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


Net heat =J (Net work)


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.
W
in
W
out

Q
in

Q
out

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).

W
in
W
out

Q
in

Q
out

in out out in
W W Q Q =
= W Q
} }
= W Q o o
Net heat =Net work

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.

1st law of thermodynamics for closed system
(control mass):
------- (1)

Considering cycle 1-A-2-B-1
---------- (2)

Considering cycle 1-C-2-B-1
---------- (3)

(2)-(3)

---------- (4)

Since A & C represent arbitrary processes, betn. states (1) & (2) we conclude that
the quantity (oQ- oW) is the same for all processes betn. states (1) & (2).
} }
= W Q o o
B A B A
W W Q Q
} } } }
+ = +
1
2
2
1
1
2
2
1
o o o o
B C B C
W W Q Q
} } } }
+ = +
1
2
2
1
1
2
2
1
o o o o

C A C A
W W Q Q
} } } }
=
2
1
2
1
2
1
2
1
o o o o
C A
W Q W Q ) ( ) (
2
1
2
1
o o o o =
} }
The quantity (oQ- oW) 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 = oQ oW

or, oQ=dE+oW --------------------------------(5)

(since E is a property its derivative is written as dE)
By integrating we get,

-----------------(6)

Where, E
1
& E
2
: initial & final values of the energy E of the
system
: heat transferred to the system during the process from state
1 to state 2
: work done by the system during the process betn. state 1 to
state 2.
12 1 2 12
W E E Q + =
12
Q
12
W
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
Since the terms comprising E are point function we can write

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


Eqn. (5) becomes;

oQ = dU + d(kE) + d(PE) + oW ---------------(7)
PE kE U E + + =
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
.
System
State-1
System
State-2
dx
y
F
x
Here, d(PE)=0 (no change in PE)
oQ=0 (no heat transfer)
dU=0 (no change in internal
energy)

Now from equ (7)

0=0+d(kE)+0+(-Fdx)
or, d(kE)=Fdx

From Newtons 2nd law of motion;
ma F =
dt
dv
m =
dx
dv
dt
dx
m =
dx
dv
mv =
mvdv kE d = ) (


State 2 g
z
dz
State 1
x
F
Let the system be acted on by a vertical
force F that is of such magnitude that it
raises (in elevation) the system with
constant velocity an amount dz.

Here, F=ma=mg

oQ=0, d(kE)=0, dU=0

oW=- Fdz = -mgdz

(work is done on the system)
Now from equ. (7) becomes,

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

or, d(PE)=mgdz
Substituting the expressions for kE & PE into equ. (7)

oQ=dU + mvdv + mgdz + oW

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

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

This is the integral from of First Law of Thermodynamics.

In the absence of kE & PE

---------- non-flow energy eqn.
12 1 2
1
2
2
2
1 2 12
) ( )
2
( W z z mg
v v
m U U Q + +

+ =
1 2 12 12
U U W Q =
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
Enthalpy:

Let us consider a control mass undergoing quasi-equilibrium
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.
|
.
|

\
|
=
T
Q
m
c
o
o 1
Specific heat at constant volume:





v
v
T
Q
m
c
|
.
|

\
|
=
o
o 1
v v v
v
T
u
T
U
m T
Q
m
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
.
|

\
|
=
1 1
o
o
Specific heat at constant pressure:
p
p
T
Q
m
c
|
.
|

\
|
=
o
o 1
p p p
p
T
h
T
H
m T
Q
m
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
.
|

\
|
=
1 1
o
o
Rate Equation of First Law:
Steady-State, Steady-Flow Process:
Application to steady flow energy equation:
( )
e i CV
h h m W =

0 =
CV
Q

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 Tv coordinates, as
in Figure.
All of the liquid present is at state f with specific volume v
f

and all of the vapor present is at state g with v
g
.
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 = m
vap
/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.
Problem:
Problem:
Problem:
Problem:
Problem:
Problem:
Problem: