People's Democratic Republic of Algeria

SCIENTIFIC RESEARCH
MHAMED BOUGARA UNIVERSITY OF BOUMERDES
FACULTY OF HYDROCARBONS AND CHEMISTRY
Common core Department

Dr [Link]
 I. Course Information
University: M’hamed Bougara University of Boumerdes

Faculty: Hydrocarbons and Chemistry

Department: STH (Hydrocarbon Science and Technology)

Target audience: 1st year degree in Hydrocarbon Science and Technology

Course title: Thermodynamic

Credit: 06

Coefficient: 03
Duration: 67h30 (Course: 1h30, TD: 3h00)

Teacher:
Courses and supervised work: [Link].H
Contact: semghounihassina69@[Link]
Classroom: zoesnrai

89
 Program
1. First law and applications
1. The ideal (perfect) gas 2. Entropy and the second law
2. Real gas behaviour 3. Entropy balance and irreversibility
3. Corresponding states and residual deviations 4. Properties of free energy and
4. Properties of liquids and solids thermodynamic equilibrium
Chapter II 5. Chemical potential and fugacity

Chapter I Chapter III

1. Mathematical review on partial derivatives Chapter IV 1. Phase equilibria of a pure substance

2. Properties and states of a thermodynamic 2. Thermodynamic properties of phase
system transitions
3. Thermodynamic process, equilibrium, and 3. Ideal behavior of gaseous, liquid and solid
cycle mixtures
4. Density, specific volume, 4. Phase equilibria of a compound in an ideal
5. Pressure, temperature and energy. mixture
5. Ideal solubility and partition coefficient
90
Thermodynamic properties of pure substances
 Chapter II: Thermodynamic properties of pure substances

01 The ideal (perfect) gas

02 Real gas behaviour

03 Corresponding states and residual deviations

04 Properties of liquids and solids

92
 Introduction
 A pure substance is one with a homogeneous and stable chemical composition.
 A pure substance is a form of matter with a constant and defined chemical
composition (Constant composition: The composition does not change, regardless of
the origin or method of preparation).
 A pure substance have a distinct characteristic properties (Unique properties: They
have fixed and precise melting and boiling points).

 A pure substance consist of only one type of particle (atoms or molecules) and
cannot be separated into simpler substances by physical methods.

 Liquid water, a mixture of water/ice or water/vapor are pure substances.

 A gas is a pure substance if it is composed of only one type of atom or molecule (ex:
O2, He,….). However, a mixture of gases, such as air, is not a pure substance.
 01 The ideal (perfect) gas

II.1.1. Ideal (perfect) gas definition

 A perfect gas is a set of particles sufficiently far apart , assumed to be

point-like (zero diameter), of negligible volume compared to the
volume of the enclosure in which it is located, which leads to the
absence of forces of attraction and repulsion between gas molecules
this implies that the pressure is low .

 Under these conditions, the equation of state is independent of the

chemical nature of the gas, which is considered ideal.

PV = nRT
 Many real gases under normal temperature and pressure conditions
satisfy the ideal gas model with excellent accuracy; this is the case
for the gases that make up air: nitrogen (N2) and oxygen (O2).
 01 The ideal (perfect) gas

II.1.2. State Equation of Ideal Gas

The ideal gas equation of state was experimentally established in the 18th century for air, within a
limited range of pressures and temperatures.
A dilute gas behaves as an ideal gas. In this case, the average distance between molecules is large
enough to neglect intermolecular forces, and particle collisions are rare, occurring mainly with
the container walls. The behavior of an ideal gas is described by the following equation of state:

P V = n RT
 P: pressure exerted by the gas (atmosphere (atm), pascal (Pa), bar (bar), …)
 V: occupied volume (L, m³, …)
 n: amount of substance (number of moles) (mol)
 R: universal gas constant (Calculated under normal conditions of temperature and pressure (C.N.T.P)):
R = 0.082 L·atm·K⁻¹·mol⁻¹ ; R = 8.32 J·K⁻¹·mol⁻¹ R = 2 cal·K⁻¹·mol⁻¹
 T: temperature of the gas (°C, kelvin (K)) T (K) = T (°C) + 273 95
 01 The ideal (perfect) gas

