States of Matter

Q 1.
Calculate density of NH3 at 30oC and 5 atm pressure (IIT JEE 1978 – 3 Marks)
Q 2.
3.7 g of a gas at 25oC occupied the same volume as 0.184g of hydrogen at 17 oC and at the same
pressure. What is the molecular weight of the gas? (IIT JEE 1979 – 4 Marks)
Q 3.
A straight glass tube has two inlets X and Y at two ends. The length of tube is 200 cm. HCI gas
through inlets X and NH3 gas through inlet Y are allowed to enter the tube at the same time.
What fumes appear at point P inside the tube. Find distance of P from X.
(IIT JEE 1980 – 3 Marks)
Q 4.
1 litre of mixture of CO and CO2 is taken. The mixture is passed through a tube containing red
hot charcoal. The volume now becomes 1.6 litre. The volumes are measured under the same
conditions. Find the composition of mixture by volume. (IIT JEE 1980 – 3 Marks)
Q 5.
The pressure in a bulb dropped from 2000 to 1500 mm of mercury in 47 minutes when the
contained oxygen leaked through a small hole. The bulb was then evacuated. A mixture of
oxygen and another gas of molecular weight 79 in the molar ratio of 1 : 1 at a total pressure of
4000 mm of mercury was introduced. Find the molar ratio of the two gases remaining in the
bulb after a period of 74 minutes. (IIT JEE 1981 – 3 Marks)
Q 6.
At room temperature, ammonia gas at 1 atm pressure and hydrogen chloride gas at P atm
pressure are allowed to effuse through identical pin holes from opposite ends of a glass tube of
one meter length and of uniform cross-section. Ammonium chloride is first formed at a distance
of 60 cm from the end through which HCI gas is sent in. what is the value of P?
(IIT JEE 1982 – 4 Marks)
Q 7.
Calculate the average of kinetic energy, in joules of the molecules in 8.0 g of methane at 27 oC.
(IIT JEE 1982 – 2 Marks)
Q 8.
Oxygen is present in 1 litre flask at a pressure of 7.6 * 10 -10 mm Hg. Calculate the number of
oxygen molecular in the flask at 0oC. (IIT JEE 1983 – 2 Marks)

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Q 9.
When 2 gm of a gas A is introduced into an evaluated flask kept at 25 oC, the pressure is found
to be one atmosphere. If 3 gm of another gas B is then added to the same flask, the total
pressure becomes 1.5 atm. Assuming ideal gas behavior, calculate the ratio of the molecular
weights MA : MB. (IIT JEE 1983 – 2 Marks)
Q 10.
E ual volu es of gases o tai e ual u e of ato s’, is true at what conditions.
(IIT JEE 1984 – 1 Marks)
Q 11.
Calculate the root mean square velocity of ozone kept in a closed vessel at 20 oC and 82 cm
mercury pressure. (IIT JEE 1985 – 2 Marks)
Q 12.
A spherical balloon of 21 cm diameter is to be filled up with hydrogen at N.T.P. from a cylinder
containing the gas at 20 atmospheres at 27oC. if the cylinder can hold 2.82 litres of water,
calculate the number of balloons that can be filled up. (IIT JEE 1987 – 5 Marks)
Q 13.
The average velocity at T1K and the most probable velocity at T2K of CO2 gas is 9.0 * 104 cm sec-
1
. Calculate the value of T1 and T2. (IIT JEE 1990 – 4 Marks)
Q 14.
Calculate the volume occupied by 5.0 g of acetylene gas at 50oC and 740 mm pressure.
(IIT JEE 1991 – 2 Marks)
Q 15.
At 27oC, hydrogen is leaked through a tiny hole into a vessel for 20 minutes. Another unknown
gas at the same temperature and pressure as that of H2 is leaked through the same hole for 20
minutes. After the effusion of the gases the mixture exerts a pressure of 6 atmosphere. The
hydrogen content of the mixture is 0.7 mole. If the volume of the container is 3 litres, what is
the molecular weight of the unknown gas? (IIT JEE 1992 – 4 Marks)
Q 16.
At room temperature the following reactions proceed nearly to complete :
2NO + o2→ 2NO2→ N2O4
The dimer, N2O4, solidifies at 262 K. A 250 ml flask and a 100 ml. flask are separated by a stop-
cock. At 300 K, the nitric oxide in the larger flask exerts a pressure of 1.053 atm. And the
smaller one contains oxygen at 0.789 atm. The gases are mixed by opening the stopcock and
after the end of the reaction the flasks are cooled at 220K. Neglecting the vapour pressure fo
the dimer, find out the pressure and composition of the gas remaining at 220 K. (Assume the
gases to behave ideally). (IIT JEE 1992 – 4 Marks)

