C H E M I S T R Y

STATES OF MATTER
WHAT IS COMMON IN LPG AND CNG?

What you already know What you will learn

• Behaviour of real gases • Liquefaction of gas • Boiling point

• Compressibility factor • Andrews isotherm • Vapour pressure
• van der Waals gas equation • Liquid state • Viscosity

Conditions for ideal behaviour of real gas

A gas such as carbon monoxide would be most likely to obey the ideal gas law at:
(a) High temperature and high pressure (b) Low temperature and low pressure
(c) High temperature and low pressure (d) Low temperature and high pressure

Solution

At high temperature and low pressure, the intermolecular forces between the gas molecules
become negligible, so does the volume of gas molecules become negligible compared to the
volume available to them at low pressure. Thus, it acts as an ideal gas.
Hence, option (c) is the correct answer.

Liquefaction of Gases

It is the physical conversion of a gas into a liquid state (condensation).

Consider Fig. 1, LPG cylinders are filled with liquefied

petroleum gas while in auto-rikshaw, the cylinder is
filled with compressed natural gas. The common thing
in both the cylinder and auto-rickshaw is liquefied
gas. When we shake the cylinder, we can feel the
liquid inside it because the gas is compressed in
such a way that it gets liquefied.
Fig. 1: Examples for liquefied gas

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Note

Liquefied petroleum gas (LPG) is a blend of light hydrocarbon compounds. It mainly consists of a
mixture of butane (C4H10), propane (C3H8) and a small fraction of some other hydrocarbons.

Why is there a need to liquefy the gas?

Since a gas has an immense expansion ability, it is difficult to transport, store, etc. However the
liquefied gas is,
• Easy to transport
• Easy to store
• Compact, hence occupies lesser volume
How can we liquefy a gas?
We know that the distance between the molecules is larger in a gas, as there is a negligible force of
attraction. If we increase the pressure and decrease the temperature, the force of attraction starts
dominating, i.e., the thermal energy decreases and the molecules come close to each other and
hence, we can liquefy the gas as in Fig. 2.

Decreasing T/
Increasing P

Fig. 2: Liquefaction of gas

Conditions for liquefaction

A gas such as carbon monoxide would be most likely be liquified at:

(a) High temperature and high pressure (b) Low temperature and low pressure
(c) High temperature and low pressure (d) Low temperature and high pressure

Solution

At low temperature and high pressure, the kinetic energy of the gas molecules decreases and the
attractive forces become dominant. Therefore, it can be liquefied easily.
Hence, option (d) is the correct answer.

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Based on liquefaction

The value of van der Waals constant (a) for gases O2, N2, NH3 and CH4 is x, y, z, and c, respectively,
where z > c > y > x. Which of the following gases can most easily be liquefied?
(a) O2 (b) N2 (c) NH3 (d) CH4

Solution

Higher the value of van der Waals constant (a) for a gas, easier will be the liquefaction since ‘a’
stands for coefficient of attraction. NH3 has the higher value for van der Waals constant a, so it will
be liquefied easily.
Hence, option (c) is the correct answer.

• Higher the value of a, and lower the value of b, easier will be the liquefaction.
• If the order of value of a or b is not given, then the gas that can form a hydrogen bonding
will be liquefied easily.

Will a decrease in temperature and an increase in pressure always result in the liquefaction of
gas?
No, a decrease in temperature and an increase in pressure do not always result in the liquefaction
of gas. The details can be understood with the help of Andrews isotherm. According to Andrews
isotherm liquefaction will not occur at extremely high temperatures, even if the pressure applied is
very high because of the higher kinetic energy of the gas molecules. Therefore, temperature plays
a major role in liquefaction.

NEET BOARDS
Andrews Isotherm

Andrews plotted the P-V-T relationship (isotherms) I

of CO2. H
Isotherms are the curves representing changes of
volume and pressure under conditions of constant P3 G
Pressure (atm)

temperature (constant temperature plot) as in Fig. 3.

O
We know that when temperature decreases and 73
(Pc) T5
pressure increases, liquefaction occurs. D
P2 F E J
However, at extremely high temperatures, if we T4
increase the pressure again and again, liquefaction T3
C T2
will not occur because of the higher kinetic energy P1
B T1
of the gas molecules due to high temperature.
A
Therefore, temperature plays a major role in
liquefaction. V3 Vc V2 V1
At T = 50 °C (T5), CO2 behaves like an ideal gas Volume (L)
because the plot is the same as the one for Boyle’s Fig. 3: Isotherms of CO2
law. (Where T1 < T2 < T3 < T4 < T5)

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For a better understanding of the curves in Fig. 3, the plots can be divided into three parts.

Part 1
Consider the isotherm obtained at a temperature of
13.1 °C (T1) as shown in Fig. 4. There are three regions

Pressure (atm)
AB, BC, and CD, where region AB is the gaseous
phase, region CD is the liquid phase, and region
BC is the liquid-gas equilibrium phase.
At point B, the liquefaction begins which causes D
a rapid decrease in the volume since the liquid
occupies less volume than gas and ends at point liquid C B gas T1
C at a constant pressure of P1. Beyond C, when we P1 (13.1 °C)
l g A

⥮
increase the pressure, there is less decrease in the
volume because the liquids are less compressible V1
than gas. So corresponding to CD, the compression Volume (L)
of liquid at a constant temperature occurs.
Fig. 4: Andrews isotherm of CO2 at 13.1 °C

Consider the isotherm obtained at 21.5 °C as shown

Pressure (atm)

in Fig. 5. We can see that the curve looks the same

as earlier. Since the temperature is more than the
first case, liquefaction occurs at a higher pressure
because of the higher kinetic energy acquired by D F E T2 > T1
P2
the molecules. T2 (21.5 °C)
Also from the Fig. 5, we can see that the region P1 C B
EF is smaller than the region BC, i.e., the liquid-gas T1
equilibrium phase becomes narrower. A
V2 V1
Volume (L)
Fig. 5: Isotherm of CO2 at 21.5 °C

Critical point
Part 2 (Point of inflection)
Pressure (atm)

The given isotherm at 30.98 °C has much importance

as there is no region, instead there is a point O O Tc = 30.98 °C
73
for liquid-gas equilibrium at a pressure of 73 atm. (Pc) liquid
Therefore, this point is known as the critical point or
point of inflection. Also, there is no rapid decrease
in the volume at this temperature as in the previous
l g gas
⥮

two cases. So, when the pressure of gas increases,

the volume decreases gradually and reaches a
point where the liquid-gas equilibrium exists and Vc
then condenses immediately.
Volume (L)
Fig. 6: Isotherm of CO2 at 30.98 °C

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Critical point is the point where the horizontal part of the isotherm merges into one point. The
pressure and the volume at this point is known as critical pressure and critical volume, and the
temperature at which such isotherm is obtained is known as critical temperature.
Critical temperature (Tc): It is the temperature above which the gas cannot be liquefied, no matter
how high is the pressure applied on the gas.
Critical pressure (Pc): Critical pressure is the minimum pressure that must be applied on a gas at
its critical temperature to just liquefy it.
Critical Volume (Vc): Critical volume is the volume of 1 mole of a gas at Tc and Pc.

I
H
T5 (50 °C)

Pressure (atm)
Part 3
T4 (31.1 °C)
The given isotherms at 31.1 °C and 50 °C look O
73
like that of an ideal gas. The gas cannot be (Pc)
liquified beyond the critical temperature of
the gas even if the pressure is very high. J

Vc
Volume (L)
Fig. 7: Isotherm of CO2 at higher temperatures

• The critical temperature varies with gases.

• When the critical temperature increases, the maxima of the curve increases accordingly.
• Higher the critical temperature, easier it is to liquefy.

∝ Intermolecular ∝ Ease of
Tc
forces liquefaction

• The gases that have Z > 1 have a low critical temperature, so they are difficult to liquefy.
• Higher the a, and lower the b, higher will be the Tc, so easier will be the liquefaction,
where a and b are the van der Waals constants.

Critical constants

Tc, Pc, and Vc are collectively known as critical constants which are calculated using the following
formulas:
Vc = 3b
a
Pc = .....(1)
27b2
8a
Tc =
27Rb

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Critical compressibility factor (Zc)

Critical compressibility factor (Zc) is the compressibility factor at the critical point.
Pc Vc .....(2)
Z=
RTc
Substituting (1) in (2),
a × 3b × 27Rb
Z=
27b2 × R × 8a
3
Z=
8
Z = 0.375
For a gas to be liquefied, Z should be less than 1, i.e., essentially true since Z = 0.375.

Boyle’s temperature

Boyle’s temperature is the temperature at which a real gas behaves like an ideal gas under low
pressure conditions.

a
Tb =
Rb

Note

8a a
The ratio of Tc and Tb = :
27Rb Rb
8
= :1
27
= 8 : 27

Based on critical temperature and Boyle’s temperature

Find the Tc and Tb for CO2 gas, where a = 3.658 bar L2 mol −2 and b = 0.04286 L mol−1.

Solution

Given,
a = 3.658 bar L2 mol −2
b = 0.04286 L mol−1
We know, R = 0.08314 L bar K−1 mol −1
Putting the values in expression of Tc and Tb,

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8a
Tc =
27Rb
8 × 3.658 bar L2 mol −2
Tc =
27 × 0.08314 L bar K −1 mol −1 × 0.04286 L mol −1
Tc = 304.16 K

a
Tb =
Rb
3.658 bar L2 mol −2
Tb =
0.08314 L bar K −1 mol −1 × 0.04286 Lmol −1
Tb = 1026.5 K

Due to the higher value of Tb than Tc, we can say that CO2 behaves like an ideal gas at an appreciable
range of pressure.
Hence, the values of Tc and Tb for CO2 gas are 304.16 K and 1026.5 K, respectively.

Based on liquefaction

‘a’ and ‘b’ are the van der Waals constants for gases. Why is chlorine more easily liquefied than
ethane?
(a) ‘a’ for Cl2 < ‘a’ for C2H6 but ‘b’ for Cl2 > ‘b’ for C2H6
(b) ’a’ for Cl2 > ‘a’ for C2H6 but ‘b’ for Cl2 < ‘b’ for C2H6
(c) ‘a’ and ‘b’ for Cl2 > ‘a’ and ‘b’ for C2H6
(d) ‘a’ and ‘b’ for Cl2 < ‘a’ and ‘b’ for C2H6

Solution

For the gas to be liquefied, the van der Waals constant ‘a’ should be greater and ‘b’ should be lower.
As ‘a’ stands for coefficient of attraction, the gas can be easily liquified when ‘a’ is high since easily
liquefiable gas has greater intermolecular forces of attraction. Also as ‘b’ is the effective volume
of gas molecules, the value of ‘b’ for any gas over a wide range of temperature and pressure
indicates that the gas molecules are incompressible. Therefore higher the value of b, lower will be
the ease of liquefaction. Here, chlorine is easily liquified than ethane, so ‘a’ value of chlorine should
be higher than ‘a’ value of ethane and ‘b’ value of chlorine should be less than ‘b’ value of ethane.
Hence, option (b) is the correct answer.

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Based on the relationship between critical temperature and liquefaction

The critical temperatures of four different gases are mentioned in the table.

Gas Critical temperature

A TC1

B TC2

C TC3

D TC4

Where, TC1 > TC2 > TC3 > TC4

Which of the following can be predicted?
(a) Ease of the liquefaction is minimum in gas D.
(b) Gas A has the maximum value of van der Waals constant ‘a’.
(c) Ease of liquefaction is directly related to the van der Waals constant ‘a’.
(d) All of the above

Solution

Gas D has the minimum critical temperature, so the ease of liquefaction is less.
Gas A has the maximum critical temperature, so the ease of liquefaction is high and its van der
Waals constant ‘a’ is also high since they are directly proportional.
We know that the ease of liquefaction is directly related to the van der Waals constant ‘a’ because
higher the ‘a’ and higher the attraction between molecules, higher will be the liquefaction. So, all
the answers are correct.
Hence, option (d) is the correct answer.

Based on critical constants

The Tc and Pc of a gas are 400 K and 41 atm respectively.

