COVENANT UNIVERSITY OTA,

NIGERIA

CHM 111: GENERAL PHYSICAL CHEMISTRY

CHEMICAL ENERGETIC KINETICS

1
 CHEMICAL ENERGETICS
At the end of this topic students are expected to be
able to:
• Identify the system and the surroundings in a chemical
process.
• Identify the ways in which energy is transferred in a
chemical process.
• Identify the sign of heat and work in chemical processes.
• Give examples of chemical reactions that do work.
• Calculate the energy required to change the temperature
of a substance using its heat capacity.
• Explain the origin of the heat of reaction.
• Understand the relationship between internal energy and 2

enthalpy.
• Define the 1st law of thermodynamics
 COURSE OUTLINE
• Definitions of some Thermodynamics Terms, Heat, work,
internal energy, enthalpy, pressure- Volume work.
• The relationship between internal energy and enthalpy.
• First law of thermodynamics and its applications.

3
 CHEMICAL ENERGETICS
Chemical energetic is the study of
chemical changes caused by energy.

In chemical energetic, we discuss

both
1. Thermodynamics and
2. kinetics of Chemical reactions.

4
 WHAT IS THERMODYNAMICS
The name can be broken into two parts:
 Thermo – heat – concerned with heat

energy
 Dynamics – physical power and forces

producing motion

Thermodynamics involves the storage,

transformation and transfer of energy

5
ENERGY is stored as:
 Internal Energy – due to temperature

 Kinetic Energy – due to motion

 Potential Energy – due to elevation

 Chemical Energy – due to chemical

composition

6
 CHEMICAL
THERMODYNAMICS

Chemical Thermodynamics is the

branch of science that describes the
relationship between the energy
changes that occur during chemical
and physical processes.

7
 LIMITATIONS OF THERMODYNAMICS

 Thermodynamics does not bother about time

factor e.g It is concerned with only the initial
and the final state of the system

o Hence, it CANNOT answer, for example the

question
 How fast processes occur?

8
 THERMODYNAMICS TERMS
AND BASIC CONCEPT
A thermodynamic system is that part of the universe
which is arbitrarily set off from the rest, for the purpose of
theoretical and experimental study

• The system is confined to a definite place in space by

boundary which separates it from the rest of the
universe.

• The portion of the universe excluded from the

system is called its surroundings.

System + Surroundings = the universe

9
THE UNIVERSE

10
THERMODYNAMIC SYSTEM
 When a system is uniform
throughout, it is called a
Homogeneous System.
e.g. mixture of gases, true solution of solid in a
liquid.
 A homogenous system is made
of one phase only
 A phase is define as a
homogeneous, physically distinct
and mechanically separable
portion of a system.
 A heterogeneous system is
one which consists of two or
more phases.
 It is not uniform throughout
 E.g ice in contact with water
11
 TYPES OF THERMODYNAMIC SYSTEMS

 Open Systems: An open system is one which can allow

exchange of energy and matter with its surrounding

 Closed Systems: A closed system is system which

allows exchange of energy in any form with its
surrounding (work, heat…) but which CANNOT exchange
any matter

 Isolated Systems: This system can exchange neither

matter nor energy with the surroundings.

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TYPES OF THERMODYNAMIC SYSTEMS

13
 TYPES OF WALL BETWEEN SYSTEM AND
SURROUNDING

Diathermal: Heat can flow

(Particles cannot).

Adiabatic: No heat flow

between them. Adiabatic
walls keep the systems
isolated

14
 PROPERTIES OF A SYSTEM
The properties of a system are those physical
attributes that are perceived by senses or are
made perceptible by certain experimental
methods of investigation.
Properties fall into two classes:
 Non-measurable e.g substance composition

and states of aggregation of its parts

 Measurable e.g pressure and volume

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 INTENSIVE AND EXTENSIVE
PROPERTIES (VARIABLES)
Extensive Properties Intensive Properties
 The state properties which are  The properties which are
proportional to the mass of the independent of mass of the
system are called Extensive system are called Intensive
variables or properties.
variables.
 Hence, has a uniform
 Examples are Internal energy,
Enthalpy, heat capacity at value in different
constant pressure or constant subdivision of a system.
volume, entropy.  Examples are pressure,
Temperature (they are
 Extensive properties of a pure identical in all points of the
species are proportional to the
number of moles the species system)
present.  Other examples are Molar
variables, specific mass,
refractive index, Density 16
 PATH AND STATE FUNCTION
PATH FUNCTION STATE FUNCTION
 If property depends on  When the state of system is
the path or history by changed and the change in the
which the state of the value of the property depends
only on initial and final
system is reached, it is states of the system. Such a
called a path variables variable is called a state
or property or function function.
 The finite change in state

function is denoted by Δ or d
(small change)
Hence, ΔV = 𝑉𝑓𝑖𝑛𝑎𝑙 − 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙

17
 EQUATION OF STATE
 An equation of state is a relationship between
some of the variables of state of a pure
species that completely defines the state of
the system.
 For a pure gas: Pressure P, molar volume V
and temperature, T
 The equation of state for ideal gas is
𝑃𝑉 = 𝑛𝑅𝑇
where R = gas constant (8.3145 J𝐾−1𝑚𝑜𝑙−1)

18
 SYMBOLS IN THERMODYNAMICS
 In thermodynamics all state functions
are symbolized by capital letters e.g
P, V, T, U, H etc.

 All path dependent functions are

symbolized by small letters. E.g. heat
is q and work is w.

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 THERMODYNAMIC PROCESSES

When a thermodynamic system

changes from one state to
another, the operation is called
a process

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 Various Types of Thermodynamic processes
1. Isothermal Processes -Processes in 4. Isochoric Processes -
which the temperature remain fixed or Processes in which the volume
constant remain constant
o This is achieved by placing the
o Achieved by heating a
system in a thermostat substance in non-expanding
o For this process dT = 0 container
2. Adiabatic Processes - Processes in o For this process dV = 0
which no heat can flow into or out of 5. Cyclic Process
the system.
o When a system in a given
o Achieved by carrying out the process
state goes through a number
in an insulated container. of different processes and
o For this process dq = 0 finally returns to its initial
3. Isobaric Processes - Processes which state. The overall process is
take place at constant pressure called cyclic process
o Heating at atmospheric pressure o For this process, dU = 0, dH

(constant Pressure) =0
o For this process dP = 0

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THERMODYNAMIC PROCESSES
Cyclic process

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 HEAT
 Heat is denoted as ‘q’. Units of heat
 Unit of heat which was used
many years is calorie (cal)
 Heat, q is not a state  A calorie is the quantity of heat
function, hence it will required to raise the
change with the path. temperature of 1 gram of
water by 1oC
 Since heat and work are
 q is an extensive interrelated, SI unit of heat is
property (depends on the joule (J)
the mass of the  1 joule = 0.2390 calories
matter)  1 calorie = 4.184 J
 1 kcal = 4.184 kJ

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 SIGN CONVENTION FOR HEAT EXCHANGE
 When a thermodynamic system receives energy in any form
from the surroundings, it is counted as a positive quantity.
i.e q = +ve

 When a system gives up energy to some part of the

surroundings, it is counted as negative quantity. i.e q = -ve

 Thermodynamic laws are expressed in such a way that the sign

of the heat exchanges is always accounted for from the system
point of view.

24
 MECHANICAL WORK

In Physics, Mechanical work (w) is defined as a force

applied (F) to produce a movement of an object times the
distance moved (d)

Work(w) = Force(F) x distance(d)

w=Fxd

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 WORK AND VOLUME CHANGE
 Consider a system made of a gas contained in a
cylindrical container closed by a piston of area A.

 Whatever does not belong to the system is called

environment or surroundings of the system.

 If volume increases during the process, the gas is

said to undergo an expansion

 If the volume decreases during the process, the

gas is said to undergo a compression
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 WORK AND VOLUME CHANGE
Let assume the only external force  The force exerted by surrounding
exerted on the piston is due to the into the piston has a magnitude of
external pressure as shown below.
𝑃𝑒𝑥𝑡𝐴
 The force is directed toward the
left.
 For ds > 0, the system does work
on the surroundings, dw is
negative
𝐹 = 𝑃𝑒𝑥𝑡𝐴
𝑑𝑤 = −𝑃𝑒𝑥𝑡𝐴 𝑑𝑆 = −𝑃𝑒𝑥𝑡𝑑𝑉
where dV = volume increase during
the process
If the pressure 𝑃𝑖𝑛𝑡 is larger than the  If the change in the state
pressure 𝑃𝑒𝑥𝑡 the piston will produced a change of volume from
V1 to V2,
spontaneously move to the right.
𝑣2
(opposite to the external force) w = -‫ 𝑣׬‬P𝑑𝑉
𝑖 27
VOLUME DECREASE - COMPRESSION

Consider a gas undergoing compression,

This occur when Pint < Pext
In this case work is done on the system by the
surroundings.

