Chemistry - Liquid Solution - Solid State - Complete Module

XII MODULE - II
LIQUID SOLUTION
& SOLID STATE
Modus Operandi for Practice

(Suggested Ideal Approach)
Step – I CatalyseR 's Practice Sheets & NCERT

{while Chapter is running in Class-Room}
(Mandatory)
Step – II
CatalyseR 's Module
(Mandatory)
Step – III Previous Years’ JEE Subjective & Objective Questions,

R C Mukherjee solved and unsolved questions
(Mandatory)
Step – IV After Completion of Step – III, if time permits, students can

solve questions from previous year’s INCHO, NCHO, KVPY
(Optional) papers, Physical chemistry books by Atkins, Bruce H. Mahan
This Study Package is Prepared by

d`fr
o f Ca talyseR
on te nt Wing
C
ELECTROSTATICS 1
LIQUID SOLUTION
INDEX
 CONCEPTS IN BRIEF 1-9

 SOLVED EXAMPLES 10 - 16
 EXERCISE # 01 OBJECTIVE EXERCISE (LEVEL # 01) 17 - 22
 EXERCISE # 02 OBJECTIVE EXERCISE (LEVEL # 02) 23 -26
 EXERCISE # 03 OBJECTIVE EXERCISE (LEVEL # 03) 27 - 35
 EXERCISE # 04 SUBJECTIVE EXERCISE (LEVEL # 01) 36 - 38
 EXERCISE # 05 SUBJECTIVE EXERCISE (LEVEL # 02) 39 - 41
 EXERCISE # 06 KVPY, OLYMPIADS QUESTIONS 42 - 43
 EXERCISE # 07 JEE (MAIN) CORNER 44 - 46
 EXERCISE # 08 JEE (ADVANCED) CORNER 47 - 49
 ANSWER KEYS 50 – 53
WEIGHTAGE OF ‘LIQUID SOLUTION’ IN JEE (MAIN & ADVANCED) in Last Three Years
JEE (MAIN) Formely known as AIEEE
MARK /
YEAR No. Of Qs.
CHEMISTRY TOTAL MARKS
2015 1 4/120
2016 0 4/120
2017 1 4/120
JEE (ADVANCED)
MARK /
YEAR No. Of Qs.
2015 1 4/168
2016 2 7/124
2017 2 7/122
LIQUID SOLUTION 1
LIQUID SOLUTION
Solution:
A homogeneous mixture of two or more substances. (Solute + solvent = solution)
Saturated Solution:
A solution that is in equilibrium with pure solid solute. No more solute can be dissolved in it.
METHODS OF EXPRESSING THE CONCENTRATION OF A SOLUTION
The concentration of a solution can be expressed in a number of ways. The important methods
are:
(i) Mass percentage or per cent by mass:

Mass of solute
%(w/w) Mass percentage of solute   100
Mass of solution
Mass of solute

Mass of solute Mass of solvent
Mass of solute

Volume of solution  Density of solution
(ii) Percent mass by volume:
Mass of solute
% w / v    100
Volume of soltuion
(iii) Parts per million (ppm) :
Mass of solute
ppm   106
Mass of solution
(iv) Mole fraction:
Let n moles of solute (A) and N moles of solvent (B) be presnet in a solution.
n
Mole fraction of solute   XA ,
N n
N
Mole fraction of solvent   XB
N n
In binary solution, X A  XB  1
Mole fraction is independent of temperature of the solution.
(v) Molality
No. of moles of solute
Molality (m) 
weight (in kg) of solvent
Let w A grams of the solute of molecular mass mA be present in w B grams of the
wA
solvent, then Molality (m)   1000
mA  wB
Nothing is impossible, the word itself says ‘I’m possible’!

2 LIQUID SOLUTION
Relation between mole fraction and Molality:

X A  1000 w  1000
m A
XB  mB wB  mB
Note: (i) Molality is the most convenient method to express the concentration because it involves
the mass of liquids rather than their volumes. It is also independent of the variation in
temperature.
(vi) Molarity (Molar concentration)

No. of moles of solute
Molarity (M) 
Volume (in litre) of solution
wA
Molarity of the solution   1000
mA  V
Relation between molarity and % solute by mass :
Let d = density of solution in g/mL and let it contains x%  w / w  solute by mass.
Number of moles of solute in 1 litre
mass of solute in gram x  d  10 x  d  10
  M
grams molecular mass of solute Msolute mA
Molarity of dilution:
Before dilution After dilution
M1V1  M2 V2
Molarity of mixing: M1V1  M2 V2  M3 V3  MR  V1  V2  V3  MR  resultant molarity
W 1
Normality (N) N 
E V lit
Relationship between molality and molarity :
molarity 1000  M
Molality (m)  
d  molarity  msolute 1000  d  M  Msolute
VAPOUR PRESSURE
The pressure exerted by the vapours of a liquid which are in equilibrium with it at a given
temperature.
Note: It depends only on temperature and on nature of the liquid. It does NOT depend on the
surface area
Factors affecting vapour pressure

(i) Temperature: Vapour pressure  Temperature (ii) Nature of liquid:
1
Vapour pressure of liquid 
The strength of intermolecular forces
acting between molecules

CatalyseR Eduventures (India) Pvt. Ltd.

LIQUID SOLUTION 3
VAPOUR PRESSURE OF SOLUTION
Raoult's Law. The equilibrium vapour pressure of a volatile component is linearly proportional to
the mole fraction of that component in liquid phase.
Mathematical Expression: Let us assume that a solution has nA moles of liquid A and nB moles
of liquid B. Let PA be the vapour pressure of the pure liquid A and PB is the vapour pressure of the
pure liquid B.
nA nB
Mole fraction of A, X A  , Mole fraction of B, XB 
nA  nB nA  nB
According to Raoult’s law,
PA  PA X A (where PA is the partial vapour pressure of liquid A in the solution)
Similarly, PB  PB XB ( PB  partial vapour pressure of B in the solution)
The total vapour pressure of an ideal solution containing components A and B is the sum of
partial vapour pressures of all the components (Dalton’s law of partial pressures)
P  PA  PB  PA0 X A  PB0 XB .....(1)
o PAo
o P XB
P X A+ B
 X A  XB  1    XA  1  XB III . P = A
Vapour pressure
PBo o XA
=P
P  PA0 1  XB   PB0 XB  PA0  PA0 XB  PB0 XB
A
 I. P
A
II.

P  PA0  PB0  PA0 XB  ......(2)
P
B =Po
B X
B
Similarly P  P  P  P
0
B
0
A
0
B X A .......(3) 0 1
XA
1 XB 0
For non-volatile solutes :

PA  X A PA  PA0 X A .......(1)
PA0
Vapour pressure
o XA
PA
=
PA
0 XA 1
1 XB 0
P solution  x solvent P0 or relative lowering of vapour pressure,

P 0
P X .
0 solute
P
A more useful form is
P 0
P n
P N
where n = total number of moles of all the free solute species in the solution finally
(i.e. at equilibrium).

4 LIQUID SOLUTION
Three cases arise.
(i) Non-electrolyte is dissolved e.g. glucose or urea. These molecules do not dissociate into ions. If
n 0.1
0.1 mol of urea is dissolved in 50 moles of water, then  simply.
N 50
(ii) Strong electrolyte is dissolved e.g. NaCl,Ca  NO3 2 etc. These dissociate nearly completely into
n 0.2
ions. If 0.1 mol of NaCl is dissolved in 50 moles of water, then  since NaCl dissociates
N 50
n 0.3
completely in 0.1 mol Na  ions and 0.1 mol Cl ions. Similarly, for Ca NO3  2 ,  if 0.1 mol
N 50
of it dissociates completely into ions.
(iii) Weak electrolyte is dissolved e.g. HCOOH,CH3NH2 etc. In such cases, we should determine the
total number of moles of all the solute species at equilibrium. e.g. if no moles of formic acid
considered non-volatile here) are dissolved in N moles of solvent then,
HCOOH  H  COOH
no 1    no    no 
n no 1   
Total number of moles at equilibrium  no 1    . Hence,  .
N N
Note : This factor, n (at equilibrium)/n(original) is referred to as van't Hoff factor.
DETERMINATION OF COMPOSITION IN VAPOUR PHASE

Dalton’s Law v/s Raoult’s Law:
Vapours (Dalton’s Law)

A B A B A B A B A B A
YA  mole fraction of A in vapour phase
YB  mole fraction of B in vapour phase
 YA  YB  1
Solution (Raoult’s Law)
A B A B A B A B A B A
XA  mole fraction of A in liquid phase
Solution of (A & B) XB  mole fraction of B in liquid phase
 XA  XB  1
From Raoult's law P  PA0 X A  PB0 XB

PA  PA0 X A and PB  PB0 XB
From Dalton's law,
Partial pressure = Mole fraction × Total pressure

LIQUID SOLUTION 5
For A PA  y A  P
PA0 X A
PA0 X A  y A  P   yA   .....(1)
P
Above formula is used for calculation of mole fraction of A in vapour phase
For B, PB  yB  P
PB0 XB
PB0 XB  yB  P  y B   .....(2)
P
Above formula is used for calculation of mole fraction of B in vapour phase
P  yA P  yB
From (1), XA  From (2) XB 
PA0 PB0
P  y A P  yB 1 y y
on adding X A  XB  0
 0
 1   A0  B0 .....(3)
PA PB P PA PB
NOTE : -
Bubble Point. When the first bubble of vapor appears in liquid solution.
Dew Point.
When the first drop of liquid condenses from a mixture of vapors. OR when the last drop
of liquid remains and rest of the liquid is completely vaporised.
TYPES OF SOLUTION
(i) Ideal Solutions. The solutions which obey Raoult's Law are called ideal solution. For
ideality :
P  PA  PB  PA0 X A  PB0 XB
Condition -
(i) Hmix  0, (ii) Vmix  0
(iii) A—B attractive force should be similar to A—A and B—B attractive forces.
examples of ideal solutions are:

benzene + toluene, chlorobenzene + bromobenzene;
ethyl bromide + ethyl iodide; n-butyl chloride + n-butyl bromide
ethyl alcohol + methyl alcohol
o PAo
o X A+ PB X B
III. P= P A
Vapour pressure
PBo o XA
=P
A
I. P
A
II.
P
B =Po
B XB
0 XA 1
1 XB 0

6 LIQUID SOLUTION
(ii) Non ideal solution (Deviations From Raoult's Law)

(1) Positive deviation. When the observed vapour pressure is more than that expected
by Raoult's law.
Condition –
(i) Hmix  0 (ii) Vmix  0
(iii) A—B attractive force should be weaker than A—A and B—B attractive forces.
Example :
acetone + ethanol acetone + CS2 water + methanol;
water + ethanol; CCl4 + toluene; CCl4 + CHCl3 ;
acetone + benzene; CCl4 + CH3 OH; cyclohexane + ethanol
(2) Negative deviation. When the observed vapor pressure is less than that
expected by Raoult's law.
Condition –
(i) Hmix  0 (ii) Vmix  0
(iii) A—B attractive force should be greater than A—A and B—B attractive forces.
Example
acetone + aniline; CH3 OH  CH3 COOH;
chloroform + diethyl ether, acetic acid + pyridine;
chloroform + benzene H2O  HNO3 ;
water + HCl Cl
CH 3
acetone + chloroform;
Cl C H OC
CH 3
Cl

LIQUID SOLUTION 7
(iii) Azeotropic Solutions. During distillation, the mole fraction of more volatile component in
vapour state is higher than that in liquid state. This makes distillation possible. However,
there exist some solutions for particular compositions of which the mole fraction of
components in liquids and vapour state is same. Thus, no advantage is derived by
distilling such a mixture and it is termed as azeotropic.
(1) Azeotropes with Max. vapour pressure and Min. BP :
Example
Components Boiling point (K)
A B Mass% of B A B Azeoterope
H2 O C2H5 OH 95.57 373 351.3 351.10
H2 O C3H7 OH 71.69 373 370.0 350.72
CHCl3 C2H5 OH 67.00 334 351.3 332.30
(2) Azeotropes with Min. vapour pressure and Max. bp :
Examples
Components Boiling point (K)
A B Mass% of B A B Azeoterope
H2 O HCl 20.3 373 188 383
H2 O HNO3 58.0 373 359 393.5
H2 O HClO 4 71.6 373 383 476
COLLIGATIVE PROPERTIES
The properties which depend only on the number of moles of solute (and not on their molecular
weights or sizes) are referred to as colligative properties.
e.g. Lowering of vapour pressure, depression of freezing point, elevation of boiling point, osmotic
pressure etc.
P0  P n w /m
1. Relative lowering of vapour Pressure.    x solute
P0 nN w /mW /M
2. Elevation in Boiling Point,  Δ Tb  . For dilute solutions,  

1 atm
 Tb  Tb  Tb0 ......(1) n
t
lv e
vapour pressure
e so
r
T  m    Pu ion
lut
So
    Tb  K b .m ......(2)
Tb0 Tb
Temperture

8 LIQUID SOLUTION
where m is molality of the solution (i.e. total number of moles of all the solute particles per kg of
solvent). K b is ebullioscopic or boiling point elevation constant which is given by
2
Kb 
 
R Tb0 Msolvent
1000 Hvap
Hvap is the enthalpy of vaporisation of solvent.
Solid solvent t
ven
3. Depression in freezing Point  Δ Tf  . For dilute solutions,  s ol n
u o
ti
s ol
 Tf  Tf0  Tf    Tf  K f m
vapour pressure
where m is the molality of the solution and K f is a constant
for a given solvent known as molal depression constant or
Tf Tf0
0 2 Temperature
R(T ) Msolvent
f
cryoscopic constant. K f  Plot of variation of vapour pressure of a solution
1000 Hfusion with temperature and depression in freezing point.
Osmosis.
Spontaneous flow of solvent molecules through a semipermeable membrane from a pure solvent
to the solution (or from a dilute solution to a concentrated solution) is termed as osmosis.
Reverse Osmosis.
If a pressure greater than the osmotic pressure is applied on the concentrated solution, the
solvent starts to flow from concentrated solution to dilute solution (or pure solvent). This is
reverse osmosis.One of its chief uses is desalination of sea water to get pure drinking water.
4. Osmotic Pressure  . The hydrostatic pressure built up on the solution which just stops
osmosis. Alternately, it may be defined as the pressure which must be applied to the
concentrated solution in order to stop osmosis.
For dilute solutions      CRT  hg
where C is the total molar concentration of all the free species present in the solution, h is the
height developed by the column of the concentrated solution and is the density of the solution in
the column.
On the basis of osmotic pressure, the solutions can be classified in three classes.
Isotonic solutions.
Two solutions having same osmotic pressures at same temperature. (This implies C1  C2 ).
Hypertonic solution.
When two solutions are being compared, then the solution with higher osmotic pressure is termed
as hypertonic. The solution with lower osmotic pressure is termed as hypotonic.
Important.
Osmotic pressures can be determined quite accurately, hence it is used in the determination of
molecular weights of large proteins and similar substances.

LIQUID SOLUTION 9
VAN’T HOFF FACTOR

In 1886, Van’t Hoff, Jacobus Henricus (Dutch chemist, 1859,-1911) introduced a factor ‘i’ known
as Van’t Hoff factor to express the extent to association or dissociation of a solute in solution. It
can be calculated as:
number of solute particles actually present in solution
i 
number of solute particles dissolved
Observed colligative property observed molality
 
normal colligative property normal molality
normal molecular weight of solute

observed molecular weight of solute
The Van’t Hoff factor for a solute can be calculated by the following modified equations:
PA0  PA
(i)  i XB (ii) Tf  iK f m (iii) Tb  iKb m (iv)   iCRT
PA0
where C is molarity of the solution.
Note: For non-electrolytes; i = 1
For electrolytes; i > 1 ( If solute particles undergo Dissociation in the solution)
i < 1 ( If solute particles undergo Association in the solution)
Application of Van’t Hoff Factor:

i) Calculation of Degree of Dissociation of solute particles:
An 


 nA
No. of moles dissolved 1 mol 0
No. of moles after dissociation 1– n
Total number of moles present in solution  1     n
Moles of solute actually present in solution
Van’t Hoff factor, i 
Moles of solute dissolved
(1   )  n i 1
  1  (n  1) or  
1 n 1
ii) Calculation of Degree of Association of solute particles: Let n moles of the solute,
A, associate to form (A)n. If  is the degree of association.
nA 


 An
No. of moles dissolved 1 mol 0

No. of moles after association 1 
n

Total number of moles present in solution  1    
n
  1  i 1 n
i  1    1    Hence    (i  1) 
  n  1 1 n
1
n


10 LIQUID SOLUTION
SOLVED EXAMPLES
1. The density of a 3 M sodium thiosulphate solution (Na2S2O3) is 1.25 g/mL. Calculate

(i) the percentage by mass of sodium thiosulphate, (ii) the mole fraction of sodium
thiosulphate and (iii) molalities of Na+ and S2O32– ions.
x  d  10 x  1.25  10
Solution: M=  3=  x = 37.92
mA 158
474
(ii) No. of moles of Na2S2O3 = =3
158
776
Mass of water = (1250 – 474) = 776 g, No. of moles of water = = 43.1
18
3 3
Mole fraction of Na2S2O3 = = = 0.065
43.1  3 46.1
(iii) No. of moles of Na+ ions = 2 × No. of moles of Na2S2O3 = 2 × 3 = 6

No. of moles of Na ions 6
Molality of Na+ ion = = × 1000 = 7.73 m
Mass of water in kg 776
No. of moles of S2O32– ions = No. of moles of Na2S2O3

3
Molality of S2O32– ions = × 1000 = 3.86 m
776
2: The vapour pressure of pure water at 37°C is 47.1 torr. What is the vapour pressure
of an aqueous solution at 37°C containing 20 g of glucose dissolved in 500 gm of
water. Also calculate vapour pressure lowering.
500
Solution: nH2 O   27.78 mol , n(glucose)  20  0.11mol
18 180
According to Raoult’s law,
Vapour pressure of solution PH2 O  PHo2 O XH2O  47.1 0.996  46.9 torr
Lowring of vapour pressure PHo2 O – PH2 O  47.1– 46.9  0.2 torr
3. The vapour pressure of ethyl alcohol at 25°C is 59.2 torr. The vapour pressure of a
solution of urea in ethyl alcohol is 51.3 torr. What is the molality of the solution?
o 7.9
Solution: Given: PA = 59.2 torr, PA = 51.3 torr By RLVP  Xsolute = = .1334
59.2
XB 1000 XB 1000
 (molality) m =  =  ( XA + XB = 1)
X A Msolvent 1  XB  Msolvent
0.1334 1000
m=  = 3.346 molal
0.8666 46

LIQUID SOLUTION 11
4. Calculate relative lowering of vapour pressure of 0.161 molal aqueous solution.

XB  1000 XB  1000
Solution : we know Molality =  0.161 =
1  XB   Msolvent 1  XB   18
XB = 0.00289  RLVP = XB = 0.00289
5. An aqueous solution containing 28% by mass of a liquid A (mol. mass = 140) has a
vapour pressure of 160 mm at 37ºC. Find the vapour pressure of the pure liquid A.
(The vapour pressure of water at 37ºC is 150 mm.)
Solution : For two miscible liquids,
28
Ptotal = PA  PB  PAo X A  PBo X B nA = = 0.2,
140
72
Liquid B is water. Its mass is (100–28), i.e. 72. nB = = 4.0
18
Total number of moles = 0.2 + 4.0 = 4.2
Given Ptotal = 160 mm, PB0 = 150 mm
0.2 4.0
So 160 =  PA0   5.0
4.2 4.2
17.15  4.2
p0A   360.15mm
0.2
6. The vapour pressures of ethanol and methanol are 44.5 mm and 88.7 mm Hg
respectively. An ideal solution is formed at the same temperature by mixing 60 g of
ethanol with 40 g of methanol. Calculate the total vapour pressure of the solution
and the mole fracion of methanol in the vapour.
60 40
Solution: No. of moles of C2H5OH = = 1.304, No. of moles of CH3OH = = 1.25
46 32
1.304
‘XA’ of ethyl alcohol = = 0.5107
1.304  1.25
1.25
‘XB’ of methyl alcohol = = 0.4893
1.304  1.25
0
Partial pressure of ethyl alcohol = XA.PA = 0.5107 × 44.5 = 22.73 mm Hg
0
Partial pressure of methyl alcohol = XB.PB = 0.4893 × 88.7 = 43.40 mm Hg
Total vapour pressure of solution = 22.73 + 43.40 = 66.13 mm Hg

Partial pressure of CH3 OH
Mole fraction of methyl alcohol in the vapour =
Total vapour pressure
43.40
= = 0.6563
66.13

12 LIQUID SOLUTION
7. Estimate the boiling point of a solution of 25.0g of urea NH2CONH2 plus 25.0g of
thiourea NH2CSNH2 in 500g of chloroform, CHCl3. The boiling point of pure
chloroform is 61.2°C, Kb of chloroform = 3.63 Km–1.
Mass of urea 25.0g
Solution: Moles of urea =   0.42mol
Molecular mass of urea 60g / mol
25.0
Moles of thiourea =  0.33mol  Total moles of solute = 0.42 + 0.33 = 075
76 g/mol
Moles of solute 0.75mol
Molality, m =   1.50m
Mass of solvent in kg (500g / 1000g)kg
Tb = Tb – Tb0 = Kbm = 3.63 × 1.50 = 5.44K = 5.445°C
0
Tb = 5.445°C + Tb = 5.445°C + 61.2°C = 66.645°C
8. What is the percent by mass of iodine needed to reduce the freezing point of
benzene to 3.5°C? The freezing point and cryoscopic constant of pure benzene are
5.5°C and 5.12 K/m respectively.
Solution: Tf = Tf0 – Tf = Kf . m
5.5°C – 3.5°C = 5.12 × m
2
m  0.39m molal
5.12
 Mass of iodine needed for 1000g of benzene = m × molecular mass of iodine I2
= 0.39 mol/kg × 254 g/mol = 99.06 g/kg
 1000g + 99.06g solution contains 99.06g I2
99.06g  100
100g solution contains  9.01%
1099.06g
9. Consider a vertical tube of corss-sectional area of 1cm2. The bottom of the tube is
closed with a semipermeable membrane and 1 g glucose is placed in the tube. The
closed end of the tube is immersed in pure water. What will be the height of the
liquid level in the tube at equilibrium? The density of solution may be taken as
1g/cm2. What is the osmotic pressure at equilibrium at 25ºC? Assume negligible
depth of immersion of tube.
Solution: Let height in tube = h cm
V = (h × 1) cm   Cross-sectional area = 1cm2
3
V = nRT
 h 1  1 134.92
 ×   = 180 × 0.0821 × 298 = atm  = h × d × g
 1000  h
134.92 h1 9.8
= × 1 atm = 101.325 KPa h = 375 cm = 3.75 m
h 100 101.325
 = h × d × g = 3.75 ×1 × 9.8 = 36.7 KPa [Ans. 3.75 m; 36.7 KPa]

