First Law of Thermodynamics

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The first law states that the energy of the system remains constant given the system is isolated. It is a
special statement for the law of conservation of energy. It was stated by Clausius who had used 2 ways
for stating and expressing the law.
In one cyclic process input output of the system are considered.

In another way the increment in the internal energy of the system is considered. Here the process
is not considered to be a cyclic one. (A process that can be repeated many times still leaving the
system in the original state).

The law states that the algebraic summation of all energy transfer across system boundaries is zero. Let
Q be the amount of heat transferred to a system and W is the amount of work transferred from the system
during the process, the net energy transfer (Q W) would be stored in the system. Hence according to
the first law:

QW=E
Q=E+W

First Law of Thermodynamics

We know that heat is just a form of energy. A system can be given energy either by supplying heat to it or
by doing mechanical work on it. Let us study first law of thermodynamics which gives the relationship
between the heat supplied and work done in the closed system. The closed system is the system where
the heat can be exchanged between system and its surroundings but not matter.

First Law of Thermodynamics Definition

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If some amount of heat is given to the closed system, a part of heat is used to increase internal energy of
the system and remaining part is used as the work done by the system.This statement was stated by
Rudolf Clausius as the First law of thermodynamics in 1850.
Mathematically, it can be stated as:

Q=U+W

Where,

Q = Heat given to the system,

U = Increase in internal energy of the system
W = Work done by the system.
Thus, the change of internal energy of the system is given by:

U = Q - WThus, we can also state it as:

The change in the internal energy of the system is equal to the amount of heat supplied to the system
minus the amount of work performed by the system on its surroundings.Hence the first law of
thermodynamics can be stated as:
"The energy of the system remains constant given the system is isolated."

The first law of thermodynamics was also stated using the cyclic process by Clausius as:

Q cycle = Wcyclewhere,
Qcycle = Heat given to the cyclic process
Wcycle= Work done in the cyclic process

First Law of Thermodynamics Equation

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For the closed system,

Increase in internal energy = Heat supplied to the system - Work done by the system

U = Q + WLet us consider an isolated system. Let the internal energy of the system be U 1
and we have supplied a heat of Q.
Let we have done a work of W on the system and hence the final internal energy of the system U 2 should
be equal to sum of U1, Q and W.
U2 = U1+ Q + Wor
U2 - U1= Q + W
Which can be expressed as,

U = U2 - U1 =Q + W
So, the Change in the internal energy of the system is equal to the work and heat change of the system.

U and Q is taken as positive as the work is done on the system.

Cyclic Process:
It is expressed for a cycle as
( Q )cycle = ( W )cycle ..................(a)where,
Q = Heat transferred to the system
W = Work done by the system
For a process it can be written as:

Q = E + W ........................(b)
= Ek + Ep + U + W
= 12 mV2 + m g Z + U + W .................... (c)
Here,
E = amount of energy stored in the system and hence is the property of the system
U = internal energy, a form of stored energy
Ek = kinetic energy, a form of stored energy
= 12 mV2
Ep = potential energy, a form of stored energy
where,
m and V are mass and Velocity of the molecules and Z is the height of the molecules.
The first law for a closed system undergoing a cycle:

Wcycle = J Qcycle ...........................(d)Where,

J is the Joules equivalent
This is also expressed as:

dW = J dQ ............................(e)

First Law of Thermodynamics Example

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1) Consider gas in the cylinder fitted with piston.

If the cylinder is heated, increase in temperature takes place, the energy of gas molecules increase which
leads to increase in internal energy of the system.

or
if the gas is compressed using the piston it also increases the internal energy of the system.

2) The evaporation of sweat from human body is a perfect example of the first law of thermodynamics.
Energy conservation is a fundamental law and hence works for many instances of our daily life.

Second Law of Thermodynamics

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The first law states that a certain energy balance will hold on even when a system undergoes a state of
change. But it does not enlighten us on feasibility of the change of state or the process. All that the first
law tells is that if the process occurs then the energy gained by one end would be equal to the energy lost
by other end. The criterion to the probability of various processes is given by the second law of
thermodynamics.
Kelvin Planck statement says, "It is impossible for a heat engine to produce net work in a

complete cycle if it exchanges heat only with bodies at a single fixed temperature."
Clausius statement says, "We cannot construct a device which operating on a cycle produces no
effect other than the transfer of heat from a cooler to a hotter body. This implies that heat energy
cannot flow from one body to another because of the temperature change, some work definitely
has to be done to achieve this."

