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1
CHEMISTRY
GASEOUS STATE
Introduction :
Matter as we know broadly exists in three states.
There are always two opposite tendencies between particles of matter which determine the state of matter
Inter molecular attractive forces.
The molecular motion / randommotion.
In this chapter the properties and behaviour of the gases will be analysed and discussed in detail. These
properties are measured with the help of the gas laws as proposed Boyle,Charles,Gay lussac etc
Boyles lawandmeasurement of pressure :
Statement :
For a fixed amount of gas at constant temperature, the volume occupied by the gas is inversely proportional
to the pressure applied on the gas or pressure of the gas.
V o
P
1
hence PV = constant
this constant will be dependent on the amount of the gas and temperature of the gas.
P
1
V
1
= P
2
V
2
P
v
P
2
P
1
V
2
V
1
B
A
Application of Boyles Law : For the two parts A and B P
1
V
1
= K & P
2
V
2
= K
hence it follows that P
1
V
1
= P
2
V
2
.
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CHEMISTRY
Units
Volume Pressure : Temperature
Volume of the gas is the Pressure = N/m
2
= Pa S.I. unit Kelvin scale Boiling point = 373 K
Volume of the container C.G.S unit = dyne-cm
2
ice point = 273 K
S.I. unit m
3
Convert 1N/m
2
into dyne/cm
2
Fahrenheit scale B.P. = 212 F
ice point = 32 F
C.G.S. unit cm
3
2 4
5
2
cm 10
dyne 10
m 1
N 1
=
Celcius scale B.P. = 100C
1 = 10
3
m
3
1N/m
2
= 10 dyne/cm
2
ice point = 0C
1 = 10
3
cm
9
1dm
3
= 1 = 10
3
m
3
1 atm = 1.013 10
5
N/m
2
32 212
32 F
273 373
273 K
0 100
0 C

1ml = 10
3
= 1 cm
3
=
) 0 ( R ) 100 ( R
) 0 ( R R

where R = Temp. on unknown scale.

Atmospheric pressure :
The pressure exerted by atmosphere on earths surface at sea level is called 1 atm.
1 atm = 1.013 bar
1 atm = 1.013 10
5
N/m
2
= 1.013 bar = 760 torr
Example-1 Arubber balloon contains some solid marbles each of volume 10 ml. Agas is filled in the balloon at
a pressure of 2 atm and the total volume of the balloon is 1 litre in this condition. If the external
pressure is increased to 4atm the volume of Balloon becomes 625 ml. Find the number of marbles
present in the balloon.
Solution : Let the no. of marbles be = n .
volume of marble = 10 n ml.
volume of balloon earlier = 1000 ml.
later = 625 ml.
Nowfor the gas inside the balloon temperature and amount of the gas is constant, hence boyles law
can be applied
P
1
V
1
= P
2
V
2
4 (625 10n) = 2 (1000 10n)
625 4 = 2000 20n + 40n
625 4 2000 = 20n
20
2000 4 625
= n.
5
125
= n ; n = 25
MEASUREMENT OF PRESSURE
Barometer :
Abarometer is an instrument that is used for the measurement of pressure.The construction of the barometer
is as follows
P
0
P
0
P
0
P = P
0 atm
Mg
Perfect Vaccum
Cross sectional view of the capillary column
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CHEMISTRY
A mercury barometer is used to measure atmospheric pressure by determining the height of a mercury
column supported in a sealed glass tube. The downward pressure of the mercury in the column is exactly
balanced by the outside atmospheric pressure that presses down on the mercury in the dish and pushes it
up the column.
Athin narrow calibrated capillary tube is filled to the brim, with a liquid such as mercury, and is inverted into
a trough filled with the same fluid.Now depending on the external atmospheric pressure, the level of the
mercury inside the tube will adjust itself, the reading of which can be monitored. When the mercury column
inside the capillary comes to rest, then the net forces on the column should be balanced.
Applying force balance, we get,
P
atm
A= mg (A is the cross-sectional area of the capillary tube)
If is the density of the fluid, then m = v
hence, P
atm
A = ( g h) A (v = A h)
(h is the height to which mercury has risen in the capillary)
or, P
atm
= gh
Normal atmospheric pressure which we call 1 atmosphere (1 atm), is defined as the pressure
exerted by the atmosphere at mean sea level. It comes out to be 760 mm of Hg = 76 cmof Hg. (at mean sea
level the reading shown by the barometer is 76 cm of Hg)
1 atm = (13.6 10
3
) 9.8 0.76 = 1.013 10
5
Pascal.
1 torr = 1 mm of Hg.
1 bar = 10
5
N/m
2
(Pa)
Faulty Barometer : An ideal barometer will show a correct reading only if the space above the mercury
column is vacuum, but in case if some gas column is trapped in the space above the mercury column, then
the barometer is classified as a faulty barometer. The reading of such a barometer will be less than the true
pressure.
For such a faulty barometer
mg
P A
atm
P A
gas
P
0
A = Mg + P
gas
A
P
0
= gh + P
gas
or gh = P
0
P
gas
Example-2 The reading of a faulty barometer is 700 mm of Hg. When actual pressure is 750 mm of Hg. The
length of the air column trapped in this case is 10 cm .Find the actual value of the atmospheric
pressure when reading of this barometer is 750 mmof Hg. Assume that the length of the Barometer
tube above mercury surface in the container remains constant.
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CHEMISTRY
Solution : P
0
= P
gas
+ 700 g
P
gas
= 750 g 700 g = 50 g
Now for the gas column in the capillary, amount and temperature are constant hence P
1
V
1
= P
2
V
2
(50 g) (100 A) =
gas
P'
(50 A)

gas
P'
= 100 g
Now, applying force balance in the new conditions :
atm
P' =
gas
P'
+ 750 g = 100 g + 750 g = 850 g
Hence, the atmospheric pressure is now, 850 cm of Hg.
Example-3 In each of the following examples, find the pressure of the trapped gas.
Solution : Total pressure of gas column
= 75 + 10 = 85 cm of Hg.
Example-4
Solution : P
gas
= 65 cm of Hg.
Example-5
P
g
= 75 + 10 cos u.
Solution : From the above problem, it can be generalised that, applying force balance every single time is not
necessary. If we are moving up in a fluid, then substract the vertical length, and while moving down
add the vertical length.
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CHEMISTRY
Charles law :
For a fixed amount of gas at constant pressure volume occupied by the gas is directly proportional to
temperature of the gas on absolute scale of temperature.
V o T or V = kT
t tan cons
T
V
= where k is a proportionality constant and is
dependent on amount of gas and pressure.
2
2
1
1
T
V
T
V
=
Temperature on absolute scale, kelvin scale or ideal gas scale.
V = a + bt Temperature on centigrade scale.
V
T
Relation : T = t + 273
Since volume is proportional to absolute temperature. The volume of a gas should be theoretically
zero at absolute zero temperature.
Infact no substance exists as gas at a temperature near absolute zero, though the straight line
plots can be extra plotted to zero volume. Absolute zero can never be attained practically
though it can be approached only.
By considering 273.15C as the lowest approachable limit, Kelvin developed temperature
scale which is known as absolute scale.
Example-6 If the temp. of a particular amount of gas is increased from27Cto 57C, find final volume of the gas,
if initial volume = 1 lt and assume pressure is constant.
Solution :
2
2
1
1
T
V
T
V
=
) 57 273 (
V
) 27 273 (
1
2
+
=
+
So V
2
= 1.1 lt.
Example-7 An open container of volume 3 litre contains air at 1 atmospheric pressure. The container is heated
from initial temperature 27C or 300 K to tC or (t + 273) K the amount of the gas expelled from the
container measured 1.45 litre at 17C and 1 atm.Find temperature t.
Solution : T
0
1
= 300 K
It can be assumed that the gas in the container was first heated to (t + 273), at which a volume AV
escaped from the container
hence applying charles law :
300
3
=
273 t
V 3
+
A +
Now, this volume AV which escapes when the container get cooled