LIQUID SOLUTION 13
10. A 5% soltuion of cane sugar is isotonic with 0.877% soltuion of urea. Calculate the
molecular mass of urea if molecular mass of cansugar is 342.
Solution: Let the molecular mass of urea be m2

w1 5 w2 0.877
Molarity of sugar = = Molarity of urea = =
m1  V1 342  0.1 m2  V2 m2  0.1
For isotonic solutions,
w1 w2 5 0.877
=  =
m1  V1 m2  V2 342  0.1 m2  0.1
0.877  342
m2 = = 59.987
5
11: 1kg of an aqueous solution of Sucrose is cooled and maintained at –4°C. How
much ice will be separated out if the molality of the solution is 0.75? Kf (H2O) =
1.86 Kg mol–1K.
Solution: Since molality of solution is .75,

hence .75 moles of sucrose are present in 1000 g of solvent (i.e. water)
 msolution = mwater + msucrose = 1000 + .75 × 342 = 1256.5 gm
256.5
 msucrose (in kg) = × 1000 = 204.14 gm ,.
1256.5
mwatrer = 1000 – 204.14 = 795.86 gm
204.14 / 342
Tf = Kf × m  4 = 1.86 ×  
W / 1000
  w = 277.15  amount of ice = 795.86 – 277.15 = 518.31 gm
12: River water is found to contain 11.7% NaCl, 9.5% MgCl2, and 8.4%. NaHCO3 by
weight of solution. Calculate its normal boiling point assuming 90% ionization of
NaCl, 70% ionization of MgCl2 and 50% ionization of NaHCO3 (Kb for water= 0.52)
11.7 9.5 8.4
Solution: nNaCl = = 0.2, nMgCl2 = = 0.1, nNaHCO3 = = 0.1
58.5 95 84
iNaCl = 1+  = 1+ 0.9 = 1.9,
iMgCl2 = 1 + 2 = 1+ 0.7  2 = 2.4
= 1+ 2 = 1+ 0.5  2 = 2.0
Weight of solvent = 100 – (11.7 + 9.5 + 8.4) = 70.4 g
(iNaCl  nNaCl  iMgCl2  nMgCl2  iNaHCO3  nNaHCO3 )  K b  1000
Tb =
Weight of solvent
(1.9  0.2  2.4  0.1  2  0.1)  0.52  1000
= = 5.94°C
70.4
 Boiling point of solution = 100 + 5.94 = 105.95°C

14 LIQUID SOLUTION
13: An aqueous solution containing 288 gm of a non–volalite compound having the

stochiometric composition CxH2xOx in 90 gm water boils at 101.24°C at 1.00
atmospheric pressure . What is the molecular formula?
Kb(H2O) = 0.512 K mol–1 kg Tb (H2O) = 100°C
Solution: Elevation in B.P. = 101.24 – 100 = 1.24°C
288 1000
Tb = Kb  i  molality  1.24 = 0.512   ( i = 1)
m 90
 m = 1321.2 gm mol–1
molar mass of CxH2xO x = 12x + 1  2x + 16x = 30x
 30x = 1321.2
 x = 44 Hence the molecular formula is = C44H88O44
14: 30 ml of CH3OH (d = 0.7980 gm cm–3) and 70 ml of H2O (d = 0.9984 gm cm–3) are

mixed at 25°C to form a solution of density 0.9575 gm cm–3. Calculate the freezing
point of the solution. Kf (H2O) is 1.86 Kg mol–1 K. Also calculate its molarity
Solution: Weight of CH3OH (w1) = 30cm3  0.7980 gm/cm3 = 23.94 gm
Weight of solvent (H2O) (w2) = 70 cm3  0.9984 gm cm3 = 69.888 gm
23.94 1000
m=  = 10.7046 molal
32 69.88
Tf = Kf  i  molality, (for CH3OH, i = 1)
Tf = 1.86  10.7046°C = 19.91°C
Freezing point of the solution = 0– 19.91°C = –19.91°C
Weight of solution = weight of solute + weight of solvent = 23.94 + 69.888 = 93.828 gm
wt. of the solution 93.828
volume of the solution = = = 97.99 ml
density of the solution 0.95751
23.94 1000
M (molarity) =  mol lit–1 = 7.63 M
32 97.99
15: A complex is represented as CoCl3.xNH3. Its 0.1 m solution in aqueous solution

shows  Tf = 0.558° Kf(H2O) = 1.86 mol–1 K and assume 100% ionization and co–
ordination number of Co(III) is six . What is the complex?
0.558
Solution: Tf = i  Kf  m, 0.558 = 1.86  0.1  i i= =3
0.186
or, i  3 indicates that complex ionize to form three ions since coordination number is 6
hence x = 5
i.e., CoCl3.5NH3  [Co(NH3)5Cl]++ + 2Cl–
 
1 Cation 2 anions
So, the complex is [Co(NH3)5Cl]Cl2

LIQUID SOLUTION 15
16: A solution comprising 0.1 mol of naphthalene and 0.9 mol of benzene is cooled
until some benzene freezes out. The solution is then decanted off from the solid
and warmed to 353 K, where its vapour pressure is found to be 670 torr. The
freezing and normal boiling point of benzene are 278.5 K and 353 K, respectively.
Calculate the temperature to which the solution was cooled originally and the
amount of benzene that must have frozen out. Assume conditions of ideal solution.
Kf for benzene = 5K kg mole–1.
Solution: Molality of the resulting solution (i.e. after the benzene freezes out) can be determined on
the basis Raoult’s law.
(760  670)
Xnaph  1000 760
m  = 1.72 mol kg–1.
Xbenzene  78 0.88  78
 1000 
Weight of benzene in the resulting solution =   0.1 = 58.1 g
 1.72 
Amount of benzene frozen = 0.9  78 – 58.1 = 12.1 g
 Tf = Kfm = 5  1.72 = 8.60 K
Hence the temp to which the solution was cooled = 278.5 – 8.60 = 269.9 K
17: Find Ka, the ionization constant of tartaric acid if a 0.100 molal aqueous solution of
tartaric acid freezes at –0.205°C. Assume that only the first ionization is of
importance and that 0.1 m = 0.1M. Kf = 1.86 kg mol–1 K.
Solution: Assuming that the tartaric acid be a monobasic as AH. It ionizes as

AH   H+
  A +
Initially conc. C 0 0
Conc. after dissociation C(1–) C C,
C(1  )  C  C
Here, i = , where  = degree of dissociation
C
C(1   )
= = 1+
C
Molal concentration = 0.1
Tf = Kf Cm  i
0.205 = 1.86  0.1  (1+)
  = 0.1
[A  ][H ] C  C  2C
Ka = = 
[AH] C(1   ) 1  
2
Ka =
0.1  0.1 –3
= 1.11  10
1  0.1
–3
 Ka = 1.11  10

16 LIQUID SOLUTION
18: The freezing point of a solution of acetic acid (mole fraction is 0.02) in benzene


277.4 K. Acetic acid exists partly as a dimer 2A 
 A2. Calculate equilibrium
constant for dimerisation.
Freezing point of benzene is 278.4 K and (Kf for benzene is 5)
Solution: 

2A 
 A2
1 0 initially moles
1– /2 moles after dimer is formed
1      2
i= = 1 – /2
1
XA = 0.02, XB = 0.98
x A 1000 0.02 1000
Molality of A in B =  =  = 0.262 mol kg–1 of Benzene
mB XB 78 0.98
Since, Tf = Kf  i  molality 278.4–277.4 = 5  i  0.262
1
or, 1 = 5  i  0.262 , i= = 0.763, 1– /2 = 0.763   = 0.47
5  0.262
Hence the molality of A after dimer is formed = (1–)  initial molality
= (1 – 0.48)  initial molality = 0.52  0.262
Molality of A2 after dimer is formed
 0.48
=  molality =  0.262 = 0.24  0.26 = 0.06288
2 2
The equilibrium constant Keq =

 A 2  = 0.06288 = 3.39 kg mol–1
2
 A 2 (0.13624)


LIQUID SOLUTION 17
EXERCISE # 01 OBJECTIVE EXERCISE (LEVEL # 01)

CONCENTRATION OF SOLUTION
1. 0.2 mole of HCl and 0.1 mole of barium chloride were dissolved in water to produce a 500-mL
solution. The molarity of the Cl– ions is -
(A) 0.06 M (B) 0.09 M (C) 0.12 M (D) 0.80 M
2. A sample of H2SO4 (density 1.8 g/ml) is 90% by weight. What is the volume of the acid that has
to be used to make 1 litre of 0.2-M H2SO4 ?
(A) 16 mL (B) 10 mL (C) 12 mL (D) 18 mL
3. 3.0 molal NaOH solution has a density of 1.110 g/ml. The molarity of the solution is-
(A) 2.9732 (B) 3.05 (C) 3.64 (D) 3.0504
4. The mole fraction of a given sample of I2 in C6H6 is 0.2. The molality of I2 in C6H6 is -
(A) 0.32 (B) 3.2 (C) 0.032 (D) 0.48
5. H3PO4 is a tribasic acid and one of its salts is NaH2PO4. What volume of 1 M NaOH should be
added to 12 g NaH2PO4 (mol. wt. 120) to exactly convert it into Na3PO4?
(A) 100 mL (B) 300 mL (C) 200 mL (D) 80 mL
6. 250 g aqueous solution of MgCO3 contains 2.5 g of magnesium carbonate. Concentration of

solution is
(A) 10 ppm (B) 100 ppm
(C) 1000 ppm (D) 10000 ppm
7. Equal volumes of 0.50 M of HCl, 0.25 M of NaOH and 0.75 M of NaCl are mixed. The molarity of
the NaCl solution is -
(A) 0.75 M (B) 1/3 M (C) 0.50 M (D) 2.00 M
8. An aqueous solution of urea containing 18 g urea in 1500 cm3 of solution has a density of 1.052
g/cm3. If the molecular weight of urea is 60, then the molality of solution is-
(A) 0.2 (B) 0.192 (C) 0.064 (D) 1.2
RAOULT’S LAW (VAPOUR PRESSURE OF A SOLUTION CONTAINING NON VOLATILE

SOLUTE)
9. Find out the weight of solute (M. wt. 60) that is required to dissolve in 180 g water to reduce the
vapour pressure to 4/5th of pure water -
(A) 130 g (B) 150 g (C) 300 g (D) 75 g
10. The molality of a solution containing a non-volatile solute if the vapour pressure is 2% below the
vapour pressure of pure water, will be -
(A) 2.213 (B) 2.518
(C) 1.133 (D) 1.891

18 LIQUID SOLUTION
11. Twenty gram of a solute are added to 100 g of water at 25ºC. The vapour pressure of pure water
is 23.76 mm Hg, vapour pressure of solution is 22.41 mm Hg. The mass of this solute that is
required in 100 g water to reduce the vapour pressure to one-half of the pure water is -
(A) 333 g (B) 666 g
(C) 166 g (D) 256 g
12. Vapour pressure of CCl4 at 25ºC is 143 mm Hg. If 0.5 gm of non-volatile solute (mol. mass 65) is
dissolved in 100 ml CCl4, then the vapour pressure of the solution at 25ºC is -
[ Given : Density of CCl4 = 1.58 g/cm3 ]
(A) 141.93 mm (B) 94.39 mm
(C) 199.34 mm (D) 143.99 mm
13. The vapour pressure of a liquid decreases by 10 torr when a non-volatile solute is dissolved. The
mole fraction of the solute in solution is 0.1. What would be the mole fraction of the liquid if the
decrease in vapour pressure is 20 torr, the same solute being dissolved -
(A) 0.2 (B) 0.9 (C) 0.8 (D) 0.6
14. The vapour pressure of a solution of a non-volatile solute B in a solvent A is 95% of the vapour
pressure of the solvent at the same temperature. If the molecular weight of the solvent is 0.3
times the molecular weight of the solute, what is the weight ratio of solvent to solute.
(A) 0.15 (B) 5.7 (C) 0.2 (D) None of these
15. For a solution containing non-volatile solute, the relative lowering of vapour pressure is 0.2. If the
solution contains 5 moles in all, which of the following are true?
I. Mole fraction of solute in the solution is 0.2
II. No. of moles of solute in the solution is 0.2
III. No. of moles of solvent in the solution is 4 IV. Mole fraction of solvent is 0.2 -
(A) I, IV (B) II, III (C) I, III (D) II, IV
VAPOUR PRESSURE OF A SOLUTION CONTAINING TWO VOLATILE LIQUIDS
16. The vapour pressure of two volatile liquid mixture is PT = (5.3 – 2XB) in cm of Hg; where XB is
mole fraction of B in mixture. What are vapour pressure of pure liquids A and B?
(A) 3.3 and 2.1 cm of Hg (B) 2.3 and 3.3 cm of Hg
(C) 5.3 and 2.3 cm of Hg (D) 5.3 and 3.3 cm of Hg
17. Benzene and toluene form an ideal solution. The vapour pressure of benzene and toluene are
respectively 75 mm and 22 mm at 20ºC. If the mole fraction of benzene and toluene in vapour
phase are 0.63 and 0.37 respectively, then :
(i) The vapour pressure of mixture is -
(A) 39.68 mm (B) 79.32 mm
(C) 58.56 mm (D) 29.24 mm
(ii) Mole fraction of benzene & toluene in liquid phase is -
(A) 0.2, 0.8 (B) 0.63, 0.37
(C) 0.54, 0.46 (D) 0.33, 0.67

LIQUID SOLUTION 19
18. 1 mole benzene (Pº = 42 mm) and 2 moles toluene (Pº = 36 mm) will have
(A) total vapour pressure 38 mm
(B) mole fraction of vapours of benzene above liquid mixture is 7/19
(C) ideal behavior (D) all of the above
19. Mole fraction of a liquid A in an ideal mixture with another liquid B is XA . If XA is the mole
fraction of component A in the vapour in equilibrium, the total pressure of the liquid mixture is -
(PºA = vapour pressure of pure A ; PºB = vapour pressure of pure B)
X'A Pº A X A PºB X'A PºB X A
(A) Pº A (B) (C) (D)
XA X 'A XA X 'A
20. Two liquids A and B form an ideal solution. At 300 K the vapour pressure of a solution of 1 mole
of A and x moles of B is 550 mm. If the vapour pressures of pure A and B are 400 mm and 600
mm respectively, then x is -
(A) 1 (B) 2 (C) 3 (D) 4
COLLIGATIVE PROPERTIES (ELEVATION IN BOILING POINT DEPRESSION IN FREEZING

POINT)
21. An aqueous solution containing 5% by weight of urea and 10% by weight of glucose. Freezing
point of solution is [Kf for H2O is 1.86 K mol–1 kg]
(A) 3.04º C (B) –3.04º C
(C) –5.96º C (D) 5.96º C
22. The amount of ice that will separate out from a solution containing 25 g of ethylene glycol in 100 g
of water and is cooled to –10ºC, will be-
[ Given : Kf for H2O =1.86 K mol–1 kg ]
(A) 50.0 g (B) 25.0 g (C) 12.5 gm (D) 30.0 gm
23. It has been found that minimum temperature recorded in a hill station is –10ºC. The amount of
glycerine to be added to 40 dm3 water used in car radiator, so that it does not freeze, is -
[  Hfusion = 6.01 kJ mol–1]
(A) 39.78 kg (B) 22.45 kg (C) 19.89 kg (D) 42.66 kg
24. Elevation in b. p of a solution of non-electrolyte in CCl4 is 0.60. What is depression in f. p. for the
–1 –1
same solution? Kf (CCl4) = 30.00 kg mol K ; Kb (CCl4) = 5.02 kg mol K.
(A) 0º (B) 5.39 º (C) 3.59º (D) 2.49º
25. A solution of a non-volatile solute in water has a boiling point of 375. 3 K. The vapour pressure of
water above this solution at 338 K is -
-1
[Given p0 (water) = 0.2467 atm at 338 K and Kb for water =0.52 K kg mol ]
(A) 0.18 atm (B) 0.23 atm (C) 0.34 atm (D) 0.42 atm
26. Glucose is added to 1 litre water to such an extent that  Tf/Kf becomes equal to 1/1000, the
weight of glucose added is
(A) 180 gm (B) 18 gm
(C) 1.8 gm (D) 0.18 gm

20 LIQUID SOLUTION
27. The normal boiling point to toluene is 110.7ºC, and its boiling point elevation constant is 3.32 K kg
-1
mol . The enthalpy of vaporization of toluene is nearly-
(A) 17.0 kJmol1 (B) 34.0 kJmol1 (C) 51.0 kJmol1 (D) 68.0 kJmol1
COLLIGATIVE PROPERTIES (OSMOTIC PRESSURE)
28. A solution containing 4 gm of a non-volatile organic solute per 100 ml was found to have an
osmotic pressure equal to 500 cm of mercury at 27ºC. The molecular weight of solute is -
(A) 14.97 (B) 29.44 (C) 149.7 (D) 137.2
29. The osmotic pressure of a solution containing 100 ml of 3.4% solution (w/v) of urea (m. wt. 60)
and 50 ml of 1.6% solution (w/v) of cane-sugar (m. wt 342) at 27ºC is -
30. Two solutions each in 100 mL having 4 g glucose and 10 g sucrose respectively. How much urea
should be added to one of them in order to make them isotonic?
(A) 0.4218 g urea in glucose solution (B) 0.77 g urea in glucose solution
(C) 0.72 g urea in sucrose solution (D) 0.421 g urea in sucrose solution
31. 5 g of a polymer of molecular weight 50kg mol–1 is dissolved in 1 dm3 solution. If the density of
this solution is 0.96 kg dm–3 at 300 K, the height of solution that will represent this pressure is -
(A) 28.13 mm (B) 20.85 mm
(C) 26.52 mm (D) 24.94 mm
32. At 10ºC, the osmotic pressure of urea solution is 500 mm. The solution is diluted and the
temperature is raised to 25ºC, when the osmotic pressure is found to be 105.3 mm. Find out the
extent of dilution
(A) 5 (B) 2.5 (C) 1.25 (D) 6.5
33. What osmotic pressure would the 1.25 molal sucrose solution exhibit at 25ºC? The density of this
solution is 1.34 g/mL.
34. At 27ºC, 36 g of glucose per litre has an osmotic pressure of 4.92 atm If the osmotic pressure of
solution is 1.5 atm at the same temperature .What should be its concentration?
(A) 10.97 g/L (B) 14.97 g/L (C) 11.86 g/L (D) 13.97 g/L
35. A beaker containing 20 g sugar in 100 g water and another containing 10 g sugar in 100 g water
are placed under a bell jar and allowed to stand until equilibrium is reached. How much water will
be transferred from one beaker to other?
(A) 33.3 g (B) 34.4 g (C) 44.4 g (D) 55.3 g
VAN’T HOFF FACTOR
36. A pentimolal solution of potassium chloride freezes at -0.68ºC. If Kf for H2O is 1.86, the degree of
dissociation of KCl is -
(A) 75% (B) 83% (C) 65% (D) 92%

LIQUID SOLUTION 21
37. Which one of the following pairs of solutions will be expected to be isotonic under the same
temperature?
(A) 0.1 M urea and 0.1 M NaCl (B) 0.1 M urea and 0.2 M MgCl2
(C) 0.1 M NaCl and 0.1 M Na2SO4 (D) 0.1 M Ca(NO3)2 and 0.1 M Na2SO4
38. What is the freezing point of a solution containing 8.1 g HBr in 100 g water, assuming the acid to
be 90% ionised. ? [Kf for water = 1.86 K kg mol-1]
(A) 0.85ºC (B) -3.53ºC (C) 0ºC (D) -0.35ºC
39. A 5.8% wt/vol. NaCl solution will exert an osmotic pressure closest to which one of the following -
(A) 5.8% (wt/vol) sucrose solution (B) 5.8% (wt/vol) glucose solution
(C) 2 molal sucrose solution (D) 1 molal glucose solution
40. How many grams of NaBr must be added to 270 gm of water to lower the vapour pressure by
3.125 mm Hg at temperature at which vapour pressure of water is 50 mm Hg. Assume 100%
ionisation of NaBr
(A) 51.5 gm (B) 103 gm (C) 75 gm (D) 37.5 gm
41. The f.p of a 0.08 molal solution of NaHSO4 is –0.372ºC. The dissociation constant for the
reaction,
HSO4  H  SO42  ; is - [Kf for water = 1.86ºC]
–4 –4
(A) 2 × 10 (B) 4 × 10 (C) 2 × 10–2 (D) 4 × 10–2
42. If the observed and normal osmotic pressures of a 1% NaCl solution are 5.75 and 3.00 atm, the
degree of dissociation of NaCl is –
(A) 0.9 (B) 1.0 (C) 0.57 (D) 0.3
43. The elevation in boiling point of a solution of 10 g of a binary electrolyte (molecular mass 100) in
100 g of water is  Tb. The value of Kb for water is –
 Tb
(A) (B) 10
2
 Tb
(C) 10  TB (D)
10
44. A 0.002 molar solution of NaCl having degree of dissociation of 90% at 27ºC has osmotic
pressure equal to -
(A) 0.94 bar (B) 9.4 bar (C) 0.094 bar (D) 9.4 × 10-4 bar
45. Decimolar solution of potassium ferricyanide, K3[Fe(CN)6] has osmotic pressure of 3.94 atm at
27ºC. Hence percent ionisation of the solute is -
(A) 10% (B) 20% (C) 30% (D) 40%
46. 2.56 g of sulphur in 100 g of CS2 has depression in f.p. of 0.010º, Kf = 0.1º (molal)–1. Hence,
atomicity of sulphur is -
(A) 2 (B) 4
(C) 6 (D) 8

22 LIQUID SOLUTION
47. pH of 1M HA (weak acid) is 2. Hence van't Hoff factor is -

(A) 1.2 (B) 1.02 (C) 1.1 (D) 1.01
48. In which case van't Hoff factor is maximum?

(A) KCl, 50% ionised (B) K 2SO 4 , 40% ionised
(C) FeCl3 , 30% ionised (D) SnCl4 , 20% ionised
49. In a 0.2 molal aqueous solution of a weak acid HX the degree of ionization is 0.3. Taking kƒ for
water as 1.85, the freezing point of the solution will be nearest to –
(A) –0.260ºC (B) + 0.480ºC (C) –0.480ºC (D) –0.360ºC
50. Aqueous solutions of 0.004 M Na2 SO4 and 0.01 M Glucose are isotonic. The degree of
dissociation of Na2 SO4 is -
(A) 25% (B) 60% (C) 75% (D) 85%
W
51. 1, 2 , 3 and 4 are the osmotic pressures of 5%   solutions of urea, fructose, sucrose and KCl
V
respectively at certain temperatures. The correct order of their magnitude is
(A) 1  4  2  3 (B) 1  4  2  3
(C) 4  1  2  3 (D) 4  1  3  2


LIQUID SOLUTION 23

1. For an ideal binary liquid solution with PA  PB , which relation between XA (mole fraction of A in
liquid phase) and YA (mole fraction of A in vapour phase) is correct?
YA X A YA X A
(A) YA < Y B (B) XA > XB (C)  (D) 
YB XB YB XB
2. Mole fraction of A vapours above the solution in mixture of A and B (XA = 0.4) will be
[Given : PA = 100 mm Hg and PB = 200 mm Hg]
(A) 0.4 (B) 0.8 (C) 0.25 (D) None of these
3. The exact mathematical expression of Raoult’s law is
P 0  Ps n P 0  Ps N P0  Ps n P 0  Ps
(A)  (B)  (C)  (D) =n×N
P0 N P0 n Ps N P0
4. A mixture contains 1 mole of volatile liquid A ( PA =100 mm Hg) and 3 moles of volatille liquid
B ( PB = 80 mm Hg). If solution behaves ideally, the total vapour pressure of the distillate is
(A) 85 mm Hg (B) 85.88 mm Hg (C) 90 mm Hg (D) 92 mm Hg
5. Which of the following aqueous solution will show maximum vapour pressure at 300 K?
(A) 1 M NaCl (B) 1 M CaCl2 (C) 1 M AlCl3 (D) 1 M C12H22O11
6. The Van’t Hoff factor for a dilute aqueous solution of glucose is

(A) zero (B) 1.0 (C) 1.5 (D) 2.0
7. The correct relationship between the boiling points of very dilute solution of AlCl3 (T1K) and
CaCl2 (T2K) having the same molar concentration is
(A) T1 = T2 (B) T1 > T2 (C) T2 > T1 (D) T2 £ T1
8. A 0.001 molal solution of a complex [MA8] in water has the freezing point of –0.0054°C.
Assuming 100% ionization of the complex salt and Kf for H2O = 1.86 Km–1, write the correct
representation for the complex
(A) [MA8] (B) [MA7]A (C) [MA6]A2 (D) [MA5]A3
9. The vapour pressure of a solution of a non-volatile electrolyte B in a solvent A is 95% of the

vapour pressure of the solvent at the same temperature. If the molecular weight of the solvent is
0.3 times the molecular weight of solute, the weight ratio of the solvent and solute are
(A) 0.15 (B) 5.7 (C) 0.2 (D) 4.0
10. At a given temperature, total vapour pressure in Torr of a mixture of volatile components A and B
is given by
PTotal = 120 – 75 XB
hence, vapour pressure of pure A and B respectively (in Torr) are
(A) 120, 75 (B) 120, 195
(C) 120, 45 (D) 75, 45

24 LIQUID SOLUTION
11. Assuming each salt to be 90 % dissociated, which of the following will have highest boiling point?
(A) Decimolar Al2(SO4)3
(B) Decimolar BaCl2
(C) Decimolar Na2SO4
(D) A solution obtained by mixing equal volumes of (B) and (C)
12. The vapour pressure of a solvent decreased by 10 mm of Hg when a non-volatile solute was
added to the solvent. The mole fraction of solute in solution is 0.2, what would be mole fraction of
the solvent if decrease in vapour pressure is 20 mm of Hg
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.8
13. Elevation of boiling point of 1 molar aqueous glucose solution (density = 1.2 g/ml) is
(A) Kb (B) 1.20 Kb
(C) 1.02 Kb (D) 0.98 Kb
14. What will be the molecular weight of CaCl2 determined in its aq. solution experimentally from
depression of freezing point?
(A) 111 (B) < 111
(C) > 111 (D) data insufficient
15. 1.0 molal aqueous solution of an electrolyte A2B3 is 60% ionised. The boiling point of the solution
at 1 atm is - ( K b(H2 O)  0.52 K kgmol1 )

(A) 274.76 K (B) 377 K
(C) 376.4 K (D) 374.76 K
16. Which of the following plots represents an ideal binary mixture?
(A) Plot of Ptotal v/s 1/XB is linear (XB = mole fraction of 'B' in liquid phase).
(B) Plot of Ptotal v/s YA is linear (YB = mole fraction of 'A' in vapour phase)
1
(C) Plot of v/s YA is linear
Ptotal
1
(D) Plot of v/s YB is non linear
Ptotal
17. Pressure over ideal binary liquid mixture containing 10 moles each of liquid A and B is gradually
decreased isothermally. If PAo =200 mm Hg and PBo =100 mm Hg, find the pressure at which half of
the liquid is converted into vapour.
(A) 150 mm Hg (B) 166.5 mm Hg (C) 133 mm Hg (D) 141.4 mm Hg
18. Two liquids A & B form an ideal solution. What is the vapour pressure of solution containing 2
moles of A and 3 moles of B at 300 K? [Given : At 300 K, Vapour pr. of pure liquid A ( PAo ) = 100
torr, Vapour pr. of pure liquid B ( PBo ) = 300 torr ]
(A) 200 torr (B) 140 torr (C) 180 torr (D) None of these

LIQUID SOLUTION 25
19. Which of the following represents correctly the changes in thermodynamic properties during the
formation of 1 mol of an ideal binary solution.
(A) (B)
(C) (D)
20. FeCl3 on reaction with K4[Fe(CN)6] in aqueous solution gives blue colour. These are separated
by a semipermeable membrane AB as shown. Due to osmosis there is
(A) blue colour formation in side X.

