Thermodynamics 4

Heat Capacity & Degrees Of Freedom

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Thermodynamics 4
Heat Capacity & Degree Of Freedom
Internal Energy
Internal energy of any system may be given as sum of
energies due to molecular motion, interaction between
electron and nucleus, etc.
U or E = Et + Er + EV + Ee + ……

OR

The total heat content of system at constant volume.

dU Or dE = qV
Internal Energy

Every system has some quantity of matter

associated with a definite amount of energy. This
energy is called as Internal energy.

Potential Kinetic
Energy Energy

Vibrationa Rotational
Intermolecular Intramolecular
TranslationalNuclear
Electronical
Energy
l Energy EnergyEnergy EnergyEnergy
Energy Or
Binding Energy
Internal Energy

1. It is an extensive property.
2. It is a state function.
3. ItThe
is not dependent
property onsystem
of the path followed.
whose
4. value
Theredepends only on
is no change ininitial and final
the internal energy in a cyclic process.
state is called as state function

5. Internal energy of an ideal gas is a

A system undergoing series of process,
function of temperature only.
once again returns to its original state is
Units – called
joulesas(SI) andprocess
cyclic ergs (CGS)
Internal Energy INTERNAL ENERGY

❑ Among these forms, the sequence of energy is

❑ When the energy of system is changed, the

contribution of different forms of energy may be
given as

ΔEe ≤ ΔEv≤ ΔEr≤ ΔEt

Variation Of Internal Energy
VARIATION OF ENERGY WITH TEMPERATURE AND VOLUME

Energy depends on T and V i.e.

E = f (T, V)
First Law Of Thermodynamics First Law of Thermodynamics

❑ The internal energy of a system can be changed

either by doing work on it or supplying heat to it

OR

❑ The total energy of an isolated system remains

constant.
First Law Of Thermodynamics

+q wtotal

E1 E1 + q E2

E2 = E1 + q + wtotal
A sample of liquid in a thermally insulated container (a calorimeter)
is stirred for 2 hr. by a mechanical linkage to a motor in the
surrounding. For this process:
A. w < 0; q = 0; ΔU = 0
B. w > 0; q > 0; ΔU > 0
C. w < 0; q > 0; ΔU = 0
D. w > 0; q = 0; ΔU > 0
A gas has constant pressure in a system. There is
a loss of 45 J of heat in the surroundings around
the system. 450 J of work is done onto the system.
Find the system’s internal energy?
(a) +405J
(b) +495J
(c) -405J
(d) -495J
The work done by a system is 8 joule, when 40 joule heat is supplied
to it. What is the increase in internal energy of system.
A gas expands from 2 L to 6 L against a constant pressure of 0.5
atm on absorbing 200 J of heat. Calculate the change in internal
energy.
A system absorb 600J of heat and work equivalent to 300J on its
surroundings. The change in internal energy is :
A. 300 J
B. 400 J
C. 500 J
D. 600 J
Applications Of First Law Of Thermodynamics

1. Isothermal Process
∆U = q + W
2. Adiabatic Process
3. Isobaric Process
4. Isochoric Process
Applications Of First Law Of Thermodynamics

1. Isothermal Process :
∆U = q + W
∆TWhat
= 0 is Isothermal
∆U = 0
A process in process?
0 which
= q +the
Wtemperature of
the system remains constant.
q= –W W= –q
Applications Of First Law Of Thermodynamics

2. Adiabatic Process :
∆U = q + W
q is=Adiabatic
0 System is thermally insulated
What
process?
∆U = 0 +
Wad
∆Uin= which heat is not allowed
A process
to enterWoradleave the system.
Applications Of First Law Of Thermodynamics

3. Isobaric Process :
∆U = q + W
A process
∆P =
in which the pressure of the
What is isobaric
0process?
system remains constant.
∆U = qp + ( – P∆V )

∆Uis=the
What qp –formula
P∆V of
W = – P∆V
work done?
qp = ∆U + P∆V
Applications Of First Law Of Thermodynamics

4. Isochoric Process :
∆U = q + W
∆V = 0
What is isochoric
∆U = process?
qv + ( – P∆V )
A process in which the volume of the
∆U = remains
system q + constant.
v 0

