JEE/NEET

Thermodynamics
 THERMODYNAMICS

Thermodynamics
1. A system whose state is completely defined by the variables like Pressure (P), Volume (V), Temperature
(T), Internal energy (U), is called a thermodynamic system. These variables are called thermodynamic
variables.
2. A P-V diagram for a system is called an indicator diagram.
3. The area under a curve on P-V diagram shows work done on or by the system.
4. Work done on or by a gas or system depends upon the initial state, final state and the path adopted
between these two states.
5. Like work done, heat exchanged by the system or a gas also depends upon the initial state, the final state
and the path.
6. Change in internal energy of a gas depends only upon the initial and the final state but not on the path. It
is a unique function of the point on the indicator diagram.
Zeroth law of thermodynamics
When two bodies A and B are in thermal equilibrium with a third body C, then A and B are in thermal
equilibrium mutually, i.e; if TA = TC TB = TC, then TA = TB.
First law of thermodynamics
First law of thermodynamics is equivalent to law of conservation of energy. According to this law ∆ Q = ∆U +
∆W, Where ∆ Q is heat added or rejected by system, ∆W is work done by or on the system and ∆U is the
change in internal energy of system.
1. ∆Q is +ive if heat is added to system and – ive if heat is rejected by system.
2. ∆W is +ive if work is done by system and – ive if work is done on system.
3. ∆U is +ive if internal energy os system increases and – ive if decreases.
Specific heats of a gas
1. Specific heat of a gas at constant volume (Cv): It is the amount of heat that must be added to unit mass
of a gas to increase its temperature by 1°C or 1 K when the volume is kept constant. If the amount of
mass considered is one mole, then Cv is called molar specific heat at constant volume. If we consider n
moles of a gas at constant volume, then dQ = nCv dT = dU (· ֽ◌· dW = P dV
=0)
2. Specific heat of a gas at constant pressure (Cp): It is the amount of heat that must be added to unit
mass of gas to increase its temperature by 1°C when the pressure of gas is kept constant. If the amount of
mass considered is 1 mole, then Cp is called molar specific heat at constant pressure. If we consider n
moles of a gas at constant pressure, then dQ = nCp dT = dU + dW
3. Mayor's relation between Cp and Cv: For one mole of a gas Cp – Cv = R
Cp 2
4. For any gas:    1  , (where  depends on atomicity of gas and f is degree of freedom).
Cv f
R R
5. Cp and Cv in terms of  and R: C v  and C p  C v 
 1  1
f f 
6. Cp and Cv in terms of f and R: C v  R and C p    1 R
2 2 
Work done in thermodynamic process
If there occurs an infinitesimal change in volume dV at a pressure P, work done dW is given by : dW = PdV.
Total work done in a variable pressure process in going from some initial state (Pi, Vi) to final state (Pf, Vf) is:
Vf
W Vi
PdV .

