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1. IIT–JEE Syllabus
Avogadro’ s law; equation of state for an ideal gas; kinetic theory of gases; root
mean square velocity and its relation with temperature; average velocity; Gay
Lussac’s law.

2. The Gas Laws


Robert Boyle was beginning his examination of the behavior of air. In addition to his
numerous observations on the properties of air and speculations of the nature of
chemical change, Boyle was the first person to use the term "chemist" to describe his
activities.

Boyle used a simple apparatus to examine the relationship between pressure and
volume. In this apparatus, a small volume of air was trapped in a glass tube by mercury.
A flexible tube connected this tube to a small reservoir of mercury that could be raised or
lowered relative to the trapped gas volume. The difference in height of the interior and
exterior mercury levels is, of course, the pressure relative to the pressure of the
atmosphere. Boyle was able to demonstrate that,

V x P = constant

or that the volume and pressure are inversely proportional. This relationship is called
Boyle's Law.

While Boyle observed that there was an additional relationship between temperature and
volume he did not examine it in detail and it remained for the Frenchman, Jacques
Charles (1746 - 1823) to report in 1787 that,

V = kT (k = constant)

or that volume is directly proportional to temperature. This relationship is Charle’s Law.

Somewhat later on in 1848, the English scientist William Thompson, who was later
raised to the Peerage as Lord Kelvin, recognized that a graph of volume vs. temperature
for any gas resulted in a straight line that intersected the temperature axis at -273.15oC.
This temperature later became known as absolute zero and was used as the basis for
an absolute temperature scale. Temperature units corresponding to the Centigrade
scale in this measure are called Kelvins.

Following in the French tradition, Joseph Lewis Gay-Lussac carried out a number of
experiments on the properties and reactions of gases, resulting in his law of combining
volumes that formed the basis for modern concepts of stoiochiometry. Gay-Lussac's
ideas directly influenced the Italian, Amedeo Avogadro to propose that equal volumes of
gases at the same temperature and pressures contained the same number of
molecules. Unlike the other ideas presented here, Avogadro's ideas were more
theoretical and (at the time) speculative, and were not accepted by the scientific
community that was just then struggling with the implications of Dalton's atomic theory.

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Another way of stating Avogadro's idea mathematically is to write V = kn (k = constant)


where n is the number of molecules. We now express n in terms of the unit "mole" which
contains one Avogadro number of molecules, atoms or particles. Avogadro's number
itself was not first measured until a student of Rutherford collected the helium formed by
alpha particles from a sample of radium. Knowing the pressure of the helium gas and the
number of alpha decays over time of the sample, the student was able to obtain an
estimate of Avogadro's number. Increasingly sophisticated experiments over the years
have now set this number as 6.023 x 1023.

Combined Gas Law

If we combine the observations of Boyle, Charles, and Avogadro we find a single


expression with four variables and one unified constant that we write as PV = nRT

In chemistry we use the following units for these quantities

 P = pressure in atmospheres
 V = volume in liters
 n = moles
 T = temperature in Kelvins
 R = 0.821 l atm/mol K

Illustration 1: Calculate the pressure exerted on the walls of a 3 litre flask when 7 gms
of N2 are introduced into the same at 27°C.

W RT 7 0.082  (273  27)


Solution: P= =  = 2.05 atm
M V 28 3

Illustration 2: An open vessel at 27 oC is heated until 3/5th of the air in it has been
expelled. Assuming that the volume of the vessel remains constant find
a) the temperature at which vessel was heated?
b) the air escaped out if vessel is heated to 900 K?
c) temperature at which half of the air escapes out?

Solution: One should clearly note the fact that on heating a gas in a vessel
there are the number of moles of gas which go out, the volume of
vessel remains constant.

Let initial moles of gas at 300 K be ‘n’. On heating 3/5 moles of air are
escaped out at temperature T.
 3  2n
Moles of air left at temperature T =  n  n  =
 5  5

a) Under similar conditions of P and V


n1T1 = n2T2
2n
n ×300 = ×T
5
T = 750 K

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b) On heating vessel to 900 K, let n1 moles be left again n1T1 = n2T2


n1×900 = 300 × n
1
 n1 = n
3
n 2
moles escaped out = n-  n moles
3 3
c) Let n/2 moles are escaped out at temperature T then
n1T1 = n2T2
n
 T = n × 300
2
T = 600 K

Exercise 1: i) An open bulb containing air at 19°C was cooled to a certain


temperature at which the no. of moles of gaseous molecules
increased by 25%. What is the final temperature?
ii) A long rectangular box is filled with Cl2 (atomic weight 35.45) which
is known to contain only 35Cl and 37Cl. If the box could be divided by
a partition and the two types of Cl2 molecules put in the two
compartments respectively, calculate where should the partition be
made if pressure on both sides are to be equal. Is this pressure the
same as the original pressure?

2.5 Relation between Molecular Mass and Gas Densities

Actual density: Density and Molecular weight

From the ideal gas equation


nRT W dRT
P=  RT 
V M V M
d/P 1.517
d
 M = RT 0.5
P
P

Hence from a knowledge of d/P density under unit pressure molecular weight can be
determined. At low pressure below 1 atm d/p has been found to decrease linearly with
pressure. Extrapolation of the line to zero pressure

P = 0 gives the ideal value of (d/P) at P  0

 d
M=   RT
 P  P 0

Vapour Density: For gases another term which is often used is vapour-density. Vapour
density of a gas is defined as the ratio of the mass of the gas occupying a certain
volume at a certain temperature and pressure to the mass of hydrogen occupying the
PVM
same volume at the same temperature and pressure i.e. W(gas) =
RT

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PV  2
and WH2  ( mol. wt.of Hydrogen is 2)
RT
Wgas M
  = Vapour density of gas
WH2 2

Vapour density of a gas is same at any temperature, pressure and volume.

Molecular Weight and Effective Molecular Weight: Molecular wt. of a gas mixture or
effective molecular weight:- Suppose we have to find the molecular weight of air and we
are told that air contains 79% nitrogen and 21% oxygen (by mole or volume).

First of all let us understand what is meant by molecular wt. of a gas. Molecular wt. of a
gas is the weight in gms of one mole of the gas (hence the unit gm/mole). Now if we take
one mole of air it would contain 79/100 moles of Nitrogen and 21/100 moles of oxygen.
The weight of one mole of air would be 0.79  28 + 0.21  2 = 22.54 gm/mole.

 Meffective = XiMi =  mole fraction of a gas  mol. wt. of a gas.

ni moles of a gas
Xi (Mole fraction) of a gas is = 
n i Total moles of gas

2.6 Dalton’s Law of Partial Pressures

“The total pressure of a mixture of non-reacting gases is equal to the sum of their partial
pressures”. By the partial pressure of a gas in a mixture is meant, the pressure that the
gas will exert if it occupies alone the total volume of the mixture at the same
temperature.

Consider n1, moles of gas 1 and n2 moles of gas 2 occupying a vessel of volume V at
temperature T K and exerting a total pressure P.

Let n1 moles of gas 1 alone occupy the same vessel of capacity V at the same
temperature TK and exert a pressure P1. Then by definition, P1 is partial pressure of gas
1 in the mixture.

Let n2 moles of gas 2 alone occupy the same volume V at the same temperature TK and
exert a pressure P2. The P2 is the partial pressure of gas 2 in the mixture.

By Dalton’s Law P = P1 + P2

Derivation: n = n1 + n2 + …
PV
n
RT
PV P1V P2 V
 + +…
RT RT RT
P = P1 + P2 + …

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Assumption: Volume of all the gases is same.

Relationship between partial pressures and number of moles

Important formula
 n1 
i) P1   P  x1P where x1 = mole fraction of gas (1)
 n1  n2 
Volume of the gas
ii) Partial pressure of a gas in the mixture = P
Total Volume

Partial pressure and aqueous tension

Dalton’s law is used to calculate the pressure of a dry Moist


gas when it is collected over water at atmospheric (Gas + Water vapour)
pressure. By Dalton’s law.

Pressure of dry gas = atmospheric pressure – aqueous


tension

Aqueous tension depends on temperature. It increases Water


with temperature and becomes 760 mm at 100°C.

Illustration 3: A mixture containing 1.6 g of O 2 and 1.4 g of N2 and 0.4 g of He


occupies a volume of 10 litre at 27 oC. Calculate the total pressure of
the mixture and partial pressure of each component.

0.4 1
Solution: PHe =   0.0821  300 = 0.2463 atm
4 10
1.6 1
PO' 2    0.0821  300 = 0.123 atm
32 10
1.4 1
PN' 2    0.0821  300 = 0.123 atm
28 10
'
Ptotal = PHe  PO' 2  PN' 2 = 0.4925 atm

3. The Kinetics Theory of Gases


Any law is an empirical generalization which describes the results of several
experiments. A law, however, only describes results; it does not explain why they have
been obtained. A theory is a description which explains the results of experiments. The
kinetic-molecular theory of gases is a theory of great explanatory power. We shall see
how it explains the ideal gas law, which includes the laws of Boyle and of Charles;
Dalton's law of partial pressures; and the law of combining volumes.

The gas equation PV = nRT was pretty much in its modern form by 1860 with the
inclusion of Avogadro's hypothesis. The remarkable success of this simple equation
prompted several scientists to attempt to derive this equation from a set of simple
assumptions. The workers primarily responsible for this were James Clerk Maxwell,
Ludwig Boltzmann and Rudolph Clausius.

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3.1 The Postulates

 A gas is made up of a large number of particles (atoms or molecules) whose size is


negligible compared to the size of the container. These particles are also small
compared to the distances between particles.

 The molecules are in constant, random motion. The distribution of kinetic energies in
the gas are described by the Maxwell-Boltzmann equation.

 The attractions and repulsions between the particles are negligible (i.e., small or
nonexistant intermolecular forces)

 Collisions between molecules can transfer energy, but the total average energy of
the collection of molecules remains constant. The collisions are "elastic" meaning
that particles bounce off of one another rather than sticking.

 The average kinetic energy is proportional to the temperature (in K) of the gas.

Note that the nature or kind of gas does not enter into these equations so the
assumptions should be true whether we're talking about oxygen or sulfurhexafluoride.

These postulates, which correspond to a physical model of a gas much like a group of
billiard balls moving around on a billiard table, describe the behavior of an ideal gas. At
room temperatures and pressures at or below normal atmospheric pressure, real gases
seem to be accurately described by these postulates, and the consequences of this
model correspond to the empirical gas laws in a quantitative way.

Gas Pressure Explained: In the kinetic molecular theory, pressure is the force exerted
against the wall of a container by the continual collision of molecules against it.
Newton's second law of motion tells us that the force exerted on a wall by a single gas
molecule is equal to the mass of the molecule multiplied by the velocity of the molecule.
The molecule rebounds elastically and no kinetic energy is lost in a collision. All the
molecules in a gas do not have the same velocity. The average velocity is used to
describe the overall energy in a container of gas.

The pressure-volume product of the ideal gas equation is directly proportional to the
average velocity of the gas molecules. If the velocity of the molecules is a function only
of the temperature, then the kinetic molecular theory gives us Boyle's Law.

The statement that the pressure-volume product of an ideal gas is directly proportional to
the total kinetic energy of the gas is also a statement of Boyle's Law, since the total
kinetic energy of an ideal gas depends only upon the temperature.

Gas Temperature Explained: If you look at the ideal gas law equation carefully you will
see that it shows that the total kinetic energy of a collection of gas molecules is directly
proportional to the absolute temeprature of the gas. The ideal gas law can be
rearranged to give an explicit expression for temperature. Temperature is a function only
of the mean kinetic energy, the mean velocity and the mean molar mass.

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As the absolute temperature decreases, the kinetic energy must decrease and thus the
mean velocity of the molecules must decrease also. At T=0, the absolute zero of
temperature, all motion of gas molecules would cease and the pressure would then also
be zero No molecules would be moving. Experimentally, the absolute zero of
temperature has never been attained, although modern experiments have made it to
temperatures as low as 0.01 K.

It has been necessary to use the average velocity of the molecules of a gas because the
actual velocities are distributed over a very wide range. This distribution, can be
described by Maxwell's law of distribution of velocities, or you can think of a
superhighway. There is an average speed on the highway. Some cars are travelling
slower, some faster, some at exactly the right speed. Even those on cruise control are
never exactly on the right speed because of the discrepancies in the speed control on
each individual engine and the ground geometry over which the car must be moved.

It is not necessary to use a Maxwell-Boltzmann distribution of velocities to explain either


the nature of temperature or Charles' law, although it is the correct expression of the
distribution. Charles' law can be obtained for any distribution in which the velocities of
the gas molecules are a function of the nature of the gas and the absolute
temperature only.

Partial-Pressure Explained: Dalton's law of partial pressures follows from the KMT of
gases. If the gas molecules in a mixture are in constant and random motion and if there
are no forces operating between the molecules except collisions, then on the average,
the net effect of collisions with other molecules must be zero. For this reason each gas
acts as if it were present alone.

3.2 The Kinetic Equation

Maxwell derived an equation on the basis of above assumption as


1
PV = mnu 2
3
Where P = Pressure of gas
V = Volume of gas
m = mass of one molecule of gas
n = no. of molecules of gas
u = root mean square velocity of molecules
For 1 mole n = N is Avogadro number
m  N = Molecular mass M.
1 3PV 3RT 3PV 3RT
 PV = Mu 2 or u2 =  or u = =
3 M M M M

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4. Velocities of gas molecules


4.1 Average Velocity

As per kinetic theory of gases, each molecule is moving with altogether different velocity.
Let ‘n’ molecules be present in a given mass of gas, each one moving with velocity v1,
v2, v3… vn. The average velocity or UaV = average of all such velocity terms.

u1  u2  u2  un n u  n2u2  n3u3


Average velocity = = 1 1
n n1  n2  n3 
8RT
Uav =
M

4.2 Root Mean Square Velocity

The root mean square velocity of a molecule can be obtained by using the formula

3RT
Vrms =
M

If we have to calculate the root-mean-square velocity of oxygen molecules at room


temperature, 25oC

3  8.314  298 .15


Vrms = = 481.2 m/s
0.0319998

So an oxygen molecule travels through the air at 481.2 m/s which is 1726 km/h, much
faster than a jetliner can fly and faster than that of most rifle bullets.

The very high speed of gas molecules under normal room conditions would indicate that
a gas molecule would travel across a room almost instantly. In fact, gas molecules do
not do so. If a small sample of a very odorous (and poisonous) gas, H2S is released in
one corner of a room, our noses will not detect it in another corner of the room for
several minutes unless the air is vigorously stirred by a mechanical fan. The slow
diffusion of gas molecules which are moving very quickly occurs because the gas
molecules travel only short distances in straight lines before they are deflected in a new
direction by collision with other gas molecules.

The distance any single molecule travels between collisions will vary from very short to
very long distances, but the average distance that a molecule travels between collisions
in a gas can be calculated. This distance is called the mean free path of the gas
molecules. If the root-mean-square velocity is divided by the mean free path of the gas
molecules, the result will be the number of collisions one molecule undergoes per
second. This number is called the collision frequency of the gas molecules.

The postulates of the kinetic molecular theory of gases permit the calculation of the
mean free path of gas molecules. The gas molecules are visualized as small hard

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spheres. Without going into the mathmatical detail; as the temperature rises the mean
free path increases; it also rises as the pressure decreases, and as the size of the
molecules decrease. Diffusion takes place slowly because even though molecules are
moving very fast, they travel only short distances in any one straight line.

4.3 Most Probable Velocity

It is the velocity which is possessed by maximum no. of molecules.


2RT
Vmp =
M

2RT 8RT 3RT


Furthermore Ump : Uav : Urms : : : :
M M M

8
2 : : 3

1 : 1.128 : 1.224
Also Uav = Urms  0.9213

Exercise 2: The average speed at T1K and the most probable speed at T2K of CO2
gas is 9 104 cm sec–1. Calculate the value of T1 and T2.

4.4 Kinetic Energy of Gas

1 2
As per kinetic equation PV = mnu rms
3

For 1 mole m n = Molecular Mass (M)

1 2 1 2 K.E. 3
 PV = 2
Mu rms   Mu 2   K.E. / mole or  RT .
3 3 2 3 mole 2

KE 3 RT 3  R
Also   kT k  
molecule 2 N 2  N

Where k is the Boltzmann constant

Illustration 4: Calculate rms speed of O2 at 273 K and 1  105Pa pressure. The density
of O2 under these conditions is 1.42 kg m–3.

Solution: Data are given in SI units

3P 3  10 5
C  = 459.63 m sec–1
d 1.42

Illustration 5: At what temperature will the r.m.s. velocity of oxygen be one and half
times of its value at N.T.P.?

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1 3
Solution: mc 2  KT
2 2
3
Suppose the temperature required is T when the velocity will be C
2
3 / 2C T 9
 or, T =  273 = 614.25°K
C T 4

Exercise 3: Calculate the rms speed of ozone kept in a closed vessel at 20°C and 82
cm Hg pressure.

Graham's Law of Effusion and Diffusion: Root-mean-square velocities of gas


molecules are sometimes directly useful, but the comparison of velocities explains the
results of, and is useful in, studies of effusion of molecules through a small hole in a
container or diffusion of molecules through porous barriers. The comparison between
two gases is most conveniently expressed as:

Vrms1 M2 d2
 
Vrms 2 M1 d1

This equation gives the velocity ratio in terms of either the molar mass ratio or the ratio
of densities. The ratio of root-mean-square velocities is also the ratio of the rates of
effusion, the process by which gases escape from containers through small holes, and
the ratio of the rates of diffusion of gases.

This equation is called Graham's law of diffusion and effusion because it was observed
by Thomas Graham well before the kinetic-molecular theory of gases was developed. As
an empirical law, it simply stated that the rates of diffusion and of effusion of gases
varied as the square root of the densities of the gases. Graham's law is the basis of
many separations of gases. The most significant is the separation of the isotopes of
uranium as the gases 238UF6 and 235UF6. Fluorine has only one isotope, so the
separation on the basis of molar mass is really a separation on the basis of isotopic
mass.

Diffusion is the spontaneous intermingling of one substance with another. This occurs
with perfumes and aftershaves and also with the fragrance of irate skunks. Diffusion is
over when the molecules of the fragrance are evenly spread within a container, be it a
room or a gas flask. Another way to look at it is to describe the process using partial
pressures. Diffusion is over when the partial pressures of all the gases involved become
identical in all parts of the container. When a fragrance is more or less concentrated in a
corner of a room, its partial pressure is higher there.

Another necessary term is the gradient. A gradient is used to describe how the
concentration or partial pressures change from one place to another. When sugar is
added to coffee it sinks to the bottom. If left alone, (and the coffee stayed hot), the sugar
would dissolve and gradially spread on its own accord throughout the coffee. (Of
course, we stir it because the time involved here is quite long.) At the bottom of the cup
we have a lot of sugar. At the top of the cup we have zero dissolved sugar. A

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concentration gradient is set up from bottom to top. Sugar will gradually move down this
gradient until it is evenly spread out. When a freshly skunked pet comes into the room, it
brings with it a high concentration of skunk perfume molecules. Where the pet enters
the house there will be a high concentration. Everywhere else in the house there will be
a zero concentration of skunk molecules. The point is, one of the great facts about
natural processes is that "Nature abhors a vacuum." Another way to say this is that
nature abhors gradients. Given the chance, gradients in nature tend to disappear,
some rapidly and some only over eons of time, until there is as much an evenness as
possible.

The effusion of a gas is its movement through an extremely tiny opening into a region of
lower pressure. The term diffusion really only speaks to the direction of gas movement.
Effusion speaks for not only the direction but the rate that a change occurs.

Thomas Graham, studied the rates at which various gases effuse, and he found that the
denser the gas is, the slower it effuses. The exact relationship between rate and gas
density, d, is called Graham's Law of Effusion.

rA  d A  rB dB

Finding the densities of gases at various temperatures is often difficult to do. With a little
chemical slight of hand we can get a formula for a much simpler answer.

rA  MA  rB  MB

Illustration 6: 32 ml of H2 diffuses through a fine hole in 1 minute. What volume of


CO2 will diffuse in 1 minute under same condition?

V1 M2
Solution: 
V2 M1
32 44
 or VCO2 = 6.82 ml
VCO2 2

Exercise 4: A gaseous mixture of O2 and X containing 20% of X diffused through a


small hole in 234 secs while pure O 2 takes 124 secs to diffuse through
the same hole. Find molecular weight of X?

5. Imperfect or Real Gases


Examining the assumptions made in the kinetic molecular theory of gases it should be
obvious that the ideal gas law (PV = nRT) should break down at some point. If the gas is
squeezed into a very small volume (or alternatively high pressure) where the volume of
the molecules themselves is no longer negligible or if the gas is at a sufficiently low
temperature so that the intermolecular forces become significant compared to the kinetic
energy, we might expect the equation to fail. And it does. To deal with this we must have
a more complex set of gas laws called real gas equations. The simplest of these
equations is the one developed by the Dutch chemist Johannes van der Waals.

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All gases exhibit, to some extent, deviations from the ideal-gas laws. When these
deviations are recognized, the gas is said to behave as a real, non ideal or
imperfect gas.

Compressibility factor Z: Real and ideal gases can be compared at various pressures
and various temperatures by noting the extent to which the value of PV/RT deviates
PV
from. The quantity is given by the symbol Z and the name compressibility factor.
RT
That is
PV
Z=
RT
Greater is the departure of Z from unity more is the deviation from ideal behaviour.
i) When Z  1, this implies that gas is more compressible.
ii) When Z  1, this means that gas is less compressible.
iii) When Z = 1, the gas is ideal.

6. Real Gases and the van der Waals Equation


The hypotheses dealing with negligible volume and intermolecular forces are clearly
approximations and it is not surprising that gas under conditions such as high pressure
and low temperature will exhibit behaviors that violate the ideal gas laws.

The simplest of the equations to try to treat real gases was developed by Johannes van
der Waals. Based on experiments on pure gases in his laboratory, van der Waals
recognized that the variation of each gas from ideal behavior could be treated by
introducing two additional terms into the ideal gas equation. These terms account for the
fact that real gas particles have some finite volume, and that they also have some
measurable intermolecular force. The two equations are presented below:

PV = nRT
(P + an2/V2)(V - nb) = nRT

In the van der Waals equation the constant "a" is a correction term for intermolecular
force and "b" is a correction for the real volume of the gas molecules. Intermolecular
forces are often lumped together and called van der Waals' forces in recognition of his
being the first to recognize their existence. Values of "a" and "b" for a number of
common atoms and molecules are given in the table below.
Van der Waals constants
Compound a (L2-atm/mol2) b (L/mol)
He 0.0341 0.02370
Ne 0.211 0.0171
Ar 1.34 0.0322
Kr 2.32 0.0398
Xe 4.19 0.0510
H2 0.244 0.0266
N2 1.39 0.0391
O2 1.36 0.0318
Cl2 6.49 0.0562
H2O 5.46 0.0305
CH4 2.25 0.0428
CO2 3.59 0.0427
CCl4 20.4 0.1383

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The "a" term is a correction for intermolecular forces and by itself is quite simple. The
magnitude of "a" is reflective of the intermolecular forces between molecules. Thus the
increase in "a" going down the noble gases reflects the increasing London forces
between these atoms. Molecules that are polar typically have larger values of "a" than
do nonpolar molecules. The surprisingly large value of a molecule like carbon
tetrachloride reflects the London forces as well as a property called polarizability.

The portion of the equation containing the "a" term is somewhat more confusing that the
term itself and requires a bit of explanation.

First, we note that the volume comes into play even though this is a term correcting for
intermolecular force. The volume term is necessary because we must have a way of
recognizing that intermolecular forces will be negligible at long distances, but significant
at small distances. The bigger the volume (notice that it's on the bottom) the smaller the
correction term because the bigger the volume the further apart the molecules are and
the less their intermolecular forces are likely to come into play.

Next we note that the term containing "a" is added to the pressure P. In other words the
corrected pressure is slightly larger than the observed pressure. How does this make
any sense? If we go back to the origins of pressure itself, we remember that pressure
arises when molecules strike the walls (not Waals) of the container. As our molecule
moves toward the wall all of its gaseous neighbors are behind it, thus any intermolecular
forces acting on the molecule are slowing it as it moves toward the wall. The molecule
striking the wall does so at a velocity that is slightly less (determined by the size of the
intermolecular forces) than it would without these forces. Or, the observed prssure is
actually slightly less than the pressure would be without the intermolecular forces. To
correct for this, a small positive pressure must be added to the observed pressure,
hence the term with "a" in it is positive. The "b" term is relatively easy to understand. Our
gas is in a container with some volume "V". If the container is sufficiently large, the
volume of the gas molecules is negligible, but if the volume of the gas molecules
themselves starts to become significant with respect to the volume, we have a problem.
Under these conditions, we may wish to think of the actual free volume in the container
as being the measured volume, V, minus the volume occupied by the molecules. We
calculate the volume occupied by the molecules by multiplying the number of moles of
molecules, n, by their effective molar volume, b.

Let's think about the values of "b" for a moment. The volume of one mole of water
molecules condensed into liquid water would be 18 ml/mole (water is 18 g/mol and the
density of water is by definition 1 g/ml). The value of "b" for water, however, is 30.5
ml/mole (notice I've taken the table value which is in liters/mol and converted it to ml/mol
since that's the easier number to think about). Why the difference? In the gas phase, our
water molecules spin around rapidly so that they occupy a larger volume than they do
when they are relatively fixed in their positions in liquid water. This is like comparing the
area around you if you were to stand still and hold your arms out compared to the area
you occupy if you were to spin around. All of the values for "b" will be somewhat larger
than the volume of one mole of that compound in its liquid form.

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Exercise 5: 2 moles of NH3 occupied a volume of 5 litres at 27°C. Calculate the


pressure if the gas obeyed Vander Waals equation. Given a = 4.17 litre2
atm mole–2, b = 0.037 litre/mole.

6.1 Vander Waals equation, different forms

i) At low pressures: ‘V’ is large and ‘b’ is 2 CO2

negligible in comparison with V. The N2

Vander Waals equation reduces to: H2


 a  a He
 P  2  V  RT ; PV + = RT Z 1 Ideal gas
 V  V
a
PV = RT - or PV  RT
V 0 P
Deviation of gases from ideal behaviour with
This accounts for the dip in PV vs P pressure.
isotherm at low pressures.

ii) At fairly high pressures 0°C


50° C
a 100°C
may be neglected in comparison 100°C
V2
Z
with P. The Vander Waals equation
1.0
becomes 50°C
0°C
P (V – b) = RT
PV – Pb = RT P (atm)
PV = RT + Pb or PV  RT The plot of Z vs P for N2 gas at different
temperature is shown here.
This accounts for the rising parts of the
PV vs P isotherm at high pressures.
a
iii) At very low pressures: V becomes so large that both b andbecome negligible
V2
and the Vander Waals equation reduces to PV = RT. This shows why gases
approach ideal behaviour at very low pressures.

iv) Hydrogen and Helium: These are two lightest gases known. Their molecules have
very small masses. The attractive forces between such molecules will be extensively
a
small. So is negligible even at ordinary temperatures. Thus PV  RT. Thus
V2
Vander Waals equation explains quantitatively the observed behaviour of real gases
and so is an improvement over the ideal gas equation.

Vander Waals equation accounts for the behaviour of real gases. At low pressures,
the gas equation can be written as,

 a 
 P  2 Vm   RT or Z = m  1 
V a
 Vm  RT VmRT

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Where Z is known as compressibility factor. Its value at low pressure is less than 1 and it
decreases with increase of P. For a given value of Vm, Z has more value at higher
temperature.

At high pressures, the gas equation can be written as


P (Vm – b) = RT
PV m Pb
Z= =1+
RT RT

Here, the compressibility factor increases with increase of pressure at constant


temperature and it decreases with increase of temperature at constant pressure. For the
gases H2 and He, the above behaviour is observed even at low pressures, since for
these gases, the value of ‘a’ is extremely small.

Illustration 7: One litre of a gas at 300 atm and 473 K is compressed to a pressure of
600 atm and 273 K. The compressibility factors found are 1.072 & 1.375
respectively at initial and final states. Calculate the final volume.

Solution: P1V1 = Z1nRT1 and P2V2 = Z2nRT2


P2 V2 T Z
 1  2
T2 P1V1 Z 1
Z 2 T2 P1 V1 1.375 273 300  1
or V2 =   =   = 370.1 ml
Z 1 T1 P2 1.072 473 600

7. Some other important definitions


7.1 Mean Free Path ()

The average distance covered by a molecule between two successive collisions is called
1
mean free path and is denoted by .   = where n = no. of molecules/cc.
2 2 n
Again, if P & T denote the pressure and temperature of the gas, from kinetic theory.

n N  10 3 P P 1 T T
P  10–3 = RT or n = 0   K   =  K1 
N0 R T T 2 K P
2
P
Thus mean free path is directly proportional to temperature and inversely to pressure.

7.2 Collision Frequency (z)


It is the number of collisions taking place per second
z = 2Nuav

where  = collision diameter. It is the distance between the centres of two molecule
without collision.
N = number of molecules per unit volume,
And uav = average velocity

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7.3 Relative Humidity (RH)

At a given temperature it is given by equation

partial pressure of w ater in air


RH =
vapour pressure of w ater

7.4 Boyle’s Temperature (Tb)

Temperature at which real gas obeys the gas laws over a wide range of pressure is
called Boyle’s Temperature. Gases which are easily liquefied have a high Boyle’s
temperature [Tb(O2)] = 46 K] whereas the gases which are difficult to liquefy have a low
Boyle’s temperature [Tb(He) = 26K].

a 1
Boyle’s temperature Tb =  Ti
Rb 2

where Ti is called Inversion Temperature and a, b are called van der Waals constant.

7.5 Critical Constants

i) Critical Temperature (Tc): It (Tc) is the maximum temperature at which a gas can be
liquefied i.e. the temperature above which a gas can’t exist as liquid.

8a
Tc 
27Rb

ii) Critical Pressure (Pc): It is the minimum pressure required to cause liquefaction
at Tc

a
Pc 
27b2

iii) Critical Volume: It is the volume occupied by one mol of a gas at Tc and Pc
Vc = 3b

Illustration 8: Calculate Vander Waals constants for ethylene


TC = 282.8 K; PC = 50 atm

1 RT C 1 0.082  282 .8
Solution: b=   = 0.057 litres/mole
8 PC 8 50

2
27 2 TC 27 1
a= R    (0.082 ) 2  (282 .8) 2  = 4.47 lit2 atm mole–2
64 PC 64 50

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8. Gas Eudiometry
The relationship amongst gases, when they react with one another, is governed by two
laws, namely Gay-Lussac law and Avogadro’s law.

Gaseous reactions for investigation purposes are studied in a closed graduated tube
open at one end and the other closed end of which is provided with platinum terminals
for the passage of electricity through the mixture of gases. Such a tube is known as
Eudiometer tube and hence the name Eudiometry also used for Gas analysis.

During Gas analysis, the Eudiometer tube filled with mercury is inverted over a trough
containing mercury. A known volume of the gas or gaseous mixture to be studied is next
introduced, which displaces an equivalent amount of mercury. Next a known excess of
oxygen is introduced and the electric spark is passed, whereby the combustible material
gets oxidised. The volumes of carbon dioxide, water vapour or other gaseous products
of combustion are next determined by absorbing them in suitable reagents. For example,
the volume of CO2 is determined by absorption in KOH solution and that of excess of
oxygen in an alkaline solution of pyrogallol. Water vapour produced during the reaction
can be determined by noting contraction in volume caused due to cooling, as by cooling
the steam formed during combustion forms liquid (water) which occupies a negligible
volume as compared to the volumes of the gases considered. The excess of oxygen left
after the combustion is also determined by difference if other gases formed during
combustion have already been determined. From the data thus collected a number of
useful conclusions regarding reactions amongst gases can be drawn.

a) Volume-volume relationship amongst Gases or simple Gaseous reactions.


b) Composition of Gaseous mixtures.
c) Molecular formulae of Gases.
d) Molecular formulae of Gaseous Hydrocarbons.

The various reagents used for absorbing different gases are


O3  turpentine oil
O2 alkaline pyrogallol
NO  FeSO4 solution
CO2,SO2 alkali solution (NaOH, KOH, Ca(OH)2, HOCH2CH2NH2, etc.)
NH3  acid solution or CuSO4 solution
Cl2  water
Equation for combustion of hydrocarbons.
 y y
CxHy +  x   O2  xCO2 + H2O
 4 2

General Assumptions: In all problems, it is assumed that the sparking occurs at room
temperature. This implies that water formed would be in liquid state and that nitrogen
gas is inert towards oxidation.

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Illustration 9: A gaseous hydrocarbon requires 6 times its own volume of O 2 for


complete oxidation and produces 4 times its volume of CO 2. What is its
formula?

Solution: The balanced equation for combustion


 y y
CxHy +  x   O2  xCO2 + H2O
 4 2
 y y
1 volume  x   volume  x  = 6 (by equation)
 4 4
or 4x + y = 24 …(1)
Again x = 4 since evolved CO2 is 4 times that of hydrocarbon
 16 + y = 24 or y = 8  formula of hydrocarbon C4H8

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9. Solution to Exercises
Exercise i) Suppose the volume of bulb is V containing n moles at 19°C (i.e.
292 K) let the temperature be TK when n moles increases to 1.25
(i.e. by 25%). Since 1.25n moles at TK occupy a volume V.
V
 n moles at TK should occupy = ml
1.25
PV PV
Applying 1 2  2 2
T2 T2
V
P
P V 1.25
 
292 T
293
or, T = = 233.6K = – 39.4°C
1.25
ii) Since 35.45 is the average atomic weight of 35Cl and 37Cl we have
35n 1  37n 2
= 35.45
n1  n 2
n1
 = 3.42. n1 : n2 = 3.44 : 1
n2
 Ratio of lengths is 3.44 : 1
Since the pressure on both sides of the partition is equal the
pressure before and after partition will be same. (no. of moles per
unit volume is same)

Exercise 2: We know for 1 mole of an ideal gas


3RT
r.m.s. speed =
M
r.m.s. speed : average speed : most probable speed = 1 : 0.9211 :
0.8165
3RT1
Average speed at T1k = 0.9211  = 9 104
M
3RT 2
 most probable speed at T2K = 0.8165  = 9  104
M
Substituting R = 8.314  107 ergs K–1 mole–1
And M = 44 we get T1 = 168 K T2 = 2143 K

Exercise 3: Volume occupied by 1 mole of O3 at 20°C and 82 cm pressure


293 76
= 22400   = 22282 ml
273 82
p = 82  13.6  981 dynes cm–2
3PV 3  82  13.6  981  22282
Now we have, C  
M 48
= 3.9  10 cm sec
4 –1

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t mix M mix
Exercise 4: We have, 
t O2 MO2
234 Mmix
or,   Mmix= 34.921
224 32
As the mixture contains 20% of X, the molar ratio of O2 and x may be
represented as 0.8 n : 0.2 n
n being total no. of moles
32  0.8n  M X  0.2n
Mmix = = 34.921
n
 Mx = 46.6

Exercise 5: Applying Vander Waal’s equation for n moles


 n2a 
 P  2  (V – nb) = nRT
 V 
 4.17  2 2 
P   (5.2 – 2  0.037) = 2  0.082  300
 52 
or, p = 9.33 atm

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10. Solved Problems


10.1 Subjective

Problem 1: One litre flask contains air, water vapour and a small amount of liquid water
at a pressure of 200 mmHg. If this is connected to another one litre
evacuated flask, what will be the final pressure of the gas mixture at
equilibrium? Assume the temperature to be 50 oC. Aqueous tension at
50°C = 93 mmHg

Solution The aqueous tension remains same in


both the flask. Also flask are at same
temperature
 P1V1 = P2V2
where P1 = 200 – 93 = 107
V1 = 1 litre
V2 = 2 litre
107 × 1 = P × 2
P = 53.5 mm
V= 1 litre V= 1 litre
Since aqueous tension is also present
in flask, equivalent to 93 mm
Pressure of gaseous mixture
= 93 + 53.5 = 146.5 mmHg

Problem 2: One way of writing the equation of state for a real gas is
 B 
PV  RT 1      
 V 
Where B is a constant. Derive an approximate expression for B in terms of
vander waal’s constant ‘a’ and ‘b’

 a 
P  V 2 V  b  RT or P = V  b  V 2
RT a
Solution:
 
RTV a  V
Multiply by [V] then, PV = 
V b V2
 V a   b
1
a 
or PV = RT    or PV = RT 1    
 V  b  VRT   V VRT 
1 2 3
 b b b b
Now 1    1         
 V V V V
 b a b 
2
 PV =RT 1      
 V VRT  V  
  a  1 b
2

or PV = RT 1   b        
  RT  V  V  
a
B=b–
RT

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Problem 3: Two containers A and B have the same volume. Container A contains 5
moles of O2 gas. Container B contains 3 moles of He and 2 moles of N 2.
Both the containers are separately kept in vacuum at the same
temperature. Both the containers have very small orifices of the same area
through which the gases leak out . Compare the rate of effusion of O 2 with
that of He gas mixture.

Solution: Since both the containers are in the same conditions of P,V and T,
rO2 Mmix
=
rmix MO2

As the mixture contains three moles of He and 2 moles of N2, the


effective molecular weight of the mixture would be.
3 2
 4   28 = 13.6
5 5
rO2 13.6
 = = 0.652
rmix 32

Though this solution looks OK, there is one big flaw in it.

The error is that we have assumed that He and N2 from vessel B would
effuse out with the same rate. This assumption was made in because we
have taken the composition of the gas mixture coming out of the vessel to
be same as that of the mixture that was inside the vessel . It should be
duly noted that the two mixtures (inside and the are that effused out) have
different compositions. Therefore first we must find the composition of the
gas mixture coming out of the vessel B.
rN 2 2 4 2 1
  = 0.252
rHe 3 28 3 7

This means that initially the ratio of moles of N2 to the moles of He coming
2
out of the vessel are in the molar ratio of 0.252 and not .
3

Let moles of the He coming out to be x


 moles of N2 coming out is 0.252 x
nN2 0.252 x
  = 0.2
ntotal 1.252 x
nHe
= 0.8  Mmix = 0.2 28 + 0.84 = 8.8
ntotal
rO2 8.8
  = 0.52
rmix 32

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Problem 4: 50 ml. of a mixture of NH 3 and H2 was completely decomposed by sparking


into nitrogen and hydrogen. 40 ml of oxygen was then added and the
mixture was sparked again. After cooling to the room temperature the
mixture was shaken with alkaline pyro-gallol and a contraction of 6 ml. was
observed. Calculate the % of NH3 in the original mixture.

Solution: Let the volume of NH3 be x ml


 volume of H2 = (50– x) ml
On sparking,
1 3
NH3  N2 + H2
2 2
Since 40 ml of O2 is added and sparked, it must have reacted with H2 to
form liquid water. Moreover since 6 ml contraction occurs with alkaline
pyrogallol, 34 ml is the volume of O2 used up.
 total volume of H2 is 68 ( 2H2 + O2  2H2O)
3
 (50–x) + x = 68
2
x
50 + = 68 ; x = 36
2
 NH3 = 72%

Problem 5: 20 ml of a mixture of methane and a gaseous compound of acetylene series


were mixed with 100 ml of oxygen and exploded to complete combustion.
The volume of the products after cooling to original room temperature and
pressure, was 80 ml and on treatment with potash solution a further
contraction of 40 ml was observed. Calculate (a) the molecular formula of
the hydrocarbon, (b) the percentage composition of the mixture.

Solution: Oxygen is present in excess. This is because the combustion has been
done completely (which means methane and the other gas are consumed
completely) and on CO2 absorption 40 ml of a gas is still left over. This left
over gas is oxygen.
 oxygen used up = 100–40=60 ml
CO2 produced = 40 ml
If the molecular formula of the gas of acetylene series is CnH2n–2 and its
volume is a ml, then the volume of CH4 is (20–a) ml.
On combustion CH4(g) + 2O2(g)  CO2(g) + 2H2O (l)
CnH2n–2 (g) +
3n  1O (g)  nCO + (n–1) H O (l)
2 2 2
2
Oxygen used up = 2(20–a) +
3n  1 a = 60
2
(from CH4) ( from CnH2n–2)
CO2 produced = (20–a) + na = 40
(from CH4) (from CnH2n–2)
Solving a = 10 ml
and n = 3
 formula of the gas is C3H4

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10
% of C3H4 =  100 = 50%
20
% of CH4 = 50%

Problem 6: Calculate % of ‘free volume’ available in 1 mol gaseous water at 1.0 atm
and 100 o C. Density of liquid water at 100 oC is 0.958 g/mol.

Solution: We know that PV = nRT


Volume occupied by 1 mol gaseous water at 100 oC and 1 atm pressure
1 0.0821  373
= = 30.62 litre
1
mass 18
volume of 1 mol liquid water = = = 1.88 × 10-2 litre
density 0.958
% of volume occupied by liquid water
1.88  10 2
=  100 = 0.0613 %
30.62
% of free volume = 100 - 0.0613 = 99.93 %

Problem 7: A vertical hollow cylinder of height 1.52m is fitted with a movable piston of
negligible mass and thickness. The lower half of the cylinder contains an
ideal gas and the upper half is filled with mercury. The cylinder is initially at
300 K. When the temperature is raised half of the mercury comes out of the
cylinder. Find the temperature assuming the thermal expansion of mercury
to be negligible?
Solution: Initially at lower end
P = 76 cm of Hg + 76 cm of air
= 152 cm, T = 300K,
V
V= 1
2
(where V1 is the volume of cylinder)
Finally at lower end
P = 76 cm of air + 38 cm of Hg
3 V1
= 114 cm, T = ?, V =
4
P1V1 P2 V2
 
T1 T2
152  V1 114  3V1

2  300 4T
 T = 337.5 K

Problem 8: A mixture of propane and methane is contained in a vessel of unknown


volume V at a temperature T and exerts a pressure of 320 mm Hg. The gas
is burnt in excess O2 and all the carbon is recovered as CO 2. The CO2 is
found to have a pressure of 448 mm Hg in a volume V 1 at the same
temperature T. Calculate mole fraction of propane in mixture.

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Solution: Let the moles of propane (C3H8) = n1


Moles of methane CH4 = n2
We know that PV = nRT
320 × V = (n1+n2) RT
after combustion
C 3H8  5O 2  3CO 2  4H2 O
n1 3n1

CH 4  2O 2  CO 2  2H2 O
n2 n2

total moles of CO2 formed = (3n1+n2)


Once again we have PV = nRT
448 ×V = 3n1  n 2 
RT
….(2)
V
Dividing eqn (2) by (1) we have
448 3n1  n1  n
  1 = 0.25
320 n1  n 2  n2
n1 0.25n 2
mol fraction of C3H8 = = = 0.2
n1  n 2 0.25n 2  n 2

Problem 9: What would be the final pressure of O 2 in following experiment? A


collapsed polethylene bag of 30 litre capacity is partially blown up by the
addition of 10 litres of N2 at 0.965 atm at 298 K. Subsequently enough O 2 is
pumped into bag so that at 298 K and external pressure of 0.990 atm, the
bag contains 30 litres N2.

Solution: Given pressure of N2 = 0.965 atm


Volume of N2 = 10 litre. Temperature of N2 = 298 K
 For N2 when bag is fully expanded,
Volume of N2 (alone) = 30 litre at 298 K
 P1V1 = P2V2
0.965  10 = P2  30  PN 2 (alone) in 30 litre bag at 298 K = 0.322 atm
Now PM = PO 2 + PN 2
0.990 = PO 2 + 0.332
 PO 2 = 0.668 atm

Problem 10: 1 mole of a gas is changed from is initial state (15 lit; 2 atm) to final state (4
lit, 10 aim) reversibly. If this change can be represented by a straight line in
p-V curve, calculate maximum temperature, the gas attained.

p2 V  15
Solution: Eqn. For the line is  ; 11p + 8V = 142
10  2 4  15
142 142
For (pV)max, 11p =  71 and 8V   71
2 2
71 71
or p  and V  then apply = (pV)max = nRTmax
11 8

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10.2 Objective

Problem 1: A gas can be liquefied by pressure alone when its temperature


(A) higher than its critical temperature
(B) lower than its critical temperature
(C) either of these
(D) none

Solution: A gas can be liquefied only if its temperature is lower than its critical
temperature
(B)

Problem 2: Boyle’s law may be expressed as


 dP  K  dP  K
(A)    (B)    2
 dV T V  dV T V
 dP  K
(C)    (D) none
 dV  T V

Solution: from Boyle’s law


PV = constant
PdV +VdP = 0
 dP  P K
    2
 dV T V V
(PV = K)
 (B)

Problem 3: A vessel has N2 gas and water vapours at a total pressure of 1 atm. The
partial pressure of water vapours is 0.3 atm. The contents of this vessel are
transferred to another vessel having one third of the capacity of original
volume, completely at the same temperature the total pressure of this
system in the new vessel is
(A) 3.0 atm (B) 1 atm
(C) 3.33 atm (D) 2.4 atm

Solution: PN' 2  PH' 2O  1atm


PH' 2O  0.3 atm
PN' 2  0.7 atm
Now new pressure of N2 in another vessel of volume V/3 at same
temperature T is given by
V
PN" 2  1  0.7V  PN" 2  2.1 atm
3
since aqueous tension remains constant, and thus total pressure in new
vessel
 PN" 2  PH' 2O = 2.1 + 0.3 = 2.4 atm
(D)

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Problem 4: For two gases A and B with molecular weights MA and MB, it is observed that
at a certain temperature T1 the mean velocity of A is equal to the root mean
square velocity of B. thus the mean velocity of A can be made equal to the
mean velocity of B if
(A) A is at temperature T and B at T, T > T
(B) A is lowered to a temperature T2 , T2 < T while B is at T
(C) Both A and B are raised to a higher temperature
(D) Both A and B are placed at lower temperature

8RT 3RT
Solution: (UAV)A = and (Urms)B =
MA MB
8 M
  A
3 MB
8RT2 8RT
for A (UAV) = for B VAV =
MA MB
T2 MA 8 8
  T2 = T or T2 < T
T MB 3 3
 (B)

Problem 5: The circulation of blood in human body supplies O 2 and releases CO2. the
concentration of O2 and CO2 is variable but on an average, 100 ml blood
contains 0.02 g of O2 and 0.08 g of CO2. The volume of O2 and CO2 at 1 atm
and at body temperature 37oC, assuming 10 lt blood in human body, is
(A) 2 lt, 4 lt (B) 1.5 lt, 4.5 lt
(C) 1.59 lt, 4.62 lt (D) 3.82 lt, 4.62 lt

Solution:  100 ml blood has 0.02 g P2 and 0.08 g CO2


 10,000 ml blood has 2 g O2 and 8 g CO2
using PV = nRT
2
for O2, 1 VO2   0.0821  310  VO2 = 1.59 litre
32
8
for CO2, 1 VCO2   0.0821  310  VCO2 = 4.62 litre
44
 (C)

Problem 6: At 100oC and 1 atm, if the density of liquid water is 1.0 g/cc and that of water
vapour is 0.0006 g/cc, then the volume occupied by water molecule in one
litre of steam at that temperature is
(A) 6 cc (B) 60 cc
(C) 0.6 cc (D) 0.06 cc

Solution: Mass of 1 lt water vapour = V ×d = 1000 × 0.0006 = 0.6g


0 .6
volume of liquid water = = 0.6cc
1
(C)

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Problem 7: The K.E. of N molecule of O 2 is x Joules at –123°C. Another sample of O2 at


27°C has a KE of 2x Joules. The latter sample contains.
(A) N molecules of O2 (B) 2N molecules of O2
(C) N/2 molecules of O2 (D) N/4 molecule of O2

3
Solution: KE = RT ; T = – 123 + 273 = + 150 K
2
3 3
 R  150   8.314  75 = xJ = 225  8.314 = xJ
2 2
At 27°C = 27+ 223 = 300K
3
KE for = 2x Joule =  8.314  300
2
N molecules
 x Joule = 3  8.314  75
In both the cases x Joules correspond to N molecules.
 (A)

Problem 8: If for two gases of molecular weights MA and MB at temperature TA and TB,
TAMB = TBMA, then which property has the same magnitude for both the
gases.
(A) density (B) pressure
(C) KE per mol (D) Vrms

PM
Solution: i) density of a gas () =
RT
MB MA
Since  ,  at the same pressure  A = B .
TB TA
But if pressure is different then  A  B .
ii) Pressure of the gases would be equal if their densities are equal other
wise not.
3
iii) KE per mol = RT
2
It will be different for the two gases.

3RT T T
iv) Vrms = , since A  B ; Vrms of A = Vrms of B
M MA MB
 (D)

Problem 9: Helium atom is two times heavier than a hydrogen molecule. At 298 K, the
average kinetic energy of a Helium atom is
(A) two times that of hydrogen molecule
(B) same as that of a hydrogen molecule
(C) four times that of a hydrogen molecule
(D) half that of a hydrogen molecule

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3
Solution: The average kinetic energy of an atom is given as kT.
2
 It does not depend on mass of the atom.
 (B)

Problem 10: Dalton’s law of partial pressure is not applicable to, at normal conditions
(A) H2 and N2 mixture (B) H2 and Cl2 mixture
(C) H2 and CO2 mixture (D) H2 and O2 mixture

Solution: H2 and Cl2 reacts to form HCl; Dalton’s law of partial pressure is valid only
for the gases which don’t react at ordinary conditions
(B)

11. Assignments
11.1 Subjective

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LEVEL - I

1. a) 3.00 moles of a gas are placed in a 4.55 L container at 245 °C. What is the
pressure in kPa?
b) 65.85 grams of nitrogen gas are placed in 17.5 L container. The pressure is
1988 mm Hg. What is the temperature, in °C?

2. a) A gas is placed in a 2.00 L container at 25 °C and 550.0 mm Hg. The gas is


now compressed to a volume of 0.75 L at constant temperature. What is the
new pressure?
b) i) A gas is placed in a heavy container. The container is now heated. What
happens to the gas and why?
ii) A gas is placed in a container with a moveable piston. It is then cooled
down at constant pressure. What happens? Explain.
iii) A gas is placed in a container at a certain temperature and pressure.
More gas is added and in order to keep the pressure and volume
constant the temperature had to change. Was the container heated or
cooled? Explain.

3. a) A gas is placed in a 3.45 L container at 45 °C and 2.7 atm. It is then


compressed to a pressure of 8.25 atm and a volume of 0.550 L. What is the
new temperature?
b) Butane (C4H10) is a fuel used in many lighters. The reaction is as follows:
2 C4H10 (g) + 13 O2 (g)  8 CO2 (g) + 10 H2O (g)
i) If 26.7 L of O2 react at STP, how many liters of butane are needed
at STP?
ii) 24.57 moles of water are formed. How many liters of butane were reacted
at STP?
iii) 13.6 L of butane are reacted at STP, how many grams of carbon dioxide
are formed?

4. a) 5.0 moles of a gas is put into a container of 2.0 L. More gas is added to the
flask so that there is now 15 moles of the gas present. What must the new
volume be if temperature and pressure are to remain constant?
b) A 7.0 L container is filled with 10.0 moles of a gas. The pressure is read at
4.00 atm, what is the temperature of the gas, in °C?

5. a) 3.0 L of a gas has a pressure of 12.0 atm. What is the new pressure if the
gas is expanded to 17.0 L?
b) A gas is at 135 °C and 455 mm Hg in a 2.00 L container. It is cooled down to
a temperature of 25 °C. If it is kept in the same container, what is its new
pressure?

6. a) How large a balloon could you fill with 4.0 g of He gas at 22 oC and 720 mm
of Hg?
b) Calculate the density of CO2 at 100 0C and 800 mm Hg pressure.

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7. a) A container has 3.2 g of a certain gas at NTP. What would be the mass of the
same gas contained in the same vessel at 200C and 16 atm. Pressure?
b) A certain quantity of a gas measured 500 mL at a temperature of 15°C and
750 mm Hg. What pressure is required to compress this quantity of gas into a
400 mL vessel at a temperature of 50°C?

8. a) Three footballs are respectively filled with N2, H2 and He. In what order are
these footballs to be reinflated?
b) The ratio of rates of diffusion of two gases A and B under same pressure is
1:4. If the ratio of their masses present in the mixture is 2:3. What is the ratio
of their mole fraction in mixture?

9. a) Calculate the rms speed in cm/sec at 25°C of a free electron and a molecule
of UF6.
b) The flask (A) and (B) have equal volumes. Flask (A) contains H2 gas at 300K,
while (B) contains equal mass of CH4 at 900K. Calculate the ratio of average
speed of molecules in flask (A) and (B).

10. a) Calculate total energy of one mole of an ideal monatomic gas at 27C?
b) How much thermal energy should be added to 3.45 g Ne in a 10 litre flask to
raise the temperature from 0°C to 100°C. (Atomic weight Ne = 20.18)?

LEVEL – II

1. a) 155.0 grams of oxygen gas are put in a 4.50 L container at 35 °C. What is the
pressure, in kPa?
b) A gas in a piston is heated up. If the pressure remains the same, what will
happen to the volume? Why?

2. You went on a road trip to Mumbai (sea level) from New Delhi and made sure to
check out your car before leaving. The tire pressures were at the recommended

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levels and your oil was full. You are driving fast through Jaipur (but not above the
speed limit of course) and need to stop for petrol. You decide to check your car's
tire pressure while stopped. The driver's manual suggests a pressure between 30
and 32 psi.
a) Knowing that the tires heat up during driving, do you expect your reading to
be high, low or the same as the recommended tire pressures? Why?
b) You arrive in Mumbai that night. The next morning you check your tire
pressure. Since you plan on staying in Mumbai a while to see the sights, what
adjustments, if any, should be made to your tires?

3. In a certain experiment a sample of helium in a vacuum system was compressed


at 25 °C from a volume of 200.0 mL to a volume of 0.240 mL where its pressure
was found to be 30.0 mm Hg. What was the original pressure of the helium?

4. A hydrogen gas volume thermometer has a volume of 100.0 cm3 when immersed
in an ice-water bath at 0 °C. When immersed in boiling liquid chlorine, the volume
of the hydrogen at the same pressure is 87.2 cm3. Find the temperature of the
boiling point of chlorine in °C.

5. 2.50 grams of XeF4 is introduced into an evacuated 3.00 liter container at


80.0 °C. Find the pressure in atmospheres in the container.

6. a) Two flasks of equal volume connected by a narrow tube (of negligible


volume) are at 27°C and contain 0.7 moles of H2 at 0.5 atm. One of the flask
is then immersed into a bath kept at 127°C, while the other remains at 27°C.
Calculate the final pressure and the number of moles of H2 is each flask.
b) 1 gm of an alloy of Al and Mg reacts with excess HCl to form AlCl3, MgCl2
and H2. The evolved H2 collected over mercury at 0°C occupied 1200 ml at
699 mm Hg. What is the composition of alloy?

7. a) Ladenburg found that a sample of ozonised oxygen containing 86.16% of O 3


by weight required 430 secs to diffuse under conditions where pure O 2
required 369.5 secs. Determine the vapour density of O3.
b) The normal density of PH3 at 0°C and at different pressure are
P (atm) 1 3/4 1/2 1/4
d/P (gm/lit) 1.5307 1.5272 1.5238 1.5205
Calculate the molecular weight of PH3 and atomic weight of P

8. Assuming O2 molecule spherical in shape and occupying the radius 150 pm.
Calculate
i) the volume of single molecule of gas
ii) the percentage of empty space in one mole of O2 at NTP

9. 9 volumes of gaseous mixture consisting of gaseous organic compound A and


just sufficient amount of O2 required for complete combustion yielded on burning

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4 volumes of CO2, 6 volumes of water vapour and 2 volumes of N2 all volumes


measured at the same temperature and pressure. If the compound A contained
only C, H and N
i) how many volumes of O2 required for complete combustion?
ii) What is the molecular formula of the compound A?

10. Two gases in adjoining vessels are brought into contact by opening a stop cock
between them. The one vessel measured 0.25 lit and contained NO at 800 torr
and 220 K, the other measured 0.1 lit and contained O2 at 600 torr and 220 K.
The reaction to form N2O4 (solid) exhausts the limiting reactant completely.
a) Neglecting the vapour pressure of N2O4 what is the pressure of the gas
remaining at 220 K after completion of the reaction?
b) What weight of N2O4 is formed?

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12.2 Objective

LEVEL – I

1. If the pressure of a given mass of gas is reduced to half and temperature is


doubled simultaneous the volume will be
(A) Same as before (B) Twice as before
(C) ¼ the as before (D) None

2. The molecules of a gas A travel four times faster than the molecules of gas B at
same temperature. The ratio of molecular weights (MA/MB) is
(A) 1/16 (B) 4
(C) 1/4 (D) 16

3. The ratio of rms velocity to average velocity of gas molecules at a particular


temperature is
(A) 1.086 : 1 (B) 1 : 1.086
(C) 2 : 1.086 (D) 1.086 : 2

4. X ml of H2 gas effuses through a hole in a container in 5 secs. The time taken for
effusion of same volume of gas specified below under identical condition is
(A) 10 secs : He (B) 20 secs : O2
(C) 25 secs : CO (D) 55 secs : CO2

5. The compressibility factor for an ideal gas is


(A) 1.5 (B) 1
(C) 2 (D) 

6. On increasing temperature, the fraction of total gas molecule which has acquired
most probable velocity will
(A) increase (B) decrease
(C) remains constant (D) cant say without knowing pressure

7. Which of the following pair will diffuse at the same rate?


(A) CO2 and N2O (B) CO2 and NO
(C) CO2 and CO (D) N2O and NO

8. The value of Vander Waals constant ‘a’ is maximum for


(A) helium (B) nitrogen
(C) CH4 (D) NH3

9. A mixture of H2 and O2 in 2:1 volume is allowed to diffuse through a porous


partition what is the composition of gas coming out initially
(A) 1:2 (B) 4:1
(C) 8:1 (D) 1:4

10. The temperature at which a real gas obeys the ideal gas laws at fairly wide range
of pressure is
(A) Critical temperature (B) Inversion temperature

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(C) Boyel’s temperature (D) Reduced temperature

11. I, II, III are three isotherm respectively at T1, T2 &


T3 temperatures will be in order
P
(A) T1 = T2 = T3

(B) T1  T2  T3 I
(C) T1  T2  T3 II
III
(D) T1  T2 = T3
V

12. NH3 is liquefied more easily than N2. Hence


(A) a and b of NH3  that of N2 (B) a(NH3)  a(N2) but b (NH3)  b(N2)
(C) a(NH3)  a(N2) but b (NH3)  b(N2) (D) None

13. 0.2 mole sample of hydrocarbon CxHy yields after complete combustion with
excess O2 gas, 0.8 mole of CO2, 1.1 mole of H2O. Hence hydrocarbon is
(A) C4H10 (B) C4H8
(C) C4H5 (D) C8H16

14. When 2 gm A gas is introduced into an evacuated flask kept at 25°C, the
pressure is found to be 1 atm. If 3g of another gas B is then added to same flask,
the total pressure becomes 0.5 atm. The ratio of molecular weights is
(A) 1:1 (B) 1:2
(C) 2:3 (D) 1:4

15. Air open vessel at 127°C is heated until 1/5th of air in it has been expelled.
Assuming that the volume of vessel remains constant the temperature to which
the vessel has been heated is
(A) 177°C (B) 277°C
(C) 377°C (D) 477°C

16. 3.2g S is heated if occupy a volume of 780 ml at 450°C and 723 mm pressure.
Formula of sulphur is
(A) S2 (B) S
(C) S4 (D) S8

17. A gas cylinder containing cooking gas can withstand a pressure of 14.9 atm. The
pressure gauge of cylinder indicates 12 atm at 27°C. Due to sudden fire in
building the temperature starts rising. The temperature at which the cylinder will
explode is.
(A) 42.5°C (B) 67.8°C
(C) 99.5°C (D) 25.7°C

18. A sample of gas is at 0oC. The temperature at which its rms speed of the
molecule will be doubled is
(A) 103oC (B) 273oC
o
(C) 723 C (D) 818oC

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19. 6 g each of the following gases at 87oC and 750 mm pressure are taken. Which
of them will have the least volume
(A) HF (B) HCl
(C) HBr (D) HI

20. The temperature at which H2 has same rms speed (at 1 atm) as that of O2 at
NTP is
(A) 37 K (B) 17 K
(C) 512 K (D) 27 K

LEVEL - II

1. Select correct statements :


(A) Gases tend to behave nonideally at low temperatures and high pressures
(B) Gases tend to behave ideally at high temperature and low pressures
(C) The extent to which Z deviates from 1 is a measure of the nonideality of a gas.
(D) Z = 1 under critical states.

2. Select correct statement (s) :


(A) Absolute zero (0 K) is the temperature reached when translational as well as
rotational motion of molecule ceases.
(B) 0 K is the lowest possible temperature on thermodynamic scale and it is unattainable
(C) Volume occupied by 1 mol of a real gas at STP is 22.4 L.
(D) At absolute zero, vibrational energy is zero.

3. Select correct statements:


(A) Vapour may be condensed to liquid by the application of pressure
(B) To liquify a gas one must lower the temperature below Tc and apply pressure
(C) At Tc there is no distinction between liquid and vapour state
(D) At Tc, density of liquid is very high as compared to its gaseous state
4. Which of the following are correct statements ?
(A) van der Waals’ constant a is a measure of attractive force
(B) van der Waals’ constant b is also called co-volume or excluded volume
(C) b is expressed in L mol-1
(D) b is one-third of critical volume

5. When a gas is expanded at constant temperature:


(A) the pressure decreases
(B) the kinetic energy of the molecules remains the same
(C) the kinetic energy of the molecules decreases
(D) the number of molecules of the gas decreases

6. Energy of sublimation of solid helium is much lower than that of ice because:
(A) large part of sublimation energy of ice is used to overcome hydrogen bonding
(B) ice melts at much higher temperature
(C) in solid helium, there is van der Waals’ force of attraction between helium atoms.
(D) none is true

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7. Consider a sample of He gas and Ne gas both at 300K and 1 atmosphere. Assuming
ideal behaviour which of the following quantities are equal for two samples ?
(A) Root mean square speed of molecules
(B) Mean translational kinetic energy of molecules
(C) Number density of molecules
(D) Kinetic energy of molecules

8. Which of the following statements is/are wrong?


(A) At a given temperature the transitional K.E. of one mole of every gas is same which
is equal to 3RT.
(B) K.E. of a gas depends on its mass.
(C) K.E. depends on the volume
(D) K.E. depends on the pressure

LEVEL - III
A Matrix-Match Type

1. Match the term (in column I) with its expression (in column II)
Column – I Column – II
(A) RMS velocity (p) 8RT /  M
(B) Average velocity (q) 1 mNu 2
3 V
(C) Most probable velocity (r) 3RT / M
(D) Pressure by kinetic theory of gases (s) 2 RT / M

