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Thermo
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 Thermodynamics

Thermo dynamic
(heat) (flow)

Definition :
Branch of science that deals with
Bytransfer
arvind of heat
Aroraand other forms of energy.
 Terminologies
System, Surrounding and Boundary.

System Surrounding

Boundary
System: It is a part of universeBy arvind
which is underArora
observation.

Surrounding: The remaining part of universe

is called surrounding.
Boundary: The surface separating system & surrounding
is known as boundary.
Terminologies
Imaginar Matter
Types of Boundaries y
Real or Imaginary Energy
Rigid or Flexible Real
Work
Pext
P Heat

By arvind Arora
Diathermic
Adiabatic Heat
 Different types of system
1 Open system 2 Closed system 3 Isolated system
. . .
Open system
When system can exchange both energy and matter
with the surrounding. It is known as open system.

Matter By arvind Arora

imaginary

Energy
 Closed system
When system can only exchange energy but not matter
with the surrounding. It is known as closed system
Pext
P Flexible
heat
work Diathermic

Isolated system
When system can neither exchangeBy arvind Arora
energy nor matter
with the surrounding. It is known as isolated system.
Adiabatic

Rigid
Macroscopic properties of the system:
The properties of the system which arise from the bulk behavior of
matter are called macroscopic properties.
Examples:P, V, T, m etc.
Extensive Properties Intensive Properties
1. Extensive properties
The properties whose magnitudeBy arvind
depends Arora
on the quantity of matter
in the system are called extensive properties.
2. Intensive properties

The properties that do not depend on the quantity of

matter present in the system are called intensive properties.
 n n C
2 2 Molar heat capacity =
n, P,V,T V V
n
T
2 , 2 , P, T
P, m
Extensive Properties Intensive Properties d=
V
Moles(n) volume(V), Pressure , temperature
,
Heat capacity (C), Energy, density, concentration,
Enthalpy(H), Entropy (S), refractive index, EMF,
Internal energy (U), dielectric constant,
Gibb’s energy (G)
By arvind Arora
molar heat capacity,
molar volume etc.
Note
:
Ratio of two extensive properties becomes intensive
 State of a system
PV = nRT
P, T, V Ideal
gas
E = 3/2nRT

The physical state of a system in terms of its measurable properties

such as P,T, V, n etc. is known as state of a system and the measurable
properties are known as state variables.

To change the state of a system, its one or more state variable have
to be changed. By arvind Arora

P1,V1, T1 P2,V2, T2 Change of state

State –1 State –2
State Function
A physical quantity is said to be a state function if its value depends only on the
state of the system and not on the path followed to attain the state.

P1 V 1 T 1 P2 V2, T2

Examples: U, H, G, S, T, V etc.
By arvind Arora
Path Function
Those functions which are dependent on path followed to reach that state are
known as path function.

Examples: W and q
Thermodynamic Process
Process of changing the state of a system by changing its one or more
state variable is known as thermodynamic process.

Types of Thermodynamic Processes

1) Isothermal process ‘T’ remains constant.
By arvind Arora
P1 V 1 P2 V 2
T T

ΔT = 0
Types of Thermodynamic
Processes
2) Isobaric process Pressure remains constant
–

P, V1, T1 P, V2, T2

ΔP = 0

3) Isochoric process VolumeBy arvind

remains Arora
constant
–

P1,V, T1 P2, V, T2

ΔV = 0
Types of Thermodynamic
Processes
4) Adiabatic process

Transfer of heat is zero, q = 0

5) Cyclic process

When a system undergoes different no. of process and finally returns to its initial
state is known as cyclic processBy arvind Arora
For cyclic process change in state function is zero

ΔP, ΔV, ΔT, ΔH, ΔU, ΔG, ΔS = 0

 Internal Energy (U or E)
The sum of all the components of energy due to internal factor of the
system is called as internal energy.
For ideal gas U
U = K.E + P.E only
K.E Translational , Rotational, Vibrational depends on T
P.E Inter-molecular PE, Bonding PE, Nuclear etc.
For an ideal gas PE = 0
3 By arvind Arora
KE = n RT (for monoatomic)
2
3
So U= n RT
2
⇒ U = ƒ (T)
Internal Energy

1) State function
2) Extensive property

Change in internal energy, ΔU = Ufinal – Uintial

By arvind Arora
Note:
We can not measure internal energy of a system.
We can only measure the change in it .
Modes of Energy Transfer
Heat (q) Energy transfer due to temperature difference between
system and surrounding
( If Tsys > Tsurr )
Tsur Tsy q
r
q ( If Tsys < Tsurr )
s

