Chapter I: General notions in thermodynamics

1 Dr. Abdou Imene

CHEMISTRY 2: Chemical thermodynamics

CHAPTER I:
General notions in thermodynamics

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

I.1. INTRODUCTION TO CHEMICAL THERMODYNAMICS

1. INTRODUCTION
The word thermodynamics is of Greek origin. It is composed of two parts: “thermo” which means
heat and “dynamic” which means work or movement. The word compound means movement
produced from heat. Thermodynamics appeared as a science from the 18th century with the
discovery of the steam engine. Its goal is to study the different forms of energy and the possibilities
of conversion between them. Thermodynamics can be described in two ways or according to two
different aspects:

a-Microscopic thermodynamics (statistics) : we are interested in the properties of matter at the

microscopic or atomic scale using as variables the individual kinetic quantities of molecules or atoms
(Pi, Vi, Ei, etc.). Static thermodynamics seeks to explain the origin and meaning of macroscopic
variables (P,T) and the notions of heat, work and entropy by linking them directly to the mechanism
of molecular agitation.

b-Phenomenological thermodynamics (classical) : studies systems on a macroscopic scale using

measurable quantities such as pressure P, temperature T and volume V. it explains the behavior of
matter or systems according to their variations energy and entropy. It only describes the initial and
final states of evolving systems and draws up the energy balance of the system. The path followed by
the transformation of the system can play a role (the notion of reversibility or irreversibility of a
process) it is this approach that is the subject of this course

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

The principles on which thermodynamics is based are:

 The first law of thermodynamics: (principle of equivalence): concerns the character

conservative of energy (internal energy U).
 The second law of thermodynamics: raises the principle of evolution, creation and
irreversibility (the entropy S).
 The third law of thermodynamics: (Nernest principle): finally focuses on the properties of
matter in the vicinity of absolute zero.
 Zeroth law of thermodynamics: The Zeroth law of thermodynamics states that if two bodies are
individually in equilibrium with a separate third body, then the first two bodies are also in
thermal equilibrium with each other.

2. THE SYSTEM

Thermodynamics has its own unique vocabulary associated with it. A good understanding of the
basic concepts forms a sound understanding of various topics discussed in thermodynamics
preventing possible misunderstandings.
The system is a portion of space that we study. It is limited by a real or fictitious (arbitrary)
surface through which the exchanges of energy and/or matter with the surroundings.
boundary is the wall that separates the system from the surroundings. This is designed to allow us
to control and keep track of all movements of matter and energy in or out of the system.
The surroundings (external environment) include everything other than the system. System and
the surroundings together constitute the universe .
System + surroundings = Universe

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

Figure 1 . System, boundary, surroundings and universe.

However, the entire universe other than the system is not affected by the changes
taking place in the system. Therefore, for all practical purposes, the surroundings are that portion of
the remaining universe which can interact with the system. Usually, the region of space in the
neighbourhood of the system constitutes its surroundings.

Different types of systems

A system takes different names depending on the nature of the exchanges carried out with the
external environment:
open system: Can exchange energy and matter with the external environment.
closed system: Can exchange energy but not matter with the external environment.

isolated system: Cannot exchange energy or matter with the external environment. Here too,
perfect insulation is impossible in practice.
A thermally insulated (adiabatic) system: cannot exchange heat energy with the external
environment. In practice, perfect insulation is impossible.

Mechanically isolated system: cannot exchange work mechanical with non-deform-able).

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

3. Sign convention

An algebraic sign is assigned to the quantity of energy or matter exchanged between the system and
the external environment in order to specify the direction of the exchange.
 Everything the system receives is counted positively (+),
 Everything that the system gives up to the outside is counted negatively (-).
By convention, we have:
 Q > 0 : heat enters the system (endothermic process).
 Q < 0 : the system transfers heat to the external environment (exothermic process).
 W > 0 : the system receives work (receiving system).
 W < 0 : the system provides work (motor system).
Unit: [ W ]: Joule; [ Q ]: Joule or calorie; with: 1 calorie = 4.18 joules.

4. The state of the system

We need to describe the system by specifying it before and after the change.The system must be
described in order to make any useful calculations by specifying quantitatively each of the
properties as well as the composition of the system. We can completely define the stat of a system
by a limited number of state variables: V, T, P and ni, (Gibbs variables) for example. The state of
the surroundings can never be completely specified; fortunately it is not necessary to do so.

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

4.1. Extensive, intensive variables

State variables: It is the set of values taken by thermodynamic quantities relating to the
macroscopic state, such as mass (m), pressure (P), volume (V), concentration (C), density (d),
change of state temperature (T), etc. There are two types of state variables:
a- The extensive variables : are proportional to the quantity of matter in the system: mass (m),
number of moles (n), volume (V), electric charge (q), etc. The extensive variables are additive , if
we double the quantity of matter (n) of the system, they also double.

b- Intensive variables : are quantities independent of the quantity of matter in the system:
temperature (T), pressure (P), concentration (C), density , redox potential (E) and all the molar
quantities Vm, Cp, Um, Sm… An intensive variable is a quality factor. It has the same value at any
point in the system.

4.2. State function

State functions or points function are physical formulas such as, for example, the equation of state
of ideal gases: PV= nRT. Thanks to these relationships, we can, from a small number of state
variables, determine all the others by calculation to completely describe the system studied.
stat function is a function of state variables (T, P, V, ...) which has a defined value for each state of
the system. The function F (P, T, V) is a state function if its value corresponding to a state of the
system depends only on the state variables (before and after the process) , but remains
independent of the process’s path undergone by the system. In contrast, those functions which
depend on the path between two points are known as path function.
Mathematical properties of a state function
If F 2 takes the same value when the system follows path a or path b to go from state 1(F1) to state 2
(F2), then F is a state function.

path a

F1=F(x1,y1) F2 = F (x2 , y2 )

path b

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

Consider a state function F(x, y) of the variables x and y. The infinitesimal variation dF of this
function during a transformation is a exact total differential :
휕 휕
dF = A(x, y)dx + B(x, y)dy = ( )dx + ( )dy
휕 휕
(∂F/∂x) y being the partial derivative of F with respect to x, y being constant and (∂F/∂y) x being the partial
derivative of F with respect to y, x being constant.

- If dF is an exact total differential , then we have (Schwarz conditions):

( )dy = ( )dx ( )=( )

휕 휕 휕2 휕2
휕 휕 휕 휕 휕 휕
either again

- The variation of F, dF (or F for a finite transformation) is independent the path followed
during a transformation; it is entirely defined by the values of the state variables of the initial
state and the final state of the system:
푠푡 푡2 푑 ( , )= 푠푡 푡2( , ) − (푠푡 푡1( , ) = ∆
푠푡 푡1

5. Thermodynamic processes

The processes studied in thermodynamics most often involve exchanges of thermal energy Q and
mechanical energy W, we then speak of Thermodynamic processes. We know that if we have to
take a thermodynamic system from the initial to the final state, we have several paths that can be
taken

Isothermal process process at constant temperature (T = cte).

Isobaric process at constant pressure (P = cte).

isochore process at constant volume (V= cte).

Adiabatic process without heat exchange with the external environment (Q = 0).

Cyclic The final state is identical to the initial state.

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Note: State variables are defined only when the thermodynamic system is in equilibrium with the
surrounding. So a process in which the system is in thermodynamic equilibrium with the
surrounding is known as a quasi-static process at each moment.
5.1. Reversible and irreversible processes
A thermodynamic processes can be carried out in a reversible or irreversible manner:

a - Reversible processes:
Theoretical transformation consisting of a series of equilibrium states and such that if it is carried
out in the opposite direction, the system goes through the same states of equilibrium as in the direct
direction. As we know, in reality, no such processes as reversible processes can exist. Thus,
reversible processes can easily be defined as idealizations or models of real processes, on which
the process would always remain close to the state of equilibrium.
A transformation is said to be reversible if it satisfies both conditions:
 It must be infinitely slow.
 It must be reversible, that is to say it goes through the same equilibrium states in the
opposite direction B→A as in the direct direction A→B.
Examples of Reversible Processes: Here, we have listed a few examples of Reversible Processes:
slow adiabatic compression or expansion of gases, electrolysis (with no resistance in the
electrolyte), the frictionless motion of solids, slow isothermal compression or expansion of gases,
extension of springs

b - Irreversible processes :
Any real transformation is irreversible, these are rapid and brutal transformations, the intermediate
state variables are not known at each moment except for the initial state and the final state. a natural
transformation is spontaneous, it is irreversible, it can only evolve in one direction. n
Examples of Irreversible Processes: A few examples of Irreversible Processes are: Throttling, Heat
transfer, Diffusion, Electricity flow through a resistance...

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

Thermodynamic equilibrium
A system is in thermodynamic equilibrium when the values of the state variables are the same at
every point in the system and remain fixed as a function of time.

- Mechanical equilibrium (the sum of the forces is zero).

- Thermal equilibrium (the temperature remains constant).

- Chemical equilibrium (no chemical reaction).

Thermodynamic equilibrium generalizes both the equilibrium thermal ,
mechanical and chemical .

6. TEMPERATURE

Temperature, denoted T, is a macroscopic quantity which measures the degree of heat of a system.
From a microscopic point of view, it represents the agitation "movement" of molecules, atoms in the
system considered.

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

6.1. Temperature scale (T)

Temperature refers to the hotness or coldness of a body. In specific terms, it is the way of
determining the kinetic energy of particles within an object.

Temperature is a measure of the average kinetic energy of the particles in an object. When the
temperature increases, the motion of these particles also increases. Temperature is measured with a
thermometer or a calorimeter.

Heat vs Temperature?

It is important to understand that heat and temperature are not the same. Although the two concepts
are linked, they mean different things.

 Heat describes the transfer of thermal energy between molecules within a system and it is
measured in joules. An object can gain or lose heat, but it cannot have heat. Heat is not a
property possessed by an object or system rather it is a measure of change.

 Temperature describes the average kinetic energy of molecules within a material or system and
is measured in Celsius (°C), Kelvin (K) and Fahrenheit (°F).

Concluding, we can say that heat is a transfer of thermal energy caused by a difference in
temperature between molecules.

6.2. Temperature unites

- Linear scale : This is the centesimal scale also called degree Celsius , denoted °C , whose
reference points are 0 and 100 corresponding respectively to the melting and boiling
temperature of water under atmospheric pressure.

- Kelvin scale : This is the universal scale also called the absolute degree , denoted °K , “ SI
unit of temperature ”. The relationship between the Kelvin scale and the Celsius scale is
given by the relationship: T (°K) = T (°C) +273.15 .

- Fahrenheit scale : Noted °F , On this scale the melting and boiling temperature of water
under atmospheric pressure is respectively 32°F and 212°F . The relationship between the
Celsius and Fahrenheit scale is given by the expression: T (°F) = 32 + 1.8T (°C).

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6.3. Thermal equilibrium

Did you know that thermometers take their own temperature, not the temperature of the object they
are measuring?

Thermometers work on the fact that any two systems placed in thermal contact (meaning heat
transfer can occur between them) will reach the same temperature. The heat will flow from the hotter
object to the cooler object until they reach the same temperature. The objects are then said to be in
thermal equilibrium, and no further changes will occur. Systems interact and change because of
temperature differences (∆T), and these changes stop once their temperatures are the same(∆T=0).

Thermal equilibrium is established when two bodies are in contact with each other and can freely
exchange energy.

6.4. Zero principle of thermodynamics

Temperature allows us to know if a system can be in thermal equilibrium with another system: If
two systems have the same temperature, then they are in thermal equilibrium. We thus define
what is sometimes called the “Zero Principle of Thermodynamics” . The principle states that:

“ Two bodies (A and B), brought into contact, tend towards a state of thermal equilibrium. They are
then characterized by the same temperature. Two bodies in thermal equilibrium with a third (C) are
in thermal equilibrium with each other .”

7. PRESSURE (P)

Pressure, denoted P, is defined as the force exerted perpendicular to the surface of a body per unit
area (the region where force is applied). Gauge pressure is a type of pressure relative to normal
atmospheric pressure. Several units are used to denote pressure. Few of the units arise from a force
unit divided by an area unit. The pascal (Pa) is the SI unit of pressure (N/m2 or newton per square
metre).

P (pascal) =
dF(Newton)
dS (m2 )
Reminder: 1 Pa = 1 N/m²

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

From a microscopic point of view, the pressure is due solely to the collisions of molecules or atoms
on the boundary of the system.
Pressure units:
-2 5
[P]: Nm = Pa (Pascal, SI unit) 1 atm= 1.01325 10 Pa
5
[P]: bar 1 bar = 10 Pa
[P]: atm (Atmosphere) 1 bar = 0.9869 atm
[P]: mmHg (Millimeter of mercury 1 atm = 760 mmHg

8. Compressibility and expansion of gases

Compressibility : is a property that allows gases to easily decrease in volume.

Expandability: is another property which allows gases to increase in volume.

8.1. Compressibility of gases (Boyle-Mariotte law): T=cte

This study consists of varying the volume of a gaseous mass, when only the pressure changes
(isothermal transformation) “ effect of pressure on volume at constant temperature ”.

On the graph “ Clapeyron diagram P = f(V) ” we see that the curve is hyperbolic. We then deduce
that at constant temperature the pressure of a gaseous mass is inversely proportional to the volume it

occupies :

Boyle-Mariotte law: At constant temperature, the product of the pressure of a gaseous mass by its
volume is constant: PV = cte

PInitial VInitial = Pfinal V final

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8.2. Gas expansion `

A - Charles' Law; P=cte

This study consists of varying the volume of a gaseous mass, when only the temperature changes
(isobaric transformation) “ effect of temperature on volume at constant pressure ”.

On this graph V = f(T) » we see that the curve is Linear. We then deduce that at constant pressure,
the volume occupied by a gaseous mass is proportional to the absolute temperature (degree Kelvin):

Charles ' law : At constant pressure, the quotient of the volume of a gaseous mass

by its temperature is constant: V ⁄� = 풄�

VInitial /T Initial = VFinal /T final

Extrapolation of the line shows a volume that appears to be zero at a temperature of -273.15°C. This
observation is repeated whatever the nature of the gas considered. This temperature would therefore
be absolute zero (0 kelvin), that is to say the temperature beyond which matter would no longer exist.
There would then be no movement of the particles of matter and zero kinetic energy.
B - Gay Lussac 's law V=cte
This study consists of varying the pressure of a gaseous mass, when only the temperature changes
(isochoric transformation) “ effect of temperature on pressure at constant volume ”.

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On this graph P = f(T) » we see that the curve is Linear. We then deduce that at constant volume, the
pressure of a gaseous mass is proportional to the absolute temperature (degree Kelvin):

Gay Lussac's law : At constant volume, the quotient of the pressure of a gas mass

= 푐푡
�
�
by its temperature is constant:

�푖푛푖푡푖 �푖푛푖푡푖
= = 푐푡
�푓푖푛 �푓푖푛

Conclusion :
If we combine the three previous laws, we find that: PV/T = cte

�푖푛푖푡푖 �푖푛푖푡푖 �푓푖푛 �푓푖푛

=
�푖푛푖푡푖 �푓푖푛

The three laws, Boyle-Mariotte, Gay Lussac and Charles, are valid for all gases.

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9 PERFECT GAS MODEL

An ideal gas is a real gas at low pressure where the molecules are very far apart from each other.
This means that the collision between molecules is negligible “molecular interactions are negligible.
9.1. Clapeyron diagram P =f(V)
This diagram represents the evolution of the transformations when we plot the pressure P on the
ordinate and the volume V on the abscissa.

9.2. Amagat representation and ideal gas law

An Amagat isotherm represents the product PV as a function of P for a given temperature T. This
representation makes it possible to visualize the differences in behavior of a real gas compared to the
ideal gas: for an ideal gas, at a fixed temperature, the product PV is constant and the isotherms are
straight lines parallel to the pressure axis P:

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

At a given temperature and when the pressure tends towards 0 the product PV tends towards a
lim �� = 푅�
�→0
constant whatever the nature of the gas.

This constant is equal to RT. We can then describe the behavior of the gas at low pressure by the
following expression which we call the ideal gas equation of state:
�� = ���
P: Pressure, V: Volume, R: Ideal gas constant, T: absolute temperature (K), and n: number of moles.
The equation of state of ideal gases is in perfect agreement with the laws of Boyle-Mariotte, Gay
Lussac and Charles:
 At constant temperature, the volume of a gas is inversely proportional to its pressure (Boyle-
Mariotte law)

 At constant volume , the volume is proportional to the absolute temperature of the gas ( Gay
Lussac's law )

 At constant pressure, the pressure of the gas is proportional to its absolute temperature
( Charles' law )

9.3. Avogadro's Law

For the same number of moles, different gases occupy the same volume under identical conditions
of pressure and temperature (the volume of a gas depends on the operating conditions T and P and
independent of the size of the molecule)
“One mole of an ideal gas occupies under normal conditions a volume of 22.4 liters”.
 Normal conditions: normal conditions are characterized by: P = 1atm and T = 273 K.

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 Standard conditions: standard conditions are characterized by: P = P°= 1bar and T = 298 K
(25°C)
Therefore we can determine the ideal gas constant (R):
R = 0.082 L.atm/mol K
R= 8.31 J/mol K
R= 62.36 L.mm of Hg/mol. K
R= 1.99 cal. /mol. K
5
Reminder : PV= n RT with n= 1mol, T = 273K, P= 1atm = 1.013 10 Pa = 760 mmHg and V=
3
22.4 L, 1J= 1Pa.m , 1cal= 4.18J.

10 . Van Der Waals REAL GAS MODEL

The equation of state of an ideal gas describes the behavior of real gases at low pressure. In practice,
no real gas strictly follows this law, especially at high pressure or when approaching the liquid state.
This is why we sought to modify the ideal gas law, which is too simple to adapt it to the reality of
experimental results. Among the equations proposed in the literature we will retain that of Van Der
Waals which is older and presents historical interest:
a
(p + n2 2 )(V − nb) = nRT
V

With: a and b being constants characteristic of the gas.

�2
: Term due to the effect of internal pressure (Cohesion pressure)

b: Term due to the proper volume of the molecules.

11 . Properties of an ideal gas

A - Volumic mass ( � )

By definition, the density of a gas is the quotient of its mass by the volume it occupies: � = �/�

V= m = n. M
nRT
p
And

�=
�
��
3
[ � ] : g/L or kg/m .

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

The volumic mass of an ideal gas is proportional to its pressure and inversely proportional to its
temperature.

B - Density (d)

By definition the density of a gas is the quotient of its density by the density of air under the same
pressure and temperature conditions:
ρgaz
d=
ρair

PMgaz /RT Mgaz Mgaz

d= = =
PMair /RT Mair 29

�=
퐠�

Ps: Unlike volumic mass (�), density (d) is independent of pressure and temperature.

13. Perfect gas mixture

A perfect gas mixture is said to be ideal when all particles (whether identical or not) experience only
elastic shocks and no other interactions. The total pressure of a mixture then does not depend on the
nature of the gases present, but only on the total quantity of material. a mixture of several
chemically inert ideal gases is an ideal gas. Consider an ideal gas A under the conditions P 1 V 1 T 1
and an ideal gas B under the conditions P 2 V 2 T 2 The mixture of these two ideal gases is an ideal
gas under the conditions n T , P, V, and T. _

� � = � � + � �

�� �1 �1 �2 �2
= +
푅� 푅�1 푅�2

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

If we consider a mixture of n ideal gases (1, 2, …i, …, n ) under the conditions n T , P ,

V , and T:

�� 푛 �푖 �푖
=
푅� 푖=1 푅�푖
a- Molar fraction (x i ):

=푛 =푛
푛 푛
+푛 +푛
And

With � � + � � = � � 푒 � � + � � =1

If we consider a mixture of n ideal gases (1, 2, …i, …, n ) under the conditions � � ,P,
V , and T:

�� ��
�� = =
�
�� ��

With � � = total number of moles = ∑ � � � 푒 ∑ � � � = 1.

b- Partial pressure ( Dalton's law )

Consider an ideal gas A under the conditions P 1 V 1 T , and an ideal gas B under the conditions P 2 ,

V 2 , T. The mixture of these two ideal gases is an ideal gas under the conditions n T , P , V, and T.

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

The partial pressure P A of the gas HAS is the pressure of gaseous constituent A alone, in the same
volume as that occupied by the gas mixture (V):
� � V= � � 푅� … (1)
�V = � � 푅� … (2)
(1)/(2) gives

푛
� = �=
푛�
P

The partial pressure P B of the gas B in the mix:

� BV = � B 푅� … (1)
�V = � � 푅� … (2)
(1)/(2) gives

푛
� = �=
푛�
P

� +� =( + )�=�

Note : � 1≠ � � 푒 � 2≠ � �

In general, The partial pressure � � of the gas A i in a mixture of n ideal gases under

the conditions � � , P , V , and T:

�� V = �� 푅� …(1)

�V = �� 푅� … (2)
푛푖
�푖 = �= 푖P
푛�

� �
�� = �� � = �
�=� �=�

With P = total pressure = ∑ �� and �� = total number of moles = ∑��

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

c- The molar mass of the mixture (M ):

�풕풐풕풂풍
mixture

��é풍풂� = = �� ��
�풕풐풕풂풍

d- Density of the mixture (d):

�=
�é퐥��퐠

e- Density of the mixture ( ρ ) :

�
�=
�é퐥��퐠

��

f- Molar concentration or molarity (ci ) : the molar concentration or molarity C i of the constituent
A i (number of moles of A, per unit volume of the solution).

��
�� =
�

The SI unit of molar concentration is mole per m3 (mol. m-3 ). In practice we rather use the mole per liter as a
unit: mol. L-1 (or mol. dm -3 ).

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

I.2 ENERGY EXCHANGES

1. THERMAL ENERGY / HEAT, Q

According to the zero principle of thermodynamics, when two bodies (systems) are brought into
contact S1 and S2 of respective temperatures T1 and T2 , their temperatures tend to equalize up to a
common final value called equilibrium temperature Te . The bodies S1 and S2 are then in thermal
equilibrium. During this operation, the hot body cools and the cold body heats up. In fact, an
exchange of energy takes place between the two systems in contact: the cooling of S2 is a
manifestation of energy loss at the microscopic level. On the other hand, the cold body S1 gains
energy. The kinetic energy of its constituents, at the microscopic level, increases: Heat is a
manifestation of energy.
2. THERMAL ENERGY TRANSFER
The transfer of thermal energy can also be done without variation in temperature of the system
studied: vaporization, fusion, etc. In these cases, there is a change of state and the energy exchanged
essentially serves to overcome the cohesive forces which hold the molecules or atoms in the
condensed state. The amount of heat exchanged by a system can be determined from the effects
produced during the process.
2.1. Thermal energy transfer with temperature change (heat capacity)

If we put in contact two bodies (systems) S� and S� of respective masses m� and m� , at the
respective temperatures T� and T� (T� >T�), the elementary quantity of heat Q exchanged by each
body when the temperature varies by dT is proportional to its mass and to the elementary variation
dT.
The amount of heat δQ� won by S�:

δQ� = m� c� dT1

The amount of heat δQ� lost by S�:

δQ� = -m� c� dT�

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δQ� = −δQ�

The proportionality coefficient denoted 풄 (respectively 풄� _ and 풄� ) is by definition the specific

heat, that is to say:

The heat necessary to raise the temperature of a mass of one gram of the body
considered by one degree. It is expressed in J/g. K or cal /g. K

The value of specific heat therefore reflects the heat exchanged by a system. It is different
depending on whether the transformation is carried out at constant pressure or at constant volume.
We will distinguish:
 Specific heat at constant pressure : 풄�

 Specific heat at constant volume : 풄�

Hence the elementary quantities of heat exchanged:

 at Constant Pressure: 휹 � = �� 풄푷� 풅�� = −휹 � = �� 풄푷� 풅��

 at Constant Volume: 휹 � = �� 풄�� 풅�� = −휹 � = �� 풄�� 풅��

The total amount of heat Q 1 gained by S 1 during the transformation is therefore written:

�1 = δQ1 = m1c1 dT1

Te
T1

And the total amount of heat Q2 lost by S2 is worth:

�2 = δQ2 = m2c2 dT2
Te
T2
With Te represents the equilibrium temperature.
In general, specific heats depend on the temperature. The integration of the two previous equations
therefore requires knowledge of the variations of c1 And c2 with the temperature. We will often
consider that c 1 And c 2 are constant :

�1 = �1 푐1 푑�1 = �1 푐1 (� − �1 ) = �1 푐1 ∆�1
�
�1

� 2 = �2 푐2 푑�2 = �2 푐2 (� − �2) = �2 푐2 ∆�2

�
�2

�1 = −�2
So, more generally, the quantity of heat exchanged by each system is written:

At constant pressure: � = �푐� ∆�

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

At constant volume:� = �푐� ∆�

With ∆� = � 푒 − � If n bodies are brought into contact, we have:

�

� �
� �
�

� � 풄� �
� �

In chemistry, mass is often replaced by the quantity of matter (number of moles). The specific heats
are then replaced by the molar heat capacities (molar heats) � �� or � 푷� , which are expressed
-1 -1
in J.mol .K . The quantity of heat exchanged by each system is written:
At constant pressure: � = 푛푐�푛 ∆�

At constant volume: � = 푛푐�푛∆�

The proportionality coefficient noted ( ��n or �푷n ) , is by definition the molar heat (molar heat
capacities), that is to say:

The heat necessary to raise the temperature of a quantity of one mole of the body
considered by one degree. It is expressed in J. mol -1 . K -1 or cal. mol -1 . K -1 .

Heat capacity or thermal , denoted ( � ) of a pure body is defined as being the product of its
specific heat by its mass ( �.풄 ) or molar heat by its number of moles ( �.c ) :

It is the heat necessary to raise the temperature of an entire body by 1 degree.

It is expressed in J. K -1 or cal. K -1 .

at constant pressure :� = 푛푐�푛 ∆� = �푐� ∆� = �� ∆�

at constant volume : � = 푛푐�푛∆� = �푐�� ∆� = �� ∆�

Noticed :

Case of pure bodies in the gaseous state : C p ≠C v

Case of pure bodies in the liquid or solid state : C p ≅ C p =C .

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

2.1. Thermal energy transfer without temperature change (State Change Heat)
For certain transformations, the transfer of a quantity of heat to a pure body does not cause a rise in
temperature. For example, ice at 0°C changes to liquid water while remaining at 0°C. The physical
state of pure bodies exists in three phases as shown in the following diagram:

The heat brought into play per mole of the pure body considered during a change in physical state is,
by definition, the latent heat denoted L. It expresses the quantity of heat exchanged with the external
environment to transform, at constant pressure and temperature , the physical state of a mole or (1g)
of the pure body considered:
Lfus : latent heat of fusion (in J. mol -1 or J. g -1 )
L vap : latent heat of vaporization (in J. mol -1 or J. g -1 )
L sub : latent heat of sublimation (in J. mol -1 or J. g -1 )
The quantity of heat exchanged at constant T and P for any quantity of matter is written:
� = �� �� = �� ��’
-1 -1
With (�� or ��’ ) represents latent heat of the body (�� ) (in J. mol or J. g ). Noticed :

�퐟� = − �풔� � �퐟� > �

�풗�� = − � � � �풗�� > �
�풔� = − �풄��풅 � �풔� > �

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

3. Heating of a pure body

Consider a pure body of mass m in the solid state at temperature T 1 . This body receives a quantity
of heat Q leading it to the gaseous state at temperature T 2 . We recorded the evolution of the
temperature as a function of time. The result is shown in the graph below:

On this graph we see the existence of five domains:

- From �� to �퐟� ∶ the temperature increases, this is the heating of the solid phase.
� 퐟�

� = ∫ � 풄푷풔� �풅 풅� = � 풄푷 풔� �풅 (�퐟� − �� )
� �

- At �퐟� ∶ Phase change from solid to liquid, this is fusion (a phase change takes place at

constant temperature):

� = � �퐟�

- From �퐟� to �퐯� ∶ the temperature increases, this is the heating of the liquid phase.

�풗��

� =∫ � 풄푷 � ��풅 풅� = � 풄 푷� ��풅 (�풗�� − T퐟� )

�퐟�

- At �퐯� ∶ Phase change from liquid to gas, this is vaporization:

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

� = � �풗��

- From �퐯� to � � ∶ the temperature increases, this is the heating of the gas phase.
��

� =∫ � 풄 푷품� 풅� = � 풄 푷품� (�� − �풗�� )

�풗��

The quantity of heat Q necessary for this mass to go from T 1 to T 2 is:

= � + � + � + � + �
�퐟� �풗�� ��

=∫ � 풄푷 풔� �풅 풅� + � �퐟� + ∫ � 풄푷 � ��풅 풅� + � �풗�� + ∫ � 풄푷 풅�품�

�� �퐟� �풗��

So :
�퐟� �풗�� ��

=∫ �푷풔� �풅 풅� + � �퐟� + ∫ �푷 � ��풅 풅� + � �풗�� + ∫ �푷 풅�

품�

�� �퐟� �풗��

Or :
�퐟� �풗�� ��

=∫ � �푷� 풔퐨퐥  풅� + � �’퐟� + ∫ � �푷� 퐪�  풅� + � �’풗�� + ∫ ��푷� 풅�

품�

�� �퐟� �풗��

� � = � � �n = 푚 � and 푚 = � ’

Latent heat of fusion of H 2 O (s) L f = 335 J/g

Latent heat of fusion of H 2 O (l) L v = 2263 J/g
Specific heat of solid water C s = 2.14 J/g K
Specific heat of liquid water C L = 4.18 J/g K
Specific heat of carbonated water C G = 2.02 J/g K

CALORIMETRY
The purpose of calorimetry is to measure heat (Q) and heat capacity (cp) . calorimetry is based on the
principle of equality of heat exchanges: when two bodies only exchange heat, the quantity of heat
received by one is equal to that given up by the other (in absolute value). When we put n body A i in
contact: the sum of heat exchanged Q i within the calorimeter is zero.
�

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

∑ � = �
�=�

3.1. Schematic of a calorimeter

A calorimeter is an instrument for measuring the quantity of heat exchanged in general between two
bodies A and B placed in contact with each other where the calorific properties of body A are known
(calorimetric body).
A calorimeter, shown in the figure below, contains a calorimetric vessel where the heat to be
measured appears (calorimetric vessel), and a protective envelope to minimize heat loss to the
outside:

Calorimeter
There are several types of calorimeter such as the BUNSEN calorimeter, the microcalorimeter, Vase
Dewar and the Berthelot calorimeter (with water heating), etc.
3.2. Measurement of heat capacities (Mixture method)
The calorimetric measurement is always assumed to be made in an adiabatic calorimeter. When we
put n body A i in contact, the sum of heat exchanged within the calorimeter is zero:

∑ � = �

The system considered is a calorimeter and its contents (example of water) at the initial
temperature TA. We add a solid with specific heat capacity (specific heat) c B and at the temperature
TB. Their temperatures tend to equalize up to a common final value called the equilibrium
temperature T e . Bodies A (water) and B (the solid) are then in thermal equilibrium.

If �� > � �� (temperature of the solid body is higher than the temperature of the water in the

calorimeter): The heat received by the water in the calorimeter + the heat received by the accessories
of the calorimeter + the heat given up by the solid body = 0

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 Chapter I: General notions in thermodynamics Dr. Abdou I.

∑ � = �

� + 풄� + � = �
� �� 풄 �� (� − �� ) + �풄� (� − �� ) + �� 풄� ( � − �� ) =�
-1
With: �풄� represents the heat capacity of the calorimeter. It is expressed in JK .

Note that if the bodies present are placed in a calorimeter, this will also see its temperature vary.
Hence the need to take into account its specific heat capacity, also called water value or water
equivalent and generally expressed in grams.
“The water value of a calorimeter, noted µ , corresponds to the mass of water having the
same heat capacity as the empty calorimeter”.
� = µ. � 풂

 C: the heat capacity of the calorimeter in J/K

 µ: The equivalent water mass of the calorimeter in (Kg) called the water value of the
calorimeter.
 c water : the specific heat capacity of liquid water, i.e. 4180 J/K Kg
So, more generally, the quantity of heat exchanged in the calorimeter is written:

� �� 풄 �� (� − �� ) + � 풄 �� (� − �� ) + �� 풄� (� − �� ) =�
With the measure calorimetric we can determine:

- The value or mass of water in the calorimeter,

- the equilibrium temperature,

- the thermal heat capacity of a liquid or solid,

- Calculation of the heat of combustion at constant pressure Q p

- Calculation of heat of combustion at constant volume Q v

- Latent heats of change of state L fus ....... Etc.

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 Chapter I: General notions in thermodynamics
Dr. Abdou I.

1.3 MECHANICAL ENERGY OR WORK (W)

1. Definition

Work is, by definition, the scalar product of the force vector and the displacement
vector. The elementary work exchanged corresponding to an elementary displacement

휹 will be denoted 휹 and not 풅 , so as to clearly indicate that 휹 is not

equal to the elementary variation of a state function.

휹 = 푭풅

When the force 푭 is collinear with 풅 (푭 and 풅 being algebraic quantities):

휹 = 푭풅
Consider a piston, represented in the diagram below, infinitely light with surface area
s , moving without friction in a cylinder containing n moles of an ideal gas:

We assume that the piston undergoes a small displacement 풅 , the elementary work

exchanged 휹 is then written:

휹 = 푭풅
The force F acting on the piston can be expressed by:
푭 = −푷 �� �
(The minus sign: because the projection of the force F on the chosen axis is negative).

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 Chapter I: General notions in thermodynamics
Dr. Abdou I.

Either :

δW =− � 푡 푆푑 δW =− � 푡 푑�

 If 풅 > � , there is expansion (expansion) of the gas and dV > 0; 휹 < � the
system provides work for 푷 �� .
 If 풅 < � , there is compression of the gas and dV < 0; 휹 > � the system
receives work from the external environment.
 If 풅 = � , the piston is in equilibrium ; 휹 = �.

After integration, the work exchanged is then written:

� 퐟 ��퐥

=−∫ 푷 �� 풅�
� ������

reversible transformation we have : � 푒� = � �� = � 푔� 푝�푟��� = �

It follows that :
w= P dV
Vfin
Vinit

 Isochoric transformation (constant volume, dV=0) :

w=0

 Isobaric transformation (constant pressure dP=0) :

w =− P dV =− P(Vfin − Vinit )
Vfin
Vinit

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 Chapter I: General notions in thermodynamics
Dr. Abdou I.

2. Compression and expansion of a gas

a- Compression : Compressing a gas means reducing its volume, increasing its

pressure and increasing its temperature (by collision between particles), the work will
be gained by the system and will count positively (Case a) . This work has been
transformed into heat (T increases) .
b- Expansion (expansion) : to expand a gas is to increase its volume, reduce its
pressure and reduce its temperature, the work is lost by the system and counts
negatively (case b), in this case it is the heat (T decreases) which transformed into work
which moves the piston.

3. Calculation of work for isothermal expansion

Let n moles of an ideal gas, represented in the diagram below, enclosed in a cylinder in

the initial state �1 , �1 , �1 . Let us consider the isothermal transition of this system

to a final state defined by �2 , �2 , �1 .

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 Chapter I: General notions in thermodynamics
Dr. Abdou I.

This transformation can be carried out reversibly or irreversibly:

Reversible ( a ) and irreversible ( b ) expansion of an ideal gas

3.1. Expansion (relaxation) reversible at T=Cte

The transformation takes place through a succession of stages. The variation of the
variables P and V between two successive stages is infinitesimal. For a reversible
transformation we have:
푷 �� 푷��� = 푷품� ��풓���� = 푷

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 Chapter I: General notions in thermodynamics
Dr. Abdou I.

The reversible work W rev exchanged during the transformation is the sum of the
infinitesimal work δ W rev exchanged during the successive stages. It is expressed
mathematically by the following integral:

�푟 =− �푖푛푡 푑� With�푖푛푡 = �푔 =
�2 푛푅�
(1→2) �1 � 푟푓 푖푡 �

�2 푑� �2 �1
�푟 =− 푛푅� =− 푛푅� 푛 =− 푛푅� 푛
� �1 �2
(1→2) �1

=
�2 �1
�1 �2
During an isotherm transformation (Boyle-Mariotte law)

3.2. Irreversible isothermal expansion

The transformation is carried out in two stages. The external pressure goes from P 1 at P
2 then the expansion of the gas takes place irreversibly (in a single step) against the
pressure P end constant. Irreversible work is expressed mathematically by the following
integral:

�푖푟푟é =− � 푡 푑� = − �푓푖푛푑� = − �2 푑�
�2 �2 �2
(1→2) �1 �1 �1

�푖푟푟é (1→2) =− �2 (�2 − �1 ) < 0

4. Calculation of work for compression at T=Cte

Isothermal compression, shown in the diagram below, corresponds to the passage of the
system from the initial state (P 2 , V 2 , T 1 ) to the final state (P 1 , V 1 , T 1 ):

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 Chapter I: General notions in thermodynamics
Dr. Abdou I.

The work exchanged is calculated in the same way as for relaxation:

�푟 =− �푖푛푡 푑� With�푖푛푡 = �푔 =
�1 푛푅�
(1→2) �2 � 푟푓 푖푡 �

�1 푑� �1 �2
�푟 =− 푛푅� =− 푛푅� 푛 =− 푛푅� 푛 >0
� �2 �1
(1→2) �2

�푖푟푟é (1→2) =− �1 (�1 − �2 ) > 0

Noticed :
By comparing the reversible and irreversible work exchanged during the expansion of a
gas, we see that:
- The work W depends on the path followed: the elementary work δ W exchanged
is therefore not equal to the elementary variation dF of a state function F.

- |Wrev | ≫ |Wirre| : the maximum work is exchanged during a reversible

transformation.
In the specific case of an expansion in a vacuum : P ext = 0 d ′ where W=0

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