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Q 17.
A gas bulb of 1 litre capacity contains 2.0 * 1021 molecules of nitrogen exerting a pressure of
7.57 * 103 Nm-2. Calculate the root mean square (r.m.s) speed and the temperature of the gas
molecules. If the ratio of the most probable speed to the root mean square speed is 0.82,
calculate the most probable speed for these molecules at this temperature.
(IIT JEE 1993 – 4 Marks)
Q 18.
A 4 : 1 molar mixture of He and CH4 is contained in a vessel at 20 bar pressure. Due to a hole in
the vessel, the gas mixture leaks out. What is the composition of the mixture effusing out
initially? (IIT JEE 1994 – 2 Marks)
Q 19.
An LPG (liquefied petroleum gas) cylinder weighs 14.8 kg when empty. When full, it weighs 29.0
kg and shows a pressure of 2.5 atm. In the course of use at 27 oC, the weight of the full cylinder
reduces to 23.3 kg. Find out the volume of the gas in cubic meters used up at the normal usage
conditions, find the final pressure inside the cylinder. Assume LPG to be n-butane with normal
boiling point of 0oC. (IIT JEE 1994 – 3 Marks)
Q 20.
A mixture of ethane (C2H6) and ethane (C2H4) occupies 40 litres at 1.00 atm and at 400 K. the
mixture reacts completely with 130 g of O2 and H2O. Assuming ideal gas behaviors, calculate the
mole fractions of C2H2 and C2H6 in the mixture. (IIT JEE 1995 – 4 Marks)
Q 21.
The composition of the equilibrium mixture (CI2⇌ 2CI), which is attained at 1200oC, is
determined by measuring the rate of effusion through a pin-hole. It is observed that at 1.80
mmHg pressure, the mixture effuses 1.16 times as fast as krypton effuses under the same
conditions. Calculate the fraction of the chlorine molecules dissociated into atoms. (relative
atomic mass of Kr = 84.) (IIT JEE 1995 – 4 Marks)
Q 22.
A 20.0 cm3 mixture of CO, CH4 and He gases is exploded by an electric discharge at room
temperature with excess of oxygen. The volume contraction is found to be 13.0 cm 3. A further
contraction of 14.0 cm3 occurs when the residual gas is treated with KOH solution. Find out the
composition of the gaseous mixture in terms of volume percentage. (IIT JEE 1995 – 4 Marks)
Q 23.
One litre of a mixture of O2 and O3 at NTP was allowed to react with an excess of acidified
solution of KI. The iodine liberated required 40 ml of M/10 sodium thiousulphate solution for
titration. What is the weight percent of ozone in the mixture? Ultraviolet radiation of
wavelength 300 nm can decompose ozone. Assuming that one photon can decompose one

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ozone molecule, how many photons would have been required for the complete decomposition
of ozone in the original mixture? (IIT JEE 1997C – 5 Marks)
Q 24.
One way of writing the equation of state for real gases is PV = RT[1 + B/V +………..] where B is a
constant. Derive on approximate expression for B in terms of the Van der Waal s constant a and
b. (IIT JEE 1997C – 2 Marks)
Q 25.
An evacuated glass vessel weghs 50.0 g when empty, 148.0 g when filled with a liquid of density
0.98 g mL-1 and 50.0 g when filledwith an ideal gas at 760 mmHg at 300K. Determine the molar
mass of the gas (IIT JEE 1998 -3 Marks)
Q 26.
The degree of dissociation is 0.4 at 400K and 1.0 atm for the gaseous reaction PCI 5⇌ PCI3 + CI2.
Assuming ideal behavior of all gases, calculate the density of equilibrium mixture at 400 K and
0.1 atmosphere. (Relative atomic mass of P = 31.0 and CI = 35.5)
(IIT JEE 1998 – 3 Marks)
Q 27.
Using van der Waal s equation, calculate the constant, a whe two oles of a gas co fi ed i
a four litre flask exerts a pressure of 11.0 atmospheres at a temperature of 300 K. The value of
b is 0.05 L ol-1. (IIT JEE 1998 – 4 Marks)
Q 28.
For the reaction, N2O5(g) = 2NO2(g) + 0.5 O2(g), calculate the mole fraction of N2O5(g)
decomposed at constant volume temperature, if the initial pressure is 600 mm Hg and the
pressure at any time is 960 mm Hg. Assume ideal gas behavior. (IIT JEE 1998 – 3 Marks)
Q 29.
One mole of nitrogen gas at 0.8 atm takes 38 s to diffuse through a pinhole, whereas one mole
of an unknown compound of xenon with fluorine at 1.6 atm takes 57 s to diffuse through the
same hole. Calculate the molecular formula of the compound. (IIT JEE 1999 – 5 Marks)
Q 30.
The pressure exerted by 12 g of an ideal gas at temperature toC in a vessel of volume Vlitre is
one atm. When the temperature is increased by 10 degrees at the same volume, the pressure
increases by 10%. Calculate the temperature t and volume V. (Molecular weight of the gas =
120.) (IIT JEE 1999 – 5 Marks)
Q 31.
Calculate the pressure exerted by one mole of CO2 gas at 273 K if the van der Waal s constant a
= 3.592 dm6 atm mol-2. Assume that the volume occupied by CO2 molecules in negligible.
(IIT JEE 2000 – 2 Marks)