Second Law of Thermodynamics

Thermodynamics is basically a phenomenological science based on certain laws of nature which are
always obeyed and never seem to be violated. These are four basic laws of thermodynamics:
1. Zeroth Law of Thermodynamics
2. First Law of Thermodynamics
3. Second Law of Thermodynamics
4. Third Law of Thermodynamics
The first law states that a certain energy balance will hold when a system undergoes a change of state.
But it does not enlighten us on if that change of state or the process is feasible or not. All that the first law
tells is that if the process occurs the energy gained by one end would be equal to the energy lost by the
other end. The criterion of the probability of various processes is given by The Second Law of
Thermodynamics.
Experimental evidence suggests strongly that it is impossible to build a heat engine that converts heat
completely to work (an engine with 100% thermal efficiency). This impossibility is the basis of one
statement of the second law of thermodynamics as follows.

Second Law of Thermodynamics Definition

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It is impossible for any system to undergo a process in which it absorbs heat from a reservoir at a
single temperature and converts the heat completely into mechanical work with the system
ending in the same state in which it began. We call this the 'engine' statement of the second law.
The basis of the second law of thermodynamics lies in the difference between the nature of internal
energy and that of macroscopic mechanical energy. In a moving body the molecules have random motion
but superimposed on this is a coordinated motion of every molecule in the direction of the body's velocity.
The kinetic energy associated with this coordinated macroscopic motion is called the kinetic energy of the

moving body. The kinetic energy and potential energy associated with the random motion constitute the
internal energy.
When a body sliding on a surface comes to rest due to friction, the organized motion of the body is
converted to random motion of molecules in the body and on the surface. Since we cannot control the
motion of individual molecules, we cannot convert this random motion completely back to organized
motion. Only a part of it can be converted and this is what a heat engine does.
If the second law was not true, we could have powered an automobile or run a power plant by cooling the
surrounding air. Neither of these impossibilities violate the first law of thermodynamics. The second law,
therefore, is not a deduction from the first, but stands by itself as a separate law of nature. The first law
denies the possibility of creating or destroying energy and the second law limits the availability of energy
and the ways in which it can be used and converted.
An alternative statement of the second law of thermodynamics states that heat flows spontaneously from
hotter to colder bodies but the reverse is never true. A refrigerator transfers heat from a colder to a hotter
body but its operation requires an input of mechanical energy or work. Generalizing this observation, we
state:
It is impossible for any process to sole result in the transfer of heat from a cooler to a hotter body.
We call this the 'refrigerator' statement of the second law.Though, it may not seem to be very closely
related to the 'engine' statement, the two statements are equivalent. For example, if we could build a
refrigerator which does not have an input of work, violating the 'refrigerator' statement of the second law,
we could use it in conjunction with a heat engine, pumping the heat rejected by the engine, back to the
hot reservoir to be reused. This composite machine shown below in the figure (b) would violate the
'engine' statement of the second law because its net effect would be to take a net quantity of heat Q H - |
QC| from the hot reservoir and convert it completely to work W.

Alternatively, if we could make an engine with 100% thermal efficiency, violating the first statement, we
could run it using heat from the hot reservoir and use the work output to drive a refrigerator that pumps
heat from the cold reservoir to the hot reservoir as shown in the figure (b) below. This composite device
would violate the "refrigerator" statement because its net effect would be to take heat Q C from the cold
reservoir and deliver it to the hot reservoir without requiring any input of work. Thus, any device that
violates one form of the second law can be used to make a device that violates the other form. If
violations of the first form are impossible so are violations of the second!
The conversion of work to heat as in friction or viscous fluid flow and heat flow from hot to cold across a
finite temperature gradient are irreversible processes. The 'engine' and 'refrigerator' statements of the
second law state that these processes can be partially reversed. We could cite other examples. Gases
always seep spontaneously through an opening from a region of high pressure to a region of low
pressure: gases and miscible liquids left to themselves, always tend to mix, not to unmix.
For a heat engine: QH - QC= W
Efficiency of a heat engine = 1 - QHQC
The second law of thermodynamics is an expression of the inherent one-way aspect of these and many
other irreversible processes. Energy conversion is an essential aspect of all plant and animal life and of
human technology. Hence, the second law of thermodynamics is of utmost fundamental importance to the
world we live in.

Second Law of Thermodynamics Examples

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Lets have a look at the movie Titanic once again. What happened when the ship hits the
iceberg? The steel pipes were ripped open. Now can you imagine it the other way round? The

ship is healing as it comes out of water and starts floating. That is improbable.
Energy always disperses for example the heat of the burning pan in the surrounding environment.

When we need more energy we use it in a highly concatenated form. For example our body gets
energy from carbohydrates that store energy in a small space.

