DP

CONTENTS
1. SOLID STATE
TOPIC PAGE NO.
Theory 03 – 29
Board Level Exercise 30 – 31
Exercise - 1 32 – 34
Question For Competative Exams 38 – 40
Answer Key 41 – 48
2. SOLUTION & COLLIGATIVE PROPERTIES
Theory 49 – 76
Board Level Exercise 77 – 78
Question For Competative Exams 88 – 91
Answer Key 92 – 99
Success is the sum
of small efforts,
repeated day
in and day out.
Solid State Boards / Medical
Solid State
State of matter depends on.
(i) Tendency of relative motion at a particular temperature.
(ii) Intermolecular forces.
Table : 1
Properties Solid Liquid Gases
No free motion Random motion to
(i) Motion of partical. Totally random.
only vibration allow. a limited extent is allowed.
(ii) Inter molecular Intermediate
Very strong Very weak (~ zero)
forces strength
Average separation is
(iii) Average separation Average separation is fixed
almost constant so almost No fixed volume.
(volume) so volume is fix.
fixed volume.
Average separation is fixed
Definate shape as
but location of partical is
(iv) Shape location of partical are No fixed shape.
not fixed so no definate
fixed.
shape..
(v) Effect of change in Liquid are also almost
Are incompressible. Highly compressible.
pressure & temperature. incompressible.
Heat capacity is
Heat capacity is dependent
(vi) Heat capacities almost independent Same as solid.
on process.
of process.
Types of Solid :
(1) Classification on the basis of forces among constituting particles
Table : 2
Ex. Identify molecular solid, covalent solid, ionic solid : P4(s), S8 (s), SiC (s), Al2O3(s), He (s), Al2Cl6(s).
Sol. Molecular solid  P4(s), S8 (s), He (s), Al2Cl6(s)
Covalent solid  SiC
Ionic solid  Al2O3(s).
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GENERAL CHARACTERISTICS OF SOLIDS :
(i) Solids have definite mass, shape and volume.
(ii) There is least intermolecular distances in solids as compared to liquids and gases.
(iii) There is strong intermolecular forces of attraction between particles in solids.
(iv) The particles of a substance cannot flow in its solid state but can flow in molten state.
(v) The constituting particles (atoms/ions/ molecules) have fixed positions. They can oscillate only about their
mean position, i.e., they have translational motions only.
(vi) They are rigid and incompressible.
(2) Types of SOLIDS on the basis of arrangement of particles :
On the basis of arrangement of partical in the solid, these can be classified into crystalline & amorphous solids.
Table : 3
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Internal arrangement of partical in crystalline solid :
Each constituent partical (Molecule of any shape, atom, ions) will be represented by a dot (.) and this dot is
called a lattice point.
Lattice : The 3-D regular and repeating arrangement of constituent partical represent by dots in solid is called
lattice.
Figure
Unit Cell :
The group of the lattice point (generally the smallest one) which on repetition parallel to its edges & equal to its
edge length generates whole of the lattice is called unit cell of the lattice.
or
Unit cell : Unit cell is the smallest portion of a crystal lattice which, when repeated in different directions,
generates the entire lattice.
CHARACTERISTICES OF A UNIT CELL :
(i) Its dimensional along the three edges, a, b and c. These edges may or may not be mutually perpendicular.
(ii) Angles between the edges,  (between b and c)  (between a and c) and  (between a and b).
(iii) Each unit cell has characteristic relation between a, b and c or , , and  to give rise different types of unit
cell.
Thus, a unit cell is characterised by six parameters, a, b, c, , , and . These parameters of a typical unit cell
are shown in figure.
Illustration of parameters of a unit cell

