Chapter 1

NATIONAL POLYTECHNIC SCHOOL
Department of Preparatory Classes

2023/2024
Chemistry 2
Thermodynamics
Chapter 1
General notions of thermodynamics
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 Thermodynamics is a science that was born at the end of the 17th

century. The main thing at the time was to build machines essential to
industry.
 The initial motivation was therefore to respond to an essential

industrial need at the time: finding the optimal conditions to
transform heat into work. We find in this sentence three
founding words of thermodynamics.
 This name (thermodynamic) comes from the Greek meaning heat and
force respectively.
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Thermodynamics can be described in two ways or according to two

different aspects:
The macroscopic aspect : we are interested in properties which are

described by macroscopic state variables (P,V, T, m,…..)
Classical thermodynamics: it explains the
behavior of matter or systems according to their
variations in energy.
It only describes the initial and final states of
evolving systems and draws up the energy
balance of the system.
The microscopic aspect: we are interested in the properties of matter at
the microscopic or atomic scale.
Static thermodynamics: it seeks to explain the

origin and meaning of macroscopic variables (P,T)
and the notions of heat, work by linking them directly
to the mechanism of molecular agitation.
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The subject of the chemistry 2 course is classical thermodynamics
The principles on which thermodynamics is based are:

 The zero principle concerns the notion of thermal equilibrium,
 The first principle (equivalence principle) concerns the conservative

nature of energy,
 The second principle raises the notion of irreversibility and the

concept of entropy
 The third principle (Nernst principle) finally focuses on the

properties of matter in the vicinity of absolute zero.
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The basic concepts

1. The concept of system
Thermodynamics studies the exchanges of matter and energy which take place
between a material environment called a system and its environment called the
exterior.
It is not possible to solve a thermodynamic problem until we have precisely

defined these two entities.
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 Definition of system
A system is a part of the universe, of determined mass and delimited in space

by a real or fictitious surface, within which the studied transformation takes
place. The rest of the universe constitutes the external environment
We call exterior everything that does not belong to the system
System + exterior = Universe
exterior
System
Border
(real or fictitious)
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It is always necessary to precisely define the nature and boundary of the

system
Example 1:
For a gas enclosed in a cylinder fitted with a sliding piston.
- the system is a gaseous mass located inside the enclosure
- The exterior will consist of everything else (organs linked to the

piston and piston itself, walls of the cylinder, surrounding atmosphere,
etc.). Although part of the exterior, the cylinder walls and piston
constitute the visible boundary of our system.
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2. Types of systems
Closed system
If it does not exchange matter with the external environment (there is an
exchange of energy with the outside),
Open system
If it exchanges matter and energy with the external environment
Isolated system
If it does not exchange energy or matter with the outside world.
ECOLE NATIONALE POLYTECHNIQUE
Département des Classes Préparatoires
Année universitaire 2022/2023
Open system Isolated system

Closed system
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3. Thermodynamic equilibrium of a system
The system is said to be in thermodynamic equilibrium if these three

equilibrium conditions are achieved:
- Thermal equilibrium
for which the temperature T is the same at every point in the system
- Mechanical equilibrium
for which the pressure P of the system does not vary over time
- Chemical equilibrium
which implies that there is no variation in the composition
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4. Definition of a transformation
The thermodynamic transformation is a process by which a

thermodynamic system passes from an initial equilibrium state E(i) to a final
equilibrium state E(f) .
State (1) Transformation state (2)

initial state final state
P1, V1, T1 P2, V2, T2
So the initial state and the final state are equilibrium states
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5.The state of a system
 The state of a system is described at a given time by a set of macroscopic

variables (measurable quantities) called "state variables", such as
temperature (T), pressure (P) or volume (V).
 If we want to describe the system more precisely, we can associate other

variables with it, such as mass,concentration, density, number of moles,
density, heat capacity, etc.
State (1) Transformation state (2)

P1, V1, T1 P2, V2, T2
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All these variables, called state variables, can be classified into two groups:
 The extensive variables are dependent on the size of the system and
the quantity of matter (volume, mass, etc.);
 The intensive variables are independent of the size of the system and
the quantity of material (temperature, pressure, etc.)
Example
Let's take two pieces of iron with the same shape and same mass at
T=20°C. If we put them together, we obtain a block of iron whose mass and
volume have doubled, but the temperature T is still the same
m, V, T m, V, T
2m, 2 V, T
m and V are extensive quantities

T is an intensive quantity
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6. Equation of state
State variables are dependent on each other,and the variation of one variable
causes the variation of the others. This dependence of state variables is
governed by a relationship called the state equation.
Example
The equation of state of an ideal gas is
PV=nRT
P pressure (Pa)
V: volume (m3)
T : temperature (K°)
N : number of moles(mole)
R : ideal gas constant(J.mol-1.K-1 )
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7. State function
We call a state function any quantity F whose value is fixed by these state
variables (x, y, z….) and whose variation depends only on its initial state and
its final state, i.e. it is independent of the path followed during its evolution.
ΔF1=FB-FA
Path N°1
ΔF2=FB-FA
Path N °2
FA(xA, yA, zA ) (A) (B) FA(xB, yB, zB )
ΔF3=FB-FA
path N°3
On a mathematical level, a state function F of several variables x, y, z is

characterized by the existence of an exact total differential dF defined by:
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F(x, y) is a state function if
 dF is an Exact total differential
• Example 1
Is g(x,y) a state function?
 dg is an Exact total differential
So g(x, y) is a state function

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8. Concept of temperature
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.
At temperature 0k (absolute zero = -273.15°C), the atoms which constitute

matter are frozen
0 K (Kelvin )correspond to the absence of

movements on the microscopic scale
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Thermometers measure temperature according to well-defined scales of

measurement.
The three most common temperature scales are Fahrenheit, Celsius, and
Kelvin.
Temperature scales are created by identifying two reproducible temperatures.
The freezing and boiling temperatures of water at

standard atmospheric pressure are commonly used.
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1. On the Celsius scale, the freezing point of

water is 0°C and the boiling point is 100°C.
The unit of temperature on this scale
is the degree Celsius (°C).
2. The Fahrenheit scale (still the most

frequently used for common purposes in the
United States) has the freezing point of water
at 32°F and the boiling point of 212°F Its unit
is the degree Fahrenheit(°F) .
3. The Kelvin scale Is The unit of T in the

international system (SI)
 The Fahrenheit scale
T°F=1,8(T°C)+32
The temperature of 0 K is equal to −273.15 °C and
corresponds to absolute zero
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Concept of ideal gas and real gas
Ideal gases
- The ideal gas is a thermodynamic model that allows us to describe the

behavior of real gases at low pressure.
Ideal gas hypothesis
1. The size of gas molecules is negligible compared to the distances that

separate them, which allows them to be assimilated to material points
2. The interaction forces between the molecules are negligible (the

molecules therefore behave independently of each other).
3. The pressure is due to the numerous shocks of the molecules on the

walls of the enclosure
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Equation of state of an ideal gas

The state variables of an ideal gas are:
The number of moles(n)
The gas pressure p(Pascal (Pa)),
The temperature T(K),
The volume V that contains the gas.
scientific observation has determined that these variables are related to one
another, and the values of these properties determine the state of the gas.
R is the ideal gas constant (8.314 J.mol-1.K-1 )

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Description of an ideal gas

On the macroscopic level, we callan ideal gas any gas which
simultaneously satisfies:
 The Boyle-Mariotte law

 Charles and Gay-Lussac's Law
 Gay-lussac's law
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 The Boyle-Mariotte law

The Irish physicist and chemist Robert Boyle (1627-1691) and the
French physicist Edme Mariotte (1620-1684) demonstrated that there
is a relationship between the pressure and the volume of a gas.
 At a constant temperature and for the same number of
molecules, they observed that the pressure of a gas
increases as its volume decreases, and vice versa.
Clapeyron diagram : P=f(V)

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Charles and Gay-Lussac's Law
The relationship between temperature and volume, at a constant number

of moles and pressure, is called Charles and Gay-Lussac's Law in
honor of the two French scientists who first investigated this relationship.
Charles did the original work, which was

verified by Gay-Lussac.
They observed that if the pressure is held

constant, the volume V is equal to a
constant times the temperature T:
V = constant * T
𝑽
= Cste
𝑻
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V = constant * T
𝑽
= Cste
𝑻
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 Gay-lussac's law
The Gay-Lussac law describes the relationship between the pressure and
temperature of a gas.
It states that, at constant volume, the pressure of a certain quantity of gas is

directly proportional to its absolute temperature.
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Ideal gas mixture, partial pressure:
Dalton's law
Consider a gas mixture made up of different gaseous chemical species at
temperature T, occupying a total volume Vtot, under a total pressure Ptot.
the mixture is said to be ideal if each species behaveslike an ideal gas alone in
the mixture, i.e. there are no interactions between the different gases which
constitute the mixture.
In this case we consider that the gases form a single ideal gas
Ptot Vtot =ntot RT

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𝒏𝒊
Pi = RT
𝑽𝒕𝒐𝒕
𝒏𝒕𝒐𝒕
Ptot Vtot =ntot RT Ptot = RT
𝑽𝒕𝒐𝒕
Pi: The partial pressure of a gas in an ideal mixture is thepressure that

would exist if that gas occupied only the same volume as the mixture
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Each gas creates a partial pressure denoted Pi such that
Ptot = P1 + P2 + P3 + …… Pn
Ptot =σ 𝑷𝒊……….. Dalton law
𝒏𝒕𝒐𝒕 𝒏𝒊
Ptot = RT Pi = RT
𝑽𝒕𝒐𝒕 𝑽𝒕𝒐𝒕
𝒏𝒊
Pi = σ Ptot
𝒏𝒊
Pi = Xi Ptot
𝒏𝒊
Xi = σ 𝒏𝒊 is the molar fraction
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Exercise
A gas mixture consisting of 0.15g of H2; 0.7 of N2; and 0.34g of NH3
under the pressure of one atmosphere and a temperature of 27°C.
Calculate:
1. Molar fractions
2. The partial pressure of each gas
3. The total volume.
Data: M(H) =1g/mol M(N) =14g/mol
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Types of transformations
During a transformation, the state variables of the system vary to reach a

another state of equilibrium.
We distinguish :
1. Isothermal transformation: it is carried out at constant temperature

(T=Cste)
2. Isochoric transformation: it is carried out at constant volume (V=Cste)
3. Isobaric transformation: it is carried out at constant pressure (P=Cste)
4. Adiabatic transformation : an adiabatic transformation is a transformation

during which the system does not exchange heat with the external environment
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Clapeyron diagram : P=f(V)

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A reversible transformation (process) is defined as a process in which the system and

surroundings can be returned to the original conditions from the final state without
producing any changes in the thermodynamics properties of the universe, if the
process is reversed.
Some Properties of Reversible Processes
 Reversible processes traverse a succession of equilibrium states.
 the process can be turned back to such that both the system and the
surroundings return to their original states, with no other change
anywhere else in the universe.
An irreversible transformation (process) can be defined as a process in which the

system and the surroundings do not return to their original condition once the
process is initiated.
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Real gas model
Many laws allowing the representation of real gases have been

proposed. They generally have the following form:
(p + 𝜋 ) ( V- nb)=nRT
is called internal pressure. It reflects the strengths of attraction between the

molecules, which are added within the gas to the pressure forces exercised
on a surface.
The parameter b is the covolume, which takes into account the fact that the
molecules are not punctual, they occupy a finite volume. It follows that the true
variable of volume for a real gas is (V- nb) and not V
The most famous relationship of this type is that of van der Waals
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Van der Waals real gas model
In 1873, Van der Waals proposed a model which takes into account in a
simplified manner the intermolecular interactions ignored in the case of the
ideal gas.
Van der Waals equation of state
Ven der Waals equation of state for n moles of gas at thermodynamic

equilibrium:
The positive constants a and b are characteristic of each real gas:

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Energy exchange (work and heat)
During a transformation, a system can exchange energy with the external

environment in different forms. In this course, only exchanges in the form of
heat and mechanical work will be taken into consideration.
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The sign convention

The rule of signs in thermodynamics is a rule that everything that enters
the thermodynamic system, work W and heat Q, is counted positively and
everything that comes out is counted negatively. It's sort of like bank accounts:
you look at it from the bank's point of view.
System
Everything that comes out
(It's negative)
Everything that comes in +
(It's positive)
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Mechanical work W (work of pressure forces)

Mechanical work results from a variation in volume due to the pressure
forces exerted on the system.
Consider a gas contained in a cylinder closed by a piston. Applying a pressing

force to the piston.
Suppose that the piston undergoes a displacement dx such that the volume
of the gas decreases (the gas undergoes compression)
F= Pext . S
Ext : external
Compression (dV<0) (dV=Vf -Vi)

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the work received by the system during a displacement dx, infinitely

small, is given by:
δW = F.dx = Pext.S.dx = PextdV
dV
By convention the work received So it Must be positive W>0

and for a compression dV<0
Hence the sign (-)
δW = - Pout dV
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Otherwise, the gas undergoes an expansion, the work provided by the

system
By convention W provided by the system is less than 0 (W<0)
and for relaxation dV >0
δW = - Pext dV
Conclusion :
δW = - Pext dV
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Calculation of work in the case
 For a reversible and isothermal transformation:
Slow transformation
Pext=Pint= pgas
δW = - Pext dV= -PgasdV
If the gas is perfect we have PV=nRT

𝑅𝑇
Pgas =n 𝑉
Ext: external 𝑅𝑇
Pext =Pint= pgas = n 𝑉
Int : interior
𝑅𝑇 𝒅𝑽
δW = - n 𝑉 dV=-nRT 𝑽
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𝑅𝑇 𝒅𝑽
δW = - n 𝑉 dV=-nRT 𝑽
Since the transformation is isothermal T= Constant :
𝑽𝟐 𝒅𝑽
Wrev = -nRT‫𝟏𝑽׬‬ 𝑽
𝑽𝟐
Wrev = -nRTln𝑽𝟏
T=Cste : P1V1 =P2 V2
𝑷𝟏
Wrev = -nRTln𝑷𝟐
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 For an irreversible transformation
Rapid and spontaneous transformation
Pext=Pfinal=Cste
Wirre=-Pext(V2-V1)= =-Pfinal(V2-V1 )
 Pour une transformation isochore:

δW = - Pext dV
V=Cste
W=0
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For an isobaric transformation:

δW = - Pext dV
P=Cste
W=-Pext (V2-V1)
V1 : initial volume V2 : final volume
 Isobaric and reversible transformation:
Slow transformation
Pout=Pint= pgas
W=-Pgas(V2-V1)

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NATIONAL POLYTECHNIC SCHOOL

Department of Preparatory Classes

 Thermodynamics is a science that was born at the end of the 17th

 The initial motivation was therefore to respond to an essential

Thermodynamics can be described in two ways or according to two

The macroscopic aspect : we are interested in properties which are

Static thermodynamics: it seeks to explain the

The subject of the chemistry 2 course is classical thermodynamics

The principles on which thermodynamics is based are:

 The first principle (equivalence principle) concerns the conservative

 The second principle raises the notion of irreversibility and the

 The third principle (Nernst principle) finally focuses on the

The basic concepts

It is not possible to solve a thermodynamic problem until we have precisely

A system is a part of the universe, of determined mass and delimited in space

We call exterior everything that does not belong to the system

System + exterior = Universe

It is always necessary to precisely define the nature and boundary of the

For a gas enclosed in a cylinder fitted with a sliding piston.

- the system is a gaseous mass located inside the enclosure

- The exterior will consist of everything else (organs linked to the

Département des Classes Préparatoires

Année universitaire 2022/2023

Open system Isolated system

3. Thermodynamic equilibrium of a system

The system is said to be in thermodynamic equilibrium if these three

The thermodynamic transformation is a process by which a

State (1) Transformation state (2)

5.The state of a system

 The state of a system is described at a given time by a set of macroscopic

 If we want to describe the system more precisely, we can associate other

State (1) Transformation state (2)

m and V are extensive quantities

The equation of state of an ideal gas is

On a mathematical level, a state function F of several variables x, y, z is

F(x, y) is a state function if

 dF is an Exact total differential

Is g(x,y) a state function?

 dg is an Exact total differential

So g(x, y) is a state function

At temperature 0k (absolute zero = -273.15°C), the atoms which constitute

0 K (Kelvin )correspond to the absence of

Thermometers measure temperature according to well-defined scales of

Temperature scales are created by identifying two reproducible temperatures.

The freezing and boiling temperatures of water at

1. On the Celsius scale, the freezing point of

2. The Fahrenheit scale (still the most

3. The Kelvin scale Is The unit of T in the

Concept of ideal gas and real gas

- The ideal gas is a thermodynamic model that allows us to describe the

Ideal gas hypothesis

1. The size of gas molecules is negligible compared to the distances that

2. The interaction forces between the molecules are negligible (the

3. The pressure is due to the numerous shocks of the molecules on the

Equation of state of an ideal gas

R is the ideal gas constant (8.314 J.mol-1.K-1 )

Description of an ideal gas

 The Boyle-Mariotte law

 The Boyle-Mariotte law

Clapeyron diagram : P=f(V)

Charles and Gay-Lussac's Law

The relationship between temperature and volume, at a constant number

Charles did the original work, which was