1

CHAPTER 10

GASES



2
CONTENT
10.1 Characteristics of Gases
10.2 Pressure
10.3 The Gas Laws
10.4 The Ideal-Gas Equation
10.5 Further Applications of The Ideal Gas Equation
10.6 Gas Mixture and Partial Pressures
10.7 Kinetic-Molecular Theory
10.8 Molecular Effusion and Diffusion
10.9 Real Gases: Deviations from Ideal Behaviour




3
Learning Outcomes
Able to apply the Ideal Gas Law in
calculations involving gaseous system
Able to calculate partial and total pressure
in a mixture of gases (with or without
reaction)
Able to differentiate effusion and diffusion
Able to apply kinetic molecular theory in
problem solving


4
Bonds
HGFGJDF



5
10.1 Characteristics of Gases

Expand spontaneously to fill its container.
Volume of gas = Volume of the container.
Highly compressible.
Form homogeneous mixtures with other gases.
Occupy about 0.1% of the volume of their
containers.




6
10.2 Pressure
Measured properties of a gas:
Temperature (T), Volume (V), Pressure (P)
Pressure, P is the force F acting on an object
per unit area, A.
P = F/A
Our atmosphere exerts a downward
force/pressure on Earths surface because of
gravity.





7
10.2.1 Atmospheric Pressure
and The Barometer
The acceleration produced by earths gravity is
9.8 ms
-2
.
A column of air 1m
2
in cross section has a mass
of roughly 10,000 kg.
The force exerted by this column is:
F = ma where, a = 9.8 m/s
2

= (10,000 kg) (9.8 m/s
2
)
= 1 10
5
kg m/s
2

= 1 10
5
N




8
Cont: 10.2.1 Atmospheric
Pressure and The Barometer
The pressure exerted by the column is the force
divided by its cross-sectional area, A:
P = F/A
= (1 10
5
N)/(1m
2
)

= 1 10
5
N/m
2
= 1 10
5
Pa
= 1 10
2
kPa
SI unit for P = N/m
2
(also called Pascal, Pa)
1Pa = 1 N/m
2
1 bar = 10
5
Pa




9
Cont: 10.2.1 Atmospheric
Pressure and The Barometer

Therefore, the atmospheric pressure at sea level
is about 100kPa.
The actual atmospheric pressure at any location
depends on weather conditions and on altitude.
Atmospheric pressure can be measured by a
mercury barometer.




10
Bonds
HGFGJDF



11
Cont: 10.2.1 Atmospheric
Pressure and The Barometer
Standard atmospheric pressure is the pressure
required to support a column of mercury 760 mm
in height.
Units: 1 atm = 760 mmHg
= 760 torr
= 1.01325 10
5
Pa

SI units: 1 atm = 1.01325 10
5
Pa
Other common units 1 atm = 14.70 psi




12
Bonds
HGFGJDF



13
Example 1
Convert 0.378 atm to: a) torr; b) pascal
(1atm = 760 torrs = 101325 Pa)




torr
atm
torr
atm 271
1
760
357 . 0 =
Pa
atm
Pa
atm 36173
1
101325
357 . 0 =


14
10.2.2 Pressure of Enclosed
Gases and Manometers
Closed-tube manometer
measures pressure below atmospheric pressure.
difference in height of mercury level equals to
pressure of enclosed gas.

Open-tube manometer
measures pressure near atmospheric pressure.
difference in height of mercury level relates to
pressure of enclosed gas.




15
Bonds
HGFGJDF

>


16
Example 2
A vessel connected to an open-end mercury
manometer is filled with gas to a pressure of
0.835 atm. The atmospheric pressure is 755
torr.
a) In which arm of the manometer will the level of
mercury be higher?

b) What is the height difference between the 2 arms
of the manometer?