What is the Vc?
400R 150R 41R 300R
(a) (b) (c) (d)
41 41 400 41

Solution

We have,
8a ...(1)
Tc =
27Rb
Substituting Tc = 400 K in (1),

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8a Dividing (4) by (2),

400 =
27Rb b2 a 50 × 27R
8a = ×
b= ...(2) b 27 × 41 a
400 × 27R
50 R ...(5)
a b=
b= 41
50 × 27R
We need to find Vc.
Also, we know that, Vc = 3b ...(6)
a ...(3) Substituting (5) in (6),
Pc =
27b2
3 × 50R
Substituting Pc = 41 atm in (3), Vc =
41
a 150R
41 = Vc =
27b2 41
a ...(4)
b2 = Hence, option (b) is the correct answer.
27 × 41

Order of liquefiability of gases

Which is the correct increasing order of liquefiability of the given gases?

(a) H2 < N2 < CH4 < CO2 (b) H2 < CO2 < CH4 < N2
(c) CO2 < CH4 < N2 < H2 (d) CO2 < CH4 < H2 < N2

Solution

Since none of the given molecules is polar, we need to consider the molecular mass of the molecules
as only forces that exist in non polar molecules is London dispersion force. Higher the molar mass
of the gas molecules, higher the london dispersion forces, so does the van der Waals constant ‘a’.
So, the ease of liquefaction is greater for the gases with high molecular mass.
Here, CO2 has a higher molecular mass followed by CH4, N2, and H2.
Hence, option (a) is the correct answer.

Based on liquefaction

Assertion: Greater the critical temperature, the more difficult it is to liquefy the gas.
Reason: Stronger the intermolecular forces, lower will be the critical temperature of that gas.
(a) Both the assertion and the reason are correct and the reason is the correct explanation of
the assertion.
(b) Both the assertion and the reason are correct, but the reason is not the correct explanation
of the assertion.
(c) The assertion is true but the reason is false.
(d) Both the assertion and the reason are false.

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Solution

We have studied,
Greater the critical temperature, the easier it is to liquefy the gas.
Stronger the intermolecular forces, higher will be the critical temperature of that gas.
Therefore, both the assertion and the reason are false.
Hence, option (d) is the correct answer.

BOARDS
Liquids

• Liquids have a definite volume, but do not have a definite shape.

• They can flow.
• They are less compressible and far denser than gases.
• The intermolecular forces are stronger than the gaseous state, but weaker than the solid state.
Properties of liquids
• Vapour pressure • Condensation
• Boiling point • Vaporisation
• Evaporation • Critical temperature and pressure
• Surface tension • Viscosity
All the properties will be studied in physics in detail. But some of the properties are discussed here
and are as follows:
Vapour pressure: Vapour pressure is defined as the pressure exerted by the vapours in equilibrium
with the liquid in a closed vessel at a given temperature.
Higher vapour pressure corresponds to higher volatility and lower boiling point.

Vapours

Liquid
Fig. 8: Representation of vapour pressure
Consider the liquid in the beaker as in Fig. 8. When it starts vaporizing, the pressure inside starts
to increase and becomes constant after a particular point of time. This pressure is known as the
vapour pressure.
At this stage, the liquid phase will be in equilibrium with the vapour phase.
Boiling point: The temperature at which the vapour pressure of the liquid is equal to the atmospheric
pressure is known as the boiling point.
Higher the vapour pressure, higher will be the volatile behaviour and lower will be the boiling point.
Higher the forces of attraction, higher will be the boiling point of the liquid.

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Vapour pressure vs Boiling point

Normal boiling point

308 K 351.3 K
349.7 K

Vapour pressure (mm Hg)

From Fig. 9, we can see that at a fixed vapour 760 373 K
pressure (say 760 mm Hg), different substances
Diethyl ether
have different boiling points. Higher the forces
of attraction between molecules, higher will Carbon
be the boiling point. Boiling point increases as tetrachloride
the tendency of the particular liquid to undergo Ethyl alcohol
hydrogen bonding increases. Since water has a
higher capability to form hydrogen bonding, it Water
200
has a higher boiling point, whereas diethyl ether
has a low boiling point because of the absence 60 298 K
of hydrogen bonding. 273 373
Temperature (K)
Fig. 9: Plot of temperature vs vapour
pressure of different gases
For a fixed temperature (say 298 K), we can see that water has less vapour pressure and diethyl
ether has high vapour pressure. Higher the vapour pressure, higher will be the volatility of the
liquids.
Surface tension: It is the tendency of the liquid to minimize the surface area so as to decrease
the surface energy. This phenomena is the reason why liquid surfaces show curvature in their
meniscus.
Higher the intermolecular forces of attraction, higher will be the surface tension.
Condensation: Condensation is the change of the physical state of matter from the gaseous phase
into the liquid phase.
Viscosity: Viscosity may be defined as the force of friction between the two layers of a liquid
moving past one another with different velocities. A fluid with large viscosity resists motion because
its molecular makeup gives it a lot of internal friction.

