Thermodynamics and Thermochemistry

 Thermodynamics and thermochemistry:
The study of the flow of heat or any other form of energy into or out of a system as
it undergoes a physical or chemical transformation is called Thermodynamics. In
studying and evaluating the flow of energy into or out of a system, it will be useful
to consider changes in certain properties of a system. These properties include
temperature, pressure, volume and concentration of the system. Measuring the
changes provide information concerning changes in energy and related quantities
such as heat and work.
Thermodynamic terms and basic concept:
In order to study the laws of thermodynamics, it is essential to understand certain

terms quite often used in thermodynamics. These terms have definite meaning.
System, Boundary and Surrounding:
1. System: A system is that part of the universe which is under thermodynamic

study and the rest of the universe is surrounding.
2. Boundary: The real or imaginary surface separating the system from the
surrounding is called the boundary.
3. Surrounding: Region outside the boundaries of any system is termed

surrounding. A system is thus separated from rest of the universe i.e.
surrounding by a real or imaginary boundary. Everything outside the system
is considered as the surrounding.
Homogeneous system and Heterogenous system:
Homogenous system: When a system is uniform throughout, it is called a

homogenous system. In other words, a system is said to be homogeneous when it
has the same chemical composition throughout. For example, a mixture of gases, a
pure single liquid or solid or a true solution forms a homogeneous system.
Thermodynamic @ Arjun Bhandari 2015 Page 1

Heterogenous system: A heterogeneous system is one which consists of two or
more phases. In other words, it is not uniform throughout.
For example: ice in contact with water, ice in contact with vapours etc. Here, ice,
water, and vapours constitute separated phases.
 Types of system:
Depending upon the nature of boundary, thermodynamic systems are classified
into following three classes:
1.Open system: A system which can exchange matter as well as energy with
surrounding is called an open system.
For example: evaporation of water from a beaker represents an open system. Here,
water vapour (matter) move into atmosphere and heat (energy) required is
absorbed by water from the surrounding.
2. Closed system: A system which may exchange energy but not matter with
surrounding is called a closed system.
For example: boiling water in a closed metallic vessel. Here heat is transferred
from the burner (surrounding) to the system; steam remains inside the vessel. Thus,
matter is not exchanged.
3. Isolated system: A system which can neither exchange matter nor energy with
the surrounding is called an isolated system.
For example: some water is taken in an insulated vessel and put small pieces of
sodium metal in it. An exothermic reaction takes place. Neither the hydrogen gas
(matter) nor heat (energy) is transferred to the surroundings.

 State of the system and State Functions:
A thermodynamics system is said to be in a certain state when all its

properties are fixed. The state of a system can be defined completely by the
following four properties: i) Mass and composition (ii) Temperature (iii) Pressure
(iv) Volume
Any change in the magnitude of these properties alters the state of the system;
therefore, these properties are referred to as state variable or state functions or
thermodynamics parameters.
A change in any function of state is measured as the difference between final
state and the initial state, because, the value of these functions depends solely on
the thermodynamics properties of the system in a given state and not on its past
history.
For example: a pure gas, the composition is fixed automatically as it is 100 percent
Thus the state of such a system can be defined by only three variables, pressure(p),
volume(v), temperature(T). Further, if the gas is ideal and one mole of the gas is
under examination, it obeys the equation, PV = RT, where R is the gas constant.
Therefore, if only two of these variables are known the third can be easily
calculated. The two variables generally specified are temperature and pressure.
These are called independent state variables. The third state variable, generally
volume is said to be a dependent state variable because its value depends upon the
values of P and T. Thus, state of a system containing definite amount of a single
gas can be completely defined by specifying only two of the three variables, i.e.
pressure, temperature and volume.
 Extensive and Intensive Properties:
The various measurable properties or the state functions may be either extensive or
intensive.
An extensive property of a system is that which depends upon the amount of

the substance or substance present in the system. For example, mass, volume,
surface area, energy, number of moles, free energy, entropy, enthalpy etc.
An intensive property of a system is that which is independent of the amount

but depends upon the concentration of the substance or substances present in the

system. For example, temperature, pressure, density, viscosity, refractive index,
surface tension, specific heat capacity, freezing point, boiling point etc.
 Equilibrium and Non-equilibrium:
A system is said to be in equilibrium when temperature, pressure, and

concentration of various species are the same at all points in the system and do not
change with time. Suppose we have a gas confined in a cylinder that has a
frictionless piston. If the piston is stationary, the state of the gas can be specified
by giving the values of pressure and volume. The system is then in a state of
equilibrium.
A system in which the state variables have different values in different parts
of the system is said to be in a non-equilibrium state.
If the gas contained in a cylinder, is compressed very rapidly by moving

down the piston, it passes through states in which pressure and temperature cannot
be specified, since these properties vary throughout the gas. The gas then would be
said to be in non-equilibrium state.
The criteria for Equilibrium:
1. The temperature of the system must be uniform and must be the same as the
temperature of the surroundings (thermal equilibrium).
2. The mechanical properties must be uniform throughout the system (mechanical

equilibrium).
3. The chemical composition of the system must be uniform with no net chemical
change (chemical equilibrium).