The second law just says that energy always gets diluted, moves from a highly concatenated
form to less one. The usefulness of energy will decrease as it moves and makes things happen.

Second Law of Thermodynamics Evolution

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From our understanding of the second law of thermodynamics we know that the entropy or the disorder
always increases. The second law does not permit order to rise from disorder. This contradicts the fact
that the macro evolution of humans with complex cells must have occurred from the single celled
ancestors.
A disorder cannot produce order randomly. There must be some procedure which contains enough details
and shows direction to such a process if it has to occur. Also there must be some type of mechanism
which converts the environmental energy into the energy used for producing higher organization of the
involved system. On the other hand, thermodynamics does not state that intelligent designs are not
possible; the thing is that it is not a factor if the calculations of thermodynamic probability are considered.
If we consider the earth as a system, a change is accompanied by a decrease in entropy and hence going
back from higher probability to lower probability is feasible as long as sufficient amount of energy is
available. The sun is finally the ultimate source of most of that energy.
The mathematical calculations of entropy change accompanying physical and chemical changes are
understood and hence are the basis of the mathematical determination of terms like free energy, emf
characteristics of voltaic cells, equilibrium constants, refrigeration cycles, operating parameters of steam
turbines etc. The creationist theory would necessarily nullify the entire
mathematical framework of thermodynamics and the basis for the engineering turbine designs, basic
design of refrigeration units, industrial pumps, etc. would not be provided.

Third Law of Thermodynamics

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The Third law of thermodynamics states that for a perfect crystal at the absolute zero temperature,
the entropy would be exactly equal to zero.When only one minimum energy state is possessed by a
perfect crystal the law holds true. If we consider systems such as glasses which are not perfect crystal

then a generalized form of 3rd law would be:

As the temperature approaches zero, the entropy of a system would approach a constant value.

Third Law of Thermodynamics

Thermodynamics means the flow of heat and it deals with quantitative relationships existing between heat
and other forms of energy in physico-chemical transformations.
We have already studied about the relationship between the heat and the work done in first law of
thermodynamics, and about energy and work done in second law of thermodynamics.
Let us study about change in entropy in third law of thermodynamics where we will discuss the concept of
entropy.

Third Law of Thermodynamics Definition

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We know that entropy is the rate of change of disorder occurring in a system. Walther Nernst introduced
the concept of entropy in the third law of thermodynamics which states that:
For a perfect crystal at the absolute zero temperature, the entropy would be exactly equal to zero.When
only one minimum energy state is possessed by a perfect crystal the law would hold true.
If we consider systems such as glasses which are not perfect crystal then a generalized form of 3rd law
would be:
When the temperature approaches zero, the randomness or entropy of a system would approach a
constant value.

The Constant value of entropy is called Residual Entropy and it should be noted that it is not necessarily
zero.

Third Law of Thermodynamics Equation

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The Third law can be expressed as:

limT0 S = 0 ...............................(a)Here,

S = entropy which is expressed as J s-1K-1.

T = absolute temperature which is expressed in K.
It can also be written as:
T 0 S Smin .....................................(b)Hence we can say if the temperature approaches zero then
the entropy approaches to its minimum value.
Another application of third law of thermodynamics:
S = 2.303 Cp log T ..........................................(c)Using this we can find the absolute entropy of any
substance at a given temperature T.
Here Cp is the heat capacity of the substance at a constant pressure.

Limitations of the law:

1. Even at 0 K Glassy solids have entropy which is greater than zero.
2. Solids that have mixtures of isotopes do not possess zero entropy at 0 K.
For example: Solid chlorine does not have zero entropy at 0 K.

3. Crystals of CO, N2O, NO, H2O, etc., do not possess perfect order even at 0 K, thus their entropy
is not equal to zero.

Third Law of Thermodynamics Examples

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We can consider H2O if we want to understand the concept of the third law of thermodynamics.
Water exists in three different states:
1. Gaseous state
2. Liquid state
3. Solid state

In Gaseous state
The entropy or randomness is very high. Here we are talking about the randomness in motion of the
molecules of which the water is made up of. They move with very high entropy.

In Liquid state
Now the randomness is reduced. It is not as free as the gaseous state and hence we can say that entropy
of the molecules is reduced. This is because the movement between the molecules is reduced.

In Solid state
In this state the moment between molecules is almost zero. The entropy approaches almost zero value.
This is because the molecules are packed very tightly in the solid state and hence the randomness is very
low. This is when it is cooled at very low temperature or at an absolute zero temperature.

Now if it cooled further then all the motion between the molecules would stop. This is because these are
no free spaces for the motion of the particles. And hence the entropy becomes almost zero.

Zeroth Law of Thermodynamics