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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.

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)

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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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.

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

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.

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

n1T1 = n2T2

2n

n ×300 = ×T

5

T = 750 K

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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

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?

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

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

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.

ni moles of a gas

Xi (Mole fraction) of a gas is =

n i Total moles of gas

“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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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

gas when it is collected over water at atmospheric (Gas + Water vapour)

pressure. By Dalton’s law.

tension

with temperature and becomes 760 mm at 100°C.

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

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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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.

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.

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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4.1 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.

Average velocity = = 1 1

n n1 n2 n3

8RT

Uav =

M

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

3RT

Vrms =

M

temperature, 25oC

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.

2RT

Vmp =

M

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.

1 2

As per kinetic equation PV = mnu rms

3

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

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.

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.

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

CO2 will diffuse in 1 minute under same condition?

V1 M2

Solution:

V2 M1

32 44

or VCO2 = 6.82 ml

VCO2 2

small hole in 234 secs while pure O 2 takes 124 secs to diffuse through

the same hole. Find molecular weight of X?

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.

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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pressure if the gas obeyed Vander Waals equation. Given a = 4.17 litre2

atm mole–2, b = 0.037 litre/mole.

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.

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.

P (Vm – b) = RT

PV m Pb

Z= =1+

RT RT

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.

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

7.1 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.

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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RH =

vapour pressure of w ater

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.

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

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.

b) Composition of Gaseous mixtures.

c) Molecular formulae of Gases.

d) Molecular formulae of Gaseous Hydrocarbons.

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

formula?

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)

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

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

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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10.1 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

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

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

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 + 0.84 = 8.8

ntotal

rO2 8.8

= 0.52

rmix 32

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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.

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%

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 1O (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.

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 4T

T = 337.5 K

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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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

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

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.

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.

p2 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

(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)

dP K dP K

(A) (B) 2

dV T V dV T V

dP K

(C) (D) none

dV T V

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

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

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

0 .6

volume of liquid water = = 0.6cc

1

(C)

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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?

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.

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 200C 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 27C?

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?

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.

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

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?

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

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

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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

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

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

(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

(A) CO2 and N2O (B) CO2 and NO

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

(A) helium (B) nitrogen

(C) CH4 (D) NH3

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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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

(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

(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.

(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.

(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

(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

(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)

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

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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,

m

PV n( RT Pb )

( RT Pb )

M

m RT Pb RT Pb

P

VM 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

M

(A) (B)

RT P

M

(C) (D) None of the above

(RT) 2

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

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

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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(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

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

2RTM

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%

(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

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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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

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

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

(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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