 Thermodynamic Processes:
When a thermodynamics system changes from one state to another, the operation is
called a Process. These processes involve the change of conditions (temperature,
pressure and volume). The various types of thermodynamic processes are,
1. Isothermal Processes: Those processes, in which the temperature remains fixed,

are termed isothermal processes. This is often achieved by placing the system in a
thermostat (a constant temperature bath).
For an isothermal process dT = 0
2. Adiabatic Processes: Those processes in which no heat can flow into or out of
the system are called adiabatic processes. Adiabatic conditions can be approached
by carrying the process in an insulated container such as thermos bottle.
For an adiabatic process dq = 0
3. Isobaric Processes: Those processes which take place at constant pressure are
called isobaric processes. For example: heating of water to its boiling point and its
vaporization take place at the same atmospheric pressure.
For an isobaric process dp = 0
4. Isochoric processes: Those processes in which the volume remains constant are
known as isochoric processes. For example: the heating of a substance in a non-
expanding chamber.
For isochoric processes dV = 0
5. Cyclic Processes: When a system in a given state goes through a number of

different processes and final returns to its initial state, the overall process is called
a cycle or cyclic process.
For a cyclic process dE = 0, dH = 0

 Reversible and Irreversible Processes:
A thermodynamic reverse process is one that takes place infinitesimally slowly and
its direction at any point can be reversed by an infinitesimal change in state of the
system.
In fact, a reversible process is considered to proceed from the initial state to

the final state through an infinite series of infinitesimally small stages. At the
initial, final and all intermediate stages, the system is in equilibrium state. This is
so because an infinitesimal change in the state of the system at each intermediate
step is negligible.
When a process goes from the initial to the final state in a single step and
cannot be carried in the reverse order, it is said to be an irreversible process. Here,
the system is in equilibrium state in the beginning and at the end, but not at points
in between.
a) Reversible Process b) Irreversible Process

 Difference between Reversible and Irreversible Processes:
Reversible Process Irreversible Process
1. It takes place in infinite number of 1. It takes place infinite time.

infinitesimally small steps and it would take
infinite time to occur.
2. It is in equilibrium state at all stages of the 2. It is in equilibrium stage only at the initial
operation. and final stages of the operation.
3. All changes are reversed when the process is 3. After this type of process has occurred all
carried out in reversible direction. changes do not return to the initial state by
themselves.
4. It is extremely slow. 4. It proceeds at measureable speed.
5. Work done by a reversible process is greater 5. Work done by a irreversible process is

than the corresponding irreversible process. smaller than the corresponding reversible
process.
 Nature of the Heat and Work:
When a change in the state of a system occurs, energy is transferred to or from the
surroundings. This energy may be transferred as heat or mechanical work.
1.Heat: When two objects at temperatures are brought in contact, the difference in
their temperature disappears. This occurs due to the transfer of heat or thermal
energy. Thus, heat energy is the energy changes resulting from a change in the
temperature of the system or its surrounding.
This form of energy is unique. All other forms of energy are completely
convertible into heat. The quantity of heat, ‘q’ is a product of two terms; heat
capacity and difference in temperature.
q = heat capacity X difference in temperature
q = C (T2 – T1 ) where C is heat capacity and T1 and T2 are the initial

and final temperature.
The heat energy is generally expressed in calorie (Cal.). A calorie is defined as

the quantity of heat required to raise the temperature of one gram of water by 1* C
in the vicinity of 15* C, i.e. (14.5-15.5* C). SI unit of heat is the joule (J).

i.e. 1 Joule = 0.2390 calories
1 Calories = 4.184 J
1 Kcal = 4.184 KJ
Sign Convention of Heat: The symbol of heat is ‘q’.
 If the heat flow from the surrounding into the system to raise the energy of
the system, it is taken to be positive, +q.
 If the heat flow from the system to the surrounding, the energy of the system
is lowered and it is taken to be negative, -q.
2. Work: Work is the product of force and displacement.
The mechanical work done (W) is given by,
W = force X displacement
W = pressure X area X length = P x ∆V or P x dV
The work is generally expressed in Joule.
1 Joule = 107 ergs
1 erg = 10-7 J
1 KJ = 1000J
Sign Convention of Work: The symbol of work is ‘w’.
 If work is done on a system by the surrounding and the energy of the system
is thus increased, it is taken to be positive, +w.
 If work is done by the system on the surrounding and energy of the system is
decreased, it is taken to be negative, -w.
 Internal Energy:
Every substance is associated with a definite amount of energy which depends

upon its chemical nature as well as upon its temperature, pressure and volume. The
energy includes not only the translational kinetic energy of the molecules but also

other molecular energies such as rotational and vibrationAL energies. The total of
all the possible kinds of the energy of a system is called its internal energy. The
kinetic and potential energy of the nuclei and electrons within the individual
molecules also contribute to the energy of the system. The internal energy of a
system, like temperature, pressure, volume etc., is determined by the state of the
system and is independent of the path by which it is obtained.
Hence internal energy of a system is a state function.
Suppose, a system is subjected to change of state from A to B. Let E A and EB be

internal energies of the system in state A and state B respectively. Then the change
in internal energy of the system is given by ΔE.
ΔE = EB – EA
Since, EA and EB are definite quantity, the change in internal energy is also a
definite quantity, irrespective of the path or the manner in which the change is
brought about. Internal energy is extensive property. Internal energy is
represented by the symbol E,
Units of Internal Energy:
The SI unit for the internal energy of a system is the joule (J).
1cal = 4.184J
 First Law of Thermodynamics:
The first law of thermodynamics is in fact, an application of the broad principle

known as the Law of Conservation of Energy to the thermodynamic system. It
state that: ‘‘The total energy of an isolated system remains constant through it
may change from one form to another.’’
Mathematical Statement of First Law of Thermodynamics:
Let EA be the energy of a system in its state A and EB be the energy in its
state B. Suppose, when the system undergoes a change from state A to state B
absorbs heat ‘q’ from surrounding and also performs some work, mechanical or
electrical, equal to ‘W’. The absorption of heat by a system tends to raise the
energy of the system.

The performance of work by the system, on the other hands, tends to the
energy of the system because performance of work requires expenditure of energy.
Hence, the change of internal energy, ΔE, accompanying the above process will be
given by,
ΔE = EB – EA = q – W
ΔE = q – W………1)
Where, q = the amount of heat supplied to the system
W = work done by the system
This equation is a mathematical statement of the first law of thermodynamics. It

also state that ‘the net energy change of a closed system is equal to the heat
transferred to the system minus the work done by the system’’.
For an infinitesimally small change, the equation (1), may be expressed as,
dE = dq – dW ………….2)
Where dE is the small increase in energy and dq and dW represent small quantities
of heat absorbed and external work done by the system respectively.
Other Definition of First Law of Thermodynamics:

1. Whenever energy of a particular type disappears equivalent amount of
another type must be produced.
2. Total energy of a system and surrounding remains constant (or conserved) .
3. It is impossible to construct a perpetual motion machine that can produce

work without spending energy on it.
Some Special Forms of First Law of Thermodynamics:
1. For a cyclic process involving isothermal expansion of an ideal gas, ΔE = 0,

thus, q = w
2. For an isochoric process there is no work of expansion, i.e.
w = 0. Hence, ΔE = q

3. For an adiabatic process there is no change in heat gained or lost i.e, q = 0.
Hence, ΔE = -w
4. For an isobaric process there is no change in pressure, i.e. p remains

constant. Hence, ΔE = q - p ΔV
Limitation of first law of thermodynamics:

1. It does not specify the direction of flow of heat and work.
2. It does not tell why the whole of heat can be converted into mechanical
work.
3. It does not tell there are many irreversible processes occur in nature.
 Spontaneous and Non-spontaneous Processes:
1. Spontaneous Processes: The processes which proceed by themselves and bring

the system closer to the equilibrium are called the spontaneous processes. It is also
called as the natural processes. All natural processes always try to tend towards
equilibrium and such are irreversible. These processes proceed with a finite
velocity. A natural process proceeds upon the establishment of equilibrium and at
equilibrium state, the process stops occurring any further change.
Thus, all irreversible processes proceed in a direction so as to bring the

equilibrium state, without the action of any external agency. The tendency of a
process to occur spontaneously is known as spontaneity.
Criteria of Spontaneity: Some important criteria of spontaneous processes are,
1. A spontaneous change is one-way or unidirectional.
2. For a spontaneous change to occur, time is no factor. It may take place

rapidly or very slowly.
3. A spontaneous process occurs without any external assistance.
4. A spontaneous process involve an increase in the disorder or randomness of

the system, i.e., an increase in the entropy of the system.

Example of spontaneous processes are,
1. Expansion of the gas from pressure of high region to low pressure region
until pressure becomes uniform.
2. Diffusion of solute into solvent or diffusion of solute from solution of higher

concentration to solution of lower concentration until the concentration
becomes uniform throughout.
3. Conduction of heat along the metallic bar which is hot at one end while cold
at the other end until the temperature becomes uniform.
4. Flow of water from higher level to the lower level.
Non-spontaneous Processes:
The processes which cannot proceed by themselves are called non-

spontaneous processes, i.e., such processes cannot proceed without any external
aid and bring the system away from the equilibrium. They also called unnatural
processes. A non-spontaneous process is always accompanied by another.
For example, water freezes readily below 0* C and melts spontaneously

above 0* C or in other words, to stop ice from melting requires, additional effort.
Entropy:
The concept of entropy was first introduced by Clausius in 1850 while working on
the formulation and application of second law of thermodynamics. It is very
important thermodynamic quantity and has proved very useful in the study of
behaviour of heat engine. Entropy is a thermodynamics state quantity that is a
measure of the randomness or disorder of the molecules of the system.The symbol
of entropy is S, while the change in disorder accompanying a process from start to
completion is represented by ΔS. The entropy of a system is a state function and
depends only on the initial and final state of the system.
The change in entropy, ΔS, for any process is given by the equation,
ΔS = Sfinal - Sinitial
When Sfinal > Sinitial , ΔS is positive. A process accompanied by an increase in

entropy tends to be spontaneous.

Statement of Second law of thermodynamics: The second law of thermodynamics
states that: whenever a spontaneous process takes place, it is accompanied by an
increase in the total energy of the universe. Specifically, the term universe mean
the system and the surroundings.
Δsuniverse = Δssyst + Δssurr.
The second law tells us that when an irreversible spontaneous process occurs. In
other words Δsuniv > 0. When a reversible process occurs, the entropy of the system
remains constant i.e., ΔS = 0. Since the entire universe is undergoing spontaneous
change, the second law can be most generally and concisely state as : the entropy
of the system is constantly increasing.
Numerical definition of entropy:
In 1850 Clausius, entropy of a system, which does not involve in chemical or

physical changes, is a constant quantity if there is no communication of heat. When
heat (q) flows into the system, the entropy increases by q/T and in case heat
flowing out of a system produces a corresponding decrease. Thus entropy can be
defined precisely as: for a reversible change taking place at a fixed temperature
(T), the change in entropy (ΔS) is equal to heat energy absorbed or evolved
divided by the temperature (T). i.e.,
For infinitesimally small change: dS = dq/T
For finite change: ΔS = q/T
If heat is absorbed, then ΔS are positive and there will be increase in entropy. If
heat is evolved, ΔS are negative and there is a decrease in entropy.
Unit of Entropy: Since entropy change is expressed by a heat term divided by the
absolute temperature, it is expressed in terms of calories per degree, i.e., Cal deg-1
.This is also known as entropy unit (e.u.). In SI unit the entropy is expressed in
terms of the Joule per Kelvin (JK-1 ).
1eu = 4.184
Entropy is an extensive property and hence its value depends upon the amount of
the substance involved.

Standard Entropy:
The entropy of one mole of a substance in pure state at one atmospheric pressure
and 25* C, is termed as standard entropy of that substance and is denoted by S *
.When a reaction involves each reactant and each product in its standard state, the
entropy change is said to be standard entropy change. This is denoted by ΔS*.
Thus, the standard entropy change in a chemical reaction can be expressed as:
ΔS* = Σ S* product - Σ S* reactant
 Isothermal reversible expansion work of an Ideal gas:
Consider an ideal gas confined in a cylinder with a frictionless piston. Suppose the
cylinder is not insulated and the gas expands in reversible manner from the
Volume V1 and V2 at constant temperature. Suppose, the pressure of the gas is
successively reduced from P1 and P2.
The reversible expansion of the gas takes place in an infinite number of

infinitesimally small intermediate steps.
Suppose, initially the external pressure (Pext) is arranged equal to the pressure
within the cylinder, P. Under this condition the piston remains stationary.

If Pext is decreased by an infinitesimally small amount ‘dP’, the gas expands
reversibly and the piston moves through a distance ‘dl’. The pressure on the piston
being equal to, P – dP, i.e.
Pext = P – dP
The workdone by the gas in one infinitesimal step dW is given by:
dW = Pext x A x dl (where A is cross-sectional area of piston)
dW = (P – dP). dV (where dV is increase in volume in one infinitesimal

step)
dW = P. dV – dP .dV
Neglecting dP. dV as both are infinitesimal small, we get:
dW = P. dV
The total amount of work done in the isothermal reversible expansion of the ideal
gas from volume V1 and V2 is therefore,
v2
Wrev. =  P . dV
v1
From, ideal gas equation we have

nRT
P =
V
Thus,
v2
nRT
Wrev. =  dV
v1 V
dV
= nRT 
V
On integration, we have
V2 dV
Wrev. = nRT ln [  = ln V ]
V1 V

We have
P1 x V1 = P2 x V2
V2 P1
=
V1 P2
Thus, P1 V2
Wrev. = nRT ln = 2.303 nRT log
P2 V1
Workdone in isothermal but not Reversible (Irriversible) Expansion of an
ideal gas:
Suppose we have an ideal gas contained in a cylinder provided with an, air tight,
weightless and frictionless piston.
Let the process of expansion of the gas from volume V1 to V2 performed

irreversibly by dropping the external pressure Pext. Instantaneously to the final
pressure P2 .
The work done by the system is now against the pressure P2, throughout the whole
expansion and is given by expansion:
V2
Pext = P2
Wirr = Pext  dV
V1
Wirr = P2 (V2 - V1) Final Position

of piston
Pext. = P
But, P1V1 = nRT and P2V2 = nRT
nRT
Wirr = P2 [ - nRT ] Initial position
P2 P1 P of piston
Ideal Gas
P2
= nRT [ 1 - ]
P1 Fig: Isothermal irreversible work of
expansion

 Maximum Work Done in Reversible Expansion:
It is important to remark here that work done in isothermal reversible expansion of

an ideal gas is always greater than of irreversible expansion. This can be proved
as follows:
We know that,
P1
Wrev. = nRT ln .......(1)
P2
P2
Wirr. = nRT [ 1 - ] ........(2)
P1
Equation (1) can be written as:
P1 P1
Wrev. = nRT ln [ 1 - 1 + ] = nRT ln [ 1 - (1 - ) ] ......(3)
P2 P2
We know that,
ln ( 1 - x ) = - x - 1/2 x2  (- x)
Thus,
P1 P1
ln [ 1 - ( 1 - )] = -( 1- ) ........(4)
P2 P2
On Substituting equation (4) in (3), we get,

P1 P1
Wrev. = -nRT ( 1 - ) = nRT ( - 1 ) .........(5)
P2 P2
On Substracting equation (2) from (5), we get,
P1 P2
Wrev. - Wirr. = nRT ( - 1 ) - nRT ( 1 - )
P2 P1
P1 P2
= nRT [ - 2+ ]
P2 P1
P12 - 2 P1P2 + P22

= nRT [ ]
P1 P2
nRT ( P - P )2 .......(6)
= 1 2
P1 P2
As ( P1 - P2 )2 is always positive quantity, it means that LHS of equation (6) should
also be positive quantity for isothermal expansion of ideal gas.
Wrev. - Wirr. > 0

Wrev. > Wirr
Therefore, workdone in isolated reversible expansion is always greater than that of

irreversible expansion of an ideal gas.
Entropy Changes:
Entropy change in isothermal expansion of an ideal gas: When the expansion of

a gas is carried out under isothermal and reversible conditions, the internal energy
does not changes, i.e. ΔE = 0. Hence, from the first law of thermodynamics, we
have,
ΔE = qrev - W
W = qrev ………1)
The work done in the expansion of ‘n’ moles of a gas from volume V 1 to
volume V2 at a constant temperature T is given by the equation,
W = nRT ln V2 / V1
W = 2.303 nRT log V2 /V1 ……2)
Since, ΔS = qrev /T, therefore, from equation 1) and 2), we have,
ΔS = 2.303 nRT/T log V2 /V1
So, ΔS = 2.303 nR log V2 /V1 ……..3)
2. Entropy change in reversible and irreversible(spontaneous) process:
Let us suppose the isothermal expansion of the ideal gas from volume V 1 to V2
is carried out reversibly at the same temperature and absorbs heat q rev from the

surroundings. The increase in entropy of the systems, Δssys is given by the
expression,
ΔS = qrev / T ……….1)
Since, the surrounding lost heat equal to qrev , reversibly at the same
temperature T, the decrease in entropy of the surrounding, ΔSsur is given by the
expression.,
ΔS = - qrev /T ……..2)
Therefore, the total entropy change of the system and its surrounding during
a reversible process is zero.
ΔStot = ΔSsys + Δssurr
ΔStot = qrev / T - qrev /T
ΔStot = 0 ………….3)
Let us suppose that same system undergoes the same change of state by an
irreversible process at constant temperature T. Then, the work done by the system,
Wirr , is less than Wrev ,therefore, the heat absorbed by the system, qirr ,is also less
than qrev . But, entropy is a state function, the increase in entropy of the system is
the same, irrespective of the fact whether the change is carried out reversibly or
irreversibly. Hence, Δssys remains same as before, i.e. equal to qrev/T as given
equation (1). But as heat absorbed by the surrounding, q irr, is also less than qrev , .
However, the loss of heat by the surrounding can be considered to take place
infinitesimally slowly, i.e. reversibly due to the infinitely large size of the
surrounding.
Hence, the entropy change of the surrounding can be expressed as:
Δ Ssurr = -qirr /T …..4)
Therefore, the total entropy change of the system and its surrounding during
an irreversible process is,
ΔS tot = ΔSsys + Δ Ssurr
ΔStot = qrev /T - qirr /T …..5)
Since, qrev > qirr

