Gastertrtereous Stateerte

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MEASURABLE PROPERTIES OF GASES
1. MASS
The amount of gas is expressed in terms of its number of moles. For a gas of molar mass (M), the
mass in gram (w) is related to the number of moles (n) as n=w/M
2. VOLUME
The volume of the gas is the space occupied by its molecules under given set of conditions.
Volume of the container in which the gas is enclosed. 1m
3
= 10
3
L = 10
3
dm
3
= 10
6
cm
3

3. PRESSURE
The force experienced by the walls of container due to bombardment of gas molecules . This
force per unit area of the walls is termed as gas pressure.
SI unit of force is kg ms
-2
which is called Newton (N). I N= 1 kg ms
-2

SI unit of pressure as N/m
2
or Nm
-2
. This SI unit of pressure is called Pascal (Pa).- Kg m
-1
S
-2

I Pa=1 N m
-2
I bar = 100 kPa = 10
5
Pa

ATMOSPHERE AND ATMOSPHERIC PRESSURE
A thick blanket of air which surrounds the earth is called atmosphere.
Molecules of various gases present in the atmosphere are under constant pull of the gravitational
force of the earth. As a result of this, atmosphere is dense near the surface of the earth than that at
high altitudes. Force experienced by any area of the earth exposed to the atmosphere is equal to
the weight of column of air above it. This force per unit area of the earth is called atmospheric
pressure.
1 atm = 76.0 cm of mercury =760 mm of mercury = 760 torr. = 1.01325 x 10
5
Pa

MEASUREMENT OF GAS PRESSURE
The pressure other than atmospheric pressure are measured by device is called manometer.
There are two types of manometer open end and closed end manometers
(a) Open end manometer. It consists of U tube partially filled with mercury. One limb of the
tube is shorter than the other. The shorter limb is connected to the vessel containing the gas
whereas the longer limb is open .The mercury in the longer tube is subjected to the
atmospheric pressure while mercury in the shorter tube is subjected to the pressure of the gas.

MEASUREMENT OF GAS PRESSURE.
There are three possibilities described as follows :
(i) If the level of Hg in the two limbs is same, then, gas pressure (P
gas
)=atmospheric pressure
(P
atm
)
GASEOUS STATE - I
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(ii) If the level of Hg in the longer limb is higher , Gas pressure (P
gas
) =P
atm
+ (difference
between the two levels)
= P
atm
+ P
h

(iii)If the level of Hg in the shorter limb is higher, then Gas pressure (P
gas
) =P
atm
-(difference
between the two levels)
= P
atm
- P
h
.
(b) Closed end manometer. This is generally used to measure low gas pressures. It also
consists of U-tube with one limb shorter than the other and partially filled with mercury.
The space above mercury on the closed end is completely evacuated. The shorter limb is
connected to the vessel containing gas. The gas exerts pressure on the mercury in the
shorter limb and forces its level down.
Gas pressure (
gas
) =[Difference in the Hg level in two limbs] Or P
gas
= P
h

Closed end manometer.

(4) TEMPERATURE
Temperature may be defined degree of hotness. Common temperature-measuring device
is thermometer.
(5) STANDARD TEMPERATURE AND PRESSURE (ST.P.)
S.T.P. conditions (O
0
or 273.15 K temperature and 1 atm (=1.01325 bar) pressure.
Standard Ambient Temperature and Pressure (SATP) . The SATP conditions are
298.15 K (25
0
C) and 1 bar (10
5
Pa) pressure the molar volume of ideal gas at SATP
conditions is 24.789 L mol
-1
.
Question 1: A manometer is connected to a gas containing bulb. The open arm reads 43.7 cm
where as the arm connected to the bulb read 15.6 cm. If barometric pressure is 743 mm Hg what
is the pressure of gas in bar?
Question 2: Side arm of an open-end mercury manometer is attached to a system. The level of
mercury in the arm attached to a system is 125 mm lower than the open end arm. Is the
pressure higher than the atmospheric pressure or lower? What is the pressure of the system
if atmospheric pressure is 760 mm Hg?
Question 3: Open end mercury manometer is connected to a gas chamber containing a gas at a
pressure of 1.38 bar. The barometric pressure is 750 mm Hg. The arm connected to gas chamber
stands at 11.3 cm. What is the reading in open arm of the manometer?
Question 4: A student reported the gas pressure as 1.4 10
5

kgm
-1
s
-2
. Report this value in kPa,
atm, mm of Hg and bar.

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GAS LAWS
BOYLES LAW
This law describes the pressure-volume relationship of gases at constant temperature. It was given
by Robert Boyle.
The volume of a fixed mass of a gas is inversely proportional to its pressure at constant
temperature.

Mathematically, the law may be expressed as: (Temperature and mass constant)

Or where k
1
is constant of proportionality Or PV=k
1
=constant.

Or P
1
V
1
=P
2
V
2

For a given amount of the gas, the product of pressure and volume is constant at constant
temperature.

