Material Science Physical Chemistry I

Definition of Terms

System:
A portion of the universe that we have
chosen for study.

Surroundings:
The remainder of the universe
 Within a system is a MATTER
 Material Science Physical Chemistry I

Definition of Terms
Thermodynamics:
A study that is concerned with the behaviour
of matter
 AIM of thermodynamics is to establish the
relationship that exist between a system
and its surroundings
 Material Science Physical Chemistry I
4 types of systems:
1.Closed System:
A system that is enclosed by an
impermeable wall or boundary such that
transfer of matter is not allowed, but allows
transfer of energy.
 Mass remains constant
2.Open System:
A system that is bounded by permeable
walls that allow transfer of both matter and
energy across the walls
 Material Science Physical Chemistry I
4 types of systems:
3. Isolated System:
A system that is enclosed by impermeable
walls that permit neither transfer of matter
nor exchange of energy.
 Such walls are called adiabatic walls

4. Homogenous System:
A system that is made up of a single phase
Heterogenous System:
A system that is made up of 2 or more phases
 Material Science Physical Chemistry I
States of Matter
1. Gas:
A fluid form of matter that fills the container it
occupies
Composed of particles that are in continuous,
rapid, and disordered motion
 Material Science Physical Chemistry I
States of Matter
1. Gas:

 A particle travels several diameters before

interacting with another particle.
There is weak interaction between particles
 Material Science Physical Chemistry I
States of Matter
2. Liquid:
A fluid form of matter that possesses a well-
defined surface and in a gravitational field
occupies the lower part of the container.
 Consists of particles that are in contact but
are able to move past one another in a
restricted manner
 Material Science Physical Chemistry I
States of Matter
2. Liquid:

Particles are in continuous motion but are

only able to travel a few fraction of a
diameter before bumping into a neighbour.
 Material Science Physical Chemistry I
States of Matter
3. Solid:
Retains its shape regardless of the container
it occupies.
 Particles are in contact and are unable to
move past one another.
 Material Science Physical Chemistry I
States of Matter
3. Solid:

Typically, particles lie in ordered arrays

 Material Science Physical Chemistry I
States of Matter

 What is the main difference between the 3

states of matter?
 Material Science Physical Chemistry I

Equations of State

4 Properties that define the state of a matter:

1. Volume, V

2. Pressure, p

3. Temperature, T

4. Amount of the substance, n

 These properties are not independent of
each other
 Material Science Physical Chemistry I

Behaviour of gases and vapors

 For any substance there exists a unique
relationship between its state properties

𝒇 𝑷, 𝑽, 𝑻 = 𝟎
 Material Science Physical Chemistry I

Equations of State

Equation of State of a low-pressure gas

 Ideal gas law

𝑷𝑽 = 𝒏𝑹𝑻
 a.k.a. Perfect gas equation of
state
 R: gas constant (experimentally
determined and the same
value for all gases)
 Material Science Physical Chemistry I

Perfect gas
 A hypothetical gas that obeys the perfect
gas equation at all pressures
Real gas
 Can behave like a perfect gas when its
pressure is reduced toward zero.
 The normal atmospheric pressure (~ 100 kPa)
is already low enough for most real gases to
behave almost perfectly.
 Material Science Physical Chemistry I

Real gas
 At low densities which are approached at
high temperatures and low pressures, most
real gases behave like an ideal gas

 The reason why a real gas behave differently

from a perfect gas can be due to the
attraction and repulsion that exist between
molecules which is absent in perfect gases.
Material Science Physical Chemistry I

Values of R in various units

𝑹 = 𝟖. 𝟑𝟏𝟒𝟒𝟕 𝑱 𝑲− 𝒎𝒐𝒍−𝟏

𝑹 = 𝟖. 𝟑𝟏𝟒𝟒𝟕 𝑳 𝒌𝑷𝒂 𝑲−𝟏 𝒎𝒐𝒍−𝟏

𝑹 = 𝟖. 𝟐𝟎𝟓𝟕𝟒 𝒙 𝟏𝟎−𝟐 𝑳 𝒂𝒕𝒎 𝑲−𝟏 𝒎𝒐𝒍−𝟏

𝑹 = 𝟔𝟐. 𝟑𝟔𝟒 𝑳 𝑻𝒐𝒓𝒓 𝑲−𝟏 𝒎𝒐𝒍−𝟏

𝑹 = 𝟏. 𝟗𝟖𝟕𝟐𝟏 𝒄𝒂𝒍 𝑲−𝟏 𝒎𝒐𝒍−𝟏

 Material Science Physical Chemistry I

Review of terms

A gram-mole (or simply mole)

 Consists of 6.022 x 1023 atoms
Molar volume, V
 The volume occupied by 1 mole of a
substance at a specified temperature and
pressure
𝐕
𝑽=
𝒏
 Material Science Physical Chemistry I

Review of terms

STP: Standard Temperature and Pressure

 00 C and 1 atm
 1 g-mole of an ideal gas occupies:
 22.415 litres
 0.022415 m3
 1 lb-mole of an ideal gas occupies:
 359.06 ft3
 Material Science Physical Chemistry I

