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First Law Of Thermodynamics

Law of Conservation Of Energy :
The law of conservation of energy states Energy can neither be created nor destroyed
but it can only be converted from one form to another. Though the law of conservation of energy
can not be proved analytically, since it is based on the mans experiences, but it has never been
diproved and on the contrary many experiments have verified its statement.
First Law of Thermodynamics (Joules Experiment) :
This law of thermodynamics is a particular statement of the general principles of law of
conservation of energy. Initially the statement of conservation of energy was quantitavely analysed
for thermodynamics systems by Joule.

It consists of a paddle wheel arrangement with the liquid filled in an insulated container.
The work is supplied across the boundary of the system by a falling weight of mass m(W = mg). The
system is formed by the liquid in the container as a closed system. The work input to the system
equals to m-g-z. As a result of work transfer the temperature of the liquid rises which is measured
by thermometer from initial temperature

to final temperature

. Next the system was kept in

contact with the water bath. While in contact, the heat is transferred from liquid to water bath till
the system to its original state of pressure and temperature.
Thus the closed system has completed a cycle.
With the help of such experiments, Joule concluded that in every case the work input W was
always proportional to heat transfer Q from the system at the end of conclusion of a cycle.


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Using the sign for cyclic integral, the results of the experiment can be put mathematically as
follows :
d W d Q
Or d W = J d Q (1)
Where, J is a constant and called mechanical equivalent of heat.
In M.K.S system, J = 4.187 kJ/k cal
However in S.I system J = 1 J/Nm, Since work W and heat Q are both measured in J or Nm.
Therefore the equation (1) can be written as:
d W = d Q (2)
The relationship expressed by the equation (2) has been found true in all cases. Its generalization
has led to formulation of first law of thermodynamics as applied to closed system undergoing a
cycle.
First Law Of Thermodynamics Statement:
When closed system executes a cyclic process the algebraic sum of work transfers is
proportional to the algebraic sum of the heat transfers i.e. ( W) cycle = ( Q) cycle.
Corollaries Of First Law :
The first law of thermodynamics has the number of important consequences which are
stated in the form of corollaries given below.

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Corollary 1 [Perpetual Motion Machine of the First Kind [PMM-1]] :
A machine operating on a cycle and producing work continuously without absorption of
energy at the same time is called perpetual motion machine of first kind (PMM-1) as shown in fig.
According to first law,
(d Q d W) = 0 and in this case since d Q = 0, it follows that d W = 0 i.e. perpetual motion
machine of first kind violates the 1
st
Law of thermodynamics.
Therefore the first law of thermodynamics can also be stated in the following form :
It is impossible to construct a perpetual motion machine of first kind, i.e. no machine working
over a cycle can produce work without corresponding expenditure of energy.
Converse of perpetual motion machine of first kind is also true. i.e. there can not be any machine
which would consume energy continuously without some other form of energy appearing
simultaneously.



(a) PMM 1

(b) converse of PMM 1
Corollary 2 (First Law for a Process and Internal Energy is Property of
System) :
When a system executes a process, the net heat transfer d Q, equals to sum of
net work transfer d W and the change in stored energy, dE. Mathematically,
d Q = d W + dE ..(1)
Proof:
The equation (1) refers to a closed system subjected to a process. Therefore let us apply the 1
st

law to a closed system to a cyclic process and then we shall deduce an important property of a
system called total energy as a consequence of the first law of thermodynamics.

Machine
W
Machine
W

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Let a closed system to be defined by state- 1 by two thermodynamic properties on (p-V) diagram.
Suppose that system changes its state from state- 1 to state 2 along the path A and then it is
brought back to its original state along the path B, thus completing the cycle (1-A-2-B-1).
Another cycle of the system is completed along the path C. So that the cycle is represented by the
path (1-A-2-C-1).
According to the First law equation
(d Q d W) = 0
Applying first law to cycle (1-A-2-B-1), we get
(

) (

) = 0

(i)
Now applying first law equation to cycle (1-A-2-C-1), we get
(

) (

) = 0

.(ii)
On subtracting the equation (ii) from (i), we get
i.e. (

) = (

..(iii)
It implies that (

) is independent of the path between the given end states 2 to 1

whether we follow the path B or path C.
Though d Q and d W are both path functions but we find from above that the combination of
(

) over a process path between the given end states is independent of path, hence the
quantity (

) is an exact differential and it must be a point function say E.

There exists a point function E such that for an infinitesimal change of state, it follows the process
law as :
d Q d W = dE ..(iv)
E is called the total energy function of the system.