GRAPHICAL REPRESENTION OF BOYLES LAW

Q. No. 1 A balloon is filled with hydrogen at room temperature. It will burst if pressure exceeds
0.2 bar. If at 1 bar pressure the gas occupies 0.27 L Volume; upto what volume can the
balloon be expanded?
2. In a J tube partially filled with mercury the volume of air column is 4.2 mL and the mercury
level in the two limbs is same. Some mercury is, now added to the tube so that the volume of
air enclosed in shorter limb is now 2.8 mL. What is the difference in the levels of mercury in
this situation? Atmospheric pressure is reported to be 1.0 bar.
3. At constant temperature, a gas occupies a volume of 200 mL at a pressure of 0.720 bar. It is
subjected to an external pressure of 0.900 bar. What is the resulting volume?
4. A vessel of 120 mL capacity contains a certain amount of a gas at 1.2 bar pressure and 35
0
C.
The gas is transferred to another vessel of volume 180 mL at 35
0
C. What would be its
pressure?

CHARLES LAW
This law describes the volume-temperature relationship of gases at constant pressure. It was put
forwarded by Jacques Charles.
The volume of a fixed mass of a gas increases or decreases by 1/273.15 of its volume at 0
0
C
for each degree rise or fall of temperature, provided pressure is kept constant.
If V
0
is the volume of given mass of the gas at 0
0
C
Then, V
1
, the volume of the gas at 1
0
C = V
0
+
15 . 273
V
0
= V
0
|
.
|
\
|
+
15 . 273
1
1
P
I
V
P
I
k V
1
=

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V
2
, The volume of the gas at 2
0
C = V
0
|
.
|
\
|
+
15 . 273
2
1
V
t
, the volume of the gas at t
0
C = V
0
|
.
|
\
|
+
15 . 273
t
1
ALTERNATIVE STATEMENT OF CHARLESS LAW
We have already derived the relationship between the volume of a given mass of the gas at t
0
C
(V
t
) and that at 0
0
C (V
0
).

Where T is corresponding temperature in kelvin scale.

Or

Thus, V = k
2
T or V T (at constant P and n)
An alternative statement of Charles law as :
The volume of the fixed mass of a gas at constant pressure is directly
proportional to the temperature in Kelvin scale.
Let V
1
be the volume of a certain mass of a gas at temperature T
1
and at pressure P. If temperature
is changed to T
2
keeping pressure constant, The volume changes to V
2
. The relationship between
four variables V
1
, T
1
, V
2
and T
2
is:
2
2
1
1
T
V
T
V
= (P and n are constant)
GRAPHICAL REPRESENTATION OF CHARLES LAW
The law can also be illustrated by volume-temperature curves. Plot of volume of a given of a gas
against temperature at constant pressure. We get a graph as shown

GAYLUSSACS LAW OR AMONTONS LAW
This law describes the pressure-temperature relationship of gases at constant volume. It states that
pressure of a fixed mass of a gas at constant volume is directly proportional to the temperature in
Kelvin scale.
Mathematically, PT (At constant n, V)

QUESTIONS
|
.
|
\
|
+ =
15 . 273
t
1 V V
0 t
0
1
0 0
15 . 273
15 . 273
T
T
V
t
V = |
.
|
\
| +
=
0
0
t
1
T
V
T
V
=
) n and P t tan cons at ( k t tan cons
T
V
2
= =
2
2
1
1
T
P
T
P
=

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1. A sample of a gas is found to occupy a volume of 900 cm
3
at 27
0
celsius. Calculate the
temperature at which it will occupy a volume of 300 cm
3
, provided the pressure is kept
constant.
2. A steel tank contains air at a pressure of 15 bar at 20
0
C. The tank is provided with a safety
value which can withstand a pressure of 35 bar. Calculate the temperature to which the tank
can be safety heated.
3. A sample of a gas occupies 10 L at 127
0
C and 1 bar pressure. The gas is cooled to 73
0
C at
the same pressure. What would be the volume of the gas?
4. A vessel of capacity 400 cm
3
contains hydrogen gas at 1 atm. Pressure at 7
0
C. In order to
expel 28.57 cm
3
of the gas at the same pressure to what temperature, the vessel should be
heated?
5. A flask having a volume of 250.0 mL and containing air is heated to 100
0
C and sealed. Then
the flask is cooled to 25
0
C, immersed in water and opened. What volume of water will be
drawn back into the flask, assuming the pressure remaining constant?

AVOGADROS LAW
Equal volumes of all the gases under similar conditions of temperature and pressure contain equal
number of molecules.
Ideal Gas Equation:- It is combination of Boyles law, Charles law and Avogadros
law.
According to Boyles law V
P
1
(at constant T and n)
According to Charles law V T (at constant P and n)
According to Avogadros law V = n (at constant T and P)
or PV nT ; PV= nRT

Where, R is constant of proportionality and is known as universal gas constant. It is also known
as equation of state for ideal gas.

RELATIONSHIP BETWEEN DENSITY AND MOLAR MASS

,
Where d is the density of gas
(
= =
V
w
Volume
Mass
d
R represents work done per degree per mole.

NUMERICAL VALUE OF R

(i) for 1 mol of gas

= 8.3144 Pa m
3
K
-1
mol
-1
or 8.3144 JK
-1
mol
-1
.

(ii) When pressure is expressed in atmosphere and volume in liters. =
0.0821LatmK
-1
mol
-1
.
(iii) When pressure is expressed in bar and volume in dm
3
.
P
nT
V =
RT
M
w
nRT PV = =
M
dRT
P or
MV
wRT
P = =
nT
PV
R =
) K 15 . 273 ( x ) mol 1 (
) m 10 x 414 . 22 ( ) Pa 101325 (
R
3 3
=
) K 15 . 273 ( x ) mol 1 (
) litres ( 414 . 22 x ) atm ( 1
R =
T
PV
R =

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We know that one mole of any gas at 1 bar pressure and 273.15 K (new S.T.P. conditions)
occupies a volume of 22.7 dm
3
or 22.7 L. Then

= 0.0831 bar dm
3
K
-1
mol
-1
.

= 1.99 calories K
-1
mol
-1
or = 2 cal K
-1
mol
-1
.

Q.No.1: A sample of nitrogen gas occupies a volume of 320 cm
3
at S.T.P. Calculate its
volume at 66
0
C and 0.825 bar pressure.
2. 1.0 mol or pure dinitrogen gas at SATP conditions was put into a vessel of volume 0.025 m
3
,
maintained at the temperature of 5
0
C. What is the pressure of the gas in the vessel?
3. How many moles of oxygen are present in 400 cm
3
sample of the gas at a pressure of 760 mm
of Hg at a temperature of 300 K. (The value of R is given to be 8.31 kPa dm
3
k
-1
mol
-1
).
4. A discharge tube containing nitrogen gas at 25
0
C is evacuated till the pressure is 2x10
-2
mm. If
the volume of discharge tube is 2 liter, calculate the number of nitrogen molecules still present
in the tube.
5. The density of certain gaseous oxide at 1.5 bar pressure at 10
0
C is same as that dioxygen at
20
0
C and 4.5 bar pressure. Calculate the molar mass of gaseous oxide.
6. Density of a gas is found to be 5.46g/dm
3
at 27
0
C and 2 bar pressure. What will be its density
at S.T.P.?
7. Temperature and pressure in Chandigarh are respectively 35
0
C and 740 mm whereas at
Shimla these are 10
0
C and 710 mm. calculate the ratio of densities of air at Chandigarh (d
1
)
and at Shimla (d
2
).
8. 2.9 g of a gas at 95
0
C occupies same volume as 0.184 g of H
2
at 17
0
C at the same pressure.
What is the molar mass of the gas?
9. Calculate the temperature of 4.0 mol of gas occupying 5 dm
3
at 3.32 bar pressure. (R=0.083
bar dm
3
K
-1
mol
-1
).
10. An air bubble has a radius of 0.50 cm at the bottom of the water tank where the temperature is
280 K and the pressure is 280 kPa. When the bubble rises to the surface, the temperature
changes to 300 K and pressure is 100 kPa. Calculate the radius of the bubble at the surface.
11. A gas balloon having a volume of 10.0 L at 25
0
C and 1 atm. Pressure rises to an altitude
where the temperature is 10
0
C and pressure 500 mm of Hg. What is the volume of balloon at
this altitude?
12. The pressure of the atmosphere 100 miles above the earth is about 2x10
-6
mm of Hg and the
temperature is 180
0
C. Calculate number of gaseous molecules per mL at this altitude.

DALTONS LAW OF PARTIAL PRESSURES
The law was given by John Dalton
At constant temperature, the pressure exerted by a mixture of two or more non-reacting
gases enclosed in a definite volume, is equal to the sum of the individual pressures which
each gas would exert if present alone in the same volume at the same temperature.
The individual pressures of gases are known as partial pressures. P=P
1
+P
2
+P
3
+ (T, V
are constant)
Question1:-

) K 15 . 273 ( x ) mol 1 (
) dm ( 414 . 22 x ) bar ( 1
R
3
=
7
7
10 x 183 . 4
10 x 314 . 8
R =

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1. A certain quantity of a gas occupies a volume of 0.1 L when collected over water at 288 K and
a pressure
0.92 bar. The same gas occupied a volume of 0.085 L at S.T.P. in dry conditions. Calculate the
aqueous tension at 288 K.
2. A sample of O
2
is collected over water at 22
0
C and 748 torr pressure. The volume of the gas
collected is 82.0 cm
3
. How many grams of oxygen are present in the gas? Vapour pressure of
water at 22
0
C is 19.8 torr.
3. A 2 L flask containing nitrogen at 60 cm pressure is put into a communication with 4 L flask
containing carbon monoxide at 48 cm pressure. If the temperature is kept constant. Calculate
the final pressure of the mixture.
4. A flask of 1.5 L capacity contains 400 mg of O
2
and 60 mg of H
2
at 100
0
C. Calculate the total
pressure of the gaseous mixture. . If the mixture is permitted to react to form water vapours
at 100
0
C, what materials will be left and what will be their partial pressures.
5. A gaseous mixture contains 5.6 g of carbon (II) oxide and rest carbon (IV) oxide when it is
enclosed in a vessel of 10 d m
3
at 298 K it recorded a pressure of 2.0 bar . What is the
partial pressure of each oxide of carbon?
6. Two bulbs A and B of equal volumes connected through stopcock (kept open) contained 0.7
mol of H
2
gas at pressure of 0.5 atm and 27
0
C. Calculate final pressure and molar
distribution of H
2
in two bulbs.
7. Pressure of 1 g of ideal gas A at 27
0
C is found to be 2 bar. When 2g of another gas is
introduced in the same flask at same temperature the pressure becomes 3 bar . Find the
relationship between their molar masses.

