
Pex dV
i
 Types of Expansion Work
• Free Expansion- work done by expansion against zero opposing
force or zero pressure

Vf
w   Pex dV
Vi

Pex 0
W 0
U q
 Types of Expansion Work
• Expansion against a constant external pressure (irreversible)

Vf
w   Pex dV
Vi
If external pressure does, not vary,
this expression can be integrated

Vf
w = -Pex  dV
V1

w = -Pex Vf -Vi 

w = -Pex ΔV
 Types of Expansion Work
• Expansion is reversible
Vf
w   Pex dV
Vi

In this case, the external pressure Pex

exactly equals the internal pressure P
at each stage of the expansion.

Vf
w = - P dV Pex = P
V1

Vf nRT
w = - dV
Vi V
The integral cannot be evaluated because
temperature is not a constant throughout the
integration.
 Types of Expansion Work
• Expansion is Isothermal, reversible
Vf
w   Pex dV Pex = P
Vi

The system is kept at a constant temperature.

The external pressure Pex equals the internal
pressure P at each stage of the expansion.

Vf nRT Vf 1
w = - dV = -nRT  dV
Vi V V i V

w = -nRT Ln
Vf ΔT = 0
Vi
 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.
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What is Heat capacity and Specific heat?

Heat capacity also depends on the mass of the object. Bigger

the mass of the object, more heat will be absorbed, so its heat
capacity will be more. While smaller the mass of the object, less
heat will be absorbed, so it’s heat capacity will be less.

Heat capacity (Hc): The ratio of heat supplied (Q) to the body to the change in its temperature ∆T is called
heat capacity (Hc) of that body.
Hc = Q/∆T

Heat capacity (Hc) is defined as the amount of heat absorbed (Q) in order to increase the temperature (∆T)
by 1 unit.
Specific heat capacity or specific heat
(C) Specific heat capacity (C): Specific heat capacity (C) is defined as the
amount of heat absorbed (Q) in order to increase the temperature (∆T) by 1
unit, of a unit mass(m).
C = Q/m∆T

In other words, if the mass of a body is unity, then the heat

capacity of the body is known as specific heat capacity or
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specific heat.
What is Heat capacity and Specific heat and Molar heat?
❑ Heat capacity (C) of a system b/n any two temperatures – the quantity of heat (q) required to
raise the temperature of the system from the lower temperature (T 1) to the higher temperature
(T2) divided by the temperature difference.

C = Q/m∆T

☻ 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’

⮚ Molar heat capacity varies with temperature

❑ Molar heat capacity at constant volume

@ constant volume w = 0 & ΔU = q

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Heat Capacity at a constant volume
Heat Capacity (Cv) is the
amount of heat needed to
change the temperature of a
system by 1 *C at either a
constant volume.

ΔU = q v CV T
ΔU dU  U 
CV = = = 
ΔT dT  T  V

We need partial derivatives

because the change holds
the volume constant
 How we can evaluate the Heat
capacity equation
 U  dU ΔU
CV =    
 T  V dT ΔT
If the heat capacity (Cv) does not vary with
temperature during the range of temperatures
used, then the equation can be broken
down to:

ΔU = CV ΔT
Because at constant volume, change in internal
energy is equal to the heat (qv).

q V = CV ΔT
 How we can evaluate the Heat
capacity equation
 H  dH ΔH
CP =    
 T  P dT ΔT
If the heat capacity (CP) does not vary with
temperature during the range of temperatures
used, then the equation can be broken
down to:

ΔH = C P ΔT
Because at constant pressure, change in
internal energy is equal to the heat (qp).

q P = C P ΔT
 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,

The molar specific heat capacity to change the temperature by 1
unit would be Cv= (3/2)R. For an ideal gas, Cp – Cv = R (Gas 73
Constant). Therefore: Cp = R + Cv = R + (3/2)R = (5/2)R. The ratio
 Enthalpy & Heat
Capacity
⮚ If the change of a system is brought about at constant pressure, there will be
change in volume.

❑ The quantity (U + PV) is called the enthalpy (H) of the system

ΔU = ΔH – PΔV
or ΔH = ΔU + PΔV
, 74
Adiabatic Expansion: work is done
but no heat enters the system
• When a gas expands adiabatically,
work is done but no heat enters or
leaves the system.
• The internal energy falls and the
temperature also falls.

U = q + w q=0

ΔU = w = CV ΔT
wad = U = C V ΔT
Adiabatic changes to an Ideal Gas can be
related by the following equations
1
 Vi  c

T f Ti   C = CV/nR
 Vf
 
1

 Vi  γ = Cp/CV
Pf Pi  
 Vf
 
The derivation of these equations is
quite long and follows the next slide
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.

( )( )
𝛾 −1
 1st law of thermodynamics: 𝑇 𝑖 𝑉 𝑓
= Þ ln
ΔU = w 𝑇 𝑓 𝑉 𝑖
(as no heat is allowed to enter/leave the system, q = 0)
 Example: A gas expanding so quickly that no heat ln 𝐶𝑝
Þ [ 𝑎𝑠 , 𝛾= ]
can be transferred. Due to the expansion work, 𝐶𝑣
temperature drops. This is exactly what happens ln
with a carbon dioxide fire extinguisher, with the Þ ― = R]
gas coming out at high pressure and cooling as it
expands at atmos. pressure Þ ln
® Expansion: w = ― ve, = ― ve;
So, T of the system falls
 Irreversible adiabatic expansion
Þ Work is done by the system at the expense of
its internal energy  Free expansion (Pex = 0) :
 w = = (for 1 mole of gas)  Expansion against a constant pressure:
 (for 1 mole of gas)
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Thermodynamic Processes for an Ideal Gas

No work is done on a system when its

volume remains constant (isochoric
process). For an ideal gas (provided the
number of moles remains constant), the
change in internal energy is

Q U nCV T .

