Section-7: Thermodynamic Laws

Laws of Thermodynamics:
The four laws of thermodynamics define fundamental physical quantities (temperature, energy,
and entropy) that characterize thermodynamic systems. The laws describe how these quantities
behave under various circumstances.

0th Law of Thermodynamics:

Statement of 0th Law of Thermodynamics:
The Zeroth Law of Thermodynamics states that if two systems are in thermodynamic
equilibrium with a third system, the two original systems are in thermal equilibrium with each
other. Basically, if system A is in thermal equilibrium with system C and system B is also in
thermal equilibrium with system C, system A and system B are in thermal equilibrium with each
other.

Explanation of 0th Law of Thermodynamics:

Essentially, two systems that are in thermodynamic equilibrium will not exchange any heat.
Systems in thermodynamic equilibrium will have the same temperature.

 In 1872 James Clerk Maxwell wrote: "If when two bodies are placed in thermal
communication, one of the two bodies loses heat, and the other gains heat, that body
which gives out heat is said to have a higher temperature than that which receives heat
from it." And, "If when two bodies are placed in thermal communication neither of them
loses or gains heat, the two bodies are said to have equal temperature or the same
temperature. The two bodies are then said to be in thermal equilibrium." Maxwell also
stated, "Bodies whose temperatures are equal to that of the same body have themselves
equal temperatures."

 In 1897 Max Planck said, "If a body, A, be in thermal equilibrium with two other bodies,
B and C, then B and C are in thermal equilibrium with one another."

The temperature of a system is a property that determines whether or not a system is in thermal
equilibrium with other systems.
The concept of thermal equilibrium is very familiar to us! For example, we all know that if we
take a cold bottle of milk from the fridge and a cup of hot water and leave them in the room for a
few hours, they both will have the same temperature as that of the room. That is they both reach
thermal equilibrium with the room.
Thus we say: Two systems are equal in temperature if no change in any property occurs when
they are bought into communication".

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We can also conclude that: "Two systems which are equal in temperature to a third system are
equal in temperature to each other".

Mathematical expression of 0th Law of Thermodynamics:

Suppose we have three materials A, B and material C. Suppose materials A, B and C have
different initial temperatures T1i, T2i and T3i. That is;

T1i ≠ T2i ≠ T3i

If these materials are brought in thermal contact with each other and they remain in contact,
according to the law all three attain a thermal equilibrium. At thermal equilibrium all these three
materials will get same final temperature, that is;

T1f = T2f = T3f

Application of 0th Law of Thermodynamics:

We put material mercury in another kind of material glass capillary. Both become in thermal
contact and attain same temperature, say the room temperature.

Now we put this instrument in some boiling water. Water starts losing heat and instrument starts
gaining heat. The glass becomes hot and so the mercury too, as these three materials are in
thermal contact. Mercury gains heat expands with in glass capillary. Ultimately all three
materials attain the same temperature, as they all at get thermal equilibrium. We mark the glass
at the level of mercury. Now we put the instrument in ice and mercury drops with in capillary. At
thermal equilibrium, we again mark the capillary. Now we can divide these two marks in further
sub division to have the instrument as “thermometer”.

This is how the Zeroth Law of Thermodynamics provides the basis for temperature
measurements instrument (the thermometers).

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1st Law of Thermodynamics:
Statement:
 The First Law of Thermodynamics (Conservation) states that energy is always conserved;
it cannot be created or destroyed.

 The First Law of Thermodynamics states that energy can be converted from one form to
another with the interaction of heat, work and internal energy, but it cannot be created nor
destroyed, under any circumstances.

Explanation of 1st Law of Thermodynamics:

The first law of thermodynamics is often called the Law of Conservation of Energy.

This law suggests that energy can be transferred from one system to another in many forms.
However, it cannot be created nor destroyed. Thus, the total amount of energy available in the
Universe is constant.

A system can gain or lose energy. But any change in the energy of the system must be
accompanied by an equivalent change in the energy of its surroundings because the total energy
of the universe is constant. As the law states that the total energy of the universe does not
change. This does not mean that the form of the energy cannot change. Indeed, chemical energies
of a molecule can be converted to thermal, electrical or mechanical energies.

Mathematical expression of 1st Law of Thermodynamics:

To understand the relationship between work (w) and heat (Q), we need to understand a third,
linking factor: the change in internal energy (E).

With the interactions of heat, work and internal energy, there are energy transfers and
conversions every time a change is made upon a system. However, no net energy is created or
lost during these transfers.

We use the following symbols to express the thermodynamic relations:

 Q is positive if heat is added to the system

 Q is negative if heat is removed
 ∆Q or “q” is the change in system’s heat
 W is positive if work is done by the system,
 W is negative if work is done on the system.
 ∆W or “w” is the amount of work done
 E is the internal energy of the system
 ∆E is the change in internal energy of the system

∆E = Q + W
This equation suggests the change in internal energy is due to some heat addition in the system
and some work has also done by the system.

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This is like having some gas in a piston cylinder system. Gas must be having some initial internal
energy Ei and now we put the cylinder over a heat reservoir (like any burner). Some heat enters
(Q) in the system. Due to heat addition (Energy added), gas expands and the piston moves up
(some work is done by the system (W). We switch off the burner. Let the system energy changes
to Ef. The difference in the initial and final energies (denoted by ∆E or sometimes ∆U) is
∆E = Ef - Ei so that we get (Work is done by the gas on the piston, i.e., compressing the piston
by some external source, “W” is positive):

∆E = Ef - Ei = Q + W
Using such analogy, for some other thermodynamic process we may have (for the case that work
is done on the gas by the piston, i.e., expanding the piston by itself, “W” is negative)

∆E = Ef - Ei = Q - W
Similar other relations may be deduced, depending upon the thermodynamic processes.

Application of 1st Law of Thermodynamics:

We rely on electricity to turn on our lights. Electricity is a form of energy; it is, however, a
secondary source. A primary source of energy must be converted into electricity before we can
flip on the lights.

For example, water energy can be hold by building a dam to hold back the water of a large lake.
If we slowly release water through a small opening in the dam, we can use the driving pressure
of the water to turn a turbine.

The work of the turbine can be used to generate electricity with the help of a generator. The
electricity is sent to our homes via power lines. The electricity was not created out of nothing; it
is the result of transforming water energy from the lake into another energy form.

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2nd Law of Thermodynamics:
Statement:
 No thermodynamic process is possible whose ultimate or final result is the absorption of heat
from a (hot) reservoir (at some temperature T2) and the conversion of this heat into work. And
during this process no heat is been transferred to a colder reservoir (at Temperature T1).
[Kelvin-Planck statement of the second law]

This is not possible (stated by Kelvin-Planck)

 No thermodynamic process is possible whose ultimate or final result is the transfer of heat
from a cooler to a hotter body, without doing some work over it. It is not a spontaneous process.
[Clausius statement of the second law]

For T2<T1 this is not possible (stated by Clausius)

Explanation of 2nd Law of Thermodynamics:

The second law of thermodynamics is formulated in many ways, but is basically a law which -
unlike most other laws in physics - deals not with how to do something, but rather deals entirely
with placing a restriction on what can be done. Second Law of Thermodynamics: It is impossible
to extract an amount of heat QH from a hot reservoir and use it all to do work W. Some amount
of heat QC must be exhausted to a cold reservoir. This stops to think about to have a perfect heat
engine.
This is sometimes called the "first form" of the second law, and is referred to as the Kelvin-
Planck statement of the second law.

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It is not possible for heat to flow from a colder body to a warmer body without any work having
been done to accomplish this flow. Energy will not flow spontaneously from a low temperature
object to a higher temperature object. This precludes a perfect refrigerator. The statements about
refrigerators apply to air conditioners and heat pumps, which embody the same principles.

This is the "second form" or Clausius statement of the second law.

3rd Law of Thermodynamics:

Statement:
 No object or system can have a temperature of zero Kelvin.
 It is impossible for a matter (any state) or a system to attain zero degree Kelvin
temperature.

Explanation of 3rd Law of Thermodynamics:

The Laws of are absolute physical laws - everything in the observable universe is subject to
them. Like time or gravity, nothing in the universe is exempt from these laws.

Third Law of Thermodynamics is also true on the basis of Second Law of Thermodynamics. The
Second Law implies that heat can never spontaneously move from a colder body to a hotter
body. So, as a system approaches absolute zero (zero degree Kelvin), it has to give its energy
(heat flow out of this system) to its surrounding (at a lower temperature for gaining heat energy)

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through the boundary. The surrounding system must be having temperature lower than the
absolute zero temperature. It is not possible because 0° Kelvin is mathematically the lowest
possible temperature in the universe. “Absolute Zero" is the bottom point on the Kelvin
temperature scale. The Kelvin scale is absolute, meaning 0° Kelvin is mathematically the
possible temperature in the universe. This corresponds to about -273.15° Celsius, or -459.7
Fahrenheit.

Another reason supporting the Third Law of Thermodynamics is the relation of kinetic energy
associated (as atom or molecule) to its temperature. As long as there is any kind of motion with
in atoms of a material, it corresponds to some kinetic energy. If there is any kinetic energy, there
exists some temperature (above than zero degree kelvin). The atoms or molecules of a matter
always have vibrational, potential and kinetics energies. The atom, for its existence cannot be in
a state of “stand still” or “stationary”. It has to be in motion. As long as there is any kind of
motion, there is kinetic energy. If there is any kinetic energy, there will be some observable
temperature and this temperature must be above Zero degree Kelvin. So we deduce that absolute
temperature is the temperature where any kind of motion does not exist. The study and
observations explains that there is always some kind of motion in a matter so we cannot attain
Zero Degree Kelvin Temperature.

Entropy:
Statement:
 The measure of disorder in a system in called the entropy of that system.

 The measure of unavailability of useful energy in a system is called the entropy of that
system.
 Entropy is the total energy inside the substance, which is not available for work during
thermodynamic process. It can be considered as the internal energy of the substance,
which depends on the movement of molecules inside the substance. The more the
movement of the molecules, the more the entropy. As the temperature of the substance
increases, the movement of the molecules inside the substance also increases and with it
the entropy of the substance also increases.

Explanation of Entropy:
By “measure of disorder” we mean that arrangement of things like arrangement of bed sheet,
window curtain, clothing, books and playing items in a bedroom in a proper way looking clean
and neat of bedroom. The broken furniture, torn curtains, un-proper arranged books, garbage in
room refers as disorder. In such situation we say that neat and clean room has “lesser entropy”
and mess in a room has “higher entropy”

The glass full of milk to drink has lesser entropy but the same glass broken on the floor with all
milk spilled, has higher entropy.

In thermodynamics the term “entropy” is referred to the unavailability of useful energy.

Before creation of this universe, it is assumed that that all mater in the form of hot gases was
enclosed in huge ball like shape. All energies were enclosed with in the boundary of that globe or

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ball. That all energy was due to its position in that globe, known as potential energy. This is
same as the huge amount of water stored in a dam, as a potential energy of water.

We could utilize all the energy stored in that globe as a work (by heat extracting from that globe
and doing work from that heat). Same as we try to have work (or energy or electrical energy)
from all the potential energy stored in the dam. In both the examples (globe and dam), the
entropy was minimum. All available energies could be converted in to useful work.

By any reason that globe exploded (known as big bang) and all that potential energy distributed
and filled up the space around, now known as universe. All the potential energy stored has
splatted in hundreds of millions system in universe. This step reduced the chances to convert the
available (potential) energy in to useful work, increased the entropy. Same as we allow the water
to fall and try to use its potential energy in to electrical energy. The falling water spreads
everywhere and only some part of falling water is utilized to play role of generating electricity.
We get only a little useful energy out of all potential energy, entropy increased.

Second law of thermodynamics also explains that we cannot use all the energy available in a hot
body in to useful work. Some of the energy is to “waste” in a colder body (at relatively lower
temperature). So in doing work the entropy increases. This phenomenon is going on in practice
everywhere in universe, deducing the result that entropy of the universe is increasing.

The Third Law of Thermodynamics states that it is not possible for a system to attain absolute
zero kelvin. This means that there must be some temperature in a system, always, at any
condition. If there is some temperature than one can have some work out of this system. If we do
some work out of this system then there must be some energy which is not useful. So the system
must have some “entropy”. If by any means a system get zero kelvin (which is not possible), at
this stage the system has zero “entropy”. Third law of thermodynamics limits the entropy that
that “Entropy” of a system is always positive or zero. A pure perfect crystal is one in which
every molecule is identical, and the molecular alignment is perfectly even throughout the
substance (which is not possible), has zero entropy. For non-pure crystals, or those with less-than
perfect alignment, there will be some energy associated with the imperfections, so the entropy
cannot become zero.

The Third Law of Thermodynamics can be visualized by thinking about water. Water in gas
form has molecules that can move around very freely. Water vapor has very high entropy
(randomness). As the gas cools, it becomes liquid. The liquid water molecules can still move
around, but not as freely. They have lost some entropy. When the water cools further, it becomes
solid ice. The solid water molecules can no longer move freely, but can only vibrate within the
ice crystals. The entropy is now very low. As the water is cooled more, closer and closer to
absolute zero, the vibration of the molecules diminishes. If the solid water reached absolute zero,
all molecular motion would stop completely. At this point, the water would have no entropy
(randomness) at all.

We know zero degree Celsius temperature, it is the temperature at which water gets converted
into ice, and hence it is also called freezing point temperature of water. There are many gases
like helium, hydrogen that can be cooled to temperatures much below zero degrees Celsius and

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at certain level they get liquefied. The lowest temperature, to which all the substances or gases
can be cooled to, is called as absolute zero temperature. There cannot be any temperature below
this point and at this temperature all the movements of all the molecules within the substance
stop.

Mathematical expression of Entropy:

Entropy (given by S) is a state function of a thermodynamic system like pressure (P), volume (V)
or temperature (T).

A reversible cycle is a process in which we start a process with some initial conditions, go
through a cyclic process and reaches back at its initial conditions. For example we fill a glass of
water from a bottle of water and the fill back the bottle from that glass of water. At the end the
bottle has same level of water and the glass is empty, which we observed earlier. An irreversible
process is the process in which we do not or cannot attain the initial conditions like burning of a
paper that we cannot bring back the paper from ash of the paper.

In fact no process is “reversible”; all processes are “irreversible”. During filling back the bottle
from the glass, it increases the internal energy due to “stir” of the water molecules. However
theoretically, we assume some systems to be “reversible” to deduce some results.

Considering a piton and cylinder system, having some gas enclosed. It has some temperature
“T”, Entropy “S1” and energy (as heat to be the useful to do work) Q1. After a reversible process,
adding small heat in to it (by increasing the pressure over the piston, such that the temperature
remains constant and there is no friction of piston with the cylinder walls, which is practically
not possible). At this stage the system gets entropy “S2” and Heat energy Q2, with same
temperature “T”. The change in entropy is the function of Change in heat at the same
temperature of a reversible system i.e.,

ΔS = ΔQrev / T

Where; ΔS is the change in entropy i.e., ΔS = S2 – S1

And ΔQ is the change in energy (heat) ΔQ = Q2 – Q1

Please note that this relation of entropy is only valid for the reversible process