 The displacement is in the direction of external force

 Hence dw is positive since the variation of volume is
negative

ΔV = A dx
Decrease of volume during the process
dx < 0, dV < 0 and dw > 0
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 EVALUATION OF THE LINE INTEGRAL
Process at constant external pressure
The work done on the system during the process is

𝑣𝑓 𝑣𝑓
𝑤= − ‫𝑣׬‬ 𝑃𝑒 𝑥 dV =−𝑃𝑒𝑥 ‫𝑣׬‬ 𝑑𝑉 = −𝑃𝑒𝑥𝑡(𝑣𝑓 − 𝑣𝑖)
𝑖 𝑖
𝑡 𝑡

 The work done on the system depends on the external

pressure (i.e the outside) and does not depend on the
inside pressure of the system.

 If Pext < Pint and Pext is constant

 𝑣𝑓 > 𝑣𝑖 𝑎𝑛𝑑 𝑤 < 0 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛

 If 𝑃𝑒𝑥𝑡 = 0 𝑡ℎ𝑒𝑛 𝑤 = 0

29
 SIGN CONVENTION FOR WORK
 If work is done on the system by the surrounding, the
energy of the system is increased. i.e work is +ve

 In above example, gas is compressed, the volume

decreases, work flow into the system. Hence w is +ve
w = PΔV

 If work is done by the system on the surroundings, the

energy of the system is decreased. i.e work is –ve

 For an expanding gas, the volume increases, work flow

from the gas to surroundings. Hence w is –ve
w = - PΔV
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 Example 1: A balloon is inflated to its full extent by heating the air inside it.
In the final stages of this process the volume of the balloon changes from
4.00 x 104 L to 4.50 x 106 L. Assuming the balloon expands against a
constant pressure of 1.0 atm, calculate the work done by process in Joules
Solution: The work done can be calculated from the expression:
w = PΔV
P = 1 atm (external pressure)
∆𝑉 = 𝑉𝑓𝑖𝑛𝑎𝑙 − 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 4.50 × 106𝐿 − 4.00 × 106𝐿 = 0.5 × 106𝐿
= 5.0 × 105𝐿
Thus 𝑤 = −1.0 𝑎𝑡𝑚 × 5.0105 𝐿 = −5.1105 𝐿𝑎𝑡𝑚
 Note: -ve sign for work make sense since the gas is expanding
and doing work on the surrounding.

To convert to Joules: 1 L atm = 101.3 J

 𝑤 = −5.0 × 105𝐿 𝑎𝑡𝑚 × 101.3𝐽 = −5.1 × 107𝐽

𝐿 𝑎𝑡𝑚 31
Example 2: Calculate the volume work done on a system during a chemical
reaction that takes place at constant external pressure. Assuming the following
reaction is complete at 25oC and 105Pa using an appropriate catalyst,
CO2 + 4H2 → CH4 + H2O
Starting with 0.5 mole of gas in stoichiometric proportion in the initial state, there is
only 0.1 mole of gas when the reaction is completed (water is liquid the volume is
negligible compared to volume of gas). Assume the gases obey the ideal gas law
Solution
If it obeys ideal gas law, the initial and final volume of the system are
𝑛𝑖 𝑅𝑇 0.5 × 8.3145 × 298 −3𝑚3
𝑣𝑖 = = = 12.39 × 10
𝑃 105
𝑛𝑓 𝑅𝑇 0.1 × 8.3145 × 298 −3𝑚3
𝑣𝑓 = = = 2.48 × 10
𝑃 105
The work done on the system is
𝑤 = −𝑃𝑒𝑥𝑡 𝑣𝑓 − 𝑣𝑖 = −105 2.48 × 10−3 − 12.39 × 10−3
= 991𝐽

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 WORK DURING AN ISOTHERMAL
(REVERSIBLE) CHANGE OF IDEAL GAS

 During an isothermal reversible change, the

temperature of the system stays constant and uniform
for the entire process which takes place as a
continuous succession of equilibrium states.

 The gas volume varies from 𝑣𝑖 to 𝑣𝑓

 We apply at every instant an external pressure

𝑃𝑒𝑥𝑡 = 𝑃𝑖𝑛𝑡

33
 WORK DURING AN ISOTHERMAL
(REVERSIBLE) CHANGE OF IDEAL GAS (cont)

 For infinitesimal process, the work done on the system

is
𝑑𝑤 = −𝑃𝑒𝑥𝑡𝑑𝑉
For infinitesimal isothermal (reversible) process of an ideal
gas

Since Pressure, 𝑃 = 𝑛𝑅𝑇

𝑉

The expression for work done on the gas is

𝑣𝑓 𝑣𝑓
𝑛𝑅𝑇 𝑑𝑉 𝑉𝑓
𝑤=−න 𝑑𝑉 = −𝑛𝑅𝑇 න = −𝑛𝑅𝑇𝑙𝑛( )
𝑉 𝑉 𝑉𝑖
𝑣𝑖 𝑣𝑖
34
Example 2: Calculate the work done on one mole of an ideal
gas when its volume doubles during an isothermal change of
volume at 500K.
Solution:
𝑉𝑓
𝑤 = −𝑛𝑅𝑇𝑙𝑛
𝑉𝑖
2
= −1 𝑚𝑜𝑙𝑒 × 8.324𝐿𝐾−1𝑚𝑜𝑙𝑒−1× 500𝐾 × 𝑙𝑛
1
= −2881𝐽 = −2.881𝑘𝐽

Since the work is negative, the gas does work on the

surroundings.
35
Example 3: One mole of an ideal gas is heated at a constant
pressure of 101.3KNm-2 from 273 to 373K
Calculate in Joules, the work involved.
Solution
𝑣2

𝑤𝑜𝑟𝑘 𝑤 = − 𝑃𝑑𝑉 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒,

𝑣1
Since gas is ideal 𝑃𝑉 = 𝑛𝑅𝑇,
Therefore, 𝑉 = 𝑛𝑅𝑇 and 𝑑𝑉 = 𝑛𝑅 𝑑𝑇 since P is constant. Hence,
𝑃 𝑃

𝑇2
𝑤 = −𝑛𝑅
𝑇1 𝑑𝑇 = -𝑛𝑅∆𝑇
= −1 × 8.314𝐽𝐾−1𝑚𝑜𝑙𝑒−1 × 100𝐾
= −831.4𝐽
36
Example 4: One mole of an ideal gas is heated at a constant pressure of 101.3KNm-2 from 273
to 373K
If the gas was expanded isothermally at 273K from 101.3kNm-2 to some other pressure, P,
what must be the final pressure if the isothermal work is equal to the work of Example 3?

The isothermal work is given by the formula

𝑣2

𝑤𝑜𝑟𝑘 𝑤 = − න 𝑃𝑑𝑉
𝑣1
Since the process is isothermal and the gas is ideal
𝑃𝑉 = 𝑛𝑅𝑇 (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒)
𝐻𝑒𝑛𝑐𝑒, 𝑉 = 𝑛𝑅𝑇
𝑃
𝑣2 𝑣2
𝑑𝑉 𝑉2
𝑤 = − න 𝑛𝑅𝑇 = −𝑛𝑅𝑇 න 𝑑𝑙𝑛 𝑉 = −𝑛𝑅𝑇𝑙
𝑛 𝑉 𝑉1
𝑣1 𝑣1
𝑉2
But 𝑃1𝑉1 = 𝑃2𝑉2 , Hence, = 𝑃1
𝑉1 𝑃2
𝑉2 𝑃1
𝑤 = −𝑛𝑅𝑇𝑙𝑛
= −𝑛𝑅𝑇𝑙𝑛
𝑉1 𝑃2
−1 −1
101.3 × 103
= −1 × 8.314𝐽𝐾 𝑚𝑜𝑙𝑒 𝑙𝑛 = −831.4 𝐽
𝑃2
3
𝑙𝑛 101.3×10 = 𝑒0.366 = 1.442
𝑃2
101.3 × 103
𝑃2 = = 70.25 × 103𝑁𝑚−2 = 70.25𝑘𝑁𝑚−2
1,442 37
 INTERNAL ENERGY
 The internal energy, U of a system is the total energy of it
contains as a result of its physical states, that is, under
specific conditions of T, p, V, etc.
 The value of U depends on the amount of matter in our
system i.e if we double the mass we double U.
 Hence U is an extensive property of the system

Internal energy is a state function. Hence a change in internal

energy of a process is define as:

ΔU = 𝑈𝑓𝑖𝑛𝑎𝑙 𝑠𝑡𝑎𝑡𝑒 − 𝑈𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑠𝑡𝑎𝑡𝑒

ΔU is +ve if 𝑈𝑓𝑖𝑛 𝑎 𝑙 𝑠𝑡𝑎𝑡 𝑒 is greater than 𝑈𝑖 𝑛 𝑖 𝑡 𝑖 𝑎 𝑙 𝑠𝑡𝑎 𝑡 𝑒 and –ve

for
the reverse 38
 INTERNAL ENERGY
Internal energy of a system came from:
 The kinetic energy of motion of individual

molecules
 The potential energy that arises from

interactions between molecules.

 The kinetic and potential energy of the

nuclei and electrons within the individual

molecules.

39
 FIRST LAW OF THERMODYNAMICS
 The first law of thermodynamics is merely the
Law of Conservation of Energy
The total energy of an isolated system
remains constant though it may change
from one form to another
or
Energy is neither created nor destroyed by
a process (it is only transformed from one
form to another)

40
 Mathematical Statement of 1st Law
When a system is changed from state 1 to another state 2,
the internal energy of the system change:
ΔU = U2 - U1

ΔU is associated with work, w or transfer of heat, q

ΔU = q - w (mathematical statement of Ist Law)

Where q is the amount of heat supplied to the system

w is the work done by the system

41
 CONSTANT VOLUME PROCESS
 If a process is carried out at constant volume, the work
involved, will be equal to zero.

 Hence the expression of 1st law of thermodynamics

becomes
ΔU = q

(Since w = 0 at constant volume, from ΔU = q – w

w = - P(Vf – Vi ) = - P x 0 = 0)

42
 CONSTANT PRESSURE PROCESS
 At constant pressure, and from the expression of
1st law of thermodynamics, the work is equal to
PdV and heat, q is given as:

𝑞𝑃 = ∆𝑈 + 𝑃𝑑𝑉
We can rewrite this as:
𝑞𝑃 = ∆𝑈 + 𝑃𝑉

The quantity ∆𝑈 + 𝑃𝑉 is another function of state

called Enthalpy. H. Thus
𝑞𝑃 = ∆𝐻
43
 ENTHALPY
 At constant pressure, the change in enthalpy
(ΔH) of a system is equal to the energy flow as
heat

 Hence, for a reaction studied at constant

pressure, the flow of heat is a measure of
change in enthalpy.

44
 CONSTANT PRESSURE PROCESS
 For a chemical reaction, the enthalpy change is give as

∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

o ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 is +ve, if the energy of product is

greater than reactants i.e endothermic reaction.

o ∆𝐻𝑟𝑒𝑐𝑡𝑖𝑜𝑛 is –ve, if the energy of the products is

less than reactants i.e exothermic reaction.

o The total heat content of a system at constant

pressure is known as the enthalpy of the system.
45
 ENTHAPLY
Consider a change between two states
A → B
𝑃1𝑉1 𝑃2𝑉2

Initial State 𝐻1 = 𝑈1 + 𝑃1𝑉1

Final State 𝐻2 = 𝑈2 + 𝑃2𝑉2

Subtracting we have, 𝐻2 − 𝐻1 = 𝑈2 − 𝑈1 + 𝑃2𝑉2 − 𝑃1𝑉1

∆𝐻 = ∆𝑈 + 𝑃∆𝑉

For an ideal gas,

∆𝐻 = ∆𝑈 + ∆𝑛 𝑅𝑇 (at constant temperature)

46
 PROPERTIES OF ENTHALPY
1. Enthalpy is an extensive property. The magnitude of
ΔH is dependent upon the amounts of reactants
consumed. Doubling the reactants, doubles the amount
of enthalpy
2. Reversing a chemical reaction results in the same
magnitude of enthalpy but of the opposite sign.
o For example, splitting two moles of water to

produce 2 moles of H2 and 1 mole of O2 gas

requires the input of +483.6kJ of energy.
3. The enthalpy change for a reaction depends upon the
state of the reactants and products. The states (i.e g, l,
s, aq) must be specified
47
 HEAT CAPACITIES
 Every system has its own capacity to absorb heat and store
energy.
 This increased kinetic energy raises the temperature of the
system
 If q calories is the heat absorbed by mass, m and the
temperature rises from 𝑇1 to 𝑇2.

Heat Capacity (c) is given as:

𝑞
𝑐=
𝑚×(𝑇2−𝑇1)

Thus,
Heat capacity of a system is the heat absorbed by unit
mass in raising the temperature by one degree (K or oC)
at a specified temperature.

48
 Molar Heat Capacity
 When mass considered is one mole, the above expression can be rewritten
as
𝑞 𝑞
𝐶= =
(𝑇2−𝑇1) ∆𝑇
𝐶 = 𝑀𝑜𝑙𝑎𝑟 𝐻𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦
Thus,

Molar heat capacity of a system is defined as the amount of

heat required to raise the temperature of one mole of
substance (system) by one degree (K or oC).

There are two important types of molar heat capacities

 At constant volume

 At constant pressure

49
Molar Heat at constant Volume
From first law of Thermodynamics, dq = dU + PdV
Divide by dT, we have

𝑑𝑞 𝑑𝑈 + 𝑃𝑑𝑉
=
𝑑𝑇 𝑑𝑇

At constant volume, dV = 0, the equation become

𝑑𝑈
𝐶𝑉 =
𝑑𝑇 𝑉
Heat capacity at constant volume is defined as the
rate of change of internal energy with temperature
at constant volume.
50
 Molar Heat Capacity at constant Pressure
From the above equation,
𝑑𝑈 𝑃𝑑𝑉
𝐶= +
𝑑𝑇 𝑑𝑇
We know that H = U + PV
Differentiating w.r.t T at constant pressure, we have,
𝑑𝐻 𝑑𝑈 𝑑𝑉
= +𝑃
𝑑𝑇 𝑃 𝑑𝑇 𝑃 𝑑𝑇 𝑃
Comparing with above equation, we have
𝑑𝐻
𝐶𝑃 =
𝑑𝑇 𝑃
Heat capacity at constant pressure is defined as
the rate of change of enthalpy with temperature
at constant pressure
51
Relation between CP and CV
𝑑𝑈
We know that: 𝐶𝑃 = 𝑑𝐻 𝑎𝑛𝑑 𝐶𝑉 =
𝑑𝑇 𝑑𝑇

By definition, H = U + PV for 1 mole of an ideal gas

or H = U + RT

Differentiating w.r.t temperature, T, we have

𝑑𝐻 𝑑𝑈
= +𝑅
𝑑𝑇 𝑑𝑇
It become,
𝐶𝑃 = 𝐶𝑉 + 𝑅
Therefore
𝐶𝑝 − 𝐶𝑉 = 𝑅

Thus CP is greater than CV by a gas constant whose value is 1.987 cal

K-1 mol-1 or 8.314 J K-1 mol-1 in SI units.

52
 Calculation of ∆𝑼
For one mole of an ideal gas, we have
𝑑𝑈
𝐶𝑉 =
𝑑𝑇
or
𝑑𝑈 = 𝐶𝑉 × 𝑑𝑇
For a finite change, we have
∆𝑈 = 𝑈2 − 𝑈1 = 𝐶𝑉(𝑇2 − 𝑇1)
And for n moles of an ideal gas we have

∆𝑈 = 𝑈2 − 𝑈1 = 𝑛 × 𝐶𝑣 × (𝑇2 − 𝑇1)
53
 Calculation of ∆𝑯
We have,
∆𝐻 = ∆ 𝑈 + 𝑃𝑉
= ∆𝑈 + ∆ 𝑃𝑉
= ∆𝑈 + ∆𝑅𝑇
(because PV=RT)

= ∆𝑈 + 𝑅∆𝑇
= 𝐶𝑉 𝑇2 − 𝑇1 + 𝑅(𝑇2 − 𝑇1)
= 𝐶𝑣 + 𝑅 𝑇2 − 𝑇1
∆𝐻 = 𝐶𝑃(𝑇2 − 𝑇1)
For n moles of an ideal gas, we have,
∆𝐻 = 𝑛 × 𝐶𝑃 × (𝑇2 − 𝑇1)
54
 APPLICATION OF FIRST LAW
Examples 1: Calculate how much heat would be liberated
when 1.00g. of H2 reacts O2 as in equation below.
1
𝐻2 𝑔 + 𝑂2 𝑔 → 𝐻2𝑂 𝑔 ∆𝐻 = −242 𝑘𝐽
2
Solution: 1 mole of H2 weighs 2.016 g
1.00 g of H2 = 1.00 𝑚𝑜𝑙𝑒 𝑜𝑓 𝐻2
2.015

= 0.496 mole of H2
From the equation, I mole of H2 → 242 𝑘𝐽
0. 496 mole of H2 → 242 × 0.496 𝑘𝐽
= 120.5 kJ

Note: when a reaction takes place between substances in their

standard states (states in which they exit at S.T.P), that
enthalpy symbol is ∆𝐻𝑜
55
 HEAT OF REACTION
Although the term “heat of reaction” is
generally applicable to any change for
which the chemical equation is specified,
there are some special types of reaction for
which heats take on special names:

1. Heat of formation or Reaction

2. Heat of Combustion
3. Heat of Neutralization
56
 APPLICATION OF FIRST LAW
HEAT OF FORMATION, ∆𝑯𝒐𝒇

When a compound is formed from it constituent elements in their

standard states we refer to the heat involved as the heat of
formation, ∆𝑯𝒐𝒇.

i.e it can be said that the standard heat of formation of gaseous water
is – 242 KJ mol –1.