Review of terms

Specific Volume, V
 The reciprocal of density
 The volume occupied by a specific amount
of the substance
 Material Science Physical Chemistry I

Review of terms

Composition
 The evolution of a reacting system can be
studied by monitoring the changes occurring
in the composition of the reaction mixture
 Mole fraction  Mass fraction
𝒏𝒊 𝒎𝒊
𝒙𝒊 =σ 𝒚=σ
𝒋 𝒏𝒋 𝒋 𝒎𝒋
 Material Science Physical Chemistry I

Virial equation of state

 Describes the behaviour of real gases
𝑷𝑽=𝒏 𝑹𝑻 + 𝑩𝑷 + 𝑪𝑷𝟐 + ⋯
 B, C, … are known as the second, third,….
virial coefficients
 For a given substance, these coefficients
are dependent on the Temperature only
 Material Science Physical Chemistry I

Virial equation of state

 Describes the behaviour of real gases
𝑷𝑽=𝒏 𝑹𝑻 + 𝑩𝑷 + 𝑪𝑷𝟐 + ⋯
 At moderate densities, the equation can be
truncated at the second term

𝑷𝑽=𝒏 𝑹𝑻 + 𝑩𝑷
 Material Science Physical Chemistry I

Virial equation of state

 Describes the behaviour of real gases
𝑷𝑽 = 𝒏 𝑹𝑻 + 𝑩𝑷 + 𝑪𝑷𝟐 + ⋯
 At low pressures, the second term becomes
insignificant

𝑷𝑽 = 𝒏𝑹𝑻
 Material Science Physical Chemistry I

Van der Waals equation of state

 Describes the behaviour of real gases
𝑷 + 𝒂Τ𝑽𝟐 𝑽 − 𝒃 = 𝑹𝑻
 a and b are constants for any given
substance and they differ from one
substance to another.
 At sufficiently low densities, where the
specific volume will be very large, 𝒂Τ𝑽𝟐 and
𝒃 become negligible and the equation
reduces to ideal gas equation
 Material Science Physical Chemistry I

Gaseous mixtures
 Dalton’s law
 Amagat’s law
Condition:
 Consider a gaseous mixture made up of 3
non-reacting components (1, 2, 3)
 The molecules of each component gas is free
to move randomly throughout the volume of
the container. That is, each gas can be
considered to occupy the entire volume
 Material Science Physical Chemistry I

Gaseous mixtures
Condition:
 Each component is expected to obey the
ideal-gas law at ordinary pressures
 Assume that there is 1 mole of each gas

𝑷𝟏 𝑽 = 𝑹𝑻 𝑷𝟐 𝑽 = 𝑹𝑻 𝑷𝟑 𝑽 = 𝑹𝑻
 Material Science Physical Chemistry I

Gaseous mixtures
Condition:
 Each component is expected to obey the
ideal-gas law at ordinary pressures
 Assume that there is 1 mole of each gas

𝑷𝟏 𝑽 = 𝑹𝑻 𝑷𝟐 𝑽 = 𝑹𝑻 𝑷𝟑 𝑽 = 𝑹𝑻
 Material Science Physical Chemistry I

Gaseous mixtures
Dalton’s Law of partial pressure
 The total pressure of the mixture is equal to
the partial pressures
𝑷 = 𝑷𝟏 + 𝑷𝟐 + 𝑷𝟑
𝑷𝟏 = 1 atm 𝑷𝟐 = 1 atm 𝑷𝟑 = 1 atm 𝑷𝑻 = 3 atm

𝑽 = 22.415 m3 𝑽 = 22.415 m3 𝑽 = 22.415 m3 𝑽 = 22.415 m3

𝒏𝟏 = 1 kg-mole 𝒏𝟐 = 1 kg-mole 𝒏𝟑 = 1 kg-mole 𝒏𝑻 = 3 kg-mole
T = 273 K T = 273 K T = 273 K T = 273 K
 Material Science Physical Chemistry I

Gaseous mixtures
Amagat’s Law of partial volume
 The total volume occupied by a gaseous
mixture at a given pressure and temperature
is equal to the sum of the pure component
volumes at the same pressure and
temperature

𝑽 = 𝑽𝟏 + 𝑽𝟐 + 𝑽𝟑
 Material Science Physical Chemistry I

Gaseous mixtures
Amagat’s Law of partial volume

𝑽𝑻 = 22.415 m3
𝑽𝟏 = 7.472 m3 𝑽𝟐 = 7.472 m3 𝑽𝟑 = 7.472 m3

𝑷 = 3 atm 𝑷 = 3 atm 𝑷 = 3 atm 𝑷 = 3 atm

𝒏𝟏 = 1 kg-mole 𝒏𝟐 = 1 kg-mole 𝒏𝟑 = 1 kg-mole 𝒏𝑻 = 3 kg-mole
T = 273 K T = 273 K T = 273 K T = 273 K
 Material Science Physical Chemistry I

