THERMODYNAMIC TERMS

System
A small part of the universe chosen for thermodynamic study at a given instant
is called as system.

Surroundings
Surroundings is the remaining part of the universe in contact with the system.

Universe

System and Surroundings together constitute the universe.

Universe = System + Surroundings
➢ Boundary
➢ The real imaginary surface or line that separates a system from its
surroundings is called boundary.

Types of boundary

1. Real boundary: Exactly see your eyes Ex.,water in bottle

2. Imaginary boundary: Which cannot see your eyes Ex.,water in beaker
3.Diathermic boundary: Which allow the passage of heat. Ex.,water in bottle
4. Adiabatic boundary: Which does not allow the passage of heat. Ex.,water in
thermoflask
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 TYPES OF THE SYSTEM On the basis of Boundary

Open System
➢ A system which can exchange both matter as well as energy with its
surroundings is called as open system.
Closed System
➢ A system which can exchange energy but not matter with its surroundings
is called as closed system.

Isolated System

➢ A system that can exchange neither matter nor energy with its
surroundings is called as isolated system.
 TYPES OF THE SYSTEM On the basis of Phases

➢ A system of a single phase or has completely uniform composition

throughout is called as Homogeneous system.

➢ A system consisting of more than one phase or phases throughout is called

as Heterogeneous system.
 The State of the System
The state of a thermodynamic system is described by its measurable or
macroscopic properties.
State Function :
The property of the system whose value depends only on initial & final states of
the system and do not depend on the path followed is called as state function.
Examples: Internal energy, Enthalpy, Entropy, Gibb's energy, Temperature,
Pressure, volume etc.

Path Function :
The property of the system whose value depends on the path followed is
called as path function Examples : Work, heat etc.
 Properties of the System :
1. Extensive Property 2. Intensive Property
Certain properties of the system Certain properties of the system whose
whose magnitude depend on the magnitude does not depend on the
quantity of matter present quantity of matter present.

Temperature, Pressure, Density,

Viscosity, Refractive index, Molar
heat capacity, Concentration, E𝟎𝒄𝒆𝒍𝒍 ,
PH, Melting and boiling points,
vapour pressure, surface tension .
 :: Make a note

➢ Extensive properties are additive in nature

➢ Intensive properties are not additive in nature

➢ The ratio of two extensive properties is an intensive property

❖ Mass and volume are extensive but density(d=m/v) is an intensive property.

❖ Number of mole and volume are extensive but Molarity (M= next/Vext) is an
intensive properties

➢ Extensive properties when expressed per unit mass, per unit mole, per unit volume
becomes intensive

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Thermodynamic Processes:
They are as follows…
➢ Isothermal Process
➢ Isobaric Process
➢ Isochoric Process
➢ Adiabatic Process
➢ Cyclic process
➢ Reversible process
➢ Irreversible process
Isothermal Process :

➢ A process in which the temperature of the system remains constant

throughout is called as Isothermal process.

∆T = 0 ∆U = 0
P

V
Isobaric Process :

➢ A process in which the pressure of the system remains constant

throughout is called as isobaric process.

∆P = 0
Example : V

All chemical reactions carried out in laboratory are at

constant pressure.
Isochoric Process :
➢ A process in which the volume of the system remains constant
throughout is called as isochoric process.

∆V = 0 W= 0 P

V
 System is thermally insulated
Adiabatic Process :
➢ A process in which heat is not allowed to enter or leave the system.

q= 0
∆T ≠ 0 ∆U ≠ 0
P
Example :
Reaction carried out in a thermas flask.
i.e – Boiling of water in thermally insulated container.
V
Cyclic process :
Initial = Final
state state
➢ When a system undergoes a series of
process and finally reaches its initial state,
then it is called as cyclic process.

In cyclic process, all the change in the state functions are

zero

q ≠ 0 But path functions

W≠ 0 are not zero
Graphical Representation of different processes

Isochoric Isobaric

P Isothermal
Adiabatic
V
 Which curve is adiabatic and isothermal?

