CHB-201: Section (B) – Physical Chemistry-I

(Thermodynamics)

The word ‘thermodynamics’ implies flow of heat. It deals with energy changes accompanying
all types of physical and chemical processes.
Limitation of thermodynamics: 1. Laws of thermodynamics are not applicable to small
particles like individual atoms or molecule, but laws can be applied to macroscopic system or
very large system.
2. Thermodynamics does not give information about rate at which a given chemical
reaction/process may proceed and also time for this change.

Basic terms used in thermodynamics

System: Any specified portion of the universe or matter, real or
imaginary, separated from the rest of the universe, which is selected
for the thermodynamic treatment is called a system.
Surroundings: Leaving the system the rest of the universe, which
may exchange matter or energy or both with the system, is called
surroundings.

Types of system
Open system:-A system which can exchange energy as well as matter with its surroundings.
Ex: water in an open beaker.
Closed system: When a system can
exchange only energy and not matter
with its surroundings. Ex: a chemical
reaction taking place in a closed
vessel can exchange only heat with
surrounding
Isolated system: A system which can
neither exchange matter nor energy
with its surrounding.
Ex: The presence of reactants in a thermos flask or any other closed insulated vessel is an
example of an isolated system.
Macroscopic system: A system which consist of a large number of atoms, particles, molecules,
radicals.
Macroscopic properties: Properties of macroscopic system is known as macroscopic properties.
Ex: pressure, temperature, volume, composition, density, viscosity, surface tension, etc. Change
of any macroscopic property changes the state of the system or vice-versa.
State of a system: It is defined by the macroscopic properties. When the macroscopic properties
of a system have specific or definite value it is said that the system is in definite state.
Thermodynamic Equilibrium: If macroscopic properties like temperature, pressure, volume
composition etc. do not change with time.

Types of thermodynamic equilibrium

1. Thermal equilibrium: A system whose temperature do not change along with the
temperature of the surroundings.
2. Mechanical equilibrium: A system which do not perform any mechanical work.
3. Chemical equilibrium: A system whose chemical composition does not change with time
(remains same throughout).

Physical properties of the system

Physical properties of the system are of two types-
1. Extensive property: This property depends on quantity or amount of matter present in the
system. Ex: Mass, volume, energy, no. of moles, enthalpy, entropy etc.
2. Intensive property: This property do not depends on quantity or amount of matter present in
the system. Ex: temperature, pressure, density, viscosity, surface tension and specific heat.
State function: It is the property of the thermodynamic system whose value is definite for a
particular state of the system. When a change is brought about in this particular state of system,
change in state function also occurs. It depends only on initial and final state of the system. Ex:
pressure, temperature, volume, energy are state function.
Path function: When a system passes from one state A to another state B depends on the nature
of the path followed, not on initial and final state. Ex: work done is path function.

Thermodynamic process: If a thermodynamic system

changes from one state to another state the operation is
known as thermodynamic process.
Types of process: 1. Isothermal process: in this process
temperature of the system remains constant throughout the
process i.e. dT=0
2. Adiabatic process: in this process no heat enters or leaves the system during any stage of the
process i.e. dq=0
3. Isobaric process: in this process pressure of the system remains constant throughout the
process i.e. dP=0
4. Isochoric process: in this process volume of the system remains constant throughout the
process i.e. dV=0
Cyclic process or cycles: When a system return to its initial state after completing the process in
various stages, that is system has completed one cycle and process is known as cyclic process.
Reversible process: If a thermodynamic process is carried out infinitesimally slowly so that at
every stage of it, the system in temperature and pressure remains in equilibrium with
surrounding, This type of process is called reversible process.
Irreversible process: If a thermodynamic process is not carried out infinitesimally slowly so
that at every stage of it, the system do not remains in equilibrium with surrounding, this type of
process is called irreversible process.
“A reversible process cannot be realized in practice because it would require infinite time for
its completion. Hence, almost all processes occurring in nature or laboratory are irreversible.”
Signs for heat (q) and work (w):
 q is positive, when heat is transferred from the surroundings to the system.
 q is negative when heat is transferred from system to the surroundings.
 w is positive when work is done on the system.
 w is negative when work is done by the system.