(B) blue colour formation in side Y.
(C) blue colour formation in both of the sides X and Y.
(D) no blue colour formation.
21. A liquid mixture having composition corresponding to point z in the figure shown is subjected to
distillation at constant pressure. Which of the following statement is correct about the process
(A) The composition of distillate differs from the mixture

(B) The boiling point goes on changing
(C) The mixture has highest vapour pressure than for any other composition.
(D) Composition of an azeotrope alters on changing the external pressure.
22. The vapour pressure of a saturated solution of sparingly soluble salt (XCl3) was 17.20 mm Hg at
27°C. If the vapour pressure of pure H2O is 17.25 mm Hg at 300 K, what is the solubility of
sparingly soluble salt XCl3 in mole/Litre.
(A) 4.04 × 10–2 (B) 8.08 ×10–2 (C) 2.02 × 10–2 (D) 4.04 × 10–3

26 LIQUID SOLUTION
23. At 300 K, the vapour pressure of an ideal solution containing 3 mole of A and 2 mole of B is 600
torr. At the same temperature, if 1.5 mole of A & 0.5 mole of C (non-volatile) are added to this
solution the vapour pressure of solution increases by 30 torr. What is the value of PBo ?
(A) 940 (B) 405 (C) 90 (D) None of these
24. The following graph represents variation of boiling point with composition of liquid and vapours of
binary liquid mixture. The graph is plotted at constant pressure.
Which of the following statement(s) is incorrect. Here X & Y stands for mole fraction in liquid and
vapour phase respectively
(A) Xbenzene = 0.5 and Ytoluene = 0.2 (B) Xtoluene = 0.3 and Ybenzene = 0.6
(C) Xbenzene = 0.3 and Ytoluene = 0.4 (D) if Xbenzene = 0.7 than Ytoluene < 0.3
25. The freezing point depression of a 0.1 M aq. solution of weak acid (HX) is –0.20°C.
What is the value of equilibrium constant for the reaction?
HX (aq) l H+(aq) + X¯ (aq)
[Given : Kf for water = 1.8 kg mol–1 K. & Molality = Molarity ]
(A) 1.46×10–4 (B) 1.35 × 10–3 (C) 1.21 × 10–2 (D) 1.35 × 10–4
26. The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74. The degree of dissociation is
(A) 91.3% (B) 87% (C) 100% (D) 74%
27. The vapour pressure of an aqueous solution is found to be 750 torr at certain temperature 'T'. If
'T' is the temperature at which pure water boils under atmospheric pressure and same solution
show elevation in boiling point  Tb = 1.04 K, find the atmospheric pressure
(Kb = 0.52 K kg mol–1 )

(A) 777 (B) 779 (C) 782 (D) 746


LIQUID SOLUTION 27

COMPREHENSION TYPE
Passage # 1 (Q.1 to 3)
FeCl3 on reaction with K4 [Fe(CN)6] in aqueous solution gives blue colour, according the
equation 4FeCl3  3K 4 Fe  CN6   Fe 4 Fe  CN  6   12KCl

3
At 300 K two aqueous solution of K4[Fe(CN)6] & FeCl3 with equal concentrations 0.1 M. These
two solutions are separated by a semipermeable membrane AB as shown in figure.
A
0.1M 0.1M
K4 [Fe(CN) 6] FeCl3
side'x' side'y'
1. What is correct – B
(A) side ‘x’ is hypotonic (B) side ‘y’ is hypotonic
(C) both are isotonic (D) None of these
2. What is true about the solutions –
(A) blue colour forms in side ‘x’ (B) blue colour forms in side ‘y’
(C) blue colour forms on both sides (D) No blue colour formation
3. By applying external pressure osmosis can be stopped it should be applied to –
(A) side ‘x’ (B) side ‘y’
(C) equal on both the sides
(D) can not be stopped by applying external pressure
Figure explains elevation in boiling point when a non-volatile solute is added to a solvent.
A B
1 atm Atmospheric Pressure
P0 Psolvent
Vapour Pressure
Tb
Psolution
0
T T
Temperature
4. Given that Tb is the elevation in boiling point of the solvent in a solution of molality ‘m’ then
 T 
lim  b  is equal to –
m0
 m 
(A) Kb (molal elevation constant) (B) Ly (latent heat of vaporisation)
(C) S (entropy change) (D) X (mole fraction of solute)

28 LIQUID SOLUTION
5. Elevation in b.p. of an aqueous urea solution is 0.52º. (Kb = 0.52º mol–1 kg). Hence, mole
fraction of urea in this solution is –
(A) 0.982 (B) 0.0567 (C) 0.943 (D) 0.018
6. A complex of iron and cyanide ions is 100% ionised at 1 m (molal) If its elevation in b.p. is 2.08º.
(kb = 0.52) then complex is –
(A) K3[Fe(CN)6] (B) Fe(CN)2 (C) K4[Fe(CN)6] (D) Fe(CN)4
Passage # 3 (Q. 7 to 9)
Dilute solutions of alkali metals in liquid NH3 is deep blue in colour. Ammoniated electron are
responsible for the blue colouration and electrical conductivity of the solution. Ammoniated
cations are also responsible for electrical conductivity of the solution.
7. What would happen if alkali metal is allowed to react with concentrated ammonia solution?
(A) Paramagnetic character of solvated electrons is retained
(B) Solvated electrons associate to form electron pairs and there by paramagnetic character
decreases
(C) Reducing character is increased (D) oxidising character is increased
8. Ammoniated electron so produced can reduce -
(A) O2 to O 2–
2 (B) K2[Ni (CN)2] to K4[Ni(CN)4]
(C) Both of the above (D) None of the above
9. What would happen if the blue solution of alkali metal in NH3 (l) is heated -
(A) colour of the solution changes to red (B) Formation of alkali metal amide
(C) formation of alkali metal nitride (D) All of the above would occur
Use the equation below to answer questions. The equation below gives the relationship between
the partial pressure of a gas Pg over a solution and its solubility Xg (here given as the mole
fraction of gas dissolved in solution). k is Henry’s law constant and varies with the type of gas and
the solvent. The equation is known as Henry’s law. Xg = kPg
10. According to Henry’s law, if the partial of a gas over a solution is doubled, its solubility is
(A) decreased by a factor of 2 (B) remains the same
(C) increased by a factor of 2 (D) increased by a factor of 4
11. Henry’s law holds for a slightly soluble gas as long as the gas :
(A) has a high molecular weight (B) has a low molecular weight
(C) is diatomic (D) don’t react chemically with the solvent.
12. The Henry’s law constant for N2 and O2 in water are 8.6 ×10–4 /kPa and 4.4×10–4/kPa
respectively. There are approximately 105 Pa in 1 atm. Air is approximately 79% nitrogen and
21% oxygen. What is the approximate ratio of nitrogen to oxygen molecules dissolved in a glass
of water that has been left exposed to 1 atm of air pressure for a long time?
(A) 1 : 2 (B) 2 : 1 (C) 4 : 1 (D) 7 : 1

LIQUID SOLUTION 29
13. 4.4 × 10–4 /kPa is the Henry’s law constant for O2 in water. There are approximately 105 Pa in 1
atm . If the air is approximately 20 % oxygen. What is the mole fraction of oxygen. What is the
mole fraction of oxygen in a glass of water that has reached equilibrium with air at 1 atm?
(A) 8.8 × 10–3 (B) 8.8 × 10–2
(C) 8.8 × 10–1 (D) 8.8
14. The graph below shows the mole fraction of hydrogen and nitrogen gas in water at 50°C and
various pressure. The slope of the dotted line is equal to Henry’s law constant for the respective
gases
X
0.007
0.006 H2
0.005
0.004
0.003 N2
0.002
0.001
100 300 500
P/atm
Deviation in Henry’s law probably occur :
(A) at low pressure (B) at high pressures
(C) with light gasses (D) with heavy gasses
Passage # 5 (Qus.15 to 19)
The vapour pressure of two pure liquids, A and B, that form an ideal solution are 300 and 800
torr, respectively, at temperature T. A mixture of the vapours of A and B for which the mole
fraction of A is 0.25 is slowly compressed at temperature T
15. What is the composition of first drop of condensate?
(A) XA = 7/17, XB = 10/17 (B) XA = 8/17, XB = 8/17
(C) XA = 8/17, XB = 9/17 (D) XA = 8/17, XB = 10/17
16. What is the total pressure when first drop of condensate is formed?
(A) 960/17 torr (B) 7600/17 torr
(C) 760 torr (D) 9600/17 torr
17. What is the composition of solution whose normal boiling point is T?
(A) XA = 0.08, XB = 0.92 (B) XA = 8/17, XB = 9/17
(C) XA = 0, XB = 1 (D) XA = 7/17, XB = 10/17
18. What is the pressure when only the last bubble of vapour remains?
(A) 760 torr (B) 9600/17 torr
(C) 600 torr (D) 675 torr
19. When last bubble of vapour remains what is the composition of the last bubble?
(A) YA = 1/4, YB = 3/4 (B) YA = 3/4, YB = 1/4
(C) YA = 8/9, YB = 1/9 (D) YA = 1/9, YB = 8/9

30 LIQUID SOLUTION
MORE THAN ONE MAY BE CORRECT
20. Consider the following vapour-pressure composition graph SP is equal to –

Total vapour pressure pBo
P
pAo pA Q
pB R
S
0.0 0.2 0.4 0.6 0.8 1.0
XB 
(A) PQ + RS (B) PQ + QR + RS (C) SR + SQ (D) PQ + QR
21. Which of the following solutions are expected to be isotonic with respect to 6% (W/V) solution of
urea?
(A) 18% solution of glucose (B) 1 M solution of NaCl
(C) 1 M solution of sucrose (D) 1 M solution of CH3COOH
22. When a solution containing non-volatile solute is diluted with water,
(A) its vapour pressure increases (B) its osmotic pressure increases
(C) its boiling point increases (D) its freezing point increases
23. For a solution containing non-volatile solute, the relative lowering of vapour pressure is 0.2. If the
solution contains 5 moles in all, which of the following are true?
(A) Mole fraction of solute in the solution is 0.2
(B) No. of moles of solute in the solution is 0.2
(C) No. of moles of solvent in the solution is 4
(D) Mole fraction of solvent is 0.2
24. Consider following solutions:
I. 1 M aq. glucose II. 1 M aq. sodium chloride
III. 1 M benzoic acid in benzene IV. 1 M ammonium phosphate
(A) all are isotonic solutions (B) III is hypotonic of I, II, IV
(C) I, II, IV are hypertonic of III (D) IV is hypertonic of I, II, III
25. Which of the following condition represent non ideal solutions?
(A) They do not obey Raoult's law (B) Hmixing  0
(C) Vmixing  0 (D) Smixing  0
26. Which of the following conditions satisfies the conditions belong to minimum boiling azeotropes?
(A) Vmixing  0
(B) Hmixing  0
(C) Observed vapour pressure is greater than the vapour pressure as per Raoult's law
(D) Solvent-solvent interaction forces and solute-solute interaction forces are greater than that
of solvent-solute interaction forces.

LIQUID SOLUTION 31
27. In a solution containing A and B, the vapour pressure over the solution changes with the mole
fraction as follows D
H
(A) AB and CD represent the saturation vapour pressure of B and A
G
B
respectively
O
(B) At point O the liquid composition of A and B are equal F
A C
(C) At point O the partial pressure of A and B are equal 0 x E
1
A
1 0
(D) EF + EG = EH xB
28. A liquid mixture having composition corresponding to M in the figure is subjected to distillation at
constant pressure. Which of the following is/are correct about the process ?
Temp.
xA = 1 xB= 1
Composition
(A) The boiling point goes on changing
(B) The composition of the solution and distillate are the same throughout
(C) The composition of distillate from the mixture
(D) The mixture has lowest vapour pressure than for any other composition.
29. Solid HgI2 is gradually added to KI solution, which of the following would occur?
(A) Freezing point increases and then becomes constant
(B) Freezing point decreases constantly
(C) Boiling point decreases and then becomes constant
(D) Vapour pressure increases to a constant value
30. The diagram given aside depicts the boiling point as the function of composition of the mixture of
CCl4 and SiCl4. Which of the following statements about the diagram is false?
a b
B.pt
c
(A) The point a represents the compostion of solution and that point b that of the vapour in
equilibrium
(B) The proportion of CCl4 in the solution is smaller than that in the vapour in equilibrium
(C) ba represents the condensation of the vapour
(D) The point c represents the composition of solution and the point b that of the vapour is
equilibrium.

32 LIQUID SOLUTION
31. As per the following figure which of the following is/are correct ?
S PM
0.1 M 0.1 M
AgNO3 BaCl2
(A) A white ppt of AgCl is formed on AgNO3 side

(B) A white ppt of AgCl is formed on BaCl2 side
(C) No ppt is formed on either side
(D) Meniscus of BaCl2 solution rises and that of AgNO3 solution falls in due course of time.
32. In which of following solutions, Cu2[Fe(CN)6] permits the solvent molecules to pass through ?
(A) Benzoic acid in benzene
(B) Urea in acetone
(C) Urea in water
(D) Thiourea in water
MATCH THE COLUMN
33. Column I Column II

Example of electrolyte Value of Van’t Hoff factor.
(a) K3[Fe(CN)3] (i) 2
(b) Benzoic acid in benzene (ii) 1
(c) NaCl (iii) 1+
 1
(d) CH3COOH (iv) 1 – 1   
 n
(e) Urea (v) 1 + 3

Colligative Properties. Their formula
(a)  (i) P0XB
nRT
(b) P0–Ps (ii)
V
(c) Tf (iii) Kb.m
1000K f WA
(d) Tb (iv)
MA WB

LIQUID SOLUTION 33

Properties Formula
1000  K f  WB
(a) Molal depression constant (Kf) (i)
WA  Tf
i 1
(b) degree of dissociation (ii)
1
1
n
Msolute (normal)
(c) degree of association (iii)
Msolute (observed)
i 1
(d) Van’t Hoff factor (iv)
n 1
R Tf 2
(e) Msolute (observed) (v)
1000  L f

(A) Relative lowering of V.P. (P) Mole fraction of solute
(B) For electrolyte CaSO4 (Q) i=1
(C) For ideal Solution (R) i>1
(D) For NaHCO3 (S) i=3
37. For an ideal binary liquid solution of A & B. PA0 = pure vapour pressure of A. PB0 = pure vapour
presure of B. XA = mole fraction of A in liquid phase. YA = mole fraction of A in vapour phase.
Column I Column II
(A) P A0 > P B0 (P) XA = YA
(B) Azeotropic mixture (Q) XA < YA
0 0
(C) Equimolar mixture of A & B with PA < PB (R) XB < YB
0 0
(D) Equimolar mixture of A & B with PA = PB (S) YB > YA

(Substance) (Variation of solubility with temperature)
(A) NaCl (P) Solubility decreases with rise in temperature
(B) KI (Q) Solubility remain nearly constant with the variation in
temperature
(C) Na2SO4, 10 H2O (R) Solubility increases with rise in temperature
(D) Ca(CH3COO)2 (S) A sharp break in the solubility curve

34 LIQUID SOLUTION
39. Match the column at constant pressure of 1 atm.

Column I Column II
(A) Mixture of two immiscible liquids (P) Composition dependent
(B) Solution of two miscible liquids (Q) Constant, independent of relative amount of
in ideal solution the liquids
(C) Maxima in the azeotrope (R) Constant along with composition
(D) Minima in the azeotrope (S) Constant composition of solution and vapour
being identical
40. Mn = Normal molecular mass of solute

Mo = Observed molecular mass of solute from colligative property measurement
Column I Column II
(A) MO < Mn (P) 0.1 (M) CH3COOH in benzene
(B) MO ~ Mn/3 (Q) 0.1 (M) urea in water
(C) MO > Mn (R) 0.05 (M) BaCl2 in water

(D) MO = Mn (S) 0.1 (M) CH3COOH in water
41.
Column I Column II
(A) Molal depression constant of water 18  (373)2  R
(P)
1000  Hvap
(B) Molal elevation constant of water (373)2  R
(Q)
1000   vap
(C) Tf of solution containing 9.0 gm of glucose 18  (273)2  R

(R)
in 50 gm of water 1000  Hfus
(D) Tb of solution containing 3.0 gm urea in 50 (273)2  R
(S)
gm of water 1000   fus
INTEGER ANSWER TYPE QUESTION
42. A current of dry air was bubbled through a bulb containing 26.66 gm of an organic compound in
200 gm of water, then through a bulb at the same temperature, containing water and finally
through a tube containing anhydrous CaCl2. The loss of mass in bulb containing water was 0.087
gm and gain in mass of the CaCl2 tube was 2.036 gm. Determine the molecular mass of the
organic compound in nearest possible integers.
43. 1000 gm of 1 (m) sucrose solution in water is cooled to –3.554ºC. What mass of ice would be
separated out in nearest possible integers in gm at this temperature?
–1
For water kf = 1.86 K mol kg

LIQUID SOLUTION 35
44. The boiling point of an aqueous solution is 100.1ºC. What is its(10 x freezing point) in nearest
possible integers in K ? Given that latent heat of fusion of water = 80 cal/gm and latent heat of
vapourisation of water = 540 cal/gm.
45. van’t Hoff factor of a mixture of two moles of KI with 1 mole HgI, in a solution of water is ………..
46. The freezing point depression of 10 3 molal aqueous solution of a compound K x Fe  CN6  is
7.44  103 K. Given K f of H2 O  1.86K mol1 kg, the value of X is ……..
47. A complex is represented as CoCl3 . XNH3 . Its 0.1 molal solution in water shows Tf  0.558C.
K f of H2 O is 1.86K molality 1. Assuming 100% ionization, calculate the no. of NH3 molecules
associated with Co.
48. A 0.4 molal aqueous solution of Mx A has freezing point 3.72C. The K f of H2 O is
1.86K molality 1. The value of x is ……..
49. 3 mole of liquid A  V.P.  60 mm  and a mole of B  V.P.  40 mm  results in a solution having V.P.
of 50 mm. The value of a is …….
50. An aqueous solution of a substance mol. wt. 240 has osmotic pressure 0.2 atm at 300 K. The

density of solution in g / dm 3 is : R  0.08 litreatmK 1 mol1 
51. The osmotic pressure of a solution in atm obtained on mixing each 50 mL of 1.2% urea solution

and 2.4% glucose solution at 300 K R  0.08 litreatmK 1 mol1 
52. The osmotic pressure of a solute is 600 mm at 300 K. The solution is diluted and the temperature
is raised to 400 K and the solution shows an osmotic pressure of 200 mm. The solution was
diluted to ……. times.
53. ‘n’ moles of a non electrolyte are added to ‘N’ moles of solvent. The addition causes a lowering in
vapour pressure of solvent by 20%. The ratio of moles of solvent and its solute is …..
54. A solution of liquids A and B having vapour pressure in pure state PA0 and PB0 . The solution
contains 30% mole of A which is in equilibrium with 60% mole of A in vapour phase. If PB0 is 2
cm, the PA0 is ….. cm.
55. A mixture of two immiscible liquids nitrobenezene and water boiling at 99C has a partial
pressure of water 733 mm and of nitrobenzene 27 mm. The ratio of weights of water and
nitrobenzene in mixture is ……


36 LIQUID SOLUTION
EXERCISE # 04 SUBJECTIVE EXERCISE (LEVEL # 01)

Raoult’s law
1. At 25C, the vapour pressure of methyl alcohol is 96.0 torr. What is the mole fraction of CH3 OH
in a solution in which the (partial) vapour pressure of CH3 OH is 23.0 torr at 25C ?
2. The vapour pressure of pure liquid solvent A is 0.80 atm. When a nonvolatile substance B is
added to the solvent its vapour pressure drops to 0.60 atm. What is the mole fraction of
component B in the solution?
3. The vapour pressure of pure water at 26C is 25.21 torr. What is the vapour pressure of a
solution which contains 20.0 glucose, C6H12O 6 , in 70 g water?
4. The vapour pressure of pure water at 25C is 23.76 torr. The vapour pressure of a solution
containing 5.40 g of a nonvolatile substance in 90.0 g water is 23.32 torr. Compute the molecular
weight of the solute.
Raoult’s law in combinaton with Dalton’s law of P.P. and V.P. lowering
5. The vapour pressure of ethanol and methanol are 44.5 mm and 88.7 mm Hg respectively. An
ideal solution is prepared at the same temperature by mixing 60 g of ethanol with 40 g of
methanol. Calculate total vapour pressure of the solution.
6. What is the composition of the vapour which is in equilibrium at 30C with a benzene-toluene
solution with a mole fraction of benzene of 0.40? With a mole fraction of benzene of 0.60?
Pb =119 torr and Pt = 37 torr
7. Two liquids A and B form an ideal solution at temperature T. When the total vapour pressure
above the solution is 400 torr, the mole fraction of A in the vapour phase is 0.40 and in the liquid
phase 0.75. What are the vapour pressure of pure A and pure B at temperature T?
8. Calculate the relative lowering in vapour pressure if 100 g of a nonvolatile solute (mol.wt.100) are
dissolved in 432 g water.
9. What weight of the non-volatile solute, urea needs to be dissolved in 100 g of water, in order to
decrease the vapour pressure of water by 25%? What will be the molality of the solution?
10. The vapour pressure of an aqueous solution of glucose is 750 mm Hg at 373 K. Calculate
molality and mole fraction of solute.
11. The vapour pressure of pure benzene at 25C is 639.7 mm of Hg and the vapour pressure of a
solution of a solute in C6H6 at the same temperature is 631.7 mm of Hg. Calculate molality of
solution.
12. The vapour pressure of pure benzene at a certain temperature is 640 mm of Hg. A nonvolatile
nonelectrolyte solid weighing 2.175 g is added to 39.0 g of benzene. The vapour pressure of the
solution is 600 mm of Hg. What is molecular weight of solid substance?

