Introduction to

Thermodynamics

José Herney Ramírez Franco

jhramirezfra@unal.edu.co
Of. 201 LIQ
 Some semantics
The word “thermo-dynamic,” used first by Thomson
(later Lord Kelvin), has Greek origin, and is
translated as the combination of:

Therme: heat, and

Dynamis: power.

Definition

Thermodynamics: the science that deals with heat

and work and those properties of matter that relate
to heat and work.
 Historical milestones
- 1593: Galileo develops a water thermometer.
- 1650: Otto von Guericke designs and builds the first
vacuum pump.
- 1662: Robert Boyle develops his law for isothermal ideal
gases.
- 1679: Denis Papin develops his steam digester, forerunner to
the steam engine.
- 1698: Thomas Savery patents an early steam engine.
- 1710: Thomas Newcomen creates a more practical steam
engine.
- 1760s: Joseph Black develops calorimetry.
- 1780s: James Watt improves the steam engine.
- 1798: Benjamin Thompson considers the mechanical
equivalent of heat from cannon boring experiments.
- 1824: Nicolas Leonard Sadi Carnot discusses idealized
heat engines.
- 1840: Germain Henri Hess considers an early version of
the first law of thermodynamics for work-free chemical
reactions.
 Historical milestones

- 1840s: Julius Robert von Mayer relates heat and work.

- 1840s: James Prescott Joule relates heat and work.
- 1847: Hermann von Helmholtz publishes his theory of energy
conservation.
- 1848: William Thomson (Lord Kelvin) postulates an absolute zero
of temperature.
- 1850: Rudolf Julius Emanuel Clausius formalizes the second law of
thermodynamics.
- 1865: Clausius introduces the concept of entropy.
- 1871: James Clerk Maxwell develops the Maxwell relations.
- 1870s: Josiah Willard Gibbs further formalizes mathematical
thermodynamics.
- 1870s: Maxwell and Ludwig Boltzmann develop statistical
thermodynamics.
- 1889: Gibbs develops statistical mechanics, giving underlying
foundations for classical and statistical thermodynamics.
 Twentieth century
- Jacobus Henricus van’t Hoff (1901), development of the general
thermodynamic relationship between the heat of conversion and the
displacement of the equilibrium as a result of temperature variation.

- Johannes van der Waals (1910), His name is primarily associated with the
van der Waals equation of state that describes the behavior of gases and
their condensation to the liquid phase. His name is also associated with van
der Waals forces (forces between stable molecules), with van der Waals
molecules.

- Heike Kamerlingh Onnes (1913), The Nobel Prize in Physics 1913 was
awarded to Heike "for his investigations on the properties of matter at low
temperatures which led to the production of liquid helium“.

- Max Planck (1918), in recognition of the services he rendered to the

advancement of Physics by his discovery of energy quanta“.

- Walther Nernst (1920), The Nobel Prize in Chemistry 1920 was awarded to
Walther Nernst "in recognition of his work in thermochemistry".
 Twentieth century

- Albert Einstein (1921), for his services to Theoretical Physics, and especially
for his discovery of the law of the photoelectric effect.

- Erwin Schrodinger (1933), The Nobel Prize in Physics 1933 was awarded
jointly to Erwin Schrödinger and Paul Adrien Maurice Dirac "for the discovery
of new productive forms of atomic theory“

- Enrico Fermi (1938), for his demonstrations of the existence of new

radioactive elements produced by neutron irradiation, and for his related
discovery of nuclear reactions brought about by slow neutrons.

- Percy Bridgman (1946), for the invention of an apparatus to produce

extremely high pressures, and for the discoveries he made therewith in the
field of high pressure physics.
 Twentieth century

- Lars Onsager (1968), the subjects of his interest came to include colloids,
dielectrics, order-disorder transitions, metals and superfluids, hydrodynamics
and fractionation theory.

- Ilya Prigogine (1977), for his contributions to non-equilibrium thermodynamics,

particularly the theory of dissipative structures.

- Kenneth Wilson (1982), for his theory for critical phenomena in connection
with phase transitions.
 Some practical applications

Hero of Alexandria, perhaps

the first recognized thermal
engineer, documented a
variety of devices. These
include an early steam
engine, a device to use fire
to open doors, pumps, and
many others.

The device used steam

power to lift a weight.
Depictions of Papin and his
device are shown in figure.
Significant improvements
were led by James Watt
(1736-1819)
Figure: a) Scottish engineer
James Watt (1736-1819); b)
Sketch of one of Watt’s steam
engines.
 Some practical applications

- Simple steam power plant

- Fuel cells
- Vapor-compression refrigeration cycle
- Air separation plant
- The gas turbine, and
- The chemical rocket engine.

Additionally, one might consider the following topics to have

thermodynamic relevance:
- Gasoline and Diesel engines
- The weather
- Cooking
- Heating, ventilation, air conditioning, and refrigeration, or
- Materials processing (metals, polymers, etc.).
• Thermodynamics is the study of energy.

• Thermodynamics is the study of the

movement of heat from one body to another
and the relations between heat and other
forms of energy.

• Thermodynamics is the study of the

connection between heat and work and the
conversion of one into the other.
 Steam Turbine Power Plant

hot gases superheated

steam
compressed Steam Generator
(Boiler / Furnace)
water
Steam
C
Pump Turbine

Gen

Condenser
saturated saturated
water cooling water steam
Schematic arrangement of equipment of a
steam power station.

• Coal received in coal storage yard of power

station is transferred in the furnace by coal
handling unit. Heat produced due to burning of
coal is utilized in converting water contained in
boiler drum into steam at suitable pressure and
temperature.
• Superheated steam then flows through the
turbine. After doing work in the turbine the
pressure of steam is reduced. Steam leaving
the turbine passes through the condenser
which is maintained the low pressure of steam
at the exhaust of turbine.
• Steam pressure in the condenser depends upon
flow rate and temperature of cooling water.
• Water circulating through the condenser may be
taken from the various sources such as river,
lake or sea. If sufficient quantity of water is not
available the hot water coming out of the
condenser may be cooled in cooling towers and
circulated again through the condenser.
• Steam taken from the turbine at suitable
extraction points is sent to low pressure and high
pressure water heaters.
• Air taken from the atmosphere is first passed
through the air pre-heater, where it is heated
by flue gases. The hot air then passes through
the furnace.
• The flue gases after passing over boiler and
super-heater tubes, flow through the dust
collector and then through economizer, air pre-
heater and finally they are exhausted to the
atmosphere through the chimney.
 Disadvantage of steam power plant

• Maintenance and operating cost are high.

• Long time required for putting into action .
• Large quantity of water is required.
• Great difficulty experienced in coal handling .
• Efficiency decreases rapidly below about 75 percent
load.
 Introduction

Properties of bulk fluid

(macroscopic properties)
Properties of individual molecules
Pressure
Position
Internal Energy
Molecular geometry
Heat Capacity
Intermolecular forces
Entropy
Viscosity
 Heat and Temperature

• Heat: A form of energy that flows from a warmer

object to a cooler object.
• Calorie: The amount of heat energy needed to raise
the temperature of one gram of water one degree
Celsius in temperature.
• Temperature: A relative term reflecting how
vigorously the atoms of a substance are moving and
colliding.
 Why is the study of
Thermodynamics important?
- The study of thermodynamics is important
because many machines and modern devices
change heat into work, such as an automobile
engine or turn work into heat or cooling, such a
with a refrigerator.

- Understanding how thermodynamics works helps

you understand how machines that use
thermodynamic work.
 What are the different forms
of energy?
• Energy has a number of different forms,
all of which measure the ability of an
object or system to do work on another
object or system. 
• In other words, there are different ways
that an object or a system can possess
energy.
 Basic Forms of Energy
 Thermal or Heat Energy: Kinetic energy due to disordered motions of
microscopic as molecules or atoms.
 Chemical Energy: Energy held in the covalent bonds between atoms in a
molecule.
 Electrical Energy: Energy made available by the flow of electric charge.
 Electrochemical Energy: A combination of electrical and chemical energy
where energy is stored in a chemical way.
 Sound Energy: Energy transmitted by pressure waves through air or
other material.
 Electromagnetic Energy: The energy that travels in waves, such as
ultraviolet radiation. It can be thought of as combination of electric and
magnetic energy
 Nuclear Energy: Energy that is created by splitting atoms of radioactive
material such as uranium.
 Major Concepts

 Energy  Energy transfer & pathways

 Potential energy  Exothermic and endothermic
 Kinetic energy reactions.
 System dynamics  Heat
 Total energy  Volume
 Temperature  Work
 Law of conservation of  Heat capacity
energy  Pressure
 Pressure and unities
The force applied normal to a unit of area.

The Pascal, or Newton per square meter. Because 1 Pa represents

a small pressure, the working unit is the kilopascal (1 kPa = 1000
Pa).

The pound force per square inch, usually abbreviated psi.

The atmosphere is an international reference condition of pressure,

defined by 1 atm = 101325 Pa.

1 mmHg = 0.019337 psia.

Since 1 inch = 25,4 mm, the inch of mercury equals (25.4)(133.322)

= 3386,4 Pa = 3.3864 kPa = 0.49116 psia.

Finally, the bar is defined as exactly 100000 Pa = 100 kPa =

14.5038 psia, 1 bar = 0,9869 atm.
Thermodynamics system
 Thermodynamic Systems: Definitions

The first step in all problems in thermodynamics is to define a

system, either a body or a defined region of space.

Types of Systems:

• Isolated: No transfer of energy or matter across the system

boundaries.

• Closed: Possible energy exchange with the environment but no

transfer of matter

• Open: Exchange of energy and matter with the environment.

 Thermodynamic Properties
 Thermodynamics is concerned with macroscopic properties of a
system, not atomic properties. Volume, density, viscosity, etc.

Divided into two classes:

 Intensive Properties: (density, pressure,…)

 Specified at each point in the system.
 Spatially uniform at equilibrium.
 Usually, specifying any 2 intensive variables defines the
values of all other intensive variables.

An intensive variable is one whose value is independent of the

amount of material. Temperature and pressure are two obvious
examples.
 Thermodynamic Properties

• Extensive Properties: (volume, mass,...)

– Additive properties, in that the system property is the

sum of the values of the constituent parts.

– Usually, specifying any 2 intensive and one extensive

(conveniently the system mass) defines the values of all
other extensive variables.

– Some quantities such as volume are directly proportional to

the amount of material.
 PROPERTY, STATE, AND PROCESS
A property is a macroscopic characteristic of a system such as mass,
volume, energy, pressure, and temperature to which a numerical value
can be assigned at a given time without knowledge of the previous
behavior (history) of the system.

The word state refers to the condition of a system as described by its

properties. Since there are normally relations among the properties of
a system, the state often can be specified by providing the values of a
subset of the properties. All other properties can be determined in
terms of these few.

When any of the properties of a system change, the state changes and
the system is said to have undergone a process. A process is a
transformation from one state to another. However, if a system exhibits
the same values of its properties at two different times, it is in the same
state at these times. A system is said to be at steady state if none of
its properties changes with time.
 Thermodynamics:
• Describes macroscopic properties of equilibrium systems
• Entirely Empirical
• Built on 4 Laws and “simple” mathematics

0th Law ⇒ Defines Temperature (T)

1st Law ⇒ Defines Energy (U)

2nd Law ⇒ Defines Entropy (S)

3rd Law ⇒ Gives Numerical Value to Entropy

 Thermodynamics terms

Internal energy: Energy of a substance associated with the motions,

interactions, and bonding of its constituent molecules (U).
External energy: Associated with the velocity and location of its center
of mass.
Total Energy: is the sum of its internal energy and its bulk potential and
kinetic energy, that means is the sum of internal and external energy.
System: Region under study.
Surroundings: part external of the system
Adiabatic system: thermally isolated from its surroundings, the system
is not in thermal contact but may be in mechanical contact.
Mechanical contact: if a changed in pressure in the surroundings
results in a pressure changed in the system.
Isothermal process: process that occurs at constant temperature
 Specific Volume

Three intensive properties that are particularly important in engineering

thermodynamics are specific volume, pressure, and temperature.

V V
Specific Volume v v
m n
The specific volume v is defined as the reciprocal of the density, It is the volume per
unit mass. Like density, specific volume is an intensive property and may vary from
point to point. SI units for density and specific volume are kg/m3 and m3/kg,
respectively. However, they are also often expressed, respectively, as g/cm3 and
cm3/g.
In certain applications it is convenient to express properties such as a specific
volume on a molar basis rather than on a mass basis.
 Measuring Temperature

A definition of temperature in terms of concepts that are independently

defined or accepted as primitive is difficult to give. However, it is possible to
arrive at an objective understanding of equality of temperature by using the
fact that when the temperature of a body changes, other properties also
change.

Kelvin Scale

Celsius Scale

Fahrenheit Scale

Rankine Scale
 Equilibrium state

The general characteristics of the equilibrium state are that:

1. It does not vary with time (steady states).

2. The system is uniform (that is, there are not internal temperature, pressure,
velocity or concentration gradients).

3. All flows of heat, mass, work between the system and its surroundings are zero
and

4. The net rate of all chemical reaction is zero.

 Equilibrium state

Mechanical equilibrium :

The necessary and sufficient conditions for a particle to be in mechanical

equilibrium is that the net force acting upon the particle is zero.

Thermal equilibrium is a theoretical physical concept, used especially in

theoretical texts, that means that all temperatures of interest are unchanging in time
and uniform in space.

Chemical equilibrium is the state in which the concentrations of the reactants and
products have not yet changed with time.

Phase equilibrium: many compositions will form a uniform single phase, but
depending on the temperature and pressure even a single substance may separate
into two or more distinct phases. Within each phase, the properties are uniform but
between the two phases properties differ.
 control volume

In most cases it is simpler to think instead in terms of a given region of space

through which mass flows. With this approach, a region within a prescribed
boundary is studied.
Matter states

120 –
Vapor Ebullición
100 –

80 –

60 –

40 – Agua

20 –
Fusión
0–
Hielo
-20 –
Calor
 Examples

Example 1.

A steel cylinder of mass 2 kg contains 4 L of liquid water at 25 oC. Find the total mass
and volume of the system. List two extensive and three intensive properties of the
water.

From table A.9 (Pag 797): steel = 8050 kg/m3, then Vsteel = 2 kg/8060 kg/m3
Again from table A.9: water = 997 kg/m3, then mwater = 997 kg/m3 * 4 L * 1 m3/1000 L
Total mass: m = msteel + mwater
Total Volume: V = Vsteel + Vwater
 Examples
Example 2.

A pressurized steel bottle is charged with 5 kg of oxygen gas and 7 kg of nitrogen

gas. How many kmoles are in the bottle?

Example 3.

A tank has two rooms separated by a membrane. Room A has 1 kg air and volume
0.5 m3, room B has 0.75 m3 air with density 0.8 kg/m3. The membrane is broken and
the air comes to a uniform state. Find the final density of the air, in lbm/ft 3.
 Examples

Example 4.

One kilogram of diatomic oxygen (O2 molecular weight 32) is contained in a 500 L
tank. Find the specific volume on both a mass and mole basis.

Example 5.

The atmosphere becomes colder at higher elevation. As an average the standard

atmospheric absolute temperature can be expressed as T atm = 288 - 6.5 × 10−3 z,
where z is the elevation in meters. How cold is it outside an airplane cruising at
12 000 m expressed in Kelvin and in Celsius?