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For a constant pressure (isobaric) process, the change in internal energy is
U Q  W
where W  PV  nRT and Q nC P T .
CP is the molar specific heat at constant pressure.
For an ideal gas CP = CV + R.

For a constant temperature (isothermal) process, U = 0 and the work done on an ideal gas is

 Vi 
W nRT ln .
 Vf 
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Example: An ideal monatomic gas is taken through a cycle in the PV diagram.
(a) If there are 0.0200 mol of this gas, what are the temperature and pressure at point C?

From the graph: Pc = 98.0 kPa

Using the ideal gas law

PcVc
Tc  1180 K.
nR

MFMcGraw Chap15d-Thermo-Revised 5/5/10 80

Example continued:

(b) What is the change in internal energy of the gas as it is taken from point A to B?

This is an isochoric process so W = 0 and U = Q.

 3   PBVB PAVA 
U Q nCV T n R    
 2   nR nR 
3
 PBVB  PAVA 
2
3
 V PB  PA   200 J
2
81
Example continued:

(c) How much work is done by this gas per cycle?

The work done per cycle is the area between the curves on the
PV diagram. Here W=½VP = 66 J.

(d) What is the total change in internal energy of this gas in one cycle?

 3   Pf Vf PiVi 
U nCV T n R    
 2   nR nR 
3
 Pf Vf  PiVi  0 The cycle ends where it
2 began (T = 0).

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Example :
An ideal gas is in contact with a heat reservoir so that it remains at constant temperature of
300.0 K. The gas is compressed from a volume of 24.0 L to a volume of 14.0 L. During the
process, the mechanical device pushing the piston to compress the gas is found to expend 5.00
kJ of energy.
How much heat flows between the heat reservoir and the gas, and in what direction does the
heat flow occur?

This is an isothermal process, so U = Q + W = 0 (for an ideal gas)

and W = Q = 5.00 kJ.
Heat flows from the gas to the reservoir.

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 Numerical from of 1st
Law
❖ Example 2: 1 mole of an ideal gas expands
against a constant external pressure of 1 atm
from a volume of 10 dm3 to a volume of 30
dm3. Calculate the work done by the gas in
Joules.

Since, conversion of water to steam is

accompanied by increase in volume, work is
done by the system on the surroundings.
Hence, w = – 3100 Jmol-1
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 Numerical from of 1st Law
 Example 3: 1 mole of an ideal monoatomic gas at 27 C expands reversibly and adiabatically from a
volume of 10 dm3 to a volume of 20 dm3. Calculate q, U, W and H. Given

Solution:
Since the process is adiabatic, q = 0 Since for an adiabatic process, q =0,
hence ΔU = w = – 1384 J
Þ ΔH = ΔU + ΔPV = ΔU + ΔnRT
Þ Tf = 189K = ΔU + nR(Tf- Ti)

𝐶𝑣 =
𝜕𝑈
𝜕𝑇 ( ) Þ
𝑣
® (1 mol)

ΔH = – 1384 J – 923 J = – 2307 J

For a finite change in n moles,
# Note: ΔH can also be calculated by
= (1 mol) using the relation
= – 1384 J
 Example 4: 10 moles of an ideal gas expands reversibly and isothermally from a pressure of 10 atm to
2 atm at 300 K. Calculate the work done.
Solution: w = = (10 mol) = 40.15 103J 86
Problem 1: A chemical reaction takes place in a
container of cross sectional area of 50.0 cm2.
As a result of the reaction, a piston is pushed
out through 15 cm against an constant external
pressure of 121 kPa. Calculate the work (in
Joules) done by the system
Problem 2: A sample consisting of 2.00 mol
of He is expanded at 22ºC from 22.8 dm3 to
31.7 dm3. Calculate q, w and ΔU (in Joules)
when the expansion occurs under the
following conditions:
(a) Freely

(b) Isothermal, and constant external pressure equal to

the final pressure of the gas

(c) Isothermal, Reversibly

Problem 3: A sample consisting of 1.00 mol of
a perfect gas, for which Cv,m = (3/2)R, initially
at P = 1.00 atm and T = 300 K, is heated reversibly
to 400 K at a constant volume. Calculate the
final pressure, ΔU, q, and w
90
Limitations of first law of thermodynamics
1). First law does not say anything about whether the process is possible or not.

2) First law of thermodynamics does not say whether the process will occur on its own or not.

3). First law does not provide any sufficient condition for a certain process to take place.

91
What is second law of thermodynamics?

92
93
The second law of thermodynamics can be stated in three
ways.

