THE PROPERTIES OF GAS

THE
PERFECT
GAS
  Equations related to perfect
gases provide the basis for the
development of many relations
THE in thermodynamics.
PERFECT
GAS  The perfect gas law is also a
good approximation for
accounting for the properties of
real gases.
  The variables needed to specify
the state of the system:

VARIABLES ❑ Amount of substance, n

OF STATE ❑ Volume,V
❑ Pressure, P
❑ Temperature, T
  The physical state of a sample of
a substance, its physical
condition, is defined by its
physical properties.
VARIABLES
OF STATE
 Two samples of the same
substance that have the same
physical properties are in the
same state.
  Pressure is defined as the force, F, a
sample of matter is subjected to,
divided by the area, A, to which that
force is applied.
𝐹
𝑃=
𝐴

 The origin of the force exerted by a gas

PRESSURE is the incessant battering of the
molecules on the walls of its container.

 The collisions are so numerous that

they exert an effectively steady force,
which is experienced as a steady
pressure.
Standard Pressure

 A pressure of 1 bar is the standard pressure reporting data;

it is denoted 𝑝⊖ .

 The standard pressure, 𝑝⊖ , for reporting physical quantities

is currently defined as 𝑝⊖ = 1 bar exactly.
Mechanical Equilibrium

 Mechanical equilibrium is a condition of

equality of pressure on either side of a
shared movable wall.
  Temperature is formally a
property that determines in
which direction energy will flow
as heat when two samples are
TEMPERATURE placed in contact through
thermally conducting walls:
energy flows from the sample
with higher temperature to a
sample with lower temperature.
Temperature Scales

 There are three temperature scales in use today:

❑ Kelvin, T (T is used to denote thermodynamic temperature)
❑ Celsius, 𝜃
❑ Fahrenheit

 Thermodynamic and Celsius temperatures are related by

the exact expression
𝑇Τ𝐾 = 𝜃/° 𝐶 + 273.15
Thermal Equilibrium
 Two types of boundary that separate two objects:
❑ Diathermic -thermally conducting
-a change of state is observed when
two objects at different
temperatures are brought into
contact.
❑ Adiabatic -thermally insulating
-no change occurs even though the two
objects have different temperatures.

 Thermal equilibrium is established if no change of

state occurs when two objects A to B are in contact
through a diathermic boundary.
Zeroth Law of Thermodynamics

 If A is in thermal equilibrium with B,

and B is in thermal equilibrium with C,
then C is also in thermal equilibrium
with A.

 The Zeroth Law justifies the concept of

temperature and the use of a
thermometer.
  An equation that interrelates the
four state variables: n,V, p,T.
EQUATIONS
OF STATE  The general form of an equation of
state is
𝑝 = 𝑓(𝑇, 𝑉, 𝑛)
The Empirical Basis

 The following individual gas laws should be familiar:

Boyle’s law: 𝑝𝑉 = constant, at constant 𝑛, 𝑇
Charles’s law: 𝑉 = constant × 𝑇, at constant 𝑛, 𝑝
𝑝 = constant × 𝑇, at constant 𝑛, 𝑉
Avogadro’s principle:
𝑉 = constant × 𝑛, at constant 𝑝, 𝑇

 Boyle’s and Charles’s law are example of limiting law, a law that is strictly true
only in a certain limit, in this case 𝑝 → 0.
 Many relations that are strictly true only at 𝑝 = 0 are nevertheless reasonably
reliable at normal pressures (p = 1 bar) and are used throughout chemistry.
 The pressure–volume
dependence of a fixed amount
of perfect gas at different
temperatures.
 Each curve is a hyperbola (pV =
constant) and is called an
isotherm.

❑ Each of the curves in the graph

corresponds to a single
temperature and hence is called
an isotherm.
 Straight lines are obtained when
the pressure is plotted against
1/V at constant temperature.

❑ Each of the curves in the graph

corresponds to a single
temperature and hence is called
an isotherm.
 The variation of the volume of a
fixed amount of gas with the
temperature at constant
pressure.
 Note that in each case the
isobars extrapolate to zero
volume at T = 0 or θ =
−273.15°C.

❑ The lines in this illustration are

examples of isobars, or lines
showing the variation of
properties at constant pressure.
 The pressure varies linearly
with the temperature at
constant volume, and
extrapolates to zero at T = 0
(−273.15°C).