Work (W) Energy transfer dueBy arvind

to change Arora
in the volume
of system on application of external pressure
Pext
Pgas Compression Pext > Pgas
Expansion Pext < Pgas
Sign Convention
Heat supplied to the system is +ve i.e q > 0

Heat given out by the system is –ve i.e q < 0

Work done on the system (compression) is +ve, i.e W > 0

Work done by the system (expansion) is –ve, i.e W < 0

By arvind Arora
 First Law of Thermodynamics:
Energy can neither be created nor be destroyed it can be simply be
converted from one from to another

E1 U1 E2
Heat or work Heat or work
or both
System or both
Surrounding
If E1 > E2 then internal energy of By
system increases
arvind to U2
Arora
Δ U = U 2 – U1 = E 1 – E 2
If E1 = E2 then internal energy of system remains constant
ΔU=0
If E1 < E2 then internal energy of system decreases to U2
Δ U = U 1 – U2 = E 2 – E 1
Internal energy of system remains constant unless energy is
transferred from surrounding in the form of heat or work.

Mathematical representation of first Law of Thermodynamics

ΔU = q + W

Where,
ΔU = Ufinal – Uinitial = ChangeBy arvind
in internal Arora
energy
q = Heat supplied to the system
W = Work done on the system
Reversible and Irreversible Processes :

Pin = Pext Pin = Pext

Reversible Irreversible
By arvind Arora
Conditions for Reversibility
1. The process should be quasistatic.

2. There should be no dissipative or non-conservative forces present.

 Characteristics of Reversible Process
1. Difference between driving force and opposing force is very small
dP O, dT O
2. It is very slow and its direction can be reversed by making a very small change
in driving force or opposing force.

3. System is in equilibrium with the surrounding

throughout the process.
By arvind Arora
4. Thermodynamic properties like P, T are defined at
all stages.
5. On retracing the path system and surrounding are
restored to their original energy state.
Characteristics of Irreversible Process
1. Difference between driving force and opposing force is large.

2. It is a fast process and its direction can not be reversed by making a small
change in driving or opposing force.

3. System is in equilibrium only at initial and final

state not during the entire process.
By arvind Arora
4. Thermodynamic properties are only defined at
initial and final stage.

5. System and Surrounding are not restored to their

original energy level when system reaches its initial state.
Pressure-Volume (PV) work
Pex
It is the work done when the gas expands or contracts
t
against external pressure dx
For dx displacement Pisto
Pi
n
Change in volume, dV = A.dx n
(A)
Force against which work is done Fext = Pext. A
So work done δW = – Fext dx
= – Pext (ABy
dx) arvind Arora
= – Pext dV
v2
W = – ∫ Pext dx
v1
Where V1 is Intial volume and V2 is final volume
Expression for Pressure-Volume (PV) work
P
1. Irreversible Pex
In irreversible process the external pressure t

remains constant throughout the process V1 V V2

V2

Wirr = –Pext ∫ dV
V1
By arvind Aroraexpression for work done
(General
Wirr = –Pext (V2 – V1)
in an irreversible process)

Work done in any process is

equal to area under PV diagram
Expression for Pressure-Volume (PV) work P
1
2. Reversible PP
2
Pext = Pint ± dP (Pint = Pgas)
V1 V V2

Wrev = – ∫ (Pint ± dP) dV

= – ∫ Pint dV ± dPdV (as dP. dV is very small)

By arvind Arora
Wrev = – ∫ Pint dP

v2
(General expression for work
Wrev ∫
= – Pgas dV
done in reversible process)
v1
Sign Convention for Work (Expansion & Compression)

During During
Expansion Compression

V2 > V1 V2 < V1

∆V is positive By arvind
∆V is Arora
negative

W = Negative W = Positive
Units of Work

W P V

L – atm atm L

Joules Nm–2 m3

Joules Pa Bymarvind
3 Arora

1 L–atm = 101.3 J
1 J = 107 ergs
1 Cal = 4.18 J
 Cyclic Process

When a system undergoes a series of Initial Final

processes and finally reaches its initial state = state
state,it is called as cyclic process.

In cyclic process, change in

ΔH, ΔU, ΔG = 0
By all the state
arvind Arorafunctions is zero
q ≠ 0
W ≠ 0
ΔU = 0 = q + W But the path functions are not zero
qNET = -WNET
Isothermal Process
A process in which the temperature of the system remains constant is
called as Isothermal process.
ΔT = 0 Hence ΔU = 0 as U = ƒ(T)
ΔU =q+W
q =–W
For an ideal gas
PV = nRT By arvind Arora
PV = constant
P P V

V T(K) T(K)
Work Done in Reversible Isothermal
v2
Wrev = – ∫P gas
dV
v1
nRT
Pgas = (Ideal gas)
V
v2
nRT dV By arvind Arora
Wrev = – ∫
v1 V
v2
dV
Wrev = – nRT ∫ (as ‘T’ is constant)
v1 V
 v2
dV
Wrev = – nRT ∫
v1 V
V2
Wrev = – nRT ln
V1
P1 (as P1V1 = P2V2 at
Wrev = – nRT ln
P2 constant
By temperature)
arvind Arora
V2
Wrev = –2.303nRT log
V1
P1
Wrev = –2.303nRT log
P2
 Reversible Expansion

P P1 -dp P
P1, 2
P1 1 P2,
V1+ dV
V1 V2

P1 W = Area under the curve

P P
By arvind V2
2 = –2.303nRT log Arora
V1
V1 V V2
 Reversible Compression

P P1 + P
P1+dp, dp 2
P1 1 P2,
V1–dV
V1 V2

The magnitude of work done in reversible isothermal expansion and compression

is same when system returns to its initial state
By arvind Arora
P W = Area under the curve
2
PP V2
= –2.303nRT log
1 V1
V2 V V1
 Irreversible Isothermal
Wirr = –P (V – V )
ext 2 1

1. Irreversible Expansion
a) Single stage
P P P
P1 P1 2
V1 1
V1 P2, 2

V2
By arvind Arora
P Wirr = Area under PV graph
1
P Wirr = –Pext (V2 – V1)
Pext =
P2 = –P2 (V2 – V1)
V1 V V2
1. Irreversible Expansion

b) Two
stage W = W1 + W 2
= – P3 (V3 – V1) + (–P2 (V2 – V3))
P
1
P
P
3
P
By arvind Arora
2

V1 V3 V2
V
Irreversible Isothermal

2. Irreversible Compression
a) Single stage

P P P
P1 P1 2
V1 1
V1 P2, 2

V2

P By arvind Arora
P
2 Wirr = Area under PV graph
P
1
Wirr = –Pext (V2 – V1)
V2 V V1 = –P2 (V2 – V1)
2. Irreversible Compression Work done on the system (compression)
is positive and it increases as the no. of
b) Two stage stages increase
W = W1 + W 2

P = – P1(V1 – V3)+ (–P3 (V3 – V2))

1
P
P
3
P
By arvind Arora
2

V1 V3 V2
V
Work done by the system during expansion is less than the work
done on the system during compression if the system returns to
initial stage.

P
1
P
P By arvind Arora
2

V1 V V2
 Comparison of work in Reversible
and Irreversible Isothermal
Expansion
P 1V re P 2V
v
1 2
irr

| W rev | > | Wirr|

P Maximum work is done by
1 Bysystem
the arvind Arora expansion
in reversible
P
P
2

V1 V V2
 Compression
P 1V re P 2V
v
1 2

Wirr > Wrev irr

Maximum work is done on

the system in irreversible compression
P P
P
1 By arvind
1
Arora
P
P P
2 2

V1 V V2 V1 V V2
Isobaric Process
When a thermodynamic process is carried out at constant pressure, it
is known as Isobaric Process.
P = Constant
Work done (W) – ∫PdV
= = – P(V2-V1)
= – nR(T2-T1)
By arvind Arora
P P V

V T T
Isochoric Process

A process in which the volume of the system remains constant

throughout is called as Isochoric Process.

∆V = 0 W = 0

P P By arvind
V Arora

V T T
Types of Process : Summary WIsobaric > WIsothermal > WAdiabatic > WIsochoric

Isobaric

Isochoric
P
Isothermal
Adiabatic

V By arvind Arora
Isothermal ΔT = 0, ΔU = 0, q= -w
Isobaric ΔP = 0
Isochoric ΔV = 0, w = 0, ΔU =q
Adiabatic q = 0, ΔU =w
Free Expansion

PEXT = 0
Gas Vacuum

Gas expands in vacuum so PEXT = 0.

The gas does no work as there is no effort put in
expansion process.
Byanarvind
It’s a sudden expansion and Arora
irreversible process.

If no heat is supplied to the gas then there is no

change in temperature too.
Such a process is both Isothermal and Adiabatic.
W = q = ΔU = 0
 Arvind Arora

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