Prof M.

Rashid Khan 2021 Unit: Thermodynamics

NMDCAT Unit:THERMODYNAMICS

Kinetic Molecular Theory Of Gases

Kinetic molecular theory(KMT) of gases is based upon following assumptions.

1. Gases consists of tiny small particles called atoms/molecules.
2. Atoms or molecules move randomly.
3. Molecules collide with each other and with walls of container elastically.
4. Molecule travel straight until they collide.
5. Laws of motion are applicable to the motion of molecules.
6. Effect of gravity is negligibly small on molecules.
7. Temperature of gas is directly proportional to the average K.E of molecules.
T ∝< K. Et >
8. P.E of gas molecules is zero.
Prof M. Rashid Khan
Internal Energy
Sum of all molecular forms of energy in a substance, is Change in internal energy of a system is
called its internal energy U. or independent of path followed by the system
U = K. Et + K. Erot + K. Ev + P. E but depends on initial and final states.
For an ideal gas
K. Erot = K. Ev = P. E = 0
Hence
U ∝ K. Et ……….. (1)
We know that
T ∝ < K. Et > ……….. (2)
Comparing Eq. (1) & Eq.(2)
U ∝ T ∝ < K. Et >
In a cyclic process change in internal energy is zero
Internal energy and temperature of a substance can be after one cycle. ∆U = 0
increased by doing some mechanical work.

Internal energy of a system is a state function like P, V, T,

m, S

Heat added/work done on system is not state function.

Prof M. Rashid Khan
Heat
According to K.M.T, every substance contain internal energy at all temperatures. When two substances at different
temperatures are brought in thermal contact, substantial energy flow from body at higher temperature to body at
lower temperature until the thermal equilibrium is achieved.
This substantial energy in transient, is called heat.
HEAT TRANSFER
Transfer of heat from one place to an other, is called heat transfer.
There are three modes of heat transfer.
1. Conduction 2. Convection 3. Radiation

In this mod heat is transferred by
vibratory motion of atoms of solids.
Heat is conducted by vibrational
motion of adjacent atoms but atoms do
not leave their original positions.
In this mod heat is transferred by In this mod heat is transferred without
translator motion of atoms of liquids and any medium. Heat propagate as
gases. Heat is carried by actual electromagnetic radiations in vacuum.
movement of molecules.
Prof M. Rashid Khan
In case of solids the conduction of heat through a metallic rod depends upon its material nature, cross-sectional area,
length, temperature difference at its ends and time for heat flow.
It is an experimental fact that heat Q conducted through a given rod of length L, cross-sectional area A, temperature
difference ∆T maintained at its end for time t is given by
A ∆T ∆t
Q∝
L

A ∆T t
Q=K
L

A(Th −TL)t
Q=K
L
Rate of heat transfer is
Q A(T −T )
=K h L
t L
Where K is coefficient of thermal conductivity. Its value depends upon material nature of the rod. Its value is
QL
K=
A(Th − TL )t
SI unit of coefficient of thermal conductivity is Jm−1 s −1 K −1 = Wm−1 K −1

Prof M. Rashid Khan

Work Done By Ideal Gas
Heat can be transformed into work by means of a system (ideal gas)
Work done by gas is +ve and work done on gas is –ve
Heat added into gas is +ve and heat expelled from gas –ve

When heat Q is added into the system at constant pressure P then

F=PA
d=∆y
W = F d = PA ∆y= P (A ∆y)=P ∆V

In case of constant P, PV- gp is a straight line parallel to V-axis as shown

In Fig.

Area under PV-gp = Area of rectangle= ℓ × b = P × ∆V = W

Prof M. Rashid Khan

First Law Of Thermodynamics
It is basically law of conservation of energy with special mentioning of heat conservation and states that
Heat can be transformed into other forms of energies ( work, internal energy, e.t.c)
and other forms conversely into heat but total energy remain constant.

For an ideal case i.e frictionless cylinder – piston system Wf = 0

Q = ∆u + W
∆u = Q − W
𝐖
This eq. measures change in internal energy of the system
∆𝐮

A thermocouple is a device which convert heat into electrical energy.

Energy transforming processes occurring with in organism is called metabolism.

As consequence of metabolism, heat is produced known as metabolic heat.

Metabolic heat maintain animals body temperature or internal energy

Prof M. Rashid Khan
Application's Of First Law Of Thermodynamics
Process Isobaric Isometric Isothermal Adiabatic
Pressure of system is kept Volume of system is kept Temperature of system No heat enter to or
Definition constant in process. constant in process. is kept constant in leave from system.
∆P = 0 ∆V = 0 ⟹W=P△V=0 process. ∆T = 0 ⟹ ∆U = 0 Q=0

System proceed at constant System proceed at constant System proceed at constant System proceed at Q=0
P V T
Working

Q=∆u + W 0 = ∆u + W
Application of Q=∆u + W
Q=∆u + W +Q = +W Exp −∆u = +W Exp
First Law of
Q=∆u −Q = −W Comp −W = +∆u Comp
thermodynamics
V∝T P∝T 1 1
Which gas P∝ P∝
V P V Vγ
law holds = constant = constant
T T PV = constant PV γ = constant
P PV-gp P P P
PV-gp PV-gp isotherm PV-gp adiabat
PV- gp

V V V V
 𝐀𝐏𝐕−𝐠𝐩 𝐚𝐭 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭 𝐏 > 𝐀𝐏𝐕−𝐠𝐩 𝐚𝐭 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭 𝐓 > 𝐀𝐏𝐕−𝐠𝐩 𝐚𝐭 𝐐=𝟎 while 𝐀𝐏𝐕−𝐠𝐩 𝐚𝐭 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭 𝐕 = 𝟎
Wat constant P > Wat constant T > Wat Q=0 while Wat constant V = 0

According to Newton for According to Laplace for

isothermal process adiabatic process Slope of adiabat = 𝛾 × Slope of isotherm
ΔP ΔP Slope of adiabat
=P = γP =𝛾
ΔV/V ΔV/V Slope of isotherm
ΔP P ΔP γP Slope of adiabat > Slope of isotherm
= =
ΔV V ΔV V Adiabat is steeper than Isotherm.
P γP
Slope of isotherm = Slope of adiabat = It shows that adiabatic process is abrupt than isotherm
V V

HEAT CAPACITY Molar Specific Heat

Heat capacity of unit mole of substance. Or
Heat required by any amount of substance to raise its H Q/∆T Q
temperature through one degree. Or mathematically Cn = = = ( Jmol−1 K −1 )
Q n n n∆T
H= ( JK −1 ) Gases response very largely to temperature variation.
∆T
So, gases are heated keeping either their volume or
Specific Heat pressure constant and molar specific heat of a gas can
Heat capacity of unit mass of substance. Or be defined in two ways.
H Q/∆T Q Molar Specific Heat Molar Specific Heat
Cm = = = ( JKg −1 K −1 )
m m m∆T at Constant Volume at Constant Pressure
QV QP
Prof M. Rashid Khan CV = CP =
n∆T n∆T
Relation Between 𝐂𝐕 , 𝐂𝐏 and R
CP − CV = R
R γR
CV = and CP =
(γ−1) (γ−1)

Q. What is molar specific heat of a system in Q. What is molar specific heat of a system in
isothermal process? adiabatic process?
Q Q
Cn = Cn =
n∆T n∆T
For isothermal process ∆T = 𝟎 ⟹ Cn = ∞ For adiabatic process 𝐐 = 𝟎 ⟹ Cn =0

Prof M. Rashid Khan