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Q 32.
The compression factor (compressibility factor) for one mole of a van der Waal s at 0oC and 100
atmospheric pressure is found to be 0.5. Assuming that the volume of a gas molecule is
negligible, calculate the van der Waals constant a. (IIT JEE 2001 – 5 Marks)
Q 33.
The density of the vapour of a substance at 1 atm pressure and 500 k is 0.36 kg m-3. The vapour
effuses through a small hole at a rate of 1.33 times faster than oxygen under the same
condition.
(a) Determine
(i) Molecular weight,
(ii) molar volume,
(iii) Compression factor (Z) of the vapour and
(iv) Which forces among the gas molecules are domination, the attractive or the repulsive?
(b) If the vapour behaves ideally at 1000 K, determine the average translational kinetic energy f
a molecule. (IIT JEE 2002 – 5 Marks)
Q 34.
The average velocity of gas molecules is 400 m/sec. Calculate its rms velocity at the same
temperature. (IIT JEE 2003 – 2 Marks)
Q 35.
A graph is plotted between PVm along Y-axis and P along X-axis, where Vm is the molar volume
of a real gas. Find the intercept along Y-axis. (IIT JEE 2004 – 2 Marks)

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 States of Matter
SOL 1.
PV = m/MRT =>P * m/V * RT/M = dRT/M
d = MP/RT
Substituting the value, we get
D = 17 *5/0.082 *303 = 3.42 g/litre

SOL 2.
Given, moles = mass/mol.wt
Mass of gas = 3.7 g, mass of hydrogen = 0.184g
T1 = 298K, T2 = 17oC = 273 + 17 = 290K
Moles of H2 = n1 = Mass/M. wt. = 0.184/2 = 0.092
Moles of gas = n2 = Mass/M. wt. = 3.7/M
For hydrogen P1V1 = n1RT1 ………….. i
For gas P2V2 = n2RT2 ……………. ii
( Pressure and volume of gas |are same)
From equation (i) and equation (ii)
P1V1/P1V1 = n1RT1/n2RT2 or 1 = 0.092 *298/n2 *290
or n2 = 0.092 *298/290 or 3.7/M = 0.092 *298/290
or 3.7/M = 0.0945
M= . / . = 39.15

SOL 3.
Let NH3 diffuse through = x cm
HCI diffuses through = y cm

According to Graham s law of diffusion

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SOL 4.
Following reaction takes places in tube
C + CO2 → CO
Volume of mixture of CO and CO2 = 1L
Let volume of CO2 in mixture = x
Volume of CO in mixture = x
original volume of CO in mixture = – x
Total volume of CO after reaction = (1 - x) + 2x = 1 + x
+x= . It is given total volume after reaction = 1.6L)
x= . L
volume of CO2 = 0.6 L
Volume of CO = 0.4 L
CO2 : CO = 3 : 2