Based on viscosity

Which of the following shows the maximum viscosity?

(a) Ethanol (b) Water (c) Glycerol (d) Ethylene glycol

Solution

Stronger the intermolecular forces of attraction, more will be the viscosity. Since glycerol has the
highest extent of hydrogen bonding of all the above substances, it has the highest viscosity.
Hence, option (c) is the correct answer.

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Note

Why does milk flow faster than honey?

It is because of the difference in the intermolecular forces of attraction. The extent of hydrogen
bonding in honey is higher when compared to milk. This makes honey more thicker, which resists
flow. However, in milk, the extent of hydrogen bonding is less and that makes it flow faster than
honey.

Previous Mindful Question

Can water exist in all the three states simultaneously? If yes, at what temperature and pressure?
Water can exist in all the three states simultaneously at 273.16 K and approx. 611 Pa. A particular
point where the three states exist simultaneously is known as the triple point.

Summary

1. Liquefaction of gases: It is the physical conversion of a gas into a liquid state (condensation).
Why is there a need to liquefy the gas?
• Easy to transport
• Easy to store
• Compact, hence occupies lesser volume
2. Andrews isotherm: Andrews has plotted the P-V-T relationship (isotherms) of CO2 and proved
that the effect of temperature is more significant than the pressure.
(Isotherms are the constant temperature plots).
I
H

Observations P3 G
Pressure (atm)

• At 13.1 °C, liquefaction occurs in the region BC. O

• At 21.5 °C, liquefaction occurs in the region 73
(Pc) T5
EF. D
• At 30.98 °C, liquefaction occurs at the point P2 F E J
O. This point is known as the critical point T4
or point of inflection and the temperature is C T3
P1 T2
known as the critical temperature. B T1
• At 31.1 °C and 50 °C, gas cannot be liquefied. A
V3 Vc V2 V1
Volume (L)
Isotherms of CO2

Conclusions
The gas cannot be liquefied at the temperature greater than the critical temperature, no matter
how much pressure we apply.

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• Critical point is the point where the horizontal part of the isotherm merges into one point. The
pressure and the volume at this point is known as critical pressure and critical volume, and
the temperature at which such isotherm is obtained is known as critical temperature.
• Critical temperature (Tc): It is the temperature above which the gas cannot be liquefied, no
matter how high the pressure is applied on the gas.
• Critical pressure (Pc): Critical pressure is the minimum pressure that must be Vc applied
= 3b on a gas
at its critical temperature to just liquefy it. a
P =
• Critical volume (Vc): Critical volume isVcthe= 3bvolume of 1 mole of a gas at Tc and P
c
27bc
. 2
a 8a
Vc = 3b Pc = 2 Tc =
27b 27Rb
a
Pc = 8a
• Critical compressibility
27b2 factor (Zc): Compressibility
Tc = factor at the critical point is,
27Rb
8a PV
Tc = Z= c c
27Rb RTc

• Boyle’s temperature: It is the temperature at which a real gas behaves like an ideal gas under
low pressure conditions.
a
Tb =
Rb
3. Liquids
• They are less compressible and far denser than gases.
• The intermolecular forces are stronger than in the gaseous state but weaker than in the solid
state.
4. Properties of liquids
• Vapour pressure
• Boiling point
• Evaporation
• Surface tension
• Condensation
• Vaporisation
• Critical temperature and pressure
• Viscosity
Vapour pressure: Vapour pressure is defined as the pressure exerted by the vapour in equilibrium
with the liquid in a closed vessel at a given temperature.
Boiling point: The temperature at which the vapour pressure of the liquid is equal to the atmospheric
pressure.
Surface tension: It is the tendency of the liquid to minimise the surface area so as to decrease the
surface energy.
Condensation: Condensation is the change of the physical state of matter from the gaseous phase
into the liquid phase.
Viscosity: Viscosity may be defined as the force of friction between the two layers of a liquid
moving past one another with different velocities.

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