Chemistry for F.S.C Showing posts with label chapter 3rd.

Show all posts

Chapter 3rd
Posted by chismtry zone on Sunday, 25 December 2011 at 00:07

Chapter No.3

GASES

States of Matter
Matter exists in four states solid , liquid , gas and plasma.
The gases are the simplest form of matter.
Properties of Gases
The general properties of gases are the following:
1. Gases have no definite volume: They occupy all the available space. The volume
of the
gas is the volume of the container.
2. Gasses have no definite shape. They take the shape of the container.
3. Gasses have low densities. Gases have low densities as compared with liquids
and
solids. The gases bubble through liquids and tend to rise up.
4. Gasses con diffuse and effuse. They can diffuse and effuse rapidly through
each other
in all directions. The odour spreads in this way. The property of diffusions
operates in
liquids as well but is negligible in solids.
5. Gases are compressible. They can easily be compressed by applying pressure
because there are large empty spaces between the molecules.
6. Gases are expendables. They can expand on heating or increasing the available
volume . They expand to fill the entire volume of their containers.
Liquids and solids do not show an appreciable increase in volume when they are
heated. On sudden expansion of gases, cooling effect is observed. this
phenomenon is
called Joule-Thomson effect.
7. Gases exert pressure. They exert pressure on the walls of the container.
 8. Gases are miscible. They can be mixed in all proportions forming a
homogeneous
mixture.
9. weak intermolecular forces. The intermolecular forces in gases are very
weak.
10. Gases are liquefiable. They may be converted to the liquid state with
sufficiently low
temperature and high pressure.
Properties of Liquids
All liquids show the following general properties.
1. Liquids have definite volume but indefinite shape. They adopt
the shape of the
container in which they are placed but their volume does not change.
2. Liquids molecules are in constant random. The evaporation and diffusion
of liquid
molecules are due to this motion.
3. Liquids are denser than gases. The densities of liquid are much greater
than those of
gases but are close to those of solids.
4. Liquid molecules are very close together. Molecules of liquid lie close
together with
very little space between them so they cannot be compressed.
5. Intermolecular attractive forces. The intermolecular attractive forces
in liquids are
intermediate between gases and solids. The melting and boiling points of
gases, liquid
and solids depend upon the strength of such forces. The strength of
these forces is
different in different liquids.
6. Liquid molecules possess kinetic energy. Molecules of liquids possess
kinetic energy
due to their motion. Liquid can be converted into solids on cooling, e I
, by decreasing
their kinetic energy. Molecules of liquid collide among them-selves and
exchange
energy but those of solid cannot do so.
Properties of Solids
1. Solid particles are very close together. The particles of
solid substances are
very close to each other and they are tightly packed. Due to tight
packing of particles
solids are non-compressible and non-diffusible.
2. Strong attractive force .There are strong attractive forces in solids
which hold the
particles together firmly. Due to this reason solids have definite shape
and volume.
3. The solid particles possess only vibration motion.
Units of Pressure
The pressure of air (Earths atmosphere) at sea level that will support a
column of
mercury 760 mm in height is called one atmosphere.
It is the force exerted by 76 cm long column of mercury on an area of 1
cm2at O0C .It is
the average pressure of atmosphere at sea level. A second common pressure
unit is
the torr. One torr is the pressure exerted by a column of mercury 1 mm in
height.
So,
1 atm=760 torr=760mm Hg
The SI unit for pressure is the Pascal (pa). Remember that pressure is force
per unit
area, so Pascal can by expressed using the SI units for force and area. The
SI unit of
force is the Newton (N), and are area is measured in square (m 2).Thus, I pa
=1Nm-2 ,
and IN =1 kg ms-2,
So,
1 pa =1 kg m-1 S-2
Hence, 1 atm =760 torr =760mm Hg=101325 pa =101.325 kpa (kilopascal).
The most commonly unit of pressure used in engineering work is pounds per
square
inch (psi).
1 atm -760=760torr =14.7 pounds inch 2 .
The unit of pressure mill bar is commonly used by meteorologists.
Gas Laws
The relationships between the volume of a given amount of gas and the
prevailing
conditions of temperature and pressure are called the gas laws.
When the external conditions of temperature and pressure are changed, the
volume of
a given quantity of all gases in affected. This effect is nearly the same
irrespective of the
nature of the gas. Thus gases show a uniform behavior towards the external
conditions.
The gas laws describe this uniform behavior of gases.
Boyle,s Law
At constant temperature, the volume of a given mass of a gas is inversely
proportional
to the pressure applied a the gas.
Mathematically:

(T and n

constant)

PV=K ----------(1)

WhereKis a proportionality constant. The value of k is different for

different amounts of the same

gas .

According to Eq (1), boyles law can be stated as follows:

At constant temperature, the product of pressure and volume of a fixed

amount of a gas remains

constant.

So, P1V1 =k and P2V2=k

Hence, P1V1 =P2 V2

Where P1 and V1 are the initial pressure and volume while P2 and V2 are the
final pressure and

volume.

Experimental Verification of Boyles,s Law

Consider a fixed amount of a gas in a cylinder at constant temperature
say at
25oC. The cylinder is fitted with a moveable piston and a manometer to read the
pressure of the gas directly .Let the initial volume of the gas is 1 dm 3 and its
pressure is
2 atm when the piston has one weight on it. When the piston is loaded with a weight
two
times greater with the help of two equal weights, the pressure becomes 4 atm and
the

volume is reduced to dm 3. Similarly when the piston is loaded with a

weight three
times greater.
Then the pressure becomes 6 atm and volume is reduced to dm 3 .Thus
P1 V1 =2atmx1dm3 =2 atm dm3 =k

P2 V2 =4atm x dm3 = 2atm dm3 =k

 P2 V2 =4atm x dm3 = 2atm dm3 =k
Hence the Byes law is verified.
The value of k will remain the same for the same quantity of a gas at
the same
temperature.

Picture

Fig, Verification of Boyle,s Law

Example 1 : A gas having a volume of 10 dm3 is enclosed in a vessel at 0oC
and the
pressure is 2.5 atmospheres . This gas is allowed to expand until the new
pressure is 2
atmospheres. what will be the new volume of this gas, if the temperature is
maintained
at 273 k.
Solution: Given: P1 =2.5atm ; P2 =2atm
V1 =10dm3 ; V2 =?
Since temperature is constant ( 0o C =273k )
Formula Used: V2 =P1 V1
V2 =

V2 =
V2 =12.5 dm3 Answer

Graphical Explanation of Boyles,s Law

Take a given amount of gas and enclose it in a cylinder having
a piston
in it. The Boyle,s law can be represented graphically in three different ways
as
described below:
(i) Keeping the temperature constant at 0o C, when the pressure of the gas is
varied, its
volume changes. On plotting a graph between pressure on the x-axis and volume
on
the y-axis, a curve is obtained. Fig (a). This graph shows that volume is
inversely
proportional to pressure. Increase in pressure decreases the volume.
The pressure volume curve obtained at constant temperature is called
isotherm
 Now increase the temperature of the same gas to 25o C .keeping the
temperature
constant graph between pressures of the gas is varied, its volume changes.
Again on
plotting a obtained .this curve goes away from both the axes, fig (b). The
reason is that,
at higher temperature, the volume of the gas has increased. Again, this
graph shows
that volume is inversely proportional to pressure. The increase in pressure
decreases
the volume.
Similarly, if we increase the temperature further, keeping it
constant, and again
plot another isotherm, It further goes away from the axes and produces the
same result.

Picture

Fig (a) . Isotherm of a gas at 0oC Fig (b). Isotherm of a gas

at different
temperatures
(ii) Keeping the temperature constant at T1, when the volume of the gas is
increased, the
gas spreads over a larger region of space. Consequently, it exerts less
pressure on the
container. It means increase in column decreases the pressure of the gas.

On plotting a graph between the reciprocal of volume ( )n x-axis

and pressure (P) on

the y-axis. It shows that p is directly proportional ( )to . It

indicates that the pressure
goes down as the gas expands. This straight line will meet at the origin
where both p

and ( )are zero. Thus we can say that p goes to zero as V goes to
infinity ( =0).
Now increase the temperature of the same gas from T1 to T2 . Keeping the
temperature
constant at T2 . When volume is varied, its pressure changes. Again plot the
graph

between ( )on x-axis, and P on y-axis, again a straight line is

obtained which meet at
the origin . This straight line will be away from the x-axis, Fig(a) . Again
the straight line

straight line indicates that P is directly proportional to ( ).

 Picture

Fig.(a) A plot between P and Fig (b) A plot between pressure and
product pf P V

(iii) Keeping the temperature constant at T1, when the pressure of the gas is
varied, its
volume changes. On plotting a graph between P on x-axis and the product PV
on y-
axis, a straight line parallel to x-axis is obtained, Fig (b). This
straight line shows that PV
remains constant even if we change pressure.
Now increase the temperature of the same gas form T 1 to T2. Keeping the
temperature
constant at T2, when the pressure of the agars is varied, its volume
change. On plotting
graph between P on x-axis and the product PV on y-axis, again a straight
line parallel to
x-axis is obtained, Fig (b) . This straight line shows that PV remains
constant even if we
change pressure. However, the value of PV increases with increase in
temperature.
Charless Law
At constant pressure, the volume of a given mass of a gas is
directly
proportional to the absolute temperature.
Mathematically: V = T (P and N are
constant)
V = kT

= k
Where k is a proportionality constant.
If the temperature is changed from T1 to T2 and the volume is changed from
V1 to
V2 then we have
= k
and = k
so, = =k

Experimental Verification of Charles, s Law

 Consider a fixed amount of a gas enclosed in a cylinder fitted with a
moveable piston.
Let the volume of the gas is V1 and its temperature is T1. If the gas in the
cylinder is
heated, the temperature and the volume of the gas will increase . The new
temperature
be T2 and volume will be V-2 . It can be shown that the ratio.

=
Hence Charles s law is verified.

Picture.