❑ The lines in this diagram are

isochores, or lines showing the
variation of properties at
constant volume.
The Perfect Gas Equation of State

 The empirical observations can be combined into single expression:

𝑝𝑉 = constant × 𝑛𝑇
 The constant of proportionality, which is found experimentally to be the
same for all gases, is denoted R and are called the (molar) gas
constant. The resulting expression:
𝑝𝑉 = 𝑛𝑅𝑇
(the perfect gas law of the perfect gas equation of state)
 A gas that obeys the equation exactly under all conditions is called a
perfect gas (or ideal gas).
The Molar Gas Constant

R
8.31447 J K-1 mol-1
8.20574 x 10-2 dm3 atm K-1 mol-1
8.31447 x 10-2 dm3 bar K-1 mol-1
8.31447 Pa m3 K-1 mol-1
62.364 dm3 Torr K-1 mol-1
1.98721 cal K-1 mol-1
  When dealing with gaseous
mixtures, we often need to
MIXTURE OF know the contribution that each
GASES component makes to the total
pressure of the sample.
Partial Pressure

 The partial pressure is the pressure that each gas would

exert if it occupied the same container alone at the same
temperature.
𝑝𝐽 = 𝑥𝐽 𝑝
where;
𝑝𝐽 = the partial pressure of gas 𝐽
𝑥𝐽 = the mole fraction of the component 𝐽
𝑝 = the total pressure exerted by a mixture of gases
Mole Fraction

𝑛𝐴
 𝑥𝐴 = ;
𝑛
 𝑛 = 𝑛𝐴 + 𝑛𝐵 + 𝑛𝐶 + ⋯ (total number of moles)

 The sum of mole fractions of all components in a mixture is

equal to 1.
𝑥𝐴 + 𝑥𝐵 + ⋯ = 1
Dalton’s Law

 The pressure exerted by a mixture of gases is the sum of

the pressures that each one would exert if it occupied the
container alone.
𝑝 = 𝑝𝐴 + 𝑝𝐵 + ⋯

 Therefore,
𝑝 = 𝑝𝐴 + 𝑝𝐵 + ⋯ = 𝑥𝐴 + 𝑥𝐵 + ⋯ 𝑝
PRACTICE EXERCISES

1. In an industrial process, nitrogen gas is introduced into a vessel of constant

volume at a pressure of 100 atm and a temperature of 300 K. The gas is then
heated to 500 K. What pressure would the gas exert, assuming that it behaved as
a perfect gas?
2. The mass percentage composition of dry air at sea level is approximately N2:
75.5; O2: 23.2; Ar: 1.3. What is the partial pressure of each component when the
total pressure is 1.20 atm?
3. A Dumas experiment to determine molar mass is conducted in which a gas
sample’s P, θ, and V are determined. If a 1.08-g sample is held in 0.250 dm3 at
303K and 101.3 kPa:
a. What would the sample’s volume be at 273.15 K, at constant pressure?
b. What is the molar mass of the sample?
ANSWERS TO PRACTICE EXERCISES

1. In an industrial process, nitrogen gas is introduced into a vessel of constant

volume at a pressure of 100 atm and a temperature of 300 K. The gas is then
heated to 500 K. What pressure would the gas exert, assuming that it behaved as
a perfect gas?
Given
n P V T
Initial Same 100 atm Same 300 K
Final Same ? Same 500 K

Solution
𝑃𝑉 = 𝑛𝑅𝑇
𝑃1 𝑉1 𝑃2 𝑉2 𝑃1 𝑉1 𝑃 𝑉
= 𝑅; = 𝑅; = 𝑛2 𝑇2
𝑛1 𝑇1 𝑛2 𝑇2 𝑛1 𝑇1 2 2
Cancelation of volumes (because V1 = V2) and amounts (because n1=n2) on each side of
the combined gas law results in

𝑃1 𝑉1 𝑃2 𝑉2
=
𝑛1 𝑇1 𝑛2 𝑇2

Which can be rearranged into

𝑇2
𝑃2 = × 𝑃1
𝑇1

Substitution of the data then gives

500 𝐾
𝑃2 = × 100 𝑎𝑡𝑚 = 𝟏𝟔𝟕 𝒂𝒕𝒎
300 𝐾
2. The mass percentage composition of dry air at sea level is approximately N2: 75.5;
O2: 23.2; Ar: 1.3. What is the partial pressure of each component when the total
pressure is 1.20 atm?

Solution
Partial pressures are defined by

𝑝𝐽 = 𝑥𝐽 𝑝

The mole fractions are independent of the total mass of the sample, so choose the
latter as to be exactly 100 g.

The amount of each type of atom or molecule present in 100 g air are, in which the
masses of N2, O2, and Ar are 75.5g, 23.2g, and 1.3g, respectively, are

N2 O2 Ar

Mole fraction 0.780 0.210 0.0096

Partial pressure/atm 0.936 0.252 0.0115

3. A Dumas experiment to determine molar mass is conducted in which a gas
sample’s P, θ, and V are determined. If a 1.08-g sample is held in 0.250 dm3 at 303K
and 101.3 kPa:
a. What would the sample’s volume be at 273.15 K, at constant pressure?
b. What is the molar mass of the sample?