∆U = qv
In an isochoric process the increase in internal energy is
A. Equal to the heat absorbed
B. Equal to the heat evolved
C. Equal to the work done
D. Equal to the sum of the heat absorbed and work done
In an isothermal expansion of an ideal gas. Select wrong statement :
A. there is no change in the temperature of the gas
B. there is no change in the internal energy of the gas
C. the work done by the gas is equal to the heat supplied to the
gas
D. the work done by the gas is equal to the change in its internal
energy
A system undergoes a process which absorbed 5 kJ of heat and
undergoing an expansion against external pressure of 1 atm, during
the process change in internal energy is 300 J. Then predict the
change in volume (lit.)
A. 1
B. 2
C. 3
D. 4
When two moles of Hydrogen atoms join together to form a mole of
hydrogen molecules in a rigid vessel
H(g) + H(g) → H2(g)
A. w < 0
B. ΔU = negative
C. qsystem = positive
D. qsurroundin = negative
Heat Capacity Heat Capacity (C)

Heat Capacity

Total Heat Molar Heat Specific Heat

Capacity (C) Capacity (Cm) Capacity (s)
Total Heat Capacity(C) Total Heat Capacity (C)

❑ The amount of energy required to raise the

temperature of a body through 1° is called Heat
Capacity (C).

dT

dq
Molar Heat Capacity(Cm)
❑ The amount of energy required to raise the
temperature of one mole of a substance
through 1° is called Molar Heat Capacity (Cm).

Molar Heat
Capacity

Solid/Liquid Gases
Specific Heat Capacity(s)

❑ The amount of energy required to raise the

temperature of one gram of a substance
through 1° is called Specific Heat Capacity (s).

Specific Heat
Capacity

Solid/Liquid Gases
Relation Between Cp & Cv
Adiabatic Constant (𝝲)

The ratio of Cp and Cv for a gas is called

adiabatic constant or adiabatic index (𝝲).
𝝲 = Cp/Cv
Molar heat capacity of water in equilibrium with
ice at constant pressure is
(a) zero
(b) ∞
(c) 40.45 kJ K–1 mol–1
(d) 75.48 JK–1 mol–1
Law Of Equipartition Of Energy LAW OF EQUIPARTITION OF ENERGY

Law of Equipartition of Energy

Translational Rotational Vibrational

½ kT ½ kT kT
Degrees Of Freedom

The number of independent methods to express the energy of molecules is called

degrees of freedom(f)
Degrees Of Freedom
Degrees Of Freedom

The number of independent methods to express the energy of molecules

❑ Translational degree of freedom = 3 for all molecules

❑ Rotational degree of freedom = 0 for monoatomic gas molecules

= 2 for diatomic or linear molecules
= 3 for tri or polyatomic nonlinear molecules

❑ Vibrational degree of freedom = 0 for monatomic gas molecule

= 1 for diatomic molecules

For any molecule having N atoms, the total degree of freedom is 3N.
Degrees Of Freedom

Degree of Freedom
Molecules
Total Translational Rotational Vibrational

He 3×1=3 3 0 0
H2 3×2=6 3 2 1
CO2 (linear) 3×3=9 3 2 9 – (3 + 2) = 4
NH3 (non-linear) 3 × 4 = 12 3 3 12 – (3 + 3) = 6
 Translation Rotationa Vibrational
Atomicity Temp. CV C P = CV + R γ = CP/CV
al motion l motion motion

Monatomic Low 3 - - 3/2R 5/2R 5/3

gases High 3 - - 3/2R 5/2R 5/3

Diatomic Low 3 2 - 5/2R 7/2R 7/5

gases High 3 2 - 7/2R 9/2R 9/7
Low 3 2 - 5/2R 7/2R 7/5
Triatomic
linear gases 13/2
High 3 2 - 15/2R 15/13
R

Triatomic Low 3 3 - 3R 4R 4/3

non-linear High 3 3 - 6R 7R 7/6
Low 3 3 - 3R 4R 4/3
3(N) – 6(Non-liner)
Polyatomic 3 3 3(N) – 5(liner)
High
3 2 N = Number of
atoms
Code - ATJEE
Degree Of Freedom

Atomicity CV CP γ
Mono 3/2R 5/2R 5/3 = 1.67
Di 5/2R 7/2R 7/5 = 1.4
Tri or polyatomic 3R 4R 4/3 = 1.33
Cp & Cv Of Mixtures

Gas 1 Gas 2 Calculation

CP CP1 CP2

CV CV1 CV2

Moles n1 n2
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