Therefore, qrev /T - qirr /T >o ………6)
In other word, for irreversible process:
ΔS tot = ΔSsys + Δ Ssurr > 0 ……7)
The entropy of the system and its surrounding taken together increases in a
thermodynamically irreversible process at constant temperature but it remains
unchanged in a thermodynamically reversible process.
Mathematically, ΔSsys + Δ Ssurr = 0 (for reversible process)
ΔSsys + Δ Ssurr > 0 (for irreversible process)
 Statement of second law of thermodynamics in terms of entropy change:
In a reversible process, the entropy of the system and surrounding taken together
remains constant while in an irreversible process the entropy of the system and
surrounding increases.
Since all process in nature occur spontaneously i.e. irreversibly it follows that
the entropy of the universe tends towards a maximum. This is another statement of
the second law of thermodynamics.
 Enthalpy or Heat Content::
When a process is carried out at constant volume the heat content of a system is
same as internal energy (E), as no PV-work is done. But when a process is carried
out 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 internal energy (E) plus the PV-energy.
This is called enthalpy (Greek: en=in, thalpos= heat) of the system and is
represented by the symbol H.
H = E + PV ……1)
Where P and V are pressure and volume of the system respectively.
Since, both P and V are function of state as E, H must also be a function of state.
Thus if H1 and H2 are the enthalpies of the system in the initial and final states,
then,

H1 = E1 + P1V1 …….2)
H2 = E2 + P2V2 ……..3)
Hence, H2- H1 =ΔH = (E2 –E1) + (P2V2 -P1V1 )
ΔH = ΔE + (P2V2 -P1V1 ) …..4)
When the pressure remain constant,
ΔH = ΔE + P(V2 –V1 )
ΔH = ΔE + P Δ V ……..5)
Thus, the change in enthalpy at constant pressure is equal to the increases in

internal energy plus any pressure –volume work done. Hence, at constant pressure
ΔH represents the heat absorbed by a system in going from an initial state to a final
state provided the only work done is PV-work.
According to the first law of thermodynamics
ΔE = q –W
Since at constant pressure, W = P ΔV
ΔE + P ΔV = q ……6)
From equation 6) and 5) we have. Δ H =q
Hence, increase in enthalpy equals the heat absorbed at constant pressure when no
work other P ΔV work is done.
The enthalpy change, ΔH, is positive if H2 > H1 and the process or reaction
will be endothermic whereas ΔH is negative if H1 > H2 and the reaction will be
exothermic.
 Calculation of ΔH from ΔE and vice versa:
The enthalpy change of a reaction at constant pressure (ΔH) and internal energy
(ΔE) are related to each other as:
ΔH = ΔE + P x Δ V

Where ΔV is the change in volume due to expansion or contraction when
measurement is done at constant pressure P. Though heat change of reaction are
usually measured at constant pressure, it is sometime necessary to carry out the
reaction at constant volume.
Let consider a reaction: aA + bB cC + dD
Change in number of moles = No. of mole of products – No. of mole of

reactant
= (c + d) – (a + b) = Δn
Let the volume occupied by one mole of the gas be V. Then the change in volume,
ΔV = Change in No. of mole x volume occupied by one mole of the gas.
ΔV = Δn x V
P x ΔV = P (Δn x V)
P x ΔV = PV x Δn
But PV = RT (for one mole of gas)
Putting RT in place of PV in above equation we get
P x ΔV = RT Δn
Substituting the value of P x ΔV in equation (1) we get
ΔH = ΔE + Δn RT
It may be pointed out that while determining the value of ΔH, only the number of
moles of gaseous reactant and products are taken into consideration. The value of
gas constant R is taken either in calories or joules per degree per mol and is 1.987
cal or 8.314 joules.

 Relation Between Enthalpy (H) and Entropy (S):
First law of thermodynamic for infinitesimally small change in the state of the
system can be:
dq = dE + PdV ….(1)
From the second law of thermodynamics;
dq /T = dS
dq = TdS ……(2)
From equation (1) and (2), we get
TdS = dE + PdV ….(3)
We know that;
H = E + PV
Differentiating the above equation, we get
dH = dE + PdV + VdP ….(4)
dH = TdS + VdP ….(5)
Equation (5) is the relationship between Enthalpy and Entropy.

 Heat of reaction:
Heat of reaction is defined as the quantity of heat evolved or absorbed when molar
quantities of substances react in amounts represented by chemical equation at a
given temperature.
If the reaction is carried out at constant temperature and constant volume, heat
evolved or absorbed is equal to the change in internal energy. Thus the heat of
reaction at constant volume at a certain temperature is defined as the change in
internal energy (ΔE) of the system when number of moles of substance reacts in
amount represented by chemical equation.
If ER and EP represent the internal energy of reactants and products

respectively, then heat of reaction at constant volume is given by:
ΔE =EP –ER = qV
Similarly, the heat of reaction at constant pressure a certain temperature is

defined as the change in enthalpy (ΔH) of the system when number of the moles of
substances reacts in amounts represented by chemical equation.
If HR and HP represented the enthalpy of reactants and products respectively,

then heat of reaction at constant pressure is:
ΔH = HP –HR =qP
 Different types of heat of Reaction:
Depending upon the nature of reaction, enthalpy changes (heat of reaction)

accompanying chemical reaction are expressed in different ways:
1. Heat of Formation: The heat (enthalpy) of formation of a compound is defined

as the change in enthalpy of the system when one mole of the compound is formed
from its elements. It is denoted by ΔHf.
For example: S(S) + O2 (g) SO2 (g) ΔHf = -70.96KCals.
This equation represented that, the heat of formation of SO2 is -70.96KCals.

Similarly, the formation of hydrochloric acid from hydrogen and chlorine,
H2 (g) + Cl2 (g) 2HCl, ΔH = -44KCals.