17
Example 2 (Answer)
a) Since the atmospheric pressure is greater
than the enclosed gas, the level attached to
the gas will be higher.

b) P
gas
= 0.835 atm 760 torr = 635 torr
1atm
P
gas
+ P
h
= P
atm

635 torr + P
h
= 755
P
h
= (755 - 635 ) torrs
= 120 torr = 120 mm Hg




18
10.3 The Gas Law
4 variables are needed to define the physical
condition or state of a gas:

1. Temperature, T
2. Pressure, P
3. Volume,V
4. Number of moles, n

Gas Laws: The equations that relate T, P, V and n.




19
10.3.1 Boyles Law: The
Pressure-Volume Relationship
Molecular Explanation of Boyles Law

A certain mass of gas enclosed in a container of
volume,V exerts a pressure, P.
Gaseous particles hitting the walls of the
container-gives P.
If T is constant - the number of collisions with the
wall remains constant.




20
Cont: 10.3.1 Boyles Law: The
Pressure-Volume Relationship
If the volume of the sample is reduced by
half,V/2, there will be twice as many molecules
per unit volume.
As a result, twice as many molecules strike the
walls in a given period of time. So that the
average force exerted on the walls is doubled.
Hence, when the volume is halved, the
pressure of the gas is doubled.




21
Bonds
HGFGJDF



22
Cont: 10.3.1 Boyles Law: The
Pressure-Volume Relationship
The volume of a fixed quantity of gas
maintained at constant temperature is
inversely proportional to the pressure.
(n,T constant)


PV = k = constant


P
V
1

23
Cont: 10.3.1 Boyles Law: The
Pressure-Volume Relationship





If V
1
and V
2
are the different volumes of a fixed
mass of gas at P
1
and P
2
, then:
P
1
V
1
= P
2
V
2



V
P


24
Example 3
A sample of gas has a volume of 54 ml at
pressure 452 mmHg. What will the
volume be if the pressure is changed to
649 mmHg while the temperature is kept
constant?





25
Example 3 (Answer)

Vol/ ml Pressure/mmHg
Initial(1) 54 452
Final(2) ? 649

P
1
V
1
= P
2
V
2

(452mmHg)(54ml) = (649mmHg)V
2

V
2
= 37.6 ml




26
10.3.2 Charles Law: The
Temperature-Volume Relationship
Molecular Explanation of Charles Law
Raising the temperature of a gas increases the
average speed of its molecules.
The molecules collide with the walls more
frequently and do so with greater impact.
Therefore they drive back the walls, and the
gas occupies a greater volume than it did
initially.
At constant volume, pressure will increase.
Particles will hit the walls of a container more
frequently.




27
Bonds
HGFGJDF



28
Cont: 10.3.2 Charles Law: The
Temperature-Volume Relationship
At constant pressure, volume will expand equally
for equal rises in temperature.


Volume

0K 273K 373K temp./K
Extrapolating - volume versus temp. at constant
pressure line, the line intercept at -273C on the
x-axis.




29
Cont: 10.3.2 Charles Law: The
Temperature-Volume Relationship
This -273C (more accurately -273.15C) was
termed absolute zero or O K (Kelvin scale).
Theoretically gases would have a zero volume at
273C.
In practice they all liquefy above this
temperature.

0 K is equal to -273.15 C
T(K) = T(C) + 273.15




30
Cont: 10.3.2 Charles Law: The
Temperature-Volume Relationship
General definition of Charles law:
The volume of a fixed amount of gas maintained
at constant pressure is directly proportional to its
absolute temperature.
V T (abs.) (n, P constant)
V/T = k = constant
If V
1
and V
2
are the different volumes of a fixed
mass at absolute temperature T
1
and T
2
, then :
V
1
/T
1
= V
2
/T
2





31
Bonds
HGFGJDF



32
Example 4

A sample of gas has a volume of 364 ml at a
temperature of 25 C. What will the volume be
if the temperature is changed to 100.0 C while
the pressure is kept constant?





