Subject Chemistry

Paper No and Title 10, Physical Chemistry- III (Classical Thermodynamics,

Non-Equilibrium Thermodynamics, Surface chemistry, Fast
kinetics)
Module No and Title 4, Isothermal and Adiabatic expansion

Module Tag CHE_P10_M4

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 TABLE OF CONTENTS

1. Learning Outcomes
2. Expansion of ideal gas
3. Isothermal expansion
3.1 Work done in reversible isothermal expansion
3.2 Work done in Reversible Isothermal Compression
3.3 Work done in Irreversible Isothermal Expansion
4. Adiabatic expansion
4.1 Final temperatures in reversible and irreversible adiabatic expansion
4.1.1. Reversible adiabatic expansion
4.1.2. Irreversible adiabatic expansion
5. Reversible isothermal expansion of real gas
5.1 Work of expansion, w
5.2 Internal energy change, U
5.3 Enthalpy change, H
5.4 Heat change, q
6. Comparison of work of expansion of an ideal gas and van der Waal gas
7. Summary

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 1. Learning Outcomes

After studying this module you shall be able to:

 Know about the effect of expansion on the thermodynamic properties like work done (w),
change in internal energy (ΔU), enthalpy change (ΔH) etc.
 Differentiate between the work done in isothermal expansion and isothermal compression.
 Know about the dependency of thermodynamic quantities q, w, H on temperature in the
case of adiabatic expansion.
 Differentiate the change in enthalpy in the case of real gas and ideal gas.

2. Expansion of ideal gas

From the first law of thermodynamics we can calculate the possible changes in
thermodynamic properties such as q, w, ΔU and ΔH when expansion occurs in ideal gas. The
expansion may be isothermal or adiabatic and expansion can be reversible or irreversible.

3. Isothermal expansion

Calculation of ΔU
In isothermal expansion, the temperature of the system does not vary. The internal energy U
of an ideal gas is the function of temperature, so at constant temperature (isothermal process)
the internal energy of the system remains constant. Therefore, ΔU=0.
Calculation of ΔH
Thermodynamically, H=U+PV …(1)
Therefore, ΔH=Δ(U+PV)
= ΔU+ΔPV = ΔU+Δ n RT (from ideal gas equation) …(2)
But in isothermal process, ΔT=0 and ΔU=0, therefore ΔH=0
Calculation of q and w
From the first law of thermodynamics we derived that ΔU= q + w. Since in isothermal process
ΔU = 0, hence w= -q. This shows that by absorption of heat the work is done by the system in
isothermal expansion.

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 3.1 Work done in reversible isothermal expansion
Consider a system in which gas is enclosed in a cylinder with frictionless and weightless
piston. The temperature of the system remains constant since system is supposed to be in
thermal equilibrium with the surroundings. The external pressure P on the piston is equal to the
pressure of the gas within the cylinder. The expansion of the gas occurs and the volume of the
gas changes from V to V+dV when the external pressure of the gas is lowered by infinitesimal
amount dP to become P-dP. Because of expansion, the pressure of the gas becomes equal to
the external pressure. The piston then comes to rest. Further if the process is repeated and the
external pressure is lowered by infinitesimal amount dP then the gas will undergo second
infinitesimal expansion dV before the pressure again equals to new external pressure.
Continuing the process, the external pressure will further be lowered which results in increase
of volume dV each time. Since the system is in thermal equilibrium with the surroundings, the
infinitesimally small cooling produced as a result of infinitesimally small expansion of the gas
at each step, is offset by the heat absorbed from the surroundings and the temperature remains
constant throughout the operation. During expansion, pressure decreases and the volume
increases. Thus the work done by the gas for the small volume change in an infinitesimal
expansion is given by :
dw = – (P – dP)dV = – PdV …(3)
Since the product dPdV is very small quantity therefore ignored. The total work done w by the
gas in expanding from volume V1 to the volume V2 will be the sum of the series of the terms
PdV in which pressure keeps on decreasing and is given by
V2
w
 V1 P dV …(4)

Substituting P = RT/V in the above expression for one mole of an ideal gas thus giving,
V2
 V1
dV V
w   RT   RT ln 2 …(5)
V V1

At constant temperature, P1V1  P2 V2 for the case of ideal gas, thus work done can also be
written as
w   RT ln (P1 / P2 ) …(6)

