C H E M I S T R Y

THERMODYNAMICS
WHO WORKS MORE?

What you already know What you will learn

• Molar heat capacity • Isothermal expansion or compression

• Specific heat capacity • Adiabatic expansion or compression
• Relationship between CP and CV • Reversible adiabatic process
• Adiabatic index • Irreversible adiabatic process
• Work done in adiabatic process
• P-V plot

NEET BOARDS
Isothermal Expansion or Compression

In an isothermal expansion or compression process, the temperature of the system remains

constant throughout the process.

Isothermal expansion Isothermal compression

Fig. 1: Isothermal processes: expansion and compression
Change in internal energy (ΔU) of an ideal gas can be given as follows:

ΔU = CV ΔT

Where,
CV = Heat capacity at constant volume
ΔT = Change in temperature
Or
qV = CV ΔT

© 2020, BYJU'S. All rights reserved

 02

Where, qV = Heat at constant volume

Similarly,

ΔH = CP ΔT

Where,
ΔH = Change in enthalpy
CP = Heat capacity at constant pressure
For an isothermal process, the change in temperature, ΔT = 0
Therefore, for a isothermal reversible or an irreversible expansion or compression of an ideal gas,
the value of ΔU and ΔH is zero.
∴ ΔU = ΔH = 0
According to the first law of thermodynamics,
ΔU = q + W
Since for an isothermal process ΔU = 0, we get,
q = −W
The magnitudes of q and W depend on the manner in which the process of expansion or
compression is carried out, i.e., whether it is carried reversibly or irreversibly.

NEET BOARDS
Adiabatic Expansion or Compression

For a small change, the first law of thermodynamics can be written as,
dU = dq + dW ... (1)
In an adiabatic process, no heat is allowed to enter or leave the system.
Hence, dq = 0

Adiabatic expansion Adiabatic compression

Fig. 2: Adiabatic processes: Expansion and compression
Putting the value of dq in equation (1), we get,
dU = dW
Change in internal energy (dU) can be given as,
dU = CVdT
So, dW = CVdT ... (2)
Total heat capacity = n × Molar heat capacity

© 2020, BYJU'S. All rights reserved

 03

C = n × Cm ... (3)
Where, ‘n’ is the number of moles.
For constant volume, equation (3) can be written as,
CV = n × CV, m ... (4)
Substituting the value of CV from equation (4) in equation (2), we get,
dW = nCV, mdT ... (5)
We know, dW = −PextdV ... (6)
From equations (5) and (6), we get,

nCV, mdT = −PextdV

Reversible Adiabatic Process

Corresponding to reversible adiabatic process equilibrium is established at each step of the

adiabatic process. For infinitesimally small quantities,
dU = dW = nCV, mdT ... (1) We know,
For an ideal gas, PV = nRT 1
∫ dx =
ln x
For n moles of an ideal gas, pressure can be x
written as, V
− R ln V  V2 =
T
C V, m ln T T2
1 1
nRT
P= ... (2)
V − R ln V2 − ln V
=  C V, m ln T2 − ln T1 
1
When the increase in the amount of external
pressure at each infinitesimal step is almost We know,
negligible, x
ln x − ln y =
ln
Pext ≈ Pint y
Work done can be written as,  V   T 
dW = −P dV ... (3) − R ln 2  =
C V, m ln 2 
 V1   T1 
From equations (1) and (3), we get
We know that from the properties of logarithm,
−P dV = nCV, mdT
x y
Substituting the value of P from equation (2), we − ln =
ln
y x
get,
nRT  V   T 
− dV =n C V, mdT R ln 1  = C V, m ln 2 
V  V2   T1 
nR n C V, m
− dV = dT R  V1   T2 
V T ln  = ln  … (4)
C V, m  V2   T1 
dV dT
−R =
C V, m We know, CP, m − CV, m = R
V T
Substituting the value of R in equation (4), we
Integrating both the sides of the equation, we get,
get,
CP, m − C V, m  V1   T2 
− R∫
V2 dV
C V, m ∫
=
T2 dT
ln  = ln 
C V, m  V2   T1 
V1 V T1 T

