Second Law of Thermodynamics FINISHED

SECOND LAW OF
THERMODYNAMICS
THERMAL MACHINES
HEAT PUMPS AND REFIGERANTS
REVERSIBLE AND IRREVERSIBLE
PROCESSES
ENTROPY
Antonio José Salcedo,

Daniel Barros,
Max Cañate,
Andrés Sierra.
Erick Martínez
Physics Heat and Waves
COAST UNIVERSITY
DEPARTMENT OF BASIC SCIENCES
HEAT AND WAVE PHYSICS AREA
FACULTY OF ENGINEERING
SECOND LAW OF THERMODYNAMICS, THERMAL MACHINES, HEAT

PUMPS AND REFIGERANTS, REVERSIBLE AND IRREVERSIBLE
PROCESSES, ENTROPY.
Antonio José Salcedo1, Daniel Barros2, Max Cañate2, Andrés Sierra1.
1Civil Engineering, 2Electronic Engineering.
Field Physics Group: JDL
Summary
The first law of thermodynamics is a statement of the conservation of energy. This

law states that a change in internal energy in a system can occur as a result of
energy transfer by heat, work, or both. Although the first law of thermodynamics is
very important, it does not distinguish between processes that occur spontaneously
and those that do not. However, only certain types of energy conversion and
energy transfer processes take place in nature. The second law of
thermodynamics, the main topic of this work, establishes which processes occur
and which do not.
The following are examples of processes that do not violate the first law of
thermodynamics if they run their course in any direction, although in reality they are
observed to run their course only in one direction:
 When two objects at different temperatures are placed in thermal contact,

the net energy transfer by heat is always from the hotter object to the colder
object, never from the colder to the hotter.
 A rubber ball dropped on the ground bounces several times and eventually
comes to rest, but a ball lying on the ground never gathers internal energy
from the ground and begins to bounce on its own.
 A swinging pendulum eventually comes to rest due to collisions with air
molecules and friction at the point of suspension. The mechanical energy of
the system is converted into internal energy in the air, the pendulum and the
suspension; the opposite conversion of energy never occurs.
All of these processes are irreversible: that is, they are processes that occur
naturally in one direction. No irreversible process has ever been observed to spin
back. Doing so would violate the second law of thermodynamics.
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1. SECOND LAW OF THERMODYNAMICS.

This law of physics states that "The amount of entropy (a magnitude that measures
the part of the energy that cannot be used to produce work) of any
thermodynamically isolated system tends to increase with time." More simply,
when one part of a closed system interacts with another part, energy tends to be
divided equally, until the system reaches thermal equilibrium. The second law of
thermodynamics establishes which processes in nature can or cannot occur. Of all
the processes allowed by the first law, only certain types of energy conversion can
occur.
Now there are different ways of stating the second law of thermodynamics, but in
its simplest version, it states that:
“Heat never flows spontaneously from a cold object to a hot object.”
As with other laws of thermodynamics, the second principle is empirical, we arrive
at it through experimentation. Thermodynamics is not concerned with
demonstrating why things are like this, and not otherwise.
The second law of thermodynamics is expressed in several equivalent
formulations:
 Kelvin-Planck Statement
A process that converts all the absorbed heat into work is not possible.
 Clausiois statement
No process is possible whose sole result is the extraction of heat from a cold body
to a hotter one.
Next we are going to study the consequences of this law, in the case of heat
engines and introduce the concept of entropy.
2. THERMAL MACHINES.
Heat engines are systems that transform heat into work. In them, the restrictions
indicated above are clearly reflected. There are many examples of devices that
are, in fact, heat engines: the steam engine, the car engine, and even a
refrigerator, which is a heat engine operating in reverse.
A heat engine transforms thermal energy into work by performing a continuous
cycle. In them there is no variation of internal energy, ∆U=0.
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Note the distinction between the first and second laws of thermodynamics. If a gas
undergoes an isothermal process in some direction, then Δ E∫ ¿=Q +W =O yW =−Q ¿
Because of that, the first law allows all heat energy input to be expelled through
work. However, in a heat engine, in which a substance undergoes a cyclic process,
only a portion of the heat energy input is expelled by work, in accordance with the
second law.
A heat engine carries some work substance through a cyclic process during which
the work substance absorbs heat energy from a high-temperature energy reservoir,
the machine consumes work, and heat energy is expelled to a higher-temperature
reservoir. low. As an example, consider the operation of a steam engine, which
uses water as the working substance. Water in a boiler absorbs energy from
burning fuel and converts it to steam, which then does work by expanding against
a piston. After the steam cools and condenses, the produced liquid water returns to
the boiler and the cycle repeats. It is useful to represent a heat engine
schematically. The machine absorbs a quantity of energy│Q h │ from the hot tank.
For the mathematical explanation of heat engines, absolute values are used to
make all energy transfers positive and the direction of transfer is indicated with an
explicit sign, positive or negative. The machine does workW maq (so the negative
workW =−W máq consumed in the machine) and then delivers an amount of energy
│Qc │ to the cold tank. Since the working substance goes through a cycle, its initial
and final internal energies are equal: ΔEint =0 . Therefore, from the first law of
thermodynamics, Δ E∫ ¿=Q +W =O yW =−Q ¿W maq =0 , and the net workW maq performed by a
heat engine is equal to the net energyQneta that is transferred to you:
Qneta=│Qh │−│Qc │ ; therefore, W maq =│Qh │−│Qc │
The thermal efficiency e of a heat engine is defined as the ratio of the net work
invested by the machine during a cycle, to the energy input at the highest
temperature during the cycle:
W maq │ Qh │−│ Qc │ │ Qc │
e= = =1−
│Qh │ │Q h │ │Qh │
You can think of efficiency as the ratio of what you gain (work) to what you give
(energy transfer at the highest temperature).
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Schematic representation of a heat engine. The machine does work W maq . The arrow at
the top represents energyQ h > 0 that enters the machine. In the background, Qc < 0
represents the energy leaving the machine.
Example 1: The efficiency of a machine

A machine transfers2.00 x 10 3 J of energy from a hot reservoir during a cycle and
transfers1.50 x 103 J as it is expelled into a cold tank.
a) Find the efficiency of the machine.
Solution.
Conceptualize: Think about the energy that goes to the machine from the hot tank
and is divided, some going out through work and the other through heat to the cold
tank.
Categorize: This example involves evaluating quantities of the equations presented
in this section, so it is classified as a substitution problem.
│ Qc│
e=1−
│ Qh │
b) How much work does this machine do in one cycle?

Find the work done by the machine by taking the difference between the input and
output energies:
3. REVERSIBLE AND IRREVERSIBLE PROCESSES
Formally, a thermodynamic process is said to be reversible if it can be reversed so

that the resulting cyclic process, for both the system and the environment, does not
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violate the Second Principle of thermodynamics. In a simpler way to explain it, it is

said that a reversible process is that process that, after being taken from an initial
state to a final state, can return to its original properties. This would lead to
declaring said processes as ideal, since time necessary for these infinite states of
intermediate equilibrium to be established would be infinite.
A reversible process must meet at least the following conditions:
1. There should be no transformations of mechanical energy into thermal
energy through friction or other types of dissipative forces.
2. Energy transfers such as heat can only occur when the temperature
differences between objects are infinitesimally small.
3. The process must be quasi-static, so that the system is always in a state of
thermodynamic equilibrium.
Any real process in nature is irreversible, as explained before, reversible processes
are actually idealizations, which in reality can be achieved approximately, but never
completely.
Irreversible processes are those that, as their name indicates, are not reversible
since they cannot return to the initial state. For their part, these processes
generally include:
1. Movement with friction.
2. Free expansion.
3. Transfer of energy as heat due to the difference.
4. Electric current through a non-zero resistance.
5. Spontaneous chemical reaction.
6. Mixture of matter of different composition or state.
4. ENTROPY
1. Meaning:
Entropy is defined as the level or degree of microscopic disorder that is present in
the different systems existing in nature. It is also known as the second principle of
thermodynamics, which defines it in a schematic way as “progress toward
destruction.”
2. History:
The word entropy comes from the Greek “em”, which means “about and near” and
“sqopg” which means “change and evolution”.
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Physical term used for the first time in the 1850s by the German scientist Rodolf
Clausius, but later, exactly in the year 1877, the physicist Ludwig Boltzmann was
able to find the mathematical device that explained entropy from the point of view
of probability. .
3. Theory:
Second principle of thermodynamics : “Considering the universe as an isolated
system, the processes in which the entropy of the universe increases will occur
spontaneously.”
In order to explain the previous definition, we have to be clear about what an
isolated system is, because in this principle the universe is considered one of
them.
Image 1.
An isolated system is defined as a system where neither the exchange of matter
nor the flow of energy occurs between it and the outside.
Once this concept is known, we can conclude the following: “the entropy of an
isolated system will always tend to increase, it will never tend to decrease.”
Analyzing the previous situation we realize that although there is no exchange of
matter, much less energy, the entropy is increasing, therefore, we conclude that it
is possible to create it, which is the main difference with energy (it is neither
created nor destroyed, it is simply transformed).
2
δQ
Entropy equation :∆ S=∫
1 T
WhereδQ is the amount of heat absorbed in the process and T is the absolute
temperature, evaluated at the initial moment and a final moment.
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The change in entropy of the universe will always be greater than zero ( ∆ Su>0 ),
defining it as the sum between the change in the entropy of the environment and
the change in the entropy of the system (∆ Su=∆ Se +∆ Ss ¿ .
Image 2.
Looking at the equation for the change in entropy of the universe, we conclude that
the change in entropy of the system can be negative (meaning that it is
decreasing), but the only way for this to occur is if the change in entropy of the
environment increases by a greater amount.
4. Proposed problems:
4.1 Let's consider that they react to 298K according to the reaction:
N ( 2 ) gr +O ( 2 ) gr =2 NOgr
At 298K is the reaction spontaneous?

Data:
J J
∆ Hf [ NO ( gr ) ] =90 S [ N ( 2 ) gr ] =191 S [ O ( 2 ) gr ] =205
3 Kj 5
/mol
mol k mol k
J
S [ NO ( gr ) ] =210
6
mol k
KJ
N (2) gr + O (2) gr = 2NOgr ∆ Hr [ NOgr ] =186
mol
Its entropy will be:
∆ Sr=2 ¿
7 J
∆ Sr=24
molK
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Therefore:
∆ Gr=( ∆ Hr−T ) ∆ Sr
4 J
∆ Gr=173.239 > 0 Which means it is not spontaneous at 298K.
mol
5. THERMAL PUMPS AND REFRIGERANTS
Refrigeration pumps work by exchanging heat between elements, the objective of

the system is to obtain heat from a space to transfer it to another environment or
element. On the other hand, we clarify at the beginning that cold as such is merely
the name we give to a thermal sensation, although for physical purposes the only
thing that really exists is heat. When we heat or subtract heat from an element,
what we are actually doing is acting on the molecular vibration of said element,
since energy is released from it in the form of heat; the lower the mobility, the lower
the energy released, therefore the lower the heat.
In the case of refrigeration pumps, their objective is heat exchange, subtracting

molecular movement from the inside and transferring it to the outside, hence our
refrigerator will be found hot in the sector intended for its mechanism and cold
inside. The exchange is promoted by a chemical called “refrigerant” which absorbs
heat and gives it away depending on the state and pressure ingested. In this way,
the refrigerant pump is made up of two well-differentiated sectors, one in
communication with the internal environment where the refrigerant is manipulated
to absorb heat, after passing through the part of the circuit that interacts with the
interior space, the gas is modified in its pressure and state so that the heat
contained in it is released to the outside.
These changes inflicted on the chemical are caused by a compressor which

defines the pressure at which it will circulate, an evaporator and a condenser which
work at constant temperatures, promoting the change of state of the chemical at
the precise moment that is required. Otherwise, obviously the same system applied
in reverse can heat the interior by obtaining heat from the outside. These pumps
are called heat pumps and we commonly see them implemented in the air
conditioning of swimming pools and air conditioners . Some of them can work in
both directions. Thanks to the technology called inverter, the system is practically
the same with changes in the redirection of the refrigerant through a system of
valves called 4-way.
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GLOSSARY
4-Way Valve:
It is responsible for reversing the flow of the refrigerant. Connection of the pipes:
- Top: download
- Confronted: aspiration
- Other 2: the 2 units
Electrically piloted
Driven by coolant pressure
Figure 1: 4-way valve

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SECOND LAW OF

Antonio José Salcedo,

SECOND LAW OF THERMODYNAMICS, THERMAL MACHINES, HEAT

The first law of thermodynamics is a statement of the conservation of energy. This

 When two objects at different temperatures are placed in thermal contact,

1. SECOND LAW OF THERMODYNAMICS.

Example 1: The efficiency of a machine

b) How much work does this machine do in one cycle?

3. REVERSIBLE AND IRREVERSIBLE PROCESSES

Formally, a thermodynamic process is said to be reversible if it can be reversed so

violate the Second Principle of thermodynamics. In a simpler way to explain it, it is

At 298K is the reaction spontaneous?

5. THERMAL PUMPS AND REFRIGERANTS

Refrigeration pumps work by exchanging heat between elements, the objective of

In the case of refrigeration pumps, their objective is heat exchange, subtracting

These changes inflicted on the chemical are caused by a compressor which

Figure 1: 4-way valve

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