1. Work done is equal to area under the curve on P-V diagram.

2. Work done by a gas during expansion is taken as positive while during compression it is taken as
negative.
3. For a cyclic process: W = area enclosed in the cycle. Work done is positive when the cycle is traced out in
clockwise direction and work is negative when the cycle is traced out in anticlockwise direction.
4. Work done in Isobaric process: W = P(Vf – Vi)
5. Work done in Isometric process: W = 0 (∆V = 0)
 V  P  V 
6. Work done in Isothermal process:W  RT log e  f   RT log e  f   Pi Vi log e  f 
 Vi   Pi   Vi 
P V  Pf Vf R (Ti  Tf )
7. Work done in Adiabatic process: W i i   C v (Ti  Tf )
 1  1
Heat added or removed from a thermo dynamical system
The amount of heat involved with (added or removed from) n moles of a gas is given by: ∆Q = nCV ∆T (for
isometric or isochoric process) and ∆Q = nCp ∆T (for isobaric process)
Internal energy of a gas
1. According to kinetic theory of gases, mean kinetic energy of a molecule is; (KE) mean = (3/2)kT. A gas
contains a large number of molecules. The internal energy of a gas is equal to sum of the kinetic and
potential energies of all the molecules of the gas. In practice, we ignore potential energies of the
molecules and neglect intermolecular forces. Thus the total KE of all the molecules of the gas is equal to
the internal energy of the gas.
2. For n moles of gas, if the system undergoes any thermodynamic process in which temperature changes
by ∆T, the change in the internal energy is: ∆U = nCV ∆T .
Different types of thermodynamical processes
Isobaric process: It is a thermodynamic process in which pressure is kept
constant. The equation of state for the process is: (V/T) = constant.
1. In isobaric compression, temperature decreases and internal energy flows
out in the form of heat energy, while in isobaric expansion, temperature
increases and heat flows into the system.
2. The amount of heat energy transferred is given by: ∆Q = nCp ∆T
3. In the adjoining figure, graphs I and II represent isobaric expansion and
compression respectively.
4. The slope of the isobaric curve on a P-V diagram is zero.
Isochoric (Isometric) process: It is a thermodynamic process in which the
volume of the system is kept constant.
1. The equation of state for the process is: (P/T) = constant.
2. For isochoric process: ∆Q = CV ∆T and ∆W = 0
3. In the adjoining figure, graphs I and II represent isometric decrease in pressure at volume V 1 and
isometric increase in pressure at volume V2 respectively.
4. The slope of the isometric curve is infinite on a P-V diagram.
Isothermal process: It is a thermodynamical process in which the temperature of the system remains
constant.
1. The equation of state for the process is: PV = constant.
2. During isothermal expansion of a gas, its volume increases while pressure
decreases, while in isothermal compression, the volume decreases while
pressure increases.
3. The isothermal curve on P-V diagram is like a hyperbola and is shown in the
figure.
4. The slope of the isothermal curve at any point M is given by: dP/dV = -(P/V)
Adiabatic process: It is a process in which heat exchanged by the system to or
from the surroundings is zero, i.e., ∆Q = 0
1. The equation of state for this process is: PV = const. where  is
the ratio of specific heats of the gas.
2. Other equation are TV -1 = const. and P1 -  T = const.
3. The adiabatic curve on the P-V diagram is shown in the adjoining
figure. The slope of the curve at any point is given by:
dP/dV = -(P/V)
4. Slope of adiabatic curve is more in magnitude in comparison to the slope of the Isothermal curve.
5. When a gas expands from some initial volume to final volume, then final pressure is less for adiabatic
expansion. But, when a gas compresses from some initial volume to a final volume, then the final
pressure is more in case of adiabatic compression.
6. In adiabatic expansion, temperature decreases while in adiabatic compression, temperature increases.
7. Isothermal and adiabatic bulk modulus of a gas are given by: Biso = P and Badi = P
Second law of thermodynamics
1. Kelvin's statement: It is impossible for an engine operating in a cyclic process to extract heat from a
reservoir and convert it completely into work, i.e., whole of heat can never be converted into work
though whole of work can be converted into heat, i.e., a perfect heat engine can never be constructed.
2. Clausius statement: It is impossible for a self-acting machine unaided by any external agency to transfer
heat from a cold to hot reservoir, i.e., heat by itself cannot pass from a colder to hotter body.
Heat engine
1. It is a device which converts heat into work continuously through a cyclic process.
2. Every heat engine consists : (a) a hot body called source (b) a working substance (c) a cold body called
sink
3. In a heat engine working substance absorbs heat (Q1) from the source at a higher temperature TH,
converts a part of it into useful work (W) and rejects the rest (Q2) to the sink (usually atmosphere) at a
lower temperature TL and comes back to its initial state.
work done W Q1  Q 2 Q
4. Efficiency of a heat engine,     1 2
heat absorbed Q1 Q1 Q1
5. A perfect heat engine is one which converts all heat into work, i.e., W = Q1 so that Q2 = 0 hence, for it  =
1.
Carnot heat engine: It consists of four parts:
1. A cylinder with perfectly insulating walls and a perfectly conducting base containing a perfect gas as
working substance and fitted with an insulating frictionless piston;
2. A source of infinite thermal capacity maintained at a constant higher temperature TH;
3. A sink of infinite thermal capacity maintained at constant lower temperature TL, and
4. A perfectly non-conducting stand for cylinder.
Carnot cycle: It consists of four operations in succession: (i) isothermal expansion at higher temperature TH .
(ii) adiabatic expansion between temperatures TH and TL. (iii) isothermal compression at constant lower
temperature TL and (iv) adiabatic compression between temperatures TL and TH.
TL Q
1. Efficiency of the engine:   1   1  1 ,  depends only on temperatures of source and sink and is
TH Q2
independent of all other factors.
2. As on kelvin scale, temperature can never be negative and TH and TL are finite, efficiency of a heat engine
is always lesser than unity, i.e., whole of heat can never be converted into work which is in accordance
with second law.
Refrigerator or heat pump
1. A refrigerator or heat pump is basically a heat engine run in reverse direction. In it working substance
takes heat Q2 from a body at a lower temperature TL, has a net amount of work done W on it by an
external agent (usually compressor) and gives out a larger amount of heat Q1 (= Q2 + W) to a hot body at
temperature TH (usually atmosphere).
2. A refrigerator or heat pump transfers heat from a cold to a hot body at the expense of mechanical energy
supplied to it by an external agent. The working substance here is called refrigerant.
3. The coefficient of performance of a refrigerator is defined as:
heat extracted from the reservoir at low temperature TL Q Q2 TL
 i.e.   2  
work done to transfer the heat W Q1  Q 2 TH  TL
4. A perfect refrigerator is one which transfers heat from a cold to a hot body without doing any work, i.e.,
W = 0 so that Q1 = Q2, and hence for it K = ∞.