II-1-3- Perfect gas laws

The perfect gas rigorously obeys the three laws: MARIOTTE, GAY LUSSAC and
CHARLES.

a) Boyle-Mariotte Law: PV = Constant at T = Constant

Boyle's-Mariotte Law states that at constant

temperature and for a fixed amount of gas, the
product of the pressure (P) and the volume (V)
it occupies is constant (P*V= constant). Thus, if
the volume decreases, the pressure increases,
and conversely, the pressure is inversely
proportional to the volume.
 01 The ideal (perfect) gas

Boyle-Mariotte law Isothermal process

An isothermal transformation of an
Initial state
Isothermal ideal gas is a process that occurs at
final state
constant temperature T = Const.
Pi Pf
Vi Vf
Ti Tf= Ti= Cst
The ideal gas law in the initial state:
Pi Vi= n R Ti 01
The ideal gas law in its final state
Pf Vf= n R Tf 02
With Tf= Ti= T= Cst
01 = 02 PiVi= PfVf nRTi = nRTf = Cst
P V = Cst Boyle Mariotte Law
 01 The ideal (perfect) gas

PV = nRT
T = Cte

PV = nRT= Cte

P = Cte / V
 01 The ideal (perfect) gas

b) GAY-LUSSAC law at V = Constant

Gay-Lussac's Law states that the pressure ( P) of a given mass of gas is directly proportional to
its absolute temperature (T) in Kelvin, provided the volume (V) remains constant. As
temperature increases, kinetic energy rises, causing more frequent, forceful collisions with
𝑃 𝑃1 𝑃2
container walls, thus increasing pressure ( = Cst or = ).
𝑇 𝑇1 𝑇2
 01 The ideal (perfect) gas

GAY-LUSSAC law Isochoric process

V = cst
Initial state final state An isochoric transformation of an
ideal gas is a process that occurs at
Pi Pf constant volume,V=Constant.
Vi Tf
Ti Vf=Vi=cst
The ideal gas law in the initial state:
Pi Vi= n R Ti
The ideal gas law in its final state
Pf Vf= n R Tf
Vf=Vi= V= cst Vi=Vf

GAY-Lussac Law
01 The ideal (perfect) gas

P = Cst T

GAY-Lussac Law
 01 The ideal (perfect) gas

c) CHARLES law at P = Constant

Charles' law states that at constant pressure 𝑃

the volume of an ideal gas is directly
proportional to the absolute temperature
(expressed in kelvins),

PV = nRT

and

P = Cst
 01 The ideal (perfect) gas

Charles law Isobaric process

isobaric An isobaric transformationof an ideal

Initial state final state gas is a process that occurs at constant
Pressure (P=Const).
Pi Pf=Pi= cst
Vi Vf
Ti Tf

The ideal gas law in the initial state:

Pi Vi= n R Ti

The ideal gas law in its final state

Pf Vf= n R Tf

With Pi = Pf =P=Cst Charles Law

 01 The ideal (perfect) gas

V = Cst T

Charles Law
 01 The ideal (perfect) gas

d) LAPLACE formula : Adiabatic transformation (Q = 0)

Laplace's law in thermodynamics describes the behavior of an ideal gas during a reversible
adiabatic transformation, that is, without heat exchange with the outside. It establishes a
relationship between pressure and volume according to the formula 𝑃𝑉𝛾=constant, where 𝛾 is
the ratio of heat capacities at constant pressure and constant volume.