Fig. Verification of Charless Law

Example 2 : 250cm3 of hydrogen is cooled from 127o C to -27o C by maintaining

the
pressure constant. Calculate the new volume of the gas at the low
temperature.
Solution: Given: V1 =250cm3 ; V2 =?
T1 =273+127=400k ; T2 =273-27=246k
Formula Used: =
V2 = xT2
V2 =
V2 = 153.75 cm3 Answer
Derivation of Absolute Zero
In order to derive absolute zero of temperature considers the following
quantitative
statement of Charless law.
Statement: At constant pressure , the volume of a given mass of gas increases
or

decreases by of its original volume at 0o C for every 1 oC rise or fall

in temperature
respectively.
In order to understand the above statement .suppose V o is the volume of a
given
Mass of gas at 0 oC and V1 is the volume at T oC .Then from the statement of
Charles,s law.
 For 1 oC rise in temperature, the increase in volume =Vo x =
And, for to C rise in temperature ,the increase in volume =xt
=
The volume , Vt of the gas at to C becomes ,
Vt =vol of gas at 0oC =increase in vol.at toC
Vt=Vo +

Vt=Vo (1+ )
This general equation can be used to know the volume of the gas at various
temperatures.
Suppose at 0oC , the original volume , Vo of the gas is 546 cm 3
.Thus
Vo =546 cm3

At 10o C, V10 =546(1+ dm3

At 100 oC V100 =

cm3

Thus , the increase in temperature from 10o C to 100 oC, increases the
volume from
566 cm3 to 746cm3 .
Applying the Charless Law,
=

The two ratios are not equal. So , Charless law is not being obeyed
when
temperature is measured on the Celsius scale. For this reason a new
temperature scale
has been developed.
The new temperature scale starts from-273oC (more correctly-273.16 oC)
which
is called zero Kelvin (0k) or zero absolute. The advantage of this scale is
that all the
temperatures on this scale are in positive figures .In order to develop the
new
temperature scale, the best way is to plot a graph between the variables of
Charles,s
law . That is, V and T.

Table: volume Temperature data for a given amount of a gas at constant

pressure

Volume (cm3) Celsius Temperature (K)

Temperature(oC) =k=cm3 k-1

1092 273 546 2

846 150 423 2
746 100 373 2
646 50 323 2
566 10 283 2
548 1 274 2
546 0 273 2
544 -1 272 2
526 -10 263 2
400 -73 200 2
346 -100 173 2
146 -200 73 2
0 -273 0 2
Graphical Explanation of Charles,s Law
Keeping the pressure of a given mass (say 1 mole) of gas constant, when the
temperature of a gas is varied, its volume changes. The volumes at different
temperatures are measured, Now if a graph is plotted between temperature (oC) on x-
axis and volume on y-axis , a straight line is obtained ,this straight line cuts
the
temperature-axis and (x-axis) at -273. 16oCif it is extrapolated. The volume of a
gas
becomes zero at -273.16oC. This temperature is the lowest temperature which is
attainable if the substance remains in the gaseous stat. Actually, all real gases
first
converted into liquid and then into solids before reaching this temperature
Picture

Fig. the graph between volume and temperature for a gas according to table.
If many plots of this type are examined. It is found that a given gas follows
different
straight lines for different masses of gas and for different pressures. Greater the
mass
of gas taken, greater will be the slope of the straight line. The reason is that
greater the
number of moles greater the volume occupied .All these straight lines when
extrapolated meet at a common point of -273.16oC (0k). It is clear that this
temperature
of -273.16oC will be attained when the volume becomes zero. It is true for an ideal
gas.
But for a real gas. Thus-273.16oC represents the coldest temperature. This is the
zero
point (0K) for an absolute scale of temperature.

Charless law is obeyed when the temperature is taken on the Kelvin scale.
For
example, at 283K (10o C) the volume is 566 cm3 and at 373 k (100o C) the volume is
746
cm3 . According to Charlies law.

==k

Hence , Charless law is obeyed .

Scales of Thermometry
For measuring temperature, three scales of thermometry are used.
(a) Celsius or Centigrade Scale
One this scale, the temperature of ice at 1 atmospheric pressure is 0oC, and
the
temperature of boiling water at 1 atmospheric pressure is 100 oC. The space between
these temperature marks is divided into 100 equal parts and each part is 1 oC
(b) Fahrenheit Scale
On this scale, the temperature of ice at 1 atmospheric pressure is 32Fand the
temperature of boiling water is 212o F .The space between these temperature marks
is
divided into 180equal parts and each part is 1oF
(c) Absolute or Kelvin scale
One the absolute or Kelvin scale, the temperature of ice at 1 atmospheric
pressure is 273 K and that of boiling water is 373 K. On the Kelvin scale, absolute
zero
(0K) is the temperature at which the volume of a gas becomes zero. It is the lowest
possible temperature that can be achieved. Thus, temperatures on the Kelvin scale
are
not divided into degrees .Temperatures on this scale are reported in units of
Kelvin , not
in degrees temperature on Kelvin Scale=273.16oC or 0K=273.16oC
Temperature on Kelvin scale=273+temperature oC
Or
T (k)=273+ oC
The following relationship helps us to understand the introversions of
various
scales of temperatures.
T (k)=273+ oC

o
C=

o
f= (oC)+32

Picture

Remember that the Fahrenheit and Celsius scales are both relative temperature
scales.
They define two reference points (such as 0oC and 100oC). The Kelvin scale,
however,
is an absolute scale. Zero on this scale is the lowest temperature that can
achieved.
Standard Temperature and Pressure (STP)
 The temperature 273.16 k (0o C) and pressure 1 atmosphere (760 mm Hg) have
been chosen as standard temperature and standard pressure.
STP 273.16K (0o C) and 1 atm (760 mm Hg)

General Gas Equation [Ideal Gas Equation]

A gas equation which is obtained by combining Boyle s law , Charles ,s
law
and Avogadro ,s law is called general gas equation.
It relates pressure, volume temperature and number of moles of gas.
According to Boyles Law V (at constant T and n)

According to Charless Law V T (at constant P and n)

According to Avogadros Law V T (at constant P and
T)
If the variables P,T and n are not Kept constant then all the above three
relationships can be combined together.

V
V=R
Where R is a general gas constant.
pV=nRT(First Form)

The above equation is called ideal or general gas equation.

The general gas equation shows that if we have any quantity of an ideal gas
then the product of its pressure and volume is equal to the product of number of
moles,
Variation on the Gas Equation
During chemical and physical processes, any of the four variables (P,V,n
,T) in
the ideal gas equation ,PV =nRT may be fixed and any of them may change.
For examples:
1. For a fixed amount of gas at constant temperature.
PV= nRT =constant [ n and T constant]
 PV=k (Boyles Law)
2. For a fixed amount of gas at constant pressure,

=[ n and P constant]

V=kT
3. For a fixed amount of gas at constant volume,

=[ n and V
constant]

P=kT
4. For a fixed pressure and temperature,

[ P and T constant ]
V=kn (Avogadros Law)
5. For a fixed volume and temperature,

[ T and V constant]

P=kn

General Gas Equation For one mole of gas

For one mole of gas , the general gas equation is
PV==RT [ n=1]
For two different pressure, volumes and absolute temperatures, the above
equation can
be written as,
Hence, we can write,
= (Second Form)
Numerical Value of Ideal Gas Constant , R
The numerical value of R depends upon the units chosen for P,V and T.
(i) When pressure is expressed in atmosphere and volume in dm3.
 For 1 mole of a gas at STP, we have
N= 1 mole, P=1 atm, T =273.16k, V=22.414dm3
Putting these value in general gas equation,
R=
R=
R=0.0821dm3 atm k -1 mol-1
(ii) when pressure is expressed in mm of mercury or torr and volume of gas in
cm3 .
R= 0.0821dm3 atm k-1 mol-1
Since 1 dm3 =1000cm3 : 1 atm =760mm of Hg

