The First Law of Thermodynamics (Lecture 02) : - Prashant Uday Manohar

CHEM F211 : Physical Chemistry-I
The first law of thermodynamics (Lecture 02)

- Prashant Uday Manohar
In the previous lecture, we learned
●
Thermodynamic system
●
Equilibrium
●
Thermal equilibrium and zeroth law
●
Thermodynamic Properties
●
Mole concept
●
Equation of state
BITSPilani, Pilani Campus

Objectives
●
Classical mechanics
●
Work, heat and internal energy
●
The first law of thermodynamics
●
Enthalpy and heat capacities
●
Calculation of the first law quantities
●
Molecular nature of Internal energy

Classical mechanics

Classical mechanics
Law of conservation of energy is central to any branch of science.

Classical mechanics
When dealing with thermodynamic system, the main aim of the study is to see one of the
following:
●
Work done at the cost of energy
●
Energy stored at the cost of work

Classical mechanics
following:
●
●
Processes in macroscopic world are governed by Newton’s laws of motion.

Newton’s second law provides the equations of motion for the system of interest.

Classical mechanics
following:
●
●

2 2 2 2
d r d x d y dv x dv dv
⃗ ⃗j + z ⃗k =m
d ⃗i + y ⃗j + z ⃗k =m d ⃗v
F
⃗ =m ⃗a =m
dt 2
=m
(
dt 2
⃗i +
dt 2 ) (
dt 2 dt dt dt ) dt

Classical mechanics
following:
●
●

2 2 2 2
⃗ ⃗j + z ⃗k =m
d ⃗i + y ⃗j + z ⃗k =m d ⃗v
F
⃗ =m ⃗a =m
dt 2
=m
(
dt 2
⃗i +
dt 2 ) (
dt 2 dt dt dt ) dt
Work is done when a body gets displaced due to external unbalanced force acting on it. If the
displacement is in the direction of the force, then the work is done on the body and if the
displacement is in the opposite direction, then the work is done by the body. In this course, we
consider the work done as work done on the body.

Classical mechanics
following:
●
●

2 2 2 2
⃗ ⃗j + z ⃗k =m
d ⃗i + y ⃗j + z ⃗k =m d ⃗v
F
⃗ =m ⃗a =m
dt 2
=m
(
dt 2
⃗i +
dt 2 ) (
dt 2 dt dt dt ) dt
Work is done when a body gets displaced due to external unbalanced force acting on it. If the
displacement is in the direction of the force, then the work is done on the body and if the
displacement is in the opposite direction, then the work is done by the body. In this course, we
consider the work done as work done on the body.
W =F
⃗⋅⃗r ; δW =F x dx + F y dy + F z dz

Classical mechanics
Mechanical energy:

Classical mechanics
Mechanical energy:
The total work done on a particle due to force acting on it is
2 2 2 2
W =∫ δW =∫ F x dx+∫ F y dy +∫ F z dz
1 1 1 1

Classical mechanics
Mechanical energy:
2 2 2 2
1 1 1 1
From Newton’s second law, we have:

dv x dv x dx dv x
F x =m a x=m =m =m v x
dt dx dt dx

Classical mechanics
Mechanical energy:
2 2 2 2
1 1 1 1

dv x dv x dx dv x
dt dx dt dx
Thus, F x dx=m v x dv x ; F y dy=m v y dv y ; F z dz=m v z dv z ;

Classical mechanics
Mechanical energy:
2 2 2 2
1 1 1 1

dv x dv x dx dv x
dt dx dt dx
Thus, F x dx=m v x dv x ; F y dy=m v y dv y ; F z dz=m v z dv z ; and it follows:

Classical mechanics
Mechanical energy:
2 2 2 2
1 1 1 1

dv x dv x dx dv x
dt dx dt dx

2 2 2 2
W =∫ δ W =∫ mv x dv x +∫ mv y dv y +∫ mv z dv z
1 1 1 1

Classical mechanics
Mechanical energy:
2 2 2 2
1 1 1 1

dv x dv x dx dv x
dt dx dt dx

2 2 2 2
1 1 1 1
1 1
= m(v 2x + v 2y +v 2z )− m(v 2x +v 2y +v 2z )=K 2 −K 1 =Δ K
2 2 2
2 2 1 1 1

Classical mechanics
Mechanical energy:
2 2 2 2
1 1 1 1

dv x dv x dx dv x
dt dx dt dx

2 2 2 2
1 1 1 1
1 1
= m(v 2x + v 2y +v 2z )− m(v 2x +v 2y +v 2z )=K 2 −K 1 =Δ K
2 2 2
2 2 1 1 1
Change in the kinetic energy