P1V1γ = P2V2 γ = Cst

 The adiabatic equation of state can also be described:
 Depending on temperature and volume: We have:
 01 The ideal (perfect) gas

 Depending on Temperature and pressure:

Cp: heat capacities at constant pressure γ= 1.66 monoatomic gas (He….)

with
Cv: heat capacities at constant volume γ= 1.4 diatomic gas (H2, O2…)
 01 The ideal (perfect) gas

 Relation between Cp​ and CV​ for an ideal gas, Mayer's relation:

The Mayer relation is a formula relating the specific heat capacities at constant
pressure Cp​ and constant volume Cv​ of an ideal gas, given by:

 R: universel constant of ideal gas (J/mol K)

 Cp: Isobaric Molar Heat capacity (at constant pressure) (J/mole K)
 Cv: Isochoric Molar Heat capacity (at constant volume) (J/mole K)
 01 The ideal (perfect) gas

Adiabatic compression : Pi< Pf; Vi >Vf Adiabatic expansion: Pi>Pf ; Vi < Vf

 01 The ideal (perfect) gas

e) DALTON’s law:

A gas mixture is made up of different gases (ni, Mi) occupying the same volume 'V': at
thermal equilibrium, these different gases are at the same temperature 'T'.
For each gas, we define a partial pressure 'Pi' and a total pressure 'Ptot' of the gas.
01 The ideal (perfect) gas

which confirms that Dalton’s law is satisfied.

 01 The ideal (perfect) gas

f) AVOGADRO’s law:

The AVOGADRO’s law state that at a given pressure and temperature, all ideal gases
have the same molar volume. That is, for any two gases 1 and 2 at the same pressure and
temperature:

where 𝑛1 and 𝑛2 are the number of moles of gases 1 and 2 respectively and 𝑉1, 𝑉2 their
volume.
 01 The ideal (perfect) gas

II-1-4- Ideal Gas Diagrams

The variations of a system’s state during a thermodynamic transformation are represented

using different thermodynamic diagrams.
These diagrams make it possible to track the evolution of state variables and to
visualize the path followed between the initial and final states.
The most commonly used diagrams are:
 Clapeyron diagram (P, V);
 Amagat diagram (PV, P).
 Clapeyron Diagram (P, V) Amagat Diagram (PV, P)
represents pressure as a function of volume. represents the product PV as a function of pressure.
For an ideal gas, at constant temperature: PV=
RT= constant

This diagram is widely used because:

 The area under the curve represents the work
The Amagat diagram is useful for:
exchanged.
 verifying ideal gas behavior
 It allows easy identification of thermodynamic
 analyzing deviations from ideality.
processes: isothermal, isobaric, isochoric and adiabatic.
 01 The ideal (perfect) gas

I.5- Heat and Work Expressions for Ideal Gas Processes

I.5.1- Isochore transformation (V = Cte)
a)- Expression of work
For a finite transformation between the initial state (1)
and the final state (2), the expression of the work is:

b)- Expression of Heat :

For a finite transformation between the initial state (1) and the final state (2), the
expression of the heat quantity is:
cv v v
 Cv Isochoric molar heat capacity (J/mol K); cv: Isochoric specific heat capacity (J/kg K)
 01 The ideal (perfect) gas

I.5.2- Isobaric transformation (P = Cte)

a)- Expression of work:
For a finite transformation between the initial state (1) and
the final state (2), the expression of the work is: :
 01 The ideal (perfect) gas

b)- Expression of Heat :

For a finite transformation between the initial state (1) and the final state
(2), the expression of the heat quantity relationship is given by:

cp

With:
Cp: Isobaric molar heat capacity (J/mol K)
cp: Isobaric specific heat capacity (J/kg K)
 01 The ideal (perfect) gas

I.5.3- Isothermal transformation (T = Cte)

a)- Expression of work:
For a finite transformation between the initial state (1) and the
final state (2), the Expression of the work is:

 Reversible case
During a reversible transformation, at any instant, we can write:

For an isothermal transformation, we have: T1 =T2 =T, and: P1 V1 = P2 V2 → P1/P2 = V2/V1

Therefore:
 The absolute value of work is determined by the area under the curve, and the sign
is positive during compression and negative during expansion.

 Irreversible case
During an irreversible transformation, at any instant, we can write:
Pext = Pfinal = P2

b)- Expression of Heat quantity:

 01 The ideal (perfect) gas

I.5.4- Adiabatic transformation (Q = 0)

a)- Expression of work:
The transformation of a system is adiabatic if it takes place
without heat exchange with the external environment. The
system is thermally isolated.

b)- Expression of Heat quantity:

 02 Real gas behaviour

II-2-1- Real Gas Vs Ideal Gas

Ideal gas Real gas
 Particles have
 Particles have
no volume.
volume.
 Collisions are
 Energy lost in
elastics
coliisions.
 No
 Intermolecular
interractions
forces.
between
particles

Real gases behave like ideal gases:

At hight Temperature.
At low Pressure.
 02 Real gas behaviour

The behavior of some real gases is represented in an

Amagat diagram, where we observe that:
 At high pressures (> 1 atm), real gases deviate
significantly from the ideal gas (horizontal R.G
curve).
 As the pressure p→0, all curves converge to a single
point RT.

Amagat Diagram (PV=f(P))

 02 Real gas behaviour

II-2-2- State Equation of Real Gases

Real gases behave very differently from perfect (ideal) gases. To analyze the behavior of a
real gas, modifications must be made to the ideal gas concept:
1. Finite molecular volume: Real gas molecules occupy a finite volume (unlike ideal gas
molecules treated as point particles), called the covolume, denoted b:
Vreal = Videal+b
2. Intermolecular forces: Each molecule interacts with the surrounding molecules.
A molecule moving toward the container wall is slowed down by neighboring molecules,
exerting a lower pressure than an ideal gas (where no molecular interactions exist).
𝒂
The resulting pressure is then given by: Preal = Pideal -
𝑽𝟐
 02 Real gas behaviour

II-2-2-1- Van der Waals Equation:

The ideal gas equation allows us to derive the equation of state for real gases:
 For one mole of a real gas:

Correction for molecular interactions Correction for molecules volume

 Van der Waals Equation (Extensive form):

 Van der Waals Equation (Intensive form):

Where Vm is the molar volume, defined as:

 02 Real gas behaviour

 Van der Waals Coefficients

Table1: Van der Waals constants for some

common gases
Gas a (L².atm/mol²) b (L/mol)
H₂ 0.244 0.0266
He 0.0341 0.0237
N₂ 1.39 0.0391
O₂ 1.36 0.0318
The experimental values of the Van der Waals constants for CO₂ 3.59 0.0427
some common gases are given in the following table: H₂O 5.46 0.0305
CO 1.49 0.0399
124
 02 Real gas behaviour

II-2-2-2- Other Equations:

The Virial coefficients B and C describe the

interactions between gas molecules.

The Berthelot equation provides an accurate

description of gas behavior up to pressures of 10
atm.
 02 Real gas behaviour

II-2-3- Thermoelastic coefficients of a gas

These coefficients can be measured experimentally and used to obtain the equation of
state by integration. They describe how the volume or pressure of a system changes with
these variables.
𝟏 𝝏𝑽
Isobaric expansion coefficient: 𝜶 =
𝑽 𝝏𝑻 𝑷

𝟏 𝝏𝑽
Isothermal compressibility coefficient: 𝝌𝑻 = − 𝑽 𝝏𝑷
𝑻

𝟏 𝝏𝑷
Isochoric pressure increase coefficient: 𝜷=
𝑷 𝝏𝑻 𝑽
 02 Real gas behaviour

Thermoelastic coefficients of a Real gas

𝑹𝑽𝟐 𝑽 − 𝒃 𝑽𝟐 𝑽 − 𝒃 𝟐 𝑹𝑽𝟐
𝜶= ; 𝝌𝑻 = ; 𝜷=
𝑹𝑻𝑽𝟑 − 𝟐𝒂 𝑽 − 𝒃 𝟐 𝑹𝑻𝑽𝟑 − 𝟐𝒂 𝑽 − 𝒃 𝟐 𝑹𝑻𝑽𝟐 − 𝒂 𝑽 − 𝒃

Thermoelastic coefficients of Ideal Gas :

Note: For a real gas at CNTP (1 atm, 0°C):

At CNTP
These coefficients conditions, real
are close to the gases exhibit
theoretical values behavior that is
of an ideal gas. close to that of an
ideal gas.
 02 Real gas behaviour

Notes:
 The fundamental relation between the coefficients is: 𝛼 = P. 𝜷. 𝝌𝑻

 The following relation is very important in thermodynamics:

It shows that the three partial derivatives are not independent.
Reciprocity Theorem
If you know two of them, you can deduce the third one. (or Triple Product Relation)

 The inversion rule is commonly applied in thermodynamic calculations:

It is a mathematical property of partial derivatives that applies when one
variable is kept constant.
 02 Real gas behaviour

II-2-4- Real Gas Diagrams

II.2.4.1. Phase Diagram (Triple point and critical point):
A phase diagram is a graphical representation of the physical states of a substance under different
conditions of temperature and pressure, typically with pressure on the y-axis and temperature on the x-axis.
It shows the conditions under which distinct phases—such as solid, liquid, and gas—exist and coexist.
By varying temperature and pressure, one can determine, for each pair of values (temperature, pressure),
the state in which the substance exists: gaseous, liquid, or solid.

 The triple point corresponds to the temperature and

pressure conditions at which the three states of matter
(solid, liquid, and gas) coexist in equilibrium.
 The critical point is reached at high temperature and
pressure where the distinction between liquid and gas
disappears. At this point, their densities become equal, and the
substance forms a supercritical fluid, exhibiting properties
intermediate between those of a liquid and a gas.
 02 Real gas behaviour

 At 1 atm, water freezes at 0 °C and boils at 100 °C. These

temperatures are valid only at atmospheric pressure.
 By changing the pressure, water can freeze or boil at different
temperatures even if the temperature is kept constant.

* At the triple point (P= 0.006 atm) and (T= 0.01°C), liquid water
boils and forms ice cubes.

* There is one and only one triple point for each pure substance.

 At the critical point, a gas/liquid mixture is obtained. This

mixture is called supercritical fluid.
 The critical point for water is T= 374 °C and P= 218 atm.
 02 Real gas behaviour

II.2.4.2. Isothermal Diagrams

When experimental isotherms of real gases are plotted on a (P, V) diagram (Clapeyron), their
behavior differs significantly from that of an ideal gas.

The dashed curve is called the

saturation curve. Below this
curve, there is always a liquid–gas
mixture, known as wet vapor.

Isotherms of Ideal gas Andrews Isotherms in P–V diagram

 02 Real gas behaviour

 Interpretation of Andrews Isotherms

 If T>TC: the fluid is compressed smoothly while remaining in the

gaseous state. The curve P=f(V) deviates significantly from that of
an ideal gas.

 If 𝑇<𝑇𝐶: from point G to L there is a liquefaction plateau, where

both phases coexist: gas and liquid. The system is therefore
heterogeneous. The proportion of liquid increases from G to L. At
𝑉=𝑉𝐿, only liquid remains and liquefaction is complete. G
L
 If 𝑇=𝑇𝐶 : the horizontal liquefaction plateau reduces to a single
inflection point with a horizontal tangent (𝑃𝐶,𝑉𝐶,𝑇𝐶): this is the
critical point C.

𝝏𝑷 𝝏𝟐 𝑷 VL VG
When: P = Pc ( ) 𝑻𝒄 = 𝟎 ( 𝟐 ) 𝑻𝒄 = 𝟎
𝝏𝑽 𝝏𝑽
Andrews Isotherms
 02 Real gas behaviour

A real fluid can change phase (liquid ⇄ vapor) through several states:

 (0): Compressed liquid

 (1): Saturated liquid (a vapor bubble appears, the rest is liquid)
 (2): Liquid–vapor mixture, called wet vapor. This mixture is
characterized by its quality ‘x’, representing the proportion of gas or
liquid:

 (3): Saturated vapor (a droplet of liquid remains, the rest is vapor)

 (4): Dry vapor (or superheated vapor)

 From (1) to (3): in the phase change plateau (liquid–vapor):

Pressure and Temperature remain constant.

 Bubble curve: set of points corresponding to the saturated liquid state.

 Dew curve: set of points corresponding to the saturated vapor state Andrews Isotherms
 02 Real gas behaviour

II.1.4.3. Critical point coordinates of Van der Waals gas

To obtain the coordinates of the critical point (Pc​, Vc, Tc), simply take the
first and second derivatives of the VDW equation and equalize to zero:

𝝏𝑷 𝝏𝟐 𝑷
( ) 𝑻𝒄 , = 𝟎 (horizontal tangent) ; ( 𝟐 ) 𝑻𝒄 = 𝟎 (Inflextion point)
𝝏𝑽 𝝏𝑽
 According to the VDW equation:

 At critical point and molar volume: (V = 𝑉/𝑛 ), we have:

Andrews Isotherms
02 Real gas behaviour

Table : Critical Point Data for Some Common Fluids

 03 Corresponding states and residual deviations

II.3.1- Corresponding states

II.3.1.1. Corresponding states Law:
Corresponding states in real gases (proposed by van der Waals (1880)),is a concept used to
compare the behavior of different real gases based on their critical conditions.
This law states that:
All gases, when expressed in terms of reduced variables, obey the same equation of state.
In other words, all real gases behave similarly when their properties are normalized
relative to their critical point values.
The reduced coordinates are obtained by dividing the physical properties of a gas (P, T, V) by
𝑷 𝑽 𝑻
their respective critical values: 𝑷𝒓 = , 𝑽𝒓 = , 𝑻𝒓 = .
𝑷𝒄 𝑽𝒄 𝑻𝒄

Reduced V.D.W equation: When written in reduced form, the Van Der Waals equation becomes:
𝒂 𝒂
𝑷+
𝑽𝟐𝑴
𝑽𝑴 − 𝒃 = 𝑹𝑻  𝑷𝒓 × 𝑷𝒄 +
(𝑽𝒓 × 𝑽𝒄 )𝟐
𝑽𝒓 × 𝑽𝒄 − 𝒃 = 𝑹 𝑻𝒓 × 𝑻𝒄
𝟑
𝒂 𝟖𝒂  𝑷𝒓 + 𝟐
𝟑𝑽𝒓 − 𝟏 = 𝟖 𝑻𝒓
With: 𝑷𝒄 = ; 𝑽𝒄 = 𝟑𝒃 and 𝑻𝒄 = 𝑽𝒓
𝟐𝟕 𝒃𝟐 𝟐𝟕 𝑹𝒃 136
 03 Corresponding states and residual deviations

This reduced equation applies to all fluids since it contains no gas-specific constants
(a, b are eliminated). It allows us to state the principle of corresponding states:

Two or more gases are said to be in corresponding states if they have the same
values of Tr​, Pr​, and Vr simultaneously.