R=0.0821x1000 cm3 x760mm Hg K-1 mol-1

R=62400 cm3 mm Hg K-1 mol-1
Since 1 mm=1 torr
R=62400 cm3 torr K-1 mol-1
(iii) When pressure is expressed in Nm-2 and volume in m3 (SI Units)
For 1 mole of gas at STP,
N= 1 mol, P=101325 Nm-2, T=273.16 K, V=0.022414m3
Substituting the values in general gas equation,
R=
R=
R=8.3143 NmK-1 mol-1
Since 1 Nm=1 j
R=8.3143jk -1 mol-1
Remember that, whenever the pressure is given in Nm-2 and the volume in
m3 ,then the
value of used must be 8.3143 jk-1 mol-1 .
Remember that when the pressure is given in Nm-2 and the volume in m3, then
the
value of R used must be 8.3143JK-1 mol-1 .joule (j) is unit of work and
energy in the
system.
(iv) When energy is expressed in ergs.
 R=8.3143jk -1 mol-1
Since 1 J =107 erg
R=8.3143x107 erg K-1 mol -1
(v) When energyis expressed in calories.
R=8.3143jk -1 mol-1
Since 1 cal=4.184j
Or 1 j=
R=
R = 1.987 cal K-1 mol-1
(vi) R can be expressed in units of work or energy per Kelvin per mole .
Form ideal gas equation, we can write
R=
If the pressure is written as force per units area and volume as area x
length,
R====
Hence R can be expressed in units of work or energy per Kelvin per mole.
Physical Meaning of Value of R
The physical meaning of the value 0.0821 dm3 atm K -1 mol-1 of R is that if
we
have one mole of an ideal gas at 273.16 K and one atmospheric pressure and its
temperature is increased by 1 K then it will absorb 0.0821 dm 3 atm of energy , dm3
atm
being the unit of energy .Hence the value of R is a universal parameter for all the
gases
. It tells us that the Avogadros number of molecules of all the ideal gases have
the
same demand of energy.
Density of an Ideal Gas
We know that, n=
Where a is the number of moles of gas .m is the mass of the substance in
grams
and M is the molar mass of the substance.
On substituting the above expression into the ideal gas equation,
We obtained
PV=RT (Third From)-------(6)
 PM==RT
PM=dRT (d=)
d= (Fourth From)---------(7)
Hence the density of an ideal gas is directly proportional to its molar mass.
Greater the pressure on the gas , the closer will be the molecules
and greater
the density temperature of the gas ,the lower will be the density of the gas.
With the help of equation (7) ,we can calculate the relative molar
mass, M of an
ideal gas if its pressure ,temperature and density are know.
Example3:
A sample of nitrogen gas is enclosed in a vessel of volume 380 cm 3
at 120oC
and pressure of 101325 Nm-2 .This gas is transferred to a 10dm3.
Flask and cooled to 27o C.Calculate the pressure in Nm-2 exerted
by the gas
at27o C.
Solution:
V1 =380cm3 =0.38 dm3 ; V2
=10dm3
P1 =101325 Nm-2 ; P2 =?
T1 =273+120=393k ; T2
=273+27=300k
Formula used:
=
P2 =
P2 =
P2 =0.028atm
P2 =0.029x101325=2938.4 Nm-2 Answer
Example 4:
Calculate the density of CH4 at 0o C and 1 atmospheric pressure, what will
happen to
the density if
(a) temperature is increase to 27o C.
(b) the pressure is increased to 2 atmospheres at 0o C.
Solution:
 MCH4=12+4=16g mol-1
P=1 atm
R= 0.0821dm3 atm K-1 mol-1
T = 273+0=273K
Formula Used:
d=
d=
d=0.7138 g dm3 Answer
(a) Density at 27o C
MCH4=16g mol -1
P= 1 atm
R=0.0821 dm3 atm K-1 mol-1
T=273+27=300K
Formula Used:d=
d=
d = 0.6496g dm3 Answer
Thus by increasing the temperature from 0o C , the density of gas has
decreased form
0.7143 to 0.6496 g dm3 .
(b) Density at 2 atm pressure and 0o C.
MCH4=16g mol-1
P = 2 atm
R =0.0821 dm3 atm K-1 mol-1
T = 273+0=273k
Formula Used: d=
d=
d=1.428 g dm-3 Answer
Thus the increasing of pressure has increased the density . the
density becomes
double by doubling the pressure .
Example 5:
 Calculate the mass of 1 dm3 of NH3 gas at 30o C and 1000 mm Hg
pressure,
considering that NH4 is behaving ideally.
Solution: Given: P=1000 mm Hg = 1.316 atm ; V=1 dm3
MNH4 =14+3=17g mol-1 : R=0.0821dm3 atm K-1 mol-1
T=273+30-303l ; m=?
Formula Used: PV =
M=
M=
M =0.0908 g Answer
Avogadro s Law
The law may be stated in a number of ways as follows;
1. Equal volumes of ideal gases at the same temperature and pressure contain
equal
number of molecules.
2. Equal number of molecules of ideal gases at the same temperature and
pressure
occupy equal volumes.
3. At constant temperature and pressure, the volume of an ideal gas is directly
proportional to the number of moles or molecules of gas.
Mathematically: V n (at P and T constant)
V=kn
Explanation:
Since one mole of an ideal gas at STP has a volume of 22.414 dm 3 ,So
22.414dm3 of an ideal gas at STP will have Avogadros number of molecules ,
i.e,
6.02x1023 .
Mathematically , it can be written as,
22.414 dm3 of an ideal gas at STP has number of molecules
=6.02x1023
1 dm3 of an ideal gas at STP has number of molecules =molecules
=2.68x1022
molecules
In other words if we have one dm3 of each of H2 ,O2 ,N2 and CH4 in separate vessels
at
STP, then the number of molecules in each will be 2.68x 10 22 .
Similarly when the temperature or pressure are equally changed for these four
gases,
then the new equal volumes will have the same number of molecules , 2.68x1022 .
One dm3 of H2 at STP weight approximately 0.0899 grams and one dm 3 of O2
at
STP weight 1.4384 grams, but their number of molecules are the same .Although ,
oxygen molecule is 16 times heavier than hydrogen but this does not disturb the
volume
occupied by the molecules because molecules , of the gases are widely separated
from
each other at STP .One molecule of gas is approximately at a distance of 300 times
its
own diameter from its neighbors at room temperature .
Daltans Law of Partial Pressure
The total pressure exerted by a mixture of non-reacting gases is equal to
the
sum of their individual partial pressure.
Mathematically: Pt =P1 +P2 +P3
Where Pt is the total pressure of the mixture of gases and P 1 ,P2 and P3
are the
partial pressure of gas1 . gas2 and gas 3 respectively in the mixture.
The partial pressure of a gas in a mixture of gases in the pressure a gas
would
exert if it were the only gas in the container. Partial pressures are commonly
represented by small ps.
Explanation: Suppose we have four 10 dm 3 cylinders. The first one contains H2 gas
at a
pressure of 400 torr; the second one contains CH4 gas at a pressure of 100 torr at
the
same temperature. Now transfer these gases to the fourth cylinder of capacity 10dm
3 at
the same temperature. According to Daltons law, the pressure in the fourth
cylinder is
found to be equal to the sum of the pressures that each gas exerted by itself.
Pt =PH2 +PCH 4 +Po2
Pt=400+500+100=1000 torr
There three non-reacting gases are behaving independently under the normal
conditions. The rapidly moving molecules of each gas in a mixture have equal
opportunities to collide with the walls of the container. Hence, each gas in the
container
exerts a pressure independent of the pressure of other gases in the container. The
total
pressure is the result of total number of collisions per unit area in a given time.
Since
the molecules of each gas move independently, so the general gas equation can be
applied to the individual gases in the gaseous mixture.

(i)PH2 V=n H2 RT PH2 =nH2 PH2 nH2

(ii)PH2 V=n H4RTPH2 =nH2 Pch2 nCh4

(iii)PO2 V=no2 RT Po2 =no2 Po2 no2

is a constant factor
H2 , CH4 and O2 have their own partial pressures . Since volume and temperature are
the same so their number of moles will be different and will be directly
proportional to
their partial pressures .
Adding Equations (i),(ii) and (iii),we get ,
(PH2 +PCH4 +Po2 )V= (nH2 + nCH4 +no2 )RT
Pt = nt RT
Where Pt =PH2 +PCH4 +Po2 , nt =nH2 +nCH4 + no2
Hence, the total pressure of the mixture of gases depends upon the total number of
.moles of the gases.
Calculation of Partial Pressure of a Gas
The partial pressure of any gas in a mixture of gases can be calculated
provided
we know the mass or number of moles of the gas, the total pressure and the total
number of moles present in the mixture of gases.
Suppose we have a mixture of gas A and gas B. The mixture is enclosed in a
container having volume (V). The total pressure of the mixture is P t . The number
of
moles of the gases A and B are NA and n B respectively .If the temperature of the
mixture is T, then we can write general gas equations
For the mixture of gases: Pt V=n t RT --------(i)
For gas A: PAV=nART --------(ii)
 For gas B: PBV=nBRT
---------(iii)
Divide Eq (ii) by Eq (i) ,we get,

PA=
Similarly, by dividing Eq (iii) by Eq (i), we get

PA =
In mole fraction form, the above equations can be written as,

PA=XA Pt [ XA = ]

PB = XB Pt [ XB
= ]
Example 6: There is a mixture of H2, He and CH4 occupying a vessel of volume 13
dm 3 at 37 oC
and pressure of 1 atmosphere. The masses of H2 and He are 0.8g and
0.12g
respectively. Calculate the partial pressure in torr Hg of each gas in
the mixture.
Solution: Given:
P=1 atm : V=13dm3
n=? ; T=273+37=310K
R=0.0821 dm3 atm K-1 mol-1
Formula Used:
PV=nRT

n=

n=

nH2 =

nHe =
 nCH4 = 0.51-(0.396+0.03)=0.51-0.426=0.084mol

PH2 =

PHe =
=0.776x760=589.76torr Answer

PHe =

PH2 =
=0.058x760=44.08 torr Answer

PCH4 =

PCH4 =

=0.164x760=124.64 torr Answer

Applications of Daltons Law of Partial pressure
The four important applications of Daltons law of partial pressures are
the
following:
1. Determination of the pressure of dry gas: The Daltons law of
partial
pressure is used to find the pressure of dry gas collected over water. When a gas
is
collected over water it becomes moist. The pressure exerted by a moist gas is ,
therefore , me sum of the partial pressure of the dry gas and the pressure of the
water
vapours which are mixed with the gas .The partial pressure exerted by the water
vapour
is called aqueous tension .Thus

Picture.

Remember that :
 While solving the numerical, the aqueous tension is subtracted
from the
total pressure (P moist gas )
2. Process of Respiration: In living beings, the process of respiration
depends
upon differences in partial pressures. When animals inhale air then oxygen moves
into
lungs as the partial pressure of oxygen in the air is 159 torr while the partial
pressure of
oxygen in the lungs is 116 torr . On the other hand, CO 2 produced during
respiration
moves out in the opposite direction as its partial pressure is low in the air
relative to its
partial pressure in the lungs .
3 Pilots feel uncomfortable breathing at higher altitudes: At higher
altitudes
,the pilot feel uncomfortable breathing because the partial pressure of oxygen in
the
unperssurized cabin is low as compared to torr in air where one feels comfortable
breathing.
4 Deep sea divers feel uncomfortable breathing: deep Sea divers take oxygen
mixed with an inert gas (He) and adjust the partial pressure of oxygen according to
the
requirement. In sea after every 100feet depth, the diver experiences about 3 atm
pressure .Therefore ,normal air cannot be breathed in depth of sea . Moreover, the
pressure of N2 increases in depth of sea and it diffuses in the blood.
Diffusion and Effusion
Diffusion
The spontaneous intermingling (intermixing) of molecules of one gas with
another at a given temperature and pressure is called diffusion.

Explanation of Diffusion from Kinetic Theory

According to the Kinetic molecular theory of gases, the molecules of the
gases
move haphazardly. They collide among themselves, collide with the walls of the
container and change their directions. In other words the molecules of gases are
scattered or intermixed due to collisions and random motion to from a homogeneous
mixture.
 Example: (1) The spreading of fragrance of a rose or a scent is
due to
diffusion.
(2) Suppose NO2 (a brown gas an d O2 ( a colorless gas )are separated from each
other
by a partition . When the partition is removed, both diffused into each other
due to
collisions and random motion. They generate a homogeneous mixture. The
partial
pressure of
Both are uniform throughout the mixture.

Picture

Effusion:
The escape of gas molecules through an extremely small opening into
a region
of low pressure is called effusion.
The spreading of molecules in effusion is not due to collisions but
to their
escape one by one .Actually the molecules of a gas are habitual in colliding
with the
walls of the vessel. When a molecule approaches just in front of the opening
it enters
the other portion of the vessel. This type of escape of gas molecules through
a small
hole into a region of low pressure or vacuum is called effusion.

Picture

Grahams Law of Diffusion

The rate of diffusion or effusion of a gas is inversely proportional
to the
square root of it s density at constant temperature and pressure.

Mathematically. Rate of diffusion (at constant T and

P)

Rate of diffusion =
 R =
Rx = =k

The constant k is same for all gases, when they are all studied at the same
temperature and pressure .

Suppose we have two gases 1 and 2 whose rates of diffusion are r 1 and r2
and densities are D1

and d2 respectively. According to Grahams law,

r1 x 1=k

r2 x 2=k

Divide the two equations and rearrange

Since the density of a given gas is directly proportional to its molecular mass.
d M
Therefore, Grahams law of diffusion can also be written as,

Where M 1 and M2 are the molecular masses of gases.