273 t
V
+
A
=
290
45 . 1
Solve the two equations and get the value of AV and t.
determine A V & calculate t that will be the answer.
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CHEMISTRY
Calculationof payload :
Pay load is defined as the maximum weight that can be lifted by a gas filled balloon.
M
Buoyancy
balloon
For maximum weight that can be lifted, applying force balance
F
buoyancy
= M
balloon
g + M
pay load
g

air
v.g. =
gas
v.g + Mg + mg.
mass of balloon = m net force on
volume of balloon = v balloon = 0
density of air =
air
(at equilibrium / when balloon is incoming
density of gas inside the with constant speed)
balloon =
gas
Example-8 Aballoon of diameter 20 mweights 100 kg. Calculate its pay-load, if it is filled with He at 1.0 atmand
27C. Density of air is 1.2 kg m
3
. [R = 0.0082 dm
3
atm K
1
mol
1
]
Solution : Weight of balloon = 100 kg = 10 10
4
g
Volume of balloon =
3
3
100
2
20
7
22
3
4
r
3
4
|
.
|

\
|
= t
= 4190 10
6
cm
3
= 4190 10
3
litre
Weight of gas (He) in balloon =
RT
PVM
|
.
|

\
|
= RT
M
w
PV
=
300 082 . 0
4 10 4190 1
3

= 68.13 10
4
g
Total weight of gas and balloon
= 68.13 10
4
+ 10 10
4
= 78.13 10
4
g
Weight of air displaced =
3
6
10
10 4190 2 . 1
= 502.8 10
4
g
Pay load = wt. of air displaced (wt. of balloon + wt. of gas)
Pay load = 502.8 10
4
78.13 10
4
= 424.67 10
4
g
Gay-lussacs law:
For a fixed amount of gas at constant volume, pressure of the gas is directly proportional to temperature of
the gas on absolute scale of temperature.
P o T
T
P
= constant dependent on amount and volume of gas
2
2
1
1
T
P
T
P
=
temperature on absolute scale
originally, the law was developed on the centigrade scale, where it was found that pressure is a linear
function of temperature P = P
0
+ bt where b is a constant and P
0
is pressure at zero degree centigrade.
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CHEMISTRY
P
T
O
P
P
0
t
(273C)
Example : PV = K V = K
1
/p
T
V
= K
2
V = K
2
T
P
K
1
= K
2
T
PT =
2
1
K
K
= const. P o =
T
1
?

where are we wrong ?
This is wrong because we are varying temperature &
K
1
= f(1) thus K
1
will change according to temperature
So
2
1
K
K
will be a function of temp & not constant.
Example-9 The temperature of a certain mass of a gas is doubled. If the initially the gas is at 1 atm pressure.
Find the % increase in pressure ?
Solution :
1
1
T
P
=
2
2
T
P
;
T
1
=
T 2
P
2
% increase =
1
1 2
x 100 = 100%
Example-10 The temperature of a certain mass of a gas was increased from 27C to 37C at constant volume.
What will be the pressure of the gas.
Solution :
1
1
T
P
=
2
2
T
P
;
300
P
=
310
P
2
; P
2
=
30
31
P
Avogadros Hypothesis :
For similar values of pressure &temperature equal number of molecules of different gases will occupy equal
volume.
N
1

V (volume of N
1
molecules at P & T of one gas)
N
1

V (volume of N
1
molecules at P & T of second gas)
Molar volume & volume occupied by one mole of each and every gas under similar conditions will be equal.
One mole of any gas or a combination of gases occupies 22.413996 L of volume at STP.
The previous standard is still often used, and applies to all chemistry data more than decade old, in this
definition StandardTemperatureand PressureSTP denotes the same temperature of 0C(273.15K), but
a slightly higher pressure of 1 atm (101.325 kPa) .
StandardAmbient TemperatureandPressure(SATP), conditions are also used in some scientific works.
SATP conditions means 298.15 K and 1 bar (i.e. exactly 10
5
Pa) At SATP (1 bar and 298.15 K), the molar
volume of an ideal gas is 24.789 L mol
1
(Ref. NCERT )
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CHEMISTRY
Equation of State :
Combining all the gas relations in a single expression which discribes relationship between pressure, volume
and temperature, of a given mass of gas we get an expression known as equation of state.
T
PV
= constant (dependent on amount of the gas (n)).
1
1 1
T
V P
=
2
2 2
T
V P
Ideal gas Equation :
nT
PV
= constant [universal constant]
= R (ideal gas constant or universal gas constant)
R = 8.314 J/Kmole ~ 25/3
= 1.987 cal/mole ~ 2
= 0.08 Latm/K/mole ~ 1/12
Example-11 Some spherical balloons each of volume 2 litre are to be filled with hydrogen gas at one atm & 27C
from a cylinder of volume 4 litres. The pressure of the H
2
gas inside the cylinder is 20 atm at 127C.
Find number of balloons which can be filled using this cylinder. Assume that temperature of the
cylinder is 27C.
Solution : No. of moles of gas taken initially =
400 R
4 20

= 2.43 L
No. of moles of gas left in cylinder =
300 R
4 1

= 0.162L
No. of moles of gas to be filled in balloons = 2.43 0.162 = 2.268
Let we have 'n' balloons that we can fill
No. of moles of gas that can be filled in 1 balloon =
300 082 . 0
2 1

= 0.081
0.081 n = 2.268
n = 28 balloons.
Daltons law of partial pressure :
Partial pressure :
In a mixture of non reacting gases partial pressure of any component of gas is
defined as pressure exerted by this component if whole of volume of mixture had
been occupied by this component only.
Partial pressure of first component gas
v
RT n
P
1
1
= ;
v
RT n
P
2
2
= ;
v
RT n
P
3
3
=
Total pressure = P
1
+ P
2
+ P
3
.
Daltons law :
For a non reacting gaseous mixture total pressure of the mixture is the summation of partial pressure of the
different component gases.
P
Total
= P
1
+ P
2
+ P
3
v
RT ) n n n (
3 2 1
+ +
=
1
T
1
T
1
x
n
n
P
P
= =
(mole fraction of first component of gas)
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CHEMISTRY
2
T
2
T
2
x
n
n
P
P
= =
(mole fraction of second component of gas)
3
T
3
T
3
x
n
n
P
P
= =
(mole fraction of third component of gas)
Example-12 The stop cock connecting the two bulbs of volume 5 litre and 10 litre containing as ideal gas at
9 atm and 6 atm respectively, is opened. What is the final pressure if the temperature remains
same.
Solution : After the opening of the stop cock the pressure of the each bulb will remain same.
At the beginning, the no. of moles of gas in A =
RT
6 x 10
At the beginning, the no. of moles of gas in B =
RT
9 x 5
total no. of moles at the beginning =
RT
105
Total no. of moles of gas before opening the stop cock
= total no. of moles of gas after opening stop cock =
RT
105
pressure after the opening of the stop cock
P =
RT
105
x
total
V
RT
=
5 10
105
+
= 7 atm
Example-13 A mixture of NO
2
& COhaving total volume of 100 ml contains 70 ml of NO
2
at 1 atm, mixture is left
for some time and same NO
2
get dimerised to N
2
O
4
such that final volume of the mixture become
80 ml at 1 atm, calculate the mole fraction of NO
2
in final equilibrium mixture.
Solution : Initial volume of NO
2
= 70 ml
Initial volume of CO = 100 70 = 30 ml
Final volume of mixture = 80 ml
Let the volume of NO
2
in final mixture be x
Let v ml NO
2
be converted to N
2
O
4
2NO
2

