Physical behavior of gases

Kinetic theory

This is useful in accounting for the known properties of gases, liquids and solids. The ideas underlying
the kinetic theory, may be summarized as follows:

(a) Matter is made up of atoms/small particles/molecules

(b) The particles in a gas are in continuous rapid random motion in straight line in every direction
and them colliding with each other and with the walls of the container. The pressure exerted by
the gas on the container wall is due to bombardment by moving particles.
(c) The particles in a gas are separated from each other by distances which are large compared to
the size of the particles (particles in a gas are very far apart and they are very small)
(d) Collision of gas particles are regarded as being perfectly elastic (such that there is no loss in
kinetic energy)

Gas laws

The following laws were formulated from results of the experimental observation in the behavior of
gases.

Gay Lussac’s law of combining volumes

States that “when gases combine together at a given temperature and pressure, the do so in
volumes which bear a simple ratio to each other and to the volume of the product if it is a gas

Example 1
40 cm3 of oxygen was added to 30 cm3 of carbon monoxide and the mixture ignited. What is the
volume and composition of the resulting mixture? (All volumes measured at the same temperature
and pressure).

2CO (g) + O2 (g)  2CO2 (g)

2 mole 1 mole 2 moles

 2 vol. 1 vol. 2 vol. (Gay-Lussac's Law)

30 cm3 15 cm3 30 cm3 (volume ratio)

The volume of CO2 produced is the same as that of CO used up, i.e. 30 cm3 of CO2 are produced.

15 cm3 of the 40 cm3 of oxygen are used up in the reaction, i.e. 25 cm3 of oxygen remain un reacted

30 cm3 of carbon dioxide produced and 25cm3 of un reacted oxygen give total volume is 55 cm3.

Trial 1
10 cm3 of a gaseous hydrocarbon were mixed with 90 cm3 of oxygen and sparked. The resulting volume
at r.t.p. was 70 cm3, which reduced to 30 cm3 on shaking with sodium hydroxide. Find the empirical
formula of the hydrocarbon.

The physical behavior of gases is described by four gas laws which include

1. Boyles’ law
2. Charles law
3. Daltons law of partial pressures
4. Graham’s law of diffusion

Boyles’ law

It state that the volume of a given mass of a gas is inversely proportional to its pressure at constant
temperature

PV =K or PV = constant.

It follows that P1V1 = P2V2

A graph of pressure versus volume

Pressure

Volume

A graph of pressure against inverse of volume gives a straight line

Pressure

1
𝑉
Charles’ Law

It states that the volume of a given mass of a gas is directly proportion to its temperature at
constant pressure.

V =KT or = constant.

It follows that =

Graphically

V/m3

-2730C 00C T/0C

0K 273K

NB: The units of temperature in all gas laws are Kelvin. However, units of pressure and volume vary,
although must be the same in a given situation.

Pressure law

It is a modified version of Charles law. it states that pressure of a given mass of a gas is directly
proportional to its temperature at constant volume.

P =KT or = constant.

It follows that =

The Ideal gas equation

Boyle’s law and Charles’ laws can be combined to give a single equation which represents the
relationship between, volume, pressure and temperature of a given mass of a gas.

That is, = constant

When the quantity of the gas is 1 mole, the constant K is referred to as a molar gas constant,
represented as R
For 1 mole of a gas PV = RT

For n moles of a gas

PV = nRT (the ideal gas equation)

Conditions at “standard temperature and pressure (s.t.p)

Temperature = 273K or 00C

Pressure = 760mmHg or 1 atmosphere or 101325 Pascal

Molar volume of a gas (volume occupied by 1 mole of a gas) = 22.4dm3 or 22400cm3

Conditions at “room temperature and pressure (r.t.p)

Temperature = 278K or 250C

Pressure = 760mmHg or 1 atmosphere or 101325 atmospheres

Molar volume of a gas (volume occupied by 1 mole of a gas) = 24dm3 or 24000cm3

NB. When using ideal gas equation PV =nRT, pressure, and volume must be changed to Pascal and
m3 while the unit of temperature must be in Kelvin.

Example 2

A certain mass of a gas occupies a volume of 24dm3 at 180C and a pressure of 100.4kPa. Calculate
the volume of a gas at s.t.p.

From = constant

V = 22.31dm3

Example 3

1.18g of a compound on vaporization occupied 300cm3 at s.t.p.

(a) Calculate the relative molecular mass of P.

300cm3 weigh 1.18g

22400cm3 weigh =88

 Trial 2

0.13g of P occupies 112 cm3 at s.t.p

Calculate the formula mass of P

Trial 3

When 0.225g of T was vaporized at 1270C and 760mmH, it occupied 119.11cm3. (Molar volume at
s.t.p is 22.4dm3).

(i) calculate the molecular mass of T

Trial 4

When vaporized 0.1g of a compound A occupied 54.5cm3 at 2080C and 98.3kPa; determine the
molecular formula of A

Deviation from Ideality

Ideal gases are those that obey ideal gas equation. These gases are not common and most gases tend to
deviate from ideality. A gas is said to be ideal (perfect) if

(i) occupies a negligible volume

(ii) when there is no forces of attraction between its molecules.

Real gases

These do not obey the ideal gas law exactly because at high pressure and low temperature the volume
occupied by gas molecules and the forces of attraction between the molecules is not negligible.

Plot of PV against pressure give a graph below:

O2
PV NH3
H2
Ideal

Pressure

NB. The higher the intermolecular forces the higher the deviation, e.g. in NH3.
Correction of volume and Pressure for the real gas to account for intermolecular forces and volume

To account for molecular volume and intermolecular forces J.H. Vander Waal proposed that

(i) The volume of gas molecules reduces the actual volume of the container the molecules are left to
move i.e. the volume of the container is not the volume in which molecules can move. The actual
volume open to them is less than that of the container. For this reason Van der Waal wrote the
volume of the gas as (V-nb) where n is the number of moles of a gas and b is the volume the volume
that is no longer available to each mole.

(ii) Intermolecular attraction reduces the pressure the gas exerts. Therefore, if the real pressure is less
than the ideal, this correction is added to the real pressure to give a value closer to ideal figure. Van
der Waal wrote the corrected pressure as (P+ )

Putting the volume and pressure in Ideal gas equation give Van der Waal equation
(P+ )(V-nb) = nRT
For 1mole,
(P+ )(V-b) =RT
Where a and b are constant.

A plot of a graph of pressure versus volume at different temperatures give lines called isotherms shown
below.

High temperature
Tc, the critical isotherm
low temperature

Region of equilibrium volume

between liquid and gas
(gas liquefy)

NB. The critical isotherm marks the border between gases and liquids. The temperature of critical
isotherm is called critical temperature, Tc. Above; Tc a gas will not liquefied no matter how high the
pressure. Each gas has its own critical temperature because the strength of the intermolecular forces in
each gas are different. Below the critical temperature a gas will be liquefied when the pressure is high
enough.
Trial 5
The curves below show a plot of pressure against molar volume at different temperatures of carbon
dioxide

GE C A
Pressure

B
D
H I J F

Molar volume

(a) State the curve which represent the highest temperature (1mark)
(b) What do the following lines represent
(i) HI (ii) GH
(c) Explain what is meant by the term critical temperature
(ii) Draw a sketch on the graph a line that represent isotherm of critical temperature.

Trial 6
(a) The diagram in figure 1 shows isotherms of a gas.

Pressure

321K
304K
B 286K
C
Molar volume

(i) What is the critical temperature

(ii) Which isotherm almost represent the behavior of an Ideal gas
(iii) What does the region ABC represent
(b) State one condition necessary for liquefying a gas.
Graham’s Law of gaseous diffusion and effusion
Diffusion is the movement of particles from a region of high concentration to a region of low
concentration.

Graham’s Law of diffusion of gases state that the relative rates of diffusion of gases, under the same
conditions, are inversely proportional to the square roots of their densities.