• Second law of thermodynamics for heat engine

(Kelvin Planck’s statement)

• Second law of thermodynamics for heat

pump/refrigerator (Clausius’s statement)

• Second law of thermodynamics based on entropy

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Second law of thermodynamics for heat engine
(Kelvin Planck’s statement)

“It is impossible to construct a device (operating in a

cycle) which works on a single heat source and converts
all of its heat completely in to work”
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This Kelvin Planck’s statement simply wants to say that – “A heat engine
must exchange the heat with at least two thermal reservoirs, one at
higher temperature and other at lower temperature, then only the
engine will operate.”
Or
“Perfect engine with 100% efficiency is impossible”

96
Second law of thermodynamics for heat
pump/refrigerator
(Clausius’s statement)

“It is impossible to construct a device (operating in a cycle)

that can transfer heat from cold body to the hot body without
absorbing any work.”

Or
“Heat can not itself flow from colder body to a hotter body.”
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“Heat always flows from higher temperature body to lower
temperature body. It’s reverse flow does not take place on
its own.”

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Second law of thermodynamics based on entropy
1.Randomness
2.Entropy

1) Randomness:
The movement of molecules is known as randomness.

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2) Entropy:
Entropy statement of Second law of thermodynamics
“In all the spontaneous processes, the entropy of the universe
increases.”
Entropy is the measurement of disorder of the system.
The measurement of randomness of the system is known as
Entropy.

→ The thermodynamic definition of entropy concentrates on the change in entropy (dS) that occurs as
the result of a physical or chemical process.
→ dqrev is the energy transferred as heat reversibly to the system at the absolute temperature T.

100
 Assume that;
-The temperature of coffee is 50 °C. (i.e 323 K)
-The temperature of surrounding is 20 °C. (i.e 293 K)
Case 1: Coffee is absorbing heat from the Case 2: Coffee is releasing heat to the surrounding
surrounding Let say coffee (system) releases 10 joules of heat to the
Let say coffee (system) absorbs 10 joules of heat from surrounding.
the surrounding. That means, the surroundings will absorb 10 joules of
That means, the surrounding will lose 10 joules of heat. heat.
So we can write, So we can write,
Qsystem = +10 J Qsystem = -10 J
Qsurrounding = -10 J Qsurrounding = +10 J
Now, change in entropy of universe is given by equation; Now, change in entropy of universe is given by equation;
∆Suniverse = ∆Ssystem + ∆Ssurrounding ∆Suniverse = ∆Ssystem + ∆Ssurrounding
= ∆Qsystem/Tsystem + ∆Qsurrounding/Tsurrounding = ∆Qsystem/Tsystem + ∆Qsurrounding/Tsurrounding
= (+10/ 323) + (-10/293) = (-10/ 323) + (+10/293)
= -0.00316 J/K = +0.00316 J/K
The entropy of the universe is decreasing here. Thus it This
Theisentropy
a positive value,
of the universe is increasing here. Thus it
violates the second law of thermodynamics satisfies the entropy statement of second law of
(∆Suniverse should be greater than 0, but here our answer is thermodynamics (∆Suniverse should be greater than 0).
101
negative).
 Heat engine: Heat engine is a device which is used for producing the
Heat engine motive power from the heat.
Or
Heat engine is a machine or a device which converts heat energy into
mechanical energy (work) by transfer of heat from high temperature to
lower temperature.

W = Q1 – Q2
The unit of work done is the same as the unit
of heat, i.e Joule (J).
 Its a device which transforms heat into work
 This happens in a cyclic process
 Heat engines require a hot reservoir to supply energy (QH) and a
cold reservoir to take in the excess energy (QC)
– QH is defined as positive, QC is defined as negative
Thermal efficiency of heat engine • The thermal efficiency () of a heat engine is

Thermal efficiency = (net output work) / (heat supplied)

= =
η = W/Q1
=
102
Heat pump
Heat pump: Heat pump is a device which is
used to transfer heat from lower
temperature to higher temperature by
using some input work.

We need to supply some work to this

device in order to transfer the heat
from lower temperature to higher
temperature.

Coefficient of performance of heat pumps/refrigerators

COP is defined as a ratio of heat absorbed (Q2) to the work

input (W) to the system.
COP = (heat absorbed) / (work input to the system)
= Q2/W 103
 Example 2: (based on Clausius’s statement)
Example 1: (based on Kelvin Planck’s statement)
A refrigerator has a coefficient of performance equal to 5
A heat engine absorbs 360 J of energy and performs 25 J
Assuming that the refrigerator absorbs 120 J of energy
of work in each cycle. Find the following;
from a cold reservoir in each cycle, find
(a) the efficiency of the engine
(a) The work required in each cycle.
(b) the energy expelled to the cold reservoir in each cycle.
(b) The energy expelled to the hot reservoir.
Here,
Q1 = 360 J,
COP = 5,
W = 25 J
Q2 = 120 J
(a) Efficiency of heat engine
(a) COP = Q2/W
η = W/Q1
Hence, W = Q2/COP
= 25 / 360
= 120 / 5
= 0.07 or 7%
= 24 J
(b) The heat energy expelled to the cold reservoir in each
(b) The energy expelled to the hot reservoir
cycle
Q1 = W + Q2
Q2 = Q1 – W
= 24 + 120
= 360 – 25
= 144 J
= 335 J

Example 3: (based on Entropy)

“Will ice having temperature 273 K placed in a surrounding having temperature 298 K will give water
having temperature 273 K ?” Prove this statement. The ice requires 6.025 kjoule/mole of heat energy for
melting.