Isobaric

Isochoric
P Isothermal
Adiabatic
V

Slope of P-V curve at a point Slope of P-V curve at a point

in adiabadic process in isothermal process

Slope of isothermal process = γ Slope of isothermal process

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Internal energy (U):

➢ Every substance is associated with definite amount of energy that is called

internal energy.

➢ It is an extensive property and a state function.

➢ Internal energy of ideal gases is a function of temperature only.

➢ Internal energy of real gases is a function of temperature and volume.

➢ For cyclic process change in internal energy zero.

Internal energy (U):
➢ Every substance is associated with definite amount of energy that is called
internal energy.
➢ It is an extensive property and a state function.
➢ Internal energy of ideal gases is a function of temperature only.
➢ Internal energy of real gases is a function of temperature and volume.
 Modes of energy transfer:
➢ There are two methods to alter the internal energy of a system viz.
1. Work
2. Heat
 Work (w):
➢ The mode of transfer of energy between system and
surroundings
➢ Path function
➢ Whenever piston shows any short of movement energy is
transferring in the form of work, except in the case of free
expansion
If Pgas > Pext If Pgas < Pext If Pgas = Pext
V2 > V1 V2 < V1 V2 = V1
expansion Compression No work

Work done by the system Work done on the system Work done is zero

W = -Ve W = +Ve W=0

At STP following reaction are given. Identify in which reaction work done by the
system and which reaction work on the system

21
Identify in which reaction work done by the system and which reaction work on
the system
<

P P

<
P

V V V
23
 Heat (Q):

➢ Mode of transfer of energy between system and surroundings

➢ Heat flow is due to temperature difference
➢ Heat always flow high temperature to low temperature
➢ Path function

➢ If T1 < T2 ➢ If T2 < T1
➢ Heat flow from surroundings to ➢ Heat flow from system to
system surroundings
➢ System absorbing heat ➢ System releasing heat
➢ Q= +Ve ➢ Q= -Ve
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 Heat Capacity:
➢ The amount of heat required to raise the system’s temperature by
10 C is called heat capacity of a substance.
➢ The increase in the temperature is directly proportional to the
heat transferred.
q  ∆T
Unit: J K-1
q= C ∆T

Where ‘C’ is called Heat Capacity.

‘C’ depends on the size, composition and nature of system.
Extensive properties
Specific Heat Capacity (S)

➢ Heat capacity per unit mass

➢ Intensive properties
S= C/M
dq/dt dq
➢ S= =
M M 𝒅𝒕
Unit: J Kg-1 K-1
Molar Heat Capacity (S)
C
➢ Heat capacity of one mole of the substance is Cm =
n
➢ The heat (q) required to raise the temperatures of a sample is

q = c × m × ∆T = C ∆T

c = specific heat of the substance

m = mass of the substance
∆T = change in temperature
 Relationship between Cp and Cv for an ideal gas:

➢ At constant volume, the heat capacity is Cv

qv = Cv ∆T = ∆U
➢ At constant pressure, the heat capacity is Cp
qp = Cp ∆T = ∆H

The difference between Cp and Cv can be derived for an ideal gas as…
Summary

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For a mole of an ideal gas:
∆H = ∆U + ∆(PV)
∆H = ∆U + ∆(RT)
∆H = ∆U + R∆T
Substituting ∆H and ∆U then
Cp ∆T = Cv ∆T + R∆T
(divide with ∆T)
Cp = Cv + R

Cp - Cv = R
Poisons Ratio:
It is a ratio between heat capacities of a substance measured at
constant pressure (Cp) and constant volume (Cv).

