CHEMISTRY

TARGET IIT JEE 2014

XI (J)

REAL GAS

A-10, "GAURAV TOWER", Road No.-1, I.P.I.A., Kota-324005 (Raj.) INDIA

Tel.: 0744-2423738, 2423739, 2421097, 2424097 Fax: 0744-2436779

E-mail: [email protected] Website : www.bansal.ac.in

 Special Highlights
BRAIN TEASERS: GENERAL MISTAKE:

TEACHERS ADVICE:
KEY CONCEPTS

THE REAL PATH

Although the ideal gas model is very useful, it is only an approximation of the
real nature of gases, and the equations derived from its assumptions (PV = nRT)
are not entirely dependable. As a consequence, the measured properties of a
real gas will often differ from the properties predicted by our calculations.

What are the two major differences which distinguish an ideal gas from real
gas?

Real gases : Deviation from ideal behaviour

The curve for the real gas has a tendency to coincide with that of an
ideal gas at low pressures when the volume is large. At higher pressures,
however deviations are observed.

Can you predict the conditions at which a real gas will behave like an ideal
gas ?

ANALYSIS OF REAL GASES

Vander Waals equation of state :
a 2
P 2 .n (V n b) = n R T .
V
a , b are Vander Waals constants ; different for each gas
unit of a atm L mol2 -2 ; S.I. unit Pa m6 mol2
unit of b L mol -1 ; S.I. unit m3 mol1

greater the value of 'a' easier the liquification of gas ;

greater the value of 'b' greater the molecular size ,

REAL GAS [2]

 The Vander Waal equation can be obtained from ideal gas equation if

'P' is read as pressure exerted when all the intermolecular attractions are
removed & 'V' is read as free volume available for the motion of molecules. The
inclusions of correction terms, then will give the Vander Waal equation.

What do you expect, "a" of a non polar gas to be more or of a polar gas to be
more?

Although, strictly speaking, a and b vary to a small extent with temperature.

For JEE purpose they are assumed to be independent of temperature and
pressure.

Compressibility factor :
PV volume occupied by real gas at given P & T
Z = =
nRT volume that ideal gas would have occupied at same P & T

Volume occupied by ideal gas is not same as "free volume available for motion".
Free volume available for motion will always be less than volume of container
where as volume occupied by ideal gas in the equation may be greater or smaller
than the volume of container depending upon values of "Z".

Can you predict where & how the graph of He will look in the above Z vs P case
if He has very negligible force of attractions?

The graph of H2, He & normal gases of Z vs P should always be remembered.

The above graph is applicable at normal temperatures only.

Boyle Temperature :
a
TB =
bR

Inversion Temperature :
2a
Ti =
bR
REAL GAS [3]
 The graph of Z vs P for any gas will be dependent on whether the gas is above
its " Critical temperature" or below its critical temperature. For any gas
above its critical temperature graph would be similar to that of H2 or He and
for a gas at a temperature less than its critical temperature, it will be similar
to majority of the gases.

Interpretation Of Deviation From Vander Waals Equation :

PV a
(i) At low pressure z = = 1
RT V R T

PV Pb
(ii) At high pressure z = = 1+
RT RT
PV a
(iii) At extremely low pressure z = = 1 ; Pb =
RT V
(iv) For H2 and He, a will have negligible effect at most of the pressures at normal
temperature.

SOME OTHER EQUATION OF STATE

Dieterici Equation :
Pena/VRT (V n b) = n R T
Berthelot Equation :
n2 a
P (V n b) = n R T (a & b are Berthlot's constant different from Vander Waal's constant)
T V2

Can you guess whether these equations are better than Vander Waal equation
or not?

Show that at low pressures Vander Waals and dielectric both give essentially
the same value of pressure.

Virial Equation Of State For 1 Mole Of Gas :

PV 1 1 1
z= = 1+B + C 2 + D 3 + ...... (B, C, D... are temp. dependent constant)
RT V V V
a
B = second virial coefficient = b -
RT gas dependent
C = third virial coefficient = b2 .

REAL GAS [4]

 LIQUIFACTION OF GASES

Critical Phenomenon : Critical Temp , Critical pressure , Critical volume

8a a
Tc = ; Pc = ; Vc = 3 b
27 R b 27 b 2

Can you guess what will be the value of 'Z' compressibility factor for a gas at
its critical condition?