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The energy E of the system which includes all forms of energy is called the total energy of the
system.
Total energy E includes all form of energy like the internal energy U due to molecular motion and
position, external K.E, external P.E, chemical energy, electrical energy etc.
Neglecting all form of energy other than internal energy U, K.E and P.E, we can write the total
energy E of the system at any given state as:
Total energy, E = Internal energy(U) + K.E (

) + P.E. (m .g . z) .(v)
For an infinitesimal change,
dE = dU + d(K.E) + d(P.E) ..(vi)
Eqn (iv) for a closed system subjected a quasistatic process with the help of Eqn (vi) can be written
as :
d Q d W = dU + d(K.E) + d(P.E) ..(vii)
If a system undergoes a process from state 1 to state 2, on integrating the Eqn (vii)

()

()
= (

) ( )

( )

( )

( )

In short,
Q W = U +(K.E) + (P.E) .(viii)
If changes in K.E and P.E are neglected then
Q W = (

) .(ix)
Corollary 3( First Law of an Isolated System):
Since in an isolated system, there are no mass and energy transfers i.e. dQ = 0,
d W = 0. On applying these conditions in Equation d Q = d W + dE we get,
()

= 0
It is evident that the total energy of an isolated system remains constant which is a corresponding
statement to the law of conservation of energy.

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Internal Energy :
The process equation of a closed system of fixed mass can be written from eqn
d Q d W = dU + d(K.E) + d(P.E) as:
If the value of K.E and P.E dont change or changes are negligible, the above eqn reduces to :
d Q d W = d U (1)
If the values of work done due to the effect of electric, magnetic, surface tension and other are
negligible then d W in the above eqn will denote the external work or displacement work for a
quasistatic process. The eqn (1) becomes
d Q p.dV = d U .(2)
On the basis of unit mass, the equation becomes :
d q pdv = du (3)
For a finite process, from eqn (1) becomes
Q W = U =

.(4)
Or, Q =

.(5)
Joules Law :
Joules law states that the internal energy of a perfect gas is the function of absolute
temperature only.
i.e. U = f(T)
Application Of First Law Of Thermodynamics as Applied To Closed
System Or Non Flow Processes :
Following processes will be considered as applied to a closed systems :
1. Constant volume process, V = C.
2. Constant pressure process, p = C.
3. Constant temperature or isothermal process, T = C or p.V = Constant.
4. Hyperbolic process (p . V = C).
5. Reversible adiabatic process, p .

= C.
6. Polytropic process, p .

= C.

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Constant Volume Process (Closed System or Non Flow Process) :
Consider a piston cylinder arrangement having an ideal gas of mass m pressure

, temperature

and occupies a volume

.
If the gas its pressure and temperature would rise and the gas will expand. In order to carry out
a constant volume process, it is necessary that the additional weights are kept on the piston in order
to equalize the increase in pressures due to heating.
Let the final pressure, volume and temperature be (

)
Since it is constant volume process

(a) Work Done :
W = = 0 (1)
Since dV = 0 (being a constant volume process).
(b) Heat supplied :
d Q = m

. dT (for infinitesimal process)

Q = m .

) (for process between state 1 to 2)

(c) Application of first law of thermodynamics :
Q = W + (

) = 0 (

)
i.e. change in internal energy U = m

)
For infinitesimal process, dU = m

. dT
On unit mass basis du =

. dT

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= (

)
It follows that : du = m

. dT will be applicable to any process though his expression has been

defined with the help of constant volume process.
Constant Pressure Process :
Closed System :
Gas is trapped in a piston cylinder arrangement at state 1 (

) and heat energy is

supplied to the system keeping the pressure constant with the help of dead weight W.
Let the final state 2 be represented by (

)
The process is shown on (p V) diagram.
Since it is constant pressure process, p = constant
i.e. p =

(a) Work done:
W = m R (

).(since, pV = mRT)
(b) Heat supplied :
By definition, d Q = m

Q = m .

)
(c) Application of 1
st
law of thermodynamics :
Q = W + U = W + (

)

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m

) = m R (

) + m

=
The above equation is called Meyers equation.
Constant Temperature or Isothermal Process :
Since the gas is assumed to be an ideal gas, at constant temperature it will follow the
Boyles law given by the equation,
p . V = C (a constant)
Process is represented on (p V) diagram in case the gas undergoes an isothermal process
from state 1 to state 2.

(a) Work Done :
W = mR

(b) Change in internal energy :
=

)
But

being a constant pressure process

= 0
(c) Heat Transfer :
From 1
st
law Q = W + U; But U = 0
Q = W =

(Since U = 0)
It implies that heat transfer during isothermal process equals to workdone .









