States of Matter

The Kinetic Theory

Course Outline
 Kinetic Molecular Theory
 Gas Laws
 Pressure
 Volume
 Temperature
 amount of substance
 The Ideal Gas Equation
 limitations in relation to real gases
 Use in determining molar masses
Properties of Gases
 Four (4) measurable properties of a gas
 Volume
 Temperature
 Pressure
 mass, which can be converted into the number
of moles.
Volume of a Gas
 The volume a gas occupies is always the
same as its container because gases
spread out to fill whatever space they are
given.
Pressure of a Gas
 Pressure is defined as force per unit area.
force mass acceleration 
Pressure  
area Area
kg(ms  2 ) 1  2
 2
 kgm s
m
 This is one of the most obvious characteristics of
a gas. A gas exerts force by constantly
bombarding the walls of its container.

 Units of pressure are:

 Pascal = 1Nm-2
 Atmosphere (atm) = 101325 Nm-2
 Torr = 1mmHg
 1 atm = 760 mmHg
 Bar: 1 bar = 105 Pa = 100 kPa
Standard Pressure
 Normal atmospheric pressure at sea level is
referred to as standard pressure.

 1 atm = 760 mmHg

 P=101325 kgm-1s-2 =1 atm

 Therefore 760 mmHg =101325 Pa=1 atm

Measurement of Pressure
 Atmospheric pressure
is usually measured
using a barometer.
The Kinetic Molecular Theory of Gases
 A gas consists of tiny particle, atoms or
molecules in constant random motion.

 The volume of the particles that make up the

gas is negligible, compared to the volume of
the gas as a whole, in other words, their
contribution to the total volume can be
ignored.

 There are no attractive forces between

individual gas particles.
The Kinetic Molecular Theory of Gases
 Collisions of the gas particles with
themselves or with the walls of their
container are elastic, i.e. the total kinetic
energy of the particles is constant at
constant temperature.

 The kinetic energy of the gas particle is

directly proportional with the temperature
of the sample.
The Ideal Gases Laws
 Charles Law: V α T……(Pressure and number of
moles constant)

 The volume of a given mass of an ideal gas

increases or decreases by the same factor as its
temperature on the absolute temperature scale

V1 V2
  V1T2  V2T1
T1 T2
http://www.grc.nasa.gov/WWW/K-12/airplane/aglussac.html
Boyle’s Law
 P α 1/V…….(Temperature and number of moles
constant)

 For a fixed amount of an ideal gas kept at

a fixed temperature, P [pressure] and V
[volume] are inversely proportional (while
one increases, the other decreases

P1V1  P2V2
http://www.grc.nasa.gov/WWW/K-12/airplane/aboyle.html
Avogadro’s Law
 Vα n……(Pressure and Temperature constant)

 Equal volumes of an ideal gas, at the

same temperature and pressure, contain
the same number of particles, or
molecules.

 Therefore the number of molecules in a

specific volume of gas is independent of
the size or mass of the gas molecules.
Avogadro’s Law
V1 V2
  constant
n1 n2
The Ideal Gas Equation
 The Gas Laws combine to give the Ideal
Gas Equation
Dalton’s Law of Partial Pressure
 The total pressure
exerted by a gaseous
mixture is equal to the
sum of the partial
pressures of each
individual component
in a gas mixture.

 The partial pressure of

a gas is the pressure
that gas would exert if
it alone were in a
container.
Dalton’s Law of partial pressure
 Ptotal = P1 + P2 + P3 …etc.

 PV=nRT
nRT
P1 
V
mass
recall no. of moles (n) 
RMM
 mass  RT
P1   
 RMM  V
Mole fraction
 The mole fraction of each component
X is defined as the number of moles of
a species ni, in a mixture, divided by
the total number of moles of the
mixture, ntotal

ni
i 
ntotal
Partial pressure & mole fraction
PtotalV  ntotal RT ............1
RT
Pi  ni ............2
V
ni
Recall  i  , therefore n i   i (ntotal )
n total
substitute in Eqn 2

Pi   i (ntotal ) 
RT
V
Pi   i Ptotal
Deviations from the kinetic
molecular theory
 A real gas deviates from the ideal gas in two
important ways.
 The volume of a real gas molecule is considered to
be negligible
 Real gas molecules have actual volumes.

 There is no force of attraction between gas

particles or between the particles and the
walls of the container.
 Real gas molecules have forces of attraction
between them.

 Real gas molecules approach ideality at low

pressures and high temperatures.
Deviations from the kinetic
molecular theory

A real gas behaves like an ideal gas at:

• High temperatures (when intermolecular forces of
attraction become less significant)
•Low pressures (when molecular volume becomes less
significant)
Deviations from the kinetic
molecular theory
 At high pressures, (low volume) the particles are
attracted to each other slightly.

 Real gases behave more ideally when the pressure is

low and the molecules are far apart, making the
attraction between them very weak.

 At low pressures, the volume that the molecules can

occupy is therefore large. 1
P
V
 The individual gas particles are therefore far apart.
The actual volume of the gas molecules themselves, is
therefore negligible compared to the volume that they
can occupy.

 At high temperature intermolecular forces of

attraction are weaken, hence can be considered to be
negligible.
Densities of Gases
 If we divide both sides of the ideal-gas
equation by V and by RT, we get

PV=nRT
n P

V RT

22
Densities of Gases
n P

 We know that V RT
moles  molecular mass = mass
n  (RMM) = m
 So multiplying both sides by the
molecular mass ( ) gives
m PRMM 

V RT
23
Densities of Gases

 Mass  volume = density

m PRMM 
 So, d 
V RT
Note: One only needs to know the
molecular mass, the pressure, and
the temperature to calculate the
density of a gas.
24
Molecular Mass
 We can manipulate the density equation
to enable us to find the molecular mass of
a gas:
PRMM 
d
RT
Therefore :
dRT
RMM 
P
25
Question 1
 State Dalton’s Law of partial pressure
and define mole fraction. (answer in
notes)

 A mixture of gas, CH4 (0.34 mol),

C6H6(0.14 mol), C2H2(0.76 mol) and
an unknown gas (0.05 mol) has a
total pressure of 1.22 atm. Calculate
the partial pressure of each gas and
the total volume the gas occupies at
51°C.
Solution 1
Pa   a Ptot
na
a 
ntot
ntot  (0.34  0.14  0.76  0.05)  1.29 moles
nCH 4
PCH 4  Ptot 
0.34 moles
1.22 atm   0.32 atm
ntot 1.29 moles
PC6 H 6  0.13 atm
PC2 H 2  0.74 atm
Punknown  0.047 atm

PV  nRT

Vtot 
n tot RT

  
1.29 moles  0.0821 Latm mol 1K 1 (51  273) K 
Ptot 1.22 atm
Vtot  28.13L
Liquids
 Intermolecular forces
 Properties of Liquids
 Surface tension
 Viscosity
 Vapour Pressure
 Phase Diagrams
Intermolecular Forces
 Three types of intermolecular forces in
liquids:
 Dipole-Dipole Forces
 London Dispersion Forces
 Hydrogen Bonding

 The properties of liquids are affected by

the strengths of the intermolecular forces
within the liquid.
Properties of Liquids
 Viscosity:
 the resistance of a liquid to flow.
 Greater the viscosity, the slower a liquid flows.
 Unit of viscosity is the poise (g cm-1 s-1)

 Viscosity is related to how easy liquid

molecules move past one other.

 It depends on the attractive forces between

molecules.
 Also on structural features that might cause
entanglement.
Properties of Liquids
 Viscosity dependent on:
 Molecular weight
 Attractive forces
 Structure, e.g., long molecules can become
entangled.

 Temperature
 At high temperatures, the average kinetic energy
of the molecule increases which enables them to
easily overcome the attractive forces between the
molecules.
 Therefore viscosity decreases.
Surface Tension
 By definition: energy required to increase
the surface area of a liquid by a unit
amount.
 H2O: 7.29 x 10-2 J m-2
 Hg: 4.6 x 10-1 J m-2

Surface molecules
interact with
neighbouring
Interior
molecules only on
molecules
one side.
interact with
molecules on all
Thus, these are
sides.
pulled towards the
interior.
Surface Tension
 The surface molecules are pulled close
together.
 Reducing surface area.
 Form a “skin”
 The "inward" molecular attraction forces
lead to “surface tension”.
 The ability of a water strider to walk on
water and the beading up of water on a
newly waxed car is due to surface tension.
Molecules inside the water
droplet get attracted to each
along the sides and inwards.
Surface Tension

 Cohesive forces: intermolecular forces that bind molecules of the

same type together.

 Adhesive forces: intermolecular forces that bind a substance to a

surface.

 Capillary action: rise of liquids in narrow tubes.

 For water- adhesive forces greater than cohesive forces.

 For mercury-cohesive forces greater than adhesive forces.
Phase Changes
 Phase Diagrams
 Display the state of a substance at various
pressures and temperatures and the places
where equilibria exist between phases.

Interfaces
Triple point
Critical point
Boiling points
Melting points
Sublimation points 37
Phase Diagram of Water

 High critical
temperature and
critical pressure.
 Slope of solid-liquid
line is negative.

38
Phase Diagram of Carbon Dioxide

 Carbon dioxide
cannot exist in the
liquid state at
pressures below 5.11
atm; CO2 sublimes
at normal pressures.
Summary of Liquids
 Intermolecular Forces
 Properties of liquids
 Viscosity
 Surface Tension
 Capillary action
 Boiling Points
 Phase diagrams