33
Example 4 (Answer)

Vol/ml Temp/C Temp/K
Initial(1) 364 25.0 25 + 273.15 = 298.15
Final (2) ? 100.0 100 + 273.15 =373.15



ml T
T
V
V
T
V
T
V
6 . 455
2
1
1
2
2
2
1
1
= =
=


34
10.3.3 Avogadros Law: The
Quantity-Volume Relationship
Avogadros hypothesis: Equal volume of gases at
the same temperature and pressure contain equal
numbers of molecules.
Ar N
2
H
2

Volume 22.4L 22.4L 22.4L
Pressure 1atm 1atm 1atm
Temperature 0
0
C 0
0
C 0
0
C
Mass of gas 39.95g 28.01g 2.02g
No. of molec. 6.02 x 10
23
6.02 x 10
23
6.02 x 10
23




35
Cont: 10.3.3 Avogadros Law: The
Quantity-Volume Relationship
Avogadros law: For a gas at constant temperature
and pressure, the volume of a gas is directly
proportional to the number of moles of the gas.
Mathematically:
V n (T, P constant)
V/n = k = constant
Note: This relationship is obeyed closely by
gases at low pressure.





36
Bonds
HGFGJDF



37
Bonds
HGFGJDF



38
Example 5
Suppose we have a 12.2 L sample containing
0.5 mol oxygen gas (O
2
) at a pressure of 1
atm. and a temperature of 25C. If all this O
2

were converted to ozone (O
3
) at the same
temperature and pressure, what would be the
volume of ozone?




39
Example 5 (Answer)
3 O
2
(g) 2 O
3
3 mol of O
2
gives 2 mol of O
3
0.5 mol of O
2
= 0.5 mol O
2
2 mol O
3
= 0.33 mol O
3

3 mol O
2



L mol
mol
L
n
n
V
V
n
V
n
V
05 . 8 33 . 0
5 . 0
2 . 12
2
1
1
2
2
2
1
1
= = =
=


40
10.4 The Ideal-Gas Equation
Boyles law: V 1/P (constant n,T)
Charles law : V T (constant n,P)
Avogadros law : V n (constant P,T)
Combine these relationships


Let the proportionality constant be R:

Rearrange: PV = nRT The ideal-gas equation


P
nT
V
P
RnT
V =


41
Cont: 10.4 The Ideal-Gas
Equation
An ideal gas is a hypothetical gas whose
pressure, volume and temperature behaviour is
completely described by the ideal-gas equation.
R in the ideal-gas equation is called the gas
constant.
In working problems with PV = nRT, the units of
P,V, n and T must agree with the units of gas
constant.
R = 8.314 J/mol.K
R = 0.0821 L.atm/mol.K




42
Example 6
Determine volume of 1 mole gas x at STP.
Standard temperature and pressure (STP):
P = 1atm
n = 1 mol
R = 0.0821 L-atm/mol K
T(K) = T(C) + 273.15
= 0C + 273.15
= 273.15K




43
Example 6 (Answer)






The volume occupied by 1 mol of ideal gas at
STP, 22.4L is known as the molar volume of
an ideal gas at STP.


L V
atm
K mol K atm L mol
V
P
nRT
V
4 . 22
0 . 1
15 . 273 / . 0821 . 0 0 . 1
=

=
=


44
Cont: 10.4 The Ideal-Gas
Equation
The ideal-gas equation does not always accurately
describe real gases.The measured volume,V for given
P, n and T might differ from the volume calculated
from PV = nRT.
The standard conditions for gas behaviour (where R is
calculated based on 0 C and 1 atm) are not the same
as the standard conditions in thermodynamics (25C
and 1 atm).
Note: Very small volume difference is noticed in
calculation involving real and ideal gas.




45
Cont: 10.4 The Ideal-Gas
Equation
From Ideal-Gas Equation : PV = nRT
1)

( constant n )


2)

(constant n & P)

3)

(constant n & V)


4)

(constant n & T)



2
2 2
1
1 1
T
V P
T
V P
=
2
2
1
1
T
V
T
V
=
2
2
1
1
T
P
T
P
=
2 2 1 1
V P V P =


46
Example 7
A gas occupies a volume of 136 cm
3
at 21
0
C
and 102 kNm
-2
.
What would its volume be at STP?
{use PV/T = constant}
STP: T = 273K, P = 1 atm = 101.3kNm
-2
V
1
= 136 cm
3
V
2
= ?
T
1
= (273 + 21)K T
2
= 273K
P
1
= 102 kNm
-2
P
2
= 101.3 kNm
-2