Type of gas Cv Cp 𝑪𝒑
=
𝑪𝒗

Monoatomic gas 3R/2 5R/2 𝟓

= 1.66
𝟑

Diatomic gas or tri atomic 5R/2 7R/2 𝟕

= 1.4
𝟓
non-linear gas

Poly atomic gas or non- 3R 4R/2 𝟖

= 1.33
𝟔
linear gas

Atomicity of gas increases the value of  decreases

 First law of thermodynamics
➢ It is law of conservation of energy which states that energy can neither be
created nor destroyed, although it can be converted one form to another.
➢ Total energy of universe remains constant.
A system expands from 5 L to 10 L against a constant external pressure of 2
atm. If it absorbs 800 J of heat during the process calculate the ∆U (J)
Enthalpy ( H ) : or Heat content of the system

Enthalpy can be defined as the sum of the internal energy of the

system and the energy arises due to its pressure and volume.

H = U + PV
➢ Enthalpy is a State Function.
➢ Enthalpy is an Extensive Property.
Expression in Enthalpy change :

H = U + PV Initial State Final State

State function H1 = U1 + P1V1 H2 = U2 + P2V2
∆H = H2 – H1
= U2 + P2V2 – ( U1 + P1V1 )
= U2 + P2V2 – U1 – P1V1
= U2 – U1 + P2V2 – P1V1
= ∆U + ∆ (PV) P1 = P2 = P

∆H = ∆U + P∆V ( At constant pressure )

= qp
Expression in Enthalpy change ( ∆H ) :

∆H = ∆U + P∆V
∆H = ∆U ( For solids )
For solids, there is negligible change
in volume at constant pressure.

∆V = 0 P∆V = 0
Expression in Enthalpy change ( ∆H ) :

∆H = ∆U + P∆V
∆H = ∆U ( For liquids )
For liquids, there is negligible change in
volume at constant pressure.

∆V = 0 P∆V = 0
 Expression in Enthalpy change ( ∆H ) :

For gases, there is considerable change in volume at

constant pressure
∆H = ∆U + P∆V
Ideal Gas
= ∆U + P(V2 – V1)
Equation
= ∆U + PV2 – PV1
= ∆U + n2RT – n1RT
In terms of
= ∆U + RT (n2 – n1) no. of moles PV1 = n1RT
= ∆U + RT ∆ng

∆H = ∆U + ∆ng RT PV2 = n2RT PV = nRT

1 mole of ideal gas undergoes a change in state (2 atm, 3L) to (2 atm, 7 L) with
change in internal energy ∆U= 30 atm L . The change in enthalpy ∆H" for the
process in atm. L will be

39
Which of the following is correct for the following exothermic reaction carries
at constant “P”
CO(g)+ 3H2(g) → CH4(g)+ H2O(g)
(a) ∆U=∆H (b) ∆U > ∆H (c) w < 0 (d) q > 0

40
Calculate the "∆U" when 2 moles of liquid water vapourises at 100oC. The heat
of vapourization of water at 100oC is 40.66 KJ/mol
37.56 KJ/mol (b) 75.1 KJ/mol (c) 150 KJ (d) NOTA

41
For the combustion of C6H5COOH(s) at 300 K and 1 atm, heat released is
300kJ. Calculate the heat released at constant volume for the combustion of
C6H5COOH(s)
C6H5COOH(s) + 15/2 O2(g) → 7CO2(g)+ 3H2O(l)

42
The value of "∆U" is found at to be -742.7 KJ/mol of NH3CN(s) at 298 K.
Calculate "∆H" for the reaction at same temperature?
NH2CN(g) + 3/2 O2(g) → N2(g) + CO2(g) + H2O(l)

43
 Reversible process Irreversible process

❖ Slow process ❖ Fast process

❖ Driving force greater the opposing ❖ Driving force very greater the
force only by small amount opposing force
❖ Imaginary process ❖ Real process
 Expansion:

Reversible expansion Irreversible expansion

Slow Fast
Pext< Pgas Pext< < < < < < < Pgas

Pgas= Pext
Wirrev = -Pext dV

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 Compression

Reversible Compression Irreversible Compression

Slow Fast
Pext> Pgas
Pext>>>>>>>>>>>> Pgas

Pgas= Pext
Wirrev = -Pext dV

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 NOTE:
Area under P-V curve = Magnitude of work

A < B
A B

P P

<
P

B A

V V V
➢ For the same amount of expansion work done by the gas reversible process is
higher than that work done in irreversible process.
➢ For the same amount of compression work done on the gas irreversible
process is more than that work done in reversible process

48
 Thermodynamic process :

The path followed to change the state of the system

50
Isobaric Process :
∆P = 0 W = -P∆V
P

Apply first law of thermodynamics.

