CH4 - THERMODYNAMIC

1. Mechanical equivalent of heat

2. Terminology of Thermodynamics
3. Zeroth Law of Thermodynamics
4. First Law of Thermodynamics
5. Process and its Types
5.1 Isothermal process
5.2 Adiabatic process
6. Mechanical work in gas expansion
7. Work done during an isothermal process
8. Work done during an adiabatic process

Dr. Gamal Elhomosy

1. Mechanical equivalent of heat

The mechanical equivalent of heat ( J Joule

equivalent ) (J = 4.187 Joule / cal )
the mechanical work ( W   F  dr Joule )
amount of heat generated or transferred ( Q  mcV T cal )
the mechanical equivalent of heat (J) W  J Q
2. Terminology of Thermodynamics
System: A gas enclosed in a cylinder fitted with a piston is a system.
Surrounding medium: Remaining part of the universe outside the system which can exchange
energy with the system
Universe: The system and its surroundings are together known as the universe.
System Boundary : The real or imaginary surface separating the system from the surrounding
Isolated system: A system which can exchange neither matter nor energy with the surroundings
Homogeneous system: consists of a single phase,. Example: A pure single solid, liquid or a gas. A
mixture of gases.
Heterogeneous system:. Example: Two immiscible liquids such as benzene and water
Mechanical Equilibrium: if no unbalanced forces and torques act between the system and the
surroundings or between different parts of the system.
Thermal Equilibrium: if the temperature of the system is the same throughout and the temperature
of the system and the surroundings is the same.
Chemical Equilibrium: if the chemical composition of the system is the same throughout.
Thermodynamic Equilibrium: if it is in mechanical, thermal and chemical equilibrium at the same
time.
Equation of a State: the equation of state for one mole a perfect gas is PV = nRT. The equation of
the state can be written in the form, f (P, V, T) = 0.
 3. Zeroth Law of Thermodynamics:

Zeroth Law of Thermodynamics: “If two bodies P and Q are in

thermal equilibrium and also P and R in thermal equilibrium then Q
and R, are also in thermal equilibrium”.
Characteristics of Thermal Equilibrium:
 When two bodies are kept in contact and there is no transfer of heat taking
place between the two bodies
 There is no heat transfer between the two bodies due to conduction or
convection.
 All bodies in thermal equilibrium are at equal temperatures.
 If thermal equilibrium does not exist, then heat flows from a body at a
higher temperature to the body at a lower temperature, till thermal
equilibrium is established.
4. First Law of Thermodynamics:

Mathematical Expression of First Law: Q  U  W

Q : Heat supplied to the system by the surrounding
W : Work done by the system on the surrounding
U : Change in internal energy of the system
1. Work done (ΔW) : The work is positive when a system expands. When a
system is compressed, the volume decreases, the work done is negative.
The work done does not depend on the initial and final thermodynamic
states; it depends on the path followed to bring a change.
2. Heat gained by ΔQ (added to) a system is taken as positive, whereas heat
lost by a system is taken as negative.
3. The ΔU increase in internal energy is taken as positive and a decrease in
internal energy is taken as negative
Example 1.1

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 on the system. Find the
system’s internal energy.

Solution

The first law of thermodynamics Q  U  W

Thermal energy is transferred from the surroundings to the system Q   45J
External work has been done on the system W   450J
  45J  U  450J
 U  45J  450J  495J
It is clear that the thermal energy absorbed from the surrounding medium and the
work done on the system are energies that were given to the system, which led to an
increase in the internal energy of the molecules of the system
 5. Process and its Types:

Process:
It is the path or the operation by which a
system changes from one state to another. A
process causes a change in the value of at
least one of the state functions
5.1 Isothermal process:
at a constant temperature, the process is called an isothermal process ΔT = 0, ΔU = 0
Characteristics of Isothermal Process.
• In this process temperature of the system remains constant T= constant .
• The exchange of heat takes place with the surroundings. ( ΔQ ≠ 0)
• Internal energy remains constant. ΔU = 0 (provided there is no change in a phase).
• The system is not thermally isolated from the surroundings.
• Expansion occurs with the absorption of heat, while compression occurs with the
evolution of heat.  Q   W
• In the case of gases, Boyle’s law is applicable i.e. PV = constant
5.1 Isothermal process:

Examples of Isothermal Changes:

 Ice is converted into the water at constant temperature.
 Water is converted into vapors at constant temperature i.e. boiling
point of water.
 The industrial application of the isothermal process is the Carnot
engine.
 A gas can be allowed to expand or is compressed isothermally by
changing the pressure on it.
 5.1 Isothermal process:

Isothermal Curves:
This graph is known as PV-diagram .
Let us suppose that the gas undergoes
an isothermal expansion from a point H
to a point K along curve HK.
Obviously, V2 > V1.

During expansion, the gas does an external work and its internal
energy decreases. The curve HK is known as Isothermal curve.
The change is made from K to H along curve KH, the gas undergoes an
isothermal compression. The volume of the gas decreases from V2 to
V1. The external work is on the gas hence its internal energy
increases.
 5.2 Adiabatic process:

A process carried out in such a manner that the system, does not exchange heat with
the surroundings (ΔQ = 0) is called an adiabatic process. The temperature of the
system changes during the adiabatic process.
Characteristics of Adiabatic Process.
• The exchange of heat with the surrounding does not take place.
( ΔQ = 0)
• Internal energy varies. (ΔU ≠ 0)
• The system is thermally isolated from the surroundings.
• In expansion, temperature and internal energy decreases,
• in compression temperature and internal energy increase.
• W  U
• In the case of gases, PV   const . , where   cP cV Ratio of
specific heat capacities of a gas
 Relation between Pressure and Volume during an
Adiabatic Process
In this process Pressure (P), Volume (V) and Temperature (T) changes
but dQ=0 . Let, n moles of a gas be made to expand from an initial
state (P₁,V₁) to a final state (P₂,V₂) adiabatically. From
at any state, dU  dW  0
dU  ncV dT dW  PdV
and
 ncV dT  PdV  0
PdV  VdP  n RdT
equation of state from PV  nRT
PdV  VdP
  n dT
 PdV  VdP  R
 cV    PdV  0
 R 
 cV  R  PdV  cVVdP  0
From Mayer’s relation  cP  cV  R    cP PdV  cVVdP  0
 Relation between Pressure and Volume during an
Adiabatic Process
 cP  dV dP
Dividing throughout by cV PV:
   0
 cV  V P
Substituting   cP cV a constant known as the ratio of specific heats
of a gas, we get: dV dP
   0
V P

V2
dV dP P2
 V2   P2   P1   V2   P1 
     ln     ln    ln    ln    ln  
V V
1 P P 1  V1   P1   P2   V1   P2 

 V2   P1   
       PV
1 1  PV
2 2
 V1   P2 

 PV
1 1

 PV
2 2

 
3 3  const .
PV  PV  constant
 6. Mechanical work in gas
expansion
Then the force F on the piston due to the gas is PA,
where A is the area of the face. the piston is pushed
outward
the work done by the gas is dW  F  d x  PAdx

change in volume of the gas is dV  Adx

 dW  PdV
V2
W   PdV
V1
At isobarically ( dP = 0 ) from A to B
V2 V2
 WAB   PdV   P1dV  P1 V2  V1 
V1 V1

AT Isochoric process V2
( dV=0, V =constant )  WBC   PdV  0
From B to C, and therefore V2
no work is done
 7. Work done during an
isothermal process

the work done by an ideal gas in an

isothermal process is T = const : From
Equation of ideal gas law PV  nRT
V2 V2
nRT V 2
dV V 
Wiso   PdV   dV nRT   nRT ln  2 
V
1 V V
1 V V
1  V1 

at isothermal process dT = 0, PV = const.

P1 V2
PV  const.  PV
1 1  PV
2 2  const.   
P2 V1
 V2   P1 
 Wiso  nRT ln    nRT ln  
 V1   P2 
.

8. Work done during an

adiabatic process

does not exchange heat with the

surroundings (ΔQ = 0). The gas is kept
isolated from the surroundings, that is,
dQ = 0 and PV   const.
 K
PV  const.  K  P  
V V V
2
K 2

 Wadia   PdV    dV
V 1 V V 1
V2
  1
V2 V2
V 
   dV  K  V  dV  K 
K 
Wadia 
V V1 V 1    1 V 1

V2
1
V 
 K  
K
V 1
 V 1

1 V 1
2 1
1
.

8. Work done during an

adiabatic process

K  V2 V1  K  PV PV  K  nRT2 nRT1 
Wadia       
2 2
  
1 1
   
1  V2 V1  1    2 2
PV 
1 1 
PV 1    K K 
nR
 Wadia  T2  T1 
1
Notice that if   1 (expansion), Work done W , as expected
in an adiabatic process

PV  const. TV  1
 const.     const.
P 1
T 

  1   1
P1  V2  T1  V2   T1   P1 
          
P2  V1  T2  V1   T2   P2 
Example 1.2

Consider a rigid sealed tank of a volume of 0.3 m3 containing Nitrogen at 10 oC and

150 kPa. The tank is heated until the temperature of the nitrogen reaches 50 oC.
Treat nitrogen as an ideal gas, Molecular mass of Nitrogen gas is M N  28 gm / mole
1. Calculate the boundary work in this process
2. Calculate the change in internal energy in this process
Solution
Isochoric process ( dV=0 , V =constant ) in a rigid sealed tank .
1- The boundary work is zero because the volume of Nitrogen remains constant
Vf

Wi to f   PdV  0
Vi
2. Change in internal energy in the process From : R = 8.314 Joule / o K  mole
and nitrogen as an ideal gas cV  0.743 kJoule /kg  o K
The number of moles of Nitrogen
PV  150 kPa   0.3 m 3 
n =   18.4 moles
RT  
8.314 Joule / o K  mole (273+10) o K 
Example 1.2

Solution

The change in internal energy

dU  m cV dT   nM N  cV dT


  18.4 mole  0.028 kg / mole  0.743 kJoule /kg  o K 
 
 ( 50  273 )  ( 10  273 ) o K  15.3 kJoule
Nitrogen absorbs 15.3 kJoule of heat in this process.
Example 1.3
A cylinder of length 50 cm contains a ideal gas at a pressure of 3 atmospheres. A
piston of diameter 36 mm inside the cylinder is forced to move outwards a
relatively small distance of 2 mm. Calculate the work done by the gas against
atmospheric pressure (T=const.). 1 atmosphere = Pa.
Solution
The volume of the gas Vi :
  50  10 2 m  5.08  10 4 m 3
2
  3

 
36 10 m
Vi  Ah    D 2  h 
2

4
 
the cylinder is forced to move outwards a relatively small distance of 2 mm: The
volume of the gas V f :

V  A  h  2mm     D 2   h  2mm 
f
2

  36  10 3 m 
2


4
 50.2  10 2
m   5.109  10 4 m 3
Calculate the work done by the gas : PV = nRT =PV
i i =Pf V f =const.
V f
 Vf   Vf 
Wi to f   PdV  nRT ln  =PV i i ln  
Vi  i
V  i
V
  m 
4 3
  3  1.013  10 5  5.08  10 4 m3  ln 
5.109 10
4 3 
=0.878 Joule
 5.08  10 m 