This means that:

 All gases at the same Tr and Pr have the same Vr​.
 All gases in the same reduced state behave identically.
Example : N2 at Tr=1.5, Pr=2 is in a corresponding state with CO2 at Tr=1.5, Pr​=2, even
though their actual T and P values differ greatly.
 Consequences:
 Homogeneous fluids can be grouped together by family or group.
 Same reduced coordinates ⟹ same family ⟹ proportional thermoelastic coefficients.
 03 Corresponding states and residual deviations

III.3.1.2. Compressibility Factor (Z)

To quantify the difference in behavior between a

real gas and the ideal gas model, the
compressibility factor, denoted Z, is used
experimentally. Z is a universal function of Tr
and Pr for all gases: Z = f(Tr​,Pr). It is given by:
𝑷𝑽
𝐙=
𝒏𝑹𝑻

If Z= 1 → ideal gas ; if Z≠ 1 → real gas Compressibility factor as a function of P

for a fixed temperature

 If Z < 1, intermolecular attractive forces dominate, making the gas more compressible than an ideal gas.
 f Z > 1, repulsive forces and/or the intrinsic volume of the molecules dominate →Less compressible gas.
 03 Corresponding states and residual deviations

The law of corresponding states (formulated by Van der Waals) states that all pure
substances in the fluid state, at the same reduced temperature (Tr) and reduced pressure
(Pr), present approximately the same compressibility factor Z — they all deviate from the
ideal gas model to the same degree.

Example :
Helium He (Tc=5.2 K; Pc=2.3 bar) at T=10.4 K and P=2.3 bar, and Hydrogen H₂ (Tc=33.2 K; Pc=13 bar) at
T=66.4 K and P=13 bar, both have the same reduced temperature Tr=T/Tc=2 and reduced pressure
Pr=P/Pc=1.
Since both gases share the same compressibility factor Z, they deviate from the ideal gas model by
the same amount. We therefore conclude that Helium and Hydrogen are in corresponding states.
03 Corresponding states and residual deviations
Compressibility Factor (Z) Diagram
 03 Corresponding states and residual deviations

III.3.2. Residual properties (or residual deviation)

A residual property ‘gres’, also called a residual deviation, expresses the difference between a
thermodynamic property ‘g’ of a real fluid (gas or liquid) and the same thermodynamic property
g∗ of an ideal gas, under the same conditions of pressure and temperature. It is a useful tool for
relating ideal behavior to real gas behavior through equations of state.

 Mathematical Definition: A residual property is defined as:

Example : Residual Volume :

 04 Properties of liquids and solids

II.4.1. Properties of Liquid

 Structure: Molecules are close together but not fixed in position — they move freely around
each other.
 Mechanical and Thermal properties :
 Fixed volume but no fixed shape (takes the shape of its container)
 Nearly incompressible
 High density compared to gases
 Can flow — have viscosity
 Moderate thermal expansion
 Evaporate below boiling point (vapor pressure)
 Higher specific heat capacity than solids

 Thermodynamic properties :
 Compressibility factor Z ≪ 1 (attractive forces dominate)
 Residual volume Vres<0 (attractive forces dominant)
 Large enthalpy change at vaporization (latent heat)
 04 Properties of liquids and solids

II.4.2. Properties of Solid

 Structure: Atoms or molecules are arranged in a fixed, highly ordered pattern (crystalline or
amorphous). Particles vibrate in place but do not move freely.
 Mechanical and Thermal properties :
 Fixed shape and fixed volume
 Incompressible: volume barely changes with pressure
 High density: Solids have a higher density than liquids, due to the close proximity of their constituent particles;
 Rigid — resist deformation
 Low thermal expansion coefficient
 High melting point (strong intermolecular forces)
 Specific heat capacity is generally low

 Thermodynamic properties :
 Residual volume ≈ 0 (very small compressibility)
 Compressibility factor Z ≈ 0
 Enthalpy and entropy change significantly at phase transitions (melting) 143
 04 Properties of liquids and solids
Comparative Table: Solid, Liquid and Gas

Whether solid, liquid, or gas, matter is

composed of the same molecules (or atoms).
The differences mainly lie in the distance
between molecules, their motion, and the
forces between them.

The following table summarizes the other

differences between these states..

Compressibility ≈0 ≪1 ≈ 1 (ideal) or varies

factor Z