N
2
O
4
V V/2
Hence final volume
= volume of CO+ volume of NO
2
left + volume of N
2
O
4
formed
= 30 + 70 V + V/2 = 80
V = 40 ml
Hence volume of NO
2
left = 70 V = 30 ml
Nowas volume moles
mole fraction = volume fraction =
80
30
=
8
3
Analysis of gaseous mixture :
Vapour density :
Vapour density of any gas is defined as the density of any gas with respect to density of the H
2
gas under
identical conditions of temperature T and pressure P.
vapour density =
T & P same under H of density
P & T at gas of density
2
P =
M
RT
.
V
m
P =
M
RT
=
RT
PM
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CHEMISTRY
vapour density =
2
H
gas
PM RT
RT PM
=
2
H
gas
M
M
=
2
M
gas
M
gas
= 2 vapour density
Average molecular mass of gaseous mixture :
total mass of the mixture divided by total no. of moles in the mixture
M
mix
=
mixture in moles of . no Total
mixture of mass Total
If wehave
n
1
, n
2
and n
3
are moles of three different gases having of molar mass M
1
, M
2
and M
3
respectively.
M
min
=
3 2 1
3 3 2 2 1 1
n n n
M n M n M n
+ +
+ +
Example-14 Calculate the mean molar mass of a mixture of gases having 7 g of Nitrogen, 22 g of CO
2
and 5.6
litres of CO at STP.
Solution : Moles of N
2
= 7/28 = 1/4
Moles of CO
2
= 22/44 = 1/2
Moles of CO = 5.6 / 22.4 = 1/4
mean molar mass = M
min
=
3 2 1
3 3 2 2 1 1
n n n
M n M n M n
+ +
+ +
= ( 7 + 7 + 22 ) / 1 = 36
Grahams Law of Diffusion/Effusion :
Diffusion :
Net spontaneous flowof gaseous molecules fromregion of high concentration (higher partial pressure) to the
region of lower concentration or lower partial pressure
flow will be from both sides, N
2
will try to equalise its partial
pressure in both the vessels, and so will O
2
.
Grahams Law:
Under similar conditions of pressure (partial pressure) the rate of diffusion of different gases is inversely
proportional to square root of the density of different gases.
rate of diffusion r
d
1
d = density of gas
2
1
r
r
=
1
2
d
d
=
1
2
M
M
=
1
2
D . V
D . V
V.D is vapour density
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CHEMISTRY
r = volume flow rate =
dt
dV
out
r = moles flow rate =
dt
dn
out
r = distance travelled by gaseous molecules per unit time =
dt
dx
The general form of the grahams law of diffusion can be stated as follows, when one or all of the
parameters are varied.
rate
TM
P
A
P Pressure, A area of hole, T Temp. , M mol. wt.
If partial pressure of gases are not equal.
Then rate of diffusion is found to be proportional to partial pressure &inversely proportional to square
root of molecular mass.
r P
r
M
1
2
1
r
r
=
2
1
P
P
1
2
M
M
Selective diffusion :
If one or more than one components of a mixture are allowed to diffuse and others are not allowed then it is
selective diffusion of those components.
Platinum allows only H
2
gas to pass through
Effusion : (forced diffusion) a gas is made to diffuse through a hole by the application of external pressure.
Example-15 In a tube of length 5 mhaving 2 identical holes at the opposite ends. H
2
&O
2
are made to effuse into
the tube from opposite ends under identical conditions. Find the point where gases will meet for the
first time.
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CHEMISTRY
Solution :
2
1
r
r
=
dt
dx

dx
dt
=
1
2
M
M
2
1
dx
dx
=
2
32
2
1
dx
dx
= 4
2
2
O by travelled ce tan dis
H by travelled ce tan dis
= 4
) x 5 (
x

= 4
x = (5 x) 4 ; x = 20 4x ; 5x = 20 ; x = 4 fromH
2
side
Example-16 Assume that you have a sample of hydrogen gas containing H
2
, HDand D
2
that you want to separate
into pure components (H =
1
H and D =
2
H). What are the relative rates of diffusion of the three
molecules according to Grahams law?
Solution : Since D
2
is the heaviest of the three molecules, it will diffuse most slowly, and let we call its relative
rate 1.00. We can then compare HD and H
2
with D
2
.
Comparing HDwith D
2
, we have
diffusion D of Rate
diffusion HD of Rate
2
=
HD of mass Molecular
D of mass Molecular
2
=
amu 0 . 3
amu 0 . 4
= 1.15
Comparing H
2
with D
2
we have
diffusion D of Rate
diffusion H of Rate
2
2
=
2
2
H of Mass
D of Mass
=
amu 0 . 2
amu 0 . 4
= 1.41
Thus, the relative rates of diffusion are H
2
(1.41) > HD (1.15) > D
2
(1.00).
Kinetic Theory of Gases :
Postulates / assumptions of KTG :
A gas consists of tiny spherical particles called molecules of the gas which are identical in shape &
size (mass)
The volume occupied by the molecules is negligible in comparision to the total volume of the gas.
For an ideal gas, volume of the ideal gas molecule ~ 0.
Gaseous molecules are always in random motion and collide with other gaseous molecules & with
the walls of the container.
Pressure of the gas is due to these molecular collisions among themselves and with walls of the
container
These collisions are elastic in nature
Molecular attraction forces are negligible. Infact, for an ideal gas attractive or repulsive forces are
equal to zero.
Newtons laws of motion are applicable on the motion of the gaseous molecules.
Effect of gravity is negligible on molecular motion.
The average K.E. of gaseous molecules is proportional to the absolute temperature of the gas.
2
1
M
) u (
2
o T (bar is for average)
Kinetic equation of gaseous state (expression for pressure of gas).
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CHEMISTRY
Derivation :
m = mass of one molecule
U

= U
x i
+ U
y
j

+ U
z k

Consider collision with faceABCD

inital
i
P

= mU
x i
; final
f
P

= mU
x i

change in momentum due to collision = 2 U

x
m
time taken between two successive collision with face ABCD = t =
x
U
2
frequency of collisions (f) =
t
1
=
2
U
x
change in momentum in one sec. = force = 2 m
2
U U
x x

=

2
x
U m
force due to all the molecules
=

m
} Ux ........ U U {
2
N
2
x
2
x
2 1
+ + +
average value of
2
N
U =
2
N
U
=
N
U . .......... U Ux
2
x
2
x
2
1
N 2
+ +
F
x
=

M
} U N {
2
x
all the three directions are equal as the motion is totally random in all directions, hence
2
x
U
=
2
y
U =
2
z
U
2
U
=
2
z
2
y
2
x
U U U + +
= 3
2
x
U
F
x
=

M
. N
3
1
2
U
Pressure =
2
x
F

=
3
1
3
N

2
U
The volume of the container V =
3
PV =
3
1
mN
2
U Kinetic equation of gases
where
2
U
is mean square speed
root mean square speed = U
rms
=
2
U
=
|
|
.
|

\
|
+ + +
N
U ...... U U U
2
N
2
3
2
2
2
1
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CHEMISTRY
Verification of Gaseous Laws Using Kinetic Equation :
From postulates ; PV =
3
1
mN
2
U
2
1
m
2
U T = T Where is a proportionality constant
PV =
3
2
|
.
|

\
|
2
U m
2
1
N ; PV =
3
2
NT (N = Total number of molecules)
Boyles Law : N : constant
T : constant
PV = constant
Charles law : N : constant
P : constant
V T
Kinetic energy of gaseous molecule (translational K.E.)
To calculate we have to use ideal gas equation (experimental equation)
PV = nRT
Kinetic equation PV =
3
2
nRT =
3
2
(nN
A
) T (n = number of moles of gas)
on comparing =
2
3

A
N
R
=
2
3
K where K =
A
N
R
= Boltzmann constant
Average K.E. of molecules =
2
1
m
2
U = T
Average K.E. =
2
3
K T (only dependent on temperature not on nature of the gas.)
Average K.E. for one mole = N
A
|
.
|

\
|
2
U m
2
1
=
2
3
K N
A
T =
2
3
RT
Root mean square speed :
U
rms
=
2
U
=
m
kT 3
=
A
N m
T R 3
Where m-mass of one molecule
Dependent on nature of gas i.e mass of the gas
U
rms
=
M
T R 3
M = molar mass
Average speed :
U
av
= U
1
+ U
2
+ U
3
+ ............ U
N
U
av
=
M
RT 8
t
=
m
KT 8
t
K is Boltzmman constant
Most probable speed :
The speed possessed by maximum number of molecules at the given temperature
U
MPS
=
M
RT 2
=
m
KT 2
"manishkumarphysics.in"
15
CHEMISTRY
Example-17 In a container of capacity 1 litre there are 10
23
molecules each of mass 10
22
gms. If root mean
square speed is 10
5
cm/sec then calculate pressure of the gas.
Solution : PV =
3
1
MN
2
U
P = ?
V = 10
3
m
3
m = 10
25
kg
N = 10
23
2
U
= 10
5
cm/sec = 10
3
m/sec
2
U = 10
6
m
2
/sec
2
P 10
3
=
3
1
10
25
10
23
10
6
P =
3
1
10
2
10
6
10
3
P =
3
1
10
7
pascals
Maxwells distributions of molecular speeds :
Postulates/Assumptions of speed distributions
It is based upon theory of probability.
It gives the statistical averages of the speed of the whole collection of gas molecules.
Speed of gaseous molecules of may vary from 0 to . The maxwell distribution of speed can be
plotted against fraction of molecules as follows.
The area under the curve will denote fraction of molecules having speeds between zero and infinity
Total area under the curve will be constant and will be unity at all temperatures.
Area under the curve between zero and u
1
will give fraction of molecules racing speed between 0 to
u
1
. This fraction is more at T
1
and is less at T
2
.
The peak corresponds to most probable speed.
At higher temperature, fraction of molecules having speed less than a particular value decreases.
For Gases with different molar masses will have following graph at a given temperature.
"manishkumarphysics.in"
16
CHEMISTRY
Real Gases :
Real gases do not obey the ideal gas laws exactly under all conditions of temperature and pressure.
Real gases deviates fromideal behaviour because
Real gas molecules have a finite volume.
{since on liquefaction real gases occupy a finite volume}
Inter molecular attractive forces between real gas molecules is not zero.
{Real gases can be converted into liquid where as ideal gases cant be}
Deviation of real gases from ideal behaviour can be measured by using compresibility factor : (Z)
Z =
ideal
real
) PV (
) PV (
(PV)
ideal
= nRT
Z=
nRT
PV
=
RT
PV
m
, V
M
is volume of onemole of gas or molar volume.
Z =
ideal m
m
V
V
Variation of Z with pressure at constant temperature :
Z=1
ideal
He/H
2
N
2
NH /CO
3 2
P
Variation of Z with pressure at different temperature (for a gas ) :
Conclusions:
Z = 1 for ideal gas ; Z > 1 at all pressures for He/H
2
Z < 1 at low pressure (for all other gases) ; Z > 1 at high pressure (for all other gases)
Vander Waal Equation of real gases :
The ideal gas equation does not consider the effect of attractive forces and molecular volume.
vander Waal's corrected the ideal gas equation by taking the effect of
(a) Molecular volume (b) Molecular attraction
Volume correction :
Ideal gas equation :
P
i
V
i
= nRT ; In the equation V
i
stands for the volume which is available for free movement of the molecules.
V
ideal
= volume available for free movement of gaseous molecule
hence, V
i
= V {volume not available for free movement} For an ideal gas
V
i
= V {V = volume of container}
but for a real gas
V
i
= V , as all the volume is not available for free movement
"manishkumarphysics.in"
17
CHEMISTRY
Molecules have finite volume :
Excluded volume per molecule =
2
1
)
`

t
3
) r 2 (
3
4
= Co-volume per molecule.
The volume that is not available for free movement is called excluded volume.
let us see, how this excluded volume is calculated.
r r
1
2
Excluded volume
(not available for free momement)
For above example, the entire shaded region is excluded, as its centre of mass cannot enter this region.
If both molecules were ideal, then they would not have experienced any excluded volume but not in the case,
of real gas as the centre of mass of 2 cannot go further.
Hence for this pair of real gas molecules,
Excluded volume per molecule =
2
1
)
`

t
3
) r 2 (
3
4
= 4
)
`

t
3
r
3
4
= excluded volume per mole of gas (b) = N
A
4
)
`

t
3
r
3
4
= 4 x N
A
x Volume of individual molecule
for n moles, excluded volume = nb
V
i
= V nb volume correction
Pressure correction or effect of molecular attraction forces :
Due to these attraction, speed during collisions will be reduced
Momentum will be less
Force applied will be less
Pressure will be less.
P
ideal
= P + {correction term}
Correction term o no. of molecules attracting the colliding molecule (n/v).
Correction term odensity of molecules (n/v).
no. of collision o density of molecules
|
.
|

\
|
v
n
net correction term
|
.
|

\
|
v
n
|
.
|

\
|
v
n
=
2
2
v
an
a is constant of proportionality
and this is dependent on force of attraction
Stronger the force of attraction greater will be a (Constant)
P
i
= P +
2
2
v
an
Vander waals equation is
|
|
.
|

\
|
+
2
2
v
an
P
(v nb) = nRT
"manishkumarphysics.in"
18
CHEMISTRY
VERIFICATION OF VANDER WAALS EQUATIONS :
Variation of Z with P for vander waals' equation at any temp.
Vander waal equation for 1mole
|
|
.
|

\
|
+
2
m
V
a
P
(V
m
b) = RT
AT LOWPRESSURE (at separate temp.)
At low pressure V
m
will be high.
Hence b can be neglected in comparision to V
m
. but 2
m
V
a
can't be neglected as pressure is low
Thus equation would be
|
|
.
|

\
|
+
2
m
V
a
P
V
m
= RT
PV
m
+
m
V
a
= RT
RT
PV
m
+
RT V
a
m
= 1
Z = 1
RT V
a
m
Z < 1
Real gas is easily compressible as compared to an ideal gas.
AT HIGHPRESSURE(moderate temp.)
V
m
will be low
so b can't be neglected in comparision to V
m
but
2
m
V
a
can be neglected as compared to much higher values of P..
Then vander Waals' equation will be
P(V
m
b) = RT
PV
m
Pb = RT
RT
PV
m
=
RT
Pb
+ 1
Z =
RT
Pb
+ 1 (Z > 1)
If Z > 1, then gas is more difficult to compress as compared to an ideal gas.
At lowpressure and very high temperature.
V
m
will be very large
hence b can't be neglected and
2
m
V
a
can also be neglected as V
m
is very large
PV
m
= RT (ideal gas condition)
For H
2
or He a ~ 0 because molecules are smaller in size or vander Wall's forces will be very weak,
these are non polar so no dipole-dipole interactions are present in the actions.
P(V
m
b) = RT so Z = 1 +
RT
Pb
a factor depends on inter molecular attractive forces.
a factor for polar molecule > a factor for non polar molecule.
"manishkumarphysics.in"
19
CHEMISTRY
Example-18 Arrange following in decreasing a factor (H
2
O, CO
2
, Ar)
H
2
O > CO
2
> Ar
polar
For non polar molecules :
Greater the size or surface area, greater will be vander waals' forces, so greater will be a constant.
Example-19 Arrange following gases according to a
He, Ar, Ne, Kr.
a
Kr
> a
Ar
> a
Ne
> a
He
More a factor means higher will be boiling point.
liquification pressure :
Is the pressure required to convert gas into liquid.
for easy liquefaction a| and P+
When Z < 1, V
m
< V
m, ideal
easily liquifiable
Z > 1, V
m
> V
m, ideal
more difficult to compress.
Example-20 Arrange the following according to liquification pressure.
n-pentane ; iso-pentane , neo pentane.
a
n-pentene
> a
iso-pentane
> a
neo-pentane
liquification pressure = LP
e tan pen n
P
L