47
Example 7 (Answer)


3
2
2
3 2
2
2
2
1
1 1
2
2
2 2
1
1 1
127
3 . 101
273
294
136 102
cm V
kNm
K
K
cm kNm
V
P
T
T
V P
V
T
V P
T
V P
=

=
= =

48
Example 8
What volume would be occupied by 100g of oxygen
(O
2
) at 18 C and 105 kNm
-2
?



n = 100 g = 3.125 mol T = 18 + 273 = 291 K
32 g/mol

R = 8.31 Nm/K.mol




( )( )( )
( )
3
2 3
0720 . 0
10 105
291 . / 31 . 8 125 . 3
m V
Nm
K K mol Nm mol
V
P
nRT
V
=

=
=

49
Example 9
A metal cylinder holds 50.0 L of oxygen at 18.5
atm and 21C. What volume will the gas occupy if
the pressure is reduced to 1.00atm and
temperature is maintained at 21C.
From PV = nRT
When T, n are constant P
1
V
1
=

P
2
V
2
V
2
= P
1
V
1


P
2
V
2
= (18.5 atm) (50.0L) = 925 L

(1.00 atm)




50
Exercise 10.1
The gas pressure in an aerosol can is 1.5
atm at 25 C. Assuming that the gas inside
obey the ideal- gas equation. What would
the pressure be if the can was heated to
450 C?
Use: ; Answer: 3.6 atm


P
1
1
2
2
T
P
T
P
=


51
Exercise 10.2
An inflated balloon has a volume of 6.0 L at sea
level (1.0 atm) and is allowed to ascend in altitude
until the pressure is 0.45 atm. During ascent the
temperature of the gas falls from 22 C to 21 C.
Calculate the volume of the balloon at its final
altitude.

Use: ; Answer: 13.3 L


1
1 1
2
2 2
T
V P
T
V P
=


52
10.5 Further Applications of
The Ideal-Gas Equations
10.5.1 Determination of Gas Densities and Molar Masses
Density = mass/volume Unit : grams/liter (g/L)
PV =nRT
Rearrange,

Molar mass, M = grams/mol
n/V has units of mol/Liter
Multiply both sides with M, thus

Density,



RT
P
V
n
=
RT
PM
V
nM
=
RT
PM
d =


53
Example 10
What is the density of CCl
4
vapour at 714 torr and
125
o
C?
Molar mass of CCl
4
, M = 12.0 + 4(35.5) = 154.0 g/mol
Pressure: 760 torr = 1 atm
714 torr : 714 torr 1 atm = 0.939 atm
760 torr



( )( )
( )( )
L g d density
K K mol atm L
mol g atm
RT
PM
d density
/ 43 . 4 ,
398 . / . 0821 . 0
/ 154 939 . 0
,
=
= =


54
Example 11

A 2.78 g sample of gas occupies a volume
of 4.24 Liter at 23.6 C and 755.1 mmHg.
What is the molecular mass of the gas?





55
Example 11 (Answer)
760 mmHg - 1 atm 755.1 mmHg - 0.994 atm




mass = 2.78 g, mol, n = 0.173 mol
molar mass, M = mass/mol
M = 2.78 g/ 0.173 mol = 16.1 g mol
-1




( )( )
( )( )
mol n
K K mol atm L
L atm
RT
PV
n
173 . 0
6 . 296 . / . 0821 . 0
24 . 4 994 . 0
=
= =


56
Example 12
The industrial synthesis of nitric acid involves the
reaction of nitrogen dioxide gas with water

3NO
2
(g) + H
2
O (l) 2HNO
3
(aq) + NO(g)

How many moles of nitric acid can be prepared
using 450 L of NO
2
at a pressure of 5.00 atm and
a temperature of 295 K?





57
Example 12 (Answer)
V
NO2
= 450L, T = 295K, P = 5.00 atm
3NO
2
(g) + H
2
O (l) 2HNO
3
(aq) + NO(g)




3 mol of NO
2
will produce 2 mol of HNO
3

92.9 mol NO
2
will produce =



( )( )
( )( )
mol n
K K mol atm L
L atm
RT
PV
n
9 . 92
295 . / . 0821 . 0
450 00 . 5
=
= =
mol
mol
mol
mol
9 . 61
2
3
9 . 92
=

58
Exercise 10.3
A large flask is evacuated and found to
weigh 134.567g. It is then filled to a
pressure of 735 torr at 31
0
C with a gas of
unknown molar mass and then reweighed; its
mass is 137.456g. The flask is then filled
with water and again weighted: its mass now
1067.9g. What is the molar mass of the
unknown gas?
{use M=dRT/P, answer 79.7 g/mol}
(the density of water at 31
0
C is 0.997g/cm
3
)




59
Exercise 10.4

The density of a gas measured at 1.50 atm
and 27C and found to be 1.95 g/L.
Calculate the molar mass of this gas.
{use M=dRT/P, answer 32.0 g/mol}





60
10.6 Gas Mixtures and Partial
Pressures
Dalton:
In gas mixtures each gas acts independently of
the other gases present
OR
Total pressure of a mixture of gases equals the
sum of the pressures that each would exert if it
were present alone.
Mathematically
P
Total
= P
1
+ P
2
+ P
3
+ ...





61
Bonds
HGFGJDF



62
Cont: 10.6 Gas Mixtures and
Partial Pressures
E.g. : a mixture of gases G
1
, G
2
and G
3
in one
container.
G
1
: P
1
, n
1
G
2
: P
2
, n
2
G
3
: P
3
, n
3
Total pressure, P
t
=

P
1
+

P
2
+ P
3
Each gases obeys the ideal gas equation.
P
1
=

n
1
(RT/V) ; P
2
=

n
2
(RT/V) ; P
3
= n
3
(RT/V)
P
t
=

n
1
(RT/V) + n
2
(RT/V) + n
3
(RT/V)
P
t
= (n
1
+

n
2
+

n
3
) (RT/V)
= n
total
(RT/V )




63
Example 13
Mixture of helium and oxygen are used in
scuba diving tanks to help prevent the bends.
For particular dive, 46 L He at 25 C and 1.0
atm and 12 L O
2
at 25 C and 1.0 atm were
pumped into a tank with a volume of 5.0 L.
Calculate the partial pressure of each gas and
the total pressure in the tank at 25 C.





64
Example 13 (Answer)
P
He
= 1.0 atm; V
He
= 46 L ; R = 0.08206 L.atm/K.mol
T
He
= 25 +273 = 298K
P
O2
= 1.0 atm ; V
O2
= 25 L ; T
O2
= 25 +273 = 298K

From n = PV/RT


( )( )
( )( )
( )( )
( )( )
mol
K K mol atm L
L atm
n
mol
K K mol atm L
L atm
n
O
He
49 . 0
298 . / . 08206 . 0
12 0 . 1
9 . 1
298 . / . 08206 . 0
46 0 . 1
2
= =
= =


65
Example 13 (Answer)
Total tank volume, V = 5.0 L; T = 298 K
From P = nRT/V





Total Pressure, P
t
= P
He
+ P
O2
= 9.3 + 2.4 = 11.7 atm



( )( )( )
( )
( )( )( )
( )
atm
L
K K mol atm L mol
P
atm
L
K K mol atm L mol
P
O
He
4 . 2
0 . 5
298 . / . 08206 . 0 49 . 0
3 . 9
0 . 5
298 . / . 08206 . 0 9 . 1
2
= =
= =


66
10.6.1 Mole Fractions and
Partial Pressure
Mole fraction,X is the ratio of number of moles of
a given component in a mixture to the total
number of moles in the mixture. X
1
= n
1
/n
T

From ideal gas equation PV = nRT:
i.e for each component in the mixture




|
.
|

\
|
=
|
.
|

\
|
=
RT
V
P n
RT
V
P n
2 2 1 1
,


67
Cont: 10.6.1 Mole Fractions
and Partial Pressure
Mole fraction represented in terms of pressure:

( )
( ) ( ) ( ) ...
3 2 1
1
1
1
+ + +
= =
RT
V
P
RT
V
P
RT
V
P
RT
V
P
n
n
X
TOTAL
( )
( )( )
TOTAL
P
P
P P P
P
P P P
RT
V
RT
V
P
1
3 2 1
1
3 2 1
1
....
....
=
+ + +
=
+ + +
=
TOTAL
i
TOTAL
i
i
P
P
n
n
X = =


68
Example 14
A 2.0 L tank containing oxygen at a pressure
of 100 kPa is connected to a 0.1 L tank
containing helium at a pressure of 3.00 MPa
and the gases are allowed to mix. What is the
final pressure assuming that the temperature is
held constant?





69
Example 14 (Answer)
Volume of He increases from 0.1 L to 2.1 L
Volume of oxygen increases from 2.0 L to 2.1 L

Dalton: The total pressure is the sum of partial pressure.
O
2
;

V
1
= 2.0 L V
2
= 2.1 L
P
1
= 100 kPa P
2
= ?
From P
1
V
1
= P
2
V
2



( )( )
( )
kPa
L
L kPa
P 95
1 . 2
0 . 2 100
2
= =


70
Example 14 (Answer)
From P
1
V
1
= P
2
V
2

He

;

V
1
= 0.1 L V
2
= 2.1 L
P
1
= 3.00 MPa P
2
= ?







( )( )
( )
kPa
L
L kPa
P 143
1 . 2
1 . 0 3000
2
= =
kPa P P P
He O t
238 143 95
2
= + = + =


71
Example 15

A mixture of 8.00 g of CH
4
and 9.00 g of
C
2
H
6
is stored at a total pressure of 500
kPa. What is the partial pressure of each
component present?









72
Example 15 (Answer)
P
1
= X
1
P
t

M of CH
4
= 16.0 g
M of C
2
H
6
= 30.0g

No. of mole of each component:
n
CH4
= 8.00g/16.00g mol
-1
= 0.50 mol
n
C2H6
= 9.00g/30.00g mol
-1
= 0.30 mol






73
Example 15 (Answer)
n
t
= n
CH4
+ n
C2H6

= 0.50 + 0.30
= 0.80 mol
Mole fraction: (mol/total mol)
X
CH4
= 0.50/0.80 = 0.625
X
C2H6
= 0.30/0.80 = 0.375
Partial Pressure:
P
1
= X
1
P
t

P
CH4
= 0.625 500kPa = 312 kPa
P
C2H6
= 0.375 500kPa = 188 kPa





74
Exercise 10.5
A gaseous mixture made from 6.00 g O
2
and 9.00 g
CH
4
is placed in a 15.0 L vessel at 0
0
C. What is the
partial pressure of each gas and what is the total
pressure in the vessel?

Note: use P
i
=

n
i
(RT/V )
{Answer: P
O2
=0.281 atm, P
CH4
=0.841 atm, P
t
=1.122 atm}






75
Exercise 10.6
A synthetic atmosphere composed of 1.5 mol
percent CO
2
, 18.0 mol percent O
2
and 80.5 mol
percent Ar.
a) Calculate the partial pressure of O
2
in the
mixture if the total pressure of the
atmosphere is to be 745 torr. {Ans.=134 torr}
b) If this atmosphere is to be held in a 120 L
space at 295 K, how many moles of O
2
are
needed?

{use n
i
=P
i
(V/RT), ans.=0.874 mol}





76
10.7 Kinetic Molecular Theory
(1822-1888) The kinetic-molecular theory
(theory of moving molecules) was developed:

Assumptions:

1) Gases consist of large numbers of molecules in
constant random motion.
2) Volume of individual molecules is negligible
compared to volume of container (total volume).





77
Cont: 10.7 Kinetic Molecular
Theory
3) Attractive and repulsive (intermolecular) forces
between gas molecules are negligible.

4) The collisions between molecules are perfectly
elastic.The average kinetic energy does not
change as the temperature is constant.