LIQUID SOLUTION 37
13. The vapour pressure of water is 17.54 mm Hg at 293 K. Calculate vapour pressure of 0.5 molal
solution of a solute in it.
14. Benzene and toluene form two ideal solution A and B at 313 K. Solution A (total pressure PA )
contains equal mole of toluene and benzene. Solution B contains equal masses of both (total
pressure PB ). The vapour pressure of benzene and toluene are 160 and 60 mm Hg respectively
PA
at 313 K. Calculate the value of .
PB
Boiling point elevation and freezing point depression
15. When 10.6 g of a nonvolatile substance is dissolved in 740 g of ether, its boiling point is raised
0.284C. What is the molecular weight of the substance? Molal boiling point constant for ether is
2.11C · kg/mol.
16. The molecular weight of an organic compound is 58.0 g/mol. Compute the boiling point of a
solution containing 24.0 g of the solute and 600 g of water, when the barometric pressure is such
that pure water boils at 99.725C.
17. Pure benzene freeze at 5.45C. A solution containing 7.24 g of C2H2Cl4 in 115.3 g of benzene
was observed to freeze at 3.55C. What is the molal freezing point constant of benzene?
18. The freezing point of a solution containing 2.40 g of a compound in 60.0 g of benzene is 0.10C
lower than that of pure benzene. What is the molecular weight of the compound?
( K f is 5.12C / m for benzene)
19. The elements X and Y form compounds having molecular formula XY2 and XY4 . When dissolved
in 20 gm of benzene, 1 gm XY2 lowers the freezing point by 2.3°, whereas 1 gm of XY4 lowers
the freezing point by 1.3C. The molal depression constant for benzene is 5.1. Calculate the
atomic masses of X and Y.
20. Calculate the molal elevation constant, K b for water and the boiling point of 0.1 molal urea
solution. Latent heat of vaporisation of water is 9.72kcalmol1 at 373.15 K.
21. A solution of 0.643 g of an organic compound in 50ml of benzene (density ; 0.879 g/ml) lowers its
freezing point from 5.51C to 5.03C. If Kf for benzene is 5.12 K, calculate the molecular weight
of the compound.
22. The cryoscopic constant for acetic acid is 3.6 K kg/mol. A solution of 1 g of a hydrocarbon in 100
g of acetic acid freezes at 16.14C instead of the usual 16.60C. The hydrocarbon contains
92.3% carbon. What is the molecular formula?

38 LIQUID SOLUTION
Osmotic pressure
23. Find the freezing point of a glucose solution whose osmotic pressure at 25C is found to be 30
atm. K f (water)  1.86kg. mol1 .K
24. At 300 K, two solutions of glucose in water of concentration 0.01 M and 0.001 M are separated by
semipermeable membrane. Pressure needs to be applied on which solution, to prevent osmosis?
Calculate the magnitude of this applied pressure.
25. At 10C, the osmotic pressure of urea solution is 500 mm. The solution is diluted and the
temperature is raised to 25C, when the osmotic pressure is found to be 105.3 mm. Determine
extent of dilution.
26. The osmotic pressure of blood is 7.65 atm at 37C. How much glucose should be used per L for
an intravenous injection that is to have the same osmotic pressure as blood?
27. What would be the osmotic pressure at 17C of an aqueous solution containing 1.75 g of
sucrose  C12H22O11  per 150cm3 of solution?
28. A solution of crab hemocyanin, a pigmented protein extracted from crabs, was prepared by
dissolving 0.750 g in 125cm3 of an aqueous medium. At 4C an osmotic pressure rise of 2.6
mm of the solution was observed. The solution had a density of 1.00 g / cm3 . Determine the
molecular weight of the protein.
29. A 5% solution (w/v) of cane-sugar (Mol. weight = 342) is isotonic with 0.877% (w/v) of urea
solution. Find molecular weight of urea.
30. 10 gm of solute A and 20 gm of solute B are both dissolved in 500 ml water. The solution has the
same osmotic pressure as 6.67 gm of A and 30 gm of B dissolved in the same amount of water at
the same temperature. What is the ratio of molar masses of A and B?
Van’t Hoff factor & colligative properties
31. A storage battery contains a solution of H2SO4 38% by weight. What will be the Van't Hoff factor
if the Tf exp eriment  in 29.08. [Given K f  1.86 mol1 kg ]
32. A certain mass of a substance, when dissolved in 100g C6H6 , lowers the freezing point by
1.28C. The same mass of solute dissolved in 100g water lowers the freezing point by 1.40C. If
the substance has normal molecular weight in benzene and is completely ionized in water, into
how many ions does it dissociate in water? K f for H2 O and C6H6 are 1.86 and 5.12 K kgmol1.
33. 0.85 % aqueous solution of NaNO3 is apparently 90% dissociated at 27C. Calculate its osmotic

pressure. R  0.082 / atmK 1 mol1 
34. A 1.2% solution (w/v) of NaCl is isotonic with 7.2% solution (w/v) of glucose. Calculate degree of
ionization and Van’t Hoff factor of NaCl.


LIQUID SOLUTION 39

1. An aqueous solution containing 288 gm of a non-volatile compound having the stoichiometric
composition CxH2 x O x in 90 gm water boils at 101.24°C at 1.00 atmospheric pressure. What is the
molecular formula?
K b H2 O   0.512K mol1kg
Tb  H2 O   100C
2. The degree of dissociation of Ca NO3  2 in a dilute aqueous solution containing 7 gm of the salt
per 100 gm of water at 100C is 70%. If the vapour pressure of water at 100C is 760 mm.
Calculate the vapour pressure of the solution.
3.  
The addition of 3 gm of substance to 100 gm CCl4 M  154 gmmol1 raises the boiling point of
CCl4 by 0.60C of K b  CCl4  is 5.03kgmol1K. Calculate -

(a) the freezing point depression
(b) the relative lowering of vapour pressure
(c) the osmotic pressure at 298 K
(d) the molar mass of the substance
Given K f  CCl4   31.8 kgmol1K and  (density) of solution  1.64 gm / cm3
4. A 10% solution of cane sugar has undergone partial inversion according to the reaction:
Sucrose + Water  Glucose + Fructose. If the boiling point of solution is 100.27C.
(a) What is the average mass of the dissolved materials?
(b) What fraction of the sugar has inverted? K b H2 O   0.512K mol1kg
5. 1.5 g of a monobasic acid when dissolved in 150g of water lowers the freezing point by 0.165C.
0.5 g of the same acid when titrated, after dissolution in water, requires 37.5 ml of N/10 alkali.
Calculate the degree of dissociation of the acid ( K f for water  1.86Cmol1 ).
6. Sea water is found to contain 5.85% NaCl and 9.50% MgCl2 by weight of solution. Calculate its
normal boiling point assuming 80% ionisation for NaCl and 50% ionisation of
MgCl2 K b  H2 O   0.51 kgmol1K  .
7. The latent heat of fusion of ice is 80 calories per gram at 0C. What is the freezing point of a
solution of KCl in water containing 7.45 grams of solute in 500 grams of water, assuming that the
salt is dissociated to the extent of 95%?
8. A complex is represented as CoCl3 . xNH3 . It's 0.1 molal solution in aq. solution shows
Tf  0.558C. K f for H2 O is 1.86K mol1 kg. Assuming 100% ionisation of complex and
coordination no. of Co is six, calculate formula of complex.

40 LIQUID SOLUTION
9. The molar volume of liquid benzene (density  0.877 g ml1 ) increases by a factor of 2750 as it
vaporizes at 20C and that of liquid toluene (density  0.867 g ml1 ) increases by a factor of
7720 at 20C . Solution of benzene & toluene has a vapour pressure of 46.0 torr. Find the mole
fraction of benzene in the vapour above the solution.
10. At 100C, benzene & toluene have vapour pressure of 1375 & 558 Torr respectively. Assuming
these two form an ideal binary solution, calculate the composition of the solution that boils at 1
atm & 100C. What is the composition of vapour issuing at these conditions?
11. Calculate the boiling point of a solution containing 0.61g of benzoic acid in 50g of carbon
disulphide assuming 84% dimerization of the acid. The boiling point and K b of CS2 are 46.2C
and 2.3K kgmol1, respectively.
12. At 25C, 1 mol of A having a vapour pressure of 100 torr and 1 mol of B having a vapour
pressure of 300 torr were mixed. The vapour at equilibrium is removed, condensed and the
condensate is heated back to 25C. The vapours now formed are again removed, recondensed
and analyzed. What is the mole fraction of A in this condensate?
13. Phenol associates in benzene to a certain extent to form a dimer. A solution containing
20  103 kg phenol in 1 kg of benzene has its freezing point depressed by 0.69 K. Calculate the
fraction of phenol that has dimerised. K f for benzene  5.12kgmol1K.
14. 
30 ml of CH3 OH d  0.7980 gm cm3  
and 70 ml of H2O d  0.9984 gm cm3  are mixed at
25C to form a solution of density 0.9575 gmcm3 . Calculate the freezing point of the solution.
K f H2 O  is 1.86kgmol1K. Also calculate its molarity.
15. Dry air was drawn thorugh bulbs containing a solution of 40 grams of urea in 300 grams of water,
then through bulbs containing pure water at the same temperature and finally through a tube in
which pumice moistened with strong H2SO4 was kept. The water bulbs lost 0.0870 grams and
the sulphuric acid tube gained 2.036 grams. Calculate the molecular weight of urea.
16. Vapour pressure of C6H6 and C7H8 mixture at 50C is given by P  mmHg   180XB  90, where XB
is the mole fraction of C6H6 . A solution is prepared by mixing 936 g benzene and 736g toluene and
if the vapours over this solution are removed and condensed into liquid and again brought to the
temperature of 50C , what would be mole fraction of C6H6 in the vapour state?
17. When the mixture of two immicible liquids (water and nitrobenzene) boils at 372 K and the vapour
pressure at this temperature are 97.7 kPa H2 O  and 3.6 kPa  C 6H5NO 2  . Calculate the weight
% of nitrobenzene in the vapour.

LIQUID SOLUTION 41
18. The vapour pressure of a certain liquid is given by the equation:

313.7
Log10 P  3.54595   1.40655 log10 T where P is the vapour pressure in mm and T =
T
Kelvin Temperature. Determine the molar latent heat of vaporisation as a function of temperature.
Calculate its value at 80 K.
19. A very dilute saturated solution of a sparingly soluble salt A 3B 4 has a vapour pressure of 20 mm
of Hg at temperature T, while pure water exerts a pressure of 20.0126 mm Hg at the same
temperature. Calculate the solubility product constant of A 3B 4 at the same temperature.
20. 
If the apparent degree of ionization of KCl KCl  74.5 gmmol1  in water at 290 K is 0.86.
Calculate the mass of KCl which must be made up to 1 dm3 of aqueous solution to the same
osmotic pressure as the 4.0% solution of glucose at that temperature.
21. An ideal solution was prepared by dissolving some amount of cane sugar (non-volatile) in 0.9
moles of water. The solution was then cooled just below its freezing temperature (271 K), where
some ice get separated out. The remaining aqueous solution registered a vapour pressure of 700
torr at 373 K. Calculate the mass of ice separated out, if the molar heat of fusion of water is 6 kJ.
22. The specific conductivity of a 0.5 M aq. solution of monobasic acid HA at 27C is 0.006Scm 1.
It's molar conductivity at infinite dilution is 200Scm2 mol1 .
atm L
Calculate osmotic pressure (in atm) of 0.5 M HA (aq) solution at 27C . Given R = 0.08 .
mol K
23. The freezing point of 0.02 mol fraction solution of acetic acid (A) in benzene (B) is 277.4K. Acetic
acid exists partly as a dimer 2A  A 2 . Calculate equilibrium constant for the dimerisation.
Freezing point of benzene is 278.4 K and its heat of fusion Hf is 10.042 kJmol1.
24. The vapour pressure of two pure liquids, A and B that form an ideal solution are 300 and 800 torr
respectively, at temperature T. A mixture of the vapour of A and B for which the mole fraction of A
is 0.25 is slowly compressed at temperature T. Calculate
(a) the composition of the first drop of the condensate,
(b) the total pressure when this drop is formed,
(c) the composition of the solution whose normal boiling point is T,
(d) the pressure when only the last bubble of vapour remains, and
(e) the composition of the last bubble.
25. Tritium, T (an isotope of H) combines with fluorine to form weak acid TF, which ionizes to give T+.
Tritium is radioactive and is a   emitter. A freshly prepared aqueous solution of TF has pT
(equivalent of pH) of 1.5 and freezes at 0.372C. If 600ml of freshly prepared solution were
allowed to stand for 24.8 years. Calculate (i) ionization constant of TF.
(ii) Number of   particles emitted.
(Given K f for water  1.86kgmolK 1,t1/2 for tritium = 12.4 years)
 

42 LIQUID SOLUTION
EXERCISE # 06 KVPY, OLYMPIADS CORNER

1. Assuming ideal behavior, the enthalpy and volume of mixing of two liquids, respectively, are -
[KVPY 2011]
(A) Zero and zero (B) +ve and zero (C) -ve and zero (D) -ve and -ve
2. At 298 K, the ratio of osmotic pressures of two solutions of a substance with concentrations of
0.01 M and 0.001 M, respectively, is - [KVPY 2011]
(A) 1 (B) 100 (C) 10 (D) 1000
3. The variation of solubility of four different gases (G1, G2, etc.) in a given solvent with pressure at
a constant temperature is shown in the plot. [KVPY 2013]
G4
G3
Solubility
G2
G1
Pressure
The gas with the highest value of Henry’s law constant is -
(A) G4 (B) G2 (C) G3 (D) G1
4. Osmotic pressure of a 2% w/v solution of glucose is same as 5% w/v solution of a nonvolatile

non-electrolyte solute. The molar mass of the solute is - [NSEC 2014]
(A) 180 (B) 450 (C) 72 (D) 45
5. The colligative property used in the determination of molar mass of a polymer is -

[NSEC 2014]
(A) Lowering of the vapour pressure (B) Elevation in the boiling point
(C) Depression in the freezing point (D) Osmotic pressure
6. The specific gravity of a HNO3 solution is 1.42 and it is 70% w/w. The molar concentration of
HNO3 is - [NSEC 2014]

(A) 15.8 (B) 31.6 (C) 11.1 (D) 14.2
3
7. A bottle of H 3 PO4 solution contains 70% (w/w) acid. If the density of the solution is 1.54 cm ,
the volume of the H 3 PO4 solution required to prepare 1 L of I N solution is -

[NSEC 2015]
(A) 90 mL (B) 45 mL
(C) 30 mL (D) 23 mL

LIQUID SOLUTION 43
8. The vapour pressure of benzene is 53.3 kPa at 60.6C , but it fall to 51.5 kPa when 19g of a
nonvolatile organic compound is dissolved in 500g benzene. The molar mass of the nonvolatile
compound is - [NSEC 2015]
(A) 82 (B) 85 (C) 88 (D) 92
9. The vapour pressure of two pure isomeric liquids X and Y are 200 torr and 100 torr respectively at
a given temperature. Assuming a solution of these components to obey Raoult’s law, the mole
fraction of component X in vapor phase in equilibrium with the solution containing equal amounts
of X and Y, at the same temperature, is - [NSEC 2015]
(A) 0.33 (B) 0.50 (C) 0.66 (D) 0.80
10. In cold climate, the water in a radiator of car gets frozen causing damage to the radiator. Ethylene
glycol is used as an antifreezing agent. The amount of ethylene glycol that should be added to 5
kg of water to prevent it from freezing at –7°C is: [NSEC 2016]
(Given: Kf for water = 1.86 k mol–1 kg; Molar mass of ethylene gycol = 62 g mol–1)
(A) 1165 g (B) 46.7 g (C) 116.7 g (D) 93.4 g


44 LIQUID SOLUTION
EXERCISE # 07 JEE (MAIN) CORNER

1. Density of a 2.05 M solution of acetic acid in water is 1.02 g/mL. The molality of the solution is
[2006]
(A) 3.28 mol Kg 1 (B) 2.28 mol Kg 1 (C) 0.44 mol Kg 1 (D) 1.14 mol Kg 1
2. A mixture of ethyl alcohol and propyl alcohol has a vapour pressure of 290 mm at 300 K. The
vapour pressure of propyl alcohol is 200 mm. If the mole fraction of ethyl alcohol is 0.6, its vapour
pressure (in mm) at the same temperature will be [2007]
(A) 700 (B) 360 (C) 350 (D) 300
3. A 5.25% solution of a substance is isotonic with a 1.5% solution of urea (molar mass = 60g mol-1)
-3
in the same solvent. If the densities of both the solutions are assumed to be equal to 1.0 g cm ,
molar mass of the substance will be [2007]
(A) 105.0 g mol-1 (B) 210.0 g mol-1 (C) 90.0 g mol-1 (D) 15.0 g mol-1
4. The vapour pressure of water at 20° C is 17.5 mm Hg. If 18g of glucose  C 6H12O 6  is added to
178.2 g of water at 20° C, the vapour pressure of the resulting solution will be [2008]
(A) 15.750 mm Hg (B) 16.500 mm Hg (C) 17.325 mm Hg (D) 17.675 mm Hg
5. At 80º C, the vapour pressure of pure liquid 'A' is 520 mm Hg and that of pure liquid 'B' is 1000
mm Hg. If a mixture solution of 'A' and 'B' boils at 80º C and 1 atm pressure, the amount of 'A' in
the mixture is (1atm = 760 mm Hg) [2008]
(A) 34 mol percent (B) 48 mol percent
(C) 50 mol percent (D) 52 mol percent
6. A binary liquid solution is prepared by mixing n-heptane and ethanol. Which one of the following
statement is correct regarding the behaviour of the solution? [2009]
(A) The solution is non-ideal, showing +ve deviation from Raoult’s Law.
(B) The solution in non-ideal, showing –ve deviation from Raoult’s Law.
(C) n-heptane shows +ve deviation while ethanol shows –ve deviation from Raoult’s Law.
(D) The solution formed is an ideal solution.
7. Two liquids X and Y form an ideal solution. At 300K, vapour pressure of the solution containing 1
mol of X and 3 mol of Y is 550 mmHg. At the same temperature, if 1 mol of Y is further added to
this solution, vapour pressure of the solution increases by 10 mmHg. Vapour pressure (in mmHg)
of X and Y in their pure states will be, respectively: [2009]
(A) 300 and 400 (B) 400 and 600 (C) 500 and 600 (D) 200 and 300
8. If sodium sulphate is considered to be completely dissociated into cations and anions in aqueous
solution, the change in freezing point of water  Tf  , when 0.01 mole of sodium sulphate is
dissolved in 1 kg of water, is (Kf = 1.86 K kg mol–1) [2010]

(A) 0.0372 K (B) 0.0558 K
(C) 0.0744 K (D) 0.0186 K

LIQUID SOLUTION 45
9. On mixing, heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two
liquid components (heptane and octane) are 105 kPa and 45 kPa respectively. Vapour pressure
of the solution obtained by mixing 25.0 g of heptane and 35 g of octane will be (molar mass of
heptane - 100 g mol–1 and of octane = 114 g mol–1) [2010]
(A) 72.0 kPa (B) 36.1 kPa (C) 96.2 kPa (D) 144.5 kPa
10. Ethylene glycol is used as an antifreeze in a cold climate. Mass of ethylene glycol which should
be added to 4 kg of water to prevent it from freezing at 6 C will be: [2011]
(A) 204.30g (B) 400.00 g (C) 304.60 g (D) 804.32 g
11. A 5.2 molal aqueous solution of methyl alcohol, CH3 OH , is supplied. What is the mole fraction of
methyl alcohol in the solution? [2011]
(A) 0.190 (B) 0.086 (C) 0.050 (D) 0.100
12. The density of a solution prepared by dissolving 120 g of urea (mol. Mass = 60 u) in 1000g of
water is 1.15 g/mL. The molarity of this solution is: [2012]
(A) 0.50 M (B) 1.78 M (C) 1.02 M (D) 2.05 M
13. Kf for water is 1.86K kgmol-1. If your automobile radiator holds 1.0 kg of water, how many grams
of ethylene glycol  C 2H6 O 2  must you add to get the freezing point of the solution lowered to
 2.8 C ? [2012]
(A) 72 g (B) 93g (C) 39g (D) 27 g
14. The molarity of a solution obtained by mixing 750 mL of 0.5 (M) HCl with 250 mL of 2 M  HCl will
be: [2013]
(A) 1.00 M (B) 1.75 M (C) 0.975 M (D) 0.875 M
15. 12 g of a nonvolatile solute dissolved in 180g of water produces the relative lowering of vaopour
pressure of 0.1. The molecular mass of the solute is:
[2013]
(A) 80 (B) 60 (C) 20 (D) 40
-1
16. The density of 3M solution of sodium chloride is 1.252 g mL . The molality of the solution will be:
[2013]
(A) 2.60 m (B) 2.18 m (C) 2.79 m (D) 3.00 m
17. Vapour pressure of pure benzene is 119 torr and that of toluene is 37.0 torr at the same
temperature. Mole fraction of toluene in vapour phase which is in equilibrium with a solution of
benzene and toluene having a mole fraction of toluene 0.50, will be [2013]
(A) 0.137 (B) 0.237 (C) 0.435 (D) 0.205
18. How many grams of methyl alcohol should be added to 10 litre tank of water t prevent its freezing
at 268 K? [2013]
(A) 880.07 g (B) 899.04 g (C) 886.02 g (D) 868.06 g

46 LIQUID SOLUTION
19. 10 mL of 2(M) NaOH solution is added to 200 mL of 0.5 (M) of NaOH solution. What is the final
concentration? [2013]
(A) 0.57 (M) (B) 5.7 (M) (C) 11.4 (M) (D) 1.14 (M)
20. Consider separate solutions of 0.500MC2H5 OH  aq  ,0.100MMg3 PO 4  2  aq  , 0.250MKBr  aq
and 0.125MNa3PO4  aq at 25 C. Which statement is true about these solutions, assuming all
salts to be strong electrolytes? [2014]
(A) 0.125MNa3PO4  aq has the highest osmotic pressure.
(B) 0.500MC2H5 OH  aq has the highest osmotic pressure.