<
e tan pen iso
P
L
<
e tan pen neo
P
L
b is roughly related with size of the molecule. (Thumb rule)
b = N
A
4
)
`

t
3
r
3
4
Example-21 Two vander waals gases have same value of b but different a values. Which of these would occupy
greater volume under identical conditions ?
Solution : If two gases have same value of 'b' but different values of 'a', then the gas having a larger value of 'a'
will occupy lesser volume. This is because the gas with a larger value of 'a' will have larger force of
attraction and hence lesser distance between its molecules.
"manishkumarphysics.in"
20
CHEMISTRY
Virial Equation of state :
It is a generalised equation of gaseous state. All other equations can be written in the form of virial equation
of state.
Z is expressed in power series expansion of P or
|
|
.
|

\
|
m
V
1
Z = 1 +
m
V
B
+ 2
m
V
C
+ 3
m
V
D
+ .....................
B second virial coefficient
C third virial coefficient
D fourth virial coefficient
Vander waals' equation in virial form :
|
|
.
|

\
|
+
2
m
V
a
P
(V
m
b) = RT
P =
) b V (
RT
m

2
m
V
a
Z =
RT
PV
m
=
) b V (
V
m
m

RT V
a
m
=
) V / b 1 (
1
m

RT V
a
m
x 1
1

= 1 + x + x
2
+ x
3
+ ..........
Z =
|
|
.
|

\
|
+ + + + .........
V
b
V
b
V
b
1
3
m
3
2
m
2
m

RT V
a
m
= 1 +
m
V
1
|
.
|

\
|

RT
a
b
+
2
m
2
V
b
+
3
m
3
V
b
+ .................
comparing vander waals equation with virial equation
B = b
RT
a
, C = b
2
, D = b
3
at low pressure : V
m
will be larger
hence 2
m
V
1
, 3
m
V
1
................ can be neglected
Z = 1 +
m
V
1
|
.
|

\
|

RT
a
b
If
|
.
|

\
|

RT
a
b
= 0 at T =
Rb
a
; Z = 1
so at T =
Rb
a
, gas will behave as an ideal gas (or follows Boyles law)
But at constant temperature, ideal gas equation is obeying Boyles law as T =
Rb
a
, so the temperature is
called Boyles' temp.
T
B
=
Rb
a
Z = 1
RT V
a
m
for a single gas, if we have two graphs as above, we must conclude T
2
< T
1
. At Boyles' temperature a/ RT
factor is compensated by 'b' factor, so Z = 1.
"manishkumarphysics.in"
21
CHEMISTRY
Critical constant of a gas :
When pressure increases at constant temperature volume of gas decreases
AB gas
BC vapour + liquid
CD liquid
critical point : At this point, all the physical properties of liquid phase will be equal to physical properties in
vapour such that
density of liquid = density of vapour
T
C
or critical temp :
Temperature above which a gas can not be liquified
P
C
or critical pressure :
minimum pressure which must be applied at critical temperature to convert the gas into liquid.
V
C
or critical volume :
volume occupied by one mole of gas at T
C
& P
C
Critical constant using vander waals' equations :
|
|
.
|

\
|
+
2
m
V
a
P
(V
m
b) = RT
( a PV
2
m
+ ) (V
m
b) = RT V
m
2
PV
m
3
+ aV
m
PbV
m
2
ab RTV
m
2
= 0
V
m
3
V
m
2
|
.
|

\
|
+
P
RT
b
+
P
a
V
m

P
ab
= 0
Given equation is cubic, hence there will be three roots of equation at any temperature and pressure.
At critical point, all three roots will coincide and will give single value of V = V
C
At critical point, Vander Waals' equation will be
V
m
3
V
m
2
|
|
.
|

\
|
+
C
C
P
RT
b
+
C
P
a
V
m

C
P
ab
= 0 ...(1)
But, at critical point, all three roots of the equation should be equal, hence equation should be :
V
m
3
3V
m
2
V
C
+ 3V
m
V
C
2
V
C
3
= 0 ...(2)
comparing with equation (1)
b +
C
C
P
RT
= 3V
C
....(i)
C
P
a
= 3 V
C
2
...(ii)
C
P
ab
= V
C
3
...(iii)
P
C
= 2
C
V 3
a
On substituting value of V
C
P
C
= 2
) b 3 ( 3
a
=
2
b 27
a
"manishkumarphysics.in"
22
CHEMISTRY
by (i)
C
C
P
RT
= 3 V
C
b = 9b b = 8b
T
C
=
Rb 27
a 8
At critical point, the slope of PV curve (slope of isotherm) will be zero
C
T
m
V
P
|
|
.
|

\
|
c
c
= 0 ...(i)
at all other point slope will be negative
0 (zero) is the maximum value of slope.
m
V c
c
C
T
m
V
P
|
|
.
|

\
|
c
c
= 0 ....(ii)
{Mathematically such points are known as point of inflection (where first two differentiation becomes zero)}
using the two, T
C
, P
C
and V
C
can be calculated
by
By any two a can be calculated but a calculated by V
C
and T
C
and a calculated by T
C
and P
C
may differ as
these values are practical values and V
C
cant be accurately calculated. So when we have V
C
T
C
& P
C
given,
use P
C
& T
C
to deduce a as they are more reliable.
Reduced Equation of state :
Reduced Temp : Temperature in any state of gas with respect to critical temp of the gas
T
r
=
C
T
T
Reduced pressure : P
r
=
C
P
P
Reduced volume : V
r
=
C
m
V
V
Vander waals' equation,
|
|
.
|

\
|
+
2
m
V
a
P
(V
m
b) = RT
Substitute values :
|
|
.
|

\
|
+
2
C
2
r
C r
V V
a
P P
(V
r
V
C
b) = R T
r
T
C
Substitute the value of P
C
T
C
and V
C
|
|
.
|

\
|
+
2 2
r
2
r
) b 3 ( V
a
b 27
a
P
(3b V
r
b) = RTr
Rb 27
a 8
|
|
.
|

\
|
+
r
r
V
1
3
P
(3 V
r
1) =
3
T R 8
r
|
|
.
|

\
|
+
2
r
r
V
3
P
(3V
r
1) = 8 T
r
(Reduced equation of state)
Above equation is independent froma, b and R, so will be followed by each and every gas, independent of its
nature.
"manishkumarphysics.in"
23
CHEMISTRY
Example-22 The vander waals constant for HCI are a = 371.843 KPa.dm
6
mol
2
and b = 40.8 cm
3
mol
1
find the
critical constant of this substance.
Solution : The critical pressure, P
C
=
2
b 27
a
=
6 2
3
10 ) 8 . 40 ( 27
10 843 . 371

=
2
9
) 8 . 40 ( 27
10 843 . 371

= 8.273 x 10
6
P
C
= 8.273 MPa
The critical pressure, T
C
=
Rb 27
a 8
R = 8.314 KPa dm
3
K
1
mol
1
T
C
=
Rb 27
a 8
=
3
10 8 . 40 27 314 . 8
843 . 371 8

