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FIRST LAW OF THERMODYNAMICS

One of the basic needs of Thermodynamics is to understand


Energy. The law which governs Conservation of Energy is known
as FIRST LAW OF THERMODYNAMICS. This law is the
cornerstone of Thermodynamics and we need to understand it
fully. However before we look at the Law itself, we need to define
two major components of the First Law which is
HEAT INTERACTION and WORK INTERACTION
HEAT INTERACTION
HEAT is the form of energy which is transferred from a system to
its surroundings , because of the Temperature Difference between
the system and the surroundings.
The form of energy which is transferred is known as
THERMAL ENERGY.
Heat Interaction is the actual transfer of Thermal Energy between
the system and its surroundings due to the temperature difference
between them. It flows from High Temp to low Temp
The Thermal Energy must cross the boundary of the system
If thermal energy crosses the boundary then the state of the
system will change , hence heat Interaction is a process. The units
of Heat Interaction is JOULES
System at T
1
Surroundings at T
2
Q = Heat flow or heat interaction as T
1
> T
2
The interaction is ve for the system and
+ve for the surroundings
Q is +ve when it is given to the system
Q is ve when it is given by the system
Since Heat interaction is a process so the change of state can be
shown as a path on a property diagram. This can be shown on a
P-T diagram
Now we can also have a process in which there is no Heat transfer
at all . Such a process is called ADIABATIC PROCESS.
Since Heat transfer is a process so we use the symbol
Q
1-2
meaning that heat transfer during process 1 to 2.
We can also have
1 2
1 2
/
Q
q Heat transfer unit mass
mass


The rate of Heat transfer is
*
1 2
Q
Q
Time

[ ]
2
* *
1 2
1
* *
1 2
varies
constant
Now if Q with time then Q Qdt
Now if Q is then Q Q time

T
2
T
1
T
P
The system undergoes the
path as shown and as a result
of the process the state of the
system changes. The process
will stop when system
achieves temperature of the
surroundings.
MODES OF HEAT TRANSFER : There are three methods by
which Heat Transfer takes place. These are Conduction,
Convection and Radiation.
CONDUCTION is the transfer of energy from high energy particles
to low energy particles. It takes place in Solids,Liquids, and Gases.
It is predominant in Solids and less dominant in Liquids and
Gases. It is governed by FOURIER LAW
*
cross sectional area
Cond
dT
Q kA where k Thermal Conductivity
dx
A
dT
Temperature Gradient in flow direction
dx

CONVECTION is the transfer of energy , due to physical


movement of mass and conduction.
The mass has to have a velocity. The velocity can be generated by
a. External Forces ( Forced Convection)
b. Density Changes (Free convection)
It is governed by NEWTONS LAW OF COOLING
( )
*
Convection
s f s f
Q hA T T with T T >
T
f
h
T
surface
A = surface area
h = Heat transfer
co-efficient due
to convection
A = surface Area
RADIATION : Thermal Energy transmitted in the form of electro-
magnetic waves. It does not need a medium. It is governed by the
STEPHAN-BOLTZMANN LAW . The energy is emitted due to the
fact that a body has temperature above absolute Zero.
It also depends upon the type of body emitting Radiation
For a perfect Radiator which is called a black body
( )
*
4
emitted
Surface
Q A T
and if the body is not a perfect radiator
then it is called a Real Body and here
( ) ( )
*
4
1
emitted
Surface
Q A T where emmissivity of body
For a black body

Bodies also have the capability to absorb Radiation. This is


governed by
RadiationAbsorbed
Radiation Recieved
1
Absorbitivity
For a black body

Black Body absorbs all Radiation Received so thus


* *
Absorbed Incident or recieved
Q Q
Thus is a body is emitting as well as absorbing .
The net Heat Transfer by Radiation is thus dependent of the rates
of emission and absorbing. If a body is completely enclosed by
another body then
1
2
( )
( )
*
4 4
1 2
1 For Body
Q A T T
We will later see how these are evaluated in Semester V
WORK is also an energy transfer between a system and its
surroundings. It is not due to difference of temperature but it is due
to a FORCE ACTING IN A SPECIFIC MANNER.
We willsee that work is generated in several ways
The units of Work is also Joules =N-m
*
W Joules
w Work per unit mass in
mass kg
W Joules
Power W in units of Watts
Time kg


Surr
System
Piston
moving
Moving Boundary
Work
System
Shaft Work
R I
Electrical Work
System
Q= -ve
Q= +ve
W = -ve
W = +ve Heat and work
interactions imply a
change of state of
system
Heat and Work Interactions
They are
a. Interactions which cross boundaries
b. They are not properties.
c. They are associated with a process and occur because
of change of state.
d. Both are path functions , and thus the value of W and
Q depend upon the path taken.
2
1 2
1
2 1
det min W W and we have to er e the Inexact Differential and
and it is not equal to W W as Work is not a property