∆Ssystem = ∆Q/T ∆Ssurrounding = ∆Q/T ∆Suniverse = ∆Ssystem + ∆Ssurrounding

= 6.025/273 = -6.025/298 = 0.0221 + (-0.0202)
= 0.0221 = -0.0202 kilojoule/K = 0.0019 kilojoule/K mole
kilojoule/mole mole
(Heat is absorbed here, so the sign
of ∆Q is negative) 104
 Entrop
y
⮚ Entropy change for the system of an isothermal expansion of a perfect gas

105
 Entrop
y
⮚ Total Entropy change in irreversible (spontaneous) process of a perfect gas

✔ example: Isothermal expansion of an ideal gas at constant temperature

into vacuum

106
107
 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

 For an ideal gas (1 mole) with variable T & V

 For an ideal gas with variable P & T

 For an ideal gas in an isothermal process

=
 For an ideal gas in an isobaric process

 For an ideal gas in an isochoric process

108
  Carnot Cycle
 A Carnot cycle (named after the French engineer Sadi Carnot) consists of four reversible
stages in which a gas (the working substance) is either expanded/compressed in various
ways
 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
Sadi Carnot designed this engine which is having efficiency of 100%.
(Note: Carnot engine is just an ideal engine (or hypothetical engine). No engine has
100% efficiency according to second law of thermodynamics)
Carnot heat engine consist of following 4 parts:
1). Insulated non conducting stand 2). Hot reservoir 3). Cold reservoir

4). Cylinder with a working fluid

109
A. 1st stroke: 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: D. 4th stroke:

Curve CD (C → D): Isothermal compression at TC, Curve DA (D → A): Adiabatic compression
Work done on the gas. Work done on the gas

110
 Carnot Cycle
 Four stages of Carnot Cycle: A. 1st stroke:
Curve AB: AB: Isothermal expansion at Th
Work done by the gas
Þ The gas is placed in thermal contact with QH (at Th) and
undergoes reversible isothermal expansion from A to B.
Þ The entropy change is qh/Th ( qh = the energy supplied to the
system as heat from the hot source) 𝑽 𝑩
𝒒 𝒉 =− 𝒘 𝟏 = 𝑹 𝑻 𝒉 𝒍𝒏
𝑽𝑨
B. 2nd stroke:
Curve BC (B → C): Adiabatic expansion,
Work done by the gas
Þ Contact with QH is broken & the gas undergoes
reversible adiabatic expansion from B to C.
Þ No energy leaves the system as heat, ΔS = 0
Þ The expansion is carried on until the temperature of
V  the gas falls from Th to Tc (the temperature of Qc)
W nRT ln i
 Vf
.

wad = U = C V ΔT
− 𝒘 𝟐=− 𝑪 𝒗 (𝑻 𝒉 − 𝑻 𝒄 ) 111
 Carnot Cycle
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 Tc.
 Energy is released as heat to the cold sink; the entropy change of
the system = qc/Tc, where qc is negative.
𝑉𝐷
−𝑞 𝑐 =𝑤 3=𝑅 𝑇 𝑐 ln
𝑉𝐶
D. 4th stroke:
Curve DA (D → A): Adiabatic compression
Work done on the gas
 Contact with Qc is broken and the gas undergoes
reversible adiabatic compression from D to A such
that the final temperature is Th.
 No energy enters the system as heat, so the change
V  in entropy is zero.
W nRT ln i
 Vf
.

wad = U = C V ΔT 𝑤 4= 𝐶 𝑣 (𝑇 h − 𝑇 𝑐 )
112
 Carnot Cycle
 The area enclosed by the four curves represents the net
work done by the engine in one cycle
 The total change in entropy around the cycle is the sum
of the changes in each of these four steps:
𝑞h 𝑞𝑐
∮ 𝑑𝑆=¿ 𝑇 + 𝑇 ¿
h 𝑐

 For an ideal gas, and

Efficiency of a heat engine

• The thermal efficiency of a heat engine is
= =
=
• Another statement of the 2nd Law:
 The “engine” statement of the 2nd Law: – It is impossible for any process to have as its sole
– it is impossible for any system to have an result the transfer of heat from a cooler object to
efficiency of 100% ( = 1) a warmer object [Clausius’s statement]
113
[Kelvin’s statement]
 Application of the Carnot Cycle

 Energy efficiency of the

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.
 The heat pumps to produce heating, ® Refrigeration, Air conditioners & Heat pumps
 the refrigerators to produce cooling, ● These appliances are heat engines operating in
 the steam turbines used in the ships, reverse.
 the combustion engines of the combustion vehicles ● By doing work, heat is extracted from the cold
 the reaction turbines of the aircraft reservoir & exhausted to the hot reservoir
114
Temperature & Free Energy

 Thermodynamic Temperature
 Suppose an engine works reversibly
between a hot source at a temperature Th
and a cold sink at a temperature Tc, then it
follows that
= = Tc = (1 − η)Th
=

 Kelvin used this expression to define the thermodynamic temperature scale in

terms of the efficiency of a heat engine in which the hot source is at a known
temperature and the cold sink is the object of interest.

 The Kelvin scale (which is a special case of the thermodynamic temperature scale) is currently
defined by using water at its triple point as the notional hot source and defining that
temperature as 273.16 K exactly.

115
Practical uses: surroundings & system
Entropy Changes in Surroundings
• Heat that flows into or out of the system also changes the entropy of the
surroundings.
• For an isothermal process:

• At constant pressure, qsys is simply H for the system.

Practical uses: surroundings & system

= – Gibbs Free Energy

Practical uses: surroundings & system

= – Gibbs Free Energy

Make this equation nicer:
Practical uses: surroundings & system
…Gibbs Free Energy

TDSuniverse is defined as the Gibbs free energy, G.

For spontaneous processes: Suniverse > 0

And therefore: G < 0

G is easier to determine than Suniverse.

So:
Use G to decide if a process is spontaneous.
 1. If DG is negative, the forward
Gibbs Free Energy reaction is spontaneous.
2. If DG is 0, the system is at
equilibrium.
3. If G is positive, the reaction
is spontaneous in the
reverse direction.
Free Energy and Temperature

By knowing the sign (+ or -) of S and H,

we can get the sign of G and determine if a reaction is
spontaneous.
 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

122
123
 Numerical from 2nd Law of Thermodynamics

 Example 1: Calculate the efficiency of a  Example 3: Heat supplied to a Carnot engine is 1897.8 kJ. How
certain power station operates with much useful work can be done by the engine which works
superheated steam at 300 (Th = 573 K) between 0 ∘C and 100 ∘C.
and discharges the waste heat into the Solution:
environment at 20 (T = 293 K).
Tc​= 0 + 273 = 273 K, Th ​= 100 + 273 = 373 K
Solution: Tc= (1 − η)Th qh = 1897.8 kJ
 η = 1 – (Tc /Th) w
Theoretical efficiency (η) = 1 – (293K/573K) = 1897.8 kJ
= 0.489 = 508.7 kJ
= 48.9 %  Work done by the engine is 508.7 kJ
# In practice, there are other losses due to
mechanical friction and the fact that
turbines do not operate reversibly.
 Example 2: Calculate the maximum efficiency of a heat engine operating between 100 ∘C and 25 ∘C
Solution: = 1 – (298 K/373 K)
Tc​= 25 + 273 = 298K Tc= (1 − η)Th
For engines, we have = 0.201
Th​= 100 + 273 = 373 K  η = 1 – (Tc /Th) = 20.1 % 124
 Numerical from 2nd Law of Thermodynamics

 Example 4: 5 mole of an ideal gas expands  Example 5: Calculate the change in entropy accompanying
reversibly from a volume of 8 dm3 to 80 the heating of 1 mole of Helium gas (assumed ideal) from
dm3 at a temperature of 27 ∘C. Calculate the a temperature of 298 K to a temperature of 1000 K at
change in entropy. constant pressure. Assume Cv =3/2 R
Solution: Solution: As
)  Cp =
Given that = 2, = 80 dm3 𝑇𝑓
∆ 𝑆 𝑃 =𝐶 𝑝 ln
𝑇𝑖 = 25.17
= (5 mol) (8.314 J K-1mol-1) (80 dm3/8 dm3)
= 95.73 JK-1
 Example 6: 1 mol of an ideal gas expands reversibly from a volume of 10 dm3 and 298 K to a volume of 20 dm3
and temperature 250 K. Assuming Cv =3/2 R, calculate the entropy change for the process.
Solution:
= 1.5 ( + ( ln (20 dm3/10 dm3)
= 3.57 JK-1mol-1

125
 3rd Law of
Thermodynamics
What is absolute zero temperature? Is it possible to achieve?
Absolute zero temperature is:
• 0 Kelvin or
• -273.15 °C or
• -459.67 °F

Third law of thermodynamics:

“The value of entropy of a completely pure crystalline substance is zero at
absolute zero temperature”
Third Law of Thermodynamics
The entropy of a pure crystalline substance at absolute zero is 0.

where, S = the entropy,

k = Boltzmann constant,
W = the number of microstates

→ When T = 0, W = 1
∴ S = k lnW
=0
128
 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)
129
What are Chemical Kinetics?
 Chemical Kinetics

Kinetics – how fast does a reaction proceed?

Thermodynamics – does a reaction take place?

Reaction speed: measured by the change in concentration with time.

Important factors which affect rates of reactions:

– reactant concentration
– temperature
– action of catalysts
– surface area
– pressure of gaseous reactants or products
Dan Reid
Champaign CHS
Kinetics
• Studies the rate at which a chemical process occurs.

• Besides information about the speed at which reactions occur,

kinetics also sheds light on the reaction mechanism (exactly how
the reaction occurs).
Outline: Kinetics

Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calculate amount left or
Integrated Rate Laws time to reach a given amount.
How long it takes to react 50% of
Half-life reactants.
How rate constant changes with
Arrhenius Equation temporature.
Link between rate and molecular
Mechanisms scale processes.
Reaction Rates
Reaction Rates

Rates of reactions can be determined by monitoring the

change in concentration of either reactants or products as a
function of time t.
Notation for Stoichiometry:
[A] = concentration of reactant A
[B] = concentration of reactant B
 Reaction Rate
• For the reaction A  B there are two ways of measuring rate:
(1) the speed at which the reactants disappear
(2) the speed at which the products appear
• Reversible reactions: as products accumulates, they can begin to
turn back into reactants.
• Early on the rate will depend on only the amount of reactants
present. We want to measure the reactants as soon as they are
mixed.
• A general way of measuring the rate of the reaction is in terms of
change in concentration per unit time…
Instantaneous rate = ∆[A]/∆t limits to d[A]/dt
Most Common Units… Rate = M/s
Dan Reid
Champaign CHS Where Molarity (M) = moles/Liter
 Chemical Kinetics