KINETIC MOLECULAR THEORY OF GASES
The various postulates of the theory are:
1. All gases are made up of very large number of extremely small particles called molecules.
2. The molecules are separated from one another by large spaces so that the actual volume
occupied by the molecules is negligible as compared to the total volume of the gas.
3. The molecules are not at rest but posses rapid random motion. During their motion, they
collide with one another and also against the walls of the container.
4. The pressure of the gas is due to bombardment of the gas molecules against the walls of the
conainer.
5. The collisions of the molecules with each other and with the walls of the container are
perfectly elastic, i.e. there may be redistribution of energy during such collision.
6. There are no attractive or repulsive forces between the molecules of the gas. They are
completely independent of each other.
7. At any instant, different molecules possess different velocities and hence, different energies.
However, the average kinetic energy of the molecules is directly proportional to the absolute
temperature.

(i) Most probable speed ( or u
mp
). It is the speed possessed by maximum fraction of molecules
of the gas at particular temperature. It is given by the expression

(or u
mp
)= (M is molar mass of gas)

(ii) Average speed ( or u
av
). It is the average of the speeds of different molecules of the gas
at particular temperature. If v
1
, v
2
, v
3
,.are speeds of different molecules, then

M
RT 2
v
N
.... v v v
) u or ( v
3 2 1
av
+ + +
=

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Average speed is given by the expression

(iii)Root mean square speed (u
r.m.s.
). It is the square root of the mean of the squares of
speeds of various molecules of the gas at a given temperature. If v
1
, v
2
,v
3
.. are speeds
of differ
ent molecules, then

Root mean square speed is given by the expressions

or

Relationship between different types of speeds.
The different types of speeds are related as :

KINETIC GAS EQUATION AND AVERAGE KINETIC ENERGY OF GAS
MOLECULES
PV=1/3 MnU
2
.
The average kinetic energy of gas molecules can be calculated on the basis of kinetic gas
equation. P=1/3 (N/V)mu
2

For one mol of the gas, PV=1/3N
A
mu
2
[N=N
A
for 1 mol]
Also for 1 mol of ideal gas, PV=RT
1/3N
A
mu
2
=RT

Now mu
2
represents average kinetic energy (K. E.) of the molecules.

Q.No. 1 Calculate (i) average kinetic energy of 32 g of methane molecules at 27
0
C R=8.314
JK
-1
mol
-1
.
(ii) Root mean square speed and (iii) Most proable speed of methane molecules at 27
0
C.

(2) Calculate the root mean square speed of oxygen molecule at 27
0
C.
(3) At what temperature rms velocity of SO
2
is equal to that CH
4
at 27
0
C?

Derivation of Gas Laws from Kinetic Gas equation
Boyle,s Law and Charles Law

At constant Temp.
M
RT 8
) u or ( v
av
=
N
..... v v v
u
2
3
2
2
2
1
. s . m . r
+ + +
=
M
PV 3
or
M
RT 3
ur
. a . m . r
=
. 224 . 1 : 128 . 1 : 1 :: u : v :
. a . m . r
RT
2
3
mu
2
1
or RT mu N
3
2
X
2
1
or
2 2
A
= =
kT
2
3
. E . K or RT
2
3
. E . K = =

2
Nu m
3
1
PV =
2
mu
2
1
X
3
2
PV = KE X
3
2
=
T KE
T
3
2
PV T
3
2
X K PV or =
P
T
3
2
X K V =
contsant T X X K =
3
2
P
X t cons V
1
tan =
D
P 3

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Or PV = constant (Boyles Law)

At constant pressure

V= constant T, Or V/T= constant
(Charles Law)

t tan cons
P 3
2
X K =

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GASEOUS STATE II

Dalton Law of Partial pressure
Let there be two gases in a container having root mean square velocity u
1
and u
2
number of
molecules N
1
and N
2
and mass of molecules m
1
and m
2
.
Pressure due to molecules of gas A Pressure due to Gas B

Molecules of two gases do not interfere each other in their motion so total pressure

=PA+PB (Daltons Law of partial pressure)

MAXWELLS DISTRIBUTION OF VELOCITIES
Molecules of a gas are in random motion and their velocities go on changing due to molecular
collision so it is not possible to find out actual velocity of a molecule but it is possible to find out
fraction of total number of molecules having a certain velociy.

Maxwell plotted vs velocity

Maxwell distribution of velocities
Important features of Maxwell distribution curve are
(i) The fraction of molecules with very low or very high velocities (speeds) is very small.
(ii) The fraction of molecules possessing higher and higher speeds goes on increasing till it
reaches the peak and thereafter it starts decreasing.
(iii)The maximum fraction of molecules possesses a velocity (or speed) corresponding to the peak
of the curve. This speed corresponding to the peak in the curve is referred to as most
probable speed.
(iv) The area under the curve gives the total number of gas molecules.

IDEAL GASES AND REAL GASES
Ideal gases are those which obey gas laws under all conditions of temperature and pressure.
No gas is an ideal gas.
REAL GASES:- All gases obey gas Laws at high temperature and low pressure but do not obey
gas laws at low temperature and high pressure . Such gases are known as real gases.
Compressibility factor Z

(i) For an ideal gas, as PV=nRT, Z=1
V
u N m
3
1
pA
1
2
1 1
=
V
u N m
3
1
pB
1
2
2 2
=
V
u N m
3
1
v
u N m
P
2
2
2 2
1
2
1 1
3
1
+ =
|
.
|
\
| A
N
N
N
N A
nRT
PV
Z =

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(ii) For a real gas, as PV nRT, Z 1. Hence, two cases arise:
(a) When Z<1, (e.g. for CH
4
, CO
2
etc.)the gas is said to show negative deviation. This implies
that the gas is more compressible than expected from ideal behaviour.
(b) When Z>1, the gas is said to show positive deviation. This implies that the gas is less
compressible than expected from ideal behavior. The temperature at which a real gas behaves
like an ideal gas over an appreciable pressure range is called Boyle temperature or Boyle
point.
Cause of Deviation from ideal Behaviour.
The derivation of the gas law (and hence of the ideal gas equation) is based upon the Kinetic
Theory of Gases which in turn is based upon certain assumptions. Thus, there must be something
wrong with certain assumptions. A careful study shows that at high pressure or low temperature,
he following two assumptions of Kinetic Theory of Gases is faulty:
(i) The volume occupied by the gas molecules is negligible as compared to the total volume of
the gas.
(ii) The force of attraction or repulsion between the gas molecules is negligible.
1
Equation of State for the Real gases (Vandar Waals equation). To explain the behavior of real
gases, J.D. Vandar Waal, in 1873, modified the ideal gas equation by applying appropriate
corrections so as to take into account
(i) the volume of the gas molecules and
(ii) the forces of attraction between the gas molecules.
He put forward the modified equation, known after him as van Waals equation. This equation for
1 mole of the gas is

And for n moles of the gas, it is

Where a and b are constants, called van der Waals constants. Their values depend upon the
nature of the gas.

Significance of Vander Waals constants
(i) Vander Waals constant a. Its value is a measure of the magnitude of the attractive forces
between the molecules of the gas. Greater the value of a stronger are the intermolecular forces of
attraction.
(ii) Vander Waals constant b. Its value is a measure of the effective size of the gas molecules.
Its value is equal to four times the actual volume of the gas molecules. It is called excluded
volume or co-volume.
Units of Vander Waals constants
(i) Units of a. As

=atm L
2
mol
-2
or bar dm
6
mol
-2

(ii) Units of b. As volume correction V = nb,

Explanation of the behaviour of real gases by Vander Waals equation
( ) RT b V
V
a
P
2
=
|
|
.
|
\
|
+
( ) nRT nb V
V
an
P
2
2
=
|
|
.
|
\
|
+
2
2
2
2
n
pXV
,
V
an
p
=
=
1 3 1
mol dm or mol L
n
v
b

= =

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(i) At very low pressures, V is very large. Hence, the correction term a/V
2
is so small that it can
be neglected. in comparison to V. Thus, Vander Waals equation reduces to the form PV=RT. i.e.
behave like ideal gases.
(ii) At moderate pressures, V decreases. Hence, a/V
2
increases and cannot be neglected.
However, V is still large enough in comparison to b so that b can be neglected. Thus, Vander
Waals equation becomes

(iii)At high pressure, V is also small that b cannot be neglected in comparison to V. The factor
a/V
2
is no doubt large but as P is very high, a/v
2
can be neglected in comparison to P. Thus,
Vander Waals equation reduces to the form
P(V-b)=RT Or PV=RT+pb

(iv) At high temperature, V is very high (at given pressure) so that both the correction factors (a/v
2

and b) become negligible as in case (I) . Hence, at high temperature, real gases behave like ideal
gas.

Explanation of the exceptional behaviour of hydrogen and helium. For H
2
and him, the
compressibility factor Z is always greater than 1 and increases with increase of pressure. This is
because H
2
and He being very small molecules, the intermolecular forces of attraction in them are
negligible i.e. a is very very small so that a/V
2
is negligible.
The Vander Waals equation, therefore, becomes
P (V-b)=RT Or PV=RT+ Pb

Thus PV/RT i.e. Z>1 and increases with increase in the value of P at constant T.
Q.No.1 Calculate the pressure exerted by 11.0 g of carbon dioxide in a vessel of 2 L capacity
at 37
0
C, Given the Vander Waals constants are a=3.59 L
2
atm mol
-2
and b=0.0427 L
mol
-1
. Compare the value with the calculated value if the gas were considered as
ideal.
Q.No.2. Calculate the temperature of 2 moles of sulphur dioxide gas contained in a 5 L vessel
at 10 bar pressure. Given that for SO
2
gas, Vander Waals constants are :a=6.7 bar L
2
mol
-
2
and b=0.0564 L mol
-1
.

Liquefaction of Gases and Critical Temperature
The liquefaction of a gas takes place when the intermolecular forces of attraction become so high
that they blind the gas molecules together to form the liquid state. The intermolecular forces of
attraction can be increased either by increasing 2 the pressure so that the molecules come close
together or by cooling the gas so that the kinetic energy of the molecules decreases and they
become slower. Hence, a gas can be liquefied by cooling or by application of pressure or the
combined effect of both. The effect of temperature on the liquefaction of gases is found to be very
important as higher the temperature of the gas, more difficult it is to liquefy it and higher is the
pressure required.

RT
V
PV or RT V
V
a
P
2
= + =
|
|
.
|
\
|
+ =
V
a
RT PV or =
RTV
a
1
RT
PV
or =
RTV
a
1 Z or =
RT
pb
1
RT
PV
or + =
RT
pb
1 Z or + =
RT
Pb
1
RT
PV
Or + =

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Critical temperature of a gas may be defined as that temperature above which it cannot be
liquefied howsoever high pressure may be applied on the gas.