2
2 1
1
2 1
V dV V V This is an exact differential because
V and V are properties

1 2 1 2
Q and W are never written as W


We will always have to specify the path.
A
B
C
2
1
A B C
A B C
W W W
Q Q Q


Lets look at a few examples of how work and heat can be
assessed considering the system and its surroundings
FORMS OF WORK
System is room which is completely
insulated.
Candle located in room.
Q=0 and W=0
Isolated system
200
o
C
System is potato at 25
o
C which is
located in an oven having T=200
o
C
Q= +ve and W=0
Potato
Room
Oven
-ve +ve
System is oven and element. The
system is completely insulated.
Q= 0 and W=-ve
Work is Electrical work
Electrons
cross
boundary
Element
Heat
Given
Oven
Oven
System is oven and is not insulated.
Q= +ve0 and W= 0
Heat given by fire.
Electrical Work: When electrons cross the from the system
boundary then electrical work is done by the system. If electrons
cross into the system then electrical work is done on system
W
e
= V(N) where V=voltage and N = Coulombs of electron
Now
*
( ) e
N
Current I soW V I Power
Time

and thus power is expressed in Watts.
( ) ( )
( ) ( ) ( )
2
1
e
e
If V and I are functions of time then W V I dT
If V and I are not functions of time then W V I t

MECHANICAL WORK
From Physics we know that W = Force X Distance = F(s)
Insulated
Ice Water
at 0
o
C
Oil at 0
o
C
10 kJ Initially Oil ( System A) and
Ice Water (System B) are at
0
o
C.
When 10 kJ of electrical work is given to system A , it converts to
heat and increases temperature of Oil and it rises.
Now as oil gets heated it gives heat to ice water and some ice
melts.
Eventually both systems go to 0
o
C.
System A gets 10 kJ of Work and gives 10 kJ of Heat to ice water
and comes back to its original state.
System B gets 10 kJ of Heat from system A

For the combined System A+B
W
in
= 10kJ and Q
out
= 0
We should be sure about our system definition and the
interactions
If force is not constant then
2
1
W Fds

This form of work is called Mechanical Work


Now in Thermodynamics we have system and surroundings.Here
Work Interaction requires that we have
a. Force Acting on system boundary
b. Movement of boundary due to force
If we have forces on boundary and no movement of boundary
W =0
If boundary moves without any force acting on it then again
W =0
So in Thermodynamics Mechanical Work is only possible due to
Moving Boundary work due to a force
Moving whole system work due to a force.
We will now look at them in details
MOVING BOUNDARY WORK
Let us look at a cylinder with gas in it. The cylinder has a piston
which can move.
Generally if the process is very fast , then properties inside the
system do not change uniformly.
THERMODYNAMICALLY PROPERTY CHANGE SHOULD BE
UNIFORM IN THE SYSTEM.
Thus to analyse processes we use the concept of QUASI-STATIC
or QUASI-EQUILIBRIUM PROCESS . This requires that the
process is so slow that the property change is uniform in the
system.
NON QUASI-STATIC PROCESS CAUSE LOSES AND EFFECT
EFFICIENCY
For our course we will assume that all processes are QUASI-
STATIC.
P
Area
The pressure of the gas will force the
piston up, and it moves a distance
ds. The Pressure is constant and is
absolute Pressure
so moving boundary work is
or PdV work
ds
Now when the boundaries expand then dV is positive. So PdV
work will be positive when the boundaries expand. So expansion
gives positive work.
When boundaries are compressed then dV is negative. So here
PdV work will be negative. Hence Compression gives negative
work.
2
1
Now PdV work is W PdV
so we plot the processs on a P V diagram

The area under the path of process 1-2 is the PdV work as
2
1
W PdV Moving Boundary Work

so if we have three different processes between the same states


Although the change of state is same but the path decides the
value of Work. Here Process A is the best.
1
2
P
V
1 2
1
2
P
V
A
B
C
2
1
2
1
2
1
10
8
5
A
B
C
W PdV kJ
W PdV kJ
W PdV kJ


Area is different under


each curve
Now supposing we have a process which undergoes a cycle as
shown in the next diagram
The process starts from State 1 goes to State 2 and again comes
back to 1.
When initial state is equal to the final state we have a cycle.
2 1
1 2
1 2 2 1
2 1
Net for cycle
Compression Work PdV ve Expansion Work PdV ve
W W W ve
because area under curve is greater

