CHE 256: PHYSICAL CHEMISTRY II: THERMODYNAMICS AND KINETICS

(UNIVERSITY OF IBADAN: 2021/2022 SESSION)

PART ONE: CHEMICAL KINETICS

Lecture materials:
1) Atkins, P. and de Paula, J. (2009). Atkins' Physical Chemistry. Chapter 21: The Rates of
Chemical Reactions. W. H. Freeman and Co., New York. 9th Edition. pg 783-811.
2) Mortimer, R. G. (2008). Physical Chemistry. Chapter 11: The Rates of Chemical
Reactions. Academic Press. USA, 3rd Edition. pg 485-522.
 CHEMICAL THERMODYNAMICS
MODULE 1: INTRODUCTION TO CHEMICAL THERMODYNAMICS
Chemical thermodynamics is the study of the transformations of energy that occur in chemical
and physical processes. There are different forms of energy which are interrelated and
interconvertible under appropriate conditions. These include heat, mechanical, electrical, radiant,
chemical energy.
Thermodynamic terms
For thermodynamic purposes, the universe is divided into 2 parts: The system and its
surroundings.

 A system is that part of the universe we are interested in at a particular time. It is the part
of the universe under study, and it is usually confined to a definite place in space by a
boundary. Examples of a system includes a reaction vessel, an engine, a cell etc.
 The surroundings comprise the region outside the system. It is usually restricted to a
region in the immediate vicinity of the system.
 The boundary or wall is the surface which separates the system from its surroundings.
Ideally, a boundary may be declared adiabatic, diathermal, impermeable, permeable or
semi-permeable. A wall that allows the transfer of a quantity is said to be permeable to
that quantity. A thermodynamic system is classified based on the permeability of its
several walls.
I. A rigid wall/boundary has fixed shape and position
II. A permeable wall to energy allows the passage of energy. A permeable wall to matter
allows the passage of matter.
III. An impermeable wall to matter prevents the passage of matter but allows the passage
of energy.
IV. An adiabatic wall prevents the exchange of both matter and energy between the system
and its surroundings.
V. A diathermal wall prevents the passage of matter but allows the passage of energy. It is
said to be impermeable to matter and non-adiabatic

Types of Systems: This is determined by the type of boundary that separates it from the
surrounding.
(a). Open system: This is a system that exchanges both matter and energy with its
surroundings. It is enclosed by boundaries that are permeable to both matter and energy.
(b). Closed system: This is a system that does not allow the exchange of matter with its
surroundings but allows the exchange of energy with its surroundings. It is enclosed by
diathermal boundaries.
(c). Isolated system: This is a system that does not allow the exchange of both matter and
energy with its surroundings. It is enclosed by adiabatic boundaries.

States of a System: A state is the condition in which a system exists at any particular time. A
system is in a definite state when each of its properties has a definite value. A change in state is
completely defined when the initial and final states are defined.

Thermodynamic Variables: These are measurable properties that completely define the state
of a system. Examples include temperature (T), pressure (P), volume (V), number of moles (n),
area, conductivity (L) etc. These variables are functions of the thermodynamic states.
State functions and State variables: These are variables which are independent of the path
taken by the system to change from one state to another, but depends only on the initial and
final states of the system. Examples include P, V, T, internal energy (E, U), entropy (S), Gibbs
free energy (G), enthalpy (H), chemical potential (), heat capacities (Cp and Cv).

Path functions: These are variables which depend on the path taken by a system in going from
one state to another. Examples, heat (q) and work (w).

Equation of states: An equation of state is a thermodynamic equation relating state variables

which describes the state of matter under a given set of physical conditions. Example is ideal
gas law PV =nRT .

Phase: A phase is a homogenous, physically distinct and mechanically separable portion of a

system. It is that portion of a system throughout which all physical and chemical properties are
essentially uniform. Distinct phases does not always mean different states of matter as more
than one phase may coexist within a given state. Example, a mixture or water and kerosene
contains two phases in liquid state.

Homogenous system: This is a system whose chemical composition and physical properties
are uniform in all parts of the system. It contains only one phase.

Heterogenous system: This is a system whose chemical composition and physical properties
vary from one point of the system to another. It is made up of more than one phase, separated
from each other by a phase boundary. Example is a mixture of ice and water.

Types of thermodynamic properties of a system: The properties of a system may be

described as extensive or intensive properties.
I. Extensive properties: These properties depend on the amount of the substance of the
system. They are proportional to the size of the system if P and T are constant.
Examples include mass, volume, number of moles, free energy, entropy, enthalpy, heat
capacity. Extensive properties per unit mass or per unit mole (specific properties) are
intensive properties.
II. Intensive properties: These properties are independent of the amount of the substance
of the system, rather, they are characteristics of the individual components of the
system. Examples include molar volume, density, temperature, pressure, viscosity,
boiling point, freezing point, specific heat, surface tension, refractive index, free energy
per mole.

Thermodynamic Process
A thermodynamic process is the method of operation through which a change in state occurs.
Examples include heating, freezing, sublimation, expansion, contraction etc. A process is
described by stating some or all of the following: the boundary, the change in state, the path or
the effect produced in the system and the effect produced in the surroundings during each stage
of the process.
Thermodynamic process can be carried out under various conditions such as:
I. Isothermal process: This is a process that takes place under constant temperature.
dt=0
II. Adiabatic process: This type of process involves no exchange of heat (and matter)
between the system and its surroundings. q=0
III. Isobaric process: Involves no change in pressure. ∆ P=0
 IV. Isochoric process: This is a process that takes place under constant volume. ∆ V =0
V. Cyclic process: This occurs if a system returns to its initial state after undergoing a
change.
VI. Isoentropic (isentropic) process: Isoentropic process occurs at constant entropy
VII. Isoenthalpic (isenthalpic) process: This type of process occur at constant enthalpy.
VIII. Reversible and irreversible process: For a system in equilibrium, there is no
difference in the pressure (mechanical equilibrium), potential (electrical equilibrium),
temperature (thermal equilibrium) and concentration of species (chemical equilibrium)
of the system. Hence, in thermodynamic sense, a reversible process occurs when the
properties of the system remain uniform at every instant of the process. Such a system
is assumed to remain in virtual equilibrium at all stages of the change. An irreversible
process involves changes in the properties of the system at one or more point during the
change. Such processes cannot be reversed by merely changing parameters by
infinitesimal amounts.
MODULE 2: FIRST LAW OF THERMODYNAMICS

CONCEPT OF HEAT AND WORK

Both heat and work refer to processes by which energy is transferred to or from a substance.
Work (w): Work is the transfer of energy resulting from a force acting through a distance. eg
lifting a load. There are many forms of work including mechanical, electrical and gravitational
etc. We will focus on pressure-volume (P-V) work which is work done in an enclosed chemical
system. eg expansion of gases.
Heat (q): Heat is the exchange of energy between a thermodynamic system and its
surroundings or between thermodynamic systems as a result of temperature difference. Heat is
transferred by conduction, convection and/or radiation.
The S. I. unit of heat and work is joules (J). Other units include calories (cal) and Ergs
1 cal=4.184 J
1 cal=4.184 ×107 Ergs
The direction of transfer of heat (q) and work (w) is specified using sign conventions.
 Heat absorbed by the system is positive (+q ; dq>0 )
 Heat released by the system is negative (−q ; dq<0 )
 Work done by the system (expansion) is negative (−w ; P1 < P2 ; dw <0 )
 Work done on the system (compression) is positive (+ w ; P 1> P2 ; dw< 0)
 THE FIRST LAW OF THERMODYNAMICS
The first law of thermodynamics is formulated from the law of conservation of energy. The law
of conservation of energy states that energy can neither be created nor destroyed but can be
transformed from one form to another. The first law of thermodynamics states that the total
internal energy (∆ U ) of a n isolated system is constant. The first law of thermodynamics states
that the change in internal energy (∆ U ) of an isolated system is equal to the sum of the amount
of heat absorbed or released by the system (q) and the amount of work done by or on the system
(w) by its surroundings.
∆ U =q+ w … … … … … … … … … … … … .(i)

Internal energy (U ), is the total energy of a system by virtue of its molecular composition and
motion. It is the energy associated with the kinetic energy and potential energy of the molecules
of the system, along with the electronic energy and energy of the nucleus. It is a state function.
Example 1: If a body with an internal energy of −900 J performs 1.65 kJ of work done on its
surroundings, calculate the heat absorbed or released by the system.
Soln: Given ∆ U =900 J ;
w=−1.65 kJ =−1,650 J ; (work done by the system is negative)
∆ U =q+ w
q=∆U −w
q=900−(−1,650)
q=900+1,650
q=+2,550 J
The body absorbs 2,550 J of heat from its surroundings

Example 2: Calculate the change in internal energy of an electrical motor which produced 75
kJ of energy per second as mechanical work and lost 350 J as heat.
Soln: Given w=−75 kJ =−75,000 J ( work done by the system )
q=−350 J
∆ U =q+ w
∆ U =−350+ (−75,000 )
∆ U =−75,350 J

Example 3: A spring was wound with a work of 100 J but 25 J of energy was lost to the
surroundings. What is the change in internal energy of the spring?
∆ U =q+ w
∆ U =−25+100
∆ U =75 J
 PRESSURE-VOLUME WORK (EXPANSION WORK)
Expansion work is the work arising from a change in pressure. It includes the work done by a
gas as it expands and work done on the gas due to compression.
(a). Definition of work (case 1)
Work is the result of action against an opposing force.
Mathematically, dw=−Fdz … … … … … … … … … … … … …(ii)
F is the opposing force (negative sign); dz is the change in distance

Pex
Pex
dz dV
V2
P V1
dV = Adz

If Pex is the external pressure, the magnitude of the opposing force will be:
F=Pex A … … … … … … … … … … … … … … … … … … … .. … . … ( iii )
dw=−Pex Adz … … … … … … … … … … … … … … … … … . … …(iv)
dw=−Pex dV … … … … … … … … … … … . … … … … … … … . …(v)
(where dV is change in volume. dV =AdZ )

If dV is positive, it is expansion, V 2 >V 1 ;dw<0 ;(−w)

If dV is negative, it is compression, V 2 <V 1 ; dw>0 ;(+ w)
Vf

w=−∫ Pex dV … … … … … … … … … … … … … … …. … … … … (vi)

Vi

Vf

w=−Pex ∫ dV … … … … … … … … … … … … … … … … … … …(vii)
Vi

(b). Free Expansion (case II)

Free expansion is expansion against zero opposing force.
It occurs when Pex=0.
(i) work done:
dw=−Pex dV … … … … … … … … … … … … … … … … … (v )
dw=0 X dV
dw=0 … … … … … … … … … … … … … … … … … … … … …(viii)
Thus, no work is done when a system expands freely. Expansion of this kind
occurs when a system expands in a vaccum.

(ii) Change in internal energy, ∆ U :

∆ U =0 (At constant temperature, ∆ T =0)

(iii) Heat change, q

q=∆U + w
q=0+ 0
 q=0

(iv) Enthalpy change,

∆ H =∆ U + ∆( PV )
∆ H =0+0
∆ H =0

(c). Expansion against constant pressure:

If a system expands against a constant external pressure, work done, w will be:
Vf

w=−Pex ∫ dV … … … … … … … … … … … … … … … … … … …(vii)
Vi

w=−Pex ∆ V … … … … … … … … … … … … … … … … … … … … …(ix)

w=−Pex (V f −V i) … … … … … … … … … … … … … … … … … … (x)

Example of such process is when a system expands against a constant atmospheric

pressure, or the expansion of a gas in a chemical reaction in a container that can expand.
w=−Pex ( V 2−V 1) … … … … … … … … … … … … … … … … … … … ..(xi)

nRT nRT
w=−P2 ( − )… … … … … … … … … … … … … … … … … …( xii)
P2 P1

w=−nRT 1−
(P2
P1 )
… … … … … … … … … … … … … … … … … . …( xiii)

If V 2 ≫V 1, work done will be

w=−P2 V 2 … … … … … … … … … … … … … … … … … … … … … . …(xiv)

nRT
w=−P2 × … … … … … … … … … … … … … … … … … … … ..(xv )
P2

w=−nRT … … … … … … … … … … … … … … … … … … … … .. …( xvi)

(ii) ∆ U =0(at constant T )

(iii) Heat change, q

q=∆U + w
q=0−w
q=−w

(iii) Change in enthalpy, ∆ H

∆ H =∆ U + ∆ ( PV )
∆ H =0+0
∆ H =0
Example 4: Calculate the work done, heat change and change in internal energy (in joules) when
a mole of helium gas expands against a constant external pressure of 3.8 atm from an initial
volume of 2.85 dm3 to a final volume of 6.15 dm3 at room temperature (1 atm dm3 = 101.323 J).

Soln:
(i) work done
w=−Pex (V f −V i)

w=−3.80 atm(6.15 dm3 −2.85 dm3 )

w=−3.80 atm ( 3.3 ) dm 3

3
w=−12,54 atm dm
3
1 atm dm =101.323 J
3
3 −12.54 atm dm ×101.323 J
−12,54 atm dm = 3
1atm dm
w=−1,270.6 J

(ii) change in internal energy, ∆ U

∆ U =0( at constant T )

(iii) Heat change, q

∆ U =q+ w
q=∆U −w
q=0−(−1,270.6 J )
q=+1,270.6 J

(d). Reversible Expansion: A reversible change in thermodynamics is a change that can be

reversed by an infinitesimal modification of a variable.
Consider a closed system of a gas whose external pressure, P ex, is equal to its
internal pressure, Pint. Such a system is in mechanical equilibrium with its surroundings
because an infinitesimal change in external pressure in either direction causes changes
in volume in the opposite direction.

Since Pex=P∫ ¿at each stage of expansion ¿

w=−Pex dV … … … … … … … … … … … … … … … … … … …..( xvii)

w=−PdV … … … … … … … … … … … … … … … … … … … … .(xviii)
Vf

w=−∫ PdV … … … … … … … … … … … … … … … … … … …( xix)

Vi
(e). Isothermal reversible expansion:
Consider the isothermal reversible expansion of a perfect gas. The expansion is made
isothermal by keeping the system in thermal constant with its surroundings.
Recall that for a reversible expansion, w is

dw=−PdV … … … … … … … … … … … … … … … … … … … … .( xviii)

nRT
(From ideal gas equation; PV =nRT . This implies that pressure, P= )
V

−nRT
dw= dV … … … … … … … … … … … … … … … … … … … … .(xviii)
V

dV
dw=−nRT … … … … … … … … … … … … … … … … … … … … .(xx )
V
V2
dV
w=−nRT ∫ … … … … … … … … … … … … … … … … … … ..(xxi)
V1
V

w=−nRT ln
V2
V1 ( )
… … … … … … … … … … … … … … … … .(xxii)

When V 2 >V 1 ; w<0 (expansion). When V 1 >V 2 ; w>0 (compression)

Example 4: 0.6 g of Mg ribbon reacts completely with HCl at 27℃ to produce MgCl2
and H2. If 15.3 g of heat is liberated, calculate workdone and the internal energy change
of the system if the reaction occurs in:
(i) a vaccum
(ii) a closed vessel of adjustable volume
(iii) a closed vessel of fixed volume.

Soln:
Given q=−15.3 J ;
mass of Mg=0.6 g;
T¿ 273+27=300 K ;
Mw of Mg=24 gmol−1
Equation of reaction: Mg(s )+2 HCl (aq) → MgCl 2 (aq)+ H 2(g )
mole ratio: 1 2 1 1

mass 0.6
(no of moles of Mg= = =0.025 moles of Mg)
molar mass 24

This implies; mole ratio: 0.025 0.05 0.025 0.025

(i) a vaccum:
w=0 ( Pex =0 )
∆ U =q+ w
∆ U =−15.3 J +0=−15.3 J
 (ii) a closed vessel of adjustable volume
w=−Pex dV

w=−Pex ( V f −V i )

nRT
but V f ≫ V i ;This implies that ∆ V =V f =
Pex

nRT
w=−Pex ×
Pex

w=−nRT
−1 −1
w=−0.025 moles ×8.314 j mol K × 300 K

w=−62.355 J

Internal energy, ∆ U :
∆ U =q+ w

∆ U =−15.3−62.355

∆ U =−77.655 J

(iii) A closed vessel of fixed volume:

workdone, w=−Pex ( V f −V i )
if volume is fixed, V f =V i ;∧∆ V =0
workdone, w=0

Change in internal energy, U

∆ U =q+ w
∆ U =−15.3+0
∆ U =−15.3 J

Practice questions
1. A sample containing 65 g of an ideal gas whose Mw is 44 g/mol was allowed to expand
isothermally and reversibly at 22℃ from 22.8 L to 31.7 L. Calculate DU and w if 1.5 kJ
of heat is absorbed.
2. Calculate the minimum work required to compress 24 kg of oxygen at 25 ℃ from a
pressure of 1 atm to a pressure of 50 atm.
 MODULE 3: HEAT AND HEAT CHANGES
HEAT
Heat is the quantity of energy exchanged between a thermodynamic system and its surroundings,
or between two or more thermodynamic systems as a result of temperature difference. The
property of matter that determines the possibility and direction of heat transfer is called
temperature. It is a measure of the intensity of heat. Heat is a path function. A positive value of
heat indicates the transfer of heat to the system while a negative value of heat indicates release of
heat by the system. Heat is expressed in units of Joules or calories.
1 cal = 4.184 J
Calorimetry is the study of heat transferred during physical and chemical processes, while a
calorimetre is a device for measuring energy transferred as heat during a chemical or physical
process. Examples include adiabatic bomb calorimetry (measures U); Differential scanning
calorimetry (measures H and phase changes); constant pressure flame calorimetry (masures H ).

VARIATIONS OF HEAT
I. Heat changes at constant volume (q v )
From the first law of thermodynamics: ∆ U =q+ w
If w is the work done as a result of expansion alone, at constant volume, ∆ V =0, and w=0 .
∆ U =q (at constant volume)
∆ U =q v … … … … … … … … … … … … … … … … …(i)
Thus, heat absorbed or released at constant volume (q v ) equals change in internal energy. In
this case, q v is a state function.

II. Enthalpy of a system (H)

The total heat content of a system (enthalpy of a system, H) at constant pressure, is the sum
of the internal energy, U, and the pressure-volume (PV) work.
H=U + PV … … … … … … … … … … … … … … …..(ii)
Where H is enthalpy and it is a state function.
For an infinitesimal change,
dH =dU + dPV … … … … … … … … … … … … … …(iii)
dH =dU + PdV +VdP … … … … … … … … … … …(iv)
For an appreciable change,
H=U + P V … … … … … … … … … … … … … …(v )

Heat change at constant pressure

From the first law: ∆ U =q+ w
∆ U =q−P V ( Expansion ) … … … … … … … .… (vi)
Recall also: H=U + P V
(substituting ∆ U with q−P ∆ V )
H=q−P V + P V … … … … … … … … … … … … .(vii)
H=q p … … … … … … … … … … … … … … … … … … .( viii)

Energy transferred as heat at constant pressure, q p, is equal to the enthalpy of a system.

For an ideal gas, H=U + nRT … … … … … … … … … … … … … … .(ix)

where n=n2−n1
(n2 is the no of moles of gaseous products while n1 is the no of moles of gaseous reactants).
Heat Capacity, C
An infinitesimal amount of heat added to a system is proportional to an infinitesimal change in
temperature of the system if there is no phase change or chemical reaction.
dq=CdT … … … … … … … … … … … … … …. …( x)
(dq represents infinitesimal change in q; dT represents infinitesimal change in temperature and C
is a constant called heat capacity).
If C is independent of temperature,
T2

q=C ∫ dT=C ∆ T =C ( T 2−T 1 ) … … … … …(xi )

T1

If heat capacity, C, depends on temperature, it can be represented by a polynomial or other

functions. Heat capacities of gases are often more strongly temperature-dependent than those of
liquids.
The heat capacity of a system is defined as the quantity of heat required to raise the temperature
of a system by 1℃ .
dq
C= … … … … … … … … … … … … … … … … … (xii)
dT
Heat capacity, C, depends on the way by which the temperature of a system is changed. Heat
capacity of any object is always positive.
If temperature is changed at constant pressure, C is denoted as C p (heat capacity at constant
Pressure).
If temperature is changed at constant volume, C is denoted as C v (heat capacity at constant
volume).
Heat capacity at constant pressure, C p
At constant pressure, the heat capacity of a system, Cp, is the rate of change of enthalpy with
temperature. It is most commonly measured for solids and liquids.
Recall: q p=∆ H … … … … … … … … … … … … … … … … … … …(viii)
dq
C= … … … … … … … … … … … … … … … … … … … … ( xii)
dT

C p= [ ]
∂H
∂T P
… … … … … … … … … … … … … … … … … … ( xiii)

For infinitesimal change in temperature at constant pressure,

dH =C P dT … … … … … … … … … … … … … … … … … … .( xiv)
If Cp is constant over a range of temperatures of interest, then for a measurable increase in T,
∆ H =C P ∆ T … … … … … … … … … … … … … … … … … …( xv )

For n moles of a gas,

 dH =n C P dT … … … … … … … … … … … … … … … … … ( xvi )

(where C p is the molar heat capacity at constant pressure)

∆ H =n C P ∆ T … … … … … … … … … … … … … … … … … ( xviii )

The symbols C V and C P or (C V ,m ∧C P ,m ) represent molar heat capacities at constant volume and
pressure respectively.
C V =n C V … … … … … … … … … … … … … … … … … … .(xviii)
C P =n C P … … … … … … … … … … … … … … … … … … .(xix)
(where n = no of moles)
For an ideal gas, the relationship between the heat capacities is given as:
C P −CV =nR … … … … … … … … … … … … … … … … …. (xx)

Hence, C P −CV =R … … … … … … … … … … … … … … … … … …( xxii)

Alternative method of deriving H
Recall: ∆ H =∆ U + ∆ ( PV ) … … … … … … … … … … … … … … ...(iii)

H 2−H 1= ( U 2−U 1 ) + ( P2 V 2−P1 V 1 ) … … … … … … .(xxiii)

∆ H =∆ U +nR T 2−nR T 1 … … … … … … … … … … … …(xxiv)

∆ H =∆ U +nR ( T 2−T 1 ) … … … … … … … … … … … … .( xxv )

Recall: ∆ U =n CV ∆ T =n CV ( T 2−T 1 ) … … … … … … … … … … .(xxvi)

∆ H =n CV ( T 2−T 1 ) +nR ( T 2−T 1) … … … … … … … …(xxvii)

∆ H =n ( CV + R ) ( T 2−T 1 ) … … … … … … … … … … … ..(xxviii )

Recall: C P −CV =R … … … … … … … … … … … … … … … … … ..(xxii)

∆ H =n C P ( T 2−T 1 ) … … … … … … … … … … … … … … ..( xxix)

Heat capacity at constant volume, C v

At constant volume, heat capacity, Cv, is defined as the rate of change in internal energy of a
system with temperature.
Recall: q v =∆U … … … … … … … … … … … … … … … … … … … … .(i)
dq
C= … … … … … … … … … … … … … … … … … … … … ..(xii)
dT

C v= [ ]
∂ qv
∂T V
… … … … … … … … … … … … … … … … … …(xxx )
 C v= [ ]
∂U
∂T V
… … … … … … … … … … … … … … … … … … .( xxxi)

For infinitesimal change in temperature at constant volume,

dU =CV ∆ T … … … … … … … … … … … … … … … … … ….( xxxiv)
If Cv is constant over a range of temperatures of interest, then for a measurable increase in T,
∆ U =CV ∆ T … … … … … … … … … … … … … … … … … ..( xxxv )
For n moles of a gas,
dU =n CV dT … … … … … … … … … … … … … … … … . … ( xxxvi )
∆ U =n CV ∆ T … … … … … … … … … … … … … … … … … .( xxxvii )

Example 1.: 4.5 moles of H2 gas in a container of volume 20 dm3 and at a temperature of 27°C,
was heated to 65°C and the volume changed to 38.5 dm3. Assuming that the H2(g) behaves ideally
under this condition, calculate the change in internal energy and change in enthalpy. Take
−1 −1 −1 −1
C V ,m =20.1 J mol K ∧C P , m=28.4 J mol K .
Soln: Given n=4.5 moles ;
V =20 dm3 ;
T 1=27 ℃=27+273=300 K ;
T 2=65 ℃=65+273=338 K ;
−1 −1
C V ,m =20.1 J mol K
−1 −1
C p ,m=28.4 J mol K

(a). Change in internal energy; U:

∆ U =n CV ∆ T
∆ U =4.5 × 20.1×(338−300)
∆ U =3,437.1 J

(b). Heat change; H: ∆ H =n C P ∆ T

∆ H =4.5 ×28.4 ×(338−300)
∆ H =4.86 kJ
 HEAT CAPACITY AS A FUNCTION OF TEMPERATURE
The dependence of CP on temperature is
−2
C P =a+bT +c T … … … … … … … … … … … … … … … … … ..( xxxviii)
C P =a' +b' T +C ' T −2 … … … … … … … … … … … … … … … … .( xxxix)
where a, b, c, a', b', c' are constants
dH =C P dT =n C P dT … … … … … … … … … … … … … … … … … … ..( xl)
dH =( a+ bT +C T −2 ) dT … … … … … … … … … … … … … … … … ..( xl)
H (T )
2
T2

∫ dH =∫ (a+bT +C T −2)dT … … … … … … … … … … … …(xl)

H(T )
1
T1

1
2
2
(
H ( T 2) −H ( T 1 ) =a ( T 2−T 1) + b ( T 2 −T 1 )−C
2 1
−
1
T2 T1)… ( xli)

Example: What is the change in molar enthalpy of N2 when it is heated from 25C to 100C if
the molar heat capacity of N2. C P =(28.58+3.77 × 10−3 T −0.5× 105 T −2 J mol−1 K−1 ).
∆ H =n C P ∆ T
∆H
=C P ∆ T
n
∆H
n
1
2
2 2
(
=a ( T 2−T 1 ) + b ( T 2 −T 1 ) −C
1 1
−
T2 T1 )
 ADIABATIC EXPANSION OF AN IDEAL GAS
A system undergoes adiabatic process if the wall of the vessel is perfectly insulated such that
there is no exchange of heat between the system and its surroundings.
q 2−q 1=0
a) Adiabatic Reversible Expansion:
From the first law: ∆ U =q+ w … … … … … … … … … … … … … … (i)
∆ U =w (For an adiabatic process , q=0)
∆ U =−PdV ( PV Expansion work)
Recall that ∆ U =CV dT ;
This implies: −PdV =C V dT … … … … … … … … … … … … … …..( ii)
nRT
for n moles of an ideal gas, P=
V

−nRT
dV =C V dT … … … … … … … … … … … … … …(iii)
V

−nR dT
dV =C V . … … … … … … … … … … … … … …(iv)
V T
V2 T2
dV dT
−nR ∫ =C V ∫ … … … … … … … … … … …(v)
V
V 1 T
T 1

−nR ln
( )
V2
V1
=C V ln
( )
T2
T1
… … … … … … … … … … …(vi)

−R ln
( ) V 2 CV
V1
=
n
ln
T2
T1( )
… … … … … … … … … … … (vii)

−R ln
( ) V2
V1
=CV ln
T2
T1( )
… … … … … … … … … … …( viii)

C V ln
( )
T2
T1
V
( )
=−R ln 2 … … … … … … … … … … …(ix)
V1

C V ln
( ) ( )
T2
T1
V
=R ln 1 … … … … … … … … … … … …(x )
V2

Recall: C P −C v =R

C V ln
( )
T2
T1
V
( )
=C P−C v ln 1 … … … … … … … … …( xi)
V2
 ln
( )
T 2 C P−Cv
T1
=
Cv
V
V2 ( )
ln 1 … … … … … … … … … …( xii)

ln
( )(
T2
T1
C V
)( )
= P −1 ln 1 … … … … … … … … … …( xiii)
CV V2

CP
but =γ
CV

ln
( )
T2
T1
V
( )
=(−1 ) ln 1 … … … … … … … … … … …(xiv)
V2

( )
−1
T2 V 1
= . … … … … … … … … … … … … … … … … ( xv)
T1 V 2

OR

( )
−1
T1 V 2
= … … … … … … … … … … … … … … … … .( xvi)
T2 V 1

γ −1 γ −1
T 1V 1 =T 2 V 2 … … … … … … … … … … … … … …( xvii)

( )
1
T2 V 2 C
= … … … … … … … … … … … … … … … … ….( xviii)
T1 V 1

CV
(where C= )
nR

P1V 1 P2V 2 T PV
From gas law: = ; this imples that 1 = 1 1
T1 T2 T 2 P2 V 2

( )
γ−1
P1V 1 V 2
= … … … … … … … … … … … … … … …( xix)
P2V 2 V 1

P1 V 1 ( V 1 ) γ−1=P2 V 2 ( V 2) γ−1 … … … … … … … … … …(xx )

γ γ
P1 V 1 =P 2 V 2 … … … … … … … … … … … … … … … …(xxi)

=
P2 V 1 ( )
P1 V 2 γ
… … … … … … … … … … … … … … … … …( xxii)

Examples: An ideal gas (C P =28.8 J mol−1 K −1) is expanded reversibily and adiabatically
from a volume of 2.0 dm3 at a pressure of 4 atm and temperature of 298 K, to a volume of 4
 dm3. Calculate (i) the final temperature and pressure of the gas (ii) q, w, U and H for the
process.
Soln.: C P =28.8 J mol−1 K −1; V 1=2 dm 3; P1=4 atm ; T 1=298 K ; V 2=4 dm3 .
(ia) Final temperature, T 2
CP CP 28.8
γ= = = =1.4058
C V C P −R 28.8−8.314