The law of corresponding states : (Definition of reduced parameters)

p T Vm
pr = p , Tr = T and Vr = V
c c c
p = prpc, T = TrTc and Vm = VrVc
Substituting these expression in the van der Waals equation

p a

(V b) = RT
T

Vm2 m

a
We obtain p r p c 2 2 (VrVc b) =RT

TrTc
Vr Vc
Replacing pc, Vc and Tc in terms of a, b and R, we get
a a 8a
p r 2
2 2 {Vr (3b)b} = RT
Tr
27 b Vr (3b) 27 Rb

i.e. (pr + 3/ Vr2 ) (3Vr 1) = 8Tr

pVm (p r p c )(Vr Vc ) p c Vc p r Vr 3 p r Vr
Z= = = T
R (Tr Tc ) T = 8 T
RT c r r

Law of corresponding states establishes the fact that behaviour of every gas
is similar if it is at "identical" condition with respect to its critical conditions.

REAL GAS [5]

 EXERCISE # I

REAL GAS AND VANDER WAALS EQUATION OF STATE

Q.1 The gas having higher value of Vander Waal's constant "a" will be __________ compressible than the
one having lower value of "a", provided Vander Waal's constant "b" is same for both the gases.

Q.2 The density of mercury is 13.6 g/cm3. Estimate the b value.Atomic mass of Hg = 200.

Q.3 Calculate the pressure exerted by 22 g of carbon dioxide in 0.5 dm3 at 300 K using:
(a) the ideal gas law and (b) Vander Waals equation. Given:
[a = 360 kPa dm mol6 2 and b = 40 cm3 mol1]
[Use : R = 0.08 atmL/mol K, 1 atm = 105 Pascal]

Q.4 Calculate from the vander waal's equation, the temperature at which 128 gm of SO2 would occupy a
vol. of 10 dm3 at 15 atm pressure.[a = 25 atm lit2 mol2, b = 0.05 lit mol1]
[Use : R = 0.08 atmL/mol K]

Q.5 The molar volume of He at 10.1325 MPa and 273 K is 0.011075 of its molar volume at 101.325 KPa
at 273 K.Calculate the radius of helium atom. The gas is assumed to show real gas nature. Neglect the
value of a for He.

Q.6 N2 molecule is spherical of radius 100 pm.

(a) What is the volume of molecules of one mole gas?
(b) What is the value of vander waal's constant b?
4
[Use : 4.2 , NA = 6 1023]
3

COMPRESSIBILITY FACTOR
Q.7 Sign of initial slope of compressibility factor (z) versus P curves is ________ if a gas is below its Boyle's
temperature and ________ if it is above its Boyle's temperature.

Q.8 Correct option regarding a container containing 1 mol of a gas in 22.4 litre container at 273 K is
(A) If compressibility factor (z) > 1 then 'P' will be less than 1 atm.
(B) If compressibility factor (z) > 1 then 'P' will be greater than 1 atm.
(C) If 'b' dominates, pressure will be less than 1 atm.
(D) If 'a' dominates, pressure will be greater than 1 atm.

Q.9 The density of water vapour at 240 atm and 527C is 90 gm/dm3.
Determine the molar volume, (Vm) of water and the compression factor.
[Use : R = 0.08 atmL/molK]

Q.10 At 300 K and under a pressure of 10.1325 MPa, the compressibility factor of O2 is 0.8. Calculate the
mass of O2 necessary to fill a gas cylinder of 100 dm3 capacity under the given conditions.
[Use : R = 0.08 atmL/molK]

REAL GAS [6]

Q.11 1 mole of CCl4 vapours at 27C occupies a volume of 40 lit. If Vander Waals constant are
24.6 L2 atm mol2 and 0.125 Lmol1. Calculate compressibility factor under
(a) Low pressure region
(b) High Pressure region
[Take : R = 0.082 lit-atm/mol/K]

BOYLE'S TEMPERATURE CRITICAL PHENOMENON AND INVERSION TEMPERATURE

Q.12 Select the incorrect statement(s):

(A) At Boyle's temperature a real gas behaves like an ideal gas irrespective of pressure.
(B) At critical condition, a real gas behaves like an ideal gas.
(C) On increasing the temperature four times,collision frequency (Z11) becomes double at constant volume
for same number of moles.
(D) At high pressure Vander Waal's constant 'b' dominates over 'a'.

Question No. 13 & 14 (2 questions)

For two gases A and B, P v/s V isotherms are drawn at T K as shown.
TA & TB are critical temperatures of A & B respectively

Q.13 Which of following is true?

(A) TA < T < TB (B) TA > T > TB (C) TA > TB > T (D) none of above

Q.14 The correct statement(s) is/are

(I) Pressure correction term will be more negligible for gas B at T K.
(II) The curve for gas 'B' will be of same shape as for gas A if T > TB
(III) Gas 'A' will show same P v/s V curve as of gas 'B' if T > TA
(A) III only (B) II and III (C) II only (D) All

Q.15 The vander waals constant for O2 are a = 1.59 atm L2 mol2 and b = 0.0318 L mol1. Calculate the
temperature at which O2 gas behaves, ideally for longer range of pressure.
[Use : R = 0.08 atmL/molK]

Q.16 The Vander Waals constants for gases A, B and C are as follows
Gas a/dm6 kPa mol2 b/dm3 mol1
A 405.3 0.027
B 1215.9 0.030
C 607.95 0.032
Which gas has (i) the highest critical temperature, (ii) the largest molecular volume, and (iii) most ideal
behaviour around 1800K?
2 105
Q.17 For a real gas (mol. mass = 30) if density at critical point is 0.40 g/cm3 and its Tc = K, then
821
calculate Vander Waal's constant a (in atm L2mol2).
REAL GAS [7]
Q.18 Find the critical constant (Pc, Vc and Tc) in terms of A and B, also find compressibility factor (z) for the
following equation of state.
A 2B
PV = RT + 2
V V
where A and B are constant, P = pressure and V = molar volume.

OTHER EQUATION OF STATE

Q.19 Show that at low densities, the vander waals equation

p a

2 (V b) = RT
T
Vm m
and the Dieterici's equation
p(Vm b) = RT exp (a/RTVm)
give essentially the same value of p.

Q.20 A commercial cylinder contains 6.91 m3 of O2 at 15 M Pa and 21C. the critical constants for O2 are
TC = 126C , PC = 50 bar . Determine the reduced pressure and reduced temperature for O2 under
these conditions.

Q.21 Calculate the value of , , Z1 and Z11 for nitrogen molecules at 25C and at pressure of 103 mm Hg.
Given that b for nitrogen is 39.1 cm3 mol1.

REAL GAS [8]

 EXERCISE # II

Q.1 One way of writing the equation for state for real gases is,
B
P V = R T 1 ...... where B is a constant.
V
Derive an approximate expression for 'B' in terms of Vander Waals constant 'a' & 'b'. [JEE 1997]

Q.2 Using Vander Waals equation, calculate the constant "a" when 2 moles of a gas confined in a 4 litre flask
exerts a pressure of 11.0 atmp at a temperature of 300 K. The value of "b" is 0.05 litre mol 1.
[JEE 1998]

Q.3 A gas will approach ideal behaviour at : [JEE 1999]

(A) low temperature and low pressure
(B) low temperature and high pressure
(C) low pressure and high temperature
(D) high temperature and high pressure .

Q.4 The compressibility of a gas is less than unity at STP. Therefore [JEE 2000]
(A) Vm > 22.4 L (B) Vm < 22.4 L (C) Vm = 22.4 L (D) Vm = 44.8 L

Q.5 The compression factor (compressibility factor) for one mole of a vander Waals gas at 0 C and 100
atmosphere pressure is found to be 0.5. Assuming that the volume of a gas molecule is negligible, calculate
the vander waals constant 'a'. [JEE 2001]

Q.6 The density of the vapour of a substance at 1 atm pressure and 500 K is 0.36 Kg m3. The vapour
effuses through a small hole at a rate of 1.33 times faster than oxygen under the same condition.
Determine
(i) mol. wt.; (ii) molar volume; (iii) compression factor (z) of the vapour and
(iv) which forces among the gas molecules are dominating, the attractive or the repulsive
[JEE 2002]

Q.7 Positive deviation from ideal behaviour takes place because of [JEE 2003]
PV
(A) molecular attraction between atoms and >1
nRT
PV
(B) molecular attraction between atoms and <1
nRT
PV
(C) finite size of atoms and >1
nRT
PV
(D) finite size of atoms and <1
nRT

Q.8 For a real gas obeying van der Waal's equation a graph is plotted between PVm (y-axis) and P(x-axis)
where Vm is molar volume. Find y-intercept of the graph. [JEE 2004]

REAL GAS [9]

 PV
Q.9 The given graph represents the variation of Z (compressibility factor = ) versus P, for three real
nRT
gases A, B and C. Identify the only incorrect statement.

Z A
1
B
C
0 P(atm)
(A) for the gas A, a = 0 and its dependence on P is linear at all pressure
(B) for the gas B, b = 0 and its dependence on P is linear at all pressure
(C) for the gas C, which is typical real gas for which neither a nor b = 0. By knowing the minima and the
point of intersection, with Z = 1, a and b can be calculated.
(D) At high pressure, the slope is positive for all real gases A, B and C. [JEE 2006]

Q.10 Match gases under specific conditions listed in Column I with their properties / laws in Column II.
Indicate your answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.

Column I Column II

(A) Hydrogen gas (P = 200 atm, T = 273 K) (P) Compressibility factor 1

(B) Hydrogen gas (P ~ 0, T = 273 K) (Q) Attractive forces are dominant

(C) CO2 (P = 1 atm, T = 273 K) (R) PV = nRT

(D) Real gas with very large molar volume (S) P (V nb) = nRT [JEE 2007]

Q.11 A gas described by van der Waals equation [JEE 2008]

(A) behaves similar to an ideal gas in the limit of large molar volumes
(B) behaves similar to an ideal gas in the limit of large pressures
(C) is characterised by van der Waals coefficients that are dependent on the identity of the gas but are
independent of the temperature
(D) has the pressure that is lower than the pressure exerted by the same gas behaving ideally

Q.12 The term that corrects for the attractive forces present in a real gas in the Vander Waals equation is
[JEE 2009]
an 2 an 2
(A) nb (B) 2 (C) (D) nb
V V2

REAL GAS [10]

Q.13 For one mole of a Vander waals gas when b = 0 and T = 300 K, the PV vs 1/V plot is shown below.
The value of the Vander waal's constant a (atm. litre2mol2) is [JEE 2012]

24.6

PV (liter-atm mol )
1
(Graph not to scale)
23.1
21.6
20.1

0
2.0 3.0
1 1
(mol liter )
V

(A) 1.0 (B) 4.5 (C) 1.5 (D) 3.0

REAL GAS [11]

 ANSWER KEY
EXERCISE # I

Q.1 more Q.2 58.82 cm3

Q.3 (a) 24 atm, (b) 21.40 atm Q.4 717C

Q.5 r = 1.33 108 cm Q.6 (a) 2.52 103 l mol1, (b) 10.08 103 dm3 mol1

Q.7 ive, +ive Q.8 B

Q.9 Molar vol = 0.2 L/mol; Z = 0.75 Q.10 16.67 kg

Q.11 (a) 0.975; (b) 1.003 Q.12 AB

Q.13 A Q.14 C

Q.15 625 K Q.16 (i) B, (ii) C, (iii) A

Q.17 1.6875

6B A2 A3 PC VC 1
Q.18 VC = ,TC = , PC = 2 , compressibility factor = RT =
A 6RB 108B C 3

Q.20 PR = 3 , TR = 2

Q.21 314 pm, 7.015 cm, 6742 s1, 1.09 1017 cm3s1

EXERCISE # II

a
Q.1 B = b Q.2 6.52 atmp L2 mol2
RT

Q.3 C Q.4 B

Q.5 1.2544 atmp L2 mol2

Q.6 (i) 18.1 g/mol , (ii) 50.25 L mol1 , (iii) 1.224 , (iv) repulsive,

Q.7 C Q.8 RT

Q.9 D Q.10 (A) P, S; (B) R; (C) P, Q; (D) R

Q.11 ACD Q.12 B

Q.13 C

REAL GAS [12]