SOL 5.
NOTE THIS STEP: Since the evacuated bulb contains a mixture of oxygen and another gas in
the molar ratio of 1 : 1 at a total pressure of 4000 mm, the partial pressure of each gas is
2000 mm.
The drop in the pressure of oxygen after 74 minutes
= 500/47 = 787.2 mm of Hg
After minutes, the pressure of oxygen
= 2000 – 787.2 = 1212.8 mm of Hg
Let the rate of diffusion of other gas be rn, then


rn 32
rO2 79
Drop in pressure for the other gas = 787.2 * 32/79
= 501.01 mm of Hg
pressure of the other gas after minutes
= 2000 – 501.01 mm = 1498.99 mm of Hg
Molar ratio = Moles of unknown gas/Moles of O2
= 1498.99/1212.8 = 1.24/1 = 1.24 : 1.
[Partial pressure ∝ mole fraction]

SOL 6.
Since the pressures of gases are different, and the temperature is constant, the rate at
which molecules of the two gases diffuse is directly proportional to the pressure. This rate
of diffusion is also directly proportional to the distance travelled by the gas. Hence
r1 (of HCI gas) at pressure P = 60 = kP/√ . …… i
and r2 (of NH3) at 1 atm. Pressure P = 40 = k * /√ …. ii
From (i) and (ii)
r1/r2 = 60/40 = kP/√ . * √ /k * , P = / * √ . /√ = 2.197 atm
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SOL 7.
TIPS/Formulae:
Total kinetic energy = n (3/2 RT0
where n = Number of moles of the gas
R = Gas constant
T = Absolute temperature
Molecular weight of methane,
CH4 = 12 + 4 * 1 = 16
Number of moles of methane in . gm of methane
= 8.0/16.0 = 0.5
R = 8.314 joules/K/mole
T = 27 + 273 = 300 K
Total kinetic energy of the molecules in . gm of methane at oC = InI * 3/2 RT
= 0.5 * 3/2 * 8.314 * 300 = 1870.65 joules
Average kinetic energy = . / . * 23 *0.5
= 6.21 * 10-21 joules/molecule

SOL 8.
NOTE THIS STEP : First we should calculate the number of moles of the gas under the given
condition by the relation PV = nRT
Here P = 7.6 * 10-10 mm Hg
= 7.6 *10-10/760 atm. = 1 * 10-12 atm.
V = 1 litre
T = 273 + 0 = 273K
R = 0.082 litre atm./K/mol
Putting the values in equation
n = PV/RT = 1 *10-12 *1/0.082 *273 moles
now since 1 mole = 6.023 * 1023 molecules
10-12/0.082 *273 moles = 6.023 *1023 *10-12/0.082 *273 molecules
= 2.7 * 1010 molecules

SOL 9.
From ideal gas equation,
PV = nRT
PV = 9m/M) RT or M = m RT/PV
Let the molecular wt. of A and B be MA and MB respectively.
Then MA = 2 RT/1 * V ; MB = 3 * RT/0.5 * V
MA/MB = 2RT/V * 0.5V/3 RT = 2 * 0.5/3 = 1/3
Therefore, the ratio MA : MB = 1 : 3

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SOL 10.
If temperature and pressure are the same. [From Avogadro s law]

SOL 11.
C √ PV/M , P1V1/T1 = P2V2/T2
Where, P1 = 82 cm = 82 * 13.61 * 981 dynes
V1 = Volume of gas at 82 cm and 20oC
P2, V2 and T2 are the conditions at NTP,
=>V1 = P2 V2/T2 * T1/P1 = 76.0 *22400/273 * 293/82 = 22282 cc
M = molecular weight of ozone (O3) = 48
C=√ * * . * . * /
= 3.9 *104 cm sec-1
ALTERNATESOLUTION
Urms = √ RT/M
Given T = 20oC = 20 + 273 = 293K
R = 8.314 * 107 erg per degree per mol
M (of O3) = 48
Urms = √ * . * 7 *293/48 = 3.9 * 104 cm sec-1