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

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

139
Factors Affecting Reaction Rate Constants
Factors that Affect the Reaction Rate Constant

1. Temperature: At higher temperatures, reactant molecules have more kinetic

energy, move faster, and collide more often and with greater energy
• Collision Theory: When two chemicals react, their molecules have to
collide with each other (in a particular orientation) with sufficient energy
for the reaction to take place.
• Kinetic Theory: Increasing temperature means the molecules move
faster.
2. Concentrations of reactants
• As the concentration of reactants increases,
so does the likelihood that reactant molecules will collide.
3. Catalysts
• Speed up reactions by lowering activation energy
4. Surface area of a solid reactant
• More area for reactants to be in contact
5. Pressure of gaseous reactants or products
• Increased number of collisions
Reaction Rate Examples
Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
• A plot of concentration vs. time for
this reaction yields a curve like
this.
• The slope of a line tangent to the
curve at any point is the
instantaneous rate at that time.
Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

• The reaction slows

down with time
because the
concentration of the
reactants decreases.
Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

• In this reaction, the

ratio of C4H9Cl to
C4H9OH is 1:1.
• Thus, the rate of
disappearance of
C4H9Cl is the same as
the rate of appearance
of C4H9OH.

-[C4H9Cl] [C4H9OH]
Rate = =
t t
Reaction Rate Laws
Concentration and Rate

Each reaction has its own equation that

expresses its rate as a function of the
concentrations of the involved species (e.g.,
reactants, products, catalysts).

This is called its Rate Law

 Rate Law

• In general, rates of reactions increase as concentrations increase

since there are more collisions occurring between reactants.
• The overall concentration dependence of reaction rate is given in a
rate law or rate expression.
• For reactions follow simple rate laws:
v = k [A]m [B]n…
- [A], [B]: reactant concentrations
- The exponents m and n: reaction order (w.r.t. specific reactant)
- The constant k: rate constant
- The overall reaction order is the sum of the reaction orders:
m+n
 Determination of Rate Laws
• Rate laws, rate constants, and orders are determined
experimentally.

• The order of a reactant is NOT generally related to its

stoichiometric coefficient in a balanced chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

1
v = k [F2][ClO2]
 Expression of Rate Laws

Reactions with simple rate laws:

Reactions with complex rate laws*:

* imply multi-step reactions (sequence of elementary steps)

however, the overall

rate cannot involve
intermediate species
Reaction Kinetics (Vallance)
 Elementary reactions

Always follow simple rate laws

Reactant order reflects molecularity (# of molecules involved in reaction)

More on this later…

Reaction Kinetics (Vallance)

Order of Reactions
 Order of Reactions

• A reaction is zero order in a reactant if the change in

concentration of that reactant produces no effect.

• A reaction is 1st order if doubling the concentration

causes the rate to double.

• A reaction is 2nd order if doubling the concentration

causes a quadruple increase in rate.
-3rd order…doubling concentration leads to 23 (or 8 times) the rate.
- extremely rare.
 Order of Reactions

Reaction Kinetics (Vallance)

Zero Order Reactions
• Occasionally, rate is independent
of the concentration of the
reactant:
• Rate = k
• These are zero order reactions.
• These reactions are linear in
concentration.

Ex. The most common type of zero-order reaction occurs when a gas undergoes
decomposition on the surface of a solid.
2N2O Pt(hot) 2N2+O2

Photochemical reaction:
H2 (g) + Cl2 (g) hv 2HCl(g)
 Plot of [A] vs Time
Zero-Order
• Rate = k[A]0 = k
• Integrated:
[A] = –kt + [A]o

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b, so a plot of [A]t vs. t is a
straight line with slope (-k) and intercept [A]0.
Zero-Order
• Half–Life:

t1 =
 A 0
2 2k
k = rate constant
[A]o = initial concentration of A

• Half–life gets shorter as the reaction progresses and the concentration of

reactants decrease.
First Order Reactions
• Some rates depend only on one reactant to the first power.
• These are first order reactions.
• The rate law becomes:
Rate = k [A]

• Integrated:
ln[A] = –kt + ln[A]o
[A] = concentration of A at time t
k = rate constant
t = time
[A]o = initial concentration of A
First-Order Processes
For 1st order reactions: ln[A]t = −kt + ln[A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of s-1
t= time in seconds
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b,
so a plot of ln[A]t vs. t is a straight line with slope (-k) and
intercept ln[A]0.
(slope= −k)

ln[A]t

Time (s)
Example: First-Order Processes
Consider the process in
which methyl isonitrile is
converted to acetonitrile.

CH3NC CH3CN

How do we know this

is a first order
reaction?
First-Order Processes
CH3NC CH3CN

This data was

collected for this
reaction at 198.9°C.

Does
rate=k[CH3NC]
for all time intervals?