+
+ +


This is how most engines work by operating in a cycle and getting
positive work.
We can also have shaft work in that we use the net work of the
cycle to rotate a shaft ( Car Engine)
The boundary can also be made to expand by heating it to get
positive work. ( Baloon rising)
Basically Mechanical work is mostly due to PdV work and Shaft
work. We represent shaft work by W
X
.We will later learn how to
evaluate the value of shaft work as it requires information about
Torque and RPM.
We shall now look at a few examples.
2
1
P
V
2 1
PROCESSES IN THERMODYNAMICS AND WORK
EVALUATION
Ideal Gas Polytropic Process:- For Ideal gases generally we have
a process where P,V and T change together. This is called a
POLYTROPIC PROCESS. It is represented by the equation
( )
2 2 1 1
2 1
b
1 1
1 1 2 2
2 2 2
b
Constant=C where n is an index depending
upon the type of polytropic process. But n 1
So for such a process the PdV work can be
W
1
W
n
n n
n
n n
n
PV
V V
PdV CV dV C
n
but C PV PV
PV V
+ +


1
+
]


( )
( ) ( )
( )
1 1
1 1 1
2 2 1 1
1 1 1 1 2 2 2 2
2 2 1 1
b
2 1
b
1 1
W tan
1
W
1
n n n
PV V
PV PV
n n
But PV mRT and PV m RT so
m RT mRT
and if m cons t
n
mR T T
n
+ +
1


1
+
1
]

This is a very important process as we shall see later.


We can also have other processes of Ideal gases. These are
( )
2
1
2
1
2
2
1
1 1
2 1
tan
Constant
ln
tan
tan
0 0
V
b
V
V
b
V
b
Isothermal with cons t mass
where PV mRT
V mRT
W PdV dV mRT
V V
Isobaric with cons t mass
W PdV P V V
Isochoric with cons t mass
W as V




GRAVITATIONAL WORK
Work done by or against a Gravitational Filed. In such work the
force acting on a body is its weight.
F = mg where g = acceleration due to gravity so
2
2 1
1
( )
g
W Fdz mg z z

where z is measured from a reference


point usually the Sea level.
ACCELERATIONAL WORK
Due to change of velocity. A body moves when it is subject to a
Force
( )
2 2
2 2
2 1
1 1
1
2
a
dV dV
F ma where a so F m
dt dt
ds
but V so ds Vdt hence
dt
dV
W Fds m Vdt m V V
dt


1
]
SHAFT WORK
The energy transmitted by a rotating shaft due to a Torque.
The shaft rotates so distance traveled in one rotation is 2 r
( )
( ) ( )
*
/ sec 2
2 2 Shaft
s
If shaft rotates at n revolutions then r n
t
Fs work
so r n n W Shaft Power
t Time r


SPRING WORK
Spring Work is produced by change in length of Spring.
For any spring its force is given by F = k (x) where
k = spring constant and x is the distance length changes
( )
( )
2 2
1 1
2 2
2 1
1
2
x x
Spring
x x
W Fdx kx dx k x x

WORK OF ELASTIC SOLID BAR behaves like a spring and hence
2
1
/
x
Elastic n n
x
F
W Adx where A c s area and
A

WORK OF A LIQUID FILM DUE TO SURFACE TENSION


2
1
.
A
ST s s
A
F
W dA where Surface Tension
Unit Length
and dA increase in length of film area

We can also have non-mechanical work such as


a. Electrical = Volts X Amps. , b. Magnetic due to dipole
movement and c. Electrical Polarization work caused by dipole
movement due to electricity
Having defined Work and Heat Interaction we now look at the
Shaft
Torque = =F r
r = radius of shaft
FIRST LAW OF THERMODYNAMICS
This law deals with Conservation of energy. It reaffirms that
Energy can neither be destroyed nor created. It can change forms.
This then points towards the Concept of Energy Balance
Total Energy going
into system
-
Total Energy
coming out of system
=
Changes in total
energy of system
E
in
- E
out
= E
system
P.E. = M
K.E. = 0
P.E. = M- N
K.E. = N
If we have a rock at a high point it has
Potential Energy and no Kinetic Energy
As it falls the PE starts changing into KE
Potential energy reduces and Kinetic Energy
increases.
Increase in KE = Decrease in PE
If we heat a closed system then the heat
energy adds to the the total energy of the
system.
Here E
System
= Q = 10kJ
Q = 10 kJ
W = 0 kJ
If we have a closed system on which we do
work then the Work energy adds to the total
energy of the system
Here E
System
= W = 10kJ
On the other hand if 10 kJ of work is taken
out of the system then E
System
= W = -10kJ
Q = 0 kJ
W = 10 kJ
E is the summation of all the different energies ( Internal, KE,PE,
Electrical , Magnetic, Surface Tension etc. )
For our simple systems we will neglect Electrical , Magnetic,
Surface Tension etc. and so for us
( ) ( ) ( ) ( )
( )
( )
2 2
2 1
2 1 2 1 2 1
1
2
0
E U KE PE or
E E m u u m v v mg z z
For Stationary systems KE PE so E U
+ +
_
+ +