First law of Thermodynamics

First law of thermodynamics states that “Energy can neither be created nor destroyed but can
only be transformed from one form to another.” This law is also known as law of conservation of
energy.
Internal Energy (U): It is sum of all possible types of energy present in the system. It is
impossible to calculate the internal energy (U) of a system. Instead, the change in the U of a
system, ΔU, must be measured.
Let UA be the energy of a system in state A and UB in state B. The
system changes from state A to state B by following path 1, path 2
and path 3. Since, U is the state function, so ΔU depends only on
initial and final state of the system i.e.
ΔU = UB – UA
The change in ΔU of a system is affected by two distinct variables.
These two variables are designated at heat (q), and work (w). Suppose the system while
undergoing change absorbs heat q from the surroundings and also perform some work equal to
w. Hence the change of internal energy ΔU in the above process will given by
ΔU = q + w ------------------------(1)
Equation (1) is the mathematical statement of the first law of thermodynamics.
For isothermal process ΔU = 0, since internal energy (U) of an ideal gas only depends on
temperature.
Case 1: if work is done on the system by the surroundings (as during the compression of gas) w
is taken as positive so that
ΔU = q + w
Case 2: if work is done by the system on surroundings (as during the expansion of gas) w is
taken as negative so that
ΔU = q - w
For infinitesimal change equation (1) can be written as
dU = dq + dw ---------------------(2)

Enthalpy (H): Suppose the change of state of a system is brought at constant pressure. In that
case, there will be change of volume. Let the volume increase from VA to VB, at constant pressure
P. Then, the work done (w) by the system will be given by
w = -P (VB-VA)
Substituting in equation (1)
ΔU = q -P (VB-VA) or UB - UA = q - PVB + PVA or (UB + PVB) – (UA + PVA) = q ------(3)
The quantity U+PV is known as enthalpy. It is equal to the internal energy of the system plus the
product of pressure and volume.
H =U + PV
The equation (3) can be written as
HB-HA = ΔH = q
Enthalpy is equivalent to the total heat content of a system.
Enthalpy is a state function which depends entirely on the state functions T, P and U. Enthalpy is
usually expressed as the change in enthalpy (ΔH) for a process between initial and final states:

ΔH = ΔU + PΔV (Where ΔV is the increase in volume undergone by the system)

For infinitesimal change the above expression can be written as:
dH = dU + PdV
 Variation of heat of reaction with temperature (Kirchhoff’s equation)
Heat Capacity: Heat capacity is defined as the amount of heat (q) required to a given mass to
raise the temperature of the system from the lower to higher temperature divide by the
temperature difference.
If the mass of the system is one gram, the heat capacity is called “specific heat”. If the mass of
the system is one mole then the heat capacity is called “molar heat capacity”. It is denoted by C.
Thus the molar heat capacity of a system between temperature T1 and T2 will be given by
expression
C = q/( T2 –T1)
Since the heat capacity varies with T, hence the C is defined by differential equation
C = dq/dT …………………….(1)
The molar heat capacity of a gaseous system is determined at constant volume and constant
pressure.
Molar Heat capacity at constant volume (Cv): From 1st law of thermodynamics
dU = dq + dw or dU = dq + PdV at constant volume dV = 0
⸫ dU = dq
From the equation C = dq/dT
⸫Cv = (∂U/ ∂T)v
Molar Heat capacity at constant pressure (Cp): At constant pressure, there is a change of
volume and some work is done. Suppose the volume increased is dV and some work is done by
the system is dw.
From 1st law of thermodynamics
dU = dq - dw (⸪ work is done by the system so dw is negative)
or dU = dq - PdV
⸫ dq = dU+PdV
or dq = dH (⸪dH = dU + PdV)