5) Average kinetic energy of the molecules is
proportional to the absolute temperature.






78
v
d









79
Cont: 10.7 Kinetic Molecular
Theory
The average kinetic energy, c is related to root
mean square speed, u and mass
c = 1/2 mu
2
u = root-mean-square (rms) speed, the speed of
a molecule possessing average kinetic energy.

A gas composed of light particles such as He will
have the same c as one composed of much
heavier particles such as Xe - provided that both
are at the same temperature.





80
10.8 Molecular Effusion and
Diffusion
The mass,m of the lighter gas is smaller than the
heavier gas. Therefore, the lighter gas must have
a higher rms speed, u.
An equation that expresses this fact:

; M=molar mass

* Less massive the gas molecules, the higher the
rms speed, u.



M
u
M
RT
u
1 3
=


81
Cont: 10.8 Molecular Effusion
and Diffusion
Consequences of the dependence of molecular speeds
on mass:

1. Effusion: the escape of gas molecules through a
tiny hole into an evacuated space.
2. Diffusion: the spread of one substance
throughout a space or throughout a second
substance. E.g. molecules of a perfume diffuse
throughout a room.







82
10.8.1 Grahams Law of
Effusion
The effusion rate of a gas is inversely proportional
to the square root of its molar mass.
Consider 2 gases at same T and P in containers with
identical pinholes (different containers).
Gas 1 : Molar mass, M
1
- rate of effusion r
1

Gas 2 : Molar mass, M
2
- rate of effusion r
2


The relative rate of effusion:






1
2
2
1
M
M
r
r
=


83
Cont: 10.8.1 Grahams Law of
Effusion

Lighter gas effuses more rapidly.
Only those molecules which hit the small hole will
escape through it.
Thus, the higher the rms speed the greater
possibility of a gas molecule hitting the hole and
effuse.







84
Cont: 10.8.1 Grahams Law of
Effusion
Rate of effusion is directly proportional to the rms
speed of the molecules.



Example:
Rubber and various plastic have tiny openings
through which gas molecules can pass.




1
2
2
1
2
1
2
1
/ 3
/ 3
M
M
M RT
M RT
u
u
r
r
= = =


85
10.8.2 Diffusion and Mean Free
Path
Diffusion (like effusion) is faster for light gas
molecules.
Molecular collisions make diffusion more complicated
than effusion.
Average distance of a gas molecule between collisions
is called mean free path.
The higher the density of a gas, the smaller the mean
free path. The more molecules are in a given volume,
the shorter the average distance traveled between
collisions.





86
v
d









87
10.9 Real Gases: Deviations
from Ideal Behaviour

Ideal gas- the molecules are assumed to occupy
no space and no attractions for one another.
Real gas- Molecules have finite volumes and they
attract one another.
At lower pressures (usually below 10 atm), the
deviation from ideal behaviour is negligible.









88
v
d









89
Cont: 10.9 Real Gases:
Deviations from Ideal Behaviour
As pressure increases (for P
ideal
V/RT = n = 1):
The free space which the molecules can move
becomes a smaller fraction of the container volume
(due to finite volumes of the molecules).
In addition, the attractive forces between
molecules becomes significant (at short distances),
the impact with the wall of the container is
lessened (P
at
<P
ideal
). {intermolecular forces
predominate}
Thus, P
at
V+ than ideal P
ideal
V;



1 (
RT
V P
at


90
v
d









91
Cont: 10.9 Real Gases:
Deviations from Ideal Behaviour
Temperature determines how effective attractive
forces between gas molecules are.

At low temperature: gases deviate from ideality:
the average kinetic energy decreases,
intermolecular attractions remain constant.

At high temperature: gas molecules are far apart,
thus the finite volumes of the molecules
predominate.









92
10.9.1 The Van der Waals
Equation
Ideal gas equation - cannot be used to predict the
pressure-volume properties of gases at high
pressure.
The ideal-gas equation predicts that the pressure
of a gas i.e.


This expression has to be corrected for the 2
effects:
i) the finite volume occupied by the gas molecules.
ii) the attractive forces between gas molecules.



V
nRT
P =


93
Cont: 10.9.1 The Van der Waals
Equation
Van der Waals introduced 2 constants, a and b to make
these corrections:


nb : accounts for the correction of the finite volume of
gas molecules.
The Van der Waals constant b is a measure of the
actual volume occupied by a mole of gas molecules -
units of L/mol.
The pressure is decreased by the factor n
2
a/V
2
:
accounts for the attractive forces.
The Van der Waals constant a - units L
2
-atm/mol
2
.



2
2
V
a n
nb V
nRT
P

=


94
Cont: 10.9.1 The Van der Waals
Equation
Van der Waals equation:


a and b - different for different gases.
Values of both a and b generally increase with an
increase in mass of the molecule and complexity of its
structure.
Larger, more massive molecules, have larger volumes
and greater intermolecular attractive forces.



( ) nRT nb V
V
a n
P =
|
|
.
|

\
|
+
2
2


95
v
d









96
Example 16
If 1.00 mol of an ideal gas were confined to
22.41 L at 0.0 C, it would exert pressure of
1.00 atm. Use the Van der Waals equation
and the constants in Table 10.3 to estimate
the pressure exerted by 1.00 mol of Cl
2
(g)
in 22.41 L at 0.0

C.






97
Example 16 (Answer)
n = 1.00 mol, R = 0.08206L.atm/mol.K,
T = 273.15K, V = 22.41L,
a = 6.49L
2
atm/mol
2
, and b = 0.0562L/mol









( ) nRT nb V
V
a n
P =
|
|
.
|

\
|
+
2
2


98
Example 16 (Answer)







( )( )( )
( ) ( )( )
( ) ( )
( )
atm P
atm atm P
L
mol atm L mol
mol L mol L
K K mol atm L mol
P
990 . 0
013 . 0 003 . 1
41 . 22
/ . 49 . 6 00 . 1
/ 0562 . 0 00 . 1 41 . 22
15 . 273 . / . 08206 . 0 00 . 1
2
2 2
2
=
=

=


99
Example 17
A sample of KClO
3
is partially decomposed,
producing O
2
gas that is collected over water. The
volume of gas collected is 0.250 l at 26C and 765
torr total pressure.
2KClO
3
(s) 2KCl (s) + 3O
2
(g)
a) How many moles of O
2
are collected?
b) How many grams of KClO
3
were decomposed?
c) When dry, what volume would the collected O
2

gas occupy at the same temperature and
pressure?





100
Example 17 (Answer)
2KClO
3
(s) 2KCl (s) + 3O
2
(g)

V
total inside
= 0.250L
T
total inside
= 26C (273.15 + 26) = 299.15K
P
total inside
= 765 torr






101
Example 17 (Answer)
a) P
O2
= (765 - 25) torr. = 740 torr




( )( )( )
( )( )
mol n
K K mol atm L
L torr atm torr
n
RT
V P
n
O
O
O
O
3
10 91 . 9
15 . 299 . / . 0821 . 0
250 . 0 760 / 1 740
2
2
2
2

=
=
=


102
Example 17 (Answer)
2KClO
3
(s) 2KCl (s) + 3O
2
(g)

b) 2 mols KClO
3
3 mols of O
2

Molar mass of KClO
3
= 122.6 g/mol


gram KClO
3






( )
g
molKClO
gKClO
molO
molKClO
molO
811 . 0
1
6 . 122
3
2
10 91 . 9
3
3
2
3
2
3
=
|
|
.
|

\
|
|
|
.
|

\
|
=



103
Example 17 (Answer)

c) Use Boyles law:


V
1
= 0.250L ; P
2
= 765 torr.(assumed as water partial
pressure replaced by O
2
)
P
1
= 740 torr (from O
2
- water vapour)
V
2
= (assumed dry O
2
without water vapour)




2
1 1
2
P
P V
V =
( )( )
( )
L V
torr
torr L
V
242 . 0
765
740 250 . 0
2
2
=
=


104



END of CHAPTER 10