Andrews Experiments on Critical phenomena. It is interesting to mention here that Andrews
in 1861 was the first to study the critical phenomena experimentally using CO
2
gas. He studied
the effect of pressure on the volume of CO
2
at different constant temperature. Some of the
isotherms thus obtained is

At the lowest temperature employed, i.e. 13.1
0
C, at low pressure, CO
2
exists as a gas, as shown at
the point A. As the pressure is increased, the volume of the gas decreases along the curve AB. At
the point B, liquefaction of the gas starts. Hence, volume decreases rapidly along BC because
liquid has much less volume than the gas. At the point C, liquefaction is complete. Now, the
increase in pressure has very little effect upon volume because liquids are very little compressible.
Hence, a steep curve CD is obtained. As the temperature is increased, horizontal portion becomes
smaller and smaller and 30.98
0
C, it reduced at a point, P. This means that above 30. 98
0
C, the gas
cannot be liquefied at all, however high pressure may be applied. Thus, 30.98
0
C is the critical
temperature. This corresponding pressure to liquefy the gas at the critical temperature is its critical
pressure, P
c
(i.e. 73.9 atm). The volume occupied by 1 mole of the gas under these conditions is
its critical volume, V
c
(i.e., 95.6 ml).
Joining the end point of the horizontal portion of the different curves, we get a dome-shaped curve
as shown in Figure 5.31. We observe that a point like A in the Fig. Represents gaseous state. A
point like D represents a liquid state and a point within the dome shaped area represent existence
of liquid and gaseous CO
2
in equilibrium. All the gases on isothermal compression show the same
behaviour as shown by CO
2
.


Contact: 9953168795, 9268789880

MCQ with only one Answer
1. At constant temperature, the product
of pressure and volume of a given
amount of a gas is constant. This is
(a) Gay-Lussac Law
(b) Charles Law
(c) Boyles Law
(d) Pressure Law
2. Charles law is represented
mathematically as:
(a) V
1
=KV
0
t
(b)

(c) (d)

3. Correct gas equation is:

(a) (b)

(c)

(d)

4. In general gas equation, PV=nRT, V is
the volume of:
(a) one moles of a gas
(b) any amount of a gas
(c) one moles of a gas
(d) one gram of gas
5. In the equation of state of an ideal gas
PV=nRT, the value of universal gas
constant would depend only on:
(a) The nature of the gas
(b) The units of measurement
(c) The pressure of the gas

(d) The temperature of the gas
6. The value of the gas constant per
degree per mol is approximately:
(a) 1 cal (b) 2 cal
(c) 3 cal (d) 4 cal
7. 10 g of a gas at atmospheric pressure
is cooled from 273
0
C to 0
0
C keeping
the volume constant; its pressure
would become:
(a) atm (b) 1/273 atm
(c) 2 atm (d) 273 atm
8. 300 mL of a gas at 27
0
C is cooled to 3
0
C at
constant pressure: the final volume is:
(a) 540 mL (b) 135 mL
(c) 270 mL (d) 350 mL
9. 273 mL of a gas at S.T.P. was taken to 27
0
C
and 600 mm pressure. The final volume of the
gas would be:
(a) 273 mL (b) 300 mL
(c) 380 mL (d) 586 mL
10. The density of a gas is 1.964 g dm
-3
at 273 K
and 76 cm Hg. The gas is:
(a) CH
4
(b) C
2
H
6

(c) CO
2
(d) Xe
11. The density of the gas is equal to:
(a) nP (b) MP/RT
(c) P/RT (d) M/V
12. A bottle of dry ammonia and a bottle of dry
hydrogen chloride connected through a long
tube are open simultaneously at both the ends.
The white ring first formed will be:
(a) At the centre of the tube
(b) Near the ammonia bottle
(c) Near the HCl bottle
(d) Throughout the length of the tube
13. Which of the following gases will have the
highest rate of diffusion?
(a) O
2
(b) CO
2

(c) NH
3
(d) N
2

14. Equal masses of methane and oxygen are
mixed in an empty container at 25
0
C. The
fraction of the total pressure exerted by oxygen
is:
(a) 1/3 (b) 1/2

(c) 2/3 (d)
15. 50 mL of a gas A diffusion through a
membrane in the same time as for the diffusion
of 40 mL of gas B under identical conditions of
pressure and temperature. If the molecular mass
of A is 64, that of B would be:
(a) 100 (b) 250 (c) 200 (d) 80
16. 3.2 g of oxygen (at. Mass =16) and 0.2 g of
hydrogen (at. Mass =1) are placed in a 1.12
t
KV
V
0
t
=
|
.
|
\
|
+ =
t
273
1 V V
0 t
|
.
|
\
|
+ =
273
t
1 V V
0 t
2
1
2 2
1 1
T
T
V P
V P
=
2
1 2
1
2 1
P
T V
P
T V
=
2
2 2
1
1 1
V
T P
V
T P
=
2 1
2 1
2 1
P P
T T
V V
=
298
273
X
3
1