From the equation C = dq/dT

Cp = (∂H/ ∂T)p
 Work done in Reversible Iothermal Expansion of an Ideal gas (Maximum work)
Consider one mole of an ideal gas is enclosed in a cylinder fitted with a weightless, frictionless,
movable piston. Let the pressure of the gas be P which is equal to external atmospheric pressure
P. Let the external pressure be reduced by an
infinitesimally small amount dP and the
corresponding small increase in volume be dV. So
the small work done in the expansion process:
dw = -Pext.dV
⸫ dw = -(P-dP).dV
⸫ dw = -(P.dV –dP.dV)
Since both dP and dV both are small so their product dP.dV is very small and can be neglected in
comparison to P.dV. Then the above equation becomes
dw = -P.dV
When the expansion of gas is carried out reversibly then there will be series of such P.dV terms.
The total maximum work can be obtained by integrating above equation between the limits V1
(initial volume) to V2 (final volume).

w=∫ =-∫

⸪ PV = RT, ⸫P = RT/V

w = -RT∫ = -RT ln = -2.303RT log

for n mole of gas: w = -2.303nRTlog

for an isothermal expansion, Boyle’s law is applicable, Hence P1V1=P2V2 or V2/V1 = P1/P2

w = -2.303nRT log (where P1 and P2 are initial and final pressure, respectively)

 In a reversible isothermal expansion maximum work is obtained because Pext ≈ P

 If, Pext ≠ P, process is not reversible.
 In vacuum, Pext = 0, hence the work done will be zero during expansion.
 Reversible Adiabatic Expansion of an Ideal gas
From first law of thermodynamics,
dU = dq + dw
For adiabatic process dq = 0, and for expansion i.e. work done by the system is -ve
⸫ dU = -dw = -PdV
For ideal gas: dU = CvdT (Cv is molar heat capacity at constant volume)
CvdT = -PdV = -(RT/V)dV (From gas law PV=RT ⸫ P=(RT/V)

= −

Integrating above equation between temperatures T1 and T2 when the corresponding volumes are
V1 and V2.

∫ = − ∫ or ln(T2/T1)= -(R/Cv)ln(V2/V1)

or (T2/T1) = (V1/V2) (R/Cv)

⸪Cp-Cv = R, ⸫ (T2/T1) = (V1/V2)(Cp-Cv /Cv)
(T2/T1) = (V1/V2)(γ-1) (γ = Cp/Cv) and γ >1
or, (T1/T2) = (V2/V1)(γ-1) ……..(1)
Thus, ⸪ V2>V1 and γ >1
⸫ T2 < T1. Hence a gas cools during reversible adiabatic expansion.
For ideal gas (P1V1)/T1 = (P2V2)/T2 or T1/T2= P1V1/ P2V2 ---------(2)
From equation (1) and (2) P1/ P2 = (V2/V1)γ or P1V1γ= P2V2γ
or PVγ= constant (This is ideal gas equation for Reversible Adiabatic Expansion)
For isothermal expansion PV = constant
The two expansions are shown in P-V diagram. The
work done is given by the area under the PV curve. The work
done in isothermal expansion is greater than the work done
in adiabatic expansion.
 Joule-Thomson effect
If the system of a gas at high pressure is allowed to expand by passing thorough a porous plug
into vacuum or region of low pressure under adiabatic conditions the gas cooled. This effect
called Joule-Thomson effect. Only hydrogen and helium gases are exceptions as they get
warmed up under expansion (compressibility factor Z>1).
Joule-Thomson Coefficient for Real gases (Vander Walls gases):

From the equation (92),

Case 1: if > → < = if T is below inversion temperature, μJ.T. is positive. Gas

cools upon expansion.
Case 2: if < → > = if T is above inversion temperature, μJ.T. is negative. Gas
heats upon expansion.

Case 3: if = → = = if T is equal to inversion temperature, μJ.T. is zero. Gas

neither cools nor heats upon expansion (ideal gas).

Conclusions: First, since µJT is positive at low temperatures and negative at high temperatures, it
must have an inversion temperature. Second, the effect seems to depend (as we expected) on the
attractive and repulsive forces acting between molecules. At low temperatures the attractive
forces predominate. At high temperatures the repulsive forces predominate. So the Joule-
Thomson effect can be explained this way: At low temperatures the intermolecular attraction is
the most important interaction. When the gas is expanded, the average distance between
molecules is increased. This means that the molecules are pulled apart. Since they attract each
other this takes energy and since the process is adiabatic, the only source of energy is the internal
energy of the gas itself. So, with the internal energy reduced, the gas cools.
On the other hand, at high enough temperatures the predominant interaction is repulsion.
The gas wants to separate. It wants to expand. When it does expand energy is obtained as the
molecules separate. This increases the internal energy of the gas and the gas heats.

“The limitation of the first law of thermodynamics is that it does not say anything about the
direction of flow of heat. It does not say anything whether the process is a spontaneous process
or not. The reverse process is not possible. In actual practice, the heat doesn't convert completely
into work.” There is thus need for another law, viz., the Second law of thermodynamics.
 Carnot Cycle
Carnot employed a reversible cycle to demonstrate the maximum convertibility of heat into
work. The system consists of one mole of an ideal gas which is subjected to series of four
operations, commonly termed as four strokes.
The Carnot cycle consists of the following four processes:

1. Reversible isothermal expansion at

thermodynamic temperature T1 with heat q1
taken in (curve AB).

2. Reversible adiabatic expansion with a fall

of temperature to T2 (curve BC).

3. Reversible isothermal compression at

temperature T2 with heat q2 given out (curve
CD).

4. Reversible adiabatic compression at

temperature back to T1 (curve DA).

1. Reversible isothermal expansion:

The gas is taken from A (P1,V1,T1) to B (P2,V2,T1). Heat q1 is absorbed from the reservoir at
temperature T1. Since the expansion is isothermal, the total change in internal energy is zero
(ΔU=0) and the heat absorbed by the gas is equal to the work done (w1) by the gas on the
surroundings, which is given as:
From 1st law of thermodynamics
ΔU = q1 + w1 (⸪ΔU=0)

⸫ q1 = -w1 = RT1ln

2. Reversible adiabatic expansion:

The gas expand adiabatically from B (P2,V2,T1) to C (P3,V3,T2). Since the expansion is
adiabatic, the heat absorbed by the gas is equal to zero (q=0). The work done (w2) by the gas on
the surroundings, which is given as:
From 1st law of thermodynamics
ΔU = q + w2 (⸪q=0)
ΔU = w2
ΔU = - w2 (by convention, w is negative because work is done by the system on the surroundings
during expansion)
The internal energy (∆U) of one mole of an ideal gas at temperature T is Cv∆T. This is the
kinetic energy of the molecules, and does not depend on the volume occupied by the gas.
Therefore, the change in internal energy in adiabatic expansion is
∆U = Cv∆T = Cv(T2-T1) = - w2
⸫ -w2 = Cv(T2-T1)

3. Reversible isothermal compression: The gas is compressed isothermally from the state C
(P3,V3,T2) to D (P4,V4,T2). Here, the work done (w3) on the gas by the surroundings is given by:

ΔU = q2 + w3 (⸪ΔU=0 and by convention, w is positive because work is done on the gas by

surroundings during compression, q2 is heat given to the surroundings)

⸫ -q2 = w3 = RT2ln

4. Reversible adiabatic compression: The gas is compressed adiabatically from the state D (P4,
V4, T2) to A (P1, V1, T1). The heat absorbed by the gas is equal to zero (q=0). The work done
(w4) on the gas by surroundings, which is given as:

From 1st law of thermodynamics

ΔU = q + w4 (⸪q=0 and by convention, w is positive because work is done on the gas by
surroundings during compression)
ΔU = w4
∆U = Cv∆T = Cv(T1-T2) = w4
⸫ w4 = Cv(T1-T2 )

The net heat absorbed (q) by the ideal gas in the whole cycle is given by:

q = q1 + (-q2) = RT1ln +RT2ln = RT1ln -RT2ln ………….(1)

Net work done (w) in the whole cycle = (-w1) +(-w2) +w3 +w4

= RT1ln + Cv(T2-T1) + RT2ln + Cv(T1-T2 )

= RT1ln + RT2ln = RT1ln - RT2ln …….(2)

From the equation (1) and (2), q = w. Thus the essential condition for cyclic process that the
net work done is equal to the net heat absorbed is fully satisfied.
A (P1,V1) and B (P2,V2) lies on same isothermal ⸫ P1V1=P2V2 …………….(3)
B (P2,V2) and C (P3,V3) lies on same adiabatic ⸫ P2V2γ= P3V3γ ……….…….(4)
Again C (P3,V3) and D (P4,V4) lies on same isothermal ⸫ P3V3=P4V4 ……….(5)
Finally D (P4, V4) and A (P1, V1) lies on same adiabatic ⸫ P4V4γ= P1V1γ ..….(6)

Multiplying equation (1), (2), (3) and (4)

P1V1* P2V2γ* P3V3* P4V4γ = P2V2* P3V3γ* P4V4* P1V1γ

or, V2γ-1* V4γ-1 = V3γ-1* V1γ-1 → V2V4=V3V1 → =

Now the equation (1) and (2) can be written as:

q = RT1ln -RT2ln = R(T1-T2)ln …..(7)

w = RT1ln - RT2ln = R(T1-T2)ln …..…(8)

Efficiency of a Heat Engine (η): The Efficiency (η) of an engine is the net work done (w) on the
surroundings divided by heat absorbed (q1).

η= = (q1- q2)/ q1=(T1- T2)/ T1……….(9)

η = 1- = 1- ……….(10)

⸪T2<T1
⸫ η<1
It means heat cannot be completely converted in to work.

Question: calculate the maximum efficiency of an engine operating between 110oC and 25oC.

Solution: η = 1- = 1- = 0.222 = 22.2%

Question: Heat supplied to a Carnot engine is 1897.8 kJ. How much useful work can be done by
the engine works between 0oC and 100oC.

Solution: η= = (T1- T2)/ T1 ⸫ w = q1(T1- T2)/ T1

Work done by the engine (w) = 1897.8kJ(373K-273K)/373K = 508.7kJ

 Entropy
From Carnot cycle: 1- = 1-

or = ……(1) or =

is the heat exchanged in a process carried out reversibly at a temperature T.

, represents a definite quantity or state function called “Entropy”. It is shown by ‘S’.

Thus, = S =Entropy

Concept of Entropy: In equation (1) giving +ve sign to heat absorbed (q1) and giving –ve sign
to heat giving out to surroundings. Thus the equation (1) can be written as

=−

or + =0

In a cyclic process carried out reversibly the summation of terms is equal to zero.

Thus in a cyclic process the entropy of system is zero.

Any cyclic process, if carried out reversibly, can be shown to
consist of a series of Carnot cycles. Consider a cyclic process in
which the change from state A to state B and back to state A
(see Fig.) is carried out reversibly. The path ABA may consider
a series of small Carnot cycles. The lines slanting horizontally
stand for an isothermal and slanting vertically stand for
adiabatic processes.
In this cyclic process,

+ + + +……………….. = 0

⸫∑ =0

When the change are infinitesimal ∑ =0

Since the cycle is performed in two steps A→B and B→A

Then ∑ =∫ +∫ =0

⸫∫ = −∫
The quantity ∫ is called entropy and denoted by S. If SA is the entropy in initial stae A and SB
is the entropy in final state B, then change in entropy is given by

∆S = SB- SA= ∫

For infinitesimal small change: dS =

At constant temperature for finite change: ∆S =

Entropy is an extensive property and its unit is J/K.

At constant Volume V1=V2, ⸫ ∆S = nCvln(T2/T1)

At constant pressure P1=P2, ⸫ ∆S = nCpln(T2/T1)

“The Second Law of Thermodynamics states that the state of entropy of the entire universe
will always increase over time. The second law also states that the changes in the entropy in the
universe can never be negative.”
ΔSuniv=ΔSsys+ΔSsurr≥0

Entropy change in spontaneous processes:

ΔSuniv >0 for spontaneous process
ΔSuniv <0 for non-spontaneous process (spontaneous in opposite direction which is impossible)
ΔSuniv =0 for reversible process (system is at equilibrium)

Physical significance of entropy: (1) Entropy is measure of disorder of system. Higher the
disorder of system higher is the entropy. Melting of a solid or evaporation of a liquid always
increases the entropy.
(2) Entropy is measure of probability. Therefore there is a relationship between entropy (S) and
thermodynamic probability (W).
S =k*lnW
A solid at absolute zero considered to be in a most ordered state. In this case W=1 i.e. S =0. The
entropy of crystalline solid at absolute zero (0 K) is zero. This is third law of thermodynamics.
 Free energy and maximum work functions
Work function (A) and the free energy function (G) are given by equatio:
A =U –TS …….(66) and G = H-TS ……………(67)
 The Gibbs-Helmholtz equation
From Maxwell’s relation: dG =-SdT +VdP ….1
At constant pressure dP = 0: ⸫(∂G/∂T)P = -S …………..2
Also ∆G = ∆H-T∆S
or -∆S = (∆G-∆H)/ T ………………3
From equation 2 and 3
(∂G/∂T)P =(∆G-∆H)/ T ⸫ ∆G=∆H+T(∂G/∂T)P ……..4 The equation (4) known as
Gibbs -Helmholtz equation. The Gibbs-Helmholtz Equation is very important because it
relates the change in Gibbs energy to its temperature dependence, and the position of
equilibrium to change in enthalpy.
 Van’t-Hoff equation
The Van't Hoff equation relates the change in the equilibrium constant, Kp, of a chemical
reaction to the change in temperature, T, given the standard enthalpy change, ΔH0, for the
process. From Gibbs -Helmholtz equation,

This is the differential form of the van 't Hoff equation; it's not the most useful thing to us though
because it only tells you the slope of a plot of lnKp against T at one given point. We usually
separate the variables and integrate with respect to both sides:

So, if you know the equilibrium constant Kp1 at a certain temperature T1 and you want to find the
equilibrium constant Kp2 at a different temperature T2, you can just plug in your values into the
equation and solve for Kp2.
Note that this equation supports what you know of Le Chatelier's principle; if the reaction is
exothermic, ΔH∘<0, and if you increase the temperature from T1 to T2>T1 then (1/T1−1/T2)>0.
The RHS of the equation is therefore negative, and that means that ln Kp2<lnKp1⇒ Kp2< Kp1
which implies that the equilibrium position has shifted to the left.

Van’t Hoff equation: The above equation can be written at temperature (T)
∆
lnKp = − +

where c is integrated constant

For an exothermic reaction, heat is released, making the net enthalpy change negative. Thus,
∆
according to the definition of the slope: slope =−

∆
For an exothermic reaction, ΔH0 < 0 (and the gas constant R > 0), so slope = − >0

Thus, for an exothermic reaction, the van 't Hoff plot should always have a positive slope.

For an endothermic reaction, heat is absorbed, making the net enthalpy change positive. Thus,
∆
according to the definition of the slope: slope =−

For an endothermic reaction, ΔH0 > 0

(and the gas constant R > 0), so

∆
slope = − <0

Thus, for an endothermic reaction, the

van 't Hoff plot should always have a
negative slope.