Thermodynamics
Lecture 06
First Law of Thermodynamics
• Joule’s law of internal energy states that
internal energy of a perfect gas is a function
of temperature only.
• In other words, internal energy of a gas is
dependent on the temperature change only
and is not affected by the change in pressure
and volume.
• We do not know how to find the absolute
quantity of internal energy in any substance;
however, what is needed in engineering is
the change of internal energy (∆U).
LAW OF CONSERVATION OF ENERGY
• In the early part of nineteenth century the
scientists developed the concept of energy
and hypothesis that it can be neither created
nor destroyed ; this came to be known as the
law of the conservation of energy.
• The first law of thermodynamics is merely
one statement of this general law/principle
with particular reference to heat energy and
mechanical energy i.e., work.
FIRST LAW OF THERMODYNAMICS
• When a system undergoes a thermodynamic
cycle, the net heat supplied to the system
from the surroundings is equal to net work
done by the system on it surroundings.
• Heat and work are mutually convertible but
since energy can neither be created nor
destroyed, the total energy associated with
an energy conversion remains constant.
The experiment show that a definite quantity of
work is always required to accomplish the same
temperature rise obtained with a unit amount of
heat.
• It can be stated as an invariable experience that
whenever a physical system passes through a
complete cycle the algebraic sum of the work
transfers during the cycle; ׯdW bears a definite
ratio to the algebraic sum of the heat transfers
during the cycle, ׯd𝑄.
This may be expressed by the equation,
• where J is the proportionality constant and is known
as Mechanical Equivalent of heat. In S.I. units its
value is unity, i.e., 1 Nm/J.
APPLICATION OF FIRST LAW TO A
PROCESS
• When a process is executed by a
system, the change in stored energy of
the system is numerically equal to the
net heat interactions minus the net
work interaction during the process.
• If E represents the total internal energy
• If the electric, magnetic and chemical
energies are absent and changes in potential
and kinetic energy for a closed system are
neglected, the above equation can be
written as;
• Generally, when heat is added to a system its
temperature rises and external work is
performed due to increase in volume of the
system.
• The rise in temperature is an indication of
increase of internal energy.
• Heat added to the system will be considered
as positive and the heat removed or
rejected, from the system, as negative.
ENERGY—A PROPERTY OF SYSTEM
• Consider a system which changes its state from
state 1 to state 2 by following the path L, and
returns from state 2 to state 1 by following the path
M (Fig. 4.2).
• So the system undergoes a cycle. Writing the first
law for path L and M;
• The processes L and M together constitute a
cycle, for which;
• Also
• Similarly, had the system returned from state 2 to
state 1 by following the path N instead of path M;
• Thus, it is seen that the change in energy between
two states of a system is the same, whatever path
the system may follow in undergoing that change
of state.
• energy has a definite value for every state of the
system. Hence, it is a point function and a property
of the system
PERPETUAL MOTION MACHINE OF
THE FIRST KIND—PMM 1
• The first law of thermodynamics states the
general principle of the conservation of energy.
• Energy is neither created nor destroyed, but only
gets transformed from one form to another.
• There can be no machine which would
continuously supply mechanical work without
some form of energy disappearing simultaneously
(Fig. 4.3).
• Such a fictitious machine is called a perpetual
motion machine of the first kind, or in brief, PMM
1. A PMM 1 is thus impossible.
• The converse of the above statement is also true,
i.e., there can be no machine which would
continuously consume work without some other
form of energy appearing simultaneously (Fig.
4.4).
ENERGY OF AN ISOLATED SYSTEM
• An isolated system is one in which there is no
interaction of the system with the
surroundings.
• For an isolated system,
dQ = 0, dW = 0
• The first law of thermodynamics gives dE = 0
or E = constant
• The energy of an isolated system is always
constant.
Specific Heat
• The specific heat of a solid or liquid is usually
defined as the heat required to raise unit mass
through one degree temperature rise.
• For small quantities, we have dQ = mcdT
• where m = mass,
• c = specific heat, and
• dT = temperature rise.
• For a gas there are an infinite number of ways in
which heat may be added between any two
temperatures, and hence a gas could have an
infinite number of specific heats.
• However, only two specific heats for gases
are defined.
• Specific heat at constant volume, cv
• and, Specific heat at constant pressure, cp.
• We have
dQ = mcpdT
For a reversible non-flow process at constant
pressure and,
dQ = mcvdT
For a reversible non-flow process at constant
volume
• The values of cp and cv, for a perfect gas, are
constant for any one gas at all pressures and
temperatures.
• Hence by integrating equations given above
we have;
• Flow of heat in a reversible constant pressure
process
= mcp (T2 – T1)
Flow of heat in a reversible constant volume
process
= mcv (T2 – T1)
Joule’s Law
• Joule’s law is stated as follows:
“The internal energy of a perfect gas is a
function of the absolute temperature only.”
i.e., u = f(T)
• To evaluate this function let 1 kg of a perfect
gas be heated at constant volume.
• According to non-flow energy equation,
…
From
and integrating u = cv T + K, K being constant.
• According to Joule’s law u = f(T), which
means that internal energy varies
linearly with absolute temperature.
• Internal energy can be made zero at any
arbitrary reference temperature.
• For a perfect gas it can be assumed that
u = 0 when T = 0, hence constant K is
zero.
• Internal energy, u = cvT for a perfect gas
• Or For mass m, of a perfect gas Internal
energy,
U = mcvT
• For a perfect gas, in any process between
states 1 and 2, gain in internal energy,
• This equation gives the gains of internal
energy for a perfect gas between two states
for any process, reversible or irreversible.
Relationship Between Two
Specific Heats
Enthalpy
• One of the fundamental quantities
which occur invariably in
thermodynamics is the sum of internal
energy (u) and pressure volume product
(pv).
• This sum is called Enthalpy (h).
h = u + pv
• The enthalpy of a fluid is the property of the
fluid, since it consists of the sum of a
property and the product of the two
properties.
• Since enthalpy is a property like internal
energy, pressure, specific volume and
temperature, it can be introduced into any
problem whether the process is a flow or a
non-flow process.
• The total enthalpy of mass, m, of a fluid can
be
H = U + pV, where H = mh.
From
And u = CvT
pv=RT
Becomes
h
APPLICATION OF FIRST LAW OF
THERMODYNAMICS TO NON-FLOW
OR CLOSED SYSTEM
Reversible Constant Volume (or
Isochoric) Process (v = constant)
• In a constant volume process the working
substance is contained in a rigid vessel,
hence the boundaries of the system are
immovable and no work can be done on or
by the system, other than paddle-wheel
work input.
• It will be assumed that ‘constant volume’
implies zero work unless stated otherwise.
• Considering mass of the working substance
unity and applying first law of
thermodynamics to the process
The work done
For mass, m, of working substance
Reversible Constant Pressure (or
Isobaric) Process (p = constant).
• for a constant pressure process, the
boundary must move against an external
resistance as heat is supplied ; for instance a
gas [Fig. 4.6 (a)] in a cylinder behind a piston
can be made to undergo a constant pressure
process.
• Since the piston is pushed through a certain
distance by the force exerted by the gas,
then the work is done by the gas on its
surroundings.
• Considering unit mass of working substance and
applying first law of thermodynamics to the
process.
The work done,
where h = Enthalpy (specific), and
cp = Specific heat at constant pressure.
For mass, m, of working substance
Reversible Temperature (or
Isothermal) Process (pv = constant, T
= constant)
• A process at a constant temperature is called
an isothermal process.
• When a working substance in a cylinder
behind a piston expands from a high
pressure to a low pressure there is a
tendency for the temperature to fall.
Reversible Temperature (or
Isothermal) Process (pv = constant, T
= constant)
• In an isothermal expansion heat must be
added continuously in order to keep the
temperature at the initial value.
• Similarly in an isothermal compression heat
must be removed from the working
substance continuously during the process.
Considering unit mass of working substance
and applying first law to the process
Reversible Adiabatic Process (pvγ
= constant)
• An adiabatic process is one in which no heat
is transferred to or from the fluid during the
process.
• Such a process can be reversible or
irreversible.
• The reversible adiabatic non-flow process
will be considered in this section.
• Considering unit mass of working substance
and applying first law to the process
• The Eqn. is true for an adiabatic process
whether the process is reversible or not.
• In an adiabatic expansion, the work done W by
the fluid is at the expense of a reduction in the
internal energy of the fluid.
• Similarly in an adiabatic compression process all
the work done on the fluid goes to increase the
internal energy of the fluid.
• For an adiabatic process to take place, perfect
thermal insulation for the system must be
available.
Expression for work W
• A reversible adiabatic process for a perfect gas is
shown on a p-v diagram in Fig. 4.8 (b).
• The work done is given by the shaded area, and
this area can be evaluated by integration.
Relationship between T and v, and
T and p:
Polytropic Reversible Process (pvn =
constant)
• It is found that many processes in practice
approximate to a reversible law of form pvn
= constant, where n is a constant.
• Both vapours and perfect gases obey this
type of law closely in many non-flow
processes.
• Such processes are internally reversible.
• The Eqn. is true for any working substance
undergoing a reversible polytropic process.
• It follows also that for any polytropic process,
we can write;
• The following relations can also be derived
(following the same procedure as was done
under reversible adiabatic process)
Heat transfer during polytropic
process (for perfect gas pv = RT)
• Using non-flow energy equation, the heat
flow/transfer during the process can be found
• On substituting
Heat transfer during polytropic
process (for perfect gas pv = RT)
• In a polytropic process, the index n depends
only on the heat and work quantities during
the process.
• The various processes considered earlier are
special cases of polytropic process for a
perfect gas.
Free Expansion
• In a free expansion, gas is allowed to expand
into a vacuum.
• This happens quickly, so there is no heat
transferred.
• No work is done, because the gas does not
displace anything.
• Therefore, there is no change in internal
energy, so the temperature stays the same.
Examples
Ex. 1
In an internal combustion engine, during
the compression stroke the heat rejected
to the cooling water is 50 kJ/kg and the
work input is 100 kJ/kg. Calculate the
change in internal energy of the working
fluid stating whether it is a gain or loss.
Ex. 2
In an air motor cylinder the compressed
air has an internal energy of 450 kJ/kg at
the beginning of the expansion and an
internal energy of 220 kJ/kg after
expansion. If the work done by the air
during the expansion is 120 kJ/kg,
calculate the heat flow to and from the
cylinder.
0.3 kg of nitrogen gas at 100 kPa and
40°C is contained in a cylinder. The piston
is moved compressing nitrogen until the
pressure becomes 1 MPa and
temperature becomes 160°C. The work
done during the process is 30 kJ.
Calculate the heat transferred from the
nitrogen to the surroundings. Cv for
nitrogen = 0.75 kJ/kg K.
Ex. 3
• When a stationary mass of gas was
compressed without friction at constant
pressure its initial state of 0.4 m3 and
0.105 MPa was found to change to final
state of 0.20 m3 and 0.105 MPa. There
was a transfer of 42.5 kJ of heat from
the gas during the process. How much
did the internal energy of the gas
change ?
EX.
A tank containing air is stirred by a
paddle wheel. The work input to the
paddle wheel is 9000 kJ and the heat
transferred to the surroundings from the
tank is 3000 kJ.
Determine :
(i) Work done ;
(ii) Change in internal energy of the
system.
Ex.
A stone of 20 kg mass and a tank containing 200 kg
water comprise a system. The stone is 15 m above
the water level initially. The stone and water are at
the same temperature initially. If the stone falls into
water, then determine ∆U, ∆PE, ∆KE, Q and W, when
(i) the stone is about to enter the water,
(ii) the stone has come to rest in the tank, and
(iii) the heat is transferred to the surroundings in
such an amount that the stone and water come to
their initial temperature.
Assignment
A closed system of constant volume
experiences a temperature rise of 25°C when
a certain process occurs. The heat transferred
in the process is 30 kJ. The specific heat at
constant volume for the pure substance
comprising the system is 1.2 kJ/kg°C, and the
system contains 2.5 kg of this substance.
Determine :
(i) The change in internal energy ;
(ii) The work done.
Ex.
A fluid system undergoes a non-flow
frictionless process following the pressure-
volume relation as p = 5/V + 1.5 where p is in
bar and V is in m3. During the process the
volume changes from 0.15 m3 to 0.05 m3 and
the system rejects 45 kJ of heat. Determine :
(i) Change in internal energy ;
(ii) Change in enthalpy.
Assignment
0.2 m3 of air at 4 bar and 130°C is contained in a
system. A reversible adiabatic expansion takes
place till the pressure falls to 1.02 bar. The gas is
then heated at constant pressure till enthalpy
increases by 72.5 kJ. Calculate :
(i) The work done ;
(ii) The index of expansion, if the above processes
are replaced by a single reversible polytropic
process giving the same work between the same
initial and final states.
Take Cp = 1 kJ/kg K, cv = 0.714 kJ/kg K
Assignment
• 0.15 m3 of an ideal gas at a pressure of 15 bar and
550 K is expanded
isothermally to 4 times the initial volume. It is then
cooled to 290 K at constant volume and then
compressed back polytropically to its initial state.
Calculate the net work done and heat transferred
during the cycle.