• John D. Bookstaver
• St. Charles Community College
First-Order Processes

If a reaction is first-order:
a plot of ln [A]t versus t will yield a straight line
with a slope of -k.
First-Order Processes

• When ln[A] is plotted as a function of time,

a straight line results.
• The process is first-order.
• k is the negative slope: 5.1  10-5 s-1.
 Relating k to [A] in a
First Order Reaction
• rate = k [A]
• rate = −Δ [A] / Δt [A] = concentration of A at time t
• So: k [A] = −Δ [A] / Δt k = rate constant
• Rearrange to: Δ [A] / [A] = − k Δt t = time
• Integrate: ln ([A] / [A]o) = − k t [A]o = initial concentration of A
• Rearrange: ln [A] = − k t + ln [A]o
• Note: this follows the equation of a line:
y = mx + b
• So, a plot of ln [A] vs. t is linear.
An Example: Conversion of Methyl
Isonitrile to Acetonitrile
• The equation for the reaction:
CH3NC → CH3CN
• It is first order.
Rate = k [CH3NC]
Finding the Rate Constant, k
• Besides using the rate law, we can find the rate constant from
the plot of ln [A] vs. t.
• Remember the integrated rate law:
ln [A] = − k t + ln [A]o
• The plot will give a line. Its slope will equal −k.

Plot of ln[N2O5] vs Time

First-Order
• Time required for a reactant to reach half its original concentration
• Half–Life:
0.693
t1 =
2 k
k = rate constant
• Half–life does not depend on the concentration of reactants.

Copyright © Cengage Learning. All rights reserved 167

 A first order reaction is 35% complete at the end of 55 minutes. What is the
value of k?
k = 7.8 × 10–3 min–1
ln [A] = − k t + ln [A]o

Copyright © Cengage Learning. All rights reserved 168

 Half-life
• Definition: The amount of time it takes
for one-half of a reactant to be used up
in a chemical reaction.
• First Order Reaction:
 ln [A] = − k t + ln [A]o
 ln ([A]o/2) = − k t½ + ln [A]o
 − ln ([A]o/2) + ln [A]o = k t½
 ln ([A]o / [A]o/2) = k t½
 ln 2 = k t½ or t½ = 0.693/k

Half–life does not depend on the concentration of reactants.

Second Order Reactions
• Some rates depend only on a reactant to the second power.
• These are second order reactions.
• The rate law becomes:
Rate = k [A]2
Integrated:
1 1
= kt +
 A  A 0
[A] = concentration of A at time t
k = rate constant
t = time
[A]o = initial concentration of A
Second-Order Processes
Similarly, integrating the rate law for a
process that is second-order in reactant A:

Rearrange, integrate:

also in the form y = mx + b

Second-Order Processes

So if a process is second-order in A, a plot of

1/[A] vs. t will yield a straight line with a slope
of k.

First order:

If a reaction is first-order, a plot of ln [A]t vs. t will yield

a straight line with a slope of -k.
Determining rxn order
The decomposition of NO2 at 300°C is described by
the equation
NO2 (g) NO (g) + 1/2 O2 (g)
and yields these data:

Time (s) [NO2], M

0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
Determining rxn order
Graphing ln [NO2] vs. t yields:

• The plot is not a straight

line, so the process is not
first-order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 -4.610
50.0 0.00787 -4.845 Does not fit:

100.0 0.00649 -5.038

200.0 0.00481 -5.337
300.0 0.00380 -5.573
Second-Order Processes
A graph of 1/[NO2] vs. t
gives this plot.

Time (s) [NO2], M 1/[NO2]

• This is a straight
line. Therefore, the
0.0 0.01000 100
process is second-
50.0 0.00787 127
order in [NO2].
100.0 0.00649 154
200.0 0.00481 208
300.0 0.00380 263
 Solving the Second Order
Reaction for A → Products
• rate = k [A]2
• rate = − Δ [A] / Δ t [A] = concentration of A at time t
k = rate constant
• So, k [A]2 = − Δ [A] / Δ t t = time
[A]o = initial concentration of A
• Rearranging: Δ [A] / [A]2 = − k Δ t
• Using calculus: 1/[A] = 1/[A]o + k t
• Notice: The linear relationships for first order and second order
reactions differ!
Plot of ln[C4H6] vs Time and Plot of 1/[C4H6] vs Time
Second-Order
• Half–Life:

1
t1 =
2 k  A 0
k = rate constant
[A]o = initial concentration of A

• Half–life gets longer as the reaction progresses and the

concentration of reactants decrease.
• Each successive half–life is double the preceding one.

Copyright © Cengage Learning. All rights reserved 178

 EXERCISE!
For a reaction aA  Products,
[A]0 = 5.0 M, and the first two half-lives are 25 and 50 minutes,
respectively.
a) Write the rate law for this reaction
b) Calculate k.
c) Calculate [A] at t = 525 minutes.

179
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.
180
Half Life
 Half-Life

• Half-life is the time taken for the concentration of a

reactant to drop to half its original value.
• Substitute into integrated rate laws: t½ is the time taken
for [A] to reach ½[A]0

NOTE: For a first-order process, the

half-life does not depend on [A]0.
Reaction Kinetics (Vallance) Dan Reid
Champaign CHS
 Half-Life - 1st order
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?

t½ = Ln 2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10 s
-4 -1

How do you know decomposition is first order?

hint: units of k (s-1)

Equations of Reactions of Various Orders
 Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
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)

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] - [A]0 = - kt t½ =
2k
Ln 2
1 rate = k [A] ln[A] - ln[A]0 = - kt t½ =
k
1 1 1
2 rate = k [A] 2 - = kt t½ =
[A] [A]0 k[A]0
186
 EXERCISE!
Consider the reaction aA  Products.
[A]0 = 5.0 M and k = 1.0 × 10–2 (assume the units are appropriate for each case).
Calculate [A] after 30.0 seconds have passed, assuming the reaction is:
a) Zero order
b) First order
c) Second order

187
 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

Unimolecular – reaction involving one molecule; first order.

