LAWS OF THERMODYNAMICS:

Thermodynamics rests upon two fundamental laws:

First law
Second law

First law of thermodynamics

- Principle of conservation of energy
- Energy can be neither created nor destroyed
Basic statement:
When any closed system is taken through a cycle, the net
work delivered to the surroundings (/ done on the system) is
proportional to the net heat taken from the surroundings (/
delivered to the surroundings). Qin

Net heat =J (Net work) Win Wout

Qout

Here, J is a proportionality factor that depends on the units

used for work and heat.
As in SI system The unit of Heat and Work are same, so the
value of J is unity.
 Qin

Net heat =Net work

Win Wout
or, Q  Q  W  W
in out out in

or,  Q   W Qout

or,  Q   W
cyclic integral of work
for a closed path
cyclic integral of heat
for a closed path
Aspects of the first law:
With the aid of this law, it is possible to calculate the amount of
heat & work which cross the boundary of a system when given
changes in properties occur.
i.e., We can calculate
- Work done by steam expanding through a given range of
pressure in a turbine
- Work required to produce a given pressure rise in an air
compressor
- Heat required to generate steam at a given pressure in a
boiler & so on.
1st law of thermodynamics for closed system
(control mass):
 Q   W ------- (1)

Considering cycle 1-A-2-B-1

1 Q A   Q   W   W ---------- (2)
2 1 2 1
2 B 1 A 2 B

Considering cycle 1-C-2-B-1

1 Q C   Q   W   W ---------- (3)
2 1 2 1
2 B 1 C 2 B

(2)-(3) 
1 Q A   Q   W   W
2 2 2 2
1 C 1 A 1 C

1
2
(Q  W )   (Q  W )
A
2
1 C
---------- (4)

Since A & C represent arbitrary processes, betn. states (1) & (2) we conclude that
the quantity (Q- W) is the same for all processes betn. states (1) & (2).
The quantity (Q- W) between states (1) & (2)
- depends only on the initial & final states & not on the path
followed between the two states
- is the point function
- is the differential property of the system (control mass).

This property is the energy, E of the system.

So, dE = Q – W

or, Q=dE+W --------------------------------(5)

(since E is a property its derivative is written as dE)

By integrating we get,

Q  E  E W
12 2 1 12
-----------------(6)

Where, E1 & E2: initial & final values of the energy E of the
system
Q : heat transferred to the system during the process from state
12

1 to state 2
W : work done by the system during the process betn. state 1 to
12

state 2.
Physical significance of E:

E represents all the energy of the system in the given state such as,
Kinetic Energy, KE
Potential energy, PE
Energy associates with the motion &
position of the molecules
Internal energy,U Energy associated with the structure of the atom
Chemical energy and so on
Internal Energy (U):

Internal Energy is an extensive property (depends on the

size/mass of the system).
The symbol is U
u: specific internal energy (internal energy per unit mass).
It is a Intensive property
Since the terms comprising E are point function we can write

dE =dU + d(kE) + d(PE)

 E  U  kE  PE

Eqn. (5) becomes;

Q = dU + d(kE) + d(PE) + W

---------------(7)
Let a system is initially at rest
The system be acted on by an external horizontal force F that
moves the system a distance dx in the direction of force
.
y
Here, d(PE)=0 (no change in PE)
Q=0 (no heat transfer)
F System System
dU=0 (no change in internal
State-1 State-2 energy)
dx x
Now from equ (7)

0=0+d(kE)+0+(-Fdx)
or, d(kE)=Fdx
From Newton’s 2nd law of motion;
 Let the system be acted on by a vertical
force F that is of such magnitude that it
State 2 g
raises (in elevation) the system with
z
constant velocity an amount dz.
dz
State 1
Here, F=ma=mg
x
F
Q=0, d(kE)=0, dU=0

W=- Fdz = -mgdz

(work is done on the system)

Now from equ. (7) becomes,

0=0+0+d(PE)+(-mgdz)

or, d(PE)=mgdz
 dE =dU + d(kE) + d(PE)

Substituting the expressions for kE & PE into equ. (7)

dE = dU + mVdV + mgdZ =Q - W

Integrating for a change of stae4 from (1) to (2);

---------- (8)

This is the integral from of First Law of Thermodynamics.

Rate Equation of First Law:
Enthalpy:
Let us consider a control mass undergoing constant pressure
process, as shown in figure.
Enthalpy:

Thermodynamic property
Extensive property
Independent of process
Combination of energy of the system due to temperature,
pressure, and volume
A property of the system that measures its heat content.
Specific heat (heat capacity):

Thermodynamic property
Intensive property
The amount of heat required per unit mass to raise the
temperature by one degree.

1  Q 
c  
m  T 
Specific heat at constant volume:

1  Q 
c   
m  T 
v
v

1  Q  1  U   u 
 c        
m  T  m  T   T 
v
v v v
Specific heat at constant pressure:
1  Q 
c   
m  T 
p
p

1  Q  1  H   h 
 c        
m  T  m  T   T 
p
p p p
Steady-State, Steady-Flow Process:
Application to steady flow energy equation:
=
Pure Substance:
A pure substance is one that has a homogeneous and
invariable chemical composition.
It may exist in more than one phase, but the chemical
composition is the same in all phases.
Thus, liquid water, a mixture of liquid water and water vapor
(steam), and a mixture of ice and liquid water are all pure
substances; every phase has the same chemical composition.
In contrast, a mixture of liquid air and gaseous air is not a pure
substance because the composition of the liquid phase is different
from that of the vapor phase.
Vapor-liquid-phase equilibrium in a pure substance:
Vapor-liquid-phase equilibrium in a pure substance:
Vapor-liquid-phase equilibrium in a pure substance:
Saturation Temperature and Saturation Pressure:
Property Diagrams for Phase-Change Processes:
Property Diagrams for Phase-Change Processes:
Property Diagrams for Phase-Change Processes:

FIGURE : T-v diagram of a pure substance

P-v Diagram::
By convention, the subscript f is used to designate a property of
a saturated liquid and the subscript g a property of a saturated
vapor.
Thus, a saturation condition involving part liquid and part vapor,
such as that shown in Figure, can be shown on T–v coordinates, as
in Figure.
All of the liquid present is at state f with specific volume vf
and all of the vapor present is at state g with vg.

The total volume is the sum of the liquid volume and the
vapor volume, or

The average specific volume of

the system v is then

The definition of quality x = mvap/m.

Using the definition

v can also be written as

Now the quality x can be viewed as the fraction (v − v f )/v f g

of the distance between saturated liquid and saturated vapor, as
indicated in Figure:
TABLES OF THERMODYNAMIC PROPERTIES

Tables of thermodynamic properties of many substances

are available, and in general, all these tables have the same
form.

In this section we will refer to the steam tables.

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