Revised Thermodynamics
Revised Thermodynamics
Thermodynamics
Sameena Bano
Department of Chemistry
Faculty of Science
Jamia Hamdard
New Delhi-110062
(24.07.2007)
CONTENTS
Introduction
Terms and Basic Concepts
Heat, Work and Energy
Internal Energy
First Law of Thermodynamics
Enthalpy
Molar Heat Capacities
Isothermal and Adiabatic Processes
Laws of Thermochemistry
Second Law of Thermodynamics
Keywords
Thermodynamics, systems, state variables, equilibrium, isothermal, adiabatic, reversibility, internal energy,
enthalpy, entropy, molar heat capacities, thermochemistry, free energy, work function
1
I. Introduction
Definition: Thermodynamics is a branch of science which deals with inter conversion of
different forms of energy, temperature and thermal manifestations. In other words
thermodynamics is the study of the flow of energy into or out of a system as it undergoes a
physical or chemical transformation. In studying and evaluating the flow of energy into or out of
the system, it will be useful to consider changes in certain properties like temperature, pressure,
volume and concentration of the system. The study of thermodynamics is based on fundamental
laws derived from well established experimental results. These are the first, second and third law
of thermodynamics. First and second laws deals with inter conversion of energy. We also have a
zeroth law that forms the basis of concept of temperature.
Scope:
i) Laws of thermodynamics can be useful to derive most of the important laws of physical
chemistry, including the Van’t Hoff law of lowering of vapour pressure, phase rule and the
distribution law.
ii) Laws of thermodynamics can be used to predict the direction in which a reaction/process
would proceed.
iii) It helps in the prediction of relationship between directly observable properties.
iv) It tells whether a particular change can occur under a given set of conditions.
Limitations:
i) It does not give specific and direct information about the internal structure of atom and
molecule because it is applicable to macroscopic systems consisting of matter in bulk and not to
microscopic systems of individual molecules or atoms.
ii) Matter finds only consideration as carrier of energy. There is however no measurable
conversion of matter into energy.
iii) It can predict only the feasibility of chemical or physical process, under a given set of
conditions and does not tell anything regarding the rate of physical or chemical change.
Types of boundaries:
i) Rigid wall boundary: Position and shape are fixed
ii) Impermeable wall boundary: Not permits the passage of matter
iii) Permeable wall boundary: Permits the passage of matter and consequently also of
energy.
iv) Adiabatic wall boundary: When held rigid it will not permit the passage of matter or
energy. e.g. thermos bottle.
v) Diathermal wall boundary: When held rigid it will not permit the passage of mater
but allow the passage of energy.
2
Types of Thermodynamics systems: There are three types of thermodynamic systems
depending upon the nature of boundary.
1) Isolated System: The system is said to be isolated when it can transfer neither matter nor
energy with its surroundings. It is a system of constant energy within which transformation of
energy may occur but total energy of the system remains constant.
Example: Water in contact with its vapour in a closed and insulated vessel.
Isolated System
ii) Closed System: A system is said to be closed when it cannot transfer matter but can transfer
energy across the boundary. In this system boundary is sealed but not insulated.
Examples:
i) A specific quantity of hot water in a sealed vessel constitutes a closed system
ii) A cylinder fitted with gas and fitted with piston also constitutes a closed system.
Closed System
iii) Open system: A system is said to be open when it can transfer both matter and energy with
its surrounding.In this type of system matter and energy is transferred to the surroundings
through the imaginary boundary.
Example: Hot water in a beaker placed on table is an open system.
Open System
3
Homogeneous and Heterogeneous Systems: When a system is made of one phase only, it is
called Homogenous system. It is uniform throughout.
Examples:
i) Pure single solid, liquid or gas.
ii) Mixture of gases or two miscible liquids.
iii) True solution of solid in a liquid.
Heterogeneous system is one which consists of more than one phase. It is not uniform
throughout.
Examples:
i) Solid in contact with liquid
ii) Solid in contact with vapour
iii) Mixture of two immiscible liquids
State of System (State Variables): The fundamental properties whose values serve to describe
the system completely are called state variables or state functions or thermodynamic properties.
A change in the magnitude of such properties alters the state of the system.
When the properties of the system are completely specified then it is said to be in a certain state.
Temperature (T), Pressure (P), Volume (V), Mass and Composition are the fundamental
properties that determine the state. Change of state of system from initial to final state is always
accompanied by the change in the state variables.
It is not necessary to state all the properties to define a system completely. In the case of a
homogenous system, the composition is uniform. The remaining state variables are related to one
another by a mathematical state equation PV=RT, called equation of state. If for a given amount
of gas of the three state variables, Temperature (T) and Pressure (P) are specified. The value of
third, Volume (V) is fixed automatically and can be calculated. The variables T and P, which
must be specified to define the state of the system, are termed as independent variables and the
third variable generally volume, which depends on temperature and pressure, is called dependent
variable.
ii) Intensive properties: Properties of a system that do not depend on the quantity of matter
present in a system are called intensive properties.
4
An extensive property may become intensive by specifying amount of the substance present in a
system. Extensive properties are additive but intensive are not. Examples of extensive and
intensive properties are given in Table-1
A system in which the state variables have different values in different parts of the system is said
to be in non-equilibrium state.
The criteria for equilibrium: Three types of equilibrium exist simultaneously in a system:
i) The temperature of the system must be same throughout the system that is called state of
thermal equilibrium.
ii) No mechanical work is done by one part of the system on any other part of the system this is
called state of mechanical equilibrium.
iii) The chemical composition of the system must be uniform and not spontaneously change with
time that is called sate of chemical equilibrium.
For a heterogeneous system, the state variables of each phase remain constant in each phase.