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Hyperbolic Process :
The plot of a rectangular hyperbola is represented by the equation p . V = constant.
Since the law of an isothermal process is also p . V = C, it follows that in case of gases the hyperbolic
and isothermal are same.
Therefore the equation derived for work, heat and change in internal energy for an isothermal
process earlier are also applicable to hyperbolic process.

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Reversible Adiabatic Process :
An adiabatic process is one in which there is no heat exchange between the system and its
surroundings,
i.e. dQ = 0, or, Q = 0 .(1)
To prove that the law of reversible adiabatic process is p .

= C
Where, =

(a) Work done:
W =

Law of process is p .

= C
Or, p =

W =

W = C(

) = p .

) = (

)


(b) Application of 1
st
law of thermodynamics :
Q = W + (

) Since it is an adiabatic process, Q = 0

0 = (

)
W =

)
It shows that the work done by the system during an adiabatic process is on the expense of
internal energy i.e. during the process the internal energy of the system decreases.
Polytropic Process :
The reversible adiabatic process described above may be extended to describe a general
process in which the heat transfer between the system and surroundings takes place.
The process equation can be represented as :
\
=

( 1)
=
(

)
( 1)

p .

= C (constant)

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Where, n = index of process or polytropic index
The value of is approximately 1.4 for perfect diatomic gases like

The value of n may be greater than or less than for polytropic process.























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Ideal and Real Gases :
An ideal gas is defined as a gas which would behave in an ideal manner at all pressures and
temperatures.
Whereas, the real gases follow the gas laws at low pressures and high temperatures only.
However, the behavior of real gases at high pressure or at low temperatures or both is
different for different gases.
An ideal gas is similar to perfect gas since both follow the ideal gas equation p . V = RT.

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Reduced Properties :
The ratio of pressure, temperature and specific volume of a real gas to their
corresponding critical values are called reduced properties represented by

. Therefore,

These reduced properties are dimensionless parameters.
Law of Corresponding States :
According to law of corresponding states there exists a functional relationship for all
substances which can be expressed in the form :

= (

)
If any two gases have equal values of reduced pressure and reduced temperature, then according to
law of corresponding states they would have the equal reduced volume.
The law of corresponding states is true in the vicinity of critical state. But, this law losses its validity
at low pressures.
Daltons Law :
The total pressure of a mixture of ideal gases is equal to the sum of the partial pressures
of the individual gas components of the mixture.
This is known as Daltons law of partial pressures.
Amagats Law :
The total volume of a mixture of ideal gases is equal to the sum of the partial(reduced)
volumes of the constituent gases. This is known as Amagat law of partial volumes.
Property of Mixture of Gases :
The working fluids employed in most of the heat engines are not homogenous gases,
but are mixture of gases such as air, combustion products. The constituent gases are assumed to be
ideal, do not interact with one another chemically and the gas mixture obeys the laws of ideal
homogenous gases.



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Mole Fraction and Mass Fraction :
The mass fraction of each component of a mixture is defined as the ratio of the
mass of a given component to the mass of the entire mixture.
1 =

Where

are the mass fractions. The sum of the parts by mass (mass fractions) of the
constituents in a mixture equals unity.
When an analysis of gas mixture is made on the mass basis, it is called a gravimetric analysis.
The mole fraction of each component of a mixture is defined as the ratio of the
moles of each constituent gas to the total number of moles contained in the gas mixture.
1 =

Where

are the mole fractions. The sum of the parts by moles (mole fractions) of the
constituents in a mixture equals unity.














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Application of First Law Of Thermodynamics as Applied to Open
Systems :
The work developed in a closed system is called non-flow work. To analyse the open
systems, we introduce the concept of control volume in which we consider a fixed region in space
through which the mass flow takes place. This fixed region is called the control volume and its
surface is called control surface.
(a) Mass Balance for Unsteady Flow System :
If the system is under unsteady state, from law of conservation of mass, we can
write :
Rate of mass flow into control volume,

= Rate of mass flow out of control volume,

+ Rate of
change of mass in control volume.
(b) Mass Balance for Steady Flow System (Continuity Equation) :
Steady flow system is defined as the system in which the mass flow rate into the system
is equal to mass flow rate out of the system.
Mass flow rate in,

= Mass flow rate out,

= A constant, say, m
Consider the flow of liquid through a pipe of cross sectional area A, specific volume v at a velocity C.
Then,
Volume flow rate = A (

) C (m/s)
Mass flow rate, m (kg/s) =