Here, 44KCals. Of heat is evolved when two moles of HCl are formed. Hence, the
heat of formation of formation of HCl will be,
-44/2 = -22 Kcals.
Standard Enthalpy(heat) of Formation:
Enthalpy changes accompanying chemical reactions are measured at certain

standard conditions of temperature and pressure. The standard state refers to one
atmosphere pressure and the temperature of 25˚ C (298 K). The standard heat of
formation of a compound is defined as the change in enthalpy of the system when
one mole of a compound is formed from its elements in their standard states (i.e. 1
atmosphere and 298 K). This is denoted by ΔHf˚ . It is assumed that the standard
enthalpies of the elements are zero. The standard enthalpy of any reaction(ΔH˚) is
equal to the difference between the ΔHf˚ values of all products and ΔHf˚ of all the
reactants,
i.e. ΔHf˚ = Σ ΔHf˚ (products) - Σ ΔHf˚ (reactants)
For example: consider a hypothetical equation:
aA + bB cC + dD
ΔH˚ = Σ Δ Hf˚(product) - Σ Δ Hf˚(reactant)
=[c Δ Hf˚(C) + dΔ Hf˚(D) –a Δ Hf˚(A) -b Δ Hf˚(B)]
2. Heat of Combustion: Heat of combustion of a substance is defined as the

enthalpy change accompanying the complete combustion of one mole of the
substance in excess of air.
Some examples are:
a) (i) C(S) + O2 (g) CO2 (g), ΔH = -94.1 KCal.
(ii) C(S) + ½ O2 (g) CO (g) ΔH = -26.0 KCal.
-26.0 KCals is not heat of combustion of carbon as CO can further oxidized to give
CO2.

Since, combustion is always accompanied by the evolution of heat; the
enthalpy (heat) of combustion is always negative.
3. Heat of solution or Hydration: The heat of solution is defined as: the change in
enthalpy when one mole of a substance is dissolved in a specified quantity of
solvent at a given temperature. Heat of solution is a function of concentration.
For example: if one mole of ethyl alcohol be dissolved in 4 mole of water the heat
evolved is 898 Cals. However, if one mole alcohol is dissolved in 9 moles of
water, the heat evolved is 1678 Cal, i.e.
C2H5OH (l) + 4H2O C2H5OH (4H2O) ΔH = -898 Cals.
C2H5OH (l) + 9H2O C2H5OH (9H2O) ΔH = -1678 Cals.

If we go on diluting the solution, a stage will come when further dilution produces
no thermal effect. This state is called the state of infinite dilution. Thus, the heat of
solution is defined as the enthalpy change when one mole of substance (solute) is
dissolved in a solvent so that further dilution does not give any change in enthalpy.
4. Heat of Neutralization: The heat of neutralization of an acid at a given

temperature is defined as the change in enthalpy (ΔH) accompanying the
neutralization of one gram equivalent of the acid by a base or vice-versa in dilute
solution at that temperature.
For example:
HNO3 (aq.) + NaOH(aq.) NaNO3(aq) + H2O (l) ΔH= -13.69 KCals
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) ΔH = -13.68 KCals.
It is clear from the above equation that all strong acids and alkalies give
approximately the same i.e.13.7 Kcal. Heat of neutralization in dilute solution no
matter which acid or base is employed. This can be explain on the basis of
ionization theory.
If HA and BOH represent any strong acid and strong base respectively and
equivalent amounts of these in dilute solution be mixed, we have,
H+(aq)+A-(aq)+ B+(aq)+OH-(aq) A-(aq)+ B+(aq)+ H2O(l) ΔH =-13.7 Kcal
Neglecting the ions which appears on both sides, we get

H+(aq) + OH-(aq) H2O(l) ; ΔH =-13.7 Kcal
Thus the heat of neutralization of an acid and a base is merely the heat of
formation of water from hydrogen and hydroxyl ions.
When weak acids or weak bases are neutralized by strong bases or strong acids
respectively, the heat of neutralization differs widely from -13.7 Kcals. In this
case, the heat of neutralization is equal to the heat given out in the union of H + and
OH- ions plus the heat accompanying the dissociation of weak acid or weak base.
The neutralization of NH4OH with HCl, can be represented as:
NH4OH (aq) NH4+ (aq) + OH- (aq) , ΔH= Q Kcal
And, H+ + OH- + Cl- H2O + Cl- , ΔH=-13.7 Kcal
Thus, NH4OH + H+ + Cl- NH4+ + Cl- + H2O, ΔH=Q-13.7 Kcal
Thus, the heat of dissociation of a weak acid or weak base is defined as the
change in enthalpy of the system when one mole of it is dissociated into ions.
5. Calorific values of foods and fules: The calorific value is defined as : the
amount of heat produced in calories (or joules) when one gram of a substance is
completely burnt. It is expressed in cal g- or kJg-1.
Let us compare the calorific values of methane and ethane. Their heat of
combustion is -890.3kJ and -1559.7kJ.
These are expressed as:
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) ΔH = -890.3 kJ
C2H6 (g) + 3 ½ O2 (g) 2CO2 (g) + 3H2O (l) ΔH = -1559.7 kJ
In case of methane heat produced per gram is 890.3/16 = 55.64 kJg -1, while for
ethane it is 1559.7/30 =51.90 kJg-1. [Molecular wt. of CH4 =16]
Thus methane has better fuel efficiency than ethane as it produces more heat per
gram.
 Hess’s Law of constant Heat Summation:
In 1840, G.H Hess stated one of the most important generalizations of thermo
chemistry known after his name as Hess’s law.

The law states that ‘the enthalpy change in a chemical or physical process is
same whether the process is carried out in one step or in several steps.’
If the reaction takes place in more than one step, the enthalpy of the reaction is
equal to the algebraic sum of the enthalpies of various step reactions.
Let us consider a process involving the conversion of reactant A into B in one step
Path II
(Path I). Let the enthalpy change of the process is ΔH. Now the same process is
carried out in two steps involving a change from A to C and C to B (Path II). C
H2
H1
H
A B
PathI
Let ΔH1 and ΔH2 be enthalpy changes from A to C and C to B respectively. Then,
according to Hess’s law
ΔH = ΔH1 + ΔH2
For example: consider the formation of sulphur trioxide from sulphur and oxygen.
There are two ways by which the change can be brought about.
i) By direct combination of sulphur and oxygen.
S(s) + 3/2 O2 (g) SO3 (g) ΔH = -395.3 KJ
ii) By converting sulphur to sulphur dioxide and subsequent oxidation of sulphur

dioxide to sulphur trioxide.
S(s) + O2 (g) SO2 (g); ΔH= -297.4KJ
SO2 (g) + ½ O2 (g) SO3 (g); ΔH=-97.9KJ
These changes may be shown as,
ΔH = ΔH1 + ΔH2 or,-395.3 = -297.4 + (-97.9)= -395.3
Application of Hess’s law:
1. Determination of heat of formation: There are a large number of compounds

such as methane, benzene, carbon monoxide, ethane etc. which cannot be directly

synthesized from their elements. In this case, the heat of formation of substances
can be determined by an indirect method based upon the Hess’s law.
For example: Determination of the heat of formation of carbon monoxide.
i) Formation of CO: C(s) + ½ O2 (g) CO (g); ΔH =?
ii) Combustion of carbon: C(s) + O2(g) CO2(g) ; ΔH=-393.5KJ
iii) Combustion of CO: CO(g) + ½ O2(g) CO2(g) ; ΔH=-283.0KJ
Subtracting equation (iii) from (ii), we have
C(s) + ½ O2 (g) CO (g) ΔH= ΔH1 –ΔH2
= -393.5- (-283.0) = -110.5 KJ
Thus, heat of formation of CO is -110.5 KJ.
2. Determination of bond energies:
Bond Energy: A chemical reaction can be viewed in many cases as a change in

which some bonds are broken and new bonds are formed. When a chemical bond is
formed in a system, the energy of the system becomes lower i.e. energy is
transferred from the system. The bond energy may be defined as the average
amount of energy required to break all bonds of a particular type in one mole of
the substance. Thus, the bond energy of H—H bond is the energy required to break
all the bonds in one mole of the gas. It is expressed in KJ mol-1 or Kcal mol-1 .Bond
energy is a measure of strength of the bond. It depends upon
i) Size of the atom,
ii) Electro negativity
iii) Bond length
The knowledge of bond energy is useful for calculating heats of reaction of

gaseous reactions for which no thermal data is available and which involves
substance having covalent bonds.
For example: Bond energy of the C—H bond in methane can be obtained if the
heat change (ΔH) for the following reaction is known:
CH4 (g) C (g) + 4H (g) ; ΔH= ?

The C—H bond energy is equal to the one-fourth of the ΔH for the above
reaction. The ΔH for the reaction can be calculated indirectly from the following
data.
i) Heat of combustion of methane :
CH4 (g) + 2O2 (g) CO2 (g) +2H2O (l) ΔH1= -891 KJ
ii) Heat of combustion of carbon
C(s) + O2 (g) CO2 (g) ΔH2= -394KJ
iii) Heat of combustion of hydrogen
H2 (g) + ½ O2 (g) H2O (l) ΔH3 = -286KJ
iv) Heat of sublimation of carbon
C(s) C (g) ΔH4 = +717 KJ
v) Heat of dissociation of hydrogen molecule
H2 (g) 2H (g) ΔH5 = +436KJ
From the above equation, heat change for the reaction:
CH4 (g) C (g) + 4H (g)
Can be shown to be equal to
ΔH= ΔH1 – ΔH2 –(2ΔH3) + ΔH4 +2ΔH5
= +1664 KJ
Therefore, the bond energy of C—H bond in methane is,
= + 1664/4 = + 416 KJ
4. Determination of enthalpy of transition: Transition implies the conversion

of one allotropic form of a substance to another.
For example: The change of graphite to diamond, rhombic sulphur to
monoclinic sulphur etc. Such reaction is very slow and enthalpy change
accompanying them cannot be measured directly. However, Hess’s law is
quite helpful in determining the enthalpy of transition. The enthalpy of

allotropic transformation of rhombic sulphur to monoclinic sulphur can be
calculated as follows:
i) Combustion of rhombic sulphur:
S (rhombic) + O2 (g) SO2 (g) ΔH1= -295.1 KJ
ii) Combustion of monoclinic sulphur
S (monoclinic) + O2 (g) SO2 (g) ΔH2 = -296.4 KJ
Subtracting equation (ii) from (i), we have
S(rhombic) –S(monoclinic) 0 ΔH = ΔH1 – ΔH2
=-295.1+296.4
= +1.3 KJ
Thus, enthalpy of transition of rhombic sulphur to monoclinic sulphur is +1.3 KJ.
 Free energy and Work Functions (Helmholtz and Gibbs free energy
Functions:
The sum of the entropy change of the system and surrounding serves as criteria of
spontaneity or feasibility of a process. If the total entropy change is positive, the
process is feasible. If it is zero, the system remains in a state of equilibrium. Thus,
in order to decide about the feasibility of a process the knowledge of entropy
change of the system as well as that of the surrounding is required. But this is not
always convenient.
Therefore, entropy change is considered in terms of other state functions which can
be determined more conveniently. Two such function are work function and free
function represented by ‘A’ and ‘G’ respectively. The work function, A is also
called Helmholtz free energy function. The free energy function, G is also called
Gibbs free energy function.
These functions are defined by the equation:
A = E –TS G = H –TS
As E, H, S depend only on the thermodynamic state, it is evident that the function

‘A’ and ‘G’ also depends upon the state of the system.

 Variation of free energy with temperature and pressure:
We know,
G = H - TS
H = E + PV
G = E + PV - TS ........(1)
Differentiating equation (1), we get
dG = dE + PdV + VdP - TdS - SdT .....(2)
From 1st law and 2nd law of thermodynamics, we get

TdS = dE + PdV ......(3)

dG = TdS + VdP - TdS - SdT
dG = VdP - SdT .....(4)

At constant temperature: dT = 0
dG = VdT .......(5)
dG = V ......(6)
dT T
At pressure kept constant: dP = 0
dG = -SdT
dG
= -S .....(7)
dT P
Let initial free energy G1 and G2 final state when an appreciable change in pressure has
taken place at constant temperature.
p2
G = G2 - G1 =  VdP
p1
nRT
For 'n' mole of ideal gas , V =
P
P2
1 P2 P2
nRT  P = nRT ln = 2.303 nRT log
G = P1 P1
P1

Fugacity and Activity:
It has been pointed that, ΔG= RT log P2 /P1, is applicable only for to ideal gas. In
order to apply this equation to non-ideal system, Lewis introduced two new
thermodynamic quantities, fugacity and activity.
Consider a system composed of liquid water and its vapour. Liquid water
has a tendency to escape into the vapour phase while the vapour tends to escape the
gaseous state and come into the liquid phase by condensation. When the system is
equilibrium, these two escaping tendencies become equal and we observed a
constant vapour pressure at constant temperature.
In general, it may be stated that each substance in a given state has a tendency
to escape from that state and this escaping tendency denoted by ‘f’ is called
fugacity.
It is related to the free energy content (G) by the expression.
G = RT ln f + B
Where B is a constant depending upon the temperature and nature of the substance.
It is not possible to evaluate B since the absolute values of the free energy are not
known.To circumvent this difficulty all free energy measurements for any given
substances are referred to as standard reference point. If we represent by G˚ the
free energy per mole and f˚ the fugacity in this standard state, then G˚ is given by;
G˚ = RT ln f˚ + B
If G is the free energy of the substance in any state, then the free energy difference
between this state and the standard state is given by;
G – G˚ = RT ln f/f˚
or, G = G˚ + RT ln f/f˚
The ratio f/f˚ is called activity and is indicated by the symbol a. the activity of any
substance may therefore, be defined as the ratio of fugacity of the substance in the
substance in the given state to the fugacity of the substance in the standard state.
G = G˚ + RT ln a

In the standard state, G = G˚, since, RT ln a = 0 or, a =1. i.e. in the standard state
the activity of a substance is equal to the unity. In any other state the value of
activity will depends upon the difference (G-G˚). The difference in free energy per
mole caused on passing from one state in which the free energy is G 1 and activity
a1 to another state in which these are G2 and a2 respectively, is given by the
expression;
ΔG = RT ln a2 / a1
For the standard state of any gas at the given temperature, the fugacity is taken as
equal to unity, viz, f˚ = 1 and on the basis of this definition the activity of any gas
becomes equal to fugacity.
a = f / f˚ = f /1 = f
For ideal gas the fugacity is equal to pressure and f / p =1. For a real gas, the
fugacity is not equal to p and the ratio f /p varies. The ratio f / p is called activity
coefficients of a gas and represented by the symbol γ.

Thermodynamics and Thermochemistry

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Thermodynamics and Thermochemistry

Uploaded by

Copyright:

Available Formats

 Thermodynamics and thermochemistry:

Thermodynamic terms and basic concept:

In order to study the laws of thermodynamics, it is essential to understand certain

System, Boundary and Surrounding:

1. System: A system is that part of the universe which is under thermodynamic

3. Surrounding: Region outside the boundaries of any system is termed

Homogeneous system and Heterogenous system:

Homogenous system: When a system is uniform throughout, it is called a

Thermodynamic @ Arjun Bhandari 2015 Page 1

Thermodynamic @ Arjun Bhandari 2015 Page 2

A thermodynamics system is said to be in a certain state when all its

 Extensive and Intensive Properties:

An extensive property of a system is that which depends upon the amount of

An intensive property of a system is that which is independent of the amount

Thermodynamic @ Arjun Bhandari 2015 Page 3

 Equilibrium and Non-equilibrium:

A system is said to be in equilibrium when temperature, pressure, and

If the gas contained in a cylinder, is compressed very rapidly by moving

The criteria for Equilibrium:

2. The mechanical properties must be uniform throughout the system (mechanical

Thermodynamic @ Arjun Bhandari 2015 Page 4

1. Isothermal Processes: Those processes, in which the temperature remains fixed,

For an isothermal process dT = 0

For an adiabatic process dq = 0

For an isobaric process dp = 0

For isochoric processes dV = 0

5. Cyclic Processes: When a system in a given state goes through a number of

For a cyclic process dE = 0, dH = 0

Thermodynamic @ Arjun Bhandari 2015 Page 5

In fact, a reversible process is considered to proceed from the initial state to

a) Reversible Process b) Irreversible Process

Thermodynamic @ Arjun Bhandari 2015 Page 6

1. It takes place in infinite number of 1. It takes place infinite time.

4. It is extremely slow. 4. It proceeds at measureable speed.

5. Work done by a reversible process is greater 5. Work done by a irreversible process is

 Nature of the Heat and Work:

q = heat capacity X difference in temperature

q = C (T2 – T1 ) where C is heat capacity and T1 and T2 are the initial

The heat energy is generally expressed in calorie (Cal.). A calorie is defined as

Thermodynamic @ Arjun Bhandari 2015 Page 7

Sign Convention of Heat: The symbol of heat is ‘q’.

2. Work: Work is the product of force and displacement.

The mechanical work done (W) is given by,

W = pressure X area X length = P x ∆V or P x dV

The work is generally expressed in Joule.

1 Joule = 107 ergs

Sign Convention of Work: The symbol of work is ‘w’.

Every substance is associated with a definite amount of energy which depends

Thermodynamic @ Arjun Bhandari 2015 Page 8

Hence internal energy of a system is a state function.

Suppose, a system is subjected to change of state from A to B. Let E A and EB be

Units of Internal Energy:

 First Law of Thermodynamics:

The first law of thermodynamics is in fact, an application of the broad principle

Mathematical Statement of First Law of Thermodynamics:

Thermodynamic @ Arjun Bhandari 2015 Page 9

Where, q = the amount of heat supplied to the system

W = work done by the system

This equation is a mathematical statement of the first law of thermodynamics. It

Other Definition of First Law of Thermodynamics:

2. Total energy of a system and surrounding remains constant (or conserved) .

3. It is impossible to construct a perpetual motion machine that can produce