Universitatea

Din Oradea

Subiect:
Termotehnica

Titlul Proiectului:
PRINCIPLES AND LAWS OF
THERMODYNAMIC

Autor:
Marco Andreas Wetzel

Decembrie 2019
 Principles of Thermodynamics
What is thermodynamics about?

Thermodynamics is about the transformation of energy from one form to another.

Thermodynamics describe macroscopic (large-scale) properties of equilibrium

systems.

Thermodynamics is an empirical science.

Everything is built on 4 basic laws.

The 4 basic laws

0th Law: Defines the temperature.

1st Law: Defines the energy.
2nd Law: Defines the entropy/direction of time
3rd Law: Gives numerical value to Entropy

These laws are universally valid and cannot be circumvented.

Introduction of a few important terminologies.

• Adiabatic process – no heat transfer

• Isothermal process – constant temperature
• Isobaric process – constant pressure
• Isochoric process – constant volumen

How to describe a System

System is the part of the universe that we choose to study.

The rest part of the universe is the surroundings.

The surface dividing the system form the surroundings is the boundary.

In order to describe a system, we will point out the following:

 • What are the components in the system.
• Whether the system is homogeneous or inhomogeneous.
• If the system is in equilibrium.
• We also need a few macroscopic physical properties.

Equilibrium State

Mechanical equilibrium: Free piston stops moving

— Equality of pressure on wither side of a shared movable Wall

Thermal Equilibrium: heat stops moving

When a hot object is placed in thermal contact with a cold object, heat flows from the
warmer to the cooler object. It continuous until they are in thermal equilibrium. At this
point the two bodies have the same temperature.
 Important ideas that may be regarded to clarify further explanations:

Physical properties:
Extensive properties:

• Depends on the amount of matter in the system.

• Mass, volume, number of molecules, …

Intensive properties:

• Independent of the amount of matter in the system

• Temperature, density, pressure, …

The Equation of State:

The physical state of a sample of a substance, its physical condition, is defined by

its physical properties.

The state is specified by giving its volume, V, amount of substance (number of

moles), n, pressure, p and temperature, T.

It is sufficient to specify only three of these variables, for then the fourth variable
is fixed. It is an experimental fact that each substance is described by an equation of
state, an equation that interrelates these four variables.

The general form of an equation of state is:

𝑝 = 𝑓(𝑇, 𝑉, 𝑛)

Perfect gas

One very important example is the equation of state of a ‘perfect gas’, which has the
form
𝑛𝑅𝑇
𝑝=
𝑉
where R is a constant.

The perfect gas law is inferred by combining a series of empirical laws.

- Boyle’s law: 𝑝𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑛, 𝑇

- Charles’s law: 𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 × 𝑇 , 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑛, 𝑝
𝑝 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 × 𝑇 , 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑛, 𝑉
- Avogadro’s principle: 𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 × 𝑛 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝, 𝑇
 Boyle’s and Charles’s laws are examples of a limiting law, a law that is strictly true
only in a certain limit, in this case p → 0. Avogadro’s principle is commonly expressed
in the form ‘equal volumes of gases at the same temperature and pressure contain the
same numbers of molecules’. In this form, it is increasingly true as p → 0. Although these
relations are strictly true only at p = 0, they are reasonably reliable at normal pressures (p
≈ 1 bar) and are used widely throughout chemistry. A real gas, an actual gas, behaves
more like a perfect gas the lower the pressure in the limit of p → 0.

Figure 1. Depicts the variation of the pressure of a

sample of gas as the volume is changed. Each of the
curves in the graph corresponds to a single temperature
and hence is called an isotherm. According to Boyle’s
law, the isotherms of gases are hyperbolas.

An alternative depiction, a plot of pressure against

1/volume, is shown in Fig. 2 The linear variation of
volume with temperature summarized by Charles’s law
is illustrated in Fig. 3 The lines in this illustration are
examples of isobars, or lines showing the variation of
properties at constant pressure. Figure 4 illustrates the
linear variation of pressure with temperature. The lines in
this diagram are isochores, or lines showing the variation
of properties at constant volume.
Figure 1. The pressure–volume dependence
of an fixed amount of perfect gas at different
temperatures. Each curve is a hyperbola
(pV = constant) and is called an isotherm.

Figure 2. Straight lines are obtained when the pressure is plotted against 1/V at constant temperature. Figure 3. The
variation of the volume of afixed amount of gas with the temperature at constant pressure. Note that in each case the
isobars extrapolate to zero volume at T =0, orθ =−273°C. Figure 4. The pressure also varies linearly with the
temperature at constant volume, and extrapolation to zero at T= 0 (−273°C).
Zeroth Law:
Considering A, B and C are thermodynamic systems:

• If A and B are in thermal equilibrium, B and C are in thermal equilibrium, then A

and C are in thermal equilibrium.

• Two systems are said to be in the relation of thermal equilibrium if they are linked
by a wall permeable only to heat and they do not change over time.

As a convenience of language, systems are sometimes also said to be in a relation of

thermal equilibrium if they are not linked so as to be able to transfer heat to each other
but would still not do so (even) if they were connected by a wall permeable only to heat.

“Common sense law”

The Zeroth Law justifies the concept of temperature and the use of a Thermometer. It
makes the measurement of temperature possible:

- A is the reference, B is the thermometer, C is the object to measure T.

On the thermodynamic temperature scale, temperatures are denoted T and are normally
reported in kelvins, K (not °K). Thermodynamic and Celsius temperatures are related by
the exact expression
𝑇/𝐾 = 𝜃/°𝐶 + 273

It implies that a difference in temperature of 1°C is equivalent to a difference of 1.

Kinetic model of gases

Now I will proceed to introduce the kinetic theory. So, this way we can understand the
microscopic behaviour of particles and allow us to appreciate some of the experimental
evidence for atoms and their motion and know how to apply the gas laws.

The kinetic model is based on 3 assumptions:

1. The gas consists of molecules of mass m in

ceaseless random motion.

2. The size of the molecules is negligible, in the

sense that their diameters are much smaller
than the average distance travelled between
collisions.

3. The molecules interact only through brief,

infrequent, and elastic collisions.

An elastic collision is a collision in which the total translational kinetic energy of the
molecules is conserved.

The molecular explanation of Boyle’s law is that, if a sample of gas is compressed to

half its volume, then twice as many molecules strike the walls in a given period of time
than before it was compressed. As a result, the average force exerted on the walls is
doubled. Hence, when the volume is halved the pressure of the gas is doubled, and p × V
is a constant. Boyle’s law applies to all gases regardless of their chemical identity
(provided the pressure is low) because at low pressures the average separation of
molecules is so great that they exert no influence on one another and hence travel
independently.

The molecular explanation of Charles’s law lies in the fact that raising the temperature
of a gas increases the average speed of its molecules. The molecules collide with the walls
more frequently and with greater impact. Therefore, they exert a greater pressure on the
walls of the container.

Pressure and molecular speed:

From the very economical assumptions of the kinetic model, we show in the following
Justification that the pressure and volume of the gas are related by
1
𝑝𝑉 = 𝑛𝑀𝑐 ?
3

where M = mNA, the molar mass of the molecules, and c is the root mean square speed
of the molecules, the square root of the mean of the squares of the speeds, v, of the
molecules:
C
𝑐 = {𝑣 ? }?

We see that if the root mean square speed of the molecules depends only on the
temperature, then at constant temperature 𝑝𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 which is the content of
Boyle’s law.
To be the equation of state of a perfect gas, its right-hand side must be equal to nRT. It
follows that the root mean square speed of the molecules in a gas at a temperature T must
be
C
3𝑅𝑇 ?
𝑐 = D E
𝑀

Compressibility factor – A measure of deviation from ideal-gas behaviour:

The compression factor, Z, of a gas is the ratio of its measured molar volume, 𝑉F =
𝑉/𝑛, to the molar volume of a perfect gas, 𝑉FG , at the same pressure and temperature:

𝑉F
𝑍 =
𝑉FG

Because the molar volume of a perfect gas is equal to 𝑅𝑇/𝑝, an equivalent expression
IJ
is 𝑍 = K M which means we can write as:
L

𝑝𝑉F = 𝑅𝑇𝑍

Because for a perfect gas Z = 1 under all conditions, deviation of Z from 1 is a measure
of departure from perfect behaviour.

- At very low pressures, all the gases shown have Z ≈ 1 and behave nearly
perfectly.

- At high pressures, all the gases have Z > 1, signifying that they have a larger
molar volume than a perfect gas. Repulsive forces are now dominant.

- At intermediate pressures, most gases have Z < 1, indicating that the attractive
forces are reducing the molar volume relative to that of a perfect gas.

Virial coefficients

At large molar volumes and high temperatures the real-gas isotherms do not differ greatly
from perfect-gas isotherms. The small differences suggest that the perfect gas law is in
fact the first term in an expression of the form

𝑝𝑉 F = 𝑅𝑇(1 + 𝐵′𝑝 + 𝐶′𝑝2 + · · · )

This expression is an example of a common procedure in physical chemistry, in which a

simple law that is known to be a good first approximation (in this case pV = nRT) is
treated as the first term in a series in powers of a variable (in this case p). A more con-
venient expansion for many applications is
 𝐵 𝐶
𝑝𝑉 F = 𝑅𝑇 D1 + + ?E
𝑉F 𝑉F

These two expressions are two versions of the virial equation of state.

We see that the term in parentheses can be identified with the compression factor, Z.
The coefficients B, C, . . ., which depend on the temperature, are the second, third, . . .
virial coefficients the first virial coefficient is 1. The third virial coefficient, C, is usually
less important than the second coefficient, B, in the sense that at typical molar volumes
𝐶/𝑉F? << 𝐵/𝑉F . We can use the virial equation to demonstrate the important point
that, although the equation of state of a real gas may coincide with the perfect gas law
as p → 0, not all its properties necessarily coincide with those of a perfect gas in that
limit.

The van der Waals equation

We can draw conclusions from the virial equations of state only by inserting specific
values of the coefficients. It is often useful to have a broader, if less precise, view of all
gases. Therefore, we introduce the approximate equation of state suggested by J.D. van
der Waals in 1873. This equation is an excellent example of an expression that can be
obtained by thinking scientifically about a mathematically complicated but physically
simple problem, that is, it is a good example of ‘model building’.

The van der Waals equation is

𝑛𝑅𝑇 𝑛 ?
𝑝= −𝑎T U
𝑉 − 𝑛𝑏 𝑉

The equation is often written in terms of the molar volume 𝑉F = V/n as

𝑅𝑇 2
𝑝= − ?
𝑉F − 𝑏 𝑉F

The constants a and b are called the van der Waals coefficients. They are characteris-
tic of each gas but independent of the temperature.
FIRST LAW of Thermodynamics

It defines a usefull property called Energy. It concentrates on the conservation of

energy. The experimental observation that energy can be neither created nor destroyed.
Thus, the energy of the universe is a constant. However, Energy can be transferred from
one part of the universe to another.

ΔEuniv=ΔEsys+ΔEsurr=0
ΔEsys=−ΔEsurr

The change in energy of a system is identical in magnitude but opposite in sign to the
change in energy of its surroundings.

Basic concepts:

The system is the part of the world in which we have a special interest. The surroundings
comprise the region outside the system and are where we make our measurements.
The type of system depends on the characteristics of the boundary that divides it from
the surroundings. If matter can be transferred through the boundary between the
system and its surroundings the system is classified as open. If matter cannot pass
through the boundary the system is classified as closed. Both open and closed systems
can exchange energy with their surroundings. For example, a closed system can expand
and thereby raise a weight in the surroundings; it may also transfer energy to them if
they are at a lower temperature. An isolated system is a closed system that has neither
mechanical nor thermal contact with its surroundings.

Work, heat, and energy

The fundamental physical property in thermodynamics is work: work is motion against

an opposing force. Doing work is equivalent to raising a weight somewhere in the
surroundings. An example of doing work is the expansion of a gas that pushes out a
piston and raises a weight. A chemical reaction that drives an electric current through a
resistance also does work, because the same current could be driven through a motor
and used to raise a weight.

The energy of a system is its capacity to do work. When work is done on an otherwise
isolated system (for instance, by compressing a gas or winding a spring), the capacity of
the system to do work is increased; in other words, the energy of the system is
increased. When the system does work (when the piston moves out or the spring
unwinds), the energy of the system is reduced and it can do less work than before.

Experiments have shown that the energy of a system may be changed by means other
than work itself. When the energy of a system changes as a result of a temperature
difference between the system and its surroundings we say that energy has been
transferred as heat.

The change in energy of a system is equal to the difference

between the heat added to the system and the work done by the
system.
Because heat and work are the only two ways in which energy can be transferred between
a system and its surroundings, any change in the internal energy of the system is the
sum of the heat transferred (q) and the work done (w):

∆𝑈 = 𝑞 + 𝑤

Being:

∆𝑼 → Change of internal energy. 𝒒 → Transferred heat 𝒘 → Work done on system

Conventions:

1. The “change” means the final state – initial state, ∆𝑈 = 𝑈` − 𝑈a

• Q is the heat transferred to the system (positive) - if it is transferred

from the system Q is negative.
• W is the work done by the system (positive) - if work is done on the
system W is negative.

2. Thermic process:
• Exothermic process: ∆𝑼 < 𝟎
• Endothermic process: ∆𝑼 > 𝟎
3. Work:
• When surroundings do work to system, w > 0
• When system does work to surroundings, w < 0
4. Heat flow:
• When heat flows from system to surroundings, q < 0
• When heat flows from surroundings to system, q > 0

The tendency of all systems, chemical or otherwise, is to move toward the state with the
lowest possible energy.

The signs of internal energy:

• Energy entering the system is POSITIVE (+), meaning heat is absorbed, 𝒒 >
𝟎. Work is thus done on the system, 𝒘 > 𝟎
• Energy leaving the system is NEGATIVE (-), meaning heat is given off by the
system, 𝒒 < 𝟎 and work is done by the system, 𝒘 < 𝟎
• Since 𝜟𝑈𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 𝑠𝑦𝑠𝑡𝑒𝑚 = 0 , 𝛥𝑈𝑠𝑦𝑠𝑡𝑒𝑚 = −𝛥𝑈𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 and energy is conserved.

We can determine 𝛥𝑈 for any process if we can measure both 𝒒 and 𝒘. Heat, 𝒒, may be
calculated by measuring a change in temperature of the surroundings. Work, 𝒘, may
come in different forms, but it too can be measured.
One important form of work for chemistry is pressure-volume work done by an
expanding gas. At a constant external pressure (for example, atmospheric pressure)

𝑤 = −𝑃𝛥𝑉

The negative sign associated with 𝑃𝑉 work done indicates that the system loses energy
when the volume increases. That is, an expanding gas does work on its surroundings,
while a gas that is compressed has work done on it by the surroundings

If we are interested in how heat transfer is converted into doing work, then the
conservation of energy principle is important.

ENTHALPY

To further understand the relationship between heat flow (q) and the resulting change in
internal energy (ΔE), we can look at two sets of limiting conditions: reactions that occur
at constant volume and reactions that occur at constant pressure. We will assume that PV
work is the only kind of work possible for the system

𝛥𝐸 = 𝑞 − 𝑃𝛥𝑉

If the reaction occurs in a closed vessel, the volume of the system is fixed, and ΔV is zero.
Under these conditions, the heat flow (often given the symbol qv to indicate constant
volume) must equal ΔE:

𝑞𝑣 = 𝛥𝐸
constant volume

No PV work can be done, and the change in the internal energy of the system is equal to
the amount of heat transferred from the system to the surroundings or vice versa.

Many chemical reactions are not, however, carried out in sealed containers at constant
volume but in open containers at a more or less constant pressure of about 1 atm. The
heat flow under these conditions is given the symbol 𝑞s to indicate constant pressure.

Replacing q in Equation
𝛥𝐸 = 𝑞 − 𝑃𝛥𝑉

by qp and rearranging to solve for qp,

𝑞𝑝 = 𝛥𝐸 + 𝑃𝛥𝑉 constant pressure

Thus, at constant pressure, the heat flow for any process is equal to the change in the
internal energy of the system plus the PV work done.

Because conditions of constant pressure are so important, a new state function called
enthalpy (H) is defined as H = E + PV. At constant pressure, the change in the enthalpy
of a system is as follows:

ΔH = ΔE + Δ(PV) = ΔE + PΔV
 Comparing the previous two equations shows that at constant pressure, the change in
the enthalpy of a system is equal to the heat flow:

𝛥𝐻 = 𝑞𝑝.

The relationship between ΔH and ΔE

If ΔH for a reaction is known, we can use the change in the enthalpy of the system to
calculate its change in internal energy. When a reaction involves only solids, liquids,
liquid solutions, or any combination of these, the volume does not change appreciably
(ΔV = 0). Under these conditions, we can simplify Equation ΔH = ΔE + Δ(PV) = ΔE +
PΔV
to ΔH = ΔE. If gases are involved, however, ΔH and ΔE can differ significantly. We can
calculate ΔE from the measured value of ΔH

ΔH = ΔE + Δ(PV) = ΔE + PΔV

Together with the ideal gas law, PV = nRT.

Recognizing that Δ(PV) = Δ(nRT)

We can rewrite: ΔH = ΔE + Δ(PV) = ΔE + Δ(nRT)

At constant temperature:

Δ(nRT) = RTΔn

where Δn is the difference between the final and initial numbers of moles of gas. Thus:

ΔE = ΔH − RTΔn

For reactions that result in a net production of gas, Δn > 0, so ΔE < ΔH.

Conversely, endothermic reactions (ΔH > 0) that result in a net consumption of gas have
Δn < 0 and ΔE > ΔH

For reactions that result in a net production of gas, ΔE < ΔH. For endothermic reactions
that result in a net consumption of gas, ΔE > ΔH.

v The energy of the universe is constant. The change in the internal energy of a system is
the sum of the heat transferred and the work done. At constant pressure, heat flow (q) and
internal energy (E) are related to the system’s enthalpy (H). The heat flow is equal to the
change in the internal energy of the system plus the PV work done. When the volume of
a system is constant, changes in its internal energy can be calculated by substituting the
ideal gas law into the equation for ΔE.
SECOND LAW

The Second Law of Thermodynamics states that the state of entropy of the entire universe,
as an isolated system, will always increase over time. It also states that the changes in
the entropy in the universe can never be negative, and is concerned with the direction
of natural processes.

It asserts that a natural process runs only in one sense, and is not reversible.
For example, heat always flows spontaneously from hotter to colder bodies, and never
the reverse, unless external work is performed on the system.

Total entropy (S) can never decrease over time for an isolated system because the entropy
of an isolated system spontaneously evolves toward thermodynamic equilibrium: the
entropy should stay the same or increase.

In a fictive reversible process, an infinitesimal increment in the entropy (dS) of a system

is defined to result from an infinitesimal transfer of heat (δQ) to a closed system (which
allows the entry or exit of energy – but not mass transfer) divided by the common
temperature (T) of the system in equilibrium and the surroundings which supply the heat:
𝛿𝑄
𝑑𝑆 =
𝑇

Different notations are used for infinitesimal amounts of heat (δ) and infinitesimal
amounts of entropy (d).

For a measurable change between two states i and f this expression integrates to
`
𝑑𝑞yz{
∆𝑆 = x
a 𝑇

That is, to calculate the difference in entropy between any two states of a system, we
find a reversible path between them, and integrate the energy supplied as heat at each
stage of the path divided by the temperature at which heating occurs.

There are several ways in which the second law of thermodynamics

can be stated.

1. No process is possible whose sole result is

the absorption of heat from a reservoir and
the conversion of this heat into work.
[Kelvin-Planck statement of the second
law]
Figure. 1 This is not possible (Kelvin-
Planck)

2. No process is possible whose sole result is

the transfer of heat from a cooler to a hotter body. [Clausius
statement of the second law]
Figure. 2 This is not
posible (Clausius)

Gibbs Free Energy

According to the First Law of Thermodynamics, positive energy flow is when work is
done on the system, or heat is added to it, and the total energy change of the universe is
zero (the energy gained by the system is lost by the surroundings, and vice versa).

Writing the first law, and equating the entropy of the universe to that of the system plus
the surroundings gives:

𝛥𝑆|}a{zy~z > 0
𝛥𝑆|}a{zy~z = 𝛥𝑆•€~•zF + 𝛥𝑆•‚yyG‚}ƒa}„~
𝛥𝑆•€~•zF + 𝛥𝑆•‚yyG‚}ƒa}„~ > 0

Noting that the system is the chemical reaction, and 𝛥𝑆…†‡ˆ‰Š‹Œ can be determined from
the standard molar entropies, gives the following expression of the second law:

𝛥𝑆Iz•Ž•aG} + 𝛥𝑆•‚yyG‚}ƒa}„~ > 0

Noting from the Clausius definition of entropy

𝑞~‚yyG‚}ƒa}„~
𝛥𝑆•‚yyG‚}ƒa}„~ =
𝑇
So
𝑞•‚yyG‚}ƒa}„~
𝛥𝑆Iz•Ž•aG} + >0
𝑇

and from the first law, that when the system loses heat, the surroundings gains heat,

𝑞~‚yyG‚}ƒa}„~ = −𝑞~€~•zF = −𝑞yz•Ž•aG}

−𝑞yz•Ž•aG}
𝛥𝑆yz•Ž•aG} + > 0
𝑇
The above equation is very important because we now define entropy change of the
universe in terms of the system, ie., the chemical reaction, where it is the change in
entropy of the reaction, plus the changed induced to the surrounding by the heat
•
transferred, that is J .
Note, if the reaction is endothermic there is a reduction in entropy of the surroundings,
and if it is exothermic, there is an increase. Noting that the enthalpy of reaction is the heat
transferred at constant pressure,
𝛥𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝑞𝑝,𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
and substituting gives:
−𝛥𝐻Iz•Ž•aG}
𝛥𝑆Iz•Ž•aG} + >0
𝑇
The equation above is very important because it allows us to
describe the Second Law of Thermodynamics in terms of the
system (chemical reaction), and not the universe.

This relationship is so important that it has been rearranged into a new equation, Gibbs
Free Energy (G).

First, multiply everything by T, giving:

𝑇𝛥𝑆yz•Ž•aG} − 𝛥𝐻yz•Ž•aG} > 0

multiplying by negative 1 (-1) and rearranging (noting the sign of the inequality switches
when you multiply by negative one).

𝛥𝐻 − 𝑇𝛥𝑆 < 0
This is the definition of ΔG
𝛥𝐺 = 𝛥𝐻 − 𝑇𝛥𝑆
And for a spontaneous reaction:
𝛥𝐺 = 𝛥𝐻 − 𝑇𝛥𝑆 < 0

v Gibbs Free Energy (G, sometimes given the symbol F), is also a state function,
and all the things we learned with enthalpy in gen chem 1 apply. Its sign switches
for the back reaction, it is an extensive property, and the values for a reaction
can be determined from standard tables of free energies of formation.
Carnot Cycle

In the early 19th century, steam engines came to play an increasingly important role in
industry and transportation. However, a systematic set of theories of the conversion of
thermal energy to motive power by steam engines had not yet been developed. Nicolas
Léonard Sadi Carnot (1796-1832), a French military engineer, published Reflections on
the Motive Power of Fire in 1824. The book proposed a generalized theory of heat
engines, as well as an idealized model of a thermodynamic system for a heat engine that
is now known as the Carnot cycle. Carnot developed the foundation of the second law
of thermodynamics, and is often described as the "Father of thermodynamics."

The Carnot cycle consists of the following four processes:

1. A reversible isothermal gas expansion process. In this process, the ideal gas in
the system absorbs qin amount heat from a heat source at a high temperature Th,
expands and does work on surroundings.

2. A reversible adiabatic gas expansion process. In this process, the system is

thermally insulated. The gas continues to expand and do work on surroundings,
which causes the system to cool to a lower temperature, Tl.

3. A reversible isothermal gas compression process. In this process, surroundings

do work to the gas at Tl, and causes a loss of heat, qout.

4. A reversible adiabatic gas compression process. In this process, the system is

thermally insulated. Surroundings continue to do work to the gas, which causes
the temperature to rise back to Th.

Ilustration 1 And ideal gas piston model of the Carnot Cycle.

P-V Diagram

The P-V diagram of the Carnot cycle is shown in Ilustration 2. In isothermal processes I
and III, ∆𝑈 = 0 because ∆𝑇 = 0. In adiabatic processes II and IV, 𝑞 = 0.

Ilustration 2. A P-V Diagram, of the Carnot Cycle.

Work, heat, ∆𝑈, and ∆𝐻 of each process in the Carnot cycle are summarized in Table1.

Tabla 1. Work, heat, ∆U, and ∆H in the P-V diagram of the Carnot Cycle.

For the expansion (or compression) of an ideal gas from an initial volume 𝑉‘ and
pressure 𝑃‘ to a final volume 𝑉 and pressure 𝑃 at any constant temperature, the
change in entropy is given by:
𝑉 𝑃
∆𝑆 = 𝑛𝑅 𝑙𝑛 = −𝑛𝑅 ln
𝑉‘ 𝑃‘
T-S Diagram
The T-S diagram of the Carnot cycle is shown in Figure 3. In isothermal processes I and
III, ∆𝑇 = 0. In adiabatic processes II and IV, ∆𝑆 = 0 because 𝑑𝑞 = 0. ∆T and ∆S of each
process in the Carnot cycle are shown in Table 2.

Ilustration 3

Tabla 2. Work, Heat and ∆U in the T-S diagram of the Carnot Cycle.

Efficency
The Carnot cycle is the most efficient engine possible based on the assumption of the
absence of incidental wasteful processes such as friction, and the assumption of no
conduction of heat between different parts of the engine at different temperatures.
The efficiency of the carnot engine is defined as the ratio of the energy output to the
energy input.

𝑛𝑒𝑡 𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 ℎ𝑒𝑎𝑡 𝑒𝑛𝑔𝑖𝑛𝑒ℎ𝑒𝑎𝑡 −𝑤𝑠𝑦𝑠

𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = =
𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑏𝑦 ℎ𝑒𝑎𝑡 𝑒𝑛𝑔𝑖𝑛𝑒 𝑞ℎ𝑖𝑔ℎ

𝑛𝑅𝑇ℎ𝑖𝑔ℎ 𝑙𝑛(𝑉2𝑉1) + 𝑛𝑅𝑇𝑙𝑜𝑤 𝑙𝑛(𝑉4𝑉3)

=
𝑛𝑅𝑇ℎ𝑖𝑔ℎ 𝑙𝑛(𝑉2𝑉1)
Since processes II (2-3) and IV (4-1) are adiabatic,

𝑇2 𝐶𝑉/𝑅
𝑉3
D E =
𝑇3 𝑉2

and

𝑇1 𝐶𝑉/𝑅
𝑉4
D E =
𝑇4 𝑉1

And since T1 = T2 and T3 = T4

𝑉– 𝑉?
=
𝑉— 𝑉C
Therefore,

𝑉2 𝑉2
𝑛𝑅𝑇ℎ𝑖𝑔ℎ 𝑙𝑛( ) + 𝑛𝑅𝑇𝑙𝑜𝑤 𝑙𝑛(𝑉1)
𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = 𝑉1
𝑉2
𝑛𝑅𝑇ℎ𝑖𝑔ℎ 𝑙𝑛( )
𝑉1

𝑻𝒉𝒊𝒈𝒉 − 𝑻𝒍𝒐𝒘
𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒄𝒚 =
𝑻𝒉𝒊𝒈𝒉

The Carnot cycle has the greatest efficiency possible of an engine (although other cycles
have the same efficiency) based on the assumption of the absence of incidental wasteful
processes such as friction, and the assumption of no conduction of heat between different
parts of the engine at different temperatures.
The third law

The third law of thermodynamic states that as the temperature of a system approaches
absolute zero, its entropy becomes constant, or the change in entropy is zero. The third
law of thermodynamics predicts the properties of a system and the behavior of entropy in
a unique environment known as absolute temperature.

The entropy of a bounded or isolated system becomes constant as its temperature

approaches absolute temperature (absolute zero). Its entropy becomes constant, or the
change in entropy is zero.
lim ∆𝑆 = 0
J→ ‘

The above equation is a modern statement of the theorem. Nernst often used a form
that avoided the concept of entropy.

The statement is represented by this equation, where T resembles the temperature and
∆𝑆 is the change in the system’s entropy. The denotation “tends to zero” represented by
an arrow pointing towards zero implies that as the temperature decreases to an
infinitesimal value, the system achieves constant entropy by drawing energy from its
surroundings, but as the first law dictates, part of this energy will add to the system’s
internal energy, thereby denying a constant entropy state.

With the development of statistical mechanichs, the third law of thermodynamics (like
other laws) changed form a fundamental law (justified by experiments) to a derived law
(derived from even more basic laws). The basic law from which it is primaly derived is
the statistical mechanics definition of entropy for a large system:

𝑆 − 𝑆‘ = 𝐾¥ ln Ω

Where S is entropy, 𝐾¥ is the Bolytzmann constant, and Ω is the number of microstates

consistent with the macroscopic configuration. The counting of states is from the
reference state of absolute zero, which corresponds to the entropy of 𝑆‘

The entropy of a perfect crystal approaches zero as the absolute temperature

approaches zero. approaches zero as the absolute temperature approaches zero point for
the determination of entropy. Theentropy determined relative to this point is the
absolute entropy. Mathematically, the absolute entropy of any system at zero
temperature is the natural log of the number of ground states times Boltzmann's
𝐾¥ constant.
Rankine ideal engine

Thermodynamic cycle with maximum thermal efficiency between two given extreme
temperatures is the Carnot cycle. However, it cannot be used in practice for building
heat cars. Theoretically one can imagine a thermal engine machine composed of two
turbines and two compressors, of which in two the working fluid is stretched,
respectively compressed, isothermal, andin the other two adiabatic. Turbine relaxation
and compressor compression are practically close to adiabatic transformations
because they can be well thermally insulated and the fluidit flows at high speed inside
them. However, isothermal expansion and compression are impossible to achieve
practically, even if theoretically it could be imagined as a process in progress with
speed tending to zero, so in time tending to infinity.

In practice, thermal machines are used that operate after formed cyclesof two
isobaric transformations and two adiabatic transformations, which can be relatively
easily achieved. If the cycle runs entirely in the gas field, it is called the Joule cycle, this
being the cycle after which gas turbine installations operate.If during the cycle
processes of change of aggregation state occurrespectively condensation and
vaporization, the cycle is called Clausius - Rankine.

K - boiler
S - overheating
T - turbine
C - capacitor
P - pump
G - electric generator
Q 1 - heat received
Q 2 - heat transferred

t w1 - the temperature at which the cooling water enters condenser

t w2 - the temperature at which the cooling water comes out from the capacitor
Δ t w - the temperature difference between the water that also comes the wáter
coming out of the condenser

Superheated steam, produced by boiler installation (K) with state 1 (also called live
steam), enter the turbine (T). In the turbine, the steam relaxes, giving mechanical work
to the turbine rotor. The transformation from the turbine is adiabatic, because the
steam flows at high speed and the turbine is well insulated from the environment. The
turbine shaft is mounted through a mechanical coupling, the electric generator (GE). The
steam exits the turbine with state 2, theoretically dry saturated steam, low pressure
(and much lower temperature). With this state he enters capacitor (C), where the
pressure remains constant. The most common capacitors are the surface ones , in which
there are pipes through which cooling water circulates, this taking over the heat of
steam condensation by increasing its temperature from t w1 to t w2 . Condensate drops
formed on the outer surface of the condenser pipes fall to its lower part. In the mixed
capacitors , used in certain situations, the cooling water is sprayed through nozzles
inside the condenser, in the steam stream. Fine drops of cooling water take over direct
contact with heat from steam, which condenses leading to increased droplets and drop
at the bottom of the capacitor. Liquid saturated with state 3 is taken up by the pump (P),
which compresses it to a pressure equal to the boiler pressure in state 4. The pressure
remains constant until the turbine enters. In boiler (K) the liquid with state 4 is heated
isobarically to the saturation temperature corresponding to the pressure at which it is
vaporized to state 6 dry saturated steam. In large capacity boilers from thermoelectric
power stations, wáter supply it enters the boiler through relatively large diameter pipes
(distributors) placed at the bottom, near the wall. From the boiler water enters the
distribution pipes screen, the diameter much smaller, located near the walls, through
which it flows upward. Inside the fossil fuel burns in the furnace in the furnace. Boiler
water takes heat from the flue gases. The water temperature increases to the saturation
value corresponding to the pressure (state 5), after which begins the vaporization
process. The flow becomes biphasic, with increasing title. In the the top of the title
screen pipes is very close to 1, the saturated steam flow dry resulting in fine droplets of
saturated liquid. At the top of the boiler, the pipes screen converges into a condensate
separator, usually drum type, where the flow section it increases sharply, the flow rate
decreases, and the liquid droplets are gravitationally separated. When the level of the
liquid reaches a certain level, it is evacuated through a pipe and is sent to the lower part
of the boiler, in the boiler feed water stream, process called purging. The dry saturated
steam from the condenser separator enters the superheater (S Î), where increase of
temperature up to the temperature corresponding to one state ( T Sat ) when entering
into the turbine. The heat required for the transformation 4 → 1 is also taken from the
flue gases resulting from burning of fuel in the boiler furnace. In Figures 3 and 4 is
represented the Clausius Rankine cycle theoretical motor (ideally) in
the pv, Ts and is diagrams respectively. In the pv diagram, the area between the
Clausius - Rankine cycle transformations is directly proportional to the specific mass-
produced cyclic mechanical work, for example as a sum algebraic between specific
mechanical things changed mass, ie product in adiabatic relaxation in the turbine (1 →
2) and respectively consumed in the adiabatic compression in pump (3 → 4).
In the T – s diagram , the area of the closed surface of the Clausius - Rankine cycle is also
directly proportional to the mass-specific cyclic mechanical work, but in this case as an
algebraic sum between the specific mass heat received from the hot source during the
isobaric transformation 4 → 1 and the specific mass heat transferred to the cold source
during the isobaric transformation 2 → 3. As the generating cycle (trigonometric path:
1 → 6 → 5 → 4 → 3 → 2 → 1) is the most often used cycle of operation of heat pumps
and refrigeration machines (also called "with mechanical vapor compression”).

Figure 3 and 4. Left (1) Rankine cycle in p-v Diagram and Right (2) Rankine cycle in T-s Diagram.