Classical mechanics
For systems and processes with conservative forces, the potential energy is purely dependent on
position(s) of the particle(s) and so are the components of the force(s).
V =V ( x , y , z); F ι=F ι (x , y , z ); ι≡x , y , z

Classical mechanics
Force is defined as
∂V
F ι=−
∂ι

Classical mechanics
Force is defined as
∂V
F ι=−
∂ι
Thus, it follows:
2 2 2
W =∫ F x dx +∫ F y dy +∫ F z dz
1 1 1

Classical mechanics
Force is defined as
∂V
F ι=−
∂ι
Thus, it follows:
2 2 2 2 2 2 2
∂V ∂V ∂V
W =∫ F x dx +∫ F y dy +∫ F z dz=−∫ dx−∫ dy−∫ dz=−∫ dV =V 1 −V 2
1 1 1 1 ∂ x 1 ∂ y 1 ∂ z 1

Classical mechanics
Force is defined as
∂V
F ι=−
∂ι
Thus, it follows:
2 2 2 2 2 2 2
∂V ∂V ∂V
1 1 1 1 ∂ x 1 ∂ y 1 ∂ z 1
Thus, we have:
K 2 −K 1 =V 1−V 2 ; K 2 +V 2 =K 1 +V 1 =K +V =E mech

Classical mechanics
V =V ( x , y , z); F ι=F ι (x , y , z); ι≡x , y , z
Force is defined as
∂V
F ι =−
∂ι
Thus, it follows:
2 2 2 2 2 2 2
∂V ∂V ∂V
1 1 1 1 ∂ x 1 ∂ y 1 ∂ z 1
Thus, we have:
K 2 −K 1 =V 1−V 2 ; K 2 +V 2 =K 1 +V 1 =K +V =E mech
Mechanical energy
(conserved)

PV work or expansion work:
W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Consider a cylinder filled with a gas and closed with a frictionless piston of mass m.
The magnitude of the downward acting gravitational force due to the piston is mg.

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Let the piston be displaced from the initial position, downward by a small distance of dz.
Then, the work done on the enclosed gas is mgdz.

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Let surface area of the piston (and hence, the area of cross-section of the cylinder) be A.

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Then, we have
W =|F⃗ ||⃗r |=mgdz= mg ⋅Adz=PdV
A

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Then, we have
A
The other forms of work are called non-expansion work and include electric work,
chemical work, etc.

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Then, we have
A
chemical work, etc.
Heat:
When two bodies are at different temperatures, the energy transfer takes place from the
more hot body(2) to the less hot body(1) till the two bodies attain mutual thermal
equilibrium.

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Then, we have
A
chemical work, etc.
Heat:
equilibrium. The amount of energy transferred in the process is defined as heat.
q=m2 c2 (T 2−T f )=m1 c1 (T f −T 1 )

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Then, we have
A
chemical work, etc.
Heat:
q=m2 c2 (T 2−T f )=m 1 c1 (T f −T 1 ); T 2 ≥T f ≥T 1

W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Then, we have
A
chemical work, etc.
Heat:
masses
W =F
⃗⋅⃗r =|F
⃗ ||⃗r |
Then, we have
A
chemical work, etc.
Heat:
(specific) heat capacities
masses
We have seen that mechanical energy of a system is the sum of the kinetic energy of its
particles and the potential energy due to the inter-particle interactions. The kinetic and
potential energies considered in this definition are the macroscopic kinetic and potential
energies. That is, the internal structure of the particles and the interactions therein are
eliminated in calculations of these quantities.

However, the individual particles do possess energy due to their internal inherent structure
and intra-particle interactions. For example, the energies due to molecular translations,
vibrations, rotations, electronic energies and the relativistic rest-mass energy. This all
contributes together to what is known as internal energy of a system (U).

Thus, the total energy of the system equals to mechanical energy plus internal energy.
E=K +V +U

E=K +V +U
Total energy of the universe is conserved.
Δ Euniverse =0=Δ E system +Δ E surrounding

E=K +V +U
What would cause the total energy of the system to change?

E=K +V +U
What would cause the total energy of the system to change?

●
Due to external forces – work done on the system/by the system
●
Thermal contact with another system at different temperature – heat transfer
●
Exchange of matter with surrounding * (for open systems only)

The first law of thermodynamics asserts that there exists an extensive property (state function,
point function), the total energy of the system (represented by E) such that for any process in a
closed-system, the change in the total energy of the system equals to the heat transferred to the
system plus the work done on the system.
Δ E=q+w

Δ E=q+w
We confine our discussion to the systems in which external fields are absent, so that there is no
net change in mechanical energy of the system. The above equation then reduces to
Δ U =q+w

Δ E=q+w
We confine our discussion to the systems in which external fields are absent, so that there is no
net change in mechanical energy of the system. The above equation then reduces to
Δ U =q+w
For infinitesimal change, one can write
d U =δ q+δ w
The internal energy (U) of the system is a state function and is one of the four important
thermodynamic potentials (more, later).
Thus, the net change in the internal energy in a cyclic process is zero.

Enthalpy
In thermodynamic process, by means of work and/or heat, the state of the system changes. In
general, this leads to change in the internal energy of the system and change in the product of
pressure and volume.
Thus, the quantities, dU and d(PV) appear frequently while calculating changes in the
properties during the process. It is therefore, very convenient to define a thermodynamic
quantity, enthalpy.

Enthalpy
In thermodynamic process, by means of work and/or heat, the state of the system changes. In
general, this leads to change in the internal energy of the system and change in the product of
pressure and volume.
Thus, the quantities, dU and d(PV) appear frequently while calculating changes in the
properties during the process. It is therefore, very convenient to define a thermodynamic
quantity, enthalpy.
H =U + PV
The enthalpy (H), defined above is also a state function. is one of the four important
thermodynamic potentials (more, later).
In a finite process, the change in enthalpy is obviously expressible as:
Δ H =H 2 −H 1=(U 2 + P2 V 2 )−(U 1 + P1 V 1 )=U 2−U 1 +( P2 V 2 −P1 V 1 )=ΔU +Δ PV

Enthalpy change
Consider a finite process in a closed system with no non-expansion work. Let the system go
from state 1 to state 2. Then, from the first law, we have:
2 2 2 2
Δ U =U 2 −U 1=∫ dU =∫ δ q+∫ δ w=q 12 +w 12 =q 12−∫ PdV

1 1 1 1

Enthalpy change
2 2 2 2

1 1 1 1
If the pressure is constant throughout the process, then it follows:

2
Δ U P =q P−P ∫ dV =q P −P Δ V ;
1
q P =(U 2 + PV 2 )−(U 1 +PV 1 )= H 2 ,P −H 1 , P =Δ H P

Enthalpy change
2 2 2 2

1 1 1 1
If the pressure is constant throughout the process, then it follows:

2
Δ U P =q P−P ∫ dV =q P −P Δ V ;
1
q P =(U 2 + PV 2 )−(U 1 +PV 1 )= H 2 ,P −H 1 , P =Δ H P
On the other hand, if the volume is constant throughout the process, then it follows:
2
Δ U V =q V −∫ PdV ; dV =0 ;
1
qV =Δ U V

Heat capacities
The heat capacity for an infinitesimal process is given by:

δ q pr
C pr =
∂T
Clearly, the heat capacity depends on the nature of the process. Two heat capacities are of
special importance in thermodynamics.
Isobaric heat capacity (Heat capacity at constant pressure) (CP):
∂H
C P= ( ) ∂T P
Isochoric heat capacity (Heat capacity at constant volume) (CV):
∂U
CV = ( )
∂T V
Heat transfer to a system will be utilized in doing work and/or increasing internal energy of
the system. Clearly, the temperature will rise faster in an isochoric process than in an isobaric
process. Thus, CV cannot be greater than CP. Moreover, from the laws of thermodynamics, one
can easily show that for a close system, both these quantities are positive definite.

Molar heat capacities
While a heat capacity is an extensive quantity, one can always

measure/calculate the heat capacities for one mole of a substance and obtain
the corresponding molar heat capacity, which would be intensive quantity.
The isobaric and isochoric molar heat capacities are thus defined by:
∂ Hm ∂U m
( )
C P ,m =
∂T P
; ( )
C V ,m =
∂T V

We now find the general relationship between, CP and CV. We start with

∂H ∂U ∂[U + PV ] ∂U ∂U ∂V ∂U
( ) ( ) (
C P −C V =
∂T P
−
∂T V
=
∂T ) ( ) ( ) ( ) ( )
P
−
∂T V
=
∂T P
+P
∂T P
−
∂T V

∂H ∂U ∂[U + PV ] ∂U ∂U ∂V ∂U
( ) ( ) (
C P −C V =
∂T P
−
∂T) ( ) ( ) ( ) ( )
V
=
∂T P
−
∂T V
=
∂T P
+P
∂T P
−
∂T V
∂U ∂U
We have dU =
(∂ T ) (∂ V ) dV
dT +
V T