Experimental Verification of Grahams Law of Diffusion
This law can be verified in the laboratory by noting the rates of
diffusion of two
gases in a glass tube when they are allowed to move from opposite ends. Two cotton
plugs soaked in NH4 OH and HCI solution are introduced in the open ends of 100cm
long tube at the same time .NH3 molecules travel a distance of 59.5 cm when HCI
molecules cover 40.5 cm in the same time. Dense white fumes of NH 4CI are produced
at the junction of two gases.

=
Form Grahams law the rates of diffusion of NH3 and HCI can be calculated by using
their molecular masses as follows:

=
This result is the same as obtained form the experiment.
Hence the law is verified
Remember that light gases diffuse more rapidly than heavy gases.

Picture

Fig: Verification of Grahams Law

Example 7: 250 cm3 of the sample of hydrogen effuses four times as rapidly as
250
cm3 of an unknown gas . Calculate the molar mass of unknown gas .
Solution: Let the symbol for the unknown gas is x.
Rate of effusion of unknown gas rx =1
Rate of effusion of hydrogen gas rH2=1x4=4
Molar of effusion of hydrogen gas MH2 =2g mol-1
Molar mass of unknown gas, Mx =?

Formula used:

Taking square of both the sides,

Mx =16x2g mol-1
Mx=32g mol -1 Answer
Kinetic Molecular Theory of Gases
 A gas model which explains the physical behavior of gases and the gas
laws is called the kinetic molecular theory of gases.
The kinetic molecular theory of gases was first suggested by
Bernoulli
(1738).R.J .Clausisus (1857) derived the Kinetic gas equation and deduced all
the gas
laws from it .Maxwell (1859) gave the law of distribution of velocities .Bolt
Mann (1870)
gave the concept of distribution of energies among the gas molecules. Vander
walls
(1873) modify the Kinetic gas equation in order to apply for real gases.
Postulates of Kinetic Molecular Theory of Gases
The basic assumptions of the Kinetic molecular theory of an ideal gas
are the
following:
1. All gases consist of a large number of very small particles called molecules.
Noble
gases (He,Ne, Ar,etc )have mono=atomic molecules .
2. The molecules of a gas mve randomly in straight lines in all directions with
various
velocities. They collide with one another and with the walls of the container
and change
their direction.
3. The pressure exerted by a gas is due to the collections of the gas molecules
with the
walls fo the container. The collisions among the molecules and with the walls
of the
container are perfectly elastic. There is no loss energy during collision or
mutual friction.
4. The molecules of a gas are widely separated from one another .There is large
empty
spaces between the gas molecules.
5. There are no attractive forces between the gas molecules .There is no force of
gravity
on gas molecules.
6. The actual volume of the gas molecules is negligible as compared to the volume
of the
gas.
7. The motion of the gas molecules due to gravity is negligible as compared to
the effect of
continued collisions between them.
8. The average kinetic energy of the gas molecules is directly proportional to
absolute
temperature of the gas.
Average K.E T
 Average K.E=
Note : The average kinetic energy is considered because the gas molecules are
moving with
different velocities . The velocity of each molecules change with each
collision .Some of
the molecules has very low velocities, while others move very rapidly.
Kinetic Gas Equation
Keeping in view the basic assumptions of kinetic molecular theory of gases,
Clausius
derived an expression for the pressure of an ideal gas . This equation
relates the
pressure of the gas with mass of a molecule of the gas, the number of
molecules of the
gas in the volume of the gas and the mean square velocities of gas
molecules .The
kinetic gas equation has the following form.

PV=
Where P=pressure of the gas
V=Volume of the gas
M=mass of one molecule of gas
N=number of gas molecules in volume
=mean square velocity (average of the square of
the
Velocities of the gas
molecules)

The idea of the mean square velocity is important because all the
molecules of a
gas at a particular temperature have different velocities .These velocities
are distributed
among the molecules.

Mean velocity ,Mean Square Velocity ,Root Mean Square Velocity

Mean(average ) velocity,
 The average value of the different velocities of all the molecules in a
sample of
gas at a particular temperature is called the mean velocit .
If there are n1 molecules with velocity c1 , n2 molecules with velocity c2
and
n3 molecules with velocity c3,then ,

Where is known as the mean of average velocity .The bar (-) over the velocity
(c )
indicates average or mean value.
In this reference n1 + n2 +n3 =N
mean square velocity ,c2
The average value of the square of the different velocities of all the
molecules in a sample of gas at a particular temperatures is called the square
velocity.

Where is known as the mean square velocity.

Root mean square Velocity ,crms

The square root of the mean of the squares of the different velocities of
all
the molecules in a sample of gas at a particular temperature is called the root
mean square velocity.

Crms =
The square root of the mean square velocity.
 The expression for the root mean square velocity deduced from the kinetic gas
equation
is written as:

Where , Cmns root mean square velocity

M =molecular mass of the gas
T = absolute temperature
This equation is a quantitative relationship between the absolute
temperature
and the velocities of the gas molecules .According to this equation ,the
higher the
temperature of a gas ,the greater the velocities .

Explanation of Gas Law From kinetic theory of Gases

1. Bo lyes Law
According to kinetic gas equation,

PV=
Multiplying and dividing by 2 on right hand side.

PV=

But =KE

PV= (K.E)
Now, according to kinetic theory of gases, kinetic is directly
proportional to
absolute temperature
K.E T
K.E =kT

PV =

If temperature is constant, then is constant

PV=constant (which is boyles law)
Thus boyles law is derived.
2. Charles,s Law
According to kinetic gas equation,

PV=
Multiplying and dividing by 2 on right hand side.

PV=

=KE

PV= (K.E)
Now ,according to kinetic theory of gases , kinetic energy is directly proportional
to
absolute temperature.
K.E T
K.E =kT

PV =

V =

If pressure is constant, then is constant

V=constant x T
V T (which is Charless law)
3 Avogadros Law
Consider two gases 1 and 2 at the same pressure P and the same volume V.Suppose
their number of molecules are N1 and N2 ,masses are m1 and m2 and mean square

velocities are respectively.

For gas 1: PV- ..(1)

For gas 2: PV- .(2)

From Eq(1) and Eq (2) ,we get,
 = ..(3)
If the temperature of the gas 1 and gas 2 are the same, their kinetic energy will
also be
the same.
Kinetic energy of gas1 =kinetic energy of gas2

=
Dividing eq(3) by eq(4)

N1 = N2
Thus ,number of molecules of gas1 =number of molecules of gas2
4. Grahams law of Diffusion
According to kinetic gas equation,

PV =

For 1 mole gas , N=NA

PV=

PV = (mNA=M)
Where M is the molecular mass of gas.

P=

P= [ =d(density of gas)]

=
Taking the square root of both the sides
 =

cnms =
Since the root mean square velocity of the gas is equal to the rate of diffusion of
the
gas,
Cnms =r

So, r=

r=
At constant pressure,

r=

r=constant x

r
Thus , Graham s law of diffusion of gases is derived

Kinetic Interpretation of Temperature

Consider one mole of the gas containing N molecules. Suppose m is the
mass
of one molecule of the gas and is the mean square velocity of the molecule.
According to kinetic gas equation,

PV= ..(1)
The Eq(1) can be rewritten as,

PV= (2)
Now , the kinetic energy of one molecule of a gas due to its
translational motion
is given by the following equation ,

Ek = .(3)
 Where Ek is the average translational kinetic energy of a gas.
On putting eq(3) in Eq (2) , we get,

PV =
Since the number of gas molecules in one mole of gas in NA (Avogadros-
number)
So,
N=NA

PV =
For I mole of the ideal gas,
PV=RT
Therefore,

=RT

Ek =
Ek
We can draw the following conclusions from the above equation:
1. Concept of Absolute Zero of Temperature

According to the equation, T= , absolute temperature of a gas is

directly
Proportional to the average translational kinetic energy of the gas molecules.
It means
that a change in temperature brings about a change in the intensity of
molecular motion
.Thus, when T=0k (-273.16o C), the translational kinetic theory, absolute zero
of
temperature, both velocity and kinetic energy of gas molecules become zero.
Also at
this temperature, the gas exerts no pressure on the walls of the container.
The absolute zero temperature cannot be attained .However, a
temperature as
low as 10-5 K is obtained.
2. Concept of Average Kinetic Energy of a gas
The average translational kinetic energy of a gas depends only on its absolute
temperature and is independent of the pressure, volume, or type of gas. The
mean
 kinetic energy of each gas molecule is the same at the same temperature. The
mean
kinetic energy of gas molecule does not depend upon its mass. Therefore, a
small
molecule such as H2 will have , at the same temperature , the same average
kinetic
energy as a much heavier molecule such as CO2 . Hence, for different gases
average
kinetic energy of molecules at the same temperature is the same. Thus at the
same
temperature.
K.E of gas 1 = K.E of gas2
3. Concept of Heat Flow
When heat flows from one body to another, the molecules in the hotter
body
give up some of their kinetic energy through collisions to molecules in the
colder body.
This process of flow of heat continues until the average translational kinetic
energies of
all the molecules become equal. Consequently, the temperature of both the
bodies
becomes equal.
4. Concept of Temperature of Gases, Liquids and solids
Temperature is the measure of average translational kinetic energies
of
molecules. In gases and liquids, temperature is the measure of average
translational of
kinetic energies of their molecules , In solids , temperature is the measure
of vibrational
kinetic energy of molecules because there is only vibrational motion about
mean
position .
Liquefaction of Gases
General Principle of Liquefaction of Gases
Under suitable conditions of temperature and pressure all gases may
be
liquefied. Liquefaction occurs only when the attractive forces between the
molecules are
greater than the kinetic energy of the molecules.
Two conditions favour this situation.
1. High pressure. High pressure is applied on gases. This brings the molecules
of a gas
close to each other. Thus the forces between the molecules increase.
2. Low temperature. Low temperature is created in gases .This decreases the
kinetic
energy of the molecules. Thus the attractive forces between the molecules
increase.
 In general, the liquefaction of a gas requires high pressure and low
temperature.
Liquefaction means the conversion of a gas into a liquid.
For each gas, there is a certain temperature above which the gas cannot be
liquefied
even if a very high pressure is applied. This temperature is known as critical
temperature. The critical temperature of a gas may be defined as, the highest
temperature which a gas con be liquefied by increasing the pressure is called
critical
temperature. The critical temperature is represented by Tc. Below the
critical
temperature a gas can be liquefied however great the pressure may be. The
value of
the critical temperature of a gas depends upon its size, shape and
intermolecular forces
present in it.
The pressure which is required to liquefy the gas at its critical
temperature is called
critical pressure.
The critical pressure is represented by Pc.
The critical temperature and the critical pressure of the gases are very
important
because they provide us the information about the condition under which gases
liquefy.
Examples:
(1) CO2 is a nonpolar gas its critical temperature is 31.1oC. It must be cooled
below this
temperature before it can be liquefied by applying high pressure. However, if
temperature is maintained below 31.1oC. Then lower pressure than critical
pressure is
required to liquefy it.
(2) NH3 is a polar gas. Its critical temperature is 132.44 oC. It must be cooled
below this
temperature before it can be liquefy by applying sufficient high pressure.

Table : Critical Temperature and Critical Pressure of Some Gases

Gas Critical Temperature Tc(oC) Critical Pressure
Pc9(atm)
Carbon dioxide , CO2 31.142(304.3k) 73.0
Freon -12 , CC12F2 111.54(384.7k) 39.6
Ammonia , NH3 132.44(405.6k) 111.5
Water Vapours, H2O 374.44(647.6k) 217
Oxygen , O2 -118.75(154.4k) 49.7
Argon , Ar -112.26(150.9k) 48
 Nitrogen, N2 -147.06(126.1k) 33.5
Joule-Thomson Effect (Joule-Kelvin Effect)
The cooling effect produced when a compressed gas is allowed to undergo
sudden expansion through the nozzle of a jet is called joule-Thomson effect.
The effect is due to energy used in overcoming the intermolecular
attractive
forces of the gas. Joule-Thomson effect is used in the liquefaction of gases by
cooling.
Explanation: In a compressed gas, the molecules are very close to each other.
Therefore, the intermolecular attraction is fairly large. When the compressed gas
is
allowed to undergo sudden expansion in passing through a small orifice (hole) into
a
region of low pressure, the molecules move apart. In doing so, the intermolecular
attractive forces must be overcome. For this purpose energy is required. This
energy is
taken from the gas itself which is thereby cooled.

Method from the liquefaction of Gases

Linds method of liquefaction of gases

The basic principle of the Lindes method of liquefaction of gases is the
joule-
Thosmson effect. The apparatus used for this purpose is shown in the fig.
For liquefaction of air, pure dry air is compression .The compressed air is
then
passed through a spiral pipe having a jet at the end. The air expands at the jet
into the
chamber where the pressure of the air falls down from 200 atm to 1atm. As a result
of
joule-Thomson effect a considerable drop of temperature occurs .The cooled air goes
up and cools the incoming compressed air of the spiral tube .the cooled air goes
again
to the compression pump .The process of compression and expansion is repeated
again and again till the air is cooled to such an extent that it liquefies. The
liquefied air
collects at the bottom of the expansion chamber from where it is drawn off. All
gases
except H2 and He can be liquefied by this method.

Picture
 Fig. lindes method for the liquefaction of air
Non-Ideal Behavior of gases
An ideal gas obeys the gas laws and general gas equation for all valyes of
temperature and pressure. All real gases, however, show marked deviations from
ideal
behavior. These deviations from ideal behavior depends on:
(i) Pressure, and (ii) temperature
A convenient way of showing the deviations of a real gas from ideal
behavior is
to plot a graph between on x-axis and on y-axis. The ratio is called the
compressibility
factor. Its value is equal to 1 for 1 mole of an ideal gas for all values of
temperature and
pressure. For a real gas, the compressibility factor deviate from 1.The extent of
deviation from 1 depends upon the pressure and temperature. it may be either
greater
than 1 or lesser than 1 . A value greater than one shows that thee gas is less
compressible than an ideal gas. On the other hand, a value less than one indicate
that
the gas is more compressible than an ideal gas.
For an ideal gas, since the increase of pressure decreases the volume in
such a
way that remains constant at constant temperature, so a straight line is obtained
parallel to the pressure axis.
In order to understand the deviations of a real gas from ideal behavior,
let us
study the plot of against p of a few real gases like He, H2, N2 and CO2 first at
0oC and
then at 100oc.
(a) Effect of Pressure Variation On Deviations at 0oC

In the fig, the curves between compressibility factor and pressure for the
four
real gases, He, H2, N2 and CO2 along with the behavior of an ideal gas, are shown.

Picture
 Fig Non-ideal behavior of gases at 0o C

(i) At low pressures, all the curves for these four gases approach to unity as
the pressure
approaches zero. Thus all real gases behave as ideal gases at low pressures
(upto10
atm).
(ii) At high pressure, the behavior of He and H2 differs from that of N2 and CO2
at 0oC.For
both he and H2 at 0oC, the compressibility factor is always greater than
one. This curves
show a continuous increase for both He. It means that these gases are less
compressible than expected from ideal behavior. For both N 2 and CO2 at 0oC,
the curve
first decreases and then increases again as the pressure increases. This
decrease in
the compressibility factor below unity is more pronounced in CO2 than in
N2.For CO2,
the dip in the curve is greatest.
The extent of deviation of these four gases show that these gases have their
own
limitations for obeying general gas equation. It depends upon the nature of
the gas that
at which value of pressure, it will start disobeying .
(b) Effect of Pressure Variation on Deviation at 100oC
In the fig, the curves between compressibility factor and pressure for the
four real
gases, He, H2, and CO2at 100oC along with the behavior of an ideal gas, are
shown. It
is clear from the shape of the curves, of these four gases that the
deviations from the
ideal behavior become less at 100oC than at 0oC. The graphs come closer to
the
expected straight line and the deviations are shifted towards higher
pressure. It means
that the increase in temperature makes the gases ideal.

Picture

Fig. Non-ideal behaviour of gases at 100oC

Conclusions:
 On the basis of experimental observations, we draw the following two
conclusions.
1. Gases are ideal at low pressure and non-ideal at high pressure.
2. Gases are ideal at high temperature and non-ideal at low temperature.
Causes for Deviation From Ideality

In the derivation of ideal gas equation, PV=nRT, it was assumed

that all gases
behaved exactly alike under all conditions of pressures and temperatures. In
1873, van
der Waals pointed out that all real gases deviate from ideal behavior at high
pressures
and low temperatures. It was found that the following two incorrect postulates
in the
kinetic theory of gases are the cause of deviation.
1. The molecules exert no forces of attraction on each other in a gas.
When the pressure on a gas is high and the temperature is low then the
intermolecular
attractive forces become significant. Therefore, the ideal gas equation does
not hold
good .Actually, under these conditions, the gas does not remain ideal .
2. The actual volume of gas molecules is negligible as compared to the volume of
the container .
The actual volume of gas molecules is very small as compared to the volume of
the
container, so it can be neglected. This volume, however, does not remain
negligible
when there is high pressure on the gas. This can be understood from the
following
figures.

Picture

Fig. A gas at low pressure when Fig . A gas at high pressure when
Actual volume is negligible Actual volume is negligible

Van der Waals equation For Real Gases

Keeping in view the molecular volume and the intermolecular attractive forces,
Van derWallls pointed out that the ideal gas equation does not hold good for real
gases
He suggested that both volume and pressure factors in ideal gas equation needed
Correction in order to make it applicable to the real gases.
Volume Correction
The volume of a gas is the free space in the container available for the
movement
of molecules . For an ideal gas, the actual volume of the molecules is considered
zero. So
the volume of an ideal gas is the same as the volume of the container . It
also
represents the volume in which the molecules are free to move. For a real
gas, the
molecules are rigid spherical particles which have a definite volume.
Consequently, they
take up part of the space in the container. Thus the volume in which the
molecules of a
real gas are actually free to move is less than the volume of the container.
Thus, van
der Walls suggested that a suitable volume correction term may be subtracted
from the
volume of the vessel containing the gas . The volume correction term for one
mole of
the gas is b. If v is the volume of the vessel containing the gas, then the
volume
available to gas molecules for their free movement is written as.
V free = V vessel =b
Where b is constant depending upon the nature of the gas . b is also
called the
excluded volume or co-volume . It has been found that b is not the actual
volume of
molecules but it is four times the actual volume of the molecules. B =4 Vm .
Where Vm is the actual volume of one mole of gas molecules.
Pressure Correction
Consider a molecule in the interior of a gas. Since it is completely
surrounded by
other molecules equally in all directions so the resultant attractive force
acting on the
molecule is zero .However, when the molecule approaches the wall of the
container, the
equal distribution of molecules about it is upset. There is now a greater
number of
molecules away from the wall with the result that these molecules exert net
inward pull
on the molecule. Thus, when a molecule is about to strike the wall of the
container, it
experiences a force of attraction towards the other molecules in the gas .So
it will strike
the wall with a lower velocity and will exert a lower pressure. Hence the
observed
pressure, P Exerted by the molecules is less than the ideal pressure, Pi by an
amount
Pi .It is, therefore, necessary to add a pressure correction term in order to
obtain the
ideal pressure.
Pi =P+ Pi
Pi is the true kinetic pressure, if the forces of attraction would have been
absent.
Pi is the amount of pressure lessened due to attractive forces.

Picture

Fig : Force of attraction and Pressure correction

It is suggested that a part of the pressure P for one mole of a gas used up
against intermolecular attractions should decrease as volume increase.
Consequently,
the value of pi in terms of a constant a which accounts for the attractive forces
and the
volume V of vessel can be written as
Pi =
How to prove it?
Pies determined by the forces of attraction between molecules of type A
which
are striking the wall of the container and molecules of type B which are pulling
inward.
The net force of attraction is proportional to the concentrations of A type and B
type
molecules.

Let n is the number of moles of A and B separately and total volume of

both
gases is v.Then concentration, C= in moles dm-3 of A and B separately. Therefore,
Pi x
Pi x

Pi =
Where a is a constant of proportionality.
If n=1 , then Pi =
Greater the attractive forces among the gas molecules, smaller the volume of
container,
greater the value of lessened pressure Pi.
This a is called coefficient of attraction or attraction per unit
volume . It has a
constant value for a particular real gas .Thus effective kinetics pressure of a gas
is
given by Pi , which is the pressure if the gas would have been ideal .
Pi+ P=

The kinetic gas equation for one mole of a gas may be written as,
(P+ )(V-b) =RT
For n moles of a gas, the kinetic gas equation may be written as
(P+) (V-b) =RT
This is called van der Waals equation. a and b are known as van der
waals
constants.
Units of a

Since Pi =

a=

a=
a=atm dm6 mol-2
In sI units, pressure is in Nm-2 and volume in m3.

So, a=
a= Nm4 mol-2

Units b: b is excluded or incompressible volume /mole of gas .So , its units

should
be dm3 mol-1 or m3 mol-1 .
The values of a and b can be determined by knowing the values of P,V
and T
of a gaseous system under two different conditions . The values of a and b for
some
common gases are given in the following table.
 Gas a (atm dm6 mol-2) b(dm3
mol-1)
Hydrogen 0.245 0.0266
Oxygen 1.360
0.0318
Nitrogen 1.390
0.0391
Carbon dioxide 3.590
0.0428
Ammonia 4.170
0.0371
Sulphur dioxide 6.170
0.0564
Chlorine 6.493
0.0562
The presence of intermolecular forces in gases like CI2 and SO2
increase their a
factor. The least valur of a for H2 is taken, then its small size and non-
palar character.
The b value of H2 is 0.0266 g (1 mol) of H2 is taken, then it will occupy
0.0266 dm3 mol-
1. It means that if 2.0266 dm3 or 266 cm3 of volume at closet approach in
the gaseous
stat.
Example 8: One mole of methane gas is maintained at 300 k. Its volume is 250
cm3 .calculate the pressure exerted by the gas under the following
conditions.
(i) When the gas is ideal (ii) When the gas is non-ideal
a=2.253 atm dm6 mol-1 b=0.0428dm3 mol-1
Solution:
(i) when methane gas is behaving as ideal, general gas equation is applied ,
that is ,
PV=nRT
v=250 cm =0.25 dm3 n=1 mol
T=300k R=0.0821atm dm3 k-1 mol-1
P=?
P=
P=
P=98.52 atm Answer
(ii) When methane gas is behaving as non-ideal, van der Waals equation
is applied,
(P)(V-nb)=nRT
One rearranging the above equation for P,
P=-

P=
 P=
P=117.286-36.048
P=81.238atm Answer
In the non-ideal situation the pressure has lessened up to
=98.52-81.238=17.282atm Answer
Plasma Stat (or Plasma)
What is Plasma?
A high temperature ionized gas mixture consisting of free electrons,
positive ions and natural atom sis called plasma.
It is the fourth state of matter, in addition to solid, liquid and gas. It
was first
identified by William Crookes in 1879. It is a gaseous state. It is a gaseous
state. It is
electrically neutral because it consists of almost equal numbers of free electrons
and
positive ions. It conducts electricity because it contains free electrons and
positive ions.
It constitutes more than 99% of the visible universe. It is everywhere in our space
environment. Naturally occurring plasma is rare on earth. Plasma is used to conduct
electricity in neon signs and fluorescent bulbs. It occurs only in lightning
discharges and
in artificial devices like fluorescent lights, neon signs, etc. Scientists have
constructed
special chambers to experiment with plasma in laboratories.

How is Plasma formed?

Plasma is formed by the interaction of energy with atoms or molecules. Atoms
or
molecules may be ionized on heating. An atom on losing an electron changes to a
positive ion. In a sufficiently heated gas, ionization occurs many times, creating
clouds
of free electrons and positive ions. However, all the atoms are not necessarily
ionized
and some of them may remain neutral atoms. A high temperature ionized gas
mixture consisting of free electrons, positive ions and natural atom sis called
plasma.
 Plasma contains a significant number of electrically charged particles which
are free
electrons and positive ions. It is due to this reason plasma shows electrical
properties
and behavior.
What plasma can potentially do?
Plasma can generate explosions, carry electrical currents and support
magnetic
fields within themselves. Space plasmas can contain enough heat to melt the
earth
thousands of times over. Crystal plasmas can freeze the earth at least a
hundred times,
one after the other.
Artificial and Natural plasma:
Artificial Plasma can be created by using charges on a gas, e.g,. in
neon signs
.Plasma at low temperature is not exist. This is because outside a vacuum, low
temperature plasma reacts rapidly with any molecule it meets. This aspect
makes it
both very useful and not easy to use.
Natural plasma exists only at very high temperatures or low
temperature
vacuums. It does not break down or react rapidly. It is extremely hot having a
temperature over 20.000 oC. Plasmas possess very high energy. They vaporize
any
material they touch.
Characteristics of Plasma:
1. Plasma shows a collective response to electric and magnetic fields. This is
because it
has sufficient numbers of charged particles. The motions of the particles in
the plasma
generate fields and electric currents from within plasma density. It refers to
the density
of the charged particles.
2. Although plasma contains free electrons and positive ions and conducts
electricity but
as whole it is electrically neutral. It contains equal number of free
electrons and positive
ions.
Where is plasma found?
Plasma is the most abundant from of matter. The entire universe is
almost of
plasma. It existed before any other forms of matter came into being .Plasmas
are found
from the sun to qarks. Quarks are the smallest particles in the universe. Most
of the
 matter in inner-stellar space is plasma. The sun is a 1.5 million kilometer
ball of plasma
which is heated by nuclear fusion.
On the earth, plasma only occurs in a few limited places such as
lightning bolts,
flames, auroras and fluorescent lights. On passing electric current through
neon gas,
both plasma and light are produced.
Applications of plasma:
The important applications of plasma are the following.
(i) A fluorescent light bulbs and tube is not like an ordinary light bulb.
Inside the tube is a
gas. When light is turned on, electricity flows through the tube. This
electricity acts as a
source of energy and chares up the gas. This charging and exciting of the
atoms
creates a glowing plasma inside the tube or bulb.
(ii) Neon signs are glass tubes filled with gas. When they are turned on,
electricity flows
through the tube. The electricity charges the gas and creates plasma inside
the tube.
The plasma glows a special colour depending on the nature of the gas inside
the tube.
(iii) They are used for processing go semiconductors, sterilization of some
medical
products, lamps ,lasers, diamond coated films , high power micro wave
sources, and
pulsed power switches.
(iv) They provide foundation for the generation of electrical energy from fusion
pollution
control, and removal of hazardous chemicals.
(v) Plasmas are used to light up offices and homes, make computers and
electronic
equipment to work.
(vi) They drive lasers and particle accelerators, help to clean up the
environment,
pasteurize foods, and make tools corrosion-resistant.
Future Horizons:
Scientists are working on putting plasma to effective use. Low energy
plasma should by
able to survive without instantly reacting and degeneration. The
application of magnetic
fields involves the use of plasma. The magnetic fields create low energy
plasma which
relate molecules which are in a metastable state. The metastable molecules
do not
react until they collide with another molecule with just the right energy.
This enables the
 met stable molecules to survive long enough to react with a designated
molecule. The
met stable molecules are selectivity. It makes a potentially unique
solution to problems
like radioactive contamination. Scientists are experimenting with mixtures
of gases to
work as met stable agents on plutonium and uranium.

EXERCISE

Q1: Select the correct answer out of the following alternative

suggestions:
(i) Pressure remaining constant, at which temperature the volume of a gas will
become
twice of what it is at 0oC .
a. 546oC b.200oC c. 546 k d. 273k
Hind: V T.
(ii) Number of molecules in one dm3 of water is close to

a. b. c. d.
Hint: 1 dm3 of H2O =1000cm3 of H2O; 1000cm3 of H2O =1000g of H2O

No of moles of H2O = moles ( 1 ml of H2O =1 f

of H2O)
(iii) Which of the following will have the same number of molecules at STP?
a. 280cm3 of CO2 and 280 cm3 of N2 O
b. 11.2dm3 of O2 and 32 g of O2
c. 44g of CO2 and 11.2 dm3 of CO
d. 28 g of N2 and 5.6 dm3 of oxygen
(iv) If 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. Increase four times

c. reduce to d. be doubled

Hint: PV = RT, V= :V
(v) How should the conditions be changed to prevent the volume of a given gas
from
expanding when its mass is increased?
a. Temperature is lowered and pressure is increased.
b. Temperature is increased and pressure is lowers.
c. Temperature and pressure both are lowered
d. Temperature and pressure both are increased.

Hint: PV = RT, V= :V ( M and R being constant)

(vi) The molar volume of CO2 is maximum at
a. STP b. 127oC and 1 atm
c. 0oC and 2 atm d. 273 oC 1 atm

Hint:For1 mole of CO2 PV = RT, V= :V

or Vm
(vii) The order of the rate of diffusion of gases NH3, SO2 C12 and CO2 si :
a. NH3 > SO2 > C12 > CO2
b. NH3 > CO2 > SO2 > C12
c. C12 >SO2 > CO2 >NH3

Hint: r
(viii) Equal masses of methane and oxygen are mixed in an empty container at 25
oC . The
fraction of total pressure exerted by oxygen is

a. b.

c. d.
Hint: In an empty container, the partial pressure of gas is directly
proportional to the
mole-fraction of the gas. Partial pressure mole fraction, at STP.
(viii) Gases deviate from ideal behavior at high pressure. Which of the
following is correct for
non-ideality?
a. At high pressure, the ga molecules move in one direction only.
b. At high pressure, the collision between the gas molecules are increased
manifold.
c. At high pressure, the intermolecular attractions become significant.
d. At high pressure, the intermolecular attractions become significant.
(ix) The deviation of a gas from ideal behavior is maximum at
a. -10oC and 5.0atm b. -10oC and 2.0atm
c. 100 oC and 2.0 atm d. 0.oC and 2.0atm
(xi) A real gas obeying van der Waals equation will
resemble ideal gas if
a. both a and b are larger b.
both a and b are small
c. a is small and b is larger d.
a is larger and b is small
Ans: (i)c (ii)d (iii)a (iv)b (v)a (iv)b
(vii)b (viii)a (ix)d (x)a (xi)b
Q2. Fill in the blanks.
(i) The product of PV has the S.I. unit of _______.
(ii) Eight grams each of O2 and H2 at 27oC will have total K.E in the ratio of
________.
(iii) Smell of the cooking gas during leakage from a gas cylinder is due to of
the property of
_______of gases.
(iv) Equal _________of ideal gases at the same temperature and pressure contain
________number of molecules.
(v) The temperature above which a substance exists only as gas is called _____.
Ans. (i) atm dm3 (ii) :16 (iii)
diffusion (iv) Volumes:
equal (v) Critical temperature
Q3. label the following sentences as true or false.
(i) Kinetic energy of molecules is zero at 0oC.
(ii) A gas in a closed container will exert much higher pressure at the bottom
due to gravity
than at the top.
(iii) Real gases show ideal gas behavior at low pressure and high temperature.
(iv) Liquefaction of gases involves decrease in intermolecular spaces.
(v) An ideal gas on expansion will show Joule-Thomson effect.
Ans. (i) False (ii) False (iii) True
(iv) False (v) False

Q4: (a) What is Boyles law of gases? Give its experimental

verification.
 (b) What are isotherms? What happen to the positions of isotherms when they
plotted at
high temperature for a particular gas.
(c) Why do we get a straight line when pressures exerted on a gas are
plotted against
inverse of volumes. This straight line changes its position in the graph
by varying the
temperature. Justify it.
(d) How will you explain that the value of the constant k in equation PV=k
depends upon
(i) The temperature of the gas (ii) the quantity of the gas.
Ans: (a) Isotherms: The P-V curves obtained at constant temperature
are called
isotherms. These curves are obtained by plotting a graph between
pressure on the x-
axis and volume on the y-axis. Similar curves are obtained at fixed
temperatures.
When the isotherms (P-V curves are plotted at high temperature, they go
away from
the axes. The reason is that, at higher temperature, the volume of the
gas increase.
Ans.(c) A plot of P versus gives a straight line at constant temperature. This
shows that p is
directly proportional to . This straight line will meet at the origin
where both P and are
zero. The P goes down as the gas expands, falling away to zero as the
volume

approaches infinity (= =0)

This straight line changes its position because both pressure and
volume varies on
varying the temperature. When temperature is increased both pressure and
volume will
increase. Keeping T constant and plotting P versus another straight line
is obtained.
This straight line goes away from x-axis. However , when temperature is
decreased
both the values of P and V will decrease. Again a straight line is
obtained. This straight
line will be closer to the x-axis
Ans.(d) General equation: PV=nRT _______(1)
The general gas equation contains the Boyles law, for which nRT are
constant at fixed
T and n.
Bolyles law: PV=k _______(2)
Form Eq (1) and Eq (2), we get
K=nRT
K=
 K=constant x mT (at fixed R and M )
K mT _______(3)
This relation indicates that
(i) k T; it means k depends upon the temperature of the gas
(ii) k m; it means k depends upon the quantity of the gas.
Q5. (a) What is the Charless law? Which scale of temperature is used to
verify that =k
(pressure and number of moles are constant)
(b) A sample of carbon monoxide gas occupies 150.0mL at 25.0o C. it is
then cooled at
constant pressure until it occupies 100.0mL. What is the new
temperature?
(c) Do you think that the volume of any quantity of a gas becomes zero at
-273oC. Is it not
against the law of conservation of mass? How do you deduce the idea of
absolute zero
from this information?
Ans.(a) The relation, =k can be verified only when T is taken on the Kelvin
scale.
Ans.(b) V1 =150 mL T1 =273+25=298K
V2 =100 mL T2 =?
Formula Used:
=
or
T2 =
T2 =
T2 =198.67k
T2 =273+toC
toC=T2 273
toC=198.67-273
=-74.33oC Answer
Ans.(c) We know that : V1 =Vo (1+)
At -273oC, V-273 = Vo (1-)= Vo (1-1) =Vo x0=0
The volume of the gas become zero at- 273oC. But it is impossible to imagine
that a
 Gas which is matter occupies no space. It goes against the law of
conservation of
mass.
Hence, it follows that -273oC is the lowest temperature which a body can
ever have. So
-273o C is called the absolute zero of temperature. The scale of
temperature on which -
273oC is taken as zero is called absolute scale of temperature.
Q6. (a) What is Kelvin scale of temperature ? Plot a graph
for one mole of an
ideal gas to prove that a gas become liquid, carlier than -273o C .
(b) Throw some light on the factor in Charless law.
Ans.(b) In Charless law, the factor (0.00366 ) is the coefficient of expansion
of given mass of
gas at constant pressure. It shows that a gas expands by parts of its
volume at 0o C for
a rise of temperature of 1oC.
Statement of Charless Law: At constant pressure, the volume of a given mass
of gas
increases or decreases by of its volume at0oC for every 1oC rise or fall
in temperature .
Mathematically.
Vt -=Vo +
It means that if we have 273 cm3 of gas at 0oC, its volume will
increase by 1 cm3 for
every 1oC rise in temperature if it is heated at constant pressure Thus,
At 1oC , the volume will become 274 cm3.
At 2oC , the volume will become 271 cm 3.

At 273oC , the volume will become 0 cm 3.

Similarly, if the gas is cooled by 1oC at constant pressure, its volume

will decrease by 1 cm 3 . Thus,

At -1oC , the volume of the gas becomes 272 cm 3.

At -2oC , the volume of the gas becomes 275 cm 3.

At -273oC , the volume of the gas becomes 546 cm 3.

Q7. (a) What is the general gas equation? Derive it in various

forms.

(b) Can we determine the molecular mass of an unknown gas if we know the
pressure, temperature and

volume along with the mass of that gas?

(c) How do you justify from general gas equation that increase in temperature
or decrease of pressure

decreases the density of gas?

 (d) Why do we feel comfortable in expressing the densities of gases in
the units of g dm-3rather than g cm -3, a

which is used to express the densities of liquids and solids.

Ans.(b) Yes, we can determine the molecular mass of an unknown gas if we

know its, P,T,V
and m by applying the following formula:
M=
Ans.(c) We know form general gas equation,
d=
d=constant x (M and R being constant)
d=
Density is directly proportional to pressure and
inversely proportional to
temperature or decrease of pressure, decreases the density of the
gas.

Ans.(d) The densities of gases are very low. They are about 1000 times
smaller than the
densities of liquids and solids. So, if gas densities are expressed
in g cm -3, then the
values will be very small. They may go to fourth place of decimal
for some gases. When
we express the densities in g dm-3, then the values of the densities
become reasonable
to be expressed. For example, the density of CH4 gas is 0.7168 g dm-
3 at STP, but if it is
expressed in g cm-3 , then it is 0.0007168 g cm-3 at STP. Therefore,
we feel comfortable
in expressing the densities of gases in the units of g dm-3 rather
than in g cm-3.

Q8. Derive the units for gas constant R in general gas equation:
(a) When the pressure is in atmosphere and volume in dm3.
(b) when the pressure is in Nm-2 and volume in m3 .
( c) when energy Is expressed in ergs.

Q9. (a) what is Avogadros law of gases?

(b) Do you think that 1 mole of H2 and 1 mole NH3 at 0oC and 1 atm
pressure will have
equal Avogadros number of particles? If not, why?
 (c) Justify that 1 cm3 of H2 and 1 cm3 of CH4 at STP will have the same
number of
molecules, when one molecules of CH4 is 8 times heavier than that of
hydrogen.

Ans (b) 1 mole of H2 and 1 mole of NH3 at 0oC and 1 atm pressure will have
equal number
of molecules under the same conditions of temperature and pressure. Hence,
1 cm3 of
H2 and 1 cm3 of CH4 at STP will have the same number of molecules.
Q10. (a) Daltons law of partial pressure is only obeyed by those gases
which do not
have attractive forces among their molecules. Explain it.
(c) Derive an equation to find out the partial pressure of a gas knowing the
individual
moles of component gases and the total pressure of the mixture.
(d) Explain that the process of respiration obeys the Daltons law of partial
pressure.
(e) How do you differentiate between diffusion and effusion? Explain Grahams
law of
diffusion.
Ans. (a) For Daltons law of partial pressure to hold, there will be
no attractive forces
among the molecules on the walls of the gases. The pressure of a gas is
due to the
collisions of the molecules on the walls of the container. In the absence
of attractive
forces each molecules of gas mixture will hit the walls of the container
with the same
number of times and with the same force. Thus the partial pressure of a
given gas is
unaffected by the presence of other gases. In this case, the total
pressure. Hence the
law will not hold in the presence of attractive forces among the
molecules.
Q11. (a) What is critical temperature of a gas? What is its importance for
Liquefaction of gases? Discuss Lindes method of liquefaction of
gases.
(b) What is Joule-Thomson Effect? Explain its importance in lindes method of
liquefaction
of gases.
Ans. (a) Importance of Critical temperature for liquefaction of
gases.
The critical temperature of the gases provides us the information about
the
Condition under which gases liquefy. For example,O2 ,has a critical
temperature
154.4k(-118,75 oC). It must be cooled below this temperature before it can
be liquefied
by applying high pressure.
 Q12. (a) What is Kinetic molecular theory of gases? Give its
postulates.
(b) How dose Kinetic molecular theory of gases explain the following gas
laws:
(i) Boyles law (ii) Charless law
(iii) Avogadros law (iv) Grahams law of diffusion.
Q13. (a) Gases show non-ideal behavior at low temperature and
high pressure.
Explain this with the help of a graph.
(b) Do you think that some of the postulates of Kinetic molecular theory of
gases are
faulty? Point out these postulates.
(c) Hydrogen and helium are ideal at room temperature, but SO 2 and C12are
non ideal.
How will you explain this?
Ans. (c) Hydrogen (b.p-253oC) and helium b.p-269oC)have a very low
boiling points
.They are far away from their boiling points at room temperature. Also,
they have
smaller number of electrons in their molecules and smaller molecular
sizes, i.e.,
molecular weight. So, intermolecular forces are negligible at room
temperature. Hence,
they behave as an ideal gases at room temperature.
On the other hand, SO2 (b.p-10oC) and C12 (b.p-34oC) have
boiling points near
to room temperature. They are not far away from their boiling points at
room
temperature. Also, they have larger number of electrons in their molecules
and larger
molecular sizes. So, sufficient intermolecular attractive forces are
present at room
temperature. Hence, they behave as non-ideal at room temperature.
Q14. (a) Derive van der Waals equation for real gases.
(b) What is the physical significance of van der Waals constant, a and b.
Give their units.
Ans. (b) Physical Significance of van der Waals constant a and b
(i) Significance of a: The value of constant a is a
measure of the
intermolecular attractive forces and greater will be the ease of its
liquefaction.
Units of a :
The units of a are related to the units of pressure, volume
and number of
moles.
 P= or
a= =
a= atm dm6 mol-2
In SI units: a= ==Nm4 mole -2
(iii) Significance of b: The value of constant b us related to the size of
the molecule.
Larger the size of the molecule, lager is the value of b. It is effective
volume of the gas
molecules.
Units of b:
b is the compressible volume per mole of gas. So the units of b
are related to
the units of volume and moles.
V=nb or b=
b==dm3 mol-1
In SI units: b===dm3 mol-1
Q15. Explain the following facts:
(a) The plot of PV versus P is a straight line at constant temperature and
with a fixed
number of moles of an ideal gas.
(b) The straight line in (a) is parallel to pressure-axis and goes away from
the pressure
axis at higher pressure for many gases.
(c) The van der walls constant b of a gas is four times the molar volume of
that gas
(d) Pressure of NH3 gas at given conditions (say 1 atm pressure and room
temperature) is
less as calculated by van der Waals equation than that calculated by
general gas
equation.
(e) Water vapors do not behave ideally at 273 k.
(f) SO2 is comparatively non-ideal at 273 k but behaves ideally at 327 K.
Ans. (a) At constant temperature and with a fixed number of moles of an
ideal gas,
when the pressure of the gas is varied, its volume changes, but the product
PV remains
constant. Thus,
P1 V1 = P2 V2 = P3 V3 =
 Hence, for any fixed temperature, the product PV when plotted against P.a
straight line
parallel to P-axis is obtained. This straight line indicates that PV remains
constant
quantity.
Ans. (b) Now, increase the temperature of the same from T1 to T2 .At
constant
temperature T2 and with the same fixed number of moles of an ideal gas, when
the
constant. However, the value of PV increase with increase in temperature. On
plotting
graph between P on x-axis is obtained. This straight line at T2 will be away
from the x-
axis. This straight line also shows that PV is a constant quantity.
Ans. (c) Excluded volume, b is four times the molar volume fo gas. The
excluding
with each other as shown in Fig. The spheres are considered to be non-
compressible.
So the molecules cannot approach each other more closely than the distance,
2r .
Therefore, the space indicated by the dotted sphere having radius, 2r will
not be
available to all other molecules of the gas. In other words, the dotted
spherical space is
excluded volume per pair of molecules.
Let each molecules be a sphere with radius =r
Volume of one molecules (volume of sphere)=
The distance of the closest approach of 2 molecules =2 r