For n moles of the gas, the work done can be written as:
𝑃1
w   nRT ln (V2 / V1)   nRT ln (P1 / P2 ) =−2.303 𝑛𝑅𝑇 𝑙𝑜𝑔 …(7)
𝑃2

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 As V2 is greater than V1 in case of expansion and P2 is less than P1 thus in above equation work
done will always be negative.
The expansion of a given amount (n mole) of gas results into decrease in the moles per unit
volume. Therefore equation (5) can be modified to represent the work done when an ideal
solution is diluted from initial concentration c1 to a final concentration c2.
𝑛𝑖 𝑐
Since 𝑐𝑖 = therefore, 𝑤 = −𝑛𝑅𝑇 𝑙𝑛 𝑐1
𝑉 2

3.2 Work done in Reversible Isothermal Compression

Now suppose gas is compressed reversibly from volume V2 to V1. In this case, the external
pressure will be greater than pressure inside the cylinder by an infinitesimal amount dP. Thus
external pressure will be P+dP. Let the gas is compressed by an infinitesimal amount, say dV.
The two parameters pressure and volume are of opposite signs as during compression the
pressure increases and the volume decreases. Now the expression for the infinitesimal amount
of work done on the system by the surroundings is
dw   (P  dP) dV   PdV …(8)

Here the term dPdV is small quantity therefore it is ignored.

Let the gas is compressed from volume V2 to V1, then the work done (w’) by the surroundings
on the gas is given by:
V1
w  
 V2 P dV
Taking the gas to be ideal, thus substituting P= RT/ V and P1V1  P2 V2 in the above expression
we get,
V1
 V2
dV
w    RT   RT ln (V1 / V2 ) = RT ln (P2 / P1 ) …(9)
V

For n moles of the gas, the work done is given by:

w   nRT ln (V1 / V2 )   nRT ln (P2 / P1) …(10)

Since during compression the initial volume V2 > V1 and P2 < P1 thus w’ will always be
positive.

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 3.3 Work done in Irreversible Isothermal Expansion
In this section two types of irreversible isothermal expansion will be discussed
These are: expansion against zero pressure i.e. in vacuum(called free expansion) and expansion
against constant external pressure which should be less than the pressure of the gas i.e. Pext <
P (called intermediate expansion)

 Free expansion
In free expansion the external pressure is zero, therefore the work done is given by
w  
 dw    P
ext
dV  0 …(11)

 Intermediate expansion
Let the volume expands from V1 to V2 against an external pressure Pext then the work done will
be
V2
w  
 V1 Pext dV   Pext (V2  V1 ) …(12)

The work done during intermediate isothermal expansion is less than the work done during
reversible isothermal expansion since Pext is less than P in the case of intermediate isothermal
expansion while Pext is almost equal to P in the case of reversible isothermal expansion.
The work done by the gas during expansion is (-w),
𝑛𝑅𝑇 𝑛𝑅𝑇
Therefore, −𝑤 = 𝑃𝑒𝑥𝑡 ( − )
𝑃2 𝑃1
𝑃
−𝑤 = 𝑛𝑅𝑇 (1 − 𝑃2 ) (if P2 ≈ Pext)
1

4. Adiabatic expansion

In adiabatic expansion no heat is transferred between the system and the surroundings i.e. q=0
Thus equation for first law of thermodynamics becomes
U  0  w or w  U …(13)

Since in expansion, work is done by the system so w will be negative. Thus U will also be
negative. Due to the decrease in internal energy the temperature of the system also decreases.
This states that work is done at the expense of internal energy of the gas. While in compression
w is positive therefore U will be positive which consequently increases the temperature of the
system. This states that the work is stored in the system in the form of rise in internal energy.

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 Calculation of U .
At constant volume the molar heat capacity for an ideal gas is given by:
CV  (U / T)V …(14)

Accordingly finite change in internal energy will be

U  CVdT …(15)

Calculation of H
From classical thermodynamics, enthalpy is given by
H = U + PV
So, change in enthalpy for one mole of the gas is
H  U  (PV)  U  RT …(16)

Substituting the value of U , we get

H  CV T  RT  (CV  R) T = CP T …(17)

Calculation of w
In adiabatic process q=0, thus from the first law equation U = q + w, the work done will be
given by:
w  U  CV T

Thus from the above equations we can say that all the three quantities U , H and w are
dependent on temperature. Since the variation in temperature depends upon the nature of the
process i.e. whether the process is reversible or irreversible, thus the magnitude of
thermodynamic properties will also vary with the nature of the process.
4.1 Final Temperatures in Reversible and Irreversible Adiabatic Expansions
4.1.1 Reversible Adiabatic Expansion. The final temperature in the case of reversible
adiabatic expansion is obtained from the expressions which relate the initial and final
temperatures to the respective volumes or pressures.
Relation between Temperature and Volume. Let the expansion is done against the external
pressure P and V be the increase in volume. Then, the external work done by the system is
equal to – P V . Hence, according to the First law equation,
U = – P V …(18)
CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 Let the fall in temperature be T and U = CV T

Therefore, CV T = – PdV ...(19)

For infinitesimally small quantities,

CV dT   PdV   RT dV / V (for 1 mole of the gas)

Dividing the above equation by T

CV dT / T   R dV / V

Or CV d(ln T)   R d(ln V)
𝐶𝑣
Or 𝑑(ln 𝑇) = −𝑑(ln 𝑉) ...(20)
𝑅

Integrating the above equation between the limits of temperatures T1 and T2 with the
corresponding volumes V1 and V2 then we get,
CV ln (T2 / T1)   R ln (V2 / V1)  R ln (V1 / V2 ) ...(21)

or ln (T2 / T1)  (R / CV ) ln (V1 / V2 )

Since, CP  CV  R and substituting CP / CV   , we get

𝑇 𝐶𝑣 𝑉
𝑙𝑛 (𝑇2 ) = = 𝑙𝑛 (𝑉1 ) (for one mole)
1 𝑅 2

𝑛𝑅 𝑅
𝑉 𝐶 𝑉 𝐶
𝑇2 = 𝑇1 (𝑉1 ) 𝑣 = 𝑇1 (𝑉1 ) 𝑣,𝑚
2 2

𝑉 𝛾−1
𝑇2 = 𝑇1 (𝑉1 ) …(22)
2

or T1 / T2  (V2 / V1)   1 (Note that  > 1)

Since in the case of expansion V2  V1and T2  T1 . Hence, a gas cools during reversible
adiabatic expansion.
4.1.2 Irreversible Adiabatic Expansion.
In this section, two cases are considered:

 Free Expansion.
In the case of free expansion the external pressure is zero, thus the work done in this expansion
is also zero. Therefore, U which is equal to w, is also zero. In the case of ideal gas, the change
CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 in the internal energy is function of temperature thus accordingly if U is zero then T is also
zero. The change in enthalpy is given by H = U + nR T , as U and T are zero therefore
H is also zero. Thus, in a free adiabatic expansion, T = 0, w = 0 and H = 0.
 Intermediate Expansion.

Let the gas expands from the volume V1 to V2 against a constant pressure P Ext of the gas. Then
the work done in this case will be:

w   PExt (V2  V1) ...(23)

In adiabatic expansion q=0, therefore from first law equation i.e. U = q + w

Thus w  U

Further, w  U  CV (T2  T1) ...(24)

From Equations (23) and (24),

PExt (V1  V2 )   C V (T2  T1)

or C V (T1  T2 )  PExt (V1  V2 )  PExt (RT1 / P1  RT2 / P2 )

= RPExt (T1P2  T2P1) / P1P2 …(25)

Thus, T2 can be calculated from the values of CV , T1, P1, P2 and P Ext .

Since the external pressure is constant, work of expansion is given by:

𝑉2
𝑛𝑅𝑇2 𝑛𝑅𝑇1
−𝑤𝑖𝑟𝑟 = ∫ 𝑃𝐸𝑥𝑡 𝑑𝑉 = 𝑃𝐸𝑥𝑡 (𝑉2 − 𝑉1 ) = 𝑃𝐸𝑥𝑡 ( − )
𝑉1 𝑃2 𝑃1

5. Reversible Isothermal expansion of a Vander Waal’s gas

Now finding the expressions for w, U , H and q for reversible isothermal expansion of a
real gas
5.1 Work of expansion, w.
It is already stated that in the expansion of the gas the work done is given by:
– dw = PdV.
Which can be written as

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 V2
w 
 V1 PdV …(26)

Since, the van der Waals gas equation is

 an 2 
 P  2  (V  nb)  nRT …(27)
 V 


Rearranging the above equation to get the expression for pressure, we get:

nRT an 2
P   …(28)
V  nb V2

Substituting equation ( 28) in (26), we get

V2  an 2  V2 V2 an 2
   V1
nRT nRT
w     dV  dV  dV
V1  V  nb V 2  V1 V  nb V2

 V  nb  2 1 1
w  nRT ln  2   an    …(29)
 V1  nb   V2 V1 

5.2 Internal Energy Change, U

Energy is the function of temperature and volume and it can be represented as:
E = E (T, V)
Taking the differential form:
𝜕𝐸 𝜕𝐸
𝑑𝐸 = (𝜕𝑇 ) 𝑑𝑇 + (𝜕𝑉) 𝑑𝑉
𝑉 𝑇

In the form of heat capacity, the above equation can be written as:
𝜕𝐸
= 𝐶𝑉 𝑑𝑇 + (𝜕𝑉) 𝑑𝑉
𝑇

For isothermal change, dT = 0

𝜕𝐸
Therefore, 𝑑𝐸 = (𝜕𝑉) 𝑑𝑉
𝑇

𝜕𝐸
(𝜕𝑉) is called internal pressure for Vander Waals gas and is given by:
𝑇

𝜕𝐸 𝑎𝑛2
(𝜕𝑉) =
𝑇 𝑉2

The internal pressure is also given by (U / V)T . Therefore,

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 (U / V)T  an 2 / V2

Rearranging the above equation, change in internal energy at constant temperature will be
dU  an 2 (dV / V2 )

Integrating the above equation, the change in internal energy will be:
V2  1 1 
  V1 an
2 dV
dU  U2  U1  U    an 2    …(30)
2
V  V2 V1 

5.3 Enthalpy Change, H

The enthalpy is given by , H = U + PV
Let at initial state the enthalpy of the gas is
H1  U1  P1V1 …(31)

The enthalpy at final state is

H2  U2  P2 V2 …(32)

So the change in enthalpy is given by:

H  H2  H1  (U2  P2 V2 )  (U1  P1V1 )

(U2  U1 )  (P2V2  P1V1)  U  (P2V2  P1V1) …(33)

Now considering the equation for van der Waals gas i.e.

nRT an 2
P  
V  nb V2

Multiplying both sides of the above equation by V:

nRTV an 2
PV  
V  nb V

Now substituting this expression of PV in the form of P2V2 and P1V1 in equation (33), we get

 V2 V1  2 1 1 
H  U  nRT     an    …(34)
 V2  nb V1  nb   V1 V2 

V2 V1
Solving for  we obtain
V2  nb V1  nb

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 V (V  nb)  V1 (V2  nb)
 2 1
(V2  nb) (V1  nb)

nb (V1  V2 ) nb nb
  …(35)
(V2  nb) (V1  nb) V2  nb V1  nb

Substituting equation (35) in equation (34)

 nb nb  2 1 1 
H  U  nRT     an   
 V2  nb V1  nb   V1 V2 

Now substituting the expression for U from equation (30), we get

 1 1  2 1 1
H  n 2 bRT     2an    …(36)
 V2  nb V1  nb   V2 V1 

5.4 Heat Change, q

From the first law of thermodynamics we can find the expression for q i.e.
q = U – w
1 1
Since, ∆𝑈 = −𝑎𝑛2 (𝑉 − 𝑉 )
2 1

Now substituting the expressions for w and U obtained from equation (29) and (30) we finally
get
𝑉 −𝑛𝑏 1 1
−𝑤 = 𝑛𝑅𝑇 𝑙𝑛 (𝑉2 −𝑛𝑏) + 𝑎𝑛2 (𝑉 − 𝑉 )
1 2 1

 V  nb 
q  nRT ln  2 
 V1  nb 

6. Comparison of work of expansion of an Ideal gas and non-ideal gas

The work done in expansion of ideal gas is given by:

- wideal  nRT ln (V2 / V1)

While that for van der Waals gas the work done is

 V2  nb  2 1 1
- w vdw  nRT ln    an    …(37)
 V1  nb   V2 V1 

If V>> nb , the equation (37) becomes

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
  V2  2 1 1
- w vdw  nRT ln    an    …(37.1)
 V1   V2 V1 

Now subtracting equation (37.1) from equation (37) we get

 1 1 an 2 (V2  V1 )
-  w ideal  ( w vdw )   an 2     …(38)
 V2 V1  V1V2

Since in expansion, final volume V2 is greater than the initial volume V1 therefore using
this in equation (38) we conclude that the reversible work done in the case of ideal gas is greater
than that for van der Waal gas. This can also be explained physically. An ideal gas has no
intermolecular forces whereas a real (van der Waals) gas has considerable intermolecular
forces. Thus, in an ideal gas, the heat supplied is fully utilized in doing the work of expansion
whereas in a real gas, a part of the heat supplied is used in overcoming the intermolecular forces
of attraction and the balance amount of heat is utilized in doing the work of expansion.
Consequently, the work done in the expansion of an ideal gas is numerically greater than the
work done in the expansion of a real gas.
Exercise
Question 1: One mole of benzene is converted reversibly into vapour at its boiling point 80.2ºC
by supplying heat. The vapour expands against the pressure of 1 atm. The heat of vaporization
of benzene is 395 J g-1. Calculate q, w, ΔE and ΔH for the process.
Solution: The process is
𝐶6 𝐻6 (𝑙𝑖𝑞) 𝐶6 𝐻6 (𝑣𝑎𝑝𝑜𝑢𝑟)
Heat supplied for conversion of 1 mole of benzene into its vapour.
q = Heat of Vapourization per g * molecular weight of benzene
q = (395 J g-1)*(78 g mol-1)
q = 30810 J mol-1
Work done will be:
-w = PΔV
= P ( Vf – Vi) = P Vf = RT (Vf >> Vi)
T= 273 + 80.2 = 353.2 K
-w = 8.314 * 353.2 = 2936.5 J mol-1

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 ΔE = q + w (First law)
= 30810 – 2936.5
= 27873.5 J mol-1
ΔH = ΔE + PΔV = qp = 30810 J mol-1
Question 2: One mole of gas is allowed to expand isothermally and reversibly from a volume
of 1 dm3 to 50 dm3 at 273 K. Calculate w, q, ΔE assuming ideal gas behavior and Vander
Walls behavior (given a = 6.5 atm dm6 mol-2, b = 0.056 dm3 mol-1 and R=0.082 atm dm-3 K-1
mol-1
Solution
(i) Ideal gas
𝑉
−𝑤 = 2.303 ∗ 𝑅𝑇 ∗ 𝑙𝑜𝑔 𝑉2
1

50
−𝑤 = 2.303 ∗ (0.082 ∗ 273) 𝑙𝑜𝑔 ( 1 )

−𝑤 = 87.6 𝑎𝑡𝑚 𝑑𝑚3 𝑚𝑜𝑙 −1

−𝑤 = 8876 𝐽
For isothermal expansion of an ideal gas
ΔE = 0
Therefore, ΔE = q + w
Will give, -w = q = 8876 J mol-1
(ii) Vander Waals gas
𝑉 −𝑛𝑏 1 1
−𝑤 = 2.303 ∗ 𝑅𝑇 ∗ 𝑙𝑜𝑔 (𝑉2 −𝑛𝑏) + 𝑎𝑛2 (𝑉 − 𝑉 )
1 2 1

−𝑤 = 8352 𝐽𝑚𝑜𝑙 −1
1 1
∆𝐸 = −𝑎 (𝑉 − 𝑉 )
2 1

1 1
= −(6.5) (50 − 1) = 645.4 𝐽𝑚𝑜𝑙 −1

𝑞 = ∆𝐸 − 𝑤
= 8997.6 𝐽𝑚𝑜𝑙 −1

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion
 7. Summary

 Work done by an ideal gas in the case of isothermal expansion is

w   nRT ln (V2 / V1)   nRT ln (P1 / P2 )

While in the case of isothermal compression is

w   nRT ln (V1 / V2 )   nRT ln (P2 / P1)

 The relation between temperature and respective volume in reversible adiabatic

expansion is given by
T1 / T2  (V2 / V1)   1
 Comparing the change in thermodynamic quantities in the case of ideal gas and real gas,
we get
Work done
V2
 V1
dV V2
w   RT   RT ln - ideal gas
V V1

 V  nb  2 1 1
w  nRT ln  2   an    - real gas
 V1  nb   V2 V1 

Heat change, q
q = -w
V2

dV V2
Thus, q  RT   RT ln - ideal gas
V1 V V1

 V  nb 
q  nRT ln  2  - real gas
 V1  nb 

Enthalpy change , ΔH
ΔH=0 - ideal gas

 1 1  2 1 1
H  n 2 bRT     2an    - real gas
 V2  nb V1  nb   V2 V1 

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 4: Isothermal and Adiabatic expansion