2. Match the compression factor under different condition (in Column I) with its value
(in Column II)
Column – I Column – II
(A) Compression factor (Z) for ideal gas (p) 3/8
(B) Z for real gas at low P (q) (1 + Pb)/ RT
(C) Z for real gas at high P (r) 1
(D) Z for critical state (s) (1 – a/RTV)

B Linked Comprehension Type

C1–3 : Paragraph for Questions Nos. 1 to 3


an 2
When the pressure is considerably high, Vm will be quite small. The pressure correction
Vm2
may become negligible and van der Waal’s equation reduces to

P (Vm – nb) = nRT

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This explains why the PVm,, after reaching a minimum value, increases with increase in
pressure. For a real gas, PV versus P plot is not linear. Hence /P or m/PV is not independent
of P,. For calculation of  and molecular mass M, we must obtain /P at P =0. As P  0,

P(V – nb) = nRT


m
 PV  n( RT  Pb ) 
( RT  Pb )
M
m  RT Pb   RT  Pb 
P    
VM M  M 
 M Mb
   P
P RT ( RT )2

1. The nature of graph plotted for P on x-axis versus /P on y-axis will be:
(A) Hyperbola (B) straight line
(B) Parallel to x-axis (D) None of the above

2. Calculate the density of N2 gas at room temperature of 25°C and atmospheric pressure,
given that b = 0.0694 dm3 mol–1.
(A) 1.36 g/L (B) 0.568 g/L
(C) 2.27 g/L (D) 13.6 g/L

3. The slope of the graph is:


M 
(A) (B)
RT P
M
(C) (D) None of the above
(RT) 2

C4–6 : Paragraph for Questions Nos. 4 to 6


Compressibility factor (Z): Real gases deviate from ideal behavior due to the following two faulty
assumptions of kinetic theory of gases.
i) Actual volume occupied by the gas molecule is negligible as compared to the total
volume of the gases.
ii) Forces of attraction and repulsion among the gas molecules are negligible.
the, extent of deviation of the real gas from ideal behaviour, is explained in terms of
compressibility factor (Z), which is function of pressure and temperature for real gas.
For ideal gas, Z = 1
For real gases, Z  1 or Z  1
When Z  1, then it is less compressible because force of repulsion dominates over
force of attraction when Z  1, force of attraction dominates over the force repulsion.
Graph in between Z & P is shown as under

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at 0 C H2
He N2
CH 4 CO 2

Z 1 ideal gas

On increasing temperature, Z increases and approaches to unity. Graph between


Z and P at different temperature for the same gas is shown as under:

T4

T3
T2
T1

Z 1 Ideal gas

The van der Waal’s equation of state for 1 mole of gas is as under:

 a 
 P  2  (V  b)  RT …(1)
 V 

Where a and b are van der Waal’s constants.


van der Waal’s constant “a” measures the amount of the force of attraction among the
gas molecules. Higher the value of “a”, higher will be the ease of liquefaction.
Case (1) For H2 and He then equation into –I will reduce P(V – b) = RT Case (2)
When pressure is too low i.e. for N2 or CH4 or, CO2 then equation (–I) reduces into
 a 
 P  2  V  RT
 V 
4. What is the correct increasing order of “a” of the gases shown as in the above graph?
(A) H2  He  N2  CO2 (B) CO2  N2  He  H2
(C) N2  CO2  H2  He (D) N2  H2  He  CO2
5. Which of the following statement is correct as shown in the above graph?
b
(A) The slope of Z vs P at constant temperature for all real gases, is
RT
b
(B) The slope of Z vs P at constant temperature for both He and H2 is .
RT
(C) The slope of Z vs P at low pressure for all real gases, at constant temperature is
b
.
RT
(D) The slope of Z vs P at high pressure and at constant temperature for real gases is
b
 .
RT

6. Which of the following statements is correct for a gas X having molar mass 5g and
density 0.3g/litre at 0.5 atmospheric pressure at 300K.

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(A) The gas “X” will behave ideally


(B) The force of attraction will dominate over the force of repulsion among the gas
molecules.
(C) The force of repulsion will dominate over the force of attraction among the gas
molecules
(D) None of these

C7–9 : Paragraph for Questions Nos. 7 to 9


Grahm’s law of diffusion: The process of spontaneous intermixing of gases against the law of
gravitation is known diffusion. If the diffusion through small orifice of the container is known as
effusion.
The rate of effusion is defined as,
PA
r
2RTM
where P is partial pressure of gas
A is area of cross-section of the orifice of the container
M is molar mass of gas
Rate of effusion is defined as the volume effused per unit time,
or moles effused per unit time.
7. 2 moles of He and 1 mole of CH4 is taken inside the container, which is made effused
through a small orifice of container having same area of cross-section at the same
temperature, then which is the correct effused volume percentage of He and CH4
initially respectively?
(A) 80%, 20% (B) 20%, 80%
(C) 30%, 70% (D) 40%, 60%

8. Which of the following is correct for diffusion?


(a) G must be positive (B) G must be negative
(c) S must be negative (D) H must be positive

9. The density of the gaseous mixture (He and N2) has density 0.9821g/litre at NTP, kept in
a container. Now a pinhole is made on the wall of the container through which N2(g) and
He gas effuses, then what will be the composition of the effusing out initially?
(A) 0.88 :1 (B) 2: 1.88
(C) 1.5: 1 (D) 1:0.88

C Assertion and Reasoning


This section contains 4 questions numbered 1 to 4. Each question contains STATEMENT-1 (Assertion) and
STATEMENT-2 (Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.

Code
(A) Statement – 1 is True, Statement – 2 is True; Statement – 2 is a correct explanation for
Statement – 1.
(B) Statement – 1 is True, Statement – 2 is True; Statement – 2 is NOT a correct explanation
for Statement – 1.
(C) Statement – 1 is True, Statement – 2 is False.
(D) Statement – 1 is False, Statement – 2 is True.

1. STATEMENT - 1

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Numerical value of van der Waals’ constant for H2O is higher than that of C6H6

STATEMENT - 2
Hydrogen bonding (dipole-dipole interaction) is present in H2O.

2. STATEMENT – 1
A gas deviation above Boyle’s temperature and negative followed by positive deviation
below Boyle’s temperature but at Boyle’s temperature a gas behaves ideally for shows
range of pressure
STATEMENT – 2
The intercept of the PV vs P isotherms of gases irrespective of nature of gas or
temperature is always equal to RT for 1 mole of the gas.

3. STATEMENT - 1
The rate of effusion of a gas directly proportional to the pressure of gas and inversely
proportional to the square root of temperature.
STATEMENT – 2
p
The rate of effusion is given by r 
T
4. STATEMENT - 1
The gases He and H2 are very different in their behavour at any temperature and
pressure but their compressibility factors are nearly the same at the critical point.
STATEMENT - 2
They have nearly the same critical constants.

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13. Hints to Subjective Assignments


LEVEL – I
w
6. a) PV = RT
M
PV PV
7. b) Apply 1 1  2 2
T1 T2
1
8. Apply r 
M
9. a) Calculate the mass of an electron.

LEVEL – II
6. a) no. of moles are same initially and finally.
b) Calculate the volume of H2 first.
7. a) Calculate the density of mixture first.
d
b) Follow curve
p
10. Calculate the no. of moles of all gases at the given conditions.

14. Answers
14.1 Subjective

LEVEL – I

1. a) 2840 kPa; b) -36 °C 2. a) 1500 mm Hg


3. a) -120 °C; b) i) 4.1 L ii) 110.1 L iii) 107 g 4. a) 6.0 L; b) -240 °C
5. a) 2.1 atm; b) 332 mm Hg 6. a) 25.65 litre; b) 1.5124 g/litre
7. a) 1.3184g; b) 1051 mm
8. a) H2  He  N2 9. a)1.16  107 cm/sec
b) 1:24 b)1.632
10. a) 900 cals
b) 51.29 cal

LEVEL – II

1. a) 2750 kPa 3. 0.0360 mm Hg


4. -35 °C 5. 0.117 atm
6. a) 0.571 atm, 0.3 and 0.4 moles 7. a)23.3
b) 45.25% Mg, 54.75% Al b)30.98
8. 1.41  1023 cc/molecule, 99.96% 9. 7 volume, C2H6N2
10. 0.30 atm, 0.402g

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14.2 Objective

LEVEL – I
1. D 2. A
3. A 4. B
5. B 6. B
7. A 8. D
9. C 10. C
11. B 12. B
13. A 14. C
15. D 16. D
17. C 18. D
19. D 20. B
LEVEL – II
1. (A, B, C) 2. (A, B)
3. (A, B, C) 4. (A, B, C, D)
5. (A, B) 6. (A, B, C)
7. (B, C, D) 8. (C, D)

LEVEL – III
A B C

Match the following Write-up Assertion and Reasoning

1. (A) – (r), 1. (B) 1. (A)


(B) – (p), 2. (A) 2. (B)
(C) – (s), 3. (C) 3. (A)
(D) – (q) 4. (A) 4. (C)
2. (A) – (r), 5. (B)
(B) – (s), 6. (B)
(C) – (q), 7. (A)
(D) – (p) 8. (B)
9. (A)

6
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