(C) They all have the same osmotic pressure.
(D) 0.100MMg3  PO4 2  aq has the highest osmotic pressure.
21. The vapour pressure of acetone at20C is 185 torr. When 1.2g of a non-volatile substance was
dissolved in 100 g of acetone at 20C , its vapour pressure was 183 torr. The molar mass
 g mol  of the substance is :

1
[2015]
(A) 64 (B) 128 (C) 488 (D) 32
22. The freezing point of benzene decreases by 0.45C when 0.2 g of acetic acid is added to 20 g
of benzene. If acetic acid associates to form a dimer in benzene, percentage association of acetic
acid in benzene will be : [2017]
1
( K f for benzene  5.12 K kg mol )
(A) 80.4% (B) 74.6% (C) 94.6% (D) 64.6%



LIQUID SOLUTION 47
EXERCISE # 08 JEE (ADVANCED) CORNER

1. 75.2g phenol (C6H5OH) is mixed with 1.0 kg of solvent (Kf = 14 K mol–1 kg). Freezing point
depression of the solution was 7K. Calcualte % of phenol in dimmer form: [2006]
2. When 20 g of naphtholic acid (C11H8O2) is dissolved in 50 g of benzene (Kf = 1.72 K kg mol–1),
a freezing point depression of 2 K is observed. The van’t Hoff factor (i) is [2007]
(A) 0.5 (B) 1 (C) 2 (D) 3
Paragraph for Question No. Q.3 to Q.5
Properties such as boiling point, freezing point and vapour pressure of a pure solvent change
when solute molecules are added to get homogeneous solution. These are called colligative
properties. Applications of colligative properties are very useful in day-to-day life. One of its
examples is the use of ethylene glycol and water mixture as anti-freezing liquid in the radiator of
automobiles.
A solution M is prepared by mixing ethanol and water. The mole fraction of ethanol in the mixture
is 0.9.
Given : Freezing point depression constant of water = 1.86 K kg mol–1
Freezing point depression constant of ethanol = 2.0 K kg mol–1
Boiling point elevation constant of water = 0.52 K kg mol–1
Boiling point elevation constant of ethanol = 1.2 K kg mol–1
Standard freezing point of water = 273 K
Standard freezing point of ethanol = 155.7 K
Standard boiling point of water = 373 K
Standard boiling point of ethanol = 351.5 K
Vapour pressure of pure water = 32.8 mm Hg
Vapour pressure of pure ethanol = 40 mm Hg
Molecular weight of water = 18 g mol–1
Molecular weight of ethanol = 46 g mol–1
In answering the following questions, consider the solutions to be ideal dilute solutions and
solutes to be non-volatile and non-dissociative.
3. The freezing point of the solution M is [2008]

(A) 268.7 K (B) 268.5 K (C) 234.2 K (D) 150.9 K
4. The vapour pressure of the solution M is [2008]

(A) 39.3 mm Hg (B) 36.0 mm Hg (C) 29.5 mm Hg (D) 28.8 mm Hg
5. Water is added to the solution M such that the mole fraction of water in the solution becomes 0.9.
The boiling point of this solution is [2008]
(A) 380.4 K (B) 376.2 K (C) 375.5 K (D) 354.7 K

48 LIQUID SOLUTION
6. The Henry’s law constant for the solubility of N2 gas in water at 298 K is 1.0 × 105 atm. The mole
fraction of N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water at
298 K and 5 atm pressure is [2009]
(A) 4.0 × 10–4 (B) 4.0 × 10–5 (C) 5.0 × 10–4 (D) 4.0 × 10–5
7. Dissolving 120g of urea (mol. wt. 60) in 1000 g of water gave a solution of density 1.15 g/mL. The
molarity of the solution is [2011]
(A) 1.78 M (B) 2.00 M (C) 2.05 M (D) 2.22 M
8. The freezing point (in °C) of a solution containing 0.1 g of K 3 Fe  CN 6  (Mol. Wt. 329) in 100 g

of water K f  1.86K kgmol1 is  [2011]
(A) 2.3  10 2 (B) 5.7  10 2 (C) 5.7  10 3 (D) 1.2  10 2
9. 29.2% (w/w) HCl stock solution has a density of 1.25 g mL-1. The molecular weight of HCl is 36.5
g mol-1. The volume (mL) of stock solution required to prepare a 200 mL solution of 0.4 M HCl is.
[2012]
10. For a dilute solution containing 2.5 g of a non – volatile non – electrolyte solute in 100 g of water,
the elevation in boiling point at 1 atm pressure is 2°C. Assuming concentration of solute is much
lower than the concentration of solvent, the vapour pressure (mm of Hg) of the solution is (take
K b = 0.76 K kg mol-1) [2012]
(A) 724 (B) 740 (C) 736 (D) 718
11. Benzene and naphthalene form an ideal solution at room temperature. For this process the true
statement(s) is (are) [2013]
(A) Gispositive (B) S system ispositive
(C) S surrounding  0 (D) H  0
12. MX2 dissociates in M2  and X  ions in an aqueous solution, with a degree of dissociation    of
0.5. The ratio of the observed depression of freezing point of the aqueous solution to the value of
the depression of freeqing point in the absence of ionic dissociation is - [2014]
13. If the freezing point of a 0.01 molal aqueous solution of a cobalt (III) chloride-ammonia
complex(which behaves as a strong electrolyte) is – 0.05580C, the number of chloride(s) in the
coordination sphere of the complex is
K f of water  1.86K kgmol 1  [2015]
14. The mole fraction of a solute in a solution is 0.1. At 298 K, molarity of this solution is the same as
its molality. Density of this solution at 298 K is 2.0 gcm 3 . The ratio of the molecular weights of
 MWsolute 
the solute and solvent,   , is - [2016]
 MWsolute 

LIQUID SOLUTION 49
15. Mixture (s) showing positive deviation from Raoult’s law at 35 C is (are) - [2016]
(A) Carbon tetrachloride + methanol (B) Carbon disulphide + acetone
(C) Benzene + toluene (D) phenol + aniline
16. For a solution formed by mixing liquids L and M, the vapour pressure of L plotted against the
mole fraction of M in solution is shown in the following figure. Here  L and  M represent mole
fractions of L and M, respectively, in the solution. The correct statement(s) applicable to this
system is(are) : [2017]
(A) The point Z represent vapour pressure of pure liquid M and Raoult’s law is obeyed when
L  0
(B) Attractive intermolecular interactions between L-L in pure liquid L and M-M in pure liquid M
are stronger than those between L-M when mixed in solution.
(C) The point Z represents vapour pressure of pure liquid L and Raoult’s law is obeye L  1
(D) The point Z represents vapour pressure of pure liquid M and Raoult’s law is obe L  0
and  L  1
17. Pure water freezes at 273 K and 1 bar. The addition of 34.5 g of ethanol to 500 g of water
changes the freezing point of the solution. Use the freezing point depression constant of water as
2 K kg mol 1. The figures shown below represent plots of vapour pressure (V.P.) versus
1
temperature (T). [molecular weight of ethanol is 46 g mol ] Among the following, the option
representing change in the freezing point is : [2017]
(A) (B)
(C) (D)


50 LIQUID SOLUTION
ANSWER KEYS
1 2 3 4 5 6 7 8 9 10
D C A B C D B B B C
11 12 13 14 15 16 17 18 19 20
(i) A, (ii)
A A C B C D D B C
D
21 22 23 24 25 26 27 28 29 30
B B C C B D B C D A
31 32 33 34 35 36 37 38 39 40
C A A A A B D B C A
41 42 43 44 45 46 47 48 49 50
D A A C B D D C C C
51
C
1 2 3 4 5 6 7 8 9 10
C C C B D B B C B C
11 12 13 14 15 16 17 18 19 20
A C D B D C D D C D
21 22 23 24 25 26 27
D A C B B B A
1 2 3 4 5 6 7 8 9 10
B D A A D A B C B C
11 12 13 14 15 16 17 18 19 20
D D A B C D A D D BC
21 22 23 24 25 26 27 28 29 30
AC AD AC BCD ABC ABCD ACD BD ACD ABC
31 32 33
CD CD (a)-(v), (b)-(iv), (c) -(i), (d)-(iii), (e)-(ii)

LIQUID SOLUTION 51
34 35
(a)-(ii), (b)-(i), (c)-(iv), (d)-(iii) (a)-(v), (b)-(iv), (c)-(ii), (d)-(iii), (e)-(i)
36 37
[A (P) ; B(R) ; CQD(R,S)] [A (Q) ; B(P) ; C R,SD (P)]
38 39
[(A)  Q; (B)  R; (C)  S; (D)  P] [(A)  Q; (B)  P; (C) R,S ; (D)  R,S]
40 41
[(A)R, S; (B)  R; (C)  P; (D)  Q] (A)R, S; (B)P,Q; (C) R,S; (D)P,Q
42 43 44 45 46 47 48 49 50 51
56 353 2726 3 3 5 4 3 2 4
52 53 54 55
4 4 7 4
Q.1 0.24 Q.2 0.25 Q.3 24.5 torr Q.4 57.24 g/mol
Q.5 66.13 mm Hg Q.6 0.682, 0.318; 0.829, 0.171
Q.7 PA = 213.33 torr, PB = 960.0 torr
Q.8 0.04 Q.9 111.1g, 18.52 molal Q.10 0.741 m, 0.013
Q.11 0.162 m Q.12 65.25 Q.13 17.38 Q.14 0.964
Q.15 106 g/mol Q.16 100.079°C
Q.17 5.08°C/m Q.18 2050 g/mol Q.19 x = 25.6, y = 42.6
Q.20 Kb= 0.512 kg mol K–1, Tb = 373.20 K Q.21 156.06
Q.22 C6H6 Q.23 Tf = –2.28oC Q.24 P = 0.2217 atm should be applied
Q.25 (Vfinal = 5.Voriginal) Q.26 54.2 g Q.27 0.81 atm
Q.28 5.4 × 105 g/mol Q.29 59.99
Q.30 MA/MB = 0.33 Q.31 i = 2.5 Q.32 3 ions
Q.33 4.64 atm Q.34 0.95; 1.95

52 LIQUID SOLUTION

Q.1 C44H88O44 Q.2 746.24 mm/Hg
Q.3 (a) 3.79°C, (b) 0.018, (c) 4.65 atm, (d) 251.5 Q.4 (a) 210.65, (b) 62.35%
Q.5 18.34% Q.6 Tb = 102.3oC Q.7 Tf = -0.73oC
Q.8 [Co(NH3)5Cl]Cl2 Q.9 0.73
Q.10 XB = 0.2472, YB = 0.4473 Q.11 46.33°C
Q.12 XA" = 0.1 Q.13 a = 0.7333 Q.14 –19.91°C, 7.63 M
Q.15 M = 53.8 Q.16 0.93 Q.17 20.11 %
Q.18 Hv at 80 K is 1659.1 calorie; Hv = R [2.303 × 313.7 + 1.40655T
Q.19 5.4 × 10–13 Q.20 8.9 gm Q.21 12.54 Q.22 12.72
Q.23 K = 3.36
Q.24 (a) 0.47, (b) 565 torr, (c) XA=0.08, XB= 0.92, (d) 675 torr, (e) X'A= 0.11, X'B= 0.89
Q.25 (i) Ka = 7.3 × 10–3 (ii) 4.55 × 1022
1 2 3 4 5 6 7 8 9 10
A C D B D A A B C A
1 2 3 4 5 6 7 8 9 10
B C B C C A B B A D
11 12 13 14 15 16 17 18 19 20
B D B D C C B D A C
21 22
A C

LIQUID SOLUTION 53
1 2 3 4 5 6 7 8 9 10
74 % A D B B A C A 8 A
11 12 13 14 15 16 17
BCD 2 1 9 AB BC C

SOLID STATE
INDEX
 CONCEPTS IN BRIEF 55 – 67
 SOLVED EXAMPLES 68 – 70
 EXERCISE # 01 OBJECTIVE EXERCISE (LEVEL # 01) 71 – 76
 EXERCISE # 04 SUBJECTIVE EXERCISE (LEVEL # 01) 87 – 88
 EXERCISE # 05 SUBJECTIVE EXERCISE (LEVEL # 02) 89 – 92
 EXERCISE # 06 KVPY, OLYMPIADS QUESTIONS 93 – 94
 EXERCISE # 07 JEE (MAIN) CORNER 95 – 96
 EXERCISE # 08 JEE (ADVANCED) CORNER 97 – 99
 ANSWER KEYS 100 – 102
WEIGHTAGE OF ‘SOLID STATE’ IN JEE (MAIN & ADVANCED) in Las Three Years
JEE (MAIN) Formely known as AIEEE
MARK /
YEAR No. Of Qs.
2015 1 4/120
2016 1 4/120
2017 1 4/120
JEE (ADVANCED)
YEAR No. Of Qs. MARK /

2015 1 4/168
2016 1 4/124
2017 1 3/122
SOLID STATE 55
SOLID STATE
CRYSTALLINE SOLIDS
Crystalline solids are those whose atom, molecules or ions have an ordered arrangement
extending over a Long Range. example-(Rock salt, NaCl).
AMORPHOUS SOLIDS
Amorphous solids are those whose constitutent particles are randomly arrange and have no
ordered long range structure. example: Rubber, Glass ect.
Crystalline solid Amorphous solid

1 The constituent particles are arranged in a 1 The constituent particles are not
regular fashion containing short range as arranged in any regular fashion. There
well as long range order. may be at the most some short range
order only.
2 They have sharp melting point 2 They melt over a range of temperature.
3 They are anisotropic i.e., properties like 3 They are isotropic i.e., properties like
electrical conductivity, thermal expansion, electrical conductivity, thermal
etc have different values is different expansion, etc have same value in
direction. different directions
4 They undergo a sharp cleavage. 4 They undergo an irregular cut
Temperature 
Temperature
a
b
Time  Times 
Crystalline substances Amorphous substances
Cooling Curve. (figure 1a) (cooling curve)
(figure 1b)
TYPES OF CRYSTALLINE SOLIDS
Type of Solid Intermolecular forces Properties Examples

Ionic Ion-Ion forces Brittle, hard high Melting NaCl, KCl, MgCl2
Dispersion
Soft, low melting non-
Molecular forces/Dipole-Dipole H2O, Br2, CO2, CH4
conducting
/H-bond
Covalent
Covalent bonds Hard: High melting C-Diamond SiO2
network
Variable hardness and melting
Metallic Metallic bonds Na, Zn, Cu, Fe
point conducting

56 SOLID STATE
TYPES OF UNIT CELL
Collection of lattice points, whose repetition produce whole lattice is called a unit cell. The whole
lattice can be considered to be made by repetition of unit cell.
1. Unit Cell:
Crystal System Bravais Lattices Parameters of Unit Cell

Intercepts Crystal angle Example
1. Cubic Primitive, Face Pb, Hg, Ag, Au
Centered, Body a=b=c  =  =  = 90o Diamond, NaCl, ZnS
Centered = 3
2. Orthorhombic Primitive, Face KNO2, K2SO4
Centered, Body
abc  =  =  = 90o
Centered, End
Centered = 4
3. Tetragonal Primitive, Body TiO2, SnO2
a=bc  =  =  = 90o
Centered =2
4. Monoclinic Primitive, End  =  = 90o, CaSO4, 2H2O
abc
Centered = 2   90o
5. Triclinic Primitive = 1 K2Cr2O7,
abc       900
CaSO45H2O
6. Hexagonal Primitive = 1 a=bc  =  = 900,  = 120o Mg, SiO2, Zn, Cd
7. Rhombohedral Primitive = 1 a=b=c  =  =   90o,   90o As, Sb, Bi, CaCO3
Total = 14

SOLID STATE 57
1.1 Primitive or simple cubic (PS/SC) unit cell: Spheres in

one layer sitting directly on top of those in previous layer, so
that all layers are identical. Each sphere is touched by six
other, hence coordination number is 6. 52% of available
space occupied by spheres.
Example: Polonium crystallises in simple cubic arrangement.
Z = 1 ; C.N. = 6
1.2 Body Centered cubic (BCC) unit cell: Spheres in one layer sit in the depression made
by first layer in a-b-a-b manner. Coordination number is 8, and 68% of available space is
occupied by atoms.
Example: Iron, sodium and 14 other metal crystallises in this manner.
Z = 2 ; C.N. = 8
1.3 Face centered cubic (FCC) unit cell:

Examples : Al, Ni, Fe, Pd all solid noble gases etc.
Z = 4 ; C.N. = 12
BRAVAIS LATTICES (Packing Fraction)
It is defined as ratio of the volume occupied by the spheres in a unit cell to the volume of the unit cell.
Pracking Fraction  Volume Occupied by Atoms Per Unit Cell / Volume of Unit Cell
Void fraction is given as = (1 – Packing fraction).
(1) Primitive Cubic Unit Cell:

Four atoms are present in such a way that the adjacent atoms touch each other.
Therefore, if the length of the unit cell is 'a', then it is equal to 2r, where r is the radius of the
sphere.
4 3 r r
r
Therefore, PF = 3 3  0.52 .
(2r )
(This implies that 52 % of the volume of a unit cell is occupied by
spheres).
 VF  0.48 a

58 SOLID STATE
(2) Body Centered Cubic Unit Cell:
In BCC the body centered atom touches the top four and the bottom four atoms, the length of the
body diagonal ( 3 a ) is equal to 4r.
4
2  r 3
The packing fraction in this case is = 3  0.68 VF  0.32
4r 3
( )
3
B
r
a
2r
a r
Body Centered Cubic unit cell C
a
(3) Face Centered Cubic Unit Cell:
Here each face centered atom touches the A

four corner atoms, the face diagonal of the
cube ( 2a ) is equal to 4r.
C
a
C
a  
4r B B
CUBIC CLOSE PACKING (CCP)

 FACE-CENTRED CUBIC (FCC)
4
4  r3
packing fraction  3  0.74
4r 3
( )
2
VF  0.26

SOLID STATE 59
(4) Hexagonal Primitive Unit Cell:
Each corner atom would be common to 6 other unit cells, therefore their contribution to one unit
cell would be 1/6. Therefore, the total number of atoms present per unit cell effectively is 6.
F
D
C
a h/2
a
E G
A B
r
A a/ 3 E
Figure
A
ABCD is the base of hexagonal unit cell AD=AB=a. The
A
sphere in the next layer has its centre F vertically above E it
touches the three spheres whose centres are A,B and D.
2
2 3 a 2r h  2r  B 
 AE   a  Hence FE = = (2r )2    B
3 2 3 3 2  3
2 A
 The height of unit cell (h) = 4r A
3
The area of the base is equal to the area of six equilateral
3 HEXAGONAL CLOSE PACKING (HCP)
triangles, = 6  (2r )2 .
4
3 2
The volume of the unit cell = 6  (2r )2  4r .
4 3
4
6 π r 3
Therefore, PF = 3  0.74 ;  VF  0.26
3 2
6 (2r )2  4r
4 3
DENSITY OF CRYSTAL LATTICE
The density of crystal lattice is same as the density of the unit cell which is calculated as
mass of unit cell number of effective atoms  mass number
= =
volume of unit cell volume of unit cell  Avogadro number
n M
=
NA  V
TYPES OF PACKING:
Closest packing of atoms: This is the most efficient way of packing 74% of available space is
occupied by spheres and coordination number is 12.
(i) Hexagonal close pack (A-B-A-B) type packing : Each layer has hexagonal arrangement of
touching sphere and 3rd layer is similar (exactly on top) of first layer.

60 SOLID STATE
(ii) Cubic close pack (A-B-C-A-B-C): AB layers are similar to HCP arrangement but third layer is
offset from both A and B layers. The fourth layer is exactly on top of first layer.
Hexagonal primitive unit cell
TYPES OF VOIDS:
Tetrahedral void
No. of Tetrahedral Void = 2  Effective no. of atoms in unit cell

Coordination No. = 4

SOLID STATE 61
Octahedral void
No. of Octahedral Void = Effective no. of atoms in unit cell

Coordination No. = 6
RADIUS RATIO:
Strcuture of compounds containing two different types of atoms.
The bigger atom or ion will form the lattice & smaller atom / ion will occupy the voids.
Generally, bigger ion is anion and smaller ion is cation.The type of void occupies by the cation is
decided by radius ratio.
r 
Radius ratio     , this gives the idea about the type of void occupied.
 r 
(i) Radius ratio for co-ordination number 3

2 r 2  3
(Triangular Arrangement): r+ + r – = 3 r– ; = = 0.155
3 r 3
(ii) Radius ratio for coordination number 4

(Tetrahedral arrangement):
3a 3 –
r+ + r – = ; 4r– = 2a= r
4 2
r 3 2
= = 0.225
r 2

62 SOLID STATE
(iii) Radius ratio for coordination number 6: (Octahedral Arrangement)

or Radius ratio for coordination number 4
(Square plannar arrangement)
r
r+ + r – = 2 r– = 2 –1 = 0.414
r
(iv) Radius ratio for coordination number 8 : (Body centered cubic crystal)
3
r+ + r – = a
2
r+ + r – = 3 r–
r
= 3 –1 = 0.732
r
r
Limiting radius ratio x Co – ordination
r Shape Example
number
x < 0.155 2 Linear BeF2

0.155  x  0.225 3 Planar Triangle AlCl3
0.225  x  0.414 4 Tetrahedron ZnS
0.414  x  0.732 4 Square planar PtCl42-
0.414  x  0.732 6 Octahedron NaCl
0.732  x  0.999 8 Body centered cubic CsCl
EFFECT OF PRESSURE AND TEMPERATURE COORDINATION NUMBER OF

COMPOUND :
On increasing pressure  C.N. tends to increase

On increasing temperature  C.N. tends to decrease
e.g.
P 
4 : 4  6 : 6
T 
8 : 8  6 : 6

SOLID STATE 63
TYPES OF IONIC STRUCTURES:
1 Rock salt structure (AB type) or 6 : 6 CN Compound :

(NaCl) Larger atom formic ccp arrangement and smaller atom filling all
octahedral voids.
2 Zinc blende (sphalerite) structure (AB type) or 4 : 4 Coordination

Compound :
(ZnS) Larger atom formic ccp arrangement and smaller atom filling half of
alternate tetrahedral voids
3 Fluorite structure (AB2 Type) or 8 : 4 CN Compound : (CaF2) Ca2+
forming ccp arrangement and F– filling all tetrahedral voids.
4 Antifluorite structure (A2B Type) or 4 : 8 CN Compound :

(Li2O) O2– ion forming ccp and Li+ taking all tetrahedral voids.
5 Cesium halide structure (AB Type) or 8 : 8 CN Compound : (CsCl) Cl–

at the corners of cube and Cs+ in the center.
6 Corundum Structure: (Al2O3) O2– forming hcp and Al3+ filling 2/3
octahedral voids.
7 Rutile structure: (TiO2) O2– forming hcp while Ti4+ ions occupy half of the octahedral voids.
8 Pervoskite structure:(CaTiO3) Ca2+ in the corner of
cube O2– at the face center and Ti4+ at the centre of cube.
9 Spinel and inverse spinel structure: (MgAl2O4) O2– forming fcc, Mg2+ filling 1/8 of tetrahedral
voids and Al3+ taking half of octahedral voids.In an inverse spinel structure, O2– ion form FCC
lattice, divalent cation ions occupy 1/8 of the tetrahedral voids and trivalent cation occupies 1/8 of
the tetrahedral voids and 1/4 of the octahedral voids.

64 SOLID STATE
CRYSTAL DEFECTS:
Point defects: When ions or atoms do not hold the theoretical position, this is called point defect.
Point defects are of two types:
(I) Stoichiometric defects:

(a) Schottky defect: Due to missing of ions from lattice point in pairs results to decrease density.
+ –
Na missing Cl missing
(b) Frenkel defect: It is caused due to the creation of lattice vacancy as a result of
misplaced ion in interstitial site.
Ag+ Br– Ag+ Br– Ag+ Br– Ag+ Br– Ag+

Br– Ag+ Br– Ag+ Br– Ag+ Br– Ag+ Br–
Ag+
Ag+ Br– Br– Ag+ Br– Ag+ Br– Ag+
Br– Ag+ Br– Ag+ Br– Ag+ Br– Ag+ Br–
Figure : Frenkel Defects in a Crystal
o Schottky defect common in ionic solid with high coordination number. NaCl, KCl, KBr
o Frenkel defect :- Solid with low coordination number ZnS, AgBr.
(II) Non-Stoichiometric defects: Ratio of positive and negative ion differ from that indicated by
chemical formula.
o Metal-excess defect :
(a) A negative ion replaced by electron. (F-centre)
Na+ Cl
–
–
e
F Centre
F-centre in a Sodium chloride crystal

Figure

SOLID STATE 65
(b) Extra metal ion present in lattice and electron also present in interstitial site.
Examples include ZnO, CdO, Fe2O3.
A+ B– A+ B– A+
+
A
– + –
B A B A+ B–
e–
A+ B– A+ B
–
A+
+
B– A B– A
+
B–
+ – + – +
A B A B A
Figure : Metal excess defects caused by interstitial cations.
o Metal-deficiency defect : caused by Cation missing from lattice point, electroneutrality

maintained by metal ions with higher oxidation state as Fe0.94O.
Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2–
O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+
Fe2+ O2– Fe2+ O2– Fe2+ O2– O2– Fe2+ O2–
O2– Fe2+ O2– Fe2+ O2– Fe+3 O2– Fe+3 O2– Fe2+
Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2–
Figure
(III) Impurity defects:

Adding impurities to crystalline solids to change their properties is called doping.
(a) In ionic solids, e.g., SrCl 2 into NaCl so that 2Na are replaced by one Sr 2  producing one
cation vacancy.
Na  Cl  Na  Cl 
Cl  Sr 2  Cl 
Na  Cl  Na  Cl 
Cl  Na  Cl  Na 

66 SOLID STATE
(b) In covalent solids:

– By doping with electron rich impurities, e.g., group 14 elements like Si or Ge
with group 15 element like P, As etc. Free electrons become available which
increase conductivity. Such solids are called n–type semiconductors.
– By doping with electron deficit impurities, e.g., group 14 elements like Si or

Ge with group 13 elements like B, Al or Ga. As a result, holes are created.
Electrons move to occupy the holes. Thus, holes move towards negatively
charged plate as if they carry positive charge. These are called p–type
semiconductors.
1. Conductivities of conductors, insulators and semiconductors, Conductors ~ 107 ohm 1m 1 ,

insulators = 10 20  1010 ohm 1m 1 , Semiconductors = 106  104 ohm 1m1 .
2. Band Theory. Atomic orbitals of metal atoms overlap to form molecular orbitals (M.O’s). The
lower half may be filled and the upper half may be empty or partially filled, two sets of molecular
orbitals may be formed, the filled m.o.s. with lower energy from valence band and empty or
partially filled M.O’s with higher energy form conduction band.
3. Distinction between metals, insulators and semiconductors on the basis of band theory.
Metals have either only valence band, lower half filled and the upper half empty or there is a
partial overlap between filled valence band and empty conduction band. Insulators have large
energy gap between valence band and conduction band. Semiconductors have a small energy
gap between valence band and conduction band.
4. Classification of substances on the basis of magnetic properties
(i) Diamagnetic – Those which are weakly repelled by the external magnetic field, e.g.,
TiO2 , H2O, NaCl , benzene etc. Thery contain fully filled orbitals and hence zero magnetic
moment.
(ii) Paramagnetic – Those which are attracted by the external magnetic field, e.g.,
O2,Cu 2 , Fe3  ,Cr 3 etc. Their atoms, ions or molecules contain unpaired electrons and
hence a net magnetic moment. They lose their magnetism in the absence of magnetic
field.
(iii) Ferromagnetic – Those which show permanent magnetism even in the absence of
magnetic field, e.g., Fe, Ni ,Co,Gd ,CrO2 etc. This is because when placed in magnetic
field, their unpaired electrons (or magnetic domains) get permanently oriented in one
direction.
(iv) Anti – ferromagnetic – Those which are expected to possess paramagnetism or

ferromagnetism but actually have zero net magnetic moment, e.g., MnO. This is because
of equal number of domains in opposite direction.

SOLID STATE 67
(v) Ferrimagnetic – Those expected to have large magnetism but actually have small net
magnetic moment, e.g., magnetite  Fe3O4  , ferrites ( M 2 Fe2O4 , where M = Mg, Cu, Zn
etc). This is because of unequal number of domains in opposite direction.
NOTE –
All magnetic ordered solids change into paramagnetic at high temperature.
Above curie temperature each ferromagnetic substance shows no ferromagnetism.
DIELECTIC PROPERTIES OF SOLIDS:
Insulators do no conduct electricity because the electrons present in them are held tightly by the
nuclei. However, when electric field is applied, polarization takes place because nuclei are
attracted to one side and the electron cloud to the other side. Thus, dipoles are formed. Such
polar crystals show the following properties:
(i) Piezoelectricity.
When mechanical stress is applied on such crystals electricity is produced due to
displacement of ions. The electricity thus produced is called piezoelectricity and the
crystals are called piezoelectric crystals, e.g., titanates of barium and lead, lead zirconate
 PbZrO3  , ammonium dihydrogen phosphate  NH4H2PO4  and quartz.
(ii) Pyroelectricity.
Some piezoelectric crystals when heated produce a small electric current. The electricity
thus produced is called pyroelectricity (pyre means heat).
(iii) Ferroelectricity.
In some of the piezoelectric crystals, the dipoles are permanently polarized even in the
absence of the electric field. However, on applying electric field, the direction of
polarization changes. This phenomenon is called ferroelectricity due to analogy with
ferromagnetism. Some examples of the ferroelectric solids are barium titanate  BaTiO3  ,
sodium potassium tartarate (Rochelle salt) and potassium dihydrogen
phosphate  KH2PO4  . It may be pointed out here that all ferroelectric solids are
piezoelectric but the reverse is not true.
(iv) Anti–ferroelectricity.
In some crystals, the dipoles align themselves in such a way that alternatively, they point
up and down so that the crystal does not possess any net dipole moment. Such crystals
are said to be anti – ferroelectric. A typical example of such crystals is lead
zirconate  PbZrO3  .



68 SOLID STATE
SOLVED EXAMPLES
1. Copper has the fcc crystal structure. Assuming an atomic radius of 130pm for copper
atom (Cu = 63.54):
(a) What is the length of unit cell of Cu?
(b) What is the volume of the unit cell?
(c) How many atoms belong to the unit cell
(d) Find the density of Cu.
n  Mm
Sol: As we know   ,
NA  a3
a) for fcc structure 4r  2 a a2 2 r  2 2  130pm  367.64pm
n  Mm 4  63.54
b) volume of unit cell  a3    4.94  1023 cm3
Na   6.023  1023  8.54
c) n4
4  63.54
d)   8.54 gm / cm3
6.023  10  (3.67  108 cm3 )3
23
2. A metal crystallizes in two cubic phases, face centered cubic (fcc) and body centered
cubic bcc whose unit cell length are 3.5 and 3.0 A° respectively. Calculate the ratio of
density of fcc and bcc.
n  Mm
Sol: 
NA  a3
4  Mm
For face center cubic (fcc) n  4, a  3.5A   fcc   --------------- (I)
NA  (3.5)3
2  Mm
For bcc lattice N  2, a  3.0 A bcc  ---------------- (ii)
NA  (3.0)3
( fcc ) 4 33 4333
From equation (i) equation (ii)      1.259
(bcc ) 2 (3.5)3 2  3.5  3.5  3.5
3. A compound formed by elements X & Y, Crystallizes in the cubic structure, where X is at

the corners of the cube and Y is at the six face centers. What is the formula of the
compound? If side length is 5A°, estimate the density of the solid assuming atomic weight
of of X and Y as 60 and 90 respectively.
Sol: From eight corner atoms one atoms (X) contributes to one unit cell.
From six face centres, three atoms (Y) contributes to one unit cell.
So, the formula of the compound is XY3 .
n  Mm
As we know that,  , here n  1
NA  a3

Molar mass of XY3 Mm  60  3  90  330 gm, a  5A  5  10 8 cm
1 330 330
 23 8 3
  4.38 gm / cm3
6.023  10  (5  10 ) 6.023  10  125  10 24
23

SOLID STATE 69
4. Calculate the atomic volume of an element whose atoms have a radius 1.414A° when
atoms are cubic closed structure. What is the length of an edge of the unit cell?
Sol: Since atoms are cubic closed structures i.e., for fcc structure.
 4r = 2a Given r  1.414 A r  2 A 4  2 A  2 a
 a  4 A  4  10 8 cm  4A
3
Since volume of a unit cell  a3  4  10 8    64  1024  6.4  1023
Since one unit cell contains 4 atoms i.e.,  4 atoms corresponds to volume 6.4  10  23 cm 3
64 –23 3
 1– atom corresponds to volume  10 23 cm3  1.6  10 cm
4
5. Prove that void space in fluorite structure per unit volume of unit cell is 0.251.
Sol: Cations form cubical closest packing and anions occupying the tetrahedral holes.
There are 4 cations per unit cell. There are 8 anions per unit cell.
Here, face diagonal. 4r+ = 2a
where, r+= radius of cation  a = 2 2r+  a = (2 2 r+)3
3
Volume of unit cell = 16 2r3
Fraction of volume occupied per unit voume of unit cell
4  4 
4   πr3   8   πr_3 
 3   3  = π   2r3  
i.e. Packing fraction = 3 1   3  
16 2r 3 2   r  
Here in fluorite structure, for tetrahedral hole
radius of anion r π
radius of cation
=   0.225
r
PF =
3 2
1  2(0.225)  = 0.7577
3
 void space = 1 – 0.7577 VF = 0.2422/unit volume of the unit cell

6. 5.35 g of a salt ACl (of weak base AOH) is dissolved in 250 ml of solution. The pH of the
resultant solution was found to be 4.827. Find the ionic radius of A+ and Cl– if ACl forms
CsCl type crystal having 2.2 g/cm3.
r
5 
Given K b  AOH  1.8  10 r = 0.732 for this cell unit
Sol: ACl(s)  A+(aq) + Cl–(aq) A+(aq) + H2O AOH(aq) + H+(aq)

at equilibrium C(1–) C C
Kw Kw  C
For salts of weak base and strong acid  = H+ = C =
K bc Kb
1 10 4 5.35  1000 ZM
antilog (–4.827) =  M = 53.5 For CsCl type structure  = 3
1.8  10 5
M  250 a  6.0923  1023
1/ 3
 1  53.5  3
a=  23 
= 3.43Å rA  rCl =  a = 0.866 a = 0.866  3.43 Å = 2.97 Å
 2.2  6.023  10  2
ro
 A
= 0.732 on solving rA = 1.255 Å rCl = 1.715 Å
rCl

70 SOLID STATE
7. In a fcc arrangement of A & B atoms, where A atoms are at the Corners of the unit cell, B
atoms at the face centers, two atoms are missing from two corners in each unit cell, then
what will be the simplest formula of the compound?
Sol: Since there are six atoms (A) in the corner of the unit cell. So, contribution of atoms in 1 unit cell
6
is . Since 3 face-centered atoms (B) contributes to one unit cell
8
So, formula is A 6/8 B 3 or A 6 B 24, or A B 4
8. Xenon crystallizes in face centre cubic lattice and the edge of the unit cell is 620 pm, what
is the radius of xenon-atom?
Sol: For fcc lattice
4r  2 a, where a = 620 pm
1 1
or, r  a   620 pm  219.20 pm
2 2 2 2
9. In closest packing of A type of atoms (radius, rA), what is the radius of atom B that can be
fitted into Octahedral void?
rB
Sol: For octahedral void  0.414 or, rB  0.414rA
rA
10. Ferrous oxide (FeO) is experimentally found to have the formula Fe0.93O. Find the
percentage of Fe ions in +3 state.
Sol:
Fe0.93O
Some Fe atom Some Fe atom

are in +2 state are in +3 state
Let there is xFe atom in +3 state
3x  2  93  x   200
x  14
14 1400
% Fe3    100%  %  15.54%
93 93


SOLID STATE 71

CRYSTAL SYSTEM
1. Which of the following is correct

Crystal system Axial distance Axial angles Examples
o Cu, KCl
(A) Cubic a b=c  =    = 90
o
(B) Monoclinic a b=c  =  =  = 90 PbCrO2, PbCrO4
o
(C) Rhombohedral a=b=c  =  =   90 CaCO3, HgS
o
(D) Triclinic a=b=c    =   90 K2Cr2O7, CuSO4. 5H2O
2. Which has no rotation of symmetry

(A) Hexagonal (B) Orthorhombic (C) Cubic (D) Triclinic
3. Which of the following molecules has three-fold axis of symmetry

(A) NH3 (B) C2 H 4 (C) CO2 (D) SO2
4. A crystal may have one or more planes and one or more axes of symmetry but it possesses -
(A) Two centres of symmetry (B) One centre of symmetry
(C) No centre of symmetry (D) None of these
5. The shaded plane abcd is referred to as –

Z
b
a
c Y
d
X
(A) Rectangular plane of symmetry (B) Diagonal plane of symmetry
(C) Unit plane (D) None of these
6. A certain metal crystallises in a simple cubic structure. At a certain temperature, it arranges to

give a body centred structure. In this transition, the density of the metal-
(A) Decreases (B) Increases
(C) Remain unchanged (D) Changes without a definite pattern
DENSITY
7. In orthorhombic, the value of a, b and c are respectively 4.2Å,8.6Å and 8.3Å . given the
molecular mass of the solute is 155 gm mol 1 and that of density is 3.3 gm / cc , the number of
formula units per unit cell is
(A) 2 (B) 3 (C) 4 (D) 6

72 SOLID STATE
8. Ferrous oxide has a cubic structure and each edge of the unit cell is 5.0 Å. Assuming density of
the oxide as 4.0g  cm3 , then the number of Fe 2  and O 2  ions present in each unit cell will be
(A) Four Fe 2  and four O 2  (B) Two Fe 2  and four O 2 
(C) Four Fe 2  and two O 2  (D) Three Fe 2  and three O 2 
9. X-ray analysis Mn–Si alloy with 75% by atoms of Mn and 25% by atoms of Si, showed that the unit
cell is cubic and lattice parameter is 2.86 Å. The density of alloy = 6850 kg/m3. How many number
of atoms are present in the unit cell ?
Mn : 55 and Si : 28
(A) 2 (B) 4 (C) 6 (D) 8
10. ‘C’ represent the height of the HCP unit cell and ‘a’ represent edge length of the hexagonal
surface of the HCP unit cell. What is the value of C/a?
2 8 32 3
(A) (B) (C) (D)
3 3 3 2
TYPES OF CELL
11. The intermetallic compound LiAg crystallizes in cubic lattice in which both lithium and silver have
coordination number of eight. The crystal class is
(A) Simple cube (B) Body-centred cube
(C) Face-centred cube (D) None of these
12. Three lines are drawn from a single corner of an FCC unit cell to meet the other corner such that
they are found to pass through exactly 1 Octahedral void only, no voids of any type and exactly 2
tetrahedral voids with exactly 1 Octahedral void only. Identify the line in the same order -
(A) Edge, Face diagonal, Body diagonal (B) Face diagonal, Edge Body diagonal
(C) Body diagonal, Face diagonal Edge (D) Edge, Body diagonal, Face diagonal
NUMBER OF ATOMS IN UNIT CELL

13. How many number of atoms are there in a cube based unit cell having one atom on each corner
and two atoms on each body diagonal of cube -
(A) 8 (B) 6 (C) 4 (D) 9
14. How many atoms are there in a unit cell of Mg which forms hexagonal crystals, there being a
face-centred atom in each end of the unit cell and 3 completely enclosed atoms within the unit
cell-
(A) 4 (B) 6 (C) 12 (D) 8
FORMULA
15. In a CCP lattice of X and Y, X atoms are present at the corners while Y atoms are at face centres.
Then the formula of the compound would be if one of the X atoms from a corner is replaced by Z
atoms (also monovalent)?
(A) X7Y24Z2 (B) X7Y24Z (C) X24Y7Z (D) ZY24Z

SOLID STATE 73
16. In a solid, oxide ions are arranged in CCP. Cations A occupy one-sixth of the tetrahedral voids
and cations B occupy one-third of the octahedral voids. The formula of the compound is -
(A) ABO3 (B) AB2O3 (C) A2BO3 (D) A2B2O3
17. In a face centred cubic arrangement of A & B atoms whose A atoms are at the corner of the unit
cell & B atoms at the face centres. One of the A atom is missing from one corner in unit cell. The
simplest formula of compound is-
(A) A7B3 (B) AB3 (C) A7B24 (D) A7/8 B3
CLOSE PACKING OF SPHERE
18. In an arrangement of type ABABA......identical atoms of I layer A and III layer A are joined by a
line passing through their centres. Suggest the correct statements -
(A) No void is found on the line
(B) Only Tetrahedral voids are found on the line
(C) Only octahedral voids are found on the line
(D) Equal number of tetrahedral and octahedral voids are found on the line
19. A CCP of n spheres of radius r, n spheres of radius 0.414 r and 2n spheres of radius 0.225r are
introduced in the octahedral and tetrahedral void respectively. Therefore packing fraction of the
lattice.
(A) 0.74 (B) 0.81 (C) 0.68 (D) 0.79
VOIDS
20. In which of the following crystals alternate tetrahedral voids are occupied?
(A) NaCl (B) ZnS (C) CaF2 (D) Na2O
21. In octahedral holes (voids)

(A) A simple triangular void surrounded by four spheres
(B) A bi-triangular void surrounded by four spheres
(C) A bi-triangular void surrounded by six spheres
(D) A bi-triangular void surrounded by eight spheres
22. MgAl2O4, is found in the Spinel structure in which O2– ions constitute CCP lattice, Mg2+ ions
3+
occupy 1/8 th of the Tetrahedral voids and Al ions occupy 1/2 of the Octahedral voids. Find the
total +ve charge contained in one unit cell.
(A) + 7/4 electronic charge (B) +6 electronic charge
(C) +2 electronic charge (D) +8 electronic charge
23. For the structure given below the site marked as S is a-
(A) Tetrahedral void (B) Cubic void (C) Octahedral void (D) None of these

74 SOLID STATE
RADIUS RATIO AND COORDINATION NUMBER
24. The maximum radius of sphere that can be fitted in the octahedral hole of cubical closed packing
of sphere of radius r is
(A) 0.732 r (B) 0.414 r (C) 0.225 r (D) 0.155 r
25. Which of the following statement(s) is/(are) not correct

(A) The coordination number of each type of ion in C sCl crystal is 8
(B) A metal that crystallizes in bcc structure has a coordination number of 12
(C) A unit cell of an ionic crystal shares some of its ions with other unit cells
(D) The length of the unit cell in N aC l is 552 pm (rNa  95 pm; rCl   181 pm)
26. 6 : 6 of NaCl coordination changes to 8 : 8 coordination on –

(A) Applying high P (B) Increase in temperature
(C) Both (D) No effect on coordination
27. A solid XY has NaCl structure. If radius of X+ is 100 pm. What is the radius of Y– ion-
(A) 120 pm (B) 136.6 to 241.6 pm
(C) 280 pm (D) Unpredictable
28. What is the diameter of the largest sphere that will fit in the void at the centre of the cube edge of
a BCC crystal of edge length a?
(A) 0.134 a (B) 0.76 A (C) 0.05548 a (D) 0.098 a
29. In cubic ZnS, the radii of the Zn and S atoms are 0.83 Å and 1.74 Å respectively. What is the
edge length of the unit cell of ZnS ?
(A) 2.57 Å (B) 3.64Å (C) 2.97Å (D) 5.935Å
30. In the following NaCl type structure :

Salt Anium-anion Cation-anion
distance distance
MT 2.40 Aº 1.70 Aº
MQ 1.63 Aº 1.15 Aº
RT 2.66 Aº 1.88 Aº
RQ 2.09 Aº 1.48 Aº MT is represented as:
(A) (B) (C) (D)
31. A solid has a B.C.C. structure. If the distance of closest approach between the two atoms is 1.73
Å. The edge length of the cell is-
3
(A) 200 pm (B) pm (C) 142.2 pm (D) 2 pm
2

SOLID STATE 75
32. The unit cell cube length for LiCl (just like NaCl structure) is 5.14 Å. Assuming anion-anion
contact, the ionic radius for chloride ion is-
(A) 1.815 Å (B) 2.8 Å (C) 3.8 Å (D) 4.815 Å
IONIC STRUCTURE
33. Which of the following statements is not true about N aC l structure

(A) Cl  ions are in fcc arrangement (B) Na ions has coordination number 4
(C) Cl  ions has coordination number 6 (D) Each unit cell contains 4N aC l molecules
34. The spinel structure (AB2O4) consists of an fcc array of O2– ions in which
(A) A cation occupies one-eight of the tetrahedral holes and B cation occupies one-half of
octahedral holes
(B) A cation occupies one-fourth of the tetrahedral holes and the B cations the octahedral
holes
(C) A cation occupies one-eighth of the octahedral hole and the B cation the tetrahedral holes
(D) A cation occupies one-fourth of the octahedral holes and the B cations the tetrahedral holes
35. Which of the following expressions is correct in the case of a sodium chloride unit cell (edge length = a)
(A) r c + r a = a/2 (B) r c + r a = a (C) r c + r a = 2a (D) r c+ r a = 2 ½ a
36. Zinc sulphide exists in two different forms- zinc blende and wurtzite. Both occur as 4 : 4 co-
ordination compounds. Choose the correct option from among the following
(A) zinc blende has a bcc structure and wurtzite an fcc structure
(B) zinc blende has an fcc structure and wurtzite an hcp structure
(C) zinc blende as well as wurtzite have a hcp structure
(D) zinc blende as well as wurtzite have a ccp structure
CRYSTAL DEFECTS
37. The correct statement regarding F  centre is

(A) Electron are held in the voids of crystals (B) F  centre produces colour to the crystals
(C) Conductivity of the crystal increases due to F  centre
(D) All
38. If N aC l is doped with 103 mol % SrCl 2 , then the concentration of cation vacancies will be
(A) 1 10 3 mol % (B) 2  103 mol %
(C) 3  103 mol % (D) 4  10 3 mol %
39. The flame colours of metal ions are due to

(A) Frenkel defect (B) Schottky defect
(C) Metal deficiency defect (D) Metal excess defect
40. Which one of the following crystals does not exhibit Frenkel defect
(A) AgBr (B) AgCl (C) KBr (D) ZnS

76 SOLID STATE
41. Non-stoichiometric cuprous oxide, Cu2O can be prepared in the laboratory. In this oxide the ratio
of copper to oxygen is slightly less than 2 : 1. Therefore, which of the following is/are correct
regarding Cu2O lattice ?
(A) The given Cu2O crystal can act as p-type semiconductor.
(B) The given Cu2O crystal can act as n-type semiconductor
(C) The given Cu2O can act as n-type or p-type semiconductor
(D) In the Cu2O lattice, there is anion vacancy
42. A silicon solar battery makes use of-
(A) n-Type semiconductor (B) p-Type semiconductor
(C) Combination of Si doped with As and B (D) p-n junction
43. To get a n- type semiconductor, the impurity to be added to silicon should have which of the
following number of valence electrons
(A) 1 (B) 2 (C) 3 (D) 5
44. Consider the following statements and choose the correct option
(i) Addition of CdCl2 to the Crystals of AgCl will produce cation vacancy
(ii) Addition of NaCl to the crystals of AgCl would not produce cation vacancy
(A) Both (i) and (ii) are true (B) Only (i) is true
(C) Only (ii) is true (D) Both are false
MISCELLANEOUS
45. Certain crystals produce electric signals on application of pressure. This phenomenon is called
(A) Pyroelectricity (B) Ferroelectricity (C) Peizoelectricity (D) Ferrielectricity

46. At what angles for the first order diffraction, spacing between two planes respectively are  and ?
2
(A) 0º, 90º (B) 90º, 0º (C) 30º, 90º (D) 90º, 30º
47. The second order Bragg diffraction of X-rays with  = 1.0 Å from a set of parallel planes in a
metal occurs at an angle 60º. The distance between the scattering planes in the crystals is -
(A) 1.155 Å (B) 1.00 Å (C) 2.00 Å (D) 1.7 Å
48. A mineral having the formula AB2 crystallize in cubic close packed lattice with the A atoms
occupying the lattice points. The coordination number of atoms of A, atoms of B and the fraction
of the tetrahedral sites occupied by B are respectively -
(A) 2, 6, 75% (B) 8, 4, 100% (C) 3, 1,25% (D) 6, 6, 50%
49. How many unit cells are present in a cube-shaped idela crystal of NaCl of mass 1.00 g?
[Atomic masses Na = 23, Cl = 35.5]
(A) 1.28 × 1021 unit cells (B) 1.71 × 1021 unit cells
21 21
(C) 2.57 × 10 unit cells (D) 5.14 × 10 unit cells
50. For a face centred unit cell (AB) of the NaCl type with lattice parameters a, the sum o the radii of
anion-anion contact is
2a 2 2a 2
(A) (B) a (C) (D) a
8 6 4 2


SOLID STATE 77

1. A solid has a structure in which W atoms are located at the corners of a cubic lattice, O atom at
the centre of the edges and Na atom at centre of the cubic. The formula for the compound is
(A) NaWO2 (B) NaWO3
(C) Na2 WO3 (D) NaWO4
2. The density of CaF2 (fluorite structure) is 3.18g / cm3 . The length of the side of the unit cell is -
(A) 253 pm (B) 344 pm (C) 546 pm (D) 273 pm
3. Which of the following statements is correct in the rock-salt structure of an ionic compounds?
(A) coordination number of cation is four whereas that of anion is six.
(B) coordination number of cation is six whereas that of anion is four.
(C) coordination number of each cation and anion is four.
(D) coordination number of each cation and anion is six.
4. The coordination number of cation and anion in Fluorite CaF2 . and CsCl are respectively
(A) 8:4 and 6:3 (B) 6:3 and 4:4 (C) 8:4 and 8:8 (D) 4:2 and 2:4
5. The interstitial hole is called tetrahedral because
(A) It is formed by four spheres.
(B) Partly same and partly different.
(C) It is formed by four spheres the centres of which form a regular tetrahedron.
(D) None of the above three.
6. The tetrahedral voids formed by ccp arrangement of Cl ions in rock salt structure are
(A) Occupied by Na  ions (B) Occupied by Cl ions
(C) Occupied by either Na  or Cl ions (D) Vacant
7. The number of nearest neighbours around each particle in a face-centred cubic lattice is
(A) 4 (B) 6 (C) 8 (D) 12
8. If the anions (A) form hexagonal closest packing and cations (C) occupy only 2/3 octahedral voids
in it, then the general formula of the compound is
(A) CA (B) CA 2 (C) C2 A 3 (D) C3 A 2
9. A solid is formed and it has three types of atoms X, Y, Z. X forms a FCC lattice with Y atoms
occupying all the tetrahedral voids and Z atoms occupying half the octrahedral voids. The formula
of the solid is:
(A) X2 Y4 Z (B) XY2 Z 4
(C) X4 Y2 Z (D) X 4 YZ 2
10. The intermetallic compound LiAg crystallizes in cubic lattice in which both lithium and silver have
coordination number of eight. The crystal class is
(A) Simple cubic (B) Body centred cubic
(C) Face centred cubic (D) None

78 SOLID STATE
11. A compound XY crystallizes in BCC lattice with unit cell edge lenght of 480 pm. If the radius of
Y  is 225 pm, then the radius of X  is
(A) 127.5 pm (B) 190.68 pm (C) 225 pm (D) 255 pm
12. The mass of a unit cell of CsCl corresponds to
(A) 1Cs and 1 Cl– (B) 1Cs and 6 Cl– (C) 4Cs  and 4 Cl– (D) 8Cs and 1 Cl–
13. In the closest packing of atoms A (radius : ra ), the radius of atom B that can be fitted
into tetrahedral voids is
(A) 0.155 ra (B) 0.225 ra (C) 0.414 ra (D) 0.732 ra
14. Which one of the following schemes of ordering closed packed sheets of equal sized spheres do
not generate close packed lattice.
(A) ABCABC (B) ABACABAC (C) ABBAABBA (D) ABCBCABCBC
15. An ionic compound AB has ZnS type structure. If the radius A  is 22.5 pm, then the ideal radius
of B– would be
(A) 54.35 pm (B) 100 pm (C) 145.16 pm (D) None of these
16. NH4 Cl crystallizes in a body-centered cubic type lattice with a unit cell edge length of 387 pm.
The distance between the oppositively charged ions in the lattice is
(A) 335.1 pm (B) 83.77 pm (C) 274.46 pm (D) 137.23 pm
17. rNa = 95 pm and rCl =181 pm in NaCl (rock salt) structure. What is the shortest distance between
Na+ ions?
(A) 778.3 pm (B) 276 pm (C) 195.7 pm (D) 390.3 pm
18. In diamond, carbon atom occupy FCC lattice points as well as alternate tetrahedral voids. If edge
length of the unit cell is 356 pm, then radius of carbon atom is
(A) 77.07 pm (B) 154.14 pm (C) 251.7 pm (D) 89 pm
19. Which of the following will show schottky defect
(A) CaF2 (B) ZnS (C) AgCl (D) CsCl
20. Give the correct order of initials T (true) or F (false) for following statements.
I. In an anti-fluorite structure anions form FCC lattice and cations occupy all tetrahedral voids.
II. If the radius of cations and anions are 0.2 Å and 0.95 Å then coordinate number of cation in
the crystal is 4.
III An atom/ion is transferred from a lattice site to an interstitial position in Frenkel defect.
IV. Density of crystal always increases due to substitutinal impurity defect.
(A) TFFF (B) FTTF (C) TFFT (D) TFTF



SOLID STATE 79

COMPREHENSION TYPE
F centre is an example of metal excess defect due to the presence of extra cations at interstitial
sites. Zinc oxide is white in colour at room temperature On heating it loses oxygen and turns yellow.
heat 2+ 1 –
ZnO   Zn + O2 + 2e
2
Now there is excess of zinc in the crystal and its formula becomes Zn1 + x O. The excess of Zn2+
ions move to interstitial sites and the electrons to neighbouring interstitial sites.
There are many solids which are difficult to prepare in the stoichiometric composition and contain
less amount of the metal as compared to stoichiometric proportion. A typical example of this type is FeO
which is mostly found with a composition of Fe0.95O. It may actually range from Fe0.93O to Fe0.96O.
1. In Fe0.95O
(A) Metal excess defect is present (B) Metal deficiency defect is present
(C) F-centre is present (D) All of the above are present
2. In the crystal of Fe0.95O.

(A) No. of Fe2+, ions missing = no of Fe3+ ions present
(B) Some Fe2+ cations are missing and the loss of positive charge is made up by the presence
of required no. of Fe3+ ions
(C) Some Fe2+ ions are missing and some protons are present
(D) None of these
3. Which of the following is true about F-centre.

(A) It is not common in alkali halides
(B) F-centre impart pink colour to the crystal of NaCl.
(C) Excess of Li makes LiCl crystals pink and excess of potassium makes KCl crystals violet
(or lilac). It is due to F-centre
(D) F-centre is a stoichiometric point defect
A metal crystallizes in a closed packed structure, the atoms stack together occupying maximum
space & leaving minimum vacant space. Each sphere in the first layer is in contact with six neighbours.
Now while arranging the second layer on the first layer, spheres are placed in depression of first layer.
Spheres of third layer lie in the depression of second layer, that do not lie directly over the atoms of first
layer. This repeating arrangement of atoms produces a giant lattice.
4. If edge length of unit cell is ‘a’ what is the shortest distance between two atoms –
a a 3a
(A) (B) a (C) (D)
2 2 4

80 SOLID STATE
5. If atomic weight of metal is 197 & a = 4.07Å then density of unit cell is –
(A) 49.8 gm / cm3 (B) 19.4 gm / cm3 (C) 56.2 gm / cm3 (D) 86.5 gm / cm3
6. Which of the following shaded plane contains the following arrangement of atoms –
(A) (B) (C) (D)
Passage # 3 (Ques. 7 to 11)

The lattice parameter of BCC lattice is "a". The plane density is defined as the number of atoms
per unit area of the plane.
7. The plane density of the (1 1 1) plane of the given BCC lattice is–
1 1 2 2
(A) (B) (C) (D)
3a2 a2 a2 a2
8. The plane density of the (110) plane of the given BCC lattice is–
1 1 2 2
(A) (B) (C) (D)
3a2 a2 a2 a2
9. The plane density of the (100) plane of the given BCC lattice is–
1 1 2 2
(A) (B) (C) (D)
3a2 a2 a2 a2
 1 1
10. What will be the size of the largest sphere that will fit an interstitial void at  0, ,  in the above
 2 4
BCC lattice ?
 5   5  3a  3  3a
(A)   1 a (B)   1 (C)   1 (D) None of these
  4  4
 3   3   5 
11. Which of the following arrangements are not possible in BCC lattice ?
(A) (B)
(C) (D)

SOLID STATE 81
The number of schottky defects(n) present in an ionic crystal containing N ions temperature T, is
given by n = N e–E/2KT where E is energy required to produce n schottky defects and K is Boltzmann
1/ 2
N –E/2KT
constant. The number of frenkel defects (n) in an ionic crystal having N ion is n =   e where
 Ni 
E is the energy required to produce n frenkel defects and Ni is the number of interstitial sites
12. What is the mole fraction of schottky defect in NaCl crystal at 1000 K ? The enthalpy of formation
of schottky defect = 2 eV and K = 1.38 × 10–23 JK–1 :
–100 –11.66
(A) e (B) e
–10 –14
(C) e (D) e
13. Absorption of photons by crystal –

(A) Has no effect on imperfection
(B) Produces atomic displacement leading to imperfections
(C) Decreases number of defects
(D) None of these
14. In which of the following defect density of crystal remains same ?

(A) Schottky (B) Vacancy
(C) Frenkel (D) Interstitial
The structure of unit cell of Perovskite - a salt of lanthanum (La), manganese (Mn) and oxygen,
2+
has Mn at the each corner, oxide on every edge centre and a lanthanum ion at the body centre.
15. What is the empirical formula of the salt ?

(A) LaMnO2 (B) LaMn2O3
(C) LaMnO3 (D) Both (B) and (C)
16. What are the co-ordination numbers of Mn, La and O, respectively?

(A) 6, 2, 8 (B) 6, 4, 12
(C) 8, 4, 8 (D) 6,12,2
17. Considering the closed packed arragement of ions, which of the following statements regarding
the ionic radii is most the appropriate ?
(A) rLa4  rO2 (B) rLa4  rMn2
(C) Edge length of unit cell = rMn2  rO2 (D) None of these

82 SOLID STATE
MORE THAN ONE MAY BE CORRECT
18. A salt MX crystallising in KCl type of structure in which K+ is forming fcc.

(A) The nearest neighbour of Cl– ion is 6 K+ ion
1.732
(B) The packing fraction is given by
8
+ –-
(C) The nearest neighbour of K ion is 6 Cl ion
(D) The second nearest neighbour of K+ ion is 12 K+ ion.
19. The co-ordination number of FCC structure for metals is 12, since
(A) each atom touches 4 others in same layer, 3 in layer above and 3 in layer below.
(B) each atom touches 4 others in same layer, 4 in layer above and 4 in layer below
(C) each atom touches 6 others in same layer, 3 in layer above and 3 in layer below
(D) each atom touches 3 others in same layer, 6 in layer above and 6 in layer below.
20. What is/are true about diamagnetic materials?

(A) They are weakly repelled by the magnetic field
(B) There are large number of unpaired electrons
(C) They have all paired electrons
(D) Benzene and TiO2 are diamagnetic substances
21. Lead metal has a density of 11.34 g/cm3 and crystallizes in a face-centered lattice. Choose the
correct alternatives -
(A) the volume of one unit cell is 1.214 × 10–22 cm3
(B) the volume of one unit cell is 1.214 × 10–19 cm3
(C) the atomic radius of lead is 165 pm (D) the atomic radius of lead is 155.1 pm
22. The ionic radii of Cs and Cl are 0.165 nm and 0.181 nm respectively. Their atomic weights are
133 and 35.5. Then -
(A) the lattice parameter is 0.4 nm
(B) the lattice parameter can not be determined from this data
3 3
(C) the density of CsCl is 4.37 × 10 kg/m
(D) the CsCl structure has a fcc structure with basis
23. The correct statement(s) regarding defects in solids is(are) -

(A) Frenkel defect is usually favoured by a very small difference in the size of cation and anion
(B) Frenkel defect is a dislocation defect
(C) Trapping of an electron in the lattice leads to the formation of F-center
(D) Schottky defects have no effect on the physical properties of solids
24. Select the correct statements from the following

(A) The non-stoichiometric form of NaCl is yellow and that of KCl is blue-lilac
(B) Solids containing F-centres are paramagnetic
(C) Conduction by electrons is called n-type semiconduction
(D) Solids containing F centres are diamagnetic

SOLID STATE 83
25. Which of the following is/are true ?

(A) Piezoelectricity is due to net dipole moment
(B) Some electric current is produced on heating polar crystals, this is pyroelectricity
(C) Ferroelectricity is due to alignment of dipole in the same direction
(D) Ferrielectricity is due to the alignment of dipole in the same direction
26. In face centred cubic close packed structure octahedral sites are present at
(A) edge centres (B) face centres (C) body centres (D) corners
27. Stacking of hexagonal close packed layers give rise to -

(A) hcp structure (B) ccp structure
(C) simple cubic structure (D) fcc structure
28. Following three planes (P1, P2, P3) in an FCC unit cell are shown :
P1 P2 P3
Consider the following statements and choose the correct option that follow :
(A) P1 contains no three dimensionsal voids
(B) P2 contains only octahedral voids
(C) P3 contains both octahedral and tertahedral voids (D) All of these
INTEGER ANSWER TYPE QUESTION
29. The density of solid argon is 2/3 (amu/ Å3) at 40 K. If the argon atom is assumed to be sphere of
3
radius Å, what percentage of solid Argon is apparently without anything.
1/3
30. In a face centred lattice of X and Y, X atoms are present at the corners while Y atoms are at face
centres,
(a) What is the formula of the Compound ?
(b) What would be the formula of the compound if
(i) one of the X atom is missing from a corner in each unit cell
(ii) two atoms of X are missing from the corners
(iii) one of the X atoms from a corner is replaced by Z atoms (also monovalent) ?
31. In Rock Salt type structure cations (radius r) occupy Octahedral holes in the FCC of anions
(radius R) such that there is no distortion in the FCC lattice. Find the perimeter of the shaded
region.

84 SOLID STATE
32. A closest packed lattice has 1024 atoms. Calculate the sum of total number of tetrahedral and
octahedral voids in the lattice.
33. Calcium crystallises in face centred cubic lattice with edge length of the unit cell = 0.556 nm.
(i) What to the density if it contain 0.1% Frenkel defect?
(ii) What is the density if contain 0.1% schottky defect?
34. How many percent tetrahedral holes are occupied in diamond :
35. The ratio of co-ordintion no. of Al and no. of Al atoms per unit cell in fcc lattice is …………..
36. FeO crystallizes in NaCl type lattice. The crystal is however non-stoichiometric as Fe0.96O and
deficient in iron. Some cation sites are vacant and some contain Fe3 so that it becomes
electricity neutral. The % of cation sites vacant are …………..
37. A crystal of sodium hydride has fcc unit cell of H

ions with Na  ions at the body centres of unit
cell and in the centre of edges. The no. of H

that touch each Na  is ……………..
38. The number of tetrahedral voids present in bcc lattice is …………….
39. If the distance between Cs   Cl  in CsCl lattice is 2 3 A . The edge length of cube is ………..
40. A mineral having the formula AB2 crystallizes in cubic close packed lattice, with A atoms
occupying the lattice point. The ratio of co-ordination no. of A and B is ……
1 3
41. Silver (at. weight 108 g mol ) has a density of 10.5 g / cm . The number of silver atoms on a
12
surface of area 10 m2 can be expressed in scientific notation as Y 10 X . The value of X is
42. The number of hexagonal faces that are present in a truncated ocrahedron is :
MATCH THE COLUMN
43. Match the column –
Column I Column II
(A) Ionic Solid (P) Metallic Bond
(B) Network Solid (Q) Coulombic Force
(C) Molecular Solid (R) Covalent Solid
(D) Metallic Solid (S) H – Bonding
44. Match the column -
Column I Column II
(A) Sulphur (P) Orthorhombic
(B) Copper (Q) Monoclinic
(C) CaCO3 (Argonite) (R) Cubic
(D) Graphite (S) Hexagonal

SOLID STATE 85
Column I (Crystal System) Column II (Possible unit cells)

(A) Cubic (P) Simple or primitive
(B) Tetragonal (Q) Body Centred
(C) Orthorhombic (R) Face Centred
(D) Monoclinic (S) End Centred
46. Match Column-I with Column-II and select the correct answer by using the codes given below:
Column I (Shapes) Column II (Radius ratio)

(P) Planar triangle (1) 0.732
(Q) Square planar (2) 0.225
(R) Body centered cubic (3) 0.115
(S) Tetrahedral (4) 0.414
Codes
P Q R S
(A) 3 4 1 2
(B) 3 2 1 4
(C) 2 1 4 3
(D) 1 3 4 2

Column I Column II
(Arrangement of the atoms/ions) (Planes in fcc lattice)
(A) (P)
(B) (Q)
(C) (R)
(D) (S)

86 SOLID STATE
Column I Column II
(A) ZnS crystal (P) fcc
(B) CaF2 crystal (Q) hcp
(C) NaCl crystal (R) 3
Distance between closest particles is a
4
(D) Diamond crystal (S) Only one type of voids are occupied

Column I Column II
(A) Spinel structure (P) ZnAl2O4
(B) Glass (Q) Pseudo solid
(C) 6 : 6 Co-ordination (R) NaCl type structure
(D) Plastics (S) Super cooled liquid
50. Match the crystal system/unit cells mentioned in Column-I with their characteristic feature
mentioned in Column-II.
Column I Column II
(A) simple cubic and face centred cubic (P) have these cell parameters a = b = c and  =  = 
(B) cubic and rhombohedral (Q) are two crystal systems
(C) cubic and tetragonal (R) have only two crystallographic angles of 90°
(D) hexagonal and monoclinic (S) belong to same crystal system



SOLID STATE 87

Formula of ionic solid from unit cell description
1. A cubic solid is made up of two elements A and B. Atoms B are at the corners of the cube and A
at the body centre. What is the formula of compound.
2. A compound alloy of gold and copper crystallizes in a cubic lattice in which gold occupy that
lattice point at corners of the cube and copper atom occupy the centres of each of the cube faces.
What is the formula of this compound.
3. A cubic solid is made by atoms A forming close pack arrangement, B occupying one. Fourth of
tetrahedral void and C occupying half of the octahedral voids. What is the formula of compound.
4. What is the percent by mass of titanium in rutile, a mineral that contain Titanium and oxygen, if
structure can be described as a closest packed array of oxide ions, with titanium in one half of the
octahedral holes. What is the oxidation number of titanium?
5. Spinel is a important class of oxides consisting of two types of metal ions with the oxide ions
arranged in CCP pattern. The normal spinel has one-eight of the tetrahedral holes occupied by
one type of metal ion and one half of the octahedral hole occupied by another type of metal ion.
Such a spinel is formed by Zn2  ,Al3  and O 2  , with Zn 2  in the tetrahedral holes. Give the
formulae of spinel.
Edge length, density and number of atoms per unit cell
6. KF crystallizes in the NaCl type structure. If the radius of K  ions 132 pm and that of F ion is
135 pm, what is the shortest K–F distance? What is the edge length of the unit cell? What is the
closet K–K distance?
7. A closed packed structure of uniform spheres has the edge length of 534 pm. Calculate the
radius of sphere, if it exist in
(a) simple cubic lattice
(b) BCC lattice
(c) FCC lattice
8. Calculate the density of diamond from the fact that it has face centered cubic structure with two
atoms per lattice point and unit cell edge length of 3.569 Å.
9. An element crystallizes into a structure which may be described by a cubic type of unit cell having
one atom on each corner of the cube and two atoms on one of its body diagonals. If the volume
of this unit cell is 24  1024 cm3 and density of element is 7.2gcm3 , calculate the number of
atoms present in 200 g of element.
10. Silver has an atomic radius of 144 pm and the density of silver is 10.6gcm3 . To which type of
cubic crystal, silver belongs?

88 SOLID STATE
11. AgCl has the same structure as that of NaCl. The edge length of unit cell of AgCl is found to be
555 pm and the density of AgCl is 5.561gcm3 . Find the percentage of sites that are unoccupied.
12. Xenon crystallises in the face-centred cubic lattice and the edge of the unit cell is 620 pm. What is
the nearest neighbour distance and what is the radius of xenon atom?
13. The two ions A  and B  have radii 88 and 200 pm respectively. In the closed packed crystal of
compound AB, predict the co-ordination number of A  .
14. CsCl has the bcc arrangement and its unit cell edge length is 400 pm. Calculate the interionic
distance in CsCl.
15. Gold crystallizes in a face centered cubic lattice. If the length of the edge of the unit cell is 407
pm, calculate the density of gold as well as its atomic radius assuming it to be spherical. Atomic
mass of gold = 197 amu.
16. The density of KBr is 2.75gcm3 . The length of the edge of the unit cell is 654 pm. Show that KBr
has face centered cubic structure.
N  6.023  10 23
mol1, At. mass : K  39,Br  80 
17. An element crystallizes in a structure having FCC unit cell of an edge 200 pm. Calculate the
density, if 200 g of this element contains 24  10 23 atoms.
18. The effective radius of the iron atom is 1.42 Å. It has rock salt like structure. Calculate its density
(Fe = 56 amu)
19. A crystal of lead (II) sulphide has NaCl structure. In this crystal the shortest distance between
Pb2 ion and S 2  ion is 297 pm. What is the length of the edge of the unit cell in lead sulphide?
Also calculate the unit cell volume.
20. If the length of the body diagonal for CsCl which crystallises into a cubic structure with Cl ions at
the corners and Cs ions at the centre of the unit cells is 7 Å and the radius of the Cs ion is
1.69 Å, what is the radii of Cl ion?


SOLID STATE 89

1. Iron has body centered cubic lattice structure. The edge length of the unit cell is found to be 286
pm. What is the radius of an iron atom?
2. Cesium chloride forms a body centered cubic lattice. Cesium and chloride ions are in contact
along the body diagonal of the unit cell. The length of the side of the unit cell is 412 pm and Cl
ion has a radius of 181 pm. Calculate the radius of Cs ion.
3. In a cubic closed packed structure of mixed oxides the lattice is made up of oxide ions, one eighth
of tetrahedral voids are occupied by divalent ions  A 2   while one half of the octahedral voids
occupied trivalent ions B 3   . What is the formula of the oxide?
4. A solid A  and B  had NaCl type closed packed structure. If the anion has a radius of 250 pm,
what should be the ideal radius of the cation? Can a cation C  having a radius of 180 pm be
slipped into the tetrahedral site of the crystal of A  B  ? Give reasons for your answer.
5. Calculate the value of Avogadro’s number from the following data:

Density of NaCl  2.165cm3
Distance between Na  and Cl in NaCl  281 pm.
6. If the radius of Mg2 ion, Cs ion, O2  ion, S 2  ion and Cl ion are 0.65 Å , 1.69 Å, 1.40 Å, 1.84
Å, and 1.81 Å respectively. Calculate the co-ordination numbers of the cations in the crystals of
MgS, MgO and CsCl.
7. Iron occurs as bcc as well as fcc unit cell. If the effective radius of an atom of iron is 124 pm.
Compute the density of iron in both these structures.
 r  r
8. KCl crystallizes in the same type of lattice as does NaCl. Given that Na  0.5 and Na  0.7
r  r
Cl K 
Calculate:
(a) The ratio of the sides of unit cell for KCl to that for NaCl and
(b) The ratio of densities of NaCl to that for KCl.
9. An element A (Atomic weight = 100) having bcc structure has unit cell edge length 400 pm.
Calculate the density of A and number of unit cells and number of atoms in 10 gm of A.
10. Prove that the void space percentage in zinc blende structure is 25%.
11. A unit cell of sodium chloride has four formula units. The edge of length of the unit cell is 0.564
nm. What is the density of sodium chloride.

90 SOLID STATE
12. In a cubic crystal of CsCl (density  3.97gm / cm3 ) the eight corners are occupied by Cl– ions
with Cs+ ions at the centre. Calculate the distance between the neighbouring Cs+ and Cl– ions.
13. KF has NaCl structure. What is the distance between K  and F in KF if density of KF is
2.48gm / cm3 .
14. The composition of a sample of wustite is Fe0.93 O1.0 . What percentage of iron is present in the
form of Fe(III)?
15. BaTiO 3 crystallizes in the prevoskite structure. This structure may be described as a cubic lattice
with barium ions occupying the corner of the unit cell, oxide ions occupying the face-centers and
titanium ion occupying the center of the unit cell.
(a) If titanium is described as occupying holes in BaO lattice, what type of holes does it
occupy?
(b) What fraction of this type hole does it occupy?
16. Rbl crystallizes in bcc structure in which each Rb  is surrounded by eight iodide ions each of
radius 2.17 Å. Find the length of one side of RbI unit cell.
17. If NaCl is dopped with 10 3 mol % SrCl2 , what is the numbers of cation vacancies?
18. Find the size of largest sphere that will fit in octahedral void in an ideal FCC crystal as a function
of atomic radius 'r'. The insertion of this sphere into void does not distort the FCC lattice.
Calculate the packing fraction of FCC lattice when all the octahedral voids are filled by this
sphere.
19. A cubic unit cell contains manganese ions at the corners and fluoride ions at the center of each
edge.
(a) What is the empirical formula of the compound?
(b) What is the co-ordination number of the Mn ion?
(c) Calculate the edge length of the unit cell, if the radius of Mn ion is 0.65 Å and that of F
ion is 1.36 Å.
20. NaH crystallizes in the same structure as that of NaCl. The edge length of the cubic unit cell of
NaH is 4.88 Å.
(a) Calculate the ionic radius of H–, provided the ionic radius of Na  is 0.95 Å.
(b) Calculate the density of NaH.
21. Metallic gold crystallises in fcc lattice. The length of the cubic unit cell is a = 4.07 Å.
(a) What is the closest distance between gold atoms.
(b) How many “nearest neighbours” does each gold atom have at the distance calculated in
(a).
(c) What is the density of gold?
(d) Prove that the packing fraction of gold is 0.74.

SOLID STATE 91
22. Ice crystallizes in a hexagonal lattice. At the low temperature at which the structure was
determined, the lattice constants were a = 4.53 Å, and b = 7.60 Å(see figure).
How many molecules are contained in a unit cell? [density (ice)  0.92gm / cm3 ]
23. Using the data given below, find the type of cubic lattice to which the crystal belongs.
Fe V Pd
a in pm 286 301 388
 in gm cm –3 7.86 5.96 12.16
24. Potassium crystallizes in a body-centered cubic lattice with edge length, a = 5.2 Å.
(a) What is the distance between nearest neighbours?
(b) What is the distance between next-nearest neighbours?
(c) How many nearest neighbours does each K atom have?
(d) How many next-nearest neighbours does each K atom have?
(e) What is the calculated density of crystalline potassium?
25. Prove that void space in fluorite structure per unit volume of unit cell is 0.242.
26. A compound formed by elements X & Y, Crystallizes in a cubic structure, where X is at the
corners of the cube and Y is at six face centers. What is the formula of the compound? If side
length is 5Å, estimate the density of the solid assuming atomic weight of X and Y as 60 and 90
respectively.
27. The metal nickel crystallizes in a face centred cubic structure. Its density is 8.9gm / cm3 .
Calculate
(a) the length of the edge of the unit cell.
(b) the radius of the nickel atom. [Atomic weight of Ni = 58.89]
28. The olivine series of minerals consists of crystals in which Fe and Mg ions may substitute for
each other causing substitutional impurity defect without changing the volume of the unit cell. In
1 th
olivine series of minerals, oxide ion exist as FCC with Si4  occupying of octahedral voids
4
1 th
and divalent ions occupying of tetrahedral voids. The density of forsterite (magnesium
4
silicate) is 3.21 g/cc and that of fayalite (ferrous silicate) is 4.34 g/cc. Find the formula of forsterite
and fayalite minerals and the percentage of fayalite in an olivine with a density of 3.88 g/cc.

92 SOLID STATE
29. The mineral hawleyite, one form of CdS, crystallizes in one of the cubic lattices, with edge length
5.87Å. The density of hawleyite is 4.63gcm3 .
(i) In which cubic lattice does hawleyite crystallize?
(ii) Find the Schottky defect in gcm3 .
30. A strong current of trivalent gaseous boron passed through a germanium crystal decreases the
density of the crystal due to part replacement of germanium by boron and due to interstitial
vacancies created by missing Ge atoms. In one such experiment, one gram of germanium is
taken and the boron atoms are found to be 150 ppm by weight, when the density of the Ge crystal
decreases by 4%. Calculate the percentage of missing vacancies due to germanium, which are
filled up by boron atoms.
Atomic wt. Ge = 72.6, B = 11
 

SOLID STATE 93

1. To obtain a diffraction peak, for a crystalline solid with interplane distance equal to the
wavelength of incident X – ray radiation, the angle of incidence should be [KVPY – 2011]
(A) 90° (B) 0° (C) 30° (D) 60°
2. Doping silicon with boron produces a [KVPY – 2012]

(A) n–type semiconductor (B) p–type semiconductor
(C) metallic conductor (D) insulator
3. If the angle of incidence of X – ray of wavelength 3A which produces a second order diffracted
beam from the (100) planes in a simple cubic lattice with interlayer spacing a  6A is 30°, the
angle of incidence that produces a first – order diffracted beam from the (200) planes is
[KVPY – 2013]
(A) 15° (B) 45° (C) 30° (D) 60°
4. An ionic compound is formed between a metal M and a non – metal Y. If M occupies half the
octahedral voids in the cubic close – packed arrangement formed by Y, the chemical formula of
the ionic compound is [KVPY – 2013]
(A) MY (B) MY2 (C) M 2Y (D) MY3.
5. In a cubic close packed structure, fractional contributions of an atom at the corner and at the face
in the unit cell are, respectively [KVPY – 2014]
(A) 1/8 and 1/2 (B) 1/2 and 1/4
(C) 1/4 and 1/2 (D) 1/4 and 1/8
6. Schottky defect in a crystal arises due to [KVPY – 2015]

(A) Creation of equal number of cation and anion vacancies
(B) Creation of unequal number of cation and anion vacancies
(C) Migration of cations to interstitial voids (D) Migration of anions to interstitial voids
7. The packing efficiency of the face centered cubic (fcc), body centered cubic (bcc) and
simple/primitive cubic (pc) lattices follows the order [KVPY – 2016]
(A) fcc  bcc  pc (B) bcc  fcc  pc
(C) pc  bcc  fcc (D) bcc  pc  fcc
8. A unit cell of calcium fluoride has four calcium ions. The number of fluoride ions in the unit cell is -
[KVPY – 2016]
(A) 2 (B) 1 (C) 6 (D) 8
9. Ionic salt AX grows in face centered cubic lattice with cell length ‘a’. The ratio rA  / rx  for this salt
will be: [NSEC – 2014]
(A) 0.155 (B) 0.225
(C) 0.414 (D) 0.732

94 SOLID STATE
10. The unit cell of a compound made up of the three elements X, Y and Z is given below:
[NSEC – 2014]
The formula of this compound is:

(A) X 2YZ3 (B) XY3 Z (C) XYZ3 (D) X 3YZ 2 .
11. Ice crystallizes in a hexagonal lattice. At a certain low temperature, the lattice constants are
 
a  4.53 A and c  7.71 A . The number of H2O molecules contained in a unit
cell( d  0.92 g cm3 at the given temperature) is
[NSEC – 2015]
(A) 4 (B) 8 (C) 12 (D) 24
12. The metal M crystallizes in a body centered lattice with cell edge 400 pm. The atomic radius of M
is [NSEC – 2015]
(A) 200 pm (B) 100 pm (C) 173 pm (D) 141 pm
13. One mole crystal of a metal halide of the type MX with molecular weight 119 g having face
centered cubic structure with unit cell length 6.58A was recrystallized. The density of the
recrystallized crystal was found to be 2.44 g cm –3. The type of defect introduced during the
recrystalization is [NSEC – 2015]
(A) additional M  and X  ions at interstitial sties
(B) schottky defect
(C) F – Centre
(D) Frenkel defect
14. In a cubic crystal structure, divalent metal – ion is located at the body – centered position, the
smaller tetravalent metal ions are located at each corner and the O 2  ions are located half way
along each of the edges of the cube. The number of nearest neighbors for oxygen is
[NSEC – 2016]
(A) 4 (B) 6 (C) 2 (D) 8


SOLID STATE 95

1. Total volume of atoms present in a face-center cubic unit cell of a metals (r is atomic radius)
[2006]
20 3 24 3 12 3 16 3
(A) r (B) r (C) r (D) r
3 3 3 3
2. In a compound, atoms of element Y form ccp lattice and those of element X occupy 2/3rd of
tetrahedral voids. The formula of the compound will be [2008]
(A) X2Y3 (B) X2Y (C) X3Y4 (D) X4Y3
3. Copper crystallises in fcc with a unit cell length of 361 pm. What is the radius of copper atom ?
[2009]
(A) 127 pm (B) 157 pm (C) 181 pm (D) 108 pm
4. The edge length of a face centred cubic cell of an ionic substance is 508 pm. If the radius of the
cation is 110 pm, the radius of the anion is [2010]
(A) 288 pm (B) 398 pm (C) 618 pm (D) 144 pm
5. Percentages of free space in cubic close packed structure and in body centered packed structure
are respectively. [2010]
(A) 30% and 26% (B) 26% and 32%
(C) 32% and 48% (D) 48% and 26%
6. In a face centred cubic lattice, atom A occupies the corner positions and atom B occupies the
face centre positions. If one atom of B is missing from one of the face centred points, the formula
of the compound is: [2011]
(A) AB2 (B) A2 B3 (C) A2 B5 (D) A2 B
7. Lithium forms body centred cubic structure. The length of the side of its unit cell is 351 pm.
Atomic radius of the lithium will be: [2012]
(A) 75 pm (B) 300 pm (C) 240 pm (D) 152 pm
8. Which of the following exists as covalent crystals in the solid state? [2013]
(A) Silicon (B) Sulphur (C) Phosphorous (D) Iodine
9. An element having an atomic radius of 0.14 nm crystallizes in an fcc unit cell. What is the length
of a side of the cell? [2013]
(A) 0.56 nm (B) 0.24 nm (C) 0.96 nm (D) 0.4 nm
10. In a face centred cubic lattice, atoms of A form the corner points and atoms of B form the face
centred points. If two atoms of A are missing from the corner points, the formula of the ionic
comound is: [2013]
(A) AB3 (B) AB4
(C) A2 B5 (D) AB2

96 SOLID STATE
11. Copper crystallizes in fcc with a unit length of 361 pm. What is the radius of copper atom?
[2013]
(A) 157 pm (B) 128 pm (C) 108 pm (D) 181 pm
12. CsCl crystallizes in body centred cubic lattice. If ‘a’ is its edge length then which of the following
expressions is correct? [2014]
(A) rCs  rCl   3a (B) rCs  rCl   3a
3a 3
(C) rCs  rCl   (D) rCs  rCl   a
2 2
13. Sodium metal crystallizes in a body centred cubic lattic with a unit cell edge of 4.29 A . The
radius of sodium atom is approximately : [2015]
(A) 3.22 A (B) 5.72 A (C) 0.93A (D) 1.86 A
14. Which of the following compounds is metallic and ferromagnetic? [2016]

(A) CrO2 (B) VO2 (C) MnO2 (D) TiO2

15. A metal crystallizes in a face centred cubic structure. If the edge length of its unit cell is ‘a’, the
closest approach between two atoms in metallic crystal will be: [2017]
a
(A) 2 2a (B) 2a (C) (D) 2a 
2


SOLID STATE 97

1. The edge length of unit cell of a metal having molecular weight 75 g/mol is 5 Å which crystallizes
in cubic lattice. If the density is 2 g/cc then find the radius of metal atom. (NA = 6 × 1023). Give
the answer in pm. [2006]

2. The edge length of unit cell of a metal having molecular weight 75 g/mol is 5 A which crystallizes
in cubic lattice. If the density is 2 g/cc then find the radius of metal atom  N A  6  10 23  . Give the
answer in pm. [2006]
3. Assertion : Micelles are formed by surfactant molecules above the critical micellar
concentration (CMC).
Reason : The conductivity of a solution having surfactant molecules decreases sharply at
the CMC. [2007]
(a) If both assertion and reason are correct, and reason is the correct explanation of the
assertion.
(b) If both assertion and reason are correct, but reason is not the correct explanation of the
assertion.
(c) If assertion is correct but reason is incorrect.
(d) If assertion is incorrect but reason is correct.
PASSAGE
In hexagonal systems of crystals, a frequently encountered arrangement of atoms is
described as a hexagonal prism. Here, the top and bottom of the cell are regular hexagons and
three atoms are sandwiched in between them. A space-fillig model of this structure, called
hexagonal close-packed (HCP), is constituted of a sphere on a flat surface surrounded in the
same plane by six identical spheres as closely as possible. There spheres are then placed over
the first layer so that they touch each other and represent the second layer. Each one of these
three spheres touches three spheres of the bottom layer. Finally, the second layer is covered with
third layer that is identical to the bottom layer in relative position. Assume radius of every sphere
to be ‘r’.
4. The number of atoms in the HCP unit cell is [2008]

(A) 4 (B) 6 (C) 12 (D) 17
5. The volume of this HCP unit cell is [2008]

(A) 24 2r 3 (B) 16 2r 3
64
(C) 12 2r 3 (D) r3
3 3
6. The empty space in this HCP unit cell is [2008]

(A) 3 (B) 6 (C) 7 (D) 7

98 SOLID STATE
rd
7. In a compound, atoms of element Y form ccp lattice and those of element X occupy 2/3 of
tetrahedral voids. The formula of the compound will be [2008]
(A) X 4Y3 (B) X 2Y3 (C) X 2Y (D) X 3Y4
8. Copper crystallizes in fcc with a unit cell length of 361 pm. What is the radius of copper atom?
[2009]
(A) 127 pm (B) 157 pm (C) 181 pm (D) 108 pm
9. The correct statement(s) regarding defects in solids is (are) [2009]

(A) Frenkel defect is usually favoured by a very small difference in the sizes of cation and
anion
(B) Frenkel defect is a dislocation defect
(C) Trapping of an electron in the lattice leads to the formation of F-centre
(D) Schottky defects have no effect on the physical properties of solids
10. The edge length of a face centered cubic cell of an ionic substance is 508 pm. If the radius of the
cation is 110 pm, the radius of the anion is [2010]
(A) 288 pm (B) 398 pm (C) 618 pm (D) 144 pm
11. Percentage of free space in cubic close packed structure and in body centered packed structure
are respectively [2010]
(A) 30% and 26% (B) 26% and 32%
(C) 32% and 48% (D) 48% and 26%
12. The packing efficiency of the two-dimensional square unit cell shown below is : [2010]
(A) 39.27% (B) 68.02% (C) 74.05% (D) 78.54%
13. A compound Mp Xq has cubic close packing (ccp) arrangement of X. Its unit cell structure is
shown below. The empirical formula of the compound is [2011]
(A) MX (B) MX 2 (C) M2 X (D) M5 X14

SOLID STATE 99
14. In a face centred cubic lattice, atom A occupies the corner positions and atom B occupies the
face centre positions. If one atom of B is missing from one of the face centred points, the formula
of the compound is : [2011]
(A) A2 B (B) AB2 (C) A2 B3 (D) A2 B5
15. The number of hexagonal faces that are present in a truncated octahedron is [2011]
(A) 3 (B) 6 (C) 7 (D) 8
16. Lithium forms body centred cubic structure. The length of the side of its unit cell is 351 pm.
Atomic radius of the lithium will be : [2012]
(A) 288 pm (B) 398 pm (C) 618 pm (D) 144 pm
17. Which of the following exists as covalent crystals in the solid state? [2013]
(A) Iodine (B) Silicon (C) Sulphur (D) Phosphorus
18. The arrangement of X  ions around A  ion in solid AX is given in the figure (not drawn to scale).
If the radius of A  is [2013]
(A) 104 pm (B) 183 pm (C) 125 pm (D) 57 pm
19. If the unit cell of a mineral has cubic close packed (ccp) array of oxygen atoms with m fraction of
octahedral holes occupied by aluminium ions and n fraction of tetrahedral holes occupied by
magnesium ions, m and n, respectively, are [2015]
1 1 1 1 1 1 1
(A) , (B) 1, (C) , (D) , 
2 8 4 2 2 4 8
20. The CORRECT statement(s) for cubic close packed (ccp) three dimensional structure is (are)
[2016]
(A) The number of nearest neighbours of an atom present in the topmost layer is 12
(B) The efficiency of atom packing is 74%
(C) The number of octahedral and tetrahedral voids per atom are 1 and 2, respectively
(D) The unit cell edge length is 2 2 times the radius of the atom
21. A crystalline solid of a pure substance has a face – centred cubic structure with a cell edge of 400
3
pm. If the density of the substance in the crystal is 8 g cm , then the number of atoms present
24
in 256 g of the crystal is N  10 . The value of N is ………….. . [2017]



100 SOLID STATE
ANSWER KEYS
1 2 3 4 5 6 7 8 9 10
C D A B B B C A A B
11 12 13 14 15 16 17 18 19 20
B A D B B A C B B B
21 22 23 24 25 26 27 28 29 30
C D C B B A B A D A
31 32 33 34 35 36 37 38 39 40
A A B A A B D A D C
41 42 43 44 45 46 47 48 49 50
A C D A C C A B C D

1 2 3 4 5 6 7 8 9 10
B C D C C D D C A B
11 12 13 14 15 16 17 18 19 20
B A B C B A D A D D
1 2 3 4 5 6 7 8 9 10
B B C C B A A C B B
11 12 13 14 15 16 17 18 19 20
D B B C C D B AC BC ACD
21 22 23 24 25 26 27 28 29 30
(a) XY3
(b) (i) X 7Y24
A AC BC ABC ABC AC AD ABCD 40
(ii) XY4
(iii) X 7Y24 Z
31 32 33 34 35 36 37 38 39 40
4  r  2R  (i) 1.5455
3072 (ii) 1.5357 50 3 4 6 4 4 2
41 42 43 44
7 8 A  Q; B  R; C  S; D  P A  P,Q; B  R; C  P; D  S
45 46

SOLID STATE 101
A  P, Q, R; B  P, Q; C  P, Q,R,S; D 
A
P,S
47 48
A  P, Q, R, S; B  P, R, S
A  S; B  R; C  P; D  Q
C  P, S; D  P, R, S
49 50
A  P; B  Q, S ; C  R; D  Q, S ; A  P, S; B  P, Q; C  Q; D  Q, R

Q.1 A-B Q.2 AuCu3
Q.3 A4B2C2 Q.4 59.95%, +4
Q.5 ZnAl2O4 Q.6 267 pm, 534 pm, 378 pm
Q.7 267 pm, 231.2 pm, 188.8 pm Q.8 3.5 g cm–3
Q.9 3.472 × 1024 atoms Q.10 FCC
Q.11 0.24% Q.12 438.5 pm, 219.25 pm
Q.13 6 Q.14 346.4 pm
Q.15 19.4g/cm3 , 143.9 pm Q.17 41.67 g cm–3
Q.18 5.74 g cm–3
Q.19 a =5.94×10–8cm, V=2.096×10–22 cm–3
Q.20 1.81Å

Q.1 123.84 pm Q.2 175.8 pm
Q.3 AB 2 O 4 Q.4 103.4 pm, No
Q.5 6.01×10 23 Q.6 4, 6, 8
Q.7 7.887 g/cc , 8.59 gm/cm 3 Q.8 (a) 1.143, (b) 1.172
Q.9 3
5.188 gm/cm , 6.023×10 22 atoms of A, 3.0115×10 22 unit cells
Q.11 2.16 gm/cm 3 Q.12 3.57 Å
Q.13 2.685 Å Q.14 15.053
Q.15 (a) octahedral, (b) 1/4 Q.16 4.34 Å
Q.17 18
6.02 × 10 mol –1 Q.18 0.414 r, 79.3%
Q.19 (a) MnF3, (b) 6, (c) 4.02Å Q.20 (a) 1.49 Å, (b) 1.37 g/cm3
Q.21 (a) 2.88 Å, (b) 12 , (c) 19.4 g/cc Q.22 4 molecules of H2O
Q.23 for Fe is bcc, for V is bcc, for Pd is face centered
Q.24 (a) 4.5 Å, (b) 5.2 Å, (c) 8, (d) 6, (e) 0.92 g/cm3
Q.26 XY3, 4.38 g/cm3 Q.27 (a) 3.52 Å,(b) 1.24 Å
Q.28 Mg2SiO4, Fe2SiO4, 59% Q.29 (i) 3.90, (ii) 0.120 g/cc
Q.30 2.376%

102 SOLID STATE
1 2 3 4 5 6 7 8 9 10
C C C B A A A D C C
11 12 13 14
C C B C
1 2 3 4 5 6 7 8 9 10
D C A D B C D A D B
11 12 13 14 15
B D D A C
1 2 3 4 5 6 7 8 9 10
216.5 pm 217 B B A D A A BC D
11 12 13 14 15 16 17 18 19 20
B D B D D D B A A BCD
21
2

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XII MODULE - II

Modus Operandi for Practice

Step – I CatalyseR 's Practice Sheets & NCERT

Step – III Previous Years’ JEE Subjective & Objective Questions,

Step – IV After Completion of Step – III, if time permits, students can

This Study Package is Prepared by

 CONCEPTS IN BRIEF 1-9

JEE (MAIN) Formely known as AIEEE

METHODS OF EXPRESSING THE CONCENTRATION OF A SOLUTION

(i) Mass percentage or per cent by mass:

Nothing is impossible, the word itself says ‘I’m possible’!

Relation between mole fraction and Molality:

(vi) Molarity (Molar concentration)

Molarity of mixing: M1V1  M2 V2  M3 V3  MR  V1  V2  V3  MR  resultant molarity

Factors affecting vapour pressure

CatalyseR Eduventures (India) Pvt. Ltd.

VAPOUR PRESSURE OF SOLUTION

For non-volatile solutes :

P solution  x solvent P0 or relative lowering of vapour pressure,

Nothing is impossible, the word itself says ‘I’m possible’!

Three cases arise.

DETERMINATION OF COMPOSITION IN VAPOUR PHASE

Vapours (Dalton’s Law)

Solution of (A & B) XB  mole fraction of B in liquid phase

From Raoult's law P  PA0 X A  PB0 XB

CatalyseR Eduventures (India) Pvt. Ltd.

examples of ideal solutions are:

Nothing is impossible, the word itself says ‘I’m possible’!

(ii) Non ideal solution (Deviations From Raoult's Law)

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(1) Azeotropes with Max. vapour pressure and Min. BP :

Components Boiling point (K)

(2) Azeotropes with Min. vapour pressure and Max. bp :

2. Elevation in Boiling Point,  Δ Tb  . For dilute solutions,  

Nothing is impossible, the word itself says ‘I’m possible’!

CatalyseR Eduventures (India) Pvt. Ltd.

VAN’T HOFF FACTOR

Application of Van’t Hoff Factor:

Nothing is impossible, the word itself says ‘I’m possible’!

1. The density of a 3 M sodium thiosulphate solution (Na2S2O3) is 1.25 g/mL. Calculate

(iii) No. of moles of Na+ ions = 2 × No. of moles of Na2S2O3 = 2 × 3 = 6

No. of moles of S2O32– ions = No. of moles of Na2S2O3

Lowring of vapour pressure PHo2 O – PH2 O  47.1– 46.9  0.2 torr

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4. Calculate relative lowering of vapour pressure of 0.161 molal aqueous solution.

Total vapour pressure of solution = 22.73 + 43.40 = 66.13 mm Hg

Nothing is impossible, the word itself says ‘I’m possible’!

CatalyseR Eduventures (India) Pvt. Ltd.

Solution: Let the molecular mass of urea be m2

Solution: Since molality of solution is .75,

Nothing is impossible, the word itself says ‘I’m possible’!

13: An aqueous solution containing 288 gm of a non–volalite compound having the

14: 30 ml of CH3OH (d = 0.7980 gm cm–3) and 70 ml of H2O (d = 0.9984 gm cm–3) are

15: A complex is represented as CoCl3.xNH3. Its 0.1 m solution in aqueous solution

CatalyseR Eduventures (India) Pvt. Ltd.

Solution: Assuming that the tartaric acid be a monobasic as AH. It ionizes as

Nothing is impossible, the word itself says ‘I’m possible’!

The equilibrium constant Keq =

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EXERCISE # 01 OBJECTIVE EXERCISE (LEVEL # 01)

6. 250 g aqueous solution of MgCO3 contains 2.5 g of magnesium carbonate. Concentration of

RAOULT’S LAW (VAPOUR PRESSURE OF A SOLUTION CONTAINING NON VOLATILE

Nothing is impossible, the word itself says ‘I’m possible’!