( )
−1
T2 V 1
= ;
T1 V 2

( )
−1
V1
()
1.4058−1
2
T 2=T 1 =298 × =224.9 K
V2 4
(ib) Final pressure, P2

( )
γ
P1 V 2
=
P2 V 1

( ) ()
γ
V1 2 1.4058
P2=P1 =4 × =1.51atm
V2 4

(ii) q=0( adiabatic process)

(iii) Workdone, w. w=∆U =n C v ∆ T =n(C P −R) ( T 2−T 1)
PV
w=
RT P
( C −R )( T 2−T 1 )
3
4 atm ×2 dm ( 28.8 J mol−1 K −1−8.314 J mol−1 K −1 ) ( 224.9 K−298 K )
¿ 3 −1 −1
0.082 atmdm mol K ×298 K
w=0.3274 mol ( 20.486 J mol K ) (−73.1 K )
−1 −1 −1

w=−490.29 J
(iv) ∆ U =q+ w
∆ U =w (q=0 for adiabatic process )
∆ U =−490.29 J
PV
(v) ∆ H =n C P ( T 2−T 1 )= C ( T −T 1)
RT P 2
4 atm ×2 dm3
∆ H= 3 −1 −1
×28.8 J mol−1 K −1 × ( 224.9−298 ) K
0.082 atm dm mol K ×298 K
∆ H =0.3274 ×28.8 J ×−73.1=−689.3 J
 ADIABATIC IRREVERSIBLE EXPANSION
q=0( adiabatic process)
i. Free expansion (Expansion in a vacuum produces no work, w = 0)
∆ U =q+ w
∆ U =0 … … … … … … … … … … … … … … … … … … … … … …(xxiii)
Also, ∆ U =n CV ( T 2−T 1 )=0
This implies that, T 2=T 1
∆ H =n C P ( T 2−T 1 )
∆ H =0 ( as T 2=T 1 ) … … … … … … … … … … … … … … …(xxiv)
This implies that w ,q , ∆ H∧∆ U are zero for adiabatic free expansion of an ideal gas

ii. Adiabatic irreversible expansion at constant external pressure

Work of expansion, w=−Pex dV (Pex is constant)
w=−P2 dV
V2

w=−P2∫ dV
V1

w irr =−P2 ( V 2−V 1 ) … … … … … … … … … … … … … … …(xxv )

Change in internal energy, U

∆ U =q+ w
∆ U =w (as q = 0 for adiabatic process)
∆ U =−P2 ( V 2−V 1 )=P 2 ( V 1−V 2) … … … … … … … … …(xxvi)

Also, ∆ U =n CV ( T 2−T 1 );
this implies that ∆ U =n CV ( T 2−T 1 )=−P 2 ( V 2−V 1) … … … … … …(xxvii)

n C V ( T 2−T 1 )=−P 2
( nRT 2 nR T 1
P2
−
P1 )
… … … … … … … … … … … (xxviii)

n C V ( T 2−T 1 )=−n RP 2
( T 2 T1
−
P2 P1 )… … … … … … … … … … … …(xxix)

T2 T1
C V T 2−C V T 1 =−R P 2 + RP 2 … … … … … … … … … … … … ( xxx)
P2 P1
T1
C V T 2−C V T 1 =−R T 2 + RP 2 … … … … … … … … … … … … … .( xxxi)
P1
T1
C V T 2−C V T 1 =RP 2 −R T 2 … … … … … … … … … … … … … …(xxxii)
P1
 T1
C V T 2 + R T 2 =RP 2 +CV T 1 … … … … … … … … … … … … … …(xxxiii)
P1

(
T 2 ( C V + R ) =T 1 R
P2
P1 )
+C V … … … … … … … … … … … … … …( xxxiv)

(
T 2 ( C P ) =T 1 R
P2
P1 )
+C V … … … … … … … … … … … … … … … ..( xxxv )

T 2=
T1
CP (P2
)
R +C V … … … … … … … … … … … … … … … …(xxxvi)
P1

Enthalpy change, H: ∆ H =n C P ( T 2−T 1 ) … … … … … … … … … …(xxxvii )

Example: Calculate H for the change of state of 1.00 mol of helium from a volume of 5 L
and a temperature of 298.15 K to a volume of 10 L and a temperature of 373.15 K. Assume
5R
that C P , m= . Assume that the gas is ideal.
2
Soln:
∆ H =n C P ( T 2−T 1 )

∆ H =1× ( 5 ×8.314
2 )
(373.15−298.15 )=1558.9 J