5
ii) Isothermal process: The process which occurs at constant temperature is called isothermal
process. In isothermal process transfer of heat can take place into or out of the system but the
temperature remains fixed.
For isothermal process, dT = 0
iii) Isochoric process: The process in which volume remains constant is called isochoric
process.
For isochoric processes, dV = 0
iv) Isobaric process: The process that takes place at constant pressure is called isobaric process.
For isobaric process dP = 0
v) Cyclic process: When a system undergoes a series of different processes and finally returns to
its initial state, the overall process is called a cyclic process.
For a cyclic process, dE = 0, dH = O
If a series of changes are conducted at a constant temperature the cycle is known as isothermal
cycle. If the changes are carried out reversibly, then the cycle is known as reversible cycle.
Reversible and irreversible processes: A thermodynamic reverse process is one which takes
place in infinite number of infinitesimally small steps and takes infinite time to occur and its
direction at any point can be reversed by an infinitesimal change in the state of the system.
In a reversible process, the system is every time in internal equilibrium i.e. all the intermediate
states can be defined by thermodynamic variables like temperature and pressure. At every step,
the system is also in virtual equilibrium with the surroundings, because by effecting an
infinitesimal amount, and finite process takes infinite time to go to completion.
6
The process which is carried out in a single step in finite time and cannot be reversed is called
irreversible process. It is in equilibrium state only at the initial and final stages of the operation.
e.g. Expansion and compression of gas rapidly in a single step.
Figure-5: Irreversible compression (a) and expansion (b) of a gas in a single step.
Isobaric
isothermal
Isochoric
adiabatic
When a system undergoes a change in its state, energy is transferred to or from the surroundings.
This energy may be transferred as heat or mechanical work.
Further, a portion of wall may be moved by the application of a force F it will move through a
distance l. Then the work done by the force is |F|l|cosθ. The symbol of work is w.
7
If the work done on a system by its surroundings is taken to be positive, + w, the energy of a
system is increased. If work is done by the system on its surroundings, it is taken to be negative,
-w, and the energy of system is decreased.
Therefore in thermodynamics, one always follows the convention of indicating the work done by
a magnitude preceded by a sign e.g. +80 Joules, -100 Joules. The ‘+’ sign shows that a work of
80 Joules has been done by the system on its surroundings and ‘-’ sign implies that a work of
100 Joules has been done by the system on its surroundings.
Energy has been defined as the capacity to do work. Any system is characterized by the
possession of a certain amount of energy. Energy possessed by a system is broadly of two kinds
Kinetic (because of motion of its parts) and Potential (because of position of its parts). When a
system does work upon its surroundings, the energy may be received from the surroundings
itself, in the form of heat.
The symbol of heat is ‘q’. The sign convention used for a quantity of heat ‘q’ is opposite to that
used for work. If the heat is taken by the system from its surroundings to increase its energy it is
taken to be positive, +q. If the heat is given by the system to its surroundings to decrease its
energy, it is taken to be negative, -q.
Unit of heat and work: In CGS system unit or work is erg (erg is work done when a resistance
of 1dyne is moved through a distance of 1 centimeter). Since the erg is so small, a bigger unit
Joule (J) is used.
1 Jouls(J) = 107 ergs.
1 Kilo Joule(KJ) =1000J
Calorie is the quantity of heat required to raise the temperature of one gram of water by 1oC in
the vicinity of 15oC.
Consider a following situation, a cylinder fitted with a frictionless piston and filled with a gas.
The pressure of gas, P exerts a force on the piston which can be balanced by an equal but
opposite pressure, Pext.
If gas expands at constant pressure the expansion of the gas pushes the piston up through a small
distance, l. The upword force, F exerted by the gas on the piston is:
F = Pext x A -------------------(1)
8
Where A is area of underside of the piston
We know that,
Work = Force x distance
w=Fxl
=Pext x A x l
w = Pext x ∆V
When ∆V is the change in volume of gas
For expansion, work is done by the system (gas) to the surroundings (piston) then;
w = -Pext x ∆V
In case of compression piston will move down and work will be done by surrounding to the
system, the sign of work will be +ve.
w = Pext x ∆V
PV work can be expressed in liter atmosphere. It may be noted that the work done by a system is
not a state function because it is related to the process carried out rather than to the initial and
final states of the system. It is a path function.
Isothermal reversible expansion work: Suppose an ideal gas confined in a cylinder with a
frictionless piston, expands reversibly from volume V1 to V2 at constant temperature and
pressure of gas successively reduced from P1 to P2.
9
Reversible expansion of gas takes place in a finite number of infinitesimally small intermediate
steps.
Suppose in a single intermediate step Pext is decreased by an infinitesimal amount dp, the gas
expands reversibly and the piston passes through a distance dl.
Since dP is so small,
Pext –dp = Pext = Pgas =P
dV = increase in volume
For isothermal reversible expansion of a gas from V1 to V2, the total amount of work done is,
therefore
On integrating we have
w = -nRT ln V2/V1
V2/V1 = P1/ P2
Expansion into vacuum: If a gas is expanding into vaccum it can consider that it is expanding
against a zero external pressure and therefore it will not be able to do any work i.e P = 0
wmax = 0
10
Isothermal irreversible expansion work:In irreversible expansion gas expands by
instantaneously dropping the external pressure, Pext to the final pressure P2.
Expansion against constant external pressure: If a gas is expanding against constant external
pressure it has no volume dependences and hence the work in this case is
Reversibility and maximum work: The work done in a reversible processes is more than the
same process if it is carried out irreversibly for the same increase in volume.
For a reversible expansion,
.
For irreversible expansion:
Figure-9: Reversible work of expansion Figure-10: The irreversible work done when the
external pressure is suddenly dropped to the final
value P2
The work done is much more in the reversible expansion than in the irreversible expansion. Thus
the mechanical work is not a state function, it is a path function.
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Internal Energy
Every thermodynamic system is associated with characteristic properties like temperature,
pressure and composition etc. One of its important characteristic properties is internal energy. It
is the energy associated with a system by virtue of its molecular constitution and the motion of
its molecules. This energy includes all type of internal potential energies and internal kinetic
energies.
The total of all possible kinds of energy of a system is called its internal energy.
Internal energy is a state property of the system since the value of internal energy of a system
depends on the quantity of matter contained in a system; it is also classified as an extensive
property.
Symbol and Sign conventions: Symbol of internal energy is E (or can be represented as U
also).
It is impossible to find out the absolute value of internal energy of a system. In thermodynamics
we consider only the change in internal energy of system (∆E) when a system undergoes a
change from one state to another.
“Energy can neither be created nor destroyed but may change from one form to another.”
First law of thermodynamics may be stated as:
First Statement: “Energy of an isolated system must remain constant although it may be
transformed from one form to another.”
Third Statement: Joule stated that, “There is an exact equivalence between the amount of work
overcome and the heat generated”
12
“When work is transformed into heat or heat into work, the quantity of work is mechanically
equivalent to the quantity of heat.”
Fourth Statement:“It is impossible to construct a perpetual motion machine that could produce
work without consuming energy.”
A I
II
B
Considering the figure, both A and B are equilibrium states of a system. The internal energy has
definite values EA and EB at A and B. If the system is taken from the initial state A to the Final
state, B along two different pathways I and II, the change in internal energy is same viz EB -
EA=∆E for both the paths. As it is the state function of a system.
These energy changes are brought about by the evolution or absorption of heat and or by work
being done by the system.
Suppose q1, q2 are the heat absorbed by the system and w1 and w2 are the work done by the
system in above two pathways. In both cases internal energy change is same. Total energy of the
system must remain same whatever thermal energy (heat) q is absorbed by the system is not
destroyed but gets converted into work done in part, the remaining part augmenting the internal
energy of the system.
q= ∆E +w
∆E = q2-w2 = q1-w1
or
∆E = q-w --(Mathematical statement of first law.)
13
Thus first law of thermodynamics may also be stated as:
“The total internal energy change of a closed system is equal to the heat absorbed by the system
minus the work done by the system.”
For a cyclic process total change in internal energy over the cyclic path is zero.
∆E =0
Therefore, q=w
Hence ∆E= -w. The decrease in internal energy is exactly equal to the work done by the system
on its surroundings.
Significance of First law of thermodynamics: It tells us that a certain quantity of heat will
produce a definite amount of work and vice versa. Work cannot appear without disappearing of
heat. There must be an internal energy change of a system when it undergoes a change from one
state to another.
State and Path Functions and Exact and Inexact Differentials: State function is a function or
property which depends only on the sate of the system and change in the sate functions depends
only on the initial and final states of the system and not on the path from the initial to the final
sate. e.g. E (internal energy) is a state function while q (heat absorbed ) and w (work done) are
path functions. The differential of a state function is an exact or perfect differential e.g. dE is an
exact differential, while dq and dw inexact differentials.
14
∂x. ∂y ∂y. ∂x
That is the order of differentiation is immaterial. All thermodynamic functions are state functions
and their differentials are exact differentials. In this respect ‘w’ and ‘q’ are not thermodynamic
functions. The difference between the two inexact differentials is an exact differential.
dE = ∂Q-∂W
dE = 0
∂2E = ∂2E
∂V. ∂T ∂T. ∂V
Enthalpy
There are two different situations of interest in thermodynamics. First is the process taking place
at constant volume and second is the processes taking place at constant pressure. For the
processes carried at constant volume no PV work is done and total heat content is same as
internal energy E. But in the processes at constant pressure the system also expends energy in
doing PV work. Therefore the total heat content of a system at constant pressure is equivalent to
the sum of internal energy E and the PV energy. This is called enthalpy of the system and
represented by the symbol H. Thus enthalpy can be defined as total heat content of system at
constant pressure.
H= E +PV -------------( i )
As E, P and V all are the state functions and value of H, depends on the value of state function,
H must also be a state function of a system and its value is independent of path by which this
change has been accomplished.
15
From the first law; ∆E = q-w ----------------------------------------(v)
At constant volume, ∆V = 0
∆q = qv = ∆E -------------------(ii)
At constant pressure
qp and qv are the heat change at constant pressure and constant volume respectively.
16
Enthalpy change ∆H is given by the following expression
∆H = ∆E + P∆V -----------------(iv)
Also, ∆H = ∆E +P∆V
qp = qv+P∆V ---------------------(vi)
If gases are involved in a reaction and we have n1 moles of gases before reaction and n2 moles of
gases after reactions. Assuming ideal gas behaviors, we have
q = heat absorbed
m = mass
17
If m = 1g then it is called specific heat capacity.
If we consider mass as 1mole then the heat capacity is known as molar heat capacity, denoted by
C.
q
C= ( m = 1 mole )
(T2 - T 1)
Molar heat capacity of a system is defined as the quantity of thermal energy that must be
absorbed by 1mole of the system to produce a change of temperature of one degree. Since the
heat capacity (C) varies with temperature, its value will be given as:
The units of molar heat capacity are calories per degree per mole (Cal K-1mol-1) or Joules per
degree per mole (J K-1mol-1)
Heat capacity is not a state function; we must specify the process by which temperature is raised
by one degree. There are two types of molar heat capacities viz at constant volume and at
constant pressure.
dq = dE +PdV
dT dT
dq = dE +PdV ---------------------(ii)
dT dT dT
At constant volume, dV = 0
Equation (ii) reduces to,
dE
Cv = ------------- (iii)
dT V
Thus the heat capacity of constant volume, Cv is defined as the rate of change of internal energy
with temperature at constant volume.
18
Differentiating this equation w.r.t temperature at constant pressure, we get
dH = dE + P dV --------------------------(iv)
dT dT dT
P P P
Comparing equation (ii) & (iv)
dH ------------------(v)
CP =
dT P
Thus the heat capacity at constant pressure (CP) is defined as the rate of change of enthalpy with
temperature at constant pressure.
dH
CP = ---------------------(i)
dT
dE --------------------(ii)
C
v = dT
H = E + PV --------------------(iii)
H = E+RT ---------------------(iv)
dH = dE +
R
dT dT
Cp – Cv =R
Thus Cp is greater than Cv by a gas constant value 1.987 Cal K-1 mol-1 or 8.314 JK-1 mol-1.
Cv = dE
dT
19
dE = Cv x dT
∆E = (E2-E1) = Cv x (T2-T1)
∆E= n x Cv (T2-T1)
We have
∆H = ∆E + P∆V
∆H = Cv (T2-T1) + R(T2-T1)
∆H = (Cv + R) (T2-T1)
For n moles,
∆H = n x CP (T2-T1)
With the help of values of molar heat capacities at constant volume and at constant pressure we
can calculate values of ∆E and ∆H accordingly.
But in adiabatic process no heat transfer between system and surrounding takes place. Thus
during expansion or compression temperature of the system must change.
Differentiation gives
PdV +VdP = 0
20
Or VdP = -PdV
Or dP = − P
dV V
Slope of curve =− P
V
On differentiation gives,
γ PV γ-1 dV + VγdP = 0
Or γ PVγ.V-1dV+VγdP = 0
Or [γ P/V dV + dP]Vγ = 0
Or γPdV +VdP = 0
Or VdP = -γPdV
Or dP - γ P
=
dV V
P
Slope of adiabatic curve - γ V
Now , = =γ
Slpe of isothermal curve -P
V
21
Adiabatic Expansion of an Ideal gas:
dq = 0
∆E = q –w (first law)
∆E = -w ---------------(i)
Consider 1 mole of ideal gas at pressure P and Volume V. In adiabatic reversible expansion, for
an infinitesimal increase in volume dV at pressure P, the work done by the gas is –PdV. The
decrease in internal energy dE is given by the following expression.
dE = -PdV -------------------(ii)
We know that
dE = CV dT ------------------(iii)
-PdV = CvdT
P = RT
V
Cv dT = - RT dV ---------------(iv)
V
Cv dT -RdV
=
T V
22
Cv ln T2/T1 = -(Cp –Cv) ln V2/V1
T2 (Cp-Cv) V2
ln = ln
T1 Cv V1
or
ln T2/T1 = -(γ-1)ln V2/ V1
γ -1
T2 V1
= -----------------------(vi)
T1 V2
γ -1 γ -1
T 2V2 = T1 V1
T2 P2V2
=
T1 P1V1
γ− 1
P2V2 V1
=
P1V1 V2
γ 1
P2 V1
P1
=
V1
V2
. V2
γ
P2 V1
=
P1 V2
23
P2V2γ = P1V1 γ
PVγ = Constant
PVγ = Constant
γPVγ-1dV + VγdP = 0
γPdV +VdP = 0
PV = RT
PdV = n RdT
1- γ
24
Integrating from T1 V1 to T2V2 with γ constant,
nR(T2-T1)
w =
max
γ -1
Since γ = Cp/Cv
In Joule-Thomson experiment an insulated tube is fitted with porous plug in middle and two
frictionless pistons on both sides A and B. Gas on side A at volume V1 and Pressure P1 is forced
through the porous plug by a slow movement of piston on this side. Gas on other side is allowed
to expand to volume V2 and pressure P2 by moving the piston outward.
Most of the gases found to undergo cooling on expansion through the porous plug except
Hydrogen and Helium. These gases show warming up instead of cooling.
Work done on the gas at chamber A is P1V1 and the work done by the gas at chamber B is P2V2.
Hence the net work (w) done by the gas is,
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w = P2V2- P1V1
∆E =-w
or
H2 =H1
Three fore ∆H = 0
It means J.T experiment takes place at constant enthalpy. At constant enthalpy, any increase in
PV during the process should be compensated by decrease in internal energy, E. This leads to
fall in Temperature i.e T2<T1 for hydrogen and helium decrease in PV with lowering of pressure,
leads to increase internal energy E and T2>T1.The change in temperature is proportional to the
difference in pressure on the two sides of the process plug. Every gas shows an inversion
temperature at a given initial pressure. Above this temperature the gas shows heating effect.
Below this temperature, the gas shows a fall in temperature.
Joule-Thomson coefficient: The change in temperature with pressure under constant enthalpy
conditions on passing a gas though the porous plug is called Joule-Thomson Coefficient.
µ = dT
dP
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Laws of Thermochemistry
In chemical reactions the energy in the form of heat is generally evolved or absorbed.
Thermochemistry deals with the thermal or heat changes caused by chemical reactions.
The difference in internal energy, ∆E is released or absorbed as heat energy during a chemical
reaction.
By definition enthalpy of a system is the sum of the internal energy and the product of its
pressure and volume.
H = E+PV
At constant pressure, total enthalpy of reactant and products HR and HP are
HR = ER +PVR
HP = EP + PVP
HP-HR= (EP – ER) + P(VP-VR)
∆H =∆E + P∆V
or
∆H = HP -HR
Thus;
For reactions involving solids and liquids volume change, ∆V is very small and P x ∆V is
negligible. For such reactions ∆H is equal to ∆E. But in case of gases one should specify that
whether the reaction has taken place at constant volume or at constant pressure because of the
remarkable volume change. Most of such reactions are studied at constant pressure and change in
enthalpy (∆H) is involved.
For exothermic reactions HP< HR, ∆H is negative and for endothermic reaction HP> HR, ∆H is
positive.
27
Calculation of ∆H and ∆E :
∆H= ∆E +P∆V
P∆V = P(∆n x V)
=PV x ∆n
P∆V = ∆nRT
∆H = ∆E + ∆nRT
∆n = nP- nR
When nP and nR are the number of moles of gaseous products and gaseous reactants.
Thermochemical equations: There are number of factors other than constant volume or
pressure conditions, on which heat of reaction or enthalpy of reaction depends. These are
i) Physical state of reactants and products.
ii) Amount of the reactants and products
iii) Temperature
A thermo chemical equation is an equation which indicates the amount of heat change in the
reaction or process. A thermo chemical equation necessarily be:
a) balanced .
b) mention the physical states of reactants and products.
c) give the value of ∆E or ∆H in accordance with the quantities of substances given by the
equation.
This is thermo chemical equation of formation of 1 mole of carbon dioxide from one mole of
carbon monoxide and 0.5 moles of oxygen and heat of reaction is 284.5 KJ
Standard heat change or standard enthalpy change: The heat change in a reaction taking
place at 298 K and one atmosphere pressure is called the standard heat change or standard
enthalpy change of that reaction. It is denoted by ∆Ho
The enthalpy of any element in its standard state is arbitrarily given a zero value.
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12C( graphite) + 11 H2 (g) +1 ½ O2(g) C12H12O11(S); ∆Hf = x K.Cals.
If the compound and its elements are in the standard state, the heat of formation is referred to as
standard heat or standard enthalpy of formation. It is denoted by ∆Hfo.
We can calculate the heat of reaction under standard conditions (∆Ho) from the values of
standards heat of formation of various reactants and products.
∆Ho = [Total standard heat of formation of products] – [Total standard heat of formation of a reactant]
∆Ho = ∆HFo (products) - ∆HFo(reactants).
Heat of combustion: Heat of combustion is the enthalpy change or heat change accompanying
the complete combustion of 1 mole of the substance in excess of air or oxygen.
E.g. combustion of benzoic acid
C6H5COOH (s) +15/2 O2 (g) 7 CO2 (g) +3 H2O (l) ∆HCo = -y k.Cals.
∆H for this reaction is the enthalpy of combustion of benzoic acid. It is denoted by ∆Hc.
As heat energy is evolved during the process of combustion, the heat of combustion of a
substance (∆Hc) is always negative. We can calculate the heat of formation of the substance with
the help of this heated combustion.
Calorific values of foods and fuels can also be calculated by the heat of combustion of organic
fuel or food because calorific value is the value of heat produced in calories (or Joules) when one
gram of a substance is completely burnt.
For example
CH4(g) + 2 O2 (g) CO2 (g) + 2 H2O (l); ∆H = -890.3KJ
Heat of combustion of methane is -890.3 KJ. The heat produced per gram of methane is
890.3
= 55.64 KJ-1g-1
16
i) Heat of Fusion: It is defined as the heat change or enthalpy change when one mole of
substance is converted from solid to the liquid state at its melting point.
For example:
29
H2O (S) H2O ( l ) ; ∆H = +1.43 Kcal.
Ice water
ii) Heat of Vapourisation: It is defined as the heat or enthalpy change when one mole
of liquid is converted into gaseous state at its boiling point.
iii) Heat of Sublimation: It is defined as the heat or enthalpy change accompanying the
conversion of 1 mole of solid directly into gaseous state at a temperature below its
melting points.
For example
I2 (S) I2 (g) ; ∆H = +14.92 Kcal.
iv) Heat of Transition: It is defined as the heat or enthalpy change when one mole of an
element changes from one allotropic form to another.
For example
C diamond C graphite ; ∆H = +3.3 Kcal.
Heat of solution: When a solute is dissolved in a solvent heat may be either liberated or
absorbed.
“The enthalpy of solution is defined as the enthalpy change when one mole of solute is dissolved
in a specified amount of solvent at a given temperature.”
For example, if one mole of solute is dissolved in 500g of water the heat change gives the value
of integral heat of solution at the concentration of 2 molal.
ii) Differential heat of enthalpy of solution: If we go on diluting the solution. A stage will
come when further dilution causes no thermal effect. This is the state of infinite dilution. Thus,
differential heat or enthalpy of solution is defined as “the change in enthalpy when one mole of a
solute is dissolved in such a large quantity of solution so that further dilution does not give any
change in enthalpy.”
30
HCl (aq) + NaOH (aq) NaCl (aq) + H2O(l) ∆H = -13.69 kcal.
HNO3 (aq0 + NaOH (aq) NaNO3 (aq) + H2O (l) ∆H = -13.38 Kcal.
It is observed that enthalpy of neutralization of any strong base by any strong acid is constant.
This constancy is due to the complete ionization of strong acid, base salt formed, and overall
reaction is formation of water.
H+(aq) + Cl-(aq) + Na+ (aq) +-OH(aq) Na+(aq) + Cl- + H2O (l) ∆H = 13.69 Kcal.
If in the neutralization either the acid or base or both are weak, enthalpy of neutralization will be
less, since dissociation of weak acid or base during neutralization requires energy e.g. heat of
neutralization of NH4OH with HCl is -12.3 Kcal which is 13.7 -12.3 =1.4 K.cal less than the
heat of neutralization. 1.4 Kcal heat is absorbed in the dissociation of NH4OH a weak base.
Hess’s law of constant heat summation:This is the direct consequence of the first law of
thermodynamics. According to Hess’s law the total thermal effect in a chemical reaction depends
on the initial sate of reactants and the final state of products and not upon the intermediate stages
involved in the conversion of reactants into products.
This law can also be stated as “The net heat change in a reaction is the same, whether the
reaction takes place in one step or several steps.”
Let us consider a general reaction of conversion of A to Z in one step and in several steps.
i) A Z+ q
q heat evolved in direct change
ii) A B +q1
B C + q2
C Z +q3
According to Hess’s law
q = q1+q2+q3
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Thermo chemical equations may be multiplied, added or subtracted, like ordinary algebraic
equations. With the help of Hess’s law we can calculate the enthalpies of certain reactions in
terms of enthalpies of other related reactions. Suppose the heat of formation of methane is to be
calculated. The relevant equation is
C(s) + 2 H2(g) CH4 (g) ; ∆H F(CH4) = x K cal / mole----------(i)
The following data are available.
C(s) + O2(g) CO2(g) ;∆H F(CO2) = -96.0 K cal ---------------(ii)
H2 (g) + 1/2O2(g) H2O(l) ;∆H F(H2O) = -68.0 K cal --------------(iii)
CH4 (g)+2O2(g) CO2(g)+2 H2O(l); ∆H C(CH4) = -212.8 K cal----(iv)
We should aim at finding the value of heat of formation of methane. We have to manipulate
these equations so as to get the required equation (equation (i) )
Bond energy: Certain amount of energy is released during the bond formation of two atoms and
same amount of energy is absorbed to break up this bond.
Bond energy is average energy required to dissociate a particular type of bond in one mole into
the gaseous atoms, separated by a distance over which there is no attraction between the atoms.
Thus the bond energy of H-H bond is the energy required to break all the bonds in one mole of
hydrogen gas. Bond energy is the measure of strength of bond. It depends upon sizes of the
atoms, their electro negativity and bond length.
Knowledge of bond enthalpy is useful for calculating heats of reaction for gaseous reactions for
which no thermal data is available. The bond energy is one fourth of the total energy required to
break all the four C-H bonds in 1 mole of methane.
CH4(g) C(g) + 4H(g) ; ∆H =?
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The energy required to dissociate completely a molecule into the constituent atom is calculated
from (i) enthalpy of formation of compound (ii) enthalpy of sublimation of solid element (Cs)
from which compound is formed(iii) enthalpy of dissociation of gaseous molecule ( H2(g) ) into
the atoms.
C(graphite)+2H2(g) CH4 ; ∆H1 =-75.0 KJ
C(graphite) C(g); ∆H2 = 720.0 KJ
H2 (g) 2H(g) ; ∆H3 = 435.0 KJ
Through the suitable rearrangement of the above thermo chemical equations and using Hess’s
law we can readily obtain the heat of desired reaction.
∆H= ( 2 x ∆H3) + ∆H2 – ∆H1
Therefore;
(Cv)1 and (Cv)2 are the heat capacities for the reactants and products respectively. Thus change in
heat of reaction with temperature at constant volume is equal to the difference in heat capacities
of products and reactants, at constant volume.
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d(∆E) = ∆Cv
dT
d(∆E) = ∆CvdT
Assuming ∆Cv remain constant in the temperature range from T1 to T2 , then ∆Cv can be
taken our of integration sign.
(Cp)2 and (Cp)1 are the heat capacities at constant pressure for products and reactants
respectively. Thus change in heat of reactant at constant pressure (enthalpy change) with
temperature is equal to the difference in heat capacities of products and reactants at constant
pressure.
d(∆H) =∆CP
dT
d(∆H) = ∆CP dT
∆H2 and ∆H1 are the enthalpy change at temperature T2 & T1 respectively.
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Assuming ∆Cp remaining constant, in the temperature range T1 and T2 , then ∆Cp can be
taken our of integration sign.
∆H2 - ∆H1 = ∆CP (T2-T1) ----------(vi)
The relations (ii), (iii), (v) and (vi) are called Kirchoff’s equations. These equations can be
used to calculate the heat of reaction at given temperature if heat of reaction at some other
temperature and ∆Cp is known.
Spontaneous and non spontaneous processes: A Process which takes place in one direction of
its own accord is a spontaneous process or natural process. The reverse process of the
spontaneous process is referred as a non spontaneous process. The tendency of a process to occur
naturally is called spontaneity.
Criteria of spontaneity:
i) A spontaneous process may occur rapidly or very slowly.
ii) A spontaneous change is unidirectional and irreversible.
iii) A spontaneous process will continue till the system attains the state of equilibrium
and after that it does not undergo further spontaneous change if left undisturbed.
iv) In most of the spontaneous change there is a decrease in internal energy or enthalpy
but there are some endothermic processes which proceed spontaneously. It means
there should be some other factor in addition to enthalpy which governs the
spontaneity.
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Entropy
It is observed that in all exothermic process which occurs spontaneously i.e. melting of ice and
evaporation of water, there is an increase in randomness or disorderness. Increase in randomness
or disorder favors a spontaneous change.
Characteristics of entropy:
i) It is a state properly and its differential is exact. Since entropy of the system is single
valued function of its state, change in entropy, ∆S, of the system depends only on
initial and final states and not on the path.
∆S = S final – S initial
For an irreversible process, ∆S of the isolated system> 0 i.e. entropy increases. A process
accompanied by an increase in entropy tends to be spontaneous. It means increase in entropy is
also a criterion for spontaneity other than the decrease in enthalpy.
If q represents the amount of heat liberated or absorbed at a temperature, T in going from one
adiabatic to other. Then the entropy changes by q/T. Thus entropy could be precisely defined as
“The thermal property of substance which remains constant during an adiabatic change is
called entropy.”
Or
For a reversible change at fixed temperature (T), the change in entropy (∆S) is equal to heat
absorbed or evolved divided by the temperature.
∆S = q/T
qrev
S2 - S 1 = ∆ S =
T
Where S1 and S2 are the entropies of initial and final state of the system
In an infinitesimal process
36
dS = dq rev
T
The quantity dqrev is an inexact differential. Where as dqrev/T is an exact differential represented
as dS. Units of entropy are cal mol -1 K-1 or entropy units (eu). In SI system the unit of entropy is
Jmol-1K-1, represented by EU
1eu = 4.184 EU
Since the entire universe is undergoing spontaneous change, second law more concisely stated
as: “The entropy of the universe is constantly increasing”
Heat engine: The heat that flows spontaneously from hotter to colder body can be used to do
work with the help of suitable device.
A machine which can do work by using heat that flows out spontaneously form a high
temperature reservoir, is called a heat engine.
A heat engine running on a periodic cyclic process can yield work continuously.
Efficiency of heat Engine :The ratio of work (w) obtained in a cyclic process to the heat taken
from the high temperature reservoir (q2) is referred to as the efficiency of a heat engine. It is
denoted by symbol η.
η = w/q2
37
Figure-16: Illustration of principle of heat engine
The Carnot Cycle: Sadi Carnot in 1824 proposed a theoretical heat engine that could perform a
series of operations between temperature T1 and T2. So that at the end of these operations it was
restored to its original state. This hypothetical four stage cycle of operations which occurred
under reversible conditions is referred to as the Carnot cycle. The working substance is an ideal
gas. The four operations in order are,
i) Isothermal reversible expansion
ii) Adiabatic reversible expansion
iii) Isothermal reversible compression
iv) Adiabatic reversible compression.
Above four operations are shown in the indicator diagram of Carnot cycle.
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Step I: (A B) : The gas expands isothermally ( at constant temperature T2) and reversible from
volume V1 to V2
Step II: (B C): The gas expands adiabatically and reversibly from volume V2 to V3 and
temperature drops from T2 to T1
Step III:(C D) The gas compressed isothermally (Temp T1) and reversibly from V3 to V4
∆E = 0
w1 = Heat given by the system.
w3 = Work done on the gas.
∆E = -q1+ w1
-q1 = w3
39
= RT1 ln V4/V3
Step IV: (D A) The gas compressed adiabatically and reversibly from volume V4 to V1
(temperature changes from T1 to T2)
q=0
∆E = w4 ( work done on the gas )
40
Or
q2 = RT2 ln V2/V1
η = T2-T1
T2
The efficiency of Carnot engine is independent on the nature of working substance and is limited
by the operating temperature of the engine. The large the temperature difference (T2-T1) between
the high and low temperature reservoir, the more the heat converted to work by the heat engine.
w = T2-T1
q2 T2
w = 1 - T1
q2 T2
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Since w/q2 < 1
Therefore q2 > w, it means that heat transferred by a spontaneous process is never completely
converted into work.
Alternative derivation for the expression of η: Here the indicator diagram makes use of
temperature (T) and entropy (S) coordinate.
I
T A B
IV II
D C
III
S
Figure 18: Indicator diagram
∆SI = q2/T2
∆SIII = - q1
T1
q1= Heat rejected to the sink at temperature T1.
q2/T2 = q1/T1
q2 T2
=
q1 T1
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Subtracting 1 both sides,
q2 T2
1 = 1
q1 T1
q2 q1 = T 2 T1
=η
q2 T1
q1 = q 2
T 1 T2
Using sign convention
q2 = - q1
T2 T1
q2 q1
T2 +
=0
T1
Or
Σ q/T = 0
Clausius suggested that any reversible cycle may be regarded as being made up of large number
of Carnot’s cycles. The smooth closed curve in the figure represents cycle. Imagine a series of
isothermal and adiabatic curves down across the diagram, so that a number of Carnot cycles are
indicated.
In figure ab and cd are isothermal, while bc and da are adiabatic. So for small Carnot cycle abcd,
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q1/T1 + q2/T2= 0
q3/T3 + q4/T4= 0
δ q rev
=0
T
This suggests that δqrev/T for any path in the cycle is an exact differential, symbolized as dS ,
where for each infinitesimally small change,
dS = dq/T
∆S is dependent only on the state of the system and can be calculated if the system, can be
brought reversibly from one state to the other.
.
Always; S final >S initial
Most of the processes occurring in nature are spontaneous and irreversible i.e. entropy of
universe is constantly increasing.
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Entropy change for an ideal gas:When n mole of an ideal gas undergoes a reversible transition
from one state (P1,V1,T1) to another (P2,V2,T2), if the system absorbs, dqrev, heat reversibly then
increase in entropy is given by;
dS= dqrev/T ---------------------(i)
dS = dE +PdV --------------(ii)
T
We know that; dE = nCVdT ( for n moles)
PV = nRT
dS = nCvdT + nRdV
T V
Integrating between the limits S1,S2; T1,T2 and V1,V2, we have
Or
∆S = 2.303 nCv log T2/T1 + 2.303 nR log V2/V1-----------(iv)
V2 = P1T2
V P T
1 2 1
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We know that
Cp –Cv = R
Cp = Cv + R
Or
From equation (iv) and (vi) we can calculate the entropy change of the system.
∆S = nR ln V2/V1
And
V2/V1 = P1/P2
∆S = nRln P1/P2
And
∆S = nCv ln T2/T1
And
And
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Entropy change during phase change:When a system undergoes change in state from one
phase to another, there is a change in entropy.
When one mole of solid melts at temperature equal to its melting point (Tm) and the process of
melting is caused out reversibly, the change in entropy is given by
∆SF = ∆Hf
Tm
Similarly when one mole of a liquid is boiled reversibly at its boiling point (Tb). It would absorb
molar heat of vaporization. The entropy change in this case is given by
∆SV = ∆HV
Tb
Similarly for reversible phase transition form one allotropic form to another at its transition
temperature Tt,
∆St= ∆Ht
Tt
First two are isothermal relations and other two are adiabatic
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Thermodynamic equations of state: The relationship between E or H with P V T data is called
Thermodynamic equation of state. There are two equations of state which are obtained from
Maxwell’s relations and are quite general, applicable to all states of matter. These are called
thermodynamic equations of state.
Free Energy (G) and work Functions (A) ,Gibb’s Helmolt’s equation: Two new functions
involving energy and entropy are A and G. A portion of energy that can be converted to useful
work is termed as available energy while net portion, which cannot be converted into useful
work, is termed as unavailable energy. Entropy is a measure of unavailable energy and TS is
amount of available energy.
q = E at constant volume.
q = H, at constant pressure.
G = H - TS
∆G = ∆H +T∆S ----------(i)
A = E – TS
We know that
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∆H = ∆E – P∆V
∆G = ∆E + P∆V -T∆S
Or
∆G = ∆A + P∆V
q rev = T∆S
∆A = ∆E – q rev
∆E = qrev – w
– w = ∆E - qrev
Or
-∆A = -w
Thus decrease in the work function ‘A’ in any process at constant temperature is equal to the
maximum work that can be obtained from the system during any change.
By definition:
G =H-TS
H = E+PV
G = E+PV-TS
Differentiating, we get
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dG = dE +PdV + VdP –TdS-SdT------(vi)
dS = dq /T
TdS = dq
And
dq = dE +PdV
Or
dG = TdS+VdP-TdS-SdT
dG =VdP – SdT--------------------(viii)
At constant pressure
dG = -SdT
dG
dT = -S
P
dG
dP = V
T
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d(∆G) = -∆SdT
∆G = ∆H –T∆S
∆G = ∆H +T(-∆S)
d(∆G)
∆G = ∆H + T
dT P
This is Gibb’s Helmoltz equation in terms free energy and enthalpy change at constant pressure.
By definition
A = E - TS
Differentiating we get
dA = dE-TdS-SdT ----------(xii)
dq = dE+PdV
dq = TdS
dE = TdS –PdV-----(xiii)
dA = TdS-PdV-TdS-SdT
dA = -PdV-SdT---------(xiv)
At constant volume;
dA = -SdT
dA -
dT = S
v
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For infinitesimal change initial and final states
d(∆A) = -∆SdT
or ∆S = d(∆A)/dT
∆A = ∆E – T∆S
We get,
d(∆A)
∆A = ∆ E + T dT
------------(xvii)
v
This equation is Gibb’s Helmolt’s equation in terms of internal energy and work function.
This equation can be used to calculate ∆G and ∆H when ∆G and ∆A at two temperature are
given.
Free energy changes for isothermal process:
By definition;
G = H –TS ----------------------------------(i)
H = E + PV
G = E + PV – TS --------------------------(ii)
Differentiating, we get;
dG = dE+PdV +VdP –TdS –SdT ---------(iii)
We know that.
dq = dE +PdV
dq = TdS
52
There fore dG = VdP –SdT -------------------------------(iv)
dG = VdP
V = RT/P
Therefore
∆G = RT ln P2/P1----------------------------- (v)
Or
∆G = RT ln V1/V2 -----------------------(vii)
For n moles;
∆G = nRT ln V1/V2
Or
With the help of above equations we can calculate the free energy change for isothermal process
having an ideal gas.
53
Thermo dynamical criteria for equilibrium and spontaneous change:
δq
Combining the we get, ds ≥
T
Since δq = dE + PdV ,
dE + PdV
So, δs ≥
T
(i) in terms of entropy change of system: If the processes occurs at Constant E and V then,
dE = dV = 0
So TdS ≥ 0
Or (dS) E.V ≥ 0
i.e if ds = 0 the process is reversible and if ds > O the process is irreversible or spontaneous .
(ii) in terms of internal energy : If the process occurs at constant S and V then, dS = dV= 0.
So eqn (i) reduces to
(iii) in terms of enthalpy change: If S and P are kept constant then eq. (i) becomes
But dE + PdV = dH
54
(iv) in terms of Free energy change: Since G = H-TS
= E+ PV-TS (Q H = E + PV)
Or dG - VdP + SdT ≤ 0
At constant P and T
dP = dT = 0
A = E - TS
Or TdS = dE - SdT - dA
dE - SdT - dA ≥ dE + PdV
- SdT - dA - PdV ≥ 0
At constant T and V
(-dA)T, V ≤ 0 , = for reversible and < for irreversible.
At constant temperature and pressure, the deciding factor for spontaneity is ∆G and not ∆H
alone or ∆S as shown below
∆G = -ve ----- Spontaneous process
∆ G = 0 ----- At equilibrium
∆G = +ve ----- Non spontaneous process.
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Condition for ∆G to be negative: sign of ∆H, ∆S and ∆G, Prediction of spontaneity.
Spontaneous at all
-ve Spontaneous
-ve Spontaneous
(∆H>T∆S)
Suggested readings
• Physical Chemistry by G.W.Castellan, 3rd edition.
• Physical Chemistry by Gordon M. Barrow, 5th edition.
• Physical Chemistry by Robert J. Silbey and Robert A. Alberty, 6th edition.
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