Dissociating Gases:
 At elevated temperatures, some gases tend
to dissociate, and the resulting gas mixture
does not obey the ideal gas law, but each
component may behave as an ideal gas
e.g. Dissociation of antimony (Sb)
𝑺𝒃𝟐 (𝒈) = 𝟐𝑺𝒃(𝒈)
 Material Science Physical Chemistry I

Dissociating Gases:
 The gas mixture: 𝑺𝒃𝒔 , 𝑺𝒃
 The pressure and volume of this gas mixture
will be in excess of what would exist if there
was no dissociation
 It means that when 1 g-mole of Sb is
vaporoized, PV=nRT alone cannot e used to
predict the exact volume occupied by the
gas
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

 When air is placed in contact with water, it

will gain vapor from the water phase
 If contact is prolonged, the air will become
saturated with water vapor.
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

 Suppose that the temperature of the dry air is

400C
 The total pressure on the piston is constant at
all times at 760 mmHg
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

 Water will vaporise and will join the dry air,

giving rise to humidified air
 The vaporisation will continue until the
pressure of the water vapor reaches 55.3
mmHg.
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

55.3 mmHg
 It is called the saturation vapor pressure of
H2O at 400C and is a function of temperature
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

 Assuming both water vapor and air behave

like an ideal gas, the partial pressure of air at
saturation can be calculated from Dalton’s
law for partial pressure
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

𝒑𝑯𝟐 𝑶 𝒗𝒂𝒑𝒐𝒓 + 𝒑𝒂𝒊𝒓 = 𝑷𝑻

𝒑𝒂𝒊𝒓 = 𝑷𝑻 − 𝒑𝑯𝟐 𝑶 𝒗𝒂𝒑𝒐𝒓
𝒑𝒂𝒊𝒓 = 𝟕𝟔𝟎 − 𝟓𝟓. 𝟑 𝒎𝒎𝑯𝒈

𝒑𝒂𝒊𝒓 = 𝟕𝟎𝟒. 𝟕 𝒎𝒎𝑯𝒈

 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

 If V is the volume of the air-vapor system at

complete saturation:
𝒑𝑯𝟐 𝑶 𝑽 = 𝒏𝑯𝟐 𝑶 𝑹𝑻 and 𝒑𝒂𝒊𝒓 𝑽 = 𝒏𝒂𝒊𝒓 𝑹𝑻
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated
𝒏𝒊
 Recall: 𝒙𝒊 =σ 𝒏  Mole fraction
𝒋 𝒋
𝒏𝒊 𝒑
𝒙𝒊 = 𝒙𝒊 = 𝒑 = 𝒙𝒊 𝑷
𝒏𝑻 𝑷
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

 When the time of contact is short, the air will

be partially saturated.
 Partial saturation is expressed in terms of
relative humidity.
 Material Science Physical Chemistry I

Air-water vapor mixtures

Dry air +
Dry air + water vapor
Dry air water vapor

water water water

Partially Completely
saturated saturated

𝒑𝑯𝟐 𝑶  Partial saturation of water vapor in the gas

𝑹𝑯 = ∗
𝒑𝑯𝟐 𝑶 mixture

 Partial saturation of water vapor in the gas

mixture if the gas mixture is saturated with
water vapor at a given temperature
 Material Science Physical Chemistry I

Dew Point
 An unsaturated air – water vapor mixture is
cooled slowly
 If the total pressure of the system is kept
constant, then the partial pressure of the H2O
vapor will not be changed by the cooling
process
 As cooling progress, a temperature is
reached when the partial pressure of the H2O
vapor becomes equal to the equilibrium
vapor pressure at that temperature
 Material Science Physical Chemistry I

Exercise # 1
The analysis of a reducing gas mixture, on a
volumetric basis is:

Gas vol. % Express the composition of

H2 70 the gas mixture on:
CO 15
CO2 5
(a) Mole - % basis
(b) Mass - % basis
H2O 5
N2 5
Total 100
 Material Science Physical Chemistry I

Exercise # 2
An iron ore sample contains Fe, Si and O. Its
analysis shows that the iron present amount to
68% by weight. Assuming that all Fe is present as
Fe2O3 and the Silicon as SiO2,

Element AW (a) Calculate the weight

Fe 55.845 % of SiO2 in the ore
Si 28.0855
(b) Express the
O 16 composition of the
ore in mole-% basis
 Material Science Physical Chemistry I
Quiz
The composition of dry air on a volume-percent basis is given
in the table below:
Gas Vol. % Element AW
N2 78.09 N 14.01
O2 20.94 O 16
Ar 0.93 Ar 39.948
CO2 0.03 C 12.01
Ne 0.0018 Ne 20.18
He 5.2 x 10-4 He 4
Kr 1 x 10-4 Kr 83.798
H2 5 x 10-5 H 1.01
(a) Find the average molecular weight of the air (MWair) and
the density 𝝆𝒂𝒊𝒓
(b) Express the composition in wt. % basis