CHAPTER 5.

0
STATES OF MATTER

5.1 Gas
5.2 Liquid
5.3 Solid
At the end of the lesson, student should be able to :

(a) Explain the general properties of gas in terms of arrangement of

particle, density and compressibility.
(b) Explain qualitatively the basic assumptions of the kinetic
molecular theory of gases for an ideal gas.
(c) Define gas laws
(i) Boyle’s Law
(ii) Charles’s Law
(iii) Avogadro’s Law
(d) Sketch and interpret the graphs of Boyle’s and Charles’s laws
(e) Perform calculations involving gas laws.
(f) derive ideal gas equation based on the gas laws
(g) perform calculations using the ideal gas equation
(h) determine the molar mass and density of a gas using ideal gas
equation
(i) Define:
 Partial pressure
 Dalton's law
(j) perform calculation using Dalton's law
(k) compare the ideal and non-ideal behaviours of gases in terms
of intermolecular forces and molecular volume
(l) explain the conditions at which real gases approach
the ideal behaviour.
(m) explain qualitatively van der Waals equation and relate the
values of a and b to intermolecular forces and molecular volume
of a gas
 General
Properties
of Gas
 Particles of gas are far apart and fill the available space.

 Gases assume the volume and shape of their containers.

 can be compressed – due to the particles being

so small and are relatively far apart from one another.

 Gases have relatively low densities.

Kinetic – Molecular Theory of Gases

 Describes the behavior of an ideal gas

 Ideal gas : gases which obey the ideal gas

equation (PV = nRT)

The theory is based on the following assumptions:

1) Gas molecules are very tiny that their size are negligible
compared to the volume of the container.
(having mass but no volume)
2) Gas molecules move in straight lines and are at
a constant motion unless they collide.
3) Molecular collisions are elastic – no energy is lost during
collisions.
4) Attractive and repulsive forces between gas particles are
negligible.
5) The average kinetic energy of the particles is proportional
to the absolute temperature.
 The Gas Laws
a) Boyle’s Law :
The volume of fixed amount of gas at constant
temperature is inversely proportional to the gas
pressure

V 
1
P
(no of mole and temperature are constant)

PV = k Where:
k = constant
V = volume
P = pressure
T = temperature
n = number of moles
  at different pressure and volume :

P1 V1 = P2 V2
Where
P1 = initial pressure
V1 = initial volume
P2 = final pressure
V2 = final volume
Graph of P versus V Graph of P versus 1
V
P
P

1
V V
pressure is inversely pressure is directly
proportional to volume proportional to 1
volume
 Graph of PV versus P

PV

PV = constant

P
Example 1

A sample of chlorine gas occupies a volume of 2 L at a pressure

of 1 atm. Calculate the pressure of the gas if the volume is
increased to 5 L at constant temperature.

0.4 atm
 Example 2

The pressure of a sample of hydrogen gas in a 50.0 mL container is

765 mmHg. The sample is then transferred into another container and
the measured pressure is 825 mmHg. What is the volume of the second
container?

46.36 mL
a) Charles’s Law :
The volume of a fixed amount of gas at
constant pressure is directly proportional to the
absolute temperature of the gas (in Kelvin).

V  T (no of mole and pressure constant)

V
=k Where :
T
k = constant
T = absolute temperature (K)
V = volume
 At different volume and temperature:

T = absolute temperature
in Kelvin (K)
V1 V2

T1 T2 T(K) = T°C + 273.15

Where V1 = initial volume

T1 = initial temperature
V2 = final volume
T2 = final temperature
 Graph of volume versus temperature :

V V

0 T(K) -273.15
T(0C)
 Example 1

A sample of carbon monoxide gas occupies 3.2 L

At 125 °C. The sample is then cooled at constant
pressure until it contracts to 1.54 L. Calculate the
final temperature in degree Celsius.

-81.54 °C
 Example 2

A sample of gas trapped in a capillary tube by a

plug of mercury at 22 oC has a volume of 4.5 mL.
Calculate the volume of the gas when the capillary
tube is heated to 60 oC.

5.08 mL
 The Combination of Boyle’s and Charles’s Law
1
Boyle’s law : V
P
Charles’s law : VT
T
V
P
T
V= k
P
PV
=k
T

P1V1 =
P2 V2
T1 T2
 Example 1

A sample of methane gas occupies 25.5 L at

298.15 K and 153.3 kPa. Find its volume at STP.

Ans : 35.32 L
Example 2

2 moles of chlorine gas kept in a cylinder with

piston occupies a volume of 49 L. When another 3
moles of chlorine gas is pumped into the cylinder
at constant temperature and pressure the piston
moves upwards to accommodate the gas.
Calculate the final volume of the gas.
Ans : 73.5 L
C) Avogadro’s Law
At constant pressure and temperature, the volume of a
gas is directly proportional to the number of moles of the
gas present
V  n (P and T are constant)
V = k n
V
=k
n
where :
n = number of moles
V1 V2 k= constant

n1 n2
Combination of Boyle's law, Charles's law and Avogadro's law :
1
Boyle's Law: V
P
Charles' Law: VT
Avogadro's Law: Vn
nT
V Where :
P
R = gas constant
V=R
nT
T = Temperature(K)
P
n = number of moles
PV = nRT V = volume
Ideal gas equation P = Pressure
Value of R depend on the unit of pressure and
volume used in the equation.
unit of unit of value of unit of R
pressure volume R
atm L or dm3 0.08206 L atm mol1 K1

Nm2 m3 8.314 Nm mol1 K1

or
J mol1 K1
Pa
Example 1

A steel gas tank has a volume of 275 L and is filled

with 0.485 kg of O2. Calculate the pressure of O2 if
the temperature is 29 oC.

Ans : 1.36 atm

Example 2

A sample of chlorine gas is kept in a 5.0 L container

at 228 torr and 27 °C. How many moles of gas are
present in the sample?

Ans : 0.06 mol

 MOLAR MASS and DENSITY CALCULATION

 Molar mass and density of a gas can be calculated

by rearranging the Ideal Gas
Equation:
PV  nRT
 m  m
PV=   RT where: n =
 Mr  Mr
mRT Mr = molar mass of a gas
Mr =
PV
Example 1

Calculate the density of ammonia (NH3) in grams

per litre (g/L) at 752 mmHg and 55 C.

Ans : 0.625 gL-1

Example 2

A chemist has synthesized a greenish-yellow compound of

chlorine and oxygen and finds that its density is 7.71 g L-1
at 36 °C and 2.88 atm. Calculate the molar mass of the
compound.

Ans : 67.9 gmol-1

Example 3

What mass of KClO3 is required to produce

2.40 L O2 gas that measured at a pressure of
1 atm and a temperature of 26 oC. The
reaction equation is
2KClO3(s) 2KCl(s) + 3O2(g)

Ans : 8.0 g
Dalton’s Law of Partial Pressure
The total pressure of mixture of non reacting gases is the
sum of the partial pressures exerted by each of the gas in
the mixture
(Partial pressure is the pressure of individual gas component in a
mixture).

- For a mixture of 3 gases, A,B and C :

PT = PA + PB + PC
 Mole fraction and pressures
Daltons theory allows us to form a relationship
between Mole fractions, partial pressure and a total
pressure.
Consider the following condition at constant T
and V
If P  n RT
A A  
Ptotal  ntotal(RT )
Thus: PA n A ( RT ) PA nA
  
Ptotal ntotal ( RT ) PTotal nTotal

PA  X A Ptotal XA = mole fraction of gas A

Example 1

A gaseous mixture of 7.00 g N2 and 3.21 g CH4 is placed in

a 12.0 L cylinder at 25 oC.

a) What is the partial pressure of each gas?

b) What is the total pressure in the cylinder?
Ans :a) 0.501 atm , 0.41 atm
b) 0.92atm
Example 2

A mixture of gases contains 4.53 moles of neon, 0.82

moles of argon and 2.25 moles of xenon. Calculate the
partial pressure of the gases if the total pressure is 2.15 atm
at a certain temperature.

Ans : P Ne = 1.28 atm,, P Ar = 0.079 atm, P Xe = 0.63 atm,

Example 3

A sample of gas at 5.88 atm contains 1.2 g CH4, 0.4 g H2 and

0.1 g He. Calculate :

a) The partial pressure of CH4, H2 and He in the mixture.

b) What is the partial pressure of CH4 and H2 if He is removed?

Ans : a) P CH4= 1.74 atm,P H2 = 3.92 atm, P He= 0.49 atm

b) P CH4= 1.6 atm,P H2 = 4.28 atm
 One of the applications of Dalton’s Law is to calculate the pressure
of a gas collected over water ( for gases that not soluble in water).

gas gas + water vapour

The gas collected is actually a mixture of the gas and water vapour.

T
P P P
gas H2O

Vapour pressure of water, Pwater = 23.8 torr

 Example 1

Consider the reaction below :

2KClO3 2KCl + 3O2

A sample of 5.45 L of oxygen is collected over water at a total
pressure of 735.5 torr at 25 °C. How many grams of oxygen have
been collected?
(at 25°C, Pwater = 23.8 torr)
Ans : 7.011 g
 Example 2

Excess amount of hydrochloric acid is added to 2.5 g of pure

zinc. The gas produced is collected over water in a gas cylinder
at 28 oC and 100.0 kNm-2. Calculate :

a) the number of mole of gas produced in the reaction.

b) the volume of gas collected in the cylinder.
Ans : a) 0.038 mol
b) 0.95 L
Ideal gas
any gas that obeys the ideal gas
equation and has the properties as
outlined by the Kinetic Molecular
Theory
 Deviation from Ideal Behavior
real gas (non-ideal gas) : gases which do not obey
ideal gas properties
Real gases do not behave ideally because:
i) gas molecules do have its own volume and they occupy
some space.
ii) gas molecules do have intermolecular forces acting
between them
Reason:
At low pressure:
• To achieve a low pressure, the volume of
a container is increased.
• Thus, the molecules will be far apart from
another, hence the intermolecular forces
can be neglected.
• At a low pressure the size of a container is
extremely large compared to the size of
molecules, thus the size of molecules can
be neglected.
Reason :
At low pressure
• At low pressure, the volume of a container is
very large
• Thus the molecules will be more far apart
from one another. Hence the intermolecular
forces can be neglected.
• At low pressure, the volume of the container
is extremely large compared to the size of
the molecules, thus the volume can be
neglected
 Graph PV/RT against P for N2
at different temperatures
PV
RT 273K
The lines
approach the
600K ideal line when
1000K T increases

The value approaches 1.0

at a very low pressure

9
 Van der Waal’s Equation
 Since real gas does not exhibit ideal gas behavior
at high pressure and low temperature :
 the ideal gas equation (PV=nRT) needs to be
adjusted
 adjusting the equation, two parameters need to
be reconsidered :
√ attractive forces between the gas molecules
√ volume of the gas molecules
 a) Attractive Forces Between Molecules
 Attractive forces which act between the gas molecules will :
 make the molecules move slower
 give less impact to the wall
 pressure exerted by the real gas is less compared to the ideal
gas
 since Preal < Pideal
2
 the term pressure need to be corrected by adding coefficient n a
V2

n=number of moles

P ideal = P real + n2a a=correcting factor for

pressure
V2 V = volume of container
(b) Volume of the gas molecules

• Since the gas occupy a sizeable portion

of a container, the space in which the
molecules are able to move are less
than the volume of the container.
Vreal < V container
• The correction factor done to the
volume is:
nb v

V = volume

V = Vcontainer - nb n = number of moles

b = size factor
• Referring to the ideal gas equation:

PV = nRT

By replacing these into the equation

P ideal = P real + n2a & V = V container - nb

V2

The van der Waals equation

Value of a :
• a is a positive constant which depends on the
strength of the attractive forces between molecules
• Molecules with a higher value of a have stronger
attractive forces.

Value of b :
• b is a constant to represent the volume occupied
by the molecules.

• Larger molecules have bigger value of b

5.2 Liquids
 At the end of this topic, students should
be able to :

a) Explain the properties of liquids : shape,

volume, surface tension, viscosity, compressibility
and diffusion.
b)Explain vaporization process and condensation
process based on kinetic molecular theory and
intermolecular forces.
c) Define vapour pressure and boiling point
d) Relate :
- intermolecular forces to vapour pressure
- vapour pressure to boiling point
 The properties of Liquids
1. Volume and Shape
 has a definite volume but not a definite shape
√ the particles are arranged closely but not rigidly

√ held together by a strong intermolecular forces

but not strong enough to hold the particles
firmly in place
√ particles are able to move freely
 thus, a liquid flows to fit the shape of its container
and is confined to a certain volume
2. Surface tension
 Surface tension is the amount of energy
required to stretch or increase the surface of
a liquid by a unit area
• Surface tension is caused by the attractive
forces and the direction of the force acting
between
molecules
√ Molecules within a liquid experienced
intermolecular attractive forces in all
directions by their neighbouring molecules
√ however, molecules at the surface are pulled
inwards and sideways from the neighbouring
Fig. 11.8

molecule at
the surface

molecule within
the liquid
√ these intermolecular attractive forces will
pull the molecules into the liquid
√ Thus, cause the surface to stretch and
tighten
√ the stronger the intermolecular attractive
forces, the higher the surface tension
3. Viscosity
 is a measure of the resistance of a liquid
to flow

 the greater the viscosity, the more slowly

the liquid flows.