The standard heat (enthalpy) of formation of a compound is

the enthalpy change when I mole of the compound is formed
from the required quantities of its component elements in their
standard states.

57
 STANDARD STATES FOR ELEMENTS AND
COMPOUNDS

Standard states for elements and compounds are simply

the states in which they exist at S.T.P
Standard conditions include:
 1 atm pressure

 1M concentration (solutions)

 Pure solid (if a solid) or pure liquid (if a liquid)

 For elements, the standard enthalpy of

formation, ΔHf0 of an element in its normal state

is 0
 There is no standard state for temperature. 298K

(i.e. 25°C) is a common temperature chosen for

standard reference value.
58
 STANDARD HEAT OF FORMATION
e.g. the standard state of Br2 is liquid, H2 is gas, and C is solid.
If we say ΔHf for SO2 is -296 kJ mol
0 -1
It means
S(s) + O2 → SO2 ΔH = -296 kJ mol-1
If we say ∆𝐻𝑓𝑜 for KClO 3(s) is −392 𝑘𝐽𝑚𝑜𝑙−1
𝐾(s) + 1Cl 2(g) + 3 𝑂2(𝑔) → 𝐾𝐶𝑙𝑂3 (𝑠) ∆𝐻 = −392 𝑘𝐽𝑚𝑜𝑙−1
2 2

By definition: the standard heat of formation of an element in its

standard state is zero
i.e ΔHf0 (H2(g)) =0, ΔHf0 (Br2(g)) =0, ΔHf0 (HCl(g)) =0

59
 HEAT OF FORMATION AND HEAT OF
REACTION

If we know the heats (enthalpies) of formation of

all the component species in a reaction, we can
calculate the overall enthalpy for that reaction.

The relationship is

∆𝐻𝑟𝑥𝑛 = ‫׬‬ 𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ‫׬‬ ∆𝐻𝑓 𝑜 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

∆𝐻𝑜 )

60
Example 2: Calculate ∆𝑯𝒐𝒇 for the reaction:
𝑭𝒆𝑶 𝒔 + 𝟏 𝑶𝟐(𝒈) → 𝑭𝒆𝟐𝑶𝟑(𝒔)
𝟐
given that the ∆𝑯𝒐𝒇 values are: for 𝑭𝒆𝑶 =
−𝟐𝟔𝟔 𝒌𝑱𝒎𝒐𝒍−𝟏; for 𝑭𝒆𝟐𝑶𝟑 = −𝟖𝟐𝟏𝒌𝑱𝒎𝒐𝒍−𝟏. State
whether the reaction is exothermic or endothermic.
Solution:
Remember that the standard state of O2 is O2 (g), hence,
∆𝑯𝒇𝒐 𝑶𝟐(𝒈) = 𝟎.
∆𝐻𝑟 𝑥 𝑛 = σ ∆𝐻𝑓𝑜 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − σ ∆𝐻𝑓𝑜 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
∆𝐻𝑟𝑥𝑛 = −821 − 2 −266 + 0 = −289𝑘𝐽
Since ∆𝐻𝑟𝑥𝑛 is –ve, the reaction is exothermic

61
 HEAT OF FORMATION
• If we know the heats (enthalpies) of formation
of all the component species in a reaction

• The overall enthalpy for that reaction can be

calculated

The relationship is:

∆𝐻𝑟𝑥𝑛 = σ ∆𝐻𝑜 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − σ ∆𝐻 𝑜 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

𝑓 𝑓

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 .

EXAMPLE 3 : Calculate ∆𝑯𝒐𝒓𝒙𝒏 for the reaction:

2FeO(s) + 𝟏𝟐 𝑶𝟐 𝒈 → 𝑭𝒆𝟐 𝑶𝟑 𝒔
given the ∆𝑯𝒐𝒇 values are: for FeO = -266 kJmol-1; for Fe2O3 = -821
kJmol-1. State whether the reaction is exothermic or endothermic
Solution:
Remember that the standard state of O2 is O2(g), hence,
ΔHf0 (O2(g)) = 0

∆𝐻𝑟 𝑥 𝑛 = σ ∆𝐻𝑓𝑜 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − σ ∆𝐻𝑓𝑜 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

∆𝐻𝑓𝑜 = −821 − 2 −266 + 0 = −289𝑘𝐽

Since ∆𝐻𝑓𝑜is –ve, the reaction is exothermic

63
HEAT OR ENTHALPY OF COMBUSTION
The heat of combustion of an element or compound is the
enthalpy change when 1 mole of that compound reacts
with oxygen to form products specified by a balanced
equation
e.g. in hydrocabons, the products are H2O and CO2
Example: When 1 mole of CH4 is burned in air to form
CO2(g) and H2O(l) , the heat evolved is 890kJ.
So we say ∆𝐻𝑜 comb. For CH4 is – 890 kJ mol -1.

CH4 (g) + 2O2(g) → CO2 (g) + 2H2O (l) ∆𝐻𝑜 = −890 𝑘𝐽

∆𝐻𝑐𝑜𝑚𝑏(𝐶𝐻4 𝑔 = −890 𝑘𝐽𝑚𝑜𝑙−1

64
HEAT OF NEUTRALIZATION
o This applies to acid – base reactions
Example:
H2SO4 + 2 NaOH → Na2SO4 + 2H2O .∆𝐻.
• The heat of neutralization of H2SO4 is ∆𝐻 for the above
reaction.
• However, the heat of neutralization for NaOH is half of
∆𝐻 for the reaction.

 Heat of evaporation e.t.c

65
 HESS’S LAW OF CONSTANT HEAT
SUMMATION

Hess’s law states that:

 The amount of heat liberated or absorbed
in a reaction is the same whether it occurs
in one step or several consecutive steps.
OR
 If a process can be considered to occur in
stages or steps, the enthalpy change for
the overall process is the summation of
the enthalpy changes for the individual
steps.
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Example 3: Calculate the enthalpy change for the reaction;
𝟑𝑪 𝒈𝒓𝒂𝒑𝒉𝒊𝒕𝒆 + 𝟒𝑯𝟐 𝒈 → 𝑪𝟑𝑯𝟖(𝒈)
given the following:
(a) 𝑪𝟑𝑯𝟖(𝒈) + 𝟓𝑶𝟐 𝒈 → 𝟑𝑪𝑶𝟐 𝒈 + 𝟒𝑯𝟐𝑶 (𝒍) ∆𝑯𝒐𝒂𝒐= −𝟐𝟐𝟐𝟎 𝒌𝑱
(b) 𝑪 𝒈𝒓𝒂𝒑𝒉𝒊𝒕𝒆 + 𝑶𝟐 𝒈 → 𝑪𝑶𝟐(𝒈) ∆𝑯𝒃 = −𝟑𝟗𝟑. 𝟓 𝒌𝑱
(c) 𝟏
𝑯𝟐 𝒈 + 𝑶𝟐 𝒈 → 𝑯𝟐𝑶(𝒍)
𝟐
∆𝑯𝒐𝒄 = −𝟐𝟖𝟓. 𝟗 𝒌𝑱
Solution
The desired reaction can be obtained by combining a, b, and c as follows
3 𝑏 − 𝑎 + 4(𝑐)
𝟑𝑪 𝒈𝒓𝒂𝒑𝒉𝒊𝒕𝒆 + 𝟑𝑶𝟐 𝒈 − 𝑪𝟑𝑯𝟖 𝒈 − 𝟓𝑶𝟐 𝒈 + 𝟒𝑯𝟐 𝒈 + 𝟐𝑶𝟐 𝒈
→ 𝟑𝑶𝟐 𝒈 − 𝟑𝑪𝑶𝟐 𝒈 − 𝟒𝑯𝟐𝑶 𝒍 + 𝟒𝑯𝟐𝑶 (𝒍)

3𝑪 𝒈𝒓𝒂𝒑𝒉𝒊𝒕𝒆 + 𝟒𝑯𝟐 𝒈 → 𝑪𝟑𝑯𝟖 𝒈

∆𝑯𝒐 = 𝟑∆𝑯𝒐 − ∆𝑯𝒐 + 𝟒∆𝑯𝒐

𝒓𝒙𝒏 𝒃 𝒃 𝒄

𝒐
∆𝑯𝒓𝒙𝒏 = 𝟑 −𝟑𝟗𝟑. 𝟓 − −𝟐𝟐𝟐𝟎. 𝟏 + 𝟒 −𝟐𝟖𝟓. 𝟗

𝒐
∆𝑯𝒓𝒙𝒏 = −𝟏𝟏𝟖𝟎. 𝟓 + 𝟐𝟐𝟐𝟎. 𝟏 − 𝟏𝟏𝟒𝟑. 𝟔 = −𝟏𝟎𝟒. 𝟎 𝒌𝑱
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Thank You for listening

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