First Law of Thermodynamics

When heat is added to a system there is an increase in the

internal energy due to the rise in temperature, an increase in
pressure or change in the state. If at the same time. a
substance is allowed to do work on its environment by
expansion. the heat Q required will be the heat necessary to
change the internal energy of the substance from U1 In the
first state to U2 in the second state plus the work W done on
the environment
Thus Q = (U2-U1)+ W
or Q = ΔU+W
Thus the change in internal energy AU = U2 — U1 is defined as
Q-W. Since it is the same for all processes concerning the
state. the first law of thermodynamics. thus can be stated as:
In any thermodynamic process, when heat Q is added to the system, this
appears as increase in internal energy ΔU stored in the system plus the
work done W done by the system on its surrounding.
We can also write:

∆E = Q – W -Using this equation we can say that:

The net change in total energy of a system (∆E) is equal to the heat
added to the system (Q) minus work done by the system (W).
 First Law of
Thermodynamics

Example of First Law of Thermodynamics

Conversion of heat energy into mechanical energy is an example of

this law. When the fuel is ignited inside the cylinder it
produces heat energy. Because of this heat energy the higher
temperature is created in the cylinder. This temperature
causes the expansion of piston which in turn produces
rotational effect. In this we can conclude that heat energy of
fuel is converted into mechanical energy.
Conversion of heat energy of solar into chemical energy in plants is
another example. All we know photosynthesis process. In this
phenomenon plants take heat energy from sun and produce
photosynthesis which appears as chemical energy. The
energy stored in glucose can also be released through cellular
respiration.
Generators uses chemical energy to do some mechanical
work and then they convert this mechanical energy into
electricity. This is another example in which chemical energy
is converted to mechanical energy and then mechanical
energy changed into electrical energy.

Thus we can also define first law of thermodynamics as:

“Energy cannot be created not it can be destroyed, but it changed from
one form to another“. First law of thermodynamics also called
law of conservation of energy.
Isothermal Process

This process or phenomenon is carried out at constant

temperature. So condition for Boyle’s Law on the gas is
fullfilled

P1V1 = P2V2
In isothermal process Potential energy remain zero. Internal
energy of an ideal gas depends only on temperature which in
this case is constant(ΔU=0). First law of thermodynamics
then reduces to:

Q=W

Thus if gas expands and does external work W. an amount of

heat Q has to be supplied to the gas In order to produce an
Isothermal change. Since transfer of heat from one place to
another requires time. hence. to keep the temperature of the
gas constant. the expansion or compression must take place
slowly. The curve representing an Isothermal process is
called an isotherm.
Adiabatic Process

In this process no heat enters or leave the system(Q = 0). In

this process heat transferred only in the form of work. We
can use the adiabatic approximation only in very rapid
processes. In these rapid processes, there is not enough time
for the transfer of energy as heat.

Adiabatic and Isothermal Graph

In case of adiabatic changes it has been seen that:

 PVγ = constant
Where y is the molar specific heat of gas at constant pressure
to molar specific heat at constant volume. The curve that
represent adiabatic process is called adiabat. Molar specific
heat at constant pressure is defined as”The amount of heat
transfer required to raise the temperaure of one mole of gas
through 1K at constant pressure and it is represented by Cp“
To raise the temperature through 1k at constant pressure the
heat transfer Qp must be equal to CpΔT
Qp = CpΔT
Limitations of First Law of Thermodynamics

It does not say about direction of flow of heat.

It says nothing whether the process is reversible or not.
All the heat not changed into work.
First law of thermodynamics tells us about amount of heat
transferred into work but does not tells us under what
conditions the conversion take place. Seconds law of
thermodynamics tells us the conditions.

Second law of thermodynamics

Before starting discussion on second law of thermodynamics
let discuss about engine. Le the engine or the system absorb
heat Q1 from the heat source at temperature T1. It does some
work and release heat Q2 to low temperature T2. As this
process is cyclic and substance reach to its initial position so
the change in internal energy is zero. Hence from the first law
of thermodynamics net heat change should be equal to net
work done. It is
W = Q1 – Q2
In practice the petrol engine of vehicles takes fuel, convert a
fraction of it into mechanical energy and release the rest into
atmosphere. It is observed that petrol engine convert
approximately 25% and diesel engine about 35% heat
energy into work. So We can describe Second law of
thermodynamics as:

Without wastage it is impossible to get 100% efficient system.

or we can also define it as:
It is impossible to covert heat extracted from a single reservoir, entirely
into work without leaving any change in the system.
Oceans and our atmosphere which contain a large amount of
heat energy but can not be converted into useful mechanical
work. As a consequence of second law of thermodynamics,
two bodies at different temperatures are essential for the
conversion of heat into work. Hence for the working of heat
engine there must be a source of heat at a high temperature
and a sink at low temperature to which heat may be expelled.
The reason for our inability to utilize the heat contents of
oceans and atmosphere is that there is no reservoir at a
temperature lower than any one of the two.

