School of Engineering

Thermodynamics
Fundamental concepts

Dr. Jorge Francisco Estela Uribe

FACULTAD DE INGENIERIA
 Thermodynamics
Dr. Jorge Francisco Estela

1.1 Definition of Thermodynamics:

Thermodynamics is the study of energy, its transformations and the

interactions of energy with matter in the form of heat and work.

Also, thermodynamics deals with the properties of matter that take part in
the transformations of energy.

In its origins, thermodynamics studied the efficiency of heat engines,

thence its name, which comes from the Greek words έ, therme
(heat) and ύς, dynamis (power).

Thermodynamics has evolved into a very powerful discipline with

applications in physics, chemistry, biology and branches of engineering
such as chemical engineering, mechanical engineering, etc.
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1.2 The thermodynamic system and the control volume:

In thermodynamics, a system is a device or combination of devices

containing a mass that is subjected to study.

The universe is the totality of mass that exists. The surroundings are the
portion of the universe that interacts strongly with the system.

The control volume is the volume that contains the matter and the devices
under study. The control surface is the boundary that separates the control
volume from the surroundings.

The control surface can be physical or imaginary, it can also be stationary

or movable.

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1.3 The thermodynamic system and the control volume:

The universe
The control surface

The surroundings

The system

An isolated system is one that has no interactions with the

surroundings, i.e. there is no mass flow nor heat or work transfer.

The term closed system refers to a system with no mass flow whereas
the term open system refers to a system open to the flow of mass.

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Interactions of the thermodynamic system:

Type of system Flow of mass Heat work

Open
  
Closed
  
Isolated
  

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 Thermodynamics
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1.4 Macroscopic and microscopic approaches:

In the macroscopic approach, called classical thermodynamics, the

properties of the system are taken in bulk and are those that can be
measured by the senses or instruments. These properties are gross
averages resulting from the effects of vast numbers of molecules or
particles. In classical thermodynamics there is no consideration to the
individual behaviour of molecules.

In the microscopic approach, called statistical thermodynamics, properties

are described from the individual behaviour of molecules. Given the
enormous number of variables, statistical techniques and probability theory
are used to produce time-average values of properties. However, the
predictions of statistical thermodynamics regarding the behaviour of a
system must coincide with those of classical thermodynamics.

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 Thermodynamics
Dr. Jorge Francisco Estela

1.5 Properties and state of a substance:

A property is any quantity that depends only on the state of a system and
is independent on the path or history that the system took to reach that
state.

Conversely, the state of a system is the condition defined by the set of

values of the properties of the system. Therefore, thermodynamic
properties are state functions.

Thermodynamic properties are divided into two categories. Intensive

properties are those whose values are independent of the extent of the
system, i.e. pressure, temperature, density. Extensive properties are
additive for subsystems, i.e. total volume, total energy, etc.

Specific properties are extensive properties per unitv mass  V / mand are
intensive properties. For instance, the specific volume is: .
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1.6 Thermodynamic equilibrium:

A system is said to be in equilibrium when its properties are evenly

distributed and do not change with time.

In this condition, the properties of the substance are significant for the
whole system.

A system can be in equilibrium with regards to temperature (thermal

equilibrium), or with regards to pressure (mechanical equilibrium) or with
regards to chemical composition (chemical equilibrium). If the system is in
equilibrium regarding these three variables, it is said to be in
thermodynamic equilibrium.

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 Thermodynamics
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Thermodynamic equilibrium and transport phenomena:

Transport phenomena concern the transfer, or exchange, of momentum,

energy and mass between parts of a system or between systems.

A gradient of pressure is the driving force for the transfer of momentum

(fluid flow).

A gradient of temperature is the driving force for the transfer of energy

(heat).

A gradient of chemical composition is the driving force for the transfer of

mass (diffusion).

Therefore, in the state of thermodynamic equilibrium there are no driving

forces for transport phenomena, i.e. there is no change in the system.
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1.7 Quasi-equilibrium processes:

When the properties of a systems change, a change of state has occurred.

The path through which that change of state occurs is called a process. If
after a number of processes the system returns to its initial state, the whole
succession of processes is called a cycle.

If thermodynamic properties describe the state of a system only at

equilibrium states, how can we describe the state of a system during a
process in which there is no equilibrium?

Quasi-equilibrium process deviate from equilibrium only by an infinitesimal

amount so that it can be considered that the system is always very close to
equilibrium during the process. Therefore, thermodynamic calculations can
be applied to quasi-equilibrium processes.
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1.8 Fundamental quantities and units:

Fundamental quantities are attributes of systems that can be measured

directly and cannot be expressed in terms of other quantities.

Time: it measures the duration of events and of the intervals between

them. The SI unit is the second, s.

Length: it measures the linear dimension of objects. The SI unit is the

metre, m.

Mass: it measures the amount of matter. The SI unit is the kilogram, kg.

Amount of substance: measures the size of an ensemble of particles

(atoms, molecules) that constitute a system. The SI unit is the mole, mol.

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1.9 Secondary quantities:

These are derived from fundamental quantities.

Force: from Newton’s second law of movement, the force F acting on a

body of mass m and acceleration a is F  ma . In the SI system, the unit of
force is the Newton, N, with 1 N = 1 kg.m/s1.

Specific volume: it is the volume per unit mass and is defined by the
V
relation v  lim
 V   V '  m , where V’ is the smallest volume for which the

system can be considered as a continuum. A continuum is a system

whose mass and size are far larger than the mass and size of the
molecules.

The SI unit for the specific volume is kg/m3. The density  is the inverse of
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Pressure: in fluids, pressure is defined as the normal force exerted per unit
area on a real or imaginary surface within the system. Therefore, pressure
 Fn
is given by the relation: p  lim
 A  A '  A

where A’ is the smallest area for which the fluid is continuous. In a fluid at
rest, the pressure is the same in all directions.

The SI unit of pressure is the pascal, Pa, with 1 Pa = 1 N/m 1. For common
engineering applications, this is a very small unit so that multiples, such as
the kilopascal and megapascal, are used. Other units of common use are
the bar, with 1 bar = 105 Pa; and the atmosphere, with 1 atm = 101.325
kPa.

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 Thermodynamics
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1.10 Temperature:

Temperature is another fundamental quantity. It is a difficult concept to

define. In everyday experience, people understand temperature as a
sense of “hotness” or “coldness” of objects. Also, people understand the
overwhelming experience that when a hot body is put in contact with a cold
body, the warmer body becomes colder and the colder body becomes
warmer until they both feel at the same state of hotness or coldness.

In the above experience, if a property is measured, i.e. the electrical

resistance, it will be found that the resistance of the hot body decreases as
the body gets colder and that of the cold body increases as it gets warmer.
After some time, the electrical resistance is the same in both bodies and it
will no longer change with time.

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Therefore, it is more convenient to speak about equality of temperature.

Thus, two bodies are said to be at equal temperatures if, when they are in
thermal communication, there is no change in any observable property.

Then, in classical thermodynamics, temperature is the property that

defines the state of thermal equilibrium.

The zeroth law of thermodynamics states that if two systems are in thermal
equilibrium with a third system, then they are also in thermal equilibrium
with each other. Thermal equilibrium is, then, a transitive relation and
systems in thermal equilibrium have the same temperatures.

This allows for the practical measurement of temperatures with

thermometers calibrated against temperature scales.

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Dr. Jorge Francisco Estela

1.11 Temperature scales:

These are the standards used to calibrate thermometers. Using the zeroth
law, the body whose temperature is to be measured is system A, the
standard is system B and the thermometer is system C. As C has been in
thermal equilibrium with B (upon calibration), when C is put in thermal
equilibrium with A it is as if A were in thermal equilibrium with B, so that A
has the same temperature as indicated by the standard.

The standards are systems that are easily reproducible and do not change.
The phase transitions of pure substances serve to this effect.

The Celsius and Fahrenheit scales were defined using two fixed points: the
ice point and the steam point of the phase transitions of water.

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 Thermodynamics
Dr. Jorge Francisco Estela

The ice point was given the value of 0°C in the Celsius scale and 32 F in
the Fahrenheit scale; whereas the steam point was given the values of
100°C and 212 F, respectively.

Currently, the Celsius scale is defined in terms of the triple point of water
with a temperature of 0.01°C.

The absolute scale associated with the Celsius scale is the Kelvin scale
with the equivalence between the two scales given by: T ( K )  T (C )  273.15
The SI unit for the Kelvin scale is the Kelvin, K, which is defined as
1/273.16 of the temperature of the triple point of water in that scale.
T ( F )  32
For practical purposes, the following conversion is useful: T (C ) 
1.8

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 Thermodynamics
Dr. Jorge Francisco Estela

1.12 Energy:

Energy is a fundamental concept in science and engineering. It is difficult

to define but, at this point, it is enough to say that energy is the capability
to produce an effect.

For an isolated system, energy is always conserved (law of conservation of

energy) although it can be transformed from one form to another.

The forms of energy of interest for engineering thermodynamics are:

Internal: associated with the microscopic structure of the system.
Kinetic: associated with the speed with respect to an external reference.
Potential: associated with the position or configuration of the system.

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1.13 Work:

Work is the effect of a force acting through a displacement. It is defined as:

 W  F  ds . Work done by force F over a finite displacement is then:

2

1W2   F  ds . (1.1)
1

If the force and the displacement are in the same direction, then:
2
W2   F  ds
1 . (1.2)
1

To link this definition to systems and its properties, in classical

thermodynamics it is defined that work is done by a system if the only
effect on the surroundings could be the lifting of a weight.

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 Thermodynamics
Dr. Jorge Francisco Estela

In this definition the lifting of a weight is actually a force acting through a

distance. Therefore, this definition is consistent with the formal definition of
Eq. (1.1).

It is important to notice that the thermodynamic definition of work does not

necessarily mean that a weight was really lifted or that a force acted
through a distance. However, work is executed if the only effect on the
external medium could be the lifting of a weight.

For instance, consider a battery and a motor that drives a fan. If the system
were the battery plus the motor, does work crosses the control surface at
the fan shaft? The answer is yes because a cable can be attached to the
shaft so that a weight could be lifted by the action of the motor.

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 Thermodynamics
Dr. Jorge Francisco Estela

Furthermore, if the system were only the battery, the flow of electricity
through the cables connecting the battery to the motor executes work
because that could be used in the surroundings to lift the weight.

Work is the transfer of energy between systems by the action of a force.

From the definition of Eq. (1) it is clear that work is no a state function, or a
property of the system, because it depends on the way the force and the
displacement are related.

Sign convention:
W > 0, if the system executes work on the surroundings.
W < 0, if the surroundings execute work on the system.

The SI unit of work is the Joule, J, with 1 J = 1 N.m

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Dr. Jorge Francisco Estela

1.14 Power:

It is the time rate at which work is executed by the system or upon the
system. Thus,
W
W  lim . (1.3)
 t 0  t

The SI unit of power is the Watt, W, with 1 W = 1 J/s. Other units of power
are of common use. For instance, the horsepower (hp) is equivalent to 1
hp = 0.7355 kW.

In the context of electrical applications it is very common to use the

kilowatt.hour (kWh). This is not a unit of power but one of work (energy)
with the equivalence 1 kWh = 103 J/s x 3600 s/h = 3.6 x 106 J.

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 Thermodynamics
Dr. Jorge Francisco Estela

1.15 Work done at the movable boundary of a system:

Consider that the system is the gas enclosed in the

cylinder by the piston. In the initial state, the system
dL is in pressure equilibrium with the external pressure.
Upon removing the weight from the piston, the gas
expands until a new equilibrium is reached.
In the process the system has to overcome an external force F that results
from the weight of the piston and the atmospheric pressure. So, the
system has to exert an opposite force to do work. The external force is the
product of the external pressure by the area of the piston. Therefore,
2 2
W2   pext AdL  1W2   pext dV .
1 (1.4)
1 1

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 Thermodynamics
Dr. Jorge Francisco Estela

Eq. (4) gives the general expression for the work executed by a system as
a result of movements of the system boundary. Clearly, if the boundary
expands, dV > 0  W > 0, i.e. work is done on the surroundings; if the
boundary contracts, dV < 0  W < 0, and work is done on the system.
p
From Eq. (4), work is the area under 1
p1
the curve of p against V on a p-V
diagram. In the case in question, as
work is executed against the
external pressure, and p2 = pext, then
the work executed is the area p2 a 2
defined by the rectangle V1-a-2-V1.
V1 V2 V
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Dr. Jorge Francisco Estela

1.16 Reversible processes:

From the above case it is clear that p
1
p1
more work would have been
obtained should the pressure of the
gas had been in equilibrium with the
external pressure at all times during
the expansion process. This p2 2
maximum work is the area under the
p-V curve. V1 V2 V
The way to achieve this is to carry out a quasi-equilibrium process from 1
to 1. Instead of removing the weight at once, we could divide it into very
small pieces and remove each one at a time. Thus, the internal pressure
is larger than the external pressure only by an infinitesimal amount.
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Dr. Jorge Francisco Estela

In this situation, we have pext = p – dp, so that Eq. (1.4) becomes:

2 2
W2   ( p  dp )dV  1W2   p dV .
1 (1.5)
1 1

Eq. (5) allows work to be calculated from the system’s properties, p and V,
and not from external effects. Therefore, in quasi-equilibrium processes,
work can be calculated only from the system’s properties. This is a very
important general result in thermodynamics.

This process was carried out by removing small weights and placing them
at a succession of heights along the piston path. Eventually, to reverse the
direction of the process, only a small weight has to be lifted a height dL
and placed on the piston for it to move downwards. This is a reversible
process, i.e. one that can be reversed at the expense of only an
infinitesimal amount of work in the external medium.
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The above conclusion is of great importance for it says that quasi-

equilibrium processes are reversible processes. The two terms are
synonyms.

However, Eq. (1.5) must be used with great care as it only applies to
quasi-equilibrium processes. For instance, let us consider a horizontal
cylinder divided by a membrane into two chambers, one contains a gas
while the other is a perfect vacuum. If the membrane suddenly ruptures, it
is obvious that the gas occupies the two chambers. Has work been done?
If the system is the gas, clearly there was an increase in volume but the
process was not quasi-equilibrium, so that Eq. (1.5) does not apply; and
there was no resistance in the expansion against the vacuum, therefore,
Eq. (1.4) yields that no work was done.
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1.17 Heat:

Heat is the transfer of energy between systems by virtue of solely the

difference in temperatures between the systems. Thus, heat is a transient
phenomenon, systems do not contain heat.

For a change of state from 1 to 2, the amount of heat transferred is:

2

1 Q2    Q . (1.6)
1
The time rate at which heat is transferred is:
Q
Q  lim . (1.7)
 t 0  t

The SI unit of heat is the Joule, J. The convention of signs is:

Q > 0, if heat is transferred to the system.

Q < 0, if heat is transferred from the system.

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1.18 Comparisons between heat and work:

There are a number of similarities between heat and work:
Both are transient phenomena. Systems do not posses heat or work.
Both are boundary phenomena. Both are energy crossing the system
boundary when the system undergoes a change of state.
Both are path functions. They are not state functions.
However, there are differences between heat and work. Consider a gas
enclosed in a cylinder surrounded by electrical wires connected to a
battery. If the system is only the gas, what crosses the control surface is
heat because the wires are hotter than the gas. If the system is the gas
plus the container plus the wires, what crosses the boundary is work
because the electrical current could do work by lifting a weight in the
external medium.
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