Comparing the rate of diffusion of gases A and B

=
where r = rate of diffusion, = density

or =
where, M = molar mass and = ’
Vm= molar volume
Graham’ Law also applies to gaseous effusion. Effusion is the passage of a gas through a very small hole
into a vacuum.
Example 4
50cm3 of a gas A effuse through a tiny aperture in 146s and the same volume of carbon dioxide effuse
under the same condition in 115s.Calculate the molar mass of A.

solution
⁄
= =
⁄

(1.27)2 =
the molar mass of A, MA =71

(ii) A gaseous Alkane diffuses through a porous partition at a rate of 2.56cm3s-1. Helium
diffuses through the same partition under the same conditions at a rate of 8.49cm3s-1.
What is the molar mass of Alkane? What is the its molecular formula a

= =√

The molar mass of alkane = 44

CnH2n+2 = 44
n =3
molecular formula of alkane = C3H8
 Trial 7
(a) (i) State Graham’s Law. (2marks)
(ii) Oxygen diffuses through a small hole 0.935 times faster than gas X. Calculate the relative
molecular mass of X (4marks)

Trial 8
(a) A gaseous compound contains 44.4% carbon, 51.9% nitrogen and hydrogen. Determine
empirical formula of X.
(b) 50ml of X diffuses through a porous plug in 25 second. Under similar conditions, the same
volume of hydrogen gas diffuses in 6.8 seconds. Calculate
(i) the molecular mass of X
(ii) The molecular formula of X

Dalton’s Law of partial Pressure

The total pressure exerted by a mixture of gases that do not react chemically is the sum of the pressure
that the individual gases would exert if they were to occupy the same volume alone.

In symbols, for a mixture of gases A and B, the total pressure (Pt) is given by

Pt = PA + PB

The mole fraction of a gas A, in the mixture is given by

XA =

Example 5

4.0dm3 of oxygen at a pressure of 400kPa and 1dm3 of nitrogen at 200kP were introduced into a
2.00dm3 vessel. What is the total pressure in the vessel?

Solution

When oxygen contracts from 4.00dm3 to 2.00dm3 the pressure increases to

400 x = 800kPa

The partial pressure of oxygen = 800kPa

When nitrogen expand from 1.0dm3 to 2.0dm3, the pressure decreases from 200kPa to

200 x = 100kPa

The partial pressure of nitrogen = 100kPa

Total pressure = P(O2) + P(NH3)

= 800+ 100 = 900kPa

the total pressure = 900kPa.

Trial 9

(a) State what is meant by the term an ideal gas. (01 mark)
(b) Explain how liquefaction of a gas can be affected by
(i) Pressure (2 ½ marks)
(ii) Temperature (2 ½ marks)
(c) The curve below shows deviation of some gases from ideal behaviours.

(i) State why hydrogen shows a small deviation from ideal behavior compared to other gases (1 ½
marks)
(ii) Compared to deviations of oxygen and carbon dioxide from ideal behavior. (2 ½ marks)
Solutions to trials in chapter 1

Trial 1
Volume of excess oxygen = 30cm3. i.e. the volume that remained un absorbed by KOH
Volume of oxygen that reacted = 90-30 = 60cm3
Volume of CO2 = volume absorbed by KOH
= (70-30) = 40cm3
Reaction equation
CxHy (g) + (x+ ) O2 → XCO2(g) + H2O (l)
volumes 10cm3 60cm3 40cm3
Volume ratio 1 6 4
 x= 4
 (x+ ) =6; y= 8
 Empirical formula of Hydrocarbon = C4H8

Trial 3
Formula mass of P = 26
Trial 1.3 (2000/1/13b)
Volume at s.t.p
=

V = 81.3 cm3

Molecular mass of T
81.3cm3 weighs 0.225g
22400cm3 weigh

= 62

molecular mass of T = 62

Trial 4
Formula mass = 74.6

Trial 5
(a) AB
(b) HI: equilibrium between a gas and a liquid (change in volume at constant pressure)
(ii) GH: represents a line of change in pressure at constant volume
Trial 6

(a)(i) 3040C

(ii) 3210C

(iii) Equilibrium between liquid and vapour

(c) – Increasing temperature
- Decreasing temperature

Trial 7 :28

Trial 8:28

Trial 9

(a)(i) HCN

(ii) 27

(iii) HCN

Trial 10:

(a) An ideal gas is one that obeys ideal gas equation.

(b) (i) Increasing pressure reduces intermolecular distance which increase intermolecular forces
leading liquefaction
(ii) when the temperature reduces, the molecules lose kinetic energy to an extent that they
cannot overcome intermolecular forces
(c) (i) has low molecular mass and low intermolecular force
(iii) CO2 deviates more than oxygen because has high molecular mass and stronger
intermolecular force.