SOL 12.
TIPS/Formulae:
No. of balloons that can be filled = V of H2 available/V of one balloon
Calculation of total volume of hydrogen in the cylinder at N.T.P
P1V1/T1 = PV2/T2
P1 = 1 atm P2 = 20 atm
V1 = ? V2 = 2.82 l
T1 = 23 K T2 = 273 + 27 = 300 K
V1 = 20 * 2.82 * 273/300 * 1 = 51.324 l = 51324 ml
Actual volume to be transferred into balloons
= 51324 – 2820 ml = 48504 ml
[ ml of H2 will remain in cylinder]
No. of balloons that can be filled up -= 48504/4851 = 9.999 = 10
Volume of one balloon = / πr3 = 4/3 * 22/7 * (21/2)3
[ r = diameter/2]
= 4851 ml = 4.851L
ALTERNATESOLUTION
Volume of balloon = 4.851 L (as calculate above)
Let no. of balloon to be filled n
Total volume occupied by n balloons = 4.851 * n
Volume of H2 present in cylinder = 2.82 L (given)
Total volume of H2 at NTP = (4.851n + .82)L
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P1 = 1 atm P2 = 20 atm
V1 = 4.85 * n + 2.82 L V2 = 2.82 L
T1 = 273 K
P1V1/T1 = P2V2/T2
or 1 * (4.85 * n + 2.82)/273 = 20 * 2.82/300
n = 48.504/4.851 = 10

SOL 13.
TIPS/Formulae:
Average velocity = √ RT/πM
and Most probable velocity = √ RT/M
Given –For CO2
Average velocity at T1 Most probable velocity at T2
= 9 * 104cm/sec = 9 * 104/100 m/sec.
= 9 * 102= m/sec.
* 2= √ * . T1/3.14 *44 * 10-3 ….. A
[Average velocity at T1K]
and 9 * 102= √ * . * T2/44 * 10-3 …..(B)
[Most probable velocity at T2]
On solving, T1 = 1682.5 K, T2 = 2143.4 K

SOL 14.
Applying the general gas equation
PV = nRT = m/M RT
Here, Mol. wt. of acetylene i.e., C2H2 (M) = 26, P = 740/760 atm,
T = 50oC = 50 + 273 = 323 K
V = mRT/MP or V 5 * 0.082 *323 *760/26 *740 = 5.23 l

SOL 15.
Using gas equation; PV = nRT
Total no. of moles of gases in the mixture (n)
= PV/RT = 6 *3/0.0821 *300 = 0.7308 mol.
Thus no. of moles of unknown gas = 0.7308 – 0.7
= 0.0308 mol.
Now we know that
r1/r2 = moles of hydrogen gas/moles of unknown gas = 0.7/0.0308
Also we know that r1/r2 = √M2/M1
M2 = (r1/r2)2M1 or M2 = (0.7/0.0308)2 * 2 = 1033

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SOL 16.
2NO + O2 → NO2 → N2O4
Calculating the number of moles of NO and O2 by applying the formula, n = PV/RT
Moles of NO in the larger flask = 1.053 *0.250/0.082 *300 = 0.0107
[250 mL = 0.250 L]
Moles of O2 in the smaller flask = 0.789 * 0.0100*0.082 * 300 = 0.0032
[100 mL = 0.100 L]
The reaction takes place as follows.
2NO + O2 → N2O4
Moles before 0.0107 0.0032 0
Reaction
Mole after 90.0107- 0 0.0032
reaction 2 * 0032)
Hence moles of NO reacting completely with 0.0032 moles of O2 = 2 * 0.0032 = 0.0064
Moles of NO left = 0.0107 – 0.0064 = 0.0043
NOTE : Oxygen will be completely changed into NO2 which in turn is completely converted
into N2O4 which solidifies at 262 K. Hence at 220 K, the dimer is in the solid state and only
NO present in excess will remain in the gaseous state occupying volume equal to 350 ml.
Hence pressure (P) of No gas left
= nR/V = 0.0043 * 0.082 * 220/0.350 = 0.221 atm
[Total volume = 0.250 + 0.100 = 0.350 L]

SOL 17.
Vrms = √ RT/M = √ P/d …
Calculation of density (d) of gas molecules.
No. of gas molecules = 2 * 1021
Since mass of 6.023 * 1023 molecules of nitrogen = 28 g
Mass of 2 * 1021 molecules of N2
= 28 * 2 *1021/6.023 * 1023 = 56/602.3 = 0.093 g
d = Mass/Volume = 0.093/1 g/1 [volume of flask = 1 L]
= 0.093 * 10-3 kg/10-3 m3 = 0.093 kg/m3
Substituting the value of d and P in equation (1)
Vrms = √ * . * 3/0.093 = 494.16 m/sec [Vrms = √ P/d]
(Vrms)2 = 3 RT/M = 3P/d = 3 * 7.57 * 103/0.093 [squaring]
RT/M 7.57 * 103/0.093
T = 7.57 * 103/0.093 * 28 * 10-3/8.314 = 274.13 K
Most probable velocity ∝ /Root mean sq. velocity (Vrms) = 0.82 [given]
=> ∝ = . * . = 405.2 m/sec
ALTERNATESOLUTION
Given V = 1L = 10-3m3, P = 7.57 * 10-3 Nm-2, R = 8.314J,
N = 2 * 1021/6.023 * 1023 moles
PV = nRT
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or T = PV/nR
= 7.57 *10-3 * 6.023 *1023/2 *1021 * 8.31 = 274.13 K
Urms = √ RT/M =√ * . * . / * -3 m/s = 494.15 m/s
(Given U)
Ump/Urms = 0.82 (given)
Ump = 0.82 * Urms = 0.82 * 494.15 = 405.2 m/sec

SOL 18.
Partial pressure = Mole fraction * Total pressure
pHe = xHe * P = 4/5 * 20 = 16 bar
[mole fraction of He = 4/5]
pCH 4 = 20 – 16 = 4 bar
Now applying the formula

  
0
rHe P He
MCH 4 16 16 16
0
4
rCH 4 P M He 4 4 4
CH 4

rHe : rCH3 = 8 : 1
Composition of the mixture (He : CH4) effusing out = 8 : 1

SOL 19.
Calculation of volume of gas :
Weight of cylinder with gas = 29.0 kg
Weight of empty cylinder = 14.8 kg
Weight of gas in the cylinder = . kg
Pressure in cylinder = 2.5 atm
No. of moles n) in 14.2 kg (14.2 * 103 g) of butane
N = Wt. of butane/Mol. wt. of butane = 14.2 * 103/58 = 244.83 mol
Applying gas equation,
V = nRT/P = 244.83 * 0.0821 * 300/2.5 = 2412 litres
[27oC = 273 + 27 = 300]
Calculation of pressure in cylinder after use.
Weight of cylinder after use = 23.2 kg
Weight of empty cylinder = 14.8 kg
Wt. of unused gas = . kg = . * 3/58 moles of butane
Thus P = nRT/V = 8.4 * 103 * 0.0821 * 300/58 * 2412 = 1.478 atm
[V = 2412 L]
Calculation of volume of used gas at 2.5 atm and 27oC.
Weight f used gas = 14.2 – 8.4 = 5.8 kg
Pressure under normal usage conditions = 1 atm
V = nRT/P = 5.8 *103/58 * 0.0821 *300/1 [ n= . / ]
= 246 litres = 2.463 m3

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SOL 20.
Let the volume of ethane in mixture = x litre
Volume of ethane = - x) litre
Combustion reactions f ethane and ethane are :
(i) C2H6(g) + 3 1/2 O2 g → CO2 (g) + 3H2O(l)
or 2C2H6 g → CO2(g) + 6H2O(l)
(ii) C2H4(g) + 3O2 g → CO2 (g) + 2H2O(l)
Volume of O2 required for complete combustion of ethane
= 7x/2 [For x litres]
Volume of O2 required for complete combustion of ethane
= (40 - x) * 3 [For (40 - x)L]
Total volume of O2 required = 7x/2 + (40 - x)3 l
Calculation of number of moles (n),
P = 1 atm, V = 7x/2 + (40 - x)3 l ; R = 0.082 l atm K-1 mol-1;
T = 400 K
Since n = PV/RT = 1*[7x/2 +(40 - x)3]/0.082 *400 = 7x +(40 -x)6/2 *0.082 *400
Mass of n moles of O2 [7x +(40 -x)6 2 * 0.082 * 400] * 32 = 130
or 130 = [7x +6 240 – 6x/65.6] * 32
=> 8528 = 32x + 240 * 32 => 32x = 848 => or x = 848/32 = 26.5
Hence mole fraction (%) of ethane = 26.5/40 * 100 = 66.25%
Mole fraction (%) of ethane = 33.75%

SOL 21.
Mixture Krypton
rmix = 1.16 rKr = 1
Mmix = ? MKr = 84
We know that
rmix/rKr = √MKr/Mmin or . / = √ /Mmix
or (1.16)2 84/Mmix =>Mmix = 84/(1.16)2 = 62.426
Determination of the composition of the equilibrium mixture/Let the fraction of CI2
molecules dissociated at equilibrium = x
CI2 ⇌ 2CI Total
Initially 1 0 1
At equilibrium 1–x 2x 1 – x + 2x = 1 + x
Total moles at equilibrium = – x + 2x = 1 + 1
Normal molecular mass/Experimental molecular mass = 1+x
/ . = +∝
∝= . = 13.7%

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SOL 22.
TIPS/Formulae:
(i) He does not react with oxygen.
(ii) KOH absorbs only CO2.
NOTE : When the mixture of CO, CH4 and He gases (20 ml) are exploded by an electric
discharge with excess of O2, He gas remain as such and the other reactions involved are :
CO(g) + 1/2 O2 g → CO2(g) ….. i
CH4(g) + 2O2 g → CO2(g) + 2H2O (l) ….. ii
Let the volumes of CO and CH4 to be a ml and b ml in the mixture then
Volume of He gas = [20 – (a + b)] ml
For the initial contraction of 13 ml
For the initial contraction of 13 ml,
Volume of left hand side in the above reactions – 13 = volume
or right hand side.
[20 – (a +b)] + (a + 1/2 a) + (b + 2b) – 13
= [20 – (a + 2b)] + a + b [neglect the volume of H2O (l)]
Since for gases, volume ∝ no. of moles
/ a + 2b = 13 or a + 4b = 26 ……. iv
NOTE THIS STEP : The CO2 produced above in reactions (ii) & (iii), (a + b) ml, reacts with
KOH sol for a further contraction of 14 ml.
CO2(g) + 2KOH(l → K2 CO3 (l) + H2O(l)
(a + b) ml
a + b = 14 …. v
Solving (iv) & (v) we get, a = 10ml &b = 4 ml
CH4 = 4/20 * 100 = 20%, CO = 10/20 * 100 = 50%
& He = 100 – (20 + 50) = 30%

SOL 23.
The concerned chemical reaction are :
O3 + 2 KI + H2O → 2KOH + I2 + O2
I2 + 2Na2S2O3 → Na2S4O6 + 2Nal
Millimoles of ozone = Millimoles of I2
mM of O3 = mM of I2 = 1/2 * mM of Na2S2O3
= 1/2 * 40 * 1/10 = 2mM = 0.002 mole
Calculation of total number of moles of O2 and O3
PV = n R T
1 * 1 = n *0.0821 *273 or n = 1/0.0821 *273
Or n = 0.044 mole
Moles of O2 = 0.044 – 0.002 = 0.042
Wt. of O2 = No. of moles * Mol. Wt. = 0.042 * 32 = 1.344 g
Similarly, Wt. of O3 = 0.002 * 48 = 0.096 g
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 weight % of O3 = 0.096/1.44 * 100 = 6.6%
[Total weight = 1.344 + 0.096 = 1.44 g]
No. of photons or molecules of O3 = 0.096 *6.023 *1023/48 = 1.2 *1021

SOL 24.
Use vander Waal s eqn.
Real gas equation for one mole is given as:
(P + a/V2) (V - b) = RT or (P + a/V2) = RT/V –b
=> P = RT/V –b – a/V2 = Rt/V(1 –b/V) – a/V2
=> PV = RT (1 – b/V)-1 – a/V
= RT (1 + b/V + b2/V2 …… – a/V
(using binomial expansion)
=> PV = RT (1 + b –a/RT /V + b2/V2 + b3/V3 +……… ….. i
Give equation :
PV = RT 1 + B/V +……. … ii
Comparing (1) and (2), we get, B = b –a/RT /V

SOL 25.
Weight of liquid = 148 – 50 =98 g
Volume of liquid = 98/0.98 = 100 ml = volume of vessel it means, vessel of 100 ml contain ideal
gas at 760 mm Hg at 300 K
Weight of gas = 50.5 - 50 = 0.5g
Using, PV = nRT = w/m RT
760/760 * 100/1000 = 0.5/m * 0.082 *300 [n = 0.5/m]
Molecular weight of gas m = 123

SOL 26.
PCI5 ⇌ PCI3 + CI2
Initial moles 1 0 0
Moles at eq 1 -0.4 0.4 0.4
Total moles at equilibrium = – 0.4 + 0.4 + 0.4 = 1.4
Also Normal mol. Wt. of PCI5/Exp. Mol. Wt. of PCI5 = 1 + ∝ = 1.4
Or 208.5/Exp. mol. Wt. of PCI5 = 1.4
Exp. mol. Wt. of PCI5 or m. wt. of mixture = 208.5/1.4
Now using, PV = w/m RT for mixture
d = w/V = Pm/RT = 1 * 208.5/1.4 *0.082 *400 = 4.53 g/litre

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SOL 27.
Van der waals equation for n moles of gas is
[P + n2a/V2] [V – nb] = nRT
Given V = 4 litre; P = 11.0 atm, T = 300 K;
b = 0.05 litre mol-1, n = 2 ;
Thus, [11 + 22a/42] [4 – 2 *0.05] = 2 * 0.082 *300
a = 6.46 atm litre2 mol-2

SOL 28.
N2O5(g) ⇌ 2NO2(g) + 1/2 O2(g)
Initial pressure 600 0 0
Final pressure 600 – P 2P P/2
P ∝ moles when V and T are constant
(where moles equivalent to pressure –P are decomposed)
Total pressure = 600 – P + 2 P + P/2 = 960 mm of Hg
P= mm Hg
Thus moles of N2O5 decomposed = 240/600 = 0.4
SOL 29.
We know that
r1/r2 = √M2/M1 * P1/P2 or n1/t1 * t2/n2 = √M2/M2 * P1/P2
or / * / = √M/ * . / .
M=
+ =
+ = x=
Thus compound of xenon with fluorine is XeF6

SOL 30.
(I) Given P = 1 atm, w = 12 g; T = (t + 273)K; V = V litre
(II) If T = t + 10 + 273 = t + 283 K; V = V litre,
P = 1 + 10/100 = 1.1 atm
Using gas equation, PV = w/m RT
Case I. 1 * V = 12/m R (t + 273) ….
Case II. 1.1 * V = 12/m R (t + 283) ….
From (1) and (2), t = - 137oC or t = 100 K
Also from (1), on substituting t and m (120), V = 0.82 litre

SOL 31.
van der Waal s eSoluation for one mole of a gas is
[P + a/V2] (V - b) = RT ….
Give that volume occupied by CO2 molecules, b =
Hence, (1) becomes [P + a/V2] V = RT or P = RT/V – a/V2
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Using R = 0.082 , T = 273K, V = 22.4 l for 1 mole of an ideal gas at 1 atm pressure.
Case I. 1 * V = 12/m R (t + 273) ….
Case I. 1 * V = 12/m R (t + 273) ….
P= . * / . – 3.592/(22.4)4 = 0.9922 atm

SOL 32.
We know that, Compressibility factor, Z = PV/RT
0.5 = 100 *V/0.082 *273
V= . L
NOTE : Further when volume of a gas molecule is negligible, van der Waal s eSoluation
becomes
(P + a/V2) (V - 0) = RT
Or PV = RT – a/V or a = RTV – PV2
Substituting the values
A = (0.082 * 0.1119 *273) – (100 * 0.1119 * 0.1119)
= 1.253 atm L2 mol-2

SOL 33.
(a) d = 0.36 kg m-3 = 0.36 g/L
i From Graham s Law of diffusion

= √ . = √
Mv = 32/(1.33)2 = 18.09;
Where Mv = MW of the vapour
(ii) Thus, 0.36g = 0.36/18.09 mol
0.36/18.09 mol occupies 1 L volume, so 1 mol occupies
18.09/0.36 L = 50.25L
Thus, molar volume of vapour = 50.25 L
Assuming ideal behavior the volume of the vapour can be calculated by
V1/T1 = V2/T2 => 22.4 * 500/273 = 41.025L
(iii) Compressibility factor (Z)
= (PV)obs/(PV)ideal = 1 *50.25/1 *41.025 = 1.224
(iv) Z is greater than unity, hence it is the short range repulsive force that would dominate.
actual density is less than given density
(b) E = 3/2 KT = 3/2 * 8.31/6.02 *1023 *100
= 2.07 *10-20 J per molecule
K, Boltzmann constant = R/N

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SOL 34.
Crms = √ RT/M , Cav √ RT/πM
Crms/Cav = √ RT/M * √πM/ RT = √ π/ = .
Crms = 1.085 * Cav = 1.085 * 400 = 434 ms-1

SOL 35.
The van der Waal eSoluation (for one mole) of a real gas is
+ (Vm - b) = RT
PVm – Pb + a/V – ab/V2 = RT
PVm = RT + Pb – a/Vm + ….. i
NOTE THIS STEP:
To calculate the intercept P → , hence Vm → ∞ due to which the last two terms on the right
side of the eSoluation (i) can be neglected.
PVm = RT + Pb
When P = 0, intercept = RT

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