Contact: 9953168795, 9268789880

litre flask at 0
0
C. The total pressure of
the gas mixture will be
(a) 1 atm (b) 2 atm
(c) 3 atm (d) 4 atm
17. The density of a gas at 27
0
C and 1 atm
is d. Pressure remaining constant, at
which of the following temperature
will its density become 0.75d?
(a) 20
0
C (b) 30
0
C
(c) 400K (d) 300K
18. Equal masses of ethane and hydrogen
are mixed in an empty container at
25
0
C . The fraction of the total
pressure exerted by hydrogen is:
(a) 1:2 (b) 1:1
(c) 1:16 (d) 15:16
19. The kinetic theory of gases predicts
that total kinetic energy of a gas
depends on:
(a) Pressure of the gas
(b) Temperature of the gas
(c) Volume of the gas
(d) Pressure, temperature and volume
of the gas
20. Deviations from ideal behaviour will
be more if the gas is subjected to:
(a) Low temperature and low pressure

(b) high temperature and low pressure
(c) Low temperature
(d) High temperature
21. The RMS speed at NTP of the species
can be calculated from the expression:

(a) (b)

(c) (d) All

22. Non-ideal gases approach ideal
behaviour:
(a) High temperature and high
pressure
(b) High temperature and low pressure
(c) Low temperature and low pressure

(d) Low temperature and low pressure
23. The critical temperature of gas is that
temperature:
(a) Above which it can no longer remain in the
gaseous state
(b) Above which it cannot be liquefied by
pressure
(c) At which it solidifies
(d) At which the volume of the gas become
zero
24. The units of a in van der Waals equation are

(a) atom litre
2
mol
-2

(b) atom litre mol
-2

(c) atom litre mol
-1

(d) atom litre
2
mol
-1

25. The value of van der Waals constant for gases
O
2
. N
2
NH
3
and CH
4
are 1.360, 1.390, 4.170
and 2.253 litre
2
are mol
-2
respectively. The gas
which can be most easily liquefied is:
(a) O
2
(b) N
2

(c) NH
3
(d) CH
4
26. According the kinetic theory of gases for a di-
atomic molecules:
(a) the pressure exerted by the gas is
proportional to the mean square speed by the
molecules
(b) the pressure exerted by the gas is
proportional to the root mean square speed of
the molecules
(c) the root mean square speed is inversely
proportional to the temperature
(d) The mean translational K.E. of the
molecules is directly proportional to the
absolute temperature.
27. The compressibility factor of a gas is defined as
nRT
PV
Z =
The compressibility factor of an ideal gas is :
(a) 0 (b) 1 (c) -1 (d) infinity
28. An ideal gas is one which obeys:
(a) gas laws (b) Boyles law
(c) Charles law (d) Avogadros law
M
PV 3
d
P 3
M
RT 3
( ) nRT nb V
V
an
P
2
2
=
|
|
.
|
\
|
+

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29. 16 g of oxygen and 3 g of hydrogen
are mixed and kept at 760 mm
pressure at 0
0
C. The total volume
occupied by the mixture will be
nearly:
(a) 22.4 litre (b) 33.6 litre
(c) 44800 mL (d) 4480 mL
30. Which of the following mixture of
gases at room temperature does not
follow Daltons law partial pressure?
(a) NO
2
and O
2
(b) NH
3
and
HCl
(c) CO and CO
2
(d) SO
2
and
O
2
31. In which of the following pairs the
gaseous species diffusion through a
porous plug with the same rate of
diffusion?
(a) NO, CO (b) NO, CO
2

(c) NH
3,
PH
3
(d) NO,
C
2
H
6
32. At S.T.P., the order of mean square
velocity of molecules of H
2
, N
2
, O
2

and HBr is:
(a) H
2
>N
2
>O
2
>HBr (b)
HBr>O
2
>N
2
>H
2

(c) HBr>H
2
>O
2
>N
2
(d)
N
2
>O
2
>H
2
>HBr
33. A balloon filled with N
2
O is prickled
with sharper point and plunged into a
tank of CO
2
under the same pressure
and temperature. The balloon will:
(a) be enlarged
(b) shrink
(c) collapse completely
(d) remain unchanged in size

34. If the universal gas constant is 8.3
joule mol
-1
K
-1
and the Avogadros
number 6X10
23
. The mean kinetic
energy of the oxygen molecules at
327
o
C will be:
(a) 415X10
-23
joule (b)
2490X10
-22
joule
(c) 1245X10
-23
joule (d) 830X10
-
22
joule
35. If increase in temperature and volume of an
ideal gas is two times, then initial pressure of P
changes to;
(a) 4P (b) 2P (c) P (d) 3P
36. At what temperature would the RMS speed of a
gas molecule have twice its value at 100
o
C?
(a) 4192 K (b) 1492 K
(c) 9142 K (d) 2491 K
37. At a temperature T K, the pressure of 4 g argon
in a bulb is P. The bulb is put in a bath having a
temperature higher by 50 K than the first one.
0.8 g of argon has had to be removed to
maintain original pressure. The temperature T
is equal to:
(a) 510 K (b) 200 K
(c) 100 K (d) 73 K
38. At 25
0
C and 730 mm pressure, 380 mL of dry
oxygen was collected. If the temperature is
constant, what volume will the oxygen occupy
at 760 mm pressure?
(a) 265 mL (b) 365 mL
(c) 569 mL (d) 621 mL
39. 4The root mean square velocity of an ideal gas
at constant pressure varies with density as:
(a) d
2
(b) d (c) (d)
(d) Cannot be predicated unless the volumes of
the gases are given
40. The coordination number of a metal crytallising
to a hexagonal close packing (hcp) structure is
:-
(a) 12 (b) 4
(c) 8 (d) 6
41. The compressibility of a gas is less than unity
at S.T.P. Therefore :
(a) V
m
>22.4 litre (b) V
m
<22.4 litre
(c) V
m
=22.4 litre (d) V
m
=44.8 litre
42. The r.m.s. velocity of hydrogen is times the
r.m.s. velocity of nitrogen. If T is the
temperature of the gas:
(a) T(H
2
)=T(N
2
)
(b) T(H
2
)>T(N
2
)
(c) T(H
2
)<T( N
2
)
(d)T(H
2
)= T(N
2
)
43. The kinetic energy of any gas molecules at 0
0
C
is:
d d / 1

