CH3- PROPERTIES OF GASES AND

VAPOURS
1. Kinetic theory of gases
2. Derivation of the Ideal Gas Law
3. Van der Waals Equation of State for Real Gases
4. The Importance of Triple Point on Phase Diagrams

Dr. Gamal Elhomosy

1. Kinetic theory of gases

The molecules of any gas move continuously at an average speed that

depends on the temperature of the gas. The higher the temperature, the
faster the molecules move, and thus their kinetic energy increases.
1 -Boyle's Law: It states that for a given mass of gas, the pressure of the
gas is inversely proportional to its volume, when the temperature of the
gas is constant.
2- Charles's Law: It states that when a certain mass of gas is heated, the
pressure of the gas increases directly with its temperature, when the
volume of the gas is constant.
3- Dalton's Law of Partial Pressures: "Every gas is a vacuum to every other
gas". This is the way Dalton stated what we now know as his law of
partial pressures. It simply means that each gas present in a mixture of
gases acts independently of the others.
3- Joule's Law: States that the internal energy of a gas does not depend
on the volume of this gas.
1. Kinetic theory of gases

4- Avogadro's Law: It states that equal volumes of gases at the same

temperature and which have the same pressure contain the same number
of molecules. number of molecules in a molecular gram of any gas, and its
value is N  6.023  10 23 molecules.
A

M : The mass per mole – m : the mass of an individual molecule of

the substance by

n : The number of moles contained in a sample of mass Msam,

consisting of N molecules, Avogadro’s number NA as given by
1. Kinetic theory of gases

some assumptions
1. Volume of the molecules negligible compared with volume of the gas.
2. They do not attract each other.
3. They move in continual random motion.
4. The collisions are elastic collisions (no loss of K.E.)
5. Duration of collisions much shorter than time between collisions.
6. Assume a gas consists of point molecules moving about at random,
continually colliding with the container walls.
7. Each collision causes a force on the container and it is the force of
these many impacts that causes the pressure of the gas on the walls.
8. Volume of Gas: Because of motion, gas particles occupy the total
volume of the container, whether it is small or big, and hence the
volume of the container is to be treated as the volume of the gases.
2. Derivation of the Ideal Gas Law

Let us take a cubic container with edge

length L containing N molecules of gas of
molecular mass m, and RMS speed vrms at
temperature T and pressure P. Among these
molecules, N1 has velocity , N2 has
velocity v2 , N3 has velocity v3 , and so on.
Let us concentrate our calculation on a single
molecule among N1 that has resultant
velocity v1 and the component velocities
are vx , v y and vz Therefore,
v 2  vx2  v y2  vz2
1
2. Derivation of the Ideal Gas Law

Therefore, the change of momentum along the x-direction for a single collision,
P  momentum   mvx   mvx   2mvx
the number of collisions per second will be vx 2L
The force F exerted
dP d  mvx    mvx   2mvx  mvx2
F    
dt dt t  2L  L
 
 vx 
2 2
F
Pressure is force per unit area per one molecule P   mv L mv
2
 3
A L L
In which V  L is the volume of the box
3
 2. Derivation of the Ideal Gas Law

we square the velocities before averaging

v 
2 v  v  v  ...  v
2
1
2
2
2
3 2
N
v
 i i
2

N N

root mean square (rms) velocity. vrms  v 2

since the molecules are moving randomly in all directions, only one-
third of their total velocity. So the total pressure exerted
by N molecules 2 2 2
N mv N mvrms N mvrms
P 3
 3

3 L 3 L 3 V
the average translational kinetic energy KE KE  mvrms
2
2
2
2N mvrms 2N
 PV    KE 
3 2 3
2. Derivation of the Ideal Gas Law

The average translational kinetic energy is directly proportional to

temperature: KE  32 k BT
R
constant kB is known as the Boltzmann constant. kB = N = 1.380  10 -23 J/ o K
A

2N mvrms2
2N 2 3 
PV    KE  yields PV  N  B   Nk BT
k T
3 2 3 3 2 
Which is the Ideal Gas law. PV  Nk BT  nRT
Vm: The molar volume of gas
R : The universal gas constant (8.314 J/oK.mole)
(Boltzmann’s constant kB = R = 1.380  10 23 J/ o K )
NA
T: The temperature ( o K )
P: The pressure ( N/m2 = Pa)
V= n Vm : The volume ( m3)
Example 1.1

Calculate the pressure of 1023 gas molecules each of the molecules

having mass m = 10−22 gm and container of volume V= 1000 cm3.
Given vrms  10 5
cm/s
Solution
Number of molecules N = 1023, mass m = 10−22 gm = 10−25 Kg,
volume V= 1000 cm3= 10−3 m3 and vrms  10 cm/sec = 103 m/sec.
5

From the kinetic gas equation,

Pressure
P
N mv 2
    
rms
10 23


10 25
10 3 2

 3.33  10 N / m3
6

3 V 3 10 
3

P = 3.33×106 Pascal
 Mean Free Path of Gas
Molecule

Between two successive collisions, a

molecule travels in a straight line.
“The distance covered by a molecule
between two successive collisions is called the free path”. All the
free paths are not equal.
mean free path. It is denoted by “ ”. Its S.I. unit is m but the
practical unit is angstrom ( oA )
If λ1, λ2, λ3, …, λN are the free paths. mean free path is given
1  2  3  ...   N
 N is a number of collisions
N
 Mean Free Path of Gas
Molecule

Assumptions:
• Molecule with finite radius r (note: point-like particles do not
collide)
• The number density n (number of molecules per unit volume)
is given by n  nV  N V
• Molecules move at an average speed v .
 spatial volume 
dn     number density 
 indicated( blue ) 
  4 r 2  vdt   N V  dn 4 r 2v N
the number of collisions per unit time
 
dt V
that other molecules besides the red one are also moving, the estimated
collision rate should be higher and it can be shown that this mean
collision rate will be larger by 2
 Mean Free Path of Gas Molecule

dn 4 2  r 2v N
 
dt V
V
The average time between collisions, tmean 
(mean free time) 4 2  r 2
vN
V 1
the mean free path   v tmean  
4 2 r N
2
4 2  r 2 nV
kT
or  we used  PV  N kT 
4 2  r2 P
 3. Van der Waals Equation of State for Real Gases

By the ideal gas law, that is, PV = nRT.

 an 2 
 P  2  V  nb   nRT
Van der Waals Equation of
State for Real Gases  V 
The volume is given as (Vm – b), Here ‘b’= volume occupied per mole
Thus, when we substitute the ideal gas law with (Vm – b) = V, it
comes as nRT = P(Vm - b)
The value of P is modified due to intermolecular attraction as
RT = ( P + a/Vm2)(Vm - b)
n : is the number of moles of gases ( n=N/V )
a and b are the constants that are specific to each gas.
Vm: The molar volume of gas, T: The temperature, P: The pressure
V= n Vm : The volume
4.The Importance of Triple Point on Phase Diagrams
4.The Importance of Triple Point on Phase Diagrams

Triple Point of Water

The triple point of water is defined
as the temperature and pressure at
which the three phases of water
coexist in thermodynamic
equilibrium. The triple point of
water is 0.01°C and 611.73 Pa.

Triple point of CO2

The triple point of CO2 is a temperature of -56.6 °C and a pressure of
5.18 bar (5.18×105 Pa ).
4.The Importance of Triple Point on Phase Diagrams

Why doesn’t helium have a triple point?

Helium does not solidify except under extreme pressure even at
extremely low temperatures. At atmospheric pressure, helium gas
does not even condense until the temperature drops to 4.2 °K, only
four degrees above Absolute Zero.
Example 1.2

Calculate the velocity of Hydrogen molecules at N.T.P ( at 20 oC and 1 atm (101.325 kPa) .
given: Density of Hydrogen at N.T.P. ρH = 8.957×10-2 kg/m3. Density of mercury = 13600
kg/m3, g = 9.8 m/s2
Solution
Density of hydrogen = ρH = 8.957×10-2 kg/m3,
Condition N.T.P.: P =1.013×105 Pa & T =20 oC= 293 oK & density of
Mercury = 13600 kg/m3, g = 9.8 m/s2.
2
N m vrms 1  Nm  2 1
P    rms
v   v 2
rms
3 V 3 V  3
3P 3  1.013×10 5 Pa   1842 m / sec
 vrms  
  8.957×10 -2
kg/m 3

velocity of hydrogen molecule is 1842 m/s 0r 1.842 km/s
Example 1.3

The density of a gas is 0.178 kg/m3 at S.T.P. Find the R.M.S. velocity of gas
molecules. By what factor will the velocity of molecules increase at 200
°C?
Solution
S.T.P. : P = 1.013×105Pa & T1= 0 oC= 273 oK , density of oxygen  = 0.178
kg/m3, Temperature = T2 = 200 oC = 473 oK
To Find: r.m.s. speed = v rms( 2 ) v rms( 1 )

3kT1 3 P1 3  1.013×10 5 N/m 2 

vrms( 1 )     1306.6 m / sec
mo o 0.178 kg/m 3

vrms( 2 ) 3kT2 3kT1 T 473

   2  1.316
vrms( 1 ) mo mo T1 273
The r.m.s. velocity of the gas molecule at STP is 1.306 km/s. The r.m.s. velocity
will increase by a factor of 1.316 at 200 °C