Carnot Engine and Carnot Theorem

Sadi Carnot in 1840 described the ideal engine that work on

adiabatic and isothermal process. It estimates the possible
maximum efficiency during the conversion process of heat
into work, engine can provide working between two
reservoirs. A carnot engine uses ideal gas as a working
substance. It consist of following steps:

 In the first step the gas is allowed to expand isothermally at

temperature T1 absorbing heat Q1 from hot reservoir.
 The gas is allowed to expand adiabatically until the temperature drop
to T2.
 The gas at this stage reject heat Q2 and at T2 to cold reservoire.
 Finally the gas restore its initial position, compressed adiabatically at
T1.
Carnot Cycle
In this case thermal and mechanical equilibrium is
maintained so internal energy remain same. The net work
done is equal to area of ABCDA. It can also be estimated from
net heat Q absorbed in one cycle.

Q = Q1 – Q2
From First law of Thermodynamics:

Q = ΔU+W

W = Q1 – Q2
The efficiency η of the heat engine is defined as:

η = output(Work) / Input(Energy)

η = Q1 – Q2/Q1
η = 1 – Q2/Q1
The energy transfer in an isothermal expansion or
compression turns out to be proportional to Kelvin
temperature. So Q1 and Q2 are proportional to Kelvin
temperatures T1 and T2 respectively and hence:
η = T1 – T2/T1
η = 1 – T2/T1
This is the efficiency which is usually taken in percentage.

η = (1 – T2/T1)100
Thus the efficiency of a system depends upon temperature of
hot and cold reservoir and independent of nature of
substance.

Carnot Theorem

No heat engine can be more efficient then carnot engine operating
between the same two temperature.
All Carnot engines operating between the same two temperatures
have same efficiency, irrespective of the nature of substance used.
Entropy

The concept of entropy was introduced into the study of

thermodynamics by Rudolph Clausius in 1856 to give a
quantitative basis for the second law. It provides another
variable to describe the state of a system to go along with
pressure. volume. temperature and internal energy. if a
system undergoes a reversible process during which it
absorbs a quantity of heat ΔQ at absolute temperature T.
then the increase in the state variable called entropy S of the
system is given by:
ΔS = ΔQ/T

Like potential energy or internal energy, it is the change in

entropy of the system which is important. Change in entropy
is positive when heat is added and negative when heat is
removed from the system. Suppose. an amount of heat Q
flows from a reservoir at temperature T1 through a
conducting rod to a reservoir at temperature T2 when T1 > T2.
The change in entropy of the reservoir. at temperature T1.
which loses heat. decreases by Q/T1 and of the reservoir at
temperature T2, which gains heat. increases by Q/T2. As T1 >
T2 so Q/T2 will be greater than Q/T1 i.e., Q/T2 > Q/T1. Hence,
net change in entropy Q/T2 – Q/T1 is positive.
It follows that in all natural processes where heat flows from
one system to another, there is always a net increase in
entropy. This is another statement of 2nd law of
thermodynamics. According to this law: “If a system undergo a
natural process it will go in the direction that will cause entropy of the
system plus environment to increase.”

Zeroth Law of Thermodynamics

There are four laws of thermodynamics:

Zeroth Law of Thermodynamics
First Law of Thermodynamics
Second Law of Thermodynamics
Third law of Thermodynamics
It is interesting to note that Zeroth law was developed after
these three laws. This law gave more accurate definition of
temperature. The most significant part of the Zeroth Law is
that it establishes temperature to be a fundamental and
measurable property of matter.

Suppose three bodies A, B and C. Let A is connected with B

and C via a conducting wall that allow the transfer of heat.
Suppose A is thermally equilibrium with B and separately in
thermal equilibrium with C. Then B and C will also be in
thermal equilibrium. The systems are in thermal equilibrium
if they do not transfer heat. If there will be temperature
difference between two different bodies then they will
transfer heat and reached to the state of equilibrium.

Zeroth law of thermodynamics takes into account that

temperature is something worth measuring because it
predicts whether the heat will transfer between objects or
not.  This is true regardless of how the objects interact. Even
if two objects are not in physical contact, heat still can flow
between them, by means of radiation mode of heat
transfer. We can also conclude from Zeroth law that heat will
only be transferred from one body to another body before
equilibrium.

This pictures describes that if A is in thermally equilibrium

with B and C then B and C will be in thermally equilibrium.
Thermal Equilibrium

Temperature is a property that distinguishes thermodynamics

from other sciences. This property can distinguish between
hot and cold body. When two bodies of different temperature
come in contact. Heat transfer from hot body to cold body.
Then after some time the temperature difference between
them become zero. In this state we said that the two bodies
are in thermal equilibrium.

Examples of Zeroth Law of Thermodynamics

Two glasses of water, One glass will have hot water and the
other will contain cold water. Now if we leave them in the
table for a few period of time, they will attain thermal
equilibrium with the temperature of the room.

We can observe the zeroth law in action by taking a very

common thermometer having mercury in a tube. As the
temperature is increased this mercury expands since the area
of the tube is constant. Due to this expansion, the height is
increased. Now, the increase in the height of the mercury
label shows the changes in temperature and basically helps
us to measure it