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(a) Zero (b) 3408 J
(c) 2 cal (d) 5.66 10
-21
J
44. Densities of two gases are in the ratio
1:2 and their temperature are in the
ratio 2:1; then the ratio of their
respective pressures is:
(a) 1:1 (b) 1:2 (c) 2:1 (d) 4:1
45. 4.4 g of a gas at STP occupies a
volume of 2.24 L. The gas can be:
(a) O
2
(b) CO
(c) NO
2
(d) CO
2
46. At 0
0
C and one atm. Pressure a gas
occupies 100 cc. If the pressure is
increased to one and a half time and
temperature is increased by one third
of absolute temperature, then final
volume of the gas will be:
(a) 80 cc (b) 88.9 cc
(c) 66.7 cc (d) 100 cc
47. Pressure of a mixture of 4 g of O
2
and
2 g of H
2
confined in a bulb of 1 litre
at 0
0
Cis:
(a) 25.215 atm (b) 31.205
atm
(c) 45.215 atm (d) 15.210
atm
48. Density ratio of O
2
and H
2
is 16:1. The
ratio of their rms velocity will be:
(a) 4:1 (b) 1:16
(c) 1:4 (d) 16:1
49. The rate of diffusion of a gas having
molecular weight just double of
nitrogen gas is 56 mL s
-1
. The rate of
diffusion of nitrogen will be:
(a) 79.19 mL s
-1
(b) 112.0 mL s
-1

(c) 56 mL s
-1
(d) 90.0 mL
s
-1
50. The density of air is 0.00130 g/mL.
The vapour density of air will be:
(a) 0.00065 (b) 0.65
(c) 14.4816 (d)
14.56
51. If 300 mL of gas at 27
0
C is cooled to 7
0
C at
constant pressure, its final volume will be:
(a) 135 mL (b) 540 mL
(c) 350 mL (d) 280 mL
52. The van der Waals equation reduces itself to
the ideal gas equation at :
(a) high pressure and low temperature
(b) low pressure and low temperature
(c) low pressure and high temperature
(d) high pressure alone
53. The maximum number of molecules is present
in:
(a) 15 L of H
2
gas at STP
(b) 5 L of N
2
gas at STP
(c) 0.5 g of H
2
gas
(d) 10 g of O
2
gas
54. The root mean square velocity of one mole of a
monoatomic gas having molar mass M is U
rms
.
The relation between average kinetic energy
(E) of the gas and U
rms
is :

(a) (b)

(c) (d)

55. A certain sample of a gas has a volume of 0.2
litre measured at 1 atm pressure and 0
0
C . At
the same pressure but 273
0
C , its volume will
be:
(a) 0.4 L (b) 0.8 L
(c) 27.8 L (d) 55.6 L
56. The pressure exerted by 1 mole of methane in a
0.25 litre container at 300 K using van der
Waals equation (given a=2.253) atm L
2
mol
-2
,
b=0.0428 L mol
-1
) is :
(a) 82.82 atm (b) 152.51 atm
(c) 190.52atm (d) 70.52 atm
57. A gas can be liquefied:
(a) above its critical temperature
(b) at its critical temperature
(c) below its critical temperature
(d) at any temperature
M 2
E 3
U
rms
=
M 3
E 2
U
rms
=
M
E 2
U
rms
=
M 3
E
U
rms
=

Contact: 9953168795, 9268789880

58. If the absolute temperature of a gas is
doubled and the pressure is reduced to
one half, the volume of the gas will:
(a) remain unchanged
(b) be doubled
(c) increase fourfold
(d) be halved
59. To what temperature must a neon gas
sample be heated to doubled the
pressure, if the initial volume of a gas
at 75
0
C is decreased by 15%?
(a) 319
0
C (b) 592
0
C
(c) 128
0
C (d) 60
0
C
60. In Which of the following crystals
alternate tetrahedral voids are
occupied
(a)NaCl (b) ZnS
(c) CaF
2
(d) Na
2
O

ANSWERS
1 c 16 d 31 b 46 b
2 d 17 c 32 d 47 a
3 a 18 d 33 a 48 c
4 a 19 b 34 d 49 a
5 b 20 a 35 c 50 d
6 b 21 d 36 c 51 d
7 a 22 b 37 d 52 c
8 c 23 b 38 b 53 a
9 c 24 d 39 d 54 b
10 b 25 a 40 a 55 a
11 c 26 c 41 b 56 a
12 c 27 d 42 c 57 c
13 c 28 b 43 d 58 c
14 a 29 a 44 a 59 a
15 a 30 c 45 d 60 b

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