V
∆U = q + w
∆U = qp – P∆V qp = ∆U + P∆V

qp = ∆H
For ideal gas
∆H = n Cp dT
W= -P ∆V = ∆ng RT
 Isochoric Process :
➢ A process in which the volume of the system remains constant throughout is
called as isochoric process.
∆V = 0 W= 0

Apply first law of thermodynamics. ∆U = q + w

P

∆U = qv = n Cv dT
V

∆U = +Ve ∆U = -Ve

∆U = n Cv (T2-T1) = +Ve ∆U = n Cv (T2-T1) = -Ve

T2 >T1 T2 <T1
Calculate the ∆U and ∆H , when 10 dm3 of He at STP is heated in a cylinder to
100oC. Assuming ideal gas behavior.

53
1 mole of Al is dropped in an aqueous solution in an open container containing
HCl at 300 K. If 95 cal of heat released during the process. Calculate the w,
∆U and ∆H
Al(s) + 3HCl(aq)→ AlCl3(aq) +3/2H2(g)

54
Calculate the work done complete decomposition of 5 moles PCl5 in cal at 300 K
PCl5(g) → PCl3(g) + Cl2(g)

55
5 moles of N2H4 undergoes complete decomposition at 27 oC. Determine the
work done in cal?
N2H4(s) → 4NH3(g) + N2(g)

56
 Isothermal process :
T-Constant So, ∆T = O
∆U = n Cv dT = 0
∆H = n Cp dT = 0
Apply first law of thermodynamics.
∆U = q + w
q = -w

Ideal gas undergoing isothermal process

W = -Ve W = +Ve

expansion Compression

Heat absorbed Heat is released

57
 Isothermal process :
During isothermal expansion of an ideal gas, heat is absorbed by system

During isothermal compression of an ideal gas, heat is released by system

58
 Work done calculation for isothermal process :
Reversible isothermal expansion:

59
 Work done calculation for isothermal process :
Irreversible isothermal expansion:

60
Calculate the q, w, ∆U and ∆H (in Cal), when 2 moles of of ideal gas expanded reversibly
and isothermally from 10 atm to 5 atm at 27oC [ Assume ln2=0.7]

61
Two litres of N2 gas at 0oC are expanded isothermally against a constant external
pressure of 1 atm until the pressure of gas reaches 1 atm. Calculate the how much heat
will be absorbed or releases?

62
6 moles of an ideal gas expand isothermally from 1 L to 10 L at 300 K. Calculate the
maximum work done by the gas

63
 System is thermally insulated
Adiabatic Process :
➢ A process in which heat is not allowed to enter or leave the system.

q= 0
∆T ≠ 0 ∆U ≠ 0
P
Example :
Reaction carried out in a thermas flask.
i.e – Boiling of water in thermally insulated container.
V
 Adiabatic process :
No heat exchange between system and surroundings, so q = O
∆U = q + W = 0 ∆U = W (Adiabatic process)

W = -Ve expansion W = +Ve Compression

∆U = -Ve ∆U = +Ve
U decreases=> T decreases U increases=> T increases

System undergoing cooling System undergoing heating

❖ During adiabatic expansion of I.G the gas undergoing cooling, i.e, T of the
system decreases
❖ During adiabatic compression of I.G the gas undergoing heating, i.e, T of the
65
system increases
Adiabatic process :

66
Adiabatic process :

67
Expansion

Compression

68
 Expansion

T1 > T3 > T2

Compression

T3 > T2 > T1
69
Work done in reversible adiabatic process :

70
Work done in irrreversible adiabatic process :

71
Calculation of final temp of reversible adiabatic process :

72
Calculation of final temp of irrreversible adiabatic process :

73
1 mole of monoatomic gas expands adiabatically at initial temp “T” against a constant
external pressure of 1 atm from 1 L to 2 L. Find the final temperature of the gas.