∂H ∂U ∂[U + PV ] ∂U ∂U ∂V ∂U
( ) ( ) (
C P −C V =
∂T P
−
∂T) ( ) ( ) ( ) ( )
V
=
∂T P
−
∂T V
=
∂T P
+P
∂T P
−
∂T V
∂U ∂U
We have dU =
(∂ T ) (∂ V ) dV
dT +
V T
For an isobaric process, it follows:

∂U ∂U dU P ∂ U ∂U dV P
dU P =
∂T( ) V
dT P +
∂V ( ) dV ; T
P ⇒
dT P
=
∂T( ) ( )
V
+
∂V T dT P

∂H ∂U ∂[U + PV ] ∂U ∂U ∂V ∂U
( ) ( ) (
C P −C V =
∂T P
−
∂T) ( ) ( ) ( ) ( )
V
=
∂T P
−
∂T V
=
∂T P
+P
∂T P
−
∂T V
∂U ∂U
We have dU =
(∂ T ) (∂ V ) dV
dT +
V T

dU P =
∂T( ) V
dT P +
∂V ( ) dV ; T
P ⇒ ( ) ( )
dT P
=
∂T V
+
∂V T dT P
dU P ∂U dV ∂V
=(
∂T ) ( ∂T ) P
For infinitesimal change, we have: ; =
dT P dT
P P P

∂H ∂U ∂[U + PV ] ∂U ∂U ∂V ∂U
( ) ( ) (
C P −C V =
∂T P
−
∂T) ( ) ( ) ( ) ( )
V
=
∂T P
−
∂T V
=
∂T P
+P
∂T P
−
∂T V
∂U ∂U
We have dU =
(∂ T ) (∂ V ) dV
dT +
V T

dU P =
∂T( ) V
dT P +
∂V ( ) dV ; T
P ⇒ ( ) ( )
dT P
=
∂T V
+
∂V T dT P
dU P ∂U dV ∂V
=(
∂T ) ( ∂T ) P
For infinitesimal change, we have: ; =
dT P dTP P P
∂U ∂U ∂U ∂V
Consequently, ( ) ( ) ( )( );
∂T P
=
∂T V
+
∂V T ∂T P
and it follows:
∂V
C P −C V =
[( ) ]( )
∂U
∂V T
+P
∂T P

Ideal (Perfect) gas heat capacities
We have obtained:
∂V
[( ) ]( )
C P −C V =
∂U
∂V T
+P
∂T P

Ideal (Perfect) gas heat capacities
We have obtained:
∂V
C P −C V =
[( ) ]( )
∂U
∂V T
+P
∂T P
For ideal gas, this equation simplifies further. The internal energy of an ideal gas is
dependent on temperature alone. Hence, the first term in the rectangular bracket vanishes.
Moreover, using the ideal gas equation of state, the above equation simplifies to
C P −C V =nR
; (for ideal gas)
C P , m−C V , m =R

The First Law of Thermodynamics (Lecture 02) : - Prashant Uday Manohar

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CHEM F211 : Physical Chemistry-I

The first law of thermodynamics (Lecture 02)

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

Processes in macroscopic world are governed by Newton’s laws of motion.

BITSPilani, Pilani Campus

Processes in macroscopic world are governed by Newton’s laws of motion.

BITSPilani, Pilani Campus

Processes in macroscopic world are governed by Newton’s laws of motion.

BITSPilani, Pilani Campus

Processes in macroscopic world are governed by Newton’s laws of motion.

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

From Newton’s second law, we have:

BITSPilani, Pilani Campus

From Newton’s second law, we have:

Thus, F x dx=m v x dv x ; F y dy=m v y dv y ; F z dz=m v z dv z ;

BITSPilani, Pilani Campus

From Newton’s second law, we have:

Thus, F x dx=m v x dv x ; F y dy=m v y dv y ; F z dz=m v z dv z ; and it follows:

BITSPilani, Pilani Campus

From Newton’s second law, we have:

Thus, F x dx=m v x dv x ; F y dy=m v y dv y ; F z dz=m v z dv z ; and it follows:

BITSPilani, Pilani Campus

From Newton’s second law, we have:

Thus, F x dx=m v x dv x ; F y dy=m v y dv y ; F z dz=m v z dv z ; and it follows:

BITSPilani, Pilani Campus

From Newton’s second law, we have:

Thus, F x dx=m v x dv x ; F y dy=m v y dv y ; F z dz=m v z dv z ; and it follows:

Change in the kinetic energy

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

BITSPilani, Pilani Campus

PV work or expansion work:

PV work or expansion work:

BITSPilani, Pilani Campus