Chapter I CONCEPTS IN THERMODYNAMICS

At the end of the lesson, the student should be able to:

- Define heat and work
- Define process
- Identify path function and point functions
- Express the equation of state of a gas

INTRODUCTION

Thermodynamics is a science in which the storage, the transformation, and the

transfer of energy are studied.
Its purpose is the study of the laws governing the conversion of one form of energy
into another. It also deals with energy exchanges occurring between different
physical systems. Thermodynamics was initially developed with the aim of
explaining the quantitative relationships between work and thermal energy, that
is, the energy associated with the disordered movements of atoms and molecules
within matter. It is based on two fundamental principles ; first law and second
law.
In this chapter, we will give definitions of some parameters which are used in
thermodynamics.

I. Closed and Open Systems (Bahrami)

System
A system is defined as a quantity of matter or a region in space chosen for study.
The mass or region outside the system is called the surroundings (milieu
extérieur).
Fig. 1: System, surroundings, and boundary

Boundary: the real or imaginary surface that separates the system from its
surroundings. The boundaries of a system can be fixed or movable.
Mathematically, the boundary has zero thickness, no mass, and no volume.

The system can have exchanges with the surroundings; there are three kinds of
exchanges:
- work exchange
- heat exchange
- matter exchange

Closed system or control mass: consists of a fixed amount of mass, and no mass
can cross its boundary (no matter exchange). But, energy in the form of heat or
work, can cross the boundary, and the volume of a closed system does not have
to be fixed.

Fig. 2: Closed system, mass cannot cross the boundaries, but energy can.

Open system or control volume: is a properly selected region in space. It usually

encloses a device that involves mass flow such as a compressor. Both mass and
energy can cross the boundary of a control volume.
Fig. 3: Control volume, both mass and energy can cross the boundaries.

Isolated system: A system that does not communicate with the surroundings by
any means. (pas d’échange de matière et d’énergie).

Rigid system: A closed system that communicates with the surroundings by

heat only. (diatherman: Said of a body that lets heat through) )
Adiabatic system: A system that does not exchange heat with the surroundings.

II. Properties of a System

A property is any characteristic or attribute of matter, which can be evaluated

quantitatively.

Intensive properties: are those that are independent of the size (mass) of a
system. They are not additive. Examples : temperature, pressure, frequency of a
sound, density.
Extensive properties: values that are dependant on size of the system. They are
additive. Examples : mass, volume, number of moles, length
Exercise
1°) Identify which of the following are extensive properties and which are
intensive properties:
 (a) 10 m3 volume, (b) 30 J of kinetic energy, (c) a pressure of 90 kPa,
(d) a stress (contrainte) of 1000 kPa, (e) a mass of 75 kg, and (f) a velocity of 60
m. s-1.
2°) Convert all extensive properties to intensive properties assuming (en
supposant) m = 75 kg.

(a) Extensive. If the mass is doubled, the volume increases.

(b) Extensive. If the mass doubles, the kinetic energy increases.
(c) Intensive. Pressure is independent of mass.
(d) Intensive. Stress is independent of mass.
(e) Extensive. If the mass doubles, the mass doubles
(f) Intensive. Velocity is independent of mass.

III. State and Equilibrium

Knowing the state of a system consists in fixing the value of the number of
quantities which makes it possible to reconstitute the system. For example, the
following system is perfectly defined: 1 mole of oxygen at 273 K in a volume of
22.4 liters. V, T and n are state variables
At a given state, all the properties of a system have fixed values. Thus, if the value
of even one property changes, the state will change to different one.

An equilibrium state is a state in which the system can exist indefinitely.

IV. Processes and Cycles

Process : Any change a system undergoes from one equilibrium state to another
is called a process, and the series of states through which a system passes during
a process is called a path (Any change of state is a transformation).
Fig. 4: To specify a process, initial and final states and path must be specified.

Quasistatic process

A process is said to be quasistatic when it evolves slowly enough for the system
to be described by a continuous succession of equilibrium states. During a
quasistatic process, all the state variables X1, X2, . . . of the system are defined
and vary continuously.

Prefix iso‐ is used to designate a process for which a particular property is

constant.

- Isothermal: is a process during which the temperature remains constant

- Isobaric: is a process during which the pressure remains constant

- Isometric (isochoric): is process during which the specific volume remains

constant.

Cycle : A system is said to have undergone (subir) a cycle if it returns to its initial
state at the end of the process.
Fig. 5: A four‐process cycle in a P‐V diagram (Clapeyron).

Reversible process

A transformation is said to be reversible when the path of the process can be

followed, in the same external environment, by reversing the direction of time (in
other words, the transformation obtained by reversing the procedure is credible).
Conversely, a transformation that is only feasible in the normal direction of time
is described as irreversible.

The concepts of quasistatic and reversible transformations are close, but distinct:

quasistatic transformation : succession of equilibrium states of the system;

reversible transformation : succession of equilibrium states of the universe:

Any reversible transformation is therefore quasistatic, however the reciprocal is

generally false (but nevertheless true in a large number of cases).
Toute transformation réversible est donc quasi-statique, cependant la
réciproque est généralement fausse (mais néanmoins vraie dans un grand
nombre de cas).

V. Heat and work

Heat is energy transferred between a system and its surroundings by virtue of a temperature
difference only. The different modes of heat transfer are: conduction, convection and radiation.
Heat is a way of changing the energy of a system by virtue of a temperature difference only.
Any other means for changing the energy of a system is called work.
Adding heat to a pure body may not raise the temperature, it may cause a change of state. It is
defined as latent heat.
(Un apport de chaleur à un corps pur peut ne pas élever la température, il peut provoquer un
changement d’état. On le définit chaleur latente).
The Specific Heats of Gases
It is useful to define two different versions of the specific heat of gases, one for
constant-volume (isochoric) processes and one for constant-pressure (isobaric)
processes. We will define these as molar specific heats because we usually do
gas calculations using moles instead of mass. The quantity of heat needed to
change the temperature of n moles of gas by ∆T is :

where CV is the molar specific heat at constant volume and CP is the molar
specific heat at constant pressure.
Work : For a moving system boundary work, the work done during a process 1-2 is given
by:
2
𝑊1−2 = − ∫ 𝑝 𝑑𝑉
1

Let’s look at work done during volume changes. Pressure exerts a force on the piston, which
moves from x1 to x2:
where ‘p’ is the pressure acting on the system boundary and ‘dV’ is the differential volume. It
is assumed that the process is carried out very slowly so that at each instant of time the system
is in equilibrium (quasi-equilibrium process).
W < 0 work is done by the system against its surroundings (expansion)
W > 0 work is done on the system (compression)
Exercise ERNST
Liquid water boils. Knowing that at 100°C the specific volume of vapor is 1.671
L. g-1 under normal pressure, what is the work done by one mole of water when
it vaporizes under atmospheric pressure?
De l’eau liquide bout. Sachant qu’à 100°C le volume spécifique de la vapeur est
de 1,671 L. g-1 sous pression normale, quel est le travail échangé par une mole
d’eau lorsqu’elle se vaporise sous la pression atmosphérique ?
Solution
W = - Pext V = - Pext (Vf – Vi)
N.A.
m = n x M = 1 mol x 18 g x mol-1 = 18 g (Liquid)
Vf = 1.671 L x g-1 x m = 1.671 L x g-1 x 18 g =1,671 x 18 L = 1,671 x 18 x 10 -3
m3
Vi = 18 cm3 = 18 x 10-6 m3 ;
V = Vf –Vi = 1.671 x 18 x 10-3 m3 - 18 x 10-6 m3
= 18 x (1.671 x 10-3 - 10-6) m3 = 18 x (1.671 x 10-3 - 10-6) m3
= 18 x (1.671 x 103 - 1) 10-6 m3
= 18 x (1,671 - 1) 10-6 m3
W = -1,0135. 105. 18. (1671 - 1). 10-6 = - 3046.6 J
The boiling of a mole of water in the open air is accompanied by a work of -
3046.6 J of the water system which must repel (repousser) the outside atmosphere.
L’ébullition d’une mole d’eau à l’air libre s’accompagne d’un travail de - 3046.6
J du système d’eau qui doit repousser l’atmosphère extérieure.
VI. Heat source (or thermostat)
It is the medium which is capable of giving up heat to the system or of receiving
it from the system while remaining at a constant temperature. Environments
containing large amounts of heat such as oceans, rivers, ambient air and
groundwater are heat sources.
Substances such as coal (le charbon), petroleum or radioactive bodies are also
sources of heat.
Des substances comme le charbon, le pétrole ou les corps radioactifs sont aussi
des sources de chaleur.

VII. Sign conventions

A system is capable of exchanging heat Q and work W with the surrounding.
These quantities are counted positively when they are received by the system
and negatively when they are supplied by the system.
 VIII. Internal energy U
The energy of a system Etot can be divided in two, the macroscopic energy and the
microscopic energy or internal energy U.
• The macroscopic energy includes the overall motion of a system (solid in rotation,
flow (écoulement) in a fluid, etc.), potential energies (electrostatic energy if the system is
charged,
potential energy of gravity, etc.), and so on.
• The internal energy represents the rest of the energy of the system: molecular motion,
energy of interaction between particles, etc.
In thermodynamics, one almost always considers situations where the macroscopic energy
is constant: the system is immobile (macroscopically), does not change altitude, etc. The
energy variations of the system are then equal to the variations of the internal energy:
∆Etot = ∆U (in most cases):
The concept of internal energy of a system is
not difficult to understand. We know that every
bulk system consists of a large number of
molecules. Internal energy is simply the sum of
the kinetic energies and potential energies of
these molecules.
IX. Temperature

The temperature of a thermodynamic system is a quantity that must verify the

following property:

When two systems A et B with different temperatures TA and TB are into contact,
the energy (in the form of heat) flows spontaneously from the body having the
highest temperature to the body having the lowest one.

Temperature is a pointer for the direction of energy transfer as heat. It is, in reality,
a measure of molecular activity.
Fig. 13: Heat transfer occurs in the direction of higher‐to‐lower‐temperature.

We can suppose that two bodies are isolated from the surroundings but placed in
contact with each other. If one is hotter than the other, the hotter body will become
cooler and the cooler body will become hotter until thermal equilibrium occurs.

When the temperatures of two bodies are the same, thermal equilibrium is
reached. The equality of temperature is the only requirement for thermal
equilibrium.

The 0th law of thermodynamics: states that if two bodies are in thermal
equilibrium with a third body, they are also in thermal equilibrium with each
other. The Zeroth Law leads to the concept of temperature; it makes a
thermometer possible.

X. Thermodynamic Functions RAC

There are two types of functions defined in thermodynamics, path function and
point function (fonction d’état). Path function depends on history of the system
(or path by which system arrived at a given state). Examples for path functions
are work and heat. Point function does not depend on the history (or path) of the
system. It only depends on the state of the system. Examples of point functions
are: temperature, pressure, density, mass, volume, enthalpy, entropy, internal
energy etc. Path functions are not properties of the system, while point functions
are properties of the system. Change in point function can be obtained by from
the initial and final values of the function, whereas path has to defined in order to
evaluate path functions.

XI. The ideal gas

The ideal gas is an ideal thermodynamic system where the interactions between
particles are neglected. For a classical ideal gas, the equation of state (ideal gas
law) is : pV = nRT

p: pressure (Pa) V : volume (m3) n: amount of substance (mol) T : temperature

(K) where R = 8.31 J. K-1. mol-1 is the ideal gas constant.

The ideal gas is a very good approximation of the usual real gases at ordinary
temperatures and pressures.

Exercise
One mole of gas occupies a volume of 22.4 L under normal conditions (0 ° C, P
= 1 atm)
1°) Calculate R in atm. L. K-1. mol-1.
2°) What is the volume of 1.5 moles of oxygen at 298 K under a pressure of 750
mm Hg? 760mm Hg -----1 atm
Answer
1°) 0.082 atm. L. K-1. mol-1 2°) 37.14 liters

Exercice
Une mole de gaz occupe un volume de 22,4 l dans les conditions normales (0°C,
P= 1 atm)
1°) Calculer R en atm. L. K-1. mol-1.
2°) Quel volume occupent 1,5 moles d’oxygène à 298 K sous une pression de 750
mm Hg ?
Réponse
1°) R = P V/ (n T) = 0.08205 atm. L. K-1. mol-1
2°) V = n R T / P = 37,14 litres
760mm Hg -----1 atm

Energy is stored as internal energy (associated with temperature), kinetic energy

(due to motion), potential energy (due to elevation) and chemical energy (due to
chemical composition); it is transformed from one of these forms to another; and
it is transferred across a boundary as either heat or work. In thermodynamics we
will develop mathematical equations that relate the transformations and transfers
of energy to material properties such as temperature, pressure, or enthalpy.

Substances and their properties thus become an important secondary theme. Much
of our work will be based on experimental observations that have been organized
into mathematical statements, or laws; the first and second laws of
thermodynamics are the most widely used.

Elle a pour objet l’étude des lois régissant la conversion d’une forme de l’énergie
en une autre. Elle traite également des échanges d’énergie se produisant entre
différents systèmes physiques. La thermodynamique fut initialement développée
dans le but d’expliquer les relations quantitatives entre le travail et l’énergie
thermique c’est-à-dire l’énergie associée aux mouvements désordonnés des
atomes et des molécules au sein de la matière. Elle est basée sur deux principes
fondamentaux.

Le système peut avoir des échanges avec le milieu extérieur ; il existe trois sortes d’échanges :
- échange de travail
- échange de chaleur
 - échange de matière
- 4°) Conventions
- Un système est capable d’échanger de la chaleur Q et du travail W avec le
milieu extérieur. Ces grandeurs sont comptées positivement quand elles sont
reçues par le système et négativement quand elles sont fournies par le
système.

3°) Source de chaleur (ou thermostat)

C’est un milieu extérieur au système qui est capable de lui céder de la chaleur ou d’en recevoir
tout en restant à température constante. Les milieux contenant d’importantes quantités de
chaleur comme les océans, les fleuves, l’air ambiant, les nappes phréatiques, constituent des
sources de chaleur.