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THERMODYNAMICS
Internal energy : (U) U = PE + KE of molecules. Where KE of molecule =
f KT (f = degree of freedom & K is Boltzmann constant) and PE of 2

molecules depends upon intermolecular distance (ro).

Zeroth law of thermodynamic : If the bodies are in thermal equilibrium with a third body separately, then those two

First law of Thermodynamics :

sum of increase in the internal energy (dU) and external work done by system (dW) dQ = dU + dW.

dQ = +ve when heat supplied = - ve when heat rejected dU = +ve when temperature increases = ve when temperature decreases dW = +ve when work is done by system. = ve when work is done on system. Specific heats of gases :

Amount of Heat required to raise the temperature of whole system by 1C is Heat capacity of a gas (C)

C
Cv Cv

dQ ndT

molar specific heat of gas at constant volume. specific heat of a gas as constant volume.

W
a) Cp Cv = r = b) Cp- CV = R

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Cp Cp and Cv are J/kg/k Cp > Cv Relation betwen Specificheats of the gas R - universal gas constant.
CP CV 1

molar specific heat of gas as constant pressure. specific heat of gas at constant pressure units of Cp and Cv are J/mole/k units of Cp

Ratio of specific heats =

As atomicity of gas increases, value of decreases

Ma
R C , C Specificheats per unit mass of gas M p v

ma .i

The amount of heat supplied to a system (dQ) capable of doing external work is equal to

bodies are in thermally in equilibrium with each other.

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1.67
For MAG For DAG =
1.4

1.33
For TAG Cp & Cv interms of

Cv

, Cp 1

Number of degrees of freedom does a gas posses is f

2 1

Cv

f R, Cp 2

2 f R 2

Isothermal Process:

When a thermodynamic system undergoes a physical change in such a way that its temperature remains constant then the change is known as isothermal changes. It follows Boyles law. P1V1 = P2V2.

du = 0

Ex. Melting of ice, Boiling of a liquid are isothermal changes. Adiabatic process :

When a thermodynamics system undergoes a physical change is such a way that no. exchange of heat takes place between system and surroundings the process is known as

W
du + dW = 0
pv constant TV 1 constant

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adiabatic process. process. In adiabatic process, dQ = 0 du = - dW In an adiabatic process
P1V1 P2 V2 T2 V2 1 T1V1 1

During adiabatic process, entropy remains constant. Hence it is also known as isoentropic

T P
1

constant

Ma
dQ = dW = pdV

During isothermal change, internal energy remains constant. U is constant

T1 P1
1

T2 P2
1

Work done in an adiabatic process is given by W =

ma .i
P1V1 P2 V2 1 nR T1 T2 1

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Second law of Thermodynamics : Kelvin statement : It is impossible to extract work from a system by cooling it below surrounding temperature. It is impossible to transfer heat energy from body at lower temperature to body at higher temperature unaided by external agency. Carnots reversible cycle: It is a reversible engine which absorbs a heat Q1 from a source maintained at a constant high temperature T1 K and rejects a heat Q2 to a sink, which is maintained at a constant low temperature T2K. The efficiency of this engine is given by :
1 Q2 Q1 100 1 T2 100 T1

T2 Refrigerator (i)

temp. of sin k, T 1

temp. of source.

A refrigerator is a reversible engine operating in the reverse direction.

In refrigerator, an amount of heat Q2 is removed from sink at lower rejected at higher temperature T1 to the source. Thus, (ii) Q2 + W = Q1

or

Coefficient of performance.

It is defined as the ratio of amount of heat removed from

Sink to the amount of work done in removing it. It is denoted by =

The heat absorbed by refrigetraor work done on the refrigerator T2 T1 T2

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greater is the entropy dS =
dQ Heat absorbed by system or dS = T Absolute temperature

Entropy is a measure of disorder of molecular motion of a system. Greater is the disorder,

It is also called second law of thermodynamics.

Ma

ma .i
W = Q1 - Q2.

Note : All isothermal and adiabatic changes are reversible if they are performed very slowly.