 Viscosity may be explained in terms of the

intermolecular forces present in a liquid
 The factors affecting the viscosity :
i) The strength of intermolecular forces
Liquids that have strong intermolecular forces have
higher viscosity

ii) The size of the molecules

Liquids with larger size (higher molar mass)
is more viscous because it has stronger
intermolecular forces
iii) The temperature of the liquid
At higher temperature, molecules have
higher
kinetic energy,
 the molecules move faster
 molecules can overcome the intermolecular
attractive forces more easily
 resistance to flow decrease
 Viscosity decrease
4. Compressibility
 in liquid, the particles are packed closely
together
 thus, there is very little empty space
between the molecules
  liquids are much more difficult to
compress than gas
5. Diffusion
 Diffusion is the movement of liquid from one
fluid through another.
 Diffusion can occur in a liquid because molecules
are not tightly packed and can move randomly
around one another.
 Vaporisation Process
 a process in which molecules escape from
liquid into gaseous state through a surface
√ molecules in a liquid moves freely, collide
with each other and posses different
magnitudes of kinetic energy
√ when the kinetic energy is sufficient
enough to overcome the intermolecular
forces acting on them, the molecules will
escape as vapour.
 Factors affecting the rate of vaporization :
√ i) Surface area
~ the surface area , the chances for the
molecules to escape from the surface 
 surface area , evaporation rate 
 √ ii) Temperature
~ temperature , the kinetic energy 
 more molecules have enough energy to
overcome the attractive intermolecular forces
and escape from the surface of the liquid
~ thus evaporation rate 
 Condensation Process
a process whereby gaseous molecules turn to liquid
√ some of the vapour molecules may lose their kinetic
energy during the collision
√ they do not have enough energy to remain as vapour
molecules
√ they reached the surface of the liquid and trapped
by the attractive forces
√ if they cannot overcome the attractive forces,
these vapour molecules return as liquid molecules
√ the process is known as condensation
Pressure exerted by the vapour molecules
on the surface of a liquid is known as the
vapour pressure
 in a closed system :
√ vapour molecules which leaves the surface are
trapped in the close container
√ these vapour molecules are in constant random
motion
√ the molecules strike the wall of container and
exert some pressure
√ As the quantity of molecules in the vapour phase
increase, some molecules may lose energy and
condense
Eventually,
the rate of evaporation = the rate of condensation.
(The system achieved dynamic equilibrium)
√ At equilibrium, the number of vapour molecules
above liquid are constant.
Boiling

• A process in which liquid molecules

change to vapour at a particular
temperature and at an atmospheric
pressure.
• Happens throughout the liquid.
Evaporation
• liquid molecules change to vapour at
any temperature and pressure.
• Occurs only at the surface of a liquid
 Boiling Point - process
• Increasing the temperature will increase in the vapour
pressure.

• As heat is applied, the vapour pressure of a system will

increase until it reaches a point whereby the vapour
pressure of the liquid system is equal to the
atmospheric pressure.

• Boiling occurs and the temperature taken at this point

is known as the boiling point.

• At this point, the change of state from liquid to gas

occurs not only at the surface of the liquid but also in
the inner part of the liquid.

• Bubbles form within the liquid.

 Factors affecting the boiling point:

1. Atmospheric pressure
When the external atmospheric pressure is
low, liquid will boil at a lower temperature

2. Intermolecular forces
A substance with weak intermolecular forces
can easily vapourise and the system requires
less heat to achieve atmospheric pressure,
thus it boils at a lower temperature.
5.3 Solid
 OBJECTIVE…
(a) State the properties of solid.
(b) Explain the process of:
- freezing - sublimation
- melting - deposition
(c) Differentiate between amorphous and crystalline
solids.
(d) Describe the types of bonding and the
interparticle/intermolecular forces involved in the
following crystalline solids using appropriate examples.
i. metallic iii. molecular covalent
ii. ionic iv. giant covalent
 Properties of solid

1.Particles are closely arranged and regularly in order

2. Rigid arrangement- particles can vibrate, rotate about
fixed position and cannot move freely without disrupting
the whole structure.
3. Has definite shape and volume.
4.Has strong forces between the particles.
5. Has high densities.
6. Incompressible.
7.Diffusion within the solid is extremely slow.
In principle, solid, liquid and gas states are
interconvertible

liquid

sublimation

deposition
solid gas 5
 Melting (Fusion) Process
 Solid is changing into a liquid
 When a solid substance is heated :
- its particles gain energy
- therefore able to vibrate more rapidly
- at certain temperature, the kinetic energy is higher
enough to overcome the intermolecular forces of
attraction between solid particles.
– the particles are free to move and the solid start to
melt
• Melting point – the temperature at which solid and
liquid coexist in equilibrium
 Freezing (Solidification) Process

 Liquid is changing into a solid

 when the temperature of a liquid is lowered, the
kinetic energy of the liquid particles decreases
 the liquid particles vibrate at a slower rate
 when the intermolecular forces are strong
enough to hold the particles together in a fixed
and orderly arrangement, the liquid freezes.

Freezing point – a temperature at which the liquid and

solid phases of a substances coexist at equilibrium.
 Sublimation Process
•The process by which a substance changes
directly from solid to the gaseous state without
passing through the liquid state.
•Occurs on solid with weak intermolecular forces
of attraction

Deposition Process
•The process where molecules from vapour state
change to the solid state.
•The opposite process of sublimation
Types of Crystalline Solid
2. Ionic solids
 consist of ions (cation & anion) held together by ionic
bonds
 Physical properties of ionic solid:
- High melting point
- Hard but brittle
- Does not conduct electricity in the solid state but
does conduct electricity in molten state or in
aqueous state.
 Example: NaCl, CsCl
3. Molecular covalent solid
 composed of molecules held together by
intermolecular forces (van der Waals
and/or hydrogen bonds)
 Example : iodine [I2 (s) ]
5.4 Phase Diagram
Learning Outcomes :

At the end of this lesson students should be able to:

(a) Define phase .

(b) Sketch the phase diagram of H2O and CO2.

(c) Define triple point and critical point.

(d) Explain the anomalous behaviour of H2O.

(e) Describe the changes in phase with respect to

i. temperature (at constant pressure)

ii. pressure (at constant temperature).

Phase is a homogeneous part of a system
in contact with other parts of the
system but separated from them by a
well-defined boundary
Phase Diagram is a diagram that describes the
stable phases and phase changes of a
substance as a function of temperature and
pressure
• used to predict the phase that exist under a
certain temperature and pressure
 (i) Phase Diagram of H2O

B C

8/16/11
Regions of the diagram

- The diagram has three main regions :

Solid, liquid and gas

- Each region corresponds to one phase of the substance.

- A particular phase is stable for any combination of pressure

and temperature.

- Any point along a line shows the pressure and temperature

at which the two phases exist in equilibrium.

8/16/11
Important Points
1. Point T :
- Known as the triple point
- Triple point is the point at which the vapour, liquid and
solid states of a substance are in equilibrium.
- Triple point for water is 0.01°C and 0.06 atm.

2. Point C :
- Known as the critical point
- Critical point is the point on a phase diagram at which
the vapour cannot be condensed to a liquid.
- The liquid – gas line ends at the critical point.
- Above the critical point, the liquid cannot be
distinguished from its vapour form.

8/16/11
 (ii) Phase Diagram of CO2
B C

8/16/11
 TRIPLE POINT

 At point T, the triple point; solid, liquid and

vapour are in equilibrium
CO2(s) ⇌ CO2(l) ⇌ CO2(g)

 Triple point for CO2 is at 5.2 atm pressure and

temperature 57 OC.

 for most compounds, the TB curve slant to

the right because solid is denser than liquid

8/16/11
ANOMALOUS BEHAVIOR OF H2O

The phase diagram for water is not typical.

The melting temperature line , TB , slopes
slant to the left (negative slope)
i.e. the melting temperature decreases with
pressure.

• This is because ice is less dense than water, the

solid occupies more space than the liquid. An
increase in pressure, favours the formation of
liquid H2O.( the phase that occupy less space)
Thus, the higher the pressure, the lower the
temperature at which solid water melts.
Exercise:

a) Describe the phase change when carbon

dioxide undergoes isobaric heating at 5.2 atm
pressure
Exercises:
b) Describe the phase change when pressure is
applied to water isothermally at 0.01 C