The excluded volume for 2 molecules=

The excluded volume for 1 molecule=

=
=4Vm =b
The excluded volume for n molecules=n b
Where Vm is the actual volume of a molecule.
Hence, the excluded volume or co-volume or non-compressible volume is equal
to 4
times the actual volume of the molecules of the gas.
Ans. (d) The pressure of NH3 calculated by general gas equation is high
because it is
considered as an ideal gas. In an ideal gas, the molecules do not exert any
force of
attraction on one another. On the other hand, when the pressure of NH 3 is
considered
 as a real gas. Actually, NH3 is a real gas. It consists of polar NH3
molecules approaches
the walls of the container, it experiences an inward pull. Clearly, the
molecule strikes the
wall with a lesser force than it would have done it these are no attractive
forces. As a
result of this , the real gas pressure is less than the ideal pressure.
Ans. (e) Water vapors present at 273K do not behave ideally because polar
water
molecules exert force of attraction on one another.
Ans. (f) At low temperature, the molecules of SO2 possess low kinetic
energy. They
come close to each other. The e intermolecular attractive forces become very
high. So,
it behave non-ideally at 273K. At high temperature, the molecules of SO2
have high
kinetic energy. The molecules are at larger distances from one other
another. The
intermolecular attractive forces become very weak. So, it behaves ideally at
327K.
Q16. Helium gas in a 100 cm3 container at a pressure of 500 torr is transferred
to a container
with a volume of 250cm3.What will be the new pressure
(a) if no change in temperature occurs
(b) if its temperature changes from 20 oC to 15 oC?
Solution:
(a) Given: P1=500 torr P2 =?
V1 =100cm3 V2 =250cm3
Formula used: P2 V2 = P1V1

P2 =

P2 =
=250torr Answer
(b) Given: P1 =500torr ; P2 =?
V1 =100cm3 ; V2 =250 cm3
T1 =273 +20=293K : T2=273+15=288K

Formula Used: =

P2 = x
 =
=196.58 torr Answer
Q17. (a) What are the densities in kg/m3 of the following gases at STP
(i) Methance, (ii) oxygen (iii) hydrogen
(P=101325Nm-2, T=273k, molecular masses are in kg mol-1 )
(b) Compare the values of densities in proportion to their mole
masses.
(c) How do you justify that increase of volume upto 100 dm 3 at 27 oC of 2
moles of
NH3 will allow the gas behave ideally.
Solution:
(a) (i)Given P=101325Nm-2
T=273K
Molar mass of CH4 =12+4=16g mol-1 =16x10-3 kg mol-1
R=8.3143NmK-1 mol-1
d=?

Formula Used: d=

d=
d= 0.714kgm-3
P=101325Nm-2
T=273k
Molar mass of O2 =32g mol-1
d= ?

Formula used: d=

d=
d=1.428kgm-3
(iii) P=101325Nm-3 ; T=273k
Molar mass of H2 =2x10-3kg mol-1 :R=8.3143 NmK-1 mol-1
 d=?

Formula Used: d=

d=
d=0.089kg m-3
Q18. A sample of krypton with a volume of 6.25 dm 3 , a pressure of 765
torr and a
temperature of 20oC is expanded to a volume of 9.55 dm3 and a pressure of
375 torr.
What will be its final temperature in oC?
Solution:
P1 = 765torr ; P2 =375torr
V1 =6.25dm3 ; V2 =9.55 dm3
T1 =273+20 =273k ;T2 =?

Formula used: x

T2 =

T2 =

T2 =
T1 =273+o C
oC =T-273=219.46-273
=-53.54 oC Answer
Q19. Working at a vacuum line, a chemist isolated a gas in a weighing bulb with a
volume of
255 cm3 , at a temperature of 25 oC and under a pressure in the bulb of
10.0torr. The
gas weight 12.1 mg. what is the molecular mass of this gas?
Solution:
V=255 cm3 =0.255 dm3

P=10.0torr =
T1 =273+25=298K
 m=12.1mg=0.0121g
R=0.0821dm3 atom K-1 mol-1

Formula Used: PV= RT

M=

M=
M=87.93 g Mol-1 Answer
Q20. What pressure is exerted by a mixture of 2.00g of H 2 and 8.00g of N2
at 273 K in
a dm3 vessel?
Solution:
Given: V=10dm3 ; T=273k
R=0.0821 dm3 atm K-1 mol-1
P H2 =? PN2 =?
Mass of H2 =2.00g Mass of N2 =8.00g
Molar mass of H2 =2g Molar mass of N2 =28g mol-1

nH2 = =1 mole ;n N2 =
=0.286 mole
n=mH2 +nN2 =1+0.286=1.286 moles
PV=nRT
P x10 dm3 =1.286 molx 0.0821dm3 atm k-1 mol-1 x 273K

P=
P=2.88 atm Answer
Q21. (a) The relative densities of two gases A and B are 1:1.5 find out the
volume of B
which will diffused in the same time in which 150 dm3 of A will diffuse?
(b) Hydrogen (H2 ) diffuses through a porpous plate at a rate of 500cm3 per
minute at 0 oC.
What is the rate of diffusion of oxygen through the same porpous plate 0 oC?
(c) The rate of effusion of an unknown gas A through a pinhole is found to be
0.279 times
the rate of effusion of H2 gas through the same pinhole.
Calculate the molecular mass of the unknown gas at STP.
Solution:
Given:
dA =1 rA=150dm3

rB=
(b) rH 2=500 cm3 per minute MH2 = 2 g mol-1
ro2=? Mo2 =32 g mol-1

=
=4
ro2==125cm3 Answer
(c) Given: rH2=1 rA=0.279
MA =? MH2=g mol-1

0.078=

MA =
MA =25.64 g mol-1 Answer
Q22. Calculate the number of molecules and the number of atoms in the given
amounts of
each gas
(a) 20cm3 of cH4 at 0oC and pressure of 700 mm of mercury
(b) 1 cm3 of NH4 at 100oC and pressure of 1.5 atm
Solution:
(a) Given: P=700 mm =0921atm
V=20cm3 =0.02dm3
R=0.0821dm3 atm K-1 mol-1
T=273+0=273K
N=?
Formula Used: PV=nRT
n=

n=
No of molecules =No of moles x NA
=8.22x1020 molecules Answer
Since 1 molecule of CH4 contains =5 atoms
Therefore, No of atoms =5x4.948x1020
=24.74x1020 atoms Answer
(b) Given P=105 atm ; R=0.0821dm3 atm K-1
mol-1
V=1 cm3 =0.001dm3 ; T=273+100=373K
n=?
Formula Used: n=

n=
No of molecules =4.89x10-5 x6.02x1023
=29.44x1018 =2.944x1019 molecules Answer
No of atoms =2.944x1019 x4=1.18x1020 atoms Answer
Q23. Calculate the masses of 1020 molecules of each of H2 ,O2 and CO2 at STP.
What will
happen to the masses of these gases, when the temperature of these gases
are
increased by 100oC and pressure is decreased by 100 torr.
Solution:
(a) Given: Molecules of H2 =1020
Now , 6.02x1023 molecules of H2 at STP =1mole =2g
1020 molecules of H2 at STP =
=0.332x10-5 g
=3.32x10-4 g Answer
(b) Given: Molecules of O2 =1020
Now, 6.02x1023 molecules of O2 at STP =32g
1020 molecules of CO2 STP =
=5.32x 10-3 g Answer

(c) Given: Molecules of CO2 =1020

Now, 6.02x1023 molecules of CO2 at STP =44g
1020 molecules of CO2 at STP =
=7.30x10-3 g Answer
Q24. (a) Two moles of NH3 are enclosed in a 5dm3 flask at 27oC. calculate
the pressure
exerted by the gas assuming that
(i) it behaves like an ideal gas
(ii) it behaves like a real gas
a=1.17 atm dm6 mol-2
b=0.0371 dm3 mol-1
(b) Also calculate the amount of pressure lessened due to forces of
attractions at these
conditions of volume and temperature.
(c) Do you expect the same decreased in the pressure of 2 moles of NH 3having a
volume
of 40dm3 and at temperature of 27oC.
Solution:
 (a.i) Given: V=5dm3 ; T=273+27=300K
n=2mole ; R=0.821dm3 atm K-1 mol-1
P=?
Formula Used: PV=nRT
P=

P==
P=9.852 atm Answer
(a.ii) Given: n=2mol
a=4.17atm dm3 mol-1
b=0.0371dm3 mol-1
V=5dm3
R=0.0821atm dm3 K-1 mol-1
T=273+27=300K
P=?

Formula Used: (V-nb)=nRT

On rearranging the equation
P=-
On substituting the values
P=-
P=-

P=-
P=9.99-0.667
P=9.32atm Answer
(b) Difference of pressure , P=9.852-9.32=053atm Answer
(c) Given: n = 2 mol ; V=40dm3;T=273+27=300K
p =?
Formula Used: PV=nRT
 P=
P=
P=1.232 atm
The decrease in pressure is not the same