74
A sample of fluorocarbon was allowed expand reversibly adiabatically to twice of its
volume. In the expansion, the temperature dropped from 400 K to 100 K. Assuming the
ideal gas condtion, calculate the Cv for the gas.

75
1 mole of a gas A (Cv=3 R) + 2 mole of gas B (Cv=3R/2) are mixed container and
expanded adiabatically and reversibly from 1 L to 4 L starting at 320 k What will be work
done in cal?

76
Calculate the work done by the system in a single stage adiabatic expansion of 2 moles
of an ideal gas (γ=4/3) from 10 atm to 1 atm at 300K. Choose the correct option
(a)227 R (b) 250 R (c) 405 R (d) NOTA

77
 Free expansion:
Expansion of the system against zero external pressure or expansion in vaccum

If Pgas = Pext

It is always irreversible

System and surroundings not exchange any energy in the form of work
78
Isothermal free expansion: Adiabatic free expansion:
Expansion (Pext = 0) Expansion (Pext = 0)
T= Constant q=0
Isothermal free expansion Adiabatic free expansion

W = 0; ∆U = 0 (isothermal process) W = 0; 𝒒 = 0 (adiabatic process)

We know ∆U = q+W, So q = 0 We know ∆U = q+W, So ∆U = 0

∆U = nCv dT So dT = 0
No heat exchange between No heat exchange between
system and surroundings system and surroundings
Note: Note:
An isothermal free expansion of an An adiabatic free expansion of an I.G
I.G is adiabatic as well is isothermal as well 79
 Polytropic process

The process which follow the equation i.e, PVx = K

❖ If x = 0 P = Constant Isobaric process

❖ If x = 1 PV = Constant thermal process

❖ If x = γ PVγ = Constant adiabatic process

❖ If x = ∞ V = Constant Isochoric process

For any process the value of x apart from above four values we can say that
process is polytropic process i.e., X= 2,3, 4, etc
81
82
Calculation of molar heat capacity (Cm) for any process
84
Calculate the molar heat capacity of a monoatomic gas for which the ratio of pressure
and volume is 1.

86
The molar heat capacity of a gas for which P and V are equal is 7R/2. What will be
nature of the gas.
(a) Monoatomic (b) Diatomic (c) Polyatomic non-linear (d) NOTA

87
Calculate the amount of heat supplied to raise the temperature 5 mole of monoatomic
gas by 50oC. The ratio of P and V is 2.

88
For one mole of monoatomic ideal gas, during any process T2=kV3. Calculate the Cm
during the process.
Types of chemical reactions:
Exothermic reaction:
➢ A chemical reaction, which occurs with the evolution of heat is
known as exothermic reaction.
Example

N2 (g) + 3H2 (g) → 2NH3 (g) + 92KJ

HP < HR H = HP – HR;

H = –ve
 Graphical representation of exothermic reaction:

Transition state

Ea Energy of Activation

Enthalpy (H) Reactants – ∆H

Products
Progress of reaction →
Endothermic reaction:
A chemical reaction which occurs with the absorption of heat from the
surroundings is known as endothermic reaction or endoergic reaction.
Example

N2 (g) + O2 (g) → 2NO (g) – 180.8 KJ

H P > HR H = HP – HR;

H = +ve
 Graphical representation of endothermic reaction:

Transition state

Ea Energy of Activation

Enthalpy (H) Products + ∆H

Reactants
Progress of reaction →
Measurements of ∆U and ∆H
➢ Measurement of energy changes are associated with chemical or
physical processes by an experimental technique called Calorimetry.
➢ The heat evolved in the process can be determined by
temperature changes.
➢ Measurements are taken under two different conditions:

❑ At constant pressure, qp

❑ At constant volume, qv