= 324.79 = 324.8 K
The critical volume, V
C
= 3b = 3 x 40.8 = 122.4 cm
3
Example-23 The vander waals constant for gases A, B and C are as follows :
Gas a/dm
6
KPa mol
2
b/dm
3
mol
1
A 405.3 0.027
B 1215.9 0.030
C 607.95 0.032
Which gas has
(i) Highest critical temperature
(ii) The largest molecular volume
(iii) Most ideal behaviour around STP ?
Solution : T
C
=
Rb 27
a 8
Since, R is constant, higher the value of a/b, higher will be critical temperature.
V
C
= 3b and V
C
V
m
(for a particular gas) therefore higher the value of V
C
, higher will be molar
volume of the gas.
If the critical temperature is close to 273 K, gas will behave ideally around the STP. Let us
illustrate the result in a tabular form.
Gas a/dm
6
KPa mol
2
b/dm
3
mol
1
T
C
V
C
a/b
A 405.3 0.027 534.97 K 0.081 1.501 x 10
4
B 1215.9 0.030 1444.42 K 0.09 4.053 x 10
4
C 607.95 0.032 677.07 K 0.096 1.89 x 10
4
(i) B gas has the largest critical temperature.
(ii) C gas has the largest molecular volume.
(iii) A gas has the most ideal behaviour around STP
Vapour pressure of a liquid (aqueous Tension of water) :
Vapour pressure depends on
(a) Temperature (T | VP | )
(b) Nature of the liquid
Vapour pressure is independent of amount of liquid & surface area of liquid.
Vapour pressure of the liquid is independent of pressure of any gas in the container,
P
total
= P
gas
+ P
water vapour
"manishkumarphysics.in"
24
CHEMISTRY
Example-24 In a container of capacity 1 litre, air and some liquid water is present in equilibriumat total pressure of
200mmof Hg. This container is connectedto another onelitreevacuatedcontainer. Findtotal pressure
inside the container when equilibrium is again stablised (aqueous tension or vapour pressure at this
temp. is 96 mm Hg).
Solution : Total pressure = 200 mm of Hg = P
gas
+ P
vapour water
P
gas
+ 96 = 200
P
gas
= 104 mm of Hg Initially
when second container is connected
P
1
= 104 mm of Hg P
2
= ?
V
1
= 1 V
2
= 2 litre
P
1
V
1
= P
2
V
2
104 1 = P
2
2
52 = P
2
After equilibrium is established
P
total
= 52 + 96 = P
gas
+ P
water
= 148 mm of Hg at equilibrium.
Eudiometry :
The analysis of gaseous mixtures is called eudiometry. The gases are identified by absorbing them in
specified and specific reagents.
Some Common Facts :
Liquids and solutions can absorb gases.
If a hydrocarbon is burnt, gases liberated will be CO
2
& H
2
O. [H
2
O is seperated out by cooling the
mixture & CO
2
by absorption by aqueous KOH]
If organic compound contains S or P, then these are converted into SO
2
& P
4
O
10
by burning the
organic compound.
If nitrogen is present, then it is converted into N
2
.
[The only exception : if organic compound contains NO
2
group then NO
2
is liberated]
If mixture contains N
2
gas & this is exploded with O
2
gas, do not assume any oxide formation unless
specified.
Ozone is absorbed in turpentine oil and oxygen in alkaline pyragallol.
Example-25 Carbon dioxide gas (CO
2
) measuring 1 litre is passed over heated coke the total volume of the gases
coming out becomes 1.6 litre. Find %conversion of CO
2
into carbon monoxide.
Solution : CO
2
+ C

2CO CO
2
CO
1 0 at time t 1 x 2x
Initial volume = 1 litre
final volume = 1.6 litre Final volume = (1 + x) litres
1 + x = 1.6
x = 0.6
x = 0.6
1
6 . 0
10 = 60% of CO
2
will be converted into CO
Example-26 100 ml of hydrocarbon is mixed with excess of oxygen and exploded. On cooling, the mixture was
reported to have a contraction of 250 ml. The remaining gas when passed through a solution of
aqueous KOH, the mixture shows a further contraction of 300 ml. Find molecular formula of the
hydrocarbon.
Solution : C
x
H
y
+
|
.
|

\
|
+
4
Y
x
O
2

x CO
2
+ O H
2
y
2
100 ml x 100
2
y
100.
mixture contains CO
2
, H
2
O & excess O
2
on cooling, H
2
O is separated, volume of H
2
O= 250 ml
2
y
100 = 250 ; y = 5,
"manishkumarphysics.in"
25
CHEMISTRY
as KOH absorbs CO
2
, hence 300 ml contraction is because of CO
2
that has been absorbed.
Volume of CO
2
= 100 x = 300 ; x = 3
Empirical formula = C
3
H
5
; molecular formula = C
6
H
10
.
Note : If water is already condensed out then total contraction in reaction mixture = {volume of reactants} {volume
of products + volume of unused species excluding volume of H
2
O}.
Example-27 100 ml of an hydrocarbon is burnt in excess of oxygen in conditions so that water formed gets
condensed out the total contraction in volume of reaction mixture was found to be 250 ml when the
reaction mixture is further exposed to aqueous KOHa further contraction of 300 ml is observed find
molecular formula of hydrocarbon.
Solution : C
x
H
y
+ O
2

CO
2
+ H
2
O
100 ml excess 300 ml
By POAC on C atoms
x 100 = 300
x = 3
POAC on H atoms
y 100 = 2 moles of H
2
O
POAC on O atoms
2 v = 2 300 + 1 H
2
O {V = volume of O
2
consumed}
2 v = 600 + 50 y
v =
2
y 50 600 +
volume of O
2
consumed
The total volume contraction is 250 ml.
Hence, 100 + V 300 = 250
200 + V = 250
2 450 600 = 50 y
50
300
= y = 6
Hydro carbon will be C
3
H
6
Alternative :
Using balanced chemical equation
C
x
H
y
+
|
.
|

\
| +
4
y x
O
2

xCO
2
+
2
y
H
2
O
t = 0 100 ml V 0 0
t 0 V 100
|
.
|

\
|
+
4
y
x
100 x ml
2
y 100
volumeremained
V100
|
.
|

\
|
+
4
y
x
+ 100x + 50y
100 V = 250
25y + 50y = 150
25y = 150
y = 6
"manishkumarphysics.in"
26
CHEMISTRY
Summary
A gas is a collection of atoms or molecules moving independently through a volume that is largely empty
space. Collisions of the randomly moving particles with the walls of their container exert a force per unit area
that we perceive as pressure. The SI unit for pressure is the pascal, but the atmosphere and the millimeter
of mercury are more commonly used. The physical condition of any gas is defined by four variables ; pressure
(P), temperature (T), volume (V) and molar amount(n). The specific relationship among these variables are
called the gas laws :
Boyle's law : The volume of a gas varies inversely with its pressure. That is, V 1/Por
PV = k at constant n. T.
Charles Law: The volume of a gas varies directly with its Kelvin temperature. That is,
V T or V/T = k at constant n, P
Avogadro's Law: The volume of a gas varies directly with its molar amount. That is, V n or
V/n = k at constant T,P.
The three individual gas laws can be combined into a single ideal gas law, PV = nRT. If any three of the four
variables P, V, T and n are known, the fourth can be calculated. The constant R in the equation is called the
gas constant and has the same value for all gases. At standard temperature and pressure (STP; 1 atm and
0C), the standard molar volume of an ideal gas is 22.414 L.
The gas laws apply to the mixture of gases as well as to pure gases According to Dalton's law of partial
pressures, the total pressure exerted by a mixture of gases in a container is equal to the sum of the partial
pressure of each individual gas would exert alone.
The behaviour of gases can be accounted for using a model called the kinetic-molecular theory, a group of
five postulates :
1. A gas consists of tiny particles moving at random.
2. The volume of the gas particles is negligible as compared with the total volume.
3. There are no forces between particles, either attractive or repulsive.
4. Collisions of gas particles are elastic.
5. The average kinetic energy of gas particles is proportional to their absolute temperature.
The connection between temperature and kinetic energy obtained fromthe kinetic- molecular theory makes
it possible to calculate the average speed of a gas particle at any temperature. An important practical
consequence of this relationship is Graham' law, which states that the rate of a gas effusion or spontaneous
passage through a pinhole in a membrane depends inversely on the square root of the molar mass of gas.
Real gases differ in their behaviour from that predicted by the ideal gas law, particularly at higher pressure,
where gas particles are forced close together and intermolecular forces become significant.
"manishkumarphysics.in"
27
CHEMISTRY
"manishkumarphysics.in"
28
CHEMISTRY
MISCELLANEOUSSOLVEDPROBLEMS(MSPs)
1. The diameter of a bubble at the surface of a lake is 4 mm and at the bottom of the lake is 1 mm. If
atmospheric pressure is 1 atm and the temperature of the lake water and the atmosphere are equal. what is
the depth of the lake ?
(The density of the lake water and mercury are 1 g/ml and 13.6 g/ml respectively. Also neglect the contribution
of the pressure due to surface tension)
Sol.
P
1
V
1
= P
2
V
2
(760 mm 13.6 g)
3
4
t (4 mm/2)
3
= (760 mm 13.6 g + h 1 g)
3
4
t (1 mm/2)
3
760 13.6 64 = (760 13.6 + h)
h = 64 760 13.6 760 13.6
h = 63 760 13.6 mm
h =
1000 1000
6 . 13 760 63

km = 0.6511 km = 651.1 m Ans.
2. A gas is initially at 1 atm pressure. To compress it to 1/4 th of initial volume, what will be the pressure
required ?
Sol. P
1
= 1 atm V
1
= V
P
2
= ? V
2
=
4
V
P
1
V
1
= P
2
V
2
at const. T & n
P
2
=
2
1 1
V
V P
=
4
V
V atm 1
= 4 atm Ans.
3. A gas column is trapped between closed end of a tube and a mercury column of length (h) when this tube is
placed with its open end upwards the length of gas column is (
1
), the length of gas column becomes (
2
)
when open end of tube is held downwards. Find atmospheric pressure in terms of height of Hg column.
Hg
h
P
0
case I
P
1