,

MECHANISM OF ENERGY TRANSFER
Energy transfer can take place by the following methods
a. Heat Transfer = Q
b. Work Transfer = W
c. Mass Flow
Now if a system is closed then mass flow is zero. So for closed
systems . Q-W = E is the FIRST LAW OF THERMODYNAMICS
tan Q W E or q w e as mass is cons t or
General Q W E
Stationary System Q W U
Closed system q w e u per unit mass
Differential form for closed system q w de





If we have a process from State 1 to State 2 then
Q
1-2
W
1-2
= E
2
E
1
If we have a cycle then E
2
= E
1
and so Q
1-2
= W
1-2
E
V
1
2
If we have a process where energy
transfer takes place then
E
System
= E
Final State
E
Initial State
= E
2
E
1
The first Law can be represented by a postulate called PMM1 or
Perpetual Motion Machine 1
A machine which operates in a cycle , and keeps on giving work
without any form of Heat Transfer
We now look at a few examples.
W
SPECIFIC HEATS
It is defined as the ENERGY REQUIRED TO RAISE
TEMPERATURE OF A UNIT MASS OF A SUBSTANCE BY ONE
DEGREE .
To achieve this we can either keep Volume constant or Pressure
constant and hence we have two types of Specific Heats in
Thermodynamics
C
V
= Specific Heat at Constant volume
C
P
= Specific heat at Constant Pressure and they are
exp
v P
v P
o o
v P
v P
o o
u h
C and C
T T
kJ kJ
with units or
kg K kg C
They can also be ressed on molar basis
u h
C and C
T T
kJ kJ
with units or
kmol K kmol C
_ _



, ,

_ _



, ,

C
P
and C
v
are expressed in terms of other properties so they are
also properties. So the specific heats are to be defined by two
independent intensive properties. They are thus not dependent
upon the process but on the state of the system.
For most substances C
p
and C
v
are functions of Temperature.
and we see this in figure 3-76
C
P
o
K
CO
2
H
2
O
Air
For ideal gases
( ) ( )
( ) ( )
v P
u f T and h f T so
C f T and C f T


So for Ideal gases they are not constants. However for simplicity
and for ease of calculation they are at times taken as constant.
Such that
2 1 2 1
2 1 2 1
( )
( )
v v
P P
du
C so u u C T T and
dT
dh
C so h h C T T
dT


If they are functions of temperature then
2 2
2 1 2 1
1 1
v P
u u C dT and h h C dT

Sometimes we take average values of C
P
and C
v
between the
temperature ranges and then we evaluate
( ) ( )
2 1 2 1 2 1 2 1
( ) ( )
v P
Avg Avg
u u C T T and h h C T T
We can thus find values of the Specific Heats from
a. Tables
b. Integratung h,u with respect to T
c. By using Average values or constant values. This method is
mostly preferred.
SPECIFIC HEAT RELATIONS OF IDEAL GASES
( )
introduce
vary
1.4
P v P v
P v u
P
P v
v
Air
We have h u Pv and for an ideal gas Pv Rt so
dh du
h u RT or dh du RdT or R
dT dT
so C C R or C C R for an ideal gas
If we use molar basis C C R
Also we a ratio of Specific Heats
C
k or f T as both C and C with T
C
F

+
+ + +
+

2 2
1 1
P v
or Ideal gases h C dt and u C dt

U,H AND C
P
AND C
V
FOR SOLIDS AND LIQUIDS
Solids and Liquids are in-compressible and their density does not
change significantly with Pressure or Temperature. For them
C
P
= C
v
= C. Values are given in Table A-3
[ ]
[ ] [ ]
2 1 2 1
2 1 2 1 2 1
2 1 2 1 2 1
0
0
. .
. .
v av
av
here du C dt so u u C T T
and for enthalpy changes h u Pv
so dh du Pdv vdP du vdP as dv
so h h C T T v P P
For solids P P so h h u u
For Liquids a if pressure is const then h u
b If const temperature h v P

+
+ + +
+



[ ]
( )
@ , @
@
2 1 2 1
@ ,
@ ,
0
1 2
P T T
T
P T f f Sat at T
P T f
as u
so for this case if we have a process from
h h v P P
so to find h h v P P
or h nearly equal to h