© 2020, BYJU'S. All rights reserved

 04

 CP, m C V, m   V1   T2  Therefore, equation (5) can be written as,

 −  ln = ln
 C V, m C V, m   V2   T1    V ( γ − 1)   T 
  ln  1   = ln 2 
  V2    T1 
 CP, m   V   T2 
 − 1  ln 1  =ln
 C V, m   V2   T1  We know,
 
ln x = ln y
We know , x=y
CP, m (γ − 1)
= γ  V1  T2
C V, m   =
 V2  T1
 V1   T2 
( γ − 1) ln  =ln  ... (5) Rearranging the above equation, we get,
 V2   T1 
T1 V1(
γ − 1)
= T2 V2(
γ − 1)
... (6)
We know that from the properties of the
Equation (6) can be written as,
logarithm,
γ−1
xln y = ln y x TV = Constant

Reversible adiabatic process in terms of pressure (P) and volume (V)

From the ideal gas equation, PV = nRT,  P1  ( γ − 1 + 1)  P2  ( γ − 1 + 1)

  V1 =   V2
PV  nR   nR 
T=
nR
 P1  γ  P2  γ
Substituting the values of T1 and T2 in equation   V1 =   V2
 nR   nR 
(6), we get,
γ γ
 P1 V1  ( γ − 1)  P2 V2  ( γ − 1) P1 V1 = P2 V2 … (7)
 nR  V1 =  V2
   nR  For an adiabatic process,
 P1  ( γ − 1) P 
=  2  V2 ⋅ V2( )
γ −1
  V1 ⋅ V1 PVγ = Constant
 nR   nR 

Reversible adiabatic process in terms of pressure (P) and temperature (T)

From the ideal gas equation, PV = nRT, P1 γ P2 γ

γ ( nRT1 ) = γ ( nRT2 )
nRT P1 P2
V=
P 1−γ 1−γ
(P1 ) T1 = (P2 )
γ
T2
γ
... (8)
nRT1 nRT2
=V1 = , V2 Equation (8) can be written as,
P1 P2
γ γ
Substituting the values of V1 and V2 in equation P1 − T = Constant
(7), we get,
γ γ
 nRT1   nRT2 
P1   = P2  
 P1   P2 

© 2020, BYJU'S. All rights reserved

 05

For an adiabatic process,

PVγ = Constant

γ−1
TV = Constant

γ γ
P1 − T = Constant

Irreversible Adiabatic Process

Let's consider an irreversible adiabatic process, −Pext(V2 − V1) = nCV, m(T2 − T1)
where, the external pressure is constant, i.e., P (V − V ) = nC (T − T ) … (4)
ext 1 2 V, m 2 1
Pext = Constant.
From the ideal gas equation, PV = nRT,
According to the first law of thermodynamics,
ΔU = q + W nRT
V=
P
In an adiabatic process, no heat is allowed to
enter or leave the system. Thus, q = 0 nRT1 nRT2
= V1 = , V2
W = ΔU = nC ΔT … (1) P1 P2
V, m

W = −PextΔV … (2) Substituting the values of V1 and V2 in equation

(4), we get,
From equations (1) and (2), we get,
−Pext ΔV = nCV, mΔT … (3)  nRT1 nRT2 
The change in the volume, ΔV = V2 − V1 nC V, m ( T2 −
= T1 ) Pext  − 
 P1 P2 
The change in the temperature, ΔT = T2 − T1
Substituting the values of ΔV and ΔT in equation
(3), we get,

Note

Once the adiabatic process is complete the value of final pressure or P2 in the above equation will
be equal to external pressure.

Work Done in an Adiabatic Process

T P −T P 
C V, m ( T2 − T1 ) =
PextR  1 2 2 1 
 P1 P2 
In an adiabatic process, no heat is allowed to enter or leave the system. Thus, q = 0.
According to the first law of thermodynamics,

ΔU = q + W ⇒ ΔU = Wadi

© 2020, BYJU'S. All rights reserved

 06

Note

1. If work is done on the system, the sign of W is positive.

2. If work is done by the system, the sign of W is negative.

In the Fig. 3, the gas in a thermally

insulated container is compressed i.e.,
adiabatic compression, and therefore
no heat exchange is possible.
So, q = 0
Work is done on the system to change
its internal energy and therefore, the
temperature increases.
Fig. 3: Adiabatic compression
When the work is done on the system, the sign of work (W) is positive, so the sign of change in
internal energy (ΔU) is also positive. Therefore, the final energy of the system increases. As a
result of the increase in the final energy, the kinetic energy of the molecules increases. So, the
thermal energy of the system also increases. In the process of adiabatic compression, i.e., in the
process of work being done on the system (gas), the temperature of the gas increases.
ΔU > 0 ⇒ Uf − Ui > 0 ⇒ Uf > Ui

Work done on an Temperature of the

adiabatic system system ↑

q=0 ΔU = W W = ΔU ⇒ +ve T↑

In the Fig. 4, the gas in a thermally insulated

container is expanded, i.e., adiabatic
expansion, and therefore no heat exchange is
possible.
So, q = 0
Work is done by the system to change its
internal energy and therefore, the temperature
decreases.
Fig. 4: Adiabatic expansion
When the work is done by the system, the sign of work (W) is negative, so the sign of change in
internal energy (ΔU) is also negative. Therefore, the final energy of the system decreases. As a
result of the decrease in the final energy, the kinetic energy of the molecules decreases. So, the
thermal energy of the system also decreases. In the process of the adiabatic expansion, i.e., the
process of work being done by the system (gas), the temperature of the gas decreases.
ΔU < 0 ⇒ Uf − Ui < 0 ⇒ Uf < Ui

© 2020, BYJU'S. All rights reserved

 07

Work done by an Temperature of the

adiabatic system system ↓

q=0 ΔU = W W = ΔU ⇒ −ve T↓

Comparing Slopes of P-V plot in Adiabatic and Isothermal Process

For an isothermal process

PV = Constant PdV + VdP = 0

Differentiating both the sides, we get, VdP = − PdV
d(PV) = d(constant)

dP P
= −
dV V
Where,
dP Pγ
== Slope
− of the pressure (P)-volume (V) curve.
dV V
In the case of an isothermal reversible process,

dP P
Slope of the curve == − ... (1)
dV V

For an adiabatic process

PVγ = Constant
dP Pγ
d(PVγ) = d(constant) = −
dV V
Pd(Vγ) + Vγ(dP) = 0
We know, Where,
d n dP Pγ
x = nx n − 1 == Slope
− of the pressure (P)-volume (V) curve.
dx dV V
P (γ Vγ − 1 dV) + Vγ dP = 0 In the case of an adiabatic reversible process,
P (γ V γ −1
dV) = − V dP γ

P
dP P γ V
−1 γ
Slope of the curve = − γ … (2)
= γ
V
dV −V
dP From equations (1) and (2), we get,
= − P γ ( V − 1 .V − )
γ γ

dV The slope of the P-V curve in an adiabatic

process = γ × (The slope of the P-V curve in an
dP
= − P γ (V − 1 − )
γ γ
isothermal process)
dV
The slope of the adiabatic P-V curve is steeper
dP than the slope of the isothermal P-V curve.
= − P γ V −1
dV

© 2020, BYJU'S. All rights reserved

 08

Note

Adiabatic Isothermal

PVγ = Constant PV = Constant

On differentiating, On differentiating,
P × γ Vγ − 1 dV + Vγ dP = 0 PdV + VdP = 0

dP P dP P
= −γ = −
dV V dV V

For an ideal gas, γ > 1 Table 1: Comparison of work in isothermal and

adiabatic processes

P-V Plot

A C
Adiabatic curve
In the Fig. 5, the P-V curve for adiabatic and isothermal
processes are shown. The steeper curve (in red
colour) represents the adiabatic process and the
Pressure

other one (in green colour) represents the isothermal Isothermal

process. For the same decrease in volume, more curve
pressure has to be applied in the case of an adiabatic
process as compared to that of an isothermal process. B
To understand whether the adiabatic work done or
D
the isothermal work done is more, we need to know
the process as well, i.e., compression or expansion. Volume
Fig. 5: Adiabatic and isothermal P-V plot

Expansion

The red curve signifies the adiabatic curve and the

green curve signifies the isothermal curve. As the
pressure is decreasing, the volume of the gas is
Pressure

Isothermal
increasing. Therefore, this is expansion. The area
under the P-V curve represents the work done in that
particular process. So, the area under the curve in the
case of isothermal expansion is more than the area Adiabatic
under the curve in the case of an adiabatic expansion
for the same change in volume.

Wiso > Wadi Volume

Fig. 6: P-V plot for adiabatic and
isothermal expansion

© 2020, BYJU'S. All rights reserved

 09

Compression

The red curve signifies the adiabatic curve and the green
curve signifies the isothermal curve. As the pressure is
increasing, the volume of the gas is decreasing, so it is

Pressure
compression. The area under the P-V curve represents
the work done in that particular process. So, the area under Adiabatic
the curve in the case of an adiabatic compression is more
than the area under the curve in the case of an isothermal
compression for the same change in volume. Isothermal

Wadi > Wiso Volume

Fig. 7: P-V plot for adiabatic and
isothermal compression

Finding the type of the thermodynamic process

Which curves represent adiabatic

processes? A
Pressure

(a) A, C Pressure
(b) B, D B C
(c) A, D
D
(d) B, C
Volume Volume

Solution

The slope of the adiabatic P-V curve is steeper than the slope of the isothermal P-V curve. In plot 1,
curve B has a steeper slope than curve A. So, the thermodynamic process ‘B’ is adiabatic. In plot 2,
curve C has a steeper slope than curve D. So, the thermodynamic process ‘C’ is adiabatic. Therefore,
B and C are the adiabatic processes.
The correct answer is option (d).

© 2020, BYJU'S. All rights reserved

 10

Quick
recap

For an adiabatic For an isothermal

process process

P1V1γ = P2V2γ P1V1 = P2V2

Expansion till the same final volume

A
Pi
Consider two thermodynamic expansion
Pressure (P)

processes taking place from the same initial Isothermal curve

volume (Vi) to the same final volume (Vf) Adiabatic curve
through isothermal and adiabatic paths. The
initial pressure (Pi) is the same for both the
processes. The final pressure is Piso for the Piso B
isothermal process and Padi for the adiabatic
process. Padi C
Vi
Volume (V) Vf
Fig. 6: Expansion till the same final volume

Isothermal process

For isothermal processes, P1V1 = P2V2

PiVi = PisoVf
Pi V
= f ... (1)
Piso Vi

Adiabatic process

For adiabatic processes,

γ γ
Pi Vi = Padi Vf
γ
Pi V
= fγ
Padi Vi
γ
Pi V 
= f ... (2)
Padi  Vi 

© 2020, BYJU'S. All rights reserved

 11

We know that the value of γ is always > 1.

γ
V  V 
So,  f  >  f  … (3)
 Vi   Vi 
From equations (1), (2), and (3), we get,
Pi P
> i
Padi Piso
1 1
>
Padi Piso

Piso > Padi

For the same expansion (from same initial to final volume) and same initial pressure, more
pressure needs to be applied in an isothermal process as compared to an adiabatic process.

Expansion till the same final pressure

Pi
Isothermal curve
Pressure (P)

Consider two thermodynamic expansion

processes occurring from the same initial Adiabatic
pressure (Pi) to the same final pressure (Pf) curve
through isothermal and adiabatic paths. The Pf
initial volume (Vi) is the same for both the
processes. The final volume is Viso for the
isothermal process and Vadi for the adiabatic
process.
Vadi
Vi Viso
Volume (V)
Fig. 7: Expansion till the same final pressure

Isothermal process

For isothermal processes, P1V1 = P2V2

PiVi = PfViso
Pi V
= iso ... (1)
Pf Vi

Adiabatic process

For adiabatic processes,

γ γ
Pi Vi = Pf Vadi
γ
Pi V
= adiγ
Pf Vi
γ
Pi  Vadi 
=  ... (2)
Pf  Vi 

© 2020, BYJU'S. All rights reserved

 12

From equations (1) and (2), we get, We know that γ > 1, so

γ
Viso  Vadi  V  V 
=  ... (3) ln  iso  > ln  adi 
Vi V
 i   Vi   Vi 
Taking loge on both the sides of equation (3), So
we get,  Viso   Vadi 
γ  > 
Viso V   Vi   Vi 
ln = ln  adi 
Vi  Vi 
Viso > Vadi
V  V 
ln  iso  = γ ln  adi 
 Vi   Vi 

Type of process ΔU ΔH

Isothermal 0 0

Isobaric nCV, mΔT nCP, mΔT

Isochoric nCV, mΔT nCP, mΔT

Adiabatic nCV, mΔT nCP, mΔT

Free expansion 0 0

Table 2: Calculation of ΔU and ΔH for different processes

Formulae of the Day

S. No Formula Process

γ(1 − γ ) γ 1− γ
 V1   T1   P1 
1.  = =    Adiabatic reversible process
 V2   T2   P2 

2. ΔU = W = 0 Free expansion
γ γ
3. P1V1 = P2V2 Reversible adiabatic process

4. P1V1 = P2V2 Isothermal process

5. W = −PextΔV Irreversible process

Table 3: Formulas for respective processes

© 2020, BYJU'S. All rights reserved