Bimolecular – reaction involving the collision of two species; second order.
Termolecular – reaction involving the collision of three species; third order. Very rare.
Molecularity

The molecularity of an elementary reaction

tells how many molecules are involved in
that step of the mechanism.
CONCEPT CHECK!
The reaction A + 2B  C has the following proposed mechanism:
A+B D (fast equilibrium)

D+B C (slow)

Write the rate law for this mechanism.

rate = k[A][B]2

Rate-Determining Step
A reaction is only as fast as its slowest step.

The rate-determining step (slowest step) determines the rate law and the
molecularity of the overall reaction.
190
Factors That Affect Reaction Rate

1. Temperature
2. Frequency of collisions
3. Orientation of molecules
4. Energy needed for the reaction to take
place (activation energy)
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 E a
• Generally, the lower the value of E a 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.
The Relationship Between
Activation Energy & Temperature
• Arrhenius noted relationship between activation
energy and temperature: k = Ae−Ea/RT
• Activation energy can be determined graphically
by reorganizing the equation: ln k = −Ea/RT + ln A
ARRHENIUS EQUATION
 Ea / RT
k = Ae
Ea  1 
ln(k ) =    + ln  A 
A = R  T  factor
frequency
Ea = activation energy
R = gas constant (8.3145 J/K·mol)
T = temperature (in K)
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
the absolute temperature as k = A .
where, k is rate constant, Ea is the activation
Arrhenius equation (non exponential form)
energy,
ln k = ln A is the pre-exponential (frequecy) factor is
ln k =  constant, and RT is the average kinetic energy i.e.,
R is the gas constant (8.314 J/mol-K), and T is the
• value of from intercept at infinite
❖ A graph of lnk versus 1/T is a straight line absolute temperature. 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.

198
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.
 EXERCISE!

Chemists commonly use a rule of thumb that an increase of 10 K in

temperature doubles the rate of a reaction. What must the activation
energy be for this statement to be true for a temperature increase from
25°C to 35°C?

Ea = 53 kJ

200
 Numericals on Chemical Kinetics
1. The half-life of a first-order reaction was found to be 10 min at a certain temperature. What is its rate constant?

Solution: k = 0.693/600 s = 0.00115 s-1

2. If 3.0 g of substance ‘A’ decomposes for 36 minutes the mass of unreacted ‘A’ remaining is found to be 0.375 g. What is the half-life
of this reaction if it follows first-order kinetics?

Solution:
0.375 g
ln
 At
 kt
ln
3g
k 
 A0 36 min

ln
 At / t  k
k = 0.0578 min-1
 A0
ln 2 0.693
t1 / 2   12 min
k 0.0578
3. The decomposition of dimethyl ether, : (CH3)2O, at 510 °C is a first-order process
with a rate constant of 6.8 x 10-4 s-1: (CH3)2O(g)CH4(g) + H2(g) + CO(g)
If the initial pressure of (CH3)2O is 135 torr, what is its pressure after 1420 s?
Solution:

ln  At  ln  A0  kt k = 6.8 x 10-4 s-1

[A]0 = 135 torr.
T = 1420 sec

ln [A]t = ln [135]  6.8 x 10-4 (1420) = 3.939

To obtain pressure of [(CH3)2O]t = 1420 s , we use the inverse natural logarithm,

or ex, function on the calculator:
[(CH3)2O]t = 1420 s = e 3.939= 51.367 torr.
4.
 5. The following data were obtained for the gas-phase decomposition of nitrogen dioxide
at 300 °C,
NO2 (g)  NO(g) + 1/2 O2 (g). Is the reaction first or second order in NO2?
Time (s) [NO2 ] (M) Solution: Plot ln [NO2]and 1/ [NO2] against time.
0.0 0.01000 If one plot or the other is linear, we will know the reaction is either
50.0 0.00787
100.0 0.00649 first or second order.
200.0 0.00481 To graph ln [NO2]and 1/ [NO2] against time, we first make the
300.0 0.00380
following calculations from the data given:

Time (s) [NO2](M) ln [NO2] 1/ [NO2] (1/M)

0.0 0.01000 -4.605 100
50.0 0.00787 -4.845 127
100.0 0.00649 -5.037 154
200.0 0.00481 -5.337 208
300.0 0.00380 -5.573 263

As Figure shows, only the plot of 1/ [NO2] versus time is linear.

Thus, the reaction obeys a second-order rate law: Rate = k [NO2]2.
From the slope of this straight-line graph, we can determine that k = 0.543 M-1 s-1 for the
disappearance of NO2.
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. 207
 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) 208
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) (glucose) (fructose
(cane sugar)
)

209
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) 

210
 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.

211
 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) 212
 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.
214
 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
Enzymes’ effect on the activation energy active 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