1
Hg h
P
0
case II
P
2
2
Sol. for gas P
1
= (P
O
+ h) P
2
= (P
O
h)
V
1
= tr
2

1
V
2
= tr
2

2
at const T. and moles.
P
1
V
1
= P
2
V
2
; (P
O
+ h) tr
2

1
= (P
O
h) tr
2

2
P
O

2
+ h
1
= P
O

2
h
2
P
O

2
P
o

1
= h, + h
2
P
0
=
) (
) ( h
1 2
2 1

+
cm of Hg column Ans.
4. If water is used in place of mercury then what should be minimum length of Barometer tube to measure
normal atmospheric pressure.
Sol.
g
H
P
=
O H
2
P = P
atm
.
0.76 m 13.6 g =
O H
2
h 1 g
O H
2
h = 0.76 13.6 = 10.336 m Ans.
"manishkumarphysics.in"
29
CHEMISTRY
5. A tube of length 50 cm is initially in open atmosphere at a pressure 75 cm of Hg. This tube is dipped in a Hg
container upto half of its length. Find the level of mercury column in side the tube.
Sol. If after dipping the tube, the
length of air column be x cm (situation shown in the adjoining figure).
Then by using, P
i
V
i
= P
f
V
f
Wehave.
75 cm Hg A = P
f
x A ....... (1) ( = 50 cm)
& also, P
f
= 75 cm Hg + (x
2

) ....... (2)
(2) & (1) [75 + (x 25)] x = 75 50
x
2
+ 50 x 3750 = 0
x = 41.14 or 91.14
But, x can't be ve x = 41.14
mercury column inside the tube = (50 41.14) cm = 8.86 cm Ans.
6. An open container of volume Vcontains air at temperature 27Cor 300 K.The container is heated to such a
temperature so that amount of gas coming out is 2/3 of
(a) amount of gas initially present in the container.
(b) amount of gas finally remaining in the container.
Find the temperature to which the container should be heated.
Sol. (a) Here , P & V are constant, n & T are changing. Let, initially the amount of gas present be n & temp
is 27C or 300K. Finally amount of gas present in container = n
3
2
n =
|
.
|

\
|
n
3
1
& final temp. be T. T.
Then using n
1
T
1
= n
2
T
2
, we have,
n 300 =
3
n
T
2
T
2
= 900K
i.e., final temp = 900K Ans.
Sol. (b) Let there be x moles of gas remaining in the container,
3
2
of x come out
(x +
3
2
x) = n
3
x 5
= n x =
5
n 3
Using n
1
T
1
= n
2
T
2
n 300 K =
5
n 3
T
2
T
2
= 500K
final temperature = 500 KAns.
7. Find the lifting power of a 100 litre balloon filled with He at 730 mm and 25C. (Density of air = 1.25 g /L).
Sol. Since, PV = nRT
PV =
M
W
RT W =
RT
PVM
=
760
730

298 082 . 0
4 100

g
i.e., Wt. of He = 15.72 g
Wt. of air displaced = 100 1.25 g/L = 125 g
Lifting power of the balloon = 125 g 15.72 g = 109.28 g Ans.
8. A weather balloon filled with hydrogen at 1 atm and 300 K has volume equal to 12000 litres. On ascending it
reaches a place where temperature is 250 K and pressure is 0.5 atm. The volume of the balloon is :
(A) 24000 litres (B) 20000 litres (C) 10000 litres (D) 12000 litres
Sol. Using
1
1 1
T
V P
=
2
2 2
T
V P
;
K 300
L 12000 atm 1
=
K 250
V atm 0.5
2

V
2
= 20,000 L
Hence Ans. (B)
"manishkumarphysics.in"
30
CHEMISTRY
9. Four one litre flasks are separately filled with the gases, O
2
, F
2
, CH
4
and CO
2
under the same conditions.
The ratio of number of molecules in these gases :
(A) 2 : 2 : 4 : 3 (B) 1 : 1 : 1 : 1 (C) 1 : 2 : 3 : 4 (D) 2 : 2 : 3 : 4
Sol. According to avogadros hypothesis.
All the flasks contains same no. of molecules
Ratio of no. of molecules of O
2
, F
2
, CH
4
& CO
2
= 1 : 1 : 1 : 1 Ans (B)
10. Asample of water gas has a composition by volume of 50%H
2
, 45%COand 5%CO
2
. Calculate the volume
in litres at STP at which water gas which on treatment with excess of steam will produce 5 litre of H
2
. The
equation for the reaction is :
CO + H
2
O CO
2
+ H
2
Sol. If x L CO in needed then
volume of H
2
in water gas =
L % 50
45 . 0
x
|
.
|

\
|

=
L
9 . 0
x
L
2
1
45 . 0
x
= |
.
|

\
|

But, from equation : CO + H
2
O CO
2
+ H
2
& Gay-Lussacs law, we get, that the volume of H
2
produced = volume of COtaken.
Volume of H
2
due to reaction = x L
Total volume of H
2
=
|
.
|

\
|
+ x
9 . 0
x
L = 5 L

9 . 0
x 9 . 1
= 5 L
x =
9 . 1
5 9 . 0
Volume of water gas =
L
45 . 0 9 . 1
5 9 . 0
L
45 . 0
x

=
= 5.263 L Ans.
11. Acar tyre has a volume of 10 litre when inflated. The tyre is inflated to a pressure of 3 atm at 17C with air.
Due to driving the temperature of tyre increases to 47C.
(a) What would be pressure at this temperature ?
(b) Howmany litres of air measured at 47C and pressure of 1 atm should be left out to restore the tyre to 3
atm at 47C ?
Sol. V = 10L P, = 3 atm T, = 17
o
C = 290K
T
2
= 47
o
C = 320K
(a) Here v & n are constant
Using
1
1
T
P
=
2
2
T
P
P
2
=
1
2 1
T
T P
=
290
320 3
atm
i.e. P
2
= 3.3103 atm
i.e. Pressuse at 47
o
C = 3.3103 atm Ans.
(b) Now, P
1
= 3 atm ; V
1
= 10L ; T
1
= 17
o
C = 290K
Final P
2
= 3atm ; V
2
= ? ; T
2
= 47
o
C = 320 K
1
1
T
V
=
2
2
T
V
V
2
=
1
2 2
T
T V
=
K 290
K 320 L 10
= 11.035L
Volume of gas should be removed at 47
o
C & 3atm = (11.035 10) L = 1.035L
Now this vol at 1atm be v' then
1.0351 3atm = v' 1atm
v' = 3.105L
Reqd vol = 3.105 L Ans.
"manishkumarphysics.in"
31
CHEMISTRY
12. The partial pressure of hydrogen in a flask containing two grams of hydrogen and 32 gm of sulphur
dioxide is :
(A) 1/16th of the total pressure (B) 1/9th of the total pressure
(C) 2/3 of the total pressure (D) 1/8th of the total pressure
Ans. (C)
Sol.
2
H
n =
mol / g 2
g 2
= 1mol.
2
SO
n =
mol / g 64
g 32
= 0.5 mol

2
H
P =
( )
2 2
2
SO H
H
n n
n
+
P
T
=
) 5 . 0 1 (
1
+
P
T
=
3
2
P
T
.
(C)
13. Equal volume of two gases which do not react together are enclosed in separate vessels. Their pressures
are 10 mm and 400 mm respectively. If the two vessels are joined together, then what will be the
pressure of the resulting mixture (temperature remaining constant) :
(A) 120 mm (B) 500 mm (C) 1000 mm (D) 205 mm
Ans. (D)
Sol. Let, vol of containers be V & temperature be T
P
1
= 10mm P
2
= 400mm
n
1
=
RT
V P
1
& n
2
=
RT
V P
2
n
1
+ n
2
=
RT
V ) P P (
2 1
+
After joining two containers final vol = (V+V) = 2V(for gases)
P
final
=
( )
final
2 1
V
RT n n +
=
RT
V ) P P (
2 1
+

V 2
RT
=
( )
2
P P
2 1
+
=
( )
2
mm 400 10 +
= 205 mm.
14. 5 ml of H
2
gas diffuses out in 1 sec froma hole. Find the volume of O
2
that will diffuse out fromthe same hole
under identical conditions in 2 sec.
Sol. Rate of diffusion of H
2
=
sec 1
ml 5
= 5ml/s =
2
H
r (say)

2
o
r =
2
H
r
4
1
= 5ml/s
4
1
Volume of O
2
diffused in 2.0 seconds
=
4
5
2 ml = 2.5 ml Ans.
15. Avessel contains H
2
& O
2
in the molar ratio of 8 : 1 respectively. This mixture of gases is allowed to diffuse
through a hole, find composition of the mixture coming out of the hole.
Sol. Here,
2
H
n :
2
O
n = 8 : 1 &
2
2
O
H
r
r
=
2
2
O
H
n
n
2
2
H
O
M
M

2
2
O
H
r
r
=
1
8

2
32
=
1
32

( )
( ) t / out g min co O of moles of . no
t / out g min co H of moles of . no
2
2
A
A
=
1
32
Required composition of H
2
: O
2
coming out = 32 : 1 Ans.
"manishkumarphysics.in"
32
CHEMISTRY
16. The rate of diffusion of a sample of a ozonized oxygen is 0.98 times than that of oxygen. Find the %
(by volume of ozone in the ozonized sample).
Sol. Let, rate of diffusion of ozonized oxygen be r
g
& Let, reat of diffusion of oxygen be
2
O
r

2
O
g
r
r
= 0.98 (given) ......... (1)
but
2
O
g
r
r
=
2 / 1
g
O
M
M
2
|
|
.
|

\
|
(mean molar mass of ozonized oxygen = M
g
)
Form (1) 0.98 =
g
M
32
(0.98)
2
=
g
M
32
M
g
=
( )
2
98 . 0
32
= 33.32
Let % of O
3
be x % O
2
= (100 x) in ozonized oxygen.

( )
100
32 x 100 x 48 +
= 33.32
3200 + 16x = 33.32 x =
16
132
= 8.25 %
i.e. % of O
3
= 8.25 % Ans.
17. (i) Calculate the pressure exerted by 10
23
gas molecules, each mass 10
22
g in a container of volume one
litre. The rms velocity is 10
5
cm/sec.
(ii) What is the total kinetic energy (in cal) of these particles ?
(iii) What must be the temperature ?
Sol. (i) Here N = 10
23
molecules m = 10
22
g , V = 1L = 1000 cm
3
rms velocity = 10
5
cm/second
PV =
3
1
Nm
2
U
P =
3
1
Nm
2
U
=
3
cm 1000 3
1

10
23
10
22
g (10
5
)
2
cm
2
/s
2
= 3.33 10
7
dyne/cm
2
Ans.
(ii) Total K
.
E of the molecules
=
2
1
Nm
2
U
=
2
1
10
23
10
25
kg (10
3
m/s)
2
=
2
J 10000
= 5000 J ~ 1195.0 Cal Ans.
(iii) Avg K
.
E of one molecule =
2
1
m
2
U
=
2
3
kT
T =
3
1

k
U m
2
=
3
1

( )
314 . 8
10 023 . 6 s / m 10 Kg 10
23
2
3 25

K
|
.
|

\
|
=
NA
R
k
= 2414.8 K Ans.
"manishkumarphysics.in"
33
CHEMISTRY
18. If for two gases of molecular weights M
A
and M
B
at temperature T
A
and T
B
; T
A
M
B
= T
B
M
A
, then which
property has the same magnitude for both the gases.
(A) Density (B) Pressure (C) KE per mol (D) RMS speed
Sol. Given that T
A
M
B
= T
B
M
A

A
A
M
T
=
B
B
M
T
But, r.m.s. =
M
RT 3
r.m.s
A
=
A
A
M
RT 3
& r.m.s
B
=
B
B
M
RT 3
r.m.s
A
= r.m.s
B
Ans. (D)
19. It has been considered that during the formation of earth H
2
gas was available at the earth. But due to the
excessive heat on the earth this had been escaped. What was the temperature of earth during its formation?
(The escape velocity is 1.1 x 10
6
cm/s)
Sol. Escape velocity of H
2
should be equal to average velocity of H
2
.
Avg velocity of H
2
= 1.1 10
6
cm/s = 1.1 10
4
m/s
But, avg. velocity =
M
RT 8
t
1.1 10
4
=
3
10 2
T 314 . 8 8
t

( ) kg 10 2 g 2 M
3
H
2
= =
T =
( )
314 . 8 8
10 2 10 1 . 1
3
2
4

t
K = 11430.5 K = 11157.5
o
C Ans.
20. Under critical states of a gas for one mole of a gas, compressibility factor is
(A)
8
3
(B)
3
8
(C) 1 (D)
4
1
Sol. For 1 mole of gas Z =
C
C C
RT
V P
(Under critical condition)
But, P
C
=
2
b 27
a
, V
C
= 3b , T
C
=
Rb 27
a 8
Z =
|
.
|

\
|
2
b 27
a

R
b 3

a 8
Rb 27
=
8
3
Ans. (A)
21. One litre of oxygen gas is passed through a ozonizer & the final volume of the mixture becomes 820 ml. If
this mixture is passed through oil of turpentine. Find the final volume of gas remaining.
Sol. The reaction that takes place in ozonizer as 3O
2
2O
3
.
If Vml of O
2
out of 1000 ml is ozonized then vol of O
3
obtained =
3
2
V
Final vol of ozonized oxygen
= (1000 V +
3
2
V) mL = 820 mL
1000
3
1
V = 820

3
V
= 180 V = 540
O
2
remaining = (1000 540) mL ( O
3
is absorbed in oil of turpentine)
= 460 mL Ans.
"manishkumarphysics.in"
34
CHEMISTRY
22. A gaseous mixture containing CO, methane CH
4
& N
2
gas has total volume of 40 ml. This mixture is
exploded with excess of oxygen on cooling this mixture a contraction of 30 ml is observed & when this
mixture is exposed to aqueous KOH a further contraction of 30 ml is observed .find the composition of the
mixture.
Sol. Let vol of CO be x mL
vol of CH
4
be y mL
vol of N
2
be z mL
On explosion with excess of oxygen the following reactions takes place
CO(g) +
2
1
O
2
(g) CO
2
(g) (By Gaylussac's lawof combing volume)
x mL x mL
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(g)
y mL y mL 2 ymL
N
2
remains unreacted
On cooling H
2
O(g) liquifies hence volume reduction of 30 mL is observed
2y = 30 y = 15
But, vol of CO
2
obtained = (x + y) mL
This is absorbed in KOH & vol reduction of 30 mL is observed.
x + y = 30 x = 30 y = (30 15) = 15
and, x + y + z = 40 z = 40 x y = 40 15 15 = 10
Composition of mixture is
vol of CO = 15 mL Ans.
vol of CH
4
= 15 mL Ans.
vol of N
2
= 10 mL Ans.