A unti cell may also be defined as a1D, 2D, 3D three dimensional group of lattice points that generates the whole
lattice by repetation or stacking.
 Generally most symmetrical and smallest volume unit cell is selected.
1-Dimensional space lattice :
Uniformly separated lattice point in 1-D
Figure
only one parameter is required  distance between two lattice point.
2-D Lattice :
Regular arrangement of point in plane 3 parameter required  Two edge lengths & angle between these two
edge.
Figure
We can only shift the unit cell parallel not rotate it.
(i) Square unit cell  a = b,  = 90º
(ii) Rectangle unit cell  a  b,  = 90º
(iii) Hexagonal unit cell  a = b,  = 60º
(iv) Rhombic unit cell  a = b,   90º &   60º
(v) Parallelogram  a  b,   90º
Most symmetrical  square unit cell.
Square unit cell :
Figure
Primitive unit cell : Unit cell having lattice point only at the corner.
Non Primitive or centered unit cell : Unit cell having lattice point at corner as well as with in the unit cell.
3-D-Lattice :
Seven Primitive unit cells in crystals
c
Cubic b a
; Tetragonal ; Orthorhombic ;
b
g c c
a b
b a
a
c
Monoclinic ; Hexagonal ;
c
b
a b
a
c c
Rhombohedral ; Triclinic
b b
a a
Figure
The type of unit cells found in different types of crystals.
1. Primitive /simple unit cell :
SC  Simple cubic.
2. Non primitive :
(a) Body centered (B.C.) : B.C.C  Body centered cubic.
(b) Face centered (F.C.) :
(c) End centered (E.C.) :
Note : (1) Which particular type of unit cell will be found in a particular crystal class is decided on the basis of ‘’the
surroundings of each & every lattice point in a particular lattice which is exactly identical.
(2) In 3-d to specify any unit cell 6 parameter are required.
 3-egde length (a,b,c) and 3-angle between these. (, , ), [a–b], b–c], [c–a–].
Seven Crystal System
Table : 4
Crystal System Features Unit cell found Examples
Cubic a=b=c SC, BCC, FCC NaCl, ZnS, Fe, Al, Cu, C
α = β = γ = 90° (diamond), CsCl, CaF2 , Na2 O,
KCl, Pb, Alum.
Tetragonal a=bc S, BC Sn (white tin), SnO2 ,TiO 2, ZnO 2,
α = β = γ = 90° NiSO 4 , urea.
Orthorhombic abc S, BC, FC, EC Rhombic sulphur, BaSO 4 , KNO3 ,
α = β = γ = 90° PbCO3 , CaCO3 (aragonite)
Rhombohedral a = b = c S CaCO3 (Calcite), HgS(Cinnabar),
or α = β = γ  90° NaNO3 , ICl.
Trigonal
Monoclinic abc S, EC Monoclinic sulphur, PbCrO4 ,
α = γ = 90°; Na2 SO4 .10H2O, Na2 B4 O7 .10H2O.
β  120°,  90°,  60°
Hexagonal a=bc S Graphite, ZnO, CdS, Mg, PbI2,

α = β = 90°, γ = 120° SiC.
Triclinic abc S K 2 Cr2O 7 , CuSO4 .5H2O, H3 BO 3.
α  β  γ  90°
Note : In 3-D 14 different types of unit cell are found and these are also known as 14 Bravais lattice.
Contribution of different Lattice point in one Cubical unit cell :
1
(i) Contribution from one corner lattice point = th.
8
1
(ii) Contribution from one face centered lattice point = .
2
1
(iii) Contribution from edge centered lattice point = th.
4
(iv) Contribution from body centered lattice point = 1.
Ex. The lattice parameters of a given crystal are a = 5.62 Å, b = 7.41 Å and c = 9.48 Å. The three coordinate
axes are mutually perpendicular to each other. The crystal is :
(A) tetragonal (B) orthorhombic (C) monoclinic (D) trigonal.
Ans. (B)
Sol. a  b  c &  =  =  = 90° the crystal system is orthorhombic.
Ex. Tetragonal crystal system has the following unit cell dimensions:
(A) a = b = c and  =  =  = 90° (B) a = b  c and  =  =  = 90°
(C) a  b  c and  =  =  = 90° (D) a = b  c and  =  = 90°,  = 120°
Ans. (B)
Ex. In a face centered cubic arrangement of A and B atoms whose A atoms are at the corner of the unit cell and
B atoms at the face centres. One of the A atom Is missing from one corner in unit cell. The simplest
formula of the compound is
(A) A7B3 (B) AB3 (C) A7B24 (D) A2B3
Ans. (C)
1 7 1
Sol. A=7 = ; B=6 =3 Formula = A 7 / 8 B3 or A7B24
8 8 2
Ex. A compound has cubical unit cell in which X atom are present at 6 corner, Y atom are at remaining corner & only
at those face centers which are not opposite to each other & Z atoms are present at remaining face center &
body center then find.
(i) Formula of compound (ii) Density if edge length = 2 Å.
Given : Atomic mass of X = 40 amu, Y = 60 amu, Z = 80 amu.
1 3 1 1 7 1 5 10
Sol. (i) X= ×6= , Y= ×2+ ×3= , Z= ×3+1+1= =
8 4 8 2 4 2 2 4
X 3 Y7 Z 10
For formula : = X3 Y7 Z10
4 4 4
1
(ii) 1 amu = 1.67 × 10–24 gram ; 1 amu = gram.
6.02  10 23
3 7 10
Mass  40   60   80 335  1.67  10 24
Density = = 4 4 4 amu/cc = = 69.8 gram/cc.
Volume (2  10 8 )3 8  10 24
Some Definations
Coordination number : The number of nearest neighbours sphere in a packing is called coordination number.
Density of unit cell : It is the ratio of mass of the spheres present in unit cell and total volume of unit cell.
z M
Density of the unit cell= gcm–3
a 3  NA  10 30
Packing efficiency : The perecentage of total space filled by the particles is called packing efficiency. Different
types of packing arrangements have different packing efficiency.
Volume of atoms in a unit cell
Packing efficiency =  100
Total volume of a unit cell
Structure of Solids :
1-D Lattice :
Figure
Figure
 Arrangement of maximum stability.  Arrangement of minimum P.E.
 Arrangement of closet packing.  Arrangement of maximum efficiency (100%).
2-D Lattice : Can be considered to be made up of one dimensional array or lines.
Table : 5
3-D Lattice : When 2-D close packed layers are kept on each other 3-D close packing will be generated.
(A) Square packed sheets :
(i) Square packed sheets are kept on another such that -
atoms / spheres of one sheet are exactly above spheres of other sheet.
 A A A A ........... pattern repeat.
 Simple cube can be taken as unit cell of this particular lattice :
Figure
(i) Relation between a & R. corner atoms are touching each other so, a = 2R.
1
(ii) Effective no. of atom (Z) (per unit cell). Z = 8 [corner] × = 1 atom.
8
4
1 R 3
3 
(iii) Packing efficiency :  = 52.33%.
3 6
(2 R )
Mass of unit cell  ZM 

 
(iv) Density = volume of unit cell   3 .
 NA  a 
(v) Co-ordination number :
Number of nearest neighbors’s or (no. of sphere which are touching any particular sphere). CN = 6.
Figure
Table : 6
Type of neighbour Distance No. of neighbours
3  8 
(i) Nearest a 6   6
 4 
3  8 
(ii) (next)1 2a 12   12
 2 
 1 8 
(iii) (next)2 3a 8   8
 1 
(iv) (next)3 2a 6
(v) (next)4 5a 24
(2) Square packed layer are placed such that sphere of one layer occupy the depression of other layer.
 AB–AB type of arrangement of square sheet in 3-D.
Figure
Body centered cubic (BCC) :
Figure
 Not so close pack arrangement.
 The lattice point in 2-D array do not touch each other. The sphere start touching each other only upon
moving from 2-D to 3-D.
 2-D array placed on top of each other such that sphere of next plane are into cavities of first plane of
sphere.
(i) Relation between a & R : (a  2 R)
Sphere are not touching along edge they touching along the body diagonal. So 3 a = 4 R.
1
(ii) Effective no. of atom (Z) = 8 × [corner] × +1=2
8
4
2 R 3
3 3
(iii) Packing fraction = 3
= = 68%.
 4R  8
 
 3
(iv) Co-ordination No. (CN) = 8.
ZM
(v) Density = where Z = 2.
N A (a)3
Table : 7
3a
(i) Nearest = 2R 8
2
(ii) (next)1 a 6
2
(iii) (next) 2a 12
11 a
(iv) (next)3 24
2
(v) (next)4 3a 8
Note : In bcc crystal structure, the co-ordination no. is 8 because each atom touches four atom in the layer above it,
four in the layer below it and none in its own layers.
Ex. How many 'nearest' and 'next nearest' neighbours respectively does potassium have in b.c.c. lattice
(A) 8, 8 (B) 8, 6 (C) 6, 8 (D) 8, 2
Ans. (B)
Ex. If a metal has a bcc crystal structure, the coordination number is 8, because :
(A) each atom touches four atoms in the layer above it, four in the layer below it and none in its
own layer.
(B) each atom touches four atoms in the layer above it, four in the layer below it and one in its
own layer.
(C) two atoms touch four atoms in the layer above them, four in the layer below them, and none in
their own layer.
(D) each atom touches eight atoms in the layer above it, eight in the layer below it and
none in its own layer.
Ans. (A)
Ex. Potassium crystallizes in body centered cubic lattice with a unit cell 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 have
(E) What is calculated density of crystalline K.
Sol. (A) 4.5 Å, (B) 5.2, (C) 8 , (D) 6 (E) 0.92 g/mL
3a 3  5.2
(A) 2r = = = 4.5 Å (B) distance = a = 5.2 Å
2 2
(C) 8 (D) 6
2  39
(E) d = 8 3 = 0.92 g/ml
(5.2  10 )  6.02  10 23
(B) Arrangement of hexagonal closed packed sheets :

 To generate close packing two dimensions arrangement must be
hexagonal.
 Sheet are arranged such that void or depressions of one sheet are
a a
occupied by sphere of other sheet.
b b b
 Only 50% void of one layer can be occupied by sphere of other
layer (II layer). a
b b
 Now there will be two method to place III layer on the II layer.
Figure
(1) Hexagonal close packing (HCP) AB–AB–AB- - - -Type.
 Sphere of III layer occupy those voids of II layer under which there are sphere of Ist layer. So third
layer is exactly identical to Ist layer.
That why this generate ABAB- - - -AB pattern.
One type of void always remain on occupied.
Unit cell : a = 2r = b;  = 120º
Figure
(i) Relation between a, b, c and R :

a = b = 2R
Figure
 1a 3 a
a a 3 3 6 3a 2
tan30 = 2  y So y= = a. Area = 6  2  2  =
2 1 2   4
calculation of c.
Figure
a 2a a
cos30º = x= =
2 x 2 3 3
a2 2
Applying pythogoras theorem : x2 + h2 = a2 so h2 = a2 – x2 = a2 – = a2
3 3
2 2
h= a so c = 2h = 2 a
3 3
so volume of hexagon = area of base × height
6. 3 2 6. 3 2
= × a2 × 2 a = × (2R)2 + 2 × (2R) = 24 2 R3
4 3 4 3
1 1
(ii) Effective no. of atoms (Z) : Z= 3 + 2 × + 12 × = 3 + 1 + 2 = 6.
2 6
4
6  R3 
(iii) Packing efficiency : = 3 = = 74%.
24 2 R 3 3 2
(iv) Coordination number, (CN) = 12

(Each sphere touch 6 sphere in its layer 3 above and 3 below)
mass  Z M 
(v) Density (d) = =  N  volume  (z = 6)
volume  A 
(2) ABC–ABC arrangement (Cubic close packing (FCC))
Third layer sphere are placed such that these occupy those 50% voids of II layer under which there are
void of Ist layer.
a a
b b b
a
b b
Figure
 IIIrd layer will be different from Ist layer as well as IInd layer.
 ABC–ABC type of arrangement.
 It is also known as cubical close packing, unit cell chosen is face centered unit cell (FCC).
Figure
Figure
Figure
(i) Relation between ‘a’ and ‘R’ :
a  2R  2a  4R (sphere are touching along the face diagonal)
1 1
(ii) Effective no. of atoms per unit cell (Z) : Z= 8 6  4
8 2
4
4  R3 
(iii) Packing fraction : P.F.  3  22 = = 0.74( 74% )
4  4  4 R3 3 2
(iv) Coordination number, (CN) = 12
ZM
(v) Density (d) =
NA . a3
Table : 8
a
Nearest 12
2
(Next)1 a 6
3
(Next)2 a 24
2
(Next)3 2a 12
5
(Next)4 a 24
2
Ex. A metal crystallizes in two cubic phases i.e., FCC and BCC whose unit cell lengths are 3.5Å and 3.0 Å
respectively. The ratio of their densities is :
(A) 3.12 (B) 2.04 (C) 1.26 (D) 0.72
Ans. (C)
ZM d1 4 (3 )3
Sol. d= d2 = (3.5)3  2 = 1.26.
a 3N A
Ex. In a ccp structure, the :

(A) first and third layers are repeated (B) first and fourth layers are repeated
(C) second and fourth layers are repeated (D) first, third and sixth layers are repeated.
Ans. (B)
Ex. Lithium borohydride crystallizes in an orthorhombic system with 4 molecules per unit cell. The unit cell
dimensions are a = 6.8 Å, b = 4.4 Å and c=7.2 Å. If the molar mass is 21.76, then the density of crystals
is :
(A) 0.6708 g cm –2 (B) 1.6708 g cm –3 (C) 2.6708 g cm –3 (D) None of these.
Ans. (A)
ZM 4  21.76
Sol. d = a 3N = = 0.6708 g cm 2–.
A 6.8  10 8  4.4  10 8  7.2  10 8  6.023  10 23
Ex. An fcc lattice has lattice parameter a = 400 pm. Calculate the molar volume of the lattice including all the
empty space:
(A) 10.8 mL (B) 96 mL (C) 8.6 mL (D) 9.6 mL
Ans. (D)
Sol. Volume of 4 atoms = a3 = (4  10–8)3 cm 3
( 4  10 8 )
volume of NA atoms =  6.023  1023 = 9.6 ml.
4
Types of voids found in close packings :
 Although the close packed structure have maximum packings efficiency, but there are some empty space
left in arrangement.
Voids (Interstitial Voids) : Although the close packed structures have the maximum packing efficiency, there
are indeed empty spaces left in the arrangements. These empty spcesa are known as voids or. Interstitial
Voids.
 Maximum size of sphere which can be place in void space is depends on size of void.
R  Radius of sphere
r  Radius of sphere placed in void.
2-Dimensions void :
(i) Triangular void [2D–3 coordinate void]
 This type of void found in close packed structure of plane when three sphere are in contact.
Figure
 R  R  r  1 r
cos30° =  R  r   R  = ; = 0.155.
    cos 30 º R
3-Dimensions void :
(i) Tetrahedral void [3D-4 coordinate void]
 If IInd layer sphere are placed over a triangular void then new void is tetrahedral.
Figure
 R  r
sin54º44’ =  R  r  = 0.225
  R
3-Octahedral void : [3D–6 coordinate void]
Octahedral void is formed when ever two sphere are placed, one on top and the other below a square arrangement
of sphere.
Figure
 This can also be obtained by placing two three ball arrangement on the top of each other.
Figure
r
2 a = 2[R + r] ; 2 2 R = 2[R + r]. = 0.414
R
(3) Cubical void (3D-8-coordinate void)
Sphere are touch along body diagonal :
3 a = 2 [R + r]
2 3 R = 2 [R + r]
r
= 0.732 Figure
R
Location of void :
(i) FCC or CCP unit cell :
(a) Tetrahedral void :
 FCC unit cell has 8 tetrahedral void per unit cell. Just below every corner of the unit cell.
 As unit cell has 8 corner that’s why FCC unit cell has 8 tetrahedral void per unit cell.
3a 3a
 Distance of tetrahedral void form corner is and distance between two tetrahedral void is = .
4 2
 FCC unit cell has 4 body diagonal and each body diagonal contain 2 tetrahedral void that’s why total
tetrahedral void = 8.
 If a large size cube is divided in 8 minicube than center of each minicube contain one tetrahedral void and
3a
distance of center of minicube from corner is .
4
 For FCC unit cell Z = 4 and tetrahedral void = 8 so tetrahedral void = 2 Z.
(b) Octahedral void (OV) :
 Each edge center of FCC unit cell have one octahedral void and body center also contain 1 OV.
1
 Number of octahedral void per unit cell (Z) = 12 [Edge center] × + 1[Body center] = 4.
4
* For FCC unit cell (Z) = 4 and octahedral void = 4.So octahedral void = Z.
Hexagonal close packing (HCP) unit cell :
(a) Tetrahedral void :
 HCP unit cell have total 12 tetrahedral void per unit cell.
 Out of which 8 are completely inside the unit cell and 12 are shared. Which are present on edge center and
1
contribution of each sphere present on edge center is so.
3
1
Tetrahedral void (TV) = 8[Inside body] + 12 [Edge center] × = 12.
3
For HCP unit cell (Z) = 6.
So tetrahedral void = (Z × 2) = 12.
(b) Octahedral void :
HCP unit cell have total 6 octahedral void, which are completely inside the unit cell.
So octahedral void = 6.
Note :
Table : 9
Unit cell Z Tetrahedral void = Z × 2 Octahedral void = Z × 1
CCP (FCC) 4 8 4
HCP 6 12 6
Ex. (a) In a face centred cubic arrangement of metallic atoms, what is the relative ratio of the sizes of tetrahedral
and octahedral voids?
(A) 0.543 (B) 0.732 (C) 0.414 (D) 0.637
Ans. (A)
rtetrahedra l 0.225 R
Sol. roctahedral = 0.414 R = 0.543.
(b) The numbers of tetrahedral and octahedral holes in a ccp array of 100 atoms are respectively
(A) 200 and 100 (B) 100 and 200 (C) 200 and 200 (D) 100 and 100
Ans. (A)
Ex. Copper has a face-centred cubic structure with a unit-cell edge length of 3.61Å. What is the size of the largest
atom which could fit into the interstices of the copper lattice without distorting it?
Figure
(Hint. : Calculate the radius of the smallest circle in the figure)
Ans. 0.53Å
Sol. roctahedral = 0.414 R
for FCC 4R = 2a
2a
R=
4
0.414 2 a 0.414 2  3.61

r= = = 0.53 Å
4 4
Structure of ionic compounds
Structure 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.
Radius Ratio Rule : Radius ratio = (r+/r–) , The ratio of radius of cation to the radius of anion is known as radius
ratio of the ionic solid. This gives the idea about the type of void occupied.
 r 
Radius ratio =  r  ,this gives the idea about the type of void occupied.
  
Type of void Coordination Ex.of ionic

Tab-10: Radius ratio occupied No. Compounds
r+/r– < 0.155 linear void 2
0.155  r+/r– < 0.225 triangular void 3 Boron oxide
0.225  r+/r– < 0.414 tetrahedral void 4 Zinc sulphide
0.414  r+/r– < 0.732 octahedral void 6 Sodium chloride
0.732  r+/r– < 1 cubical void 8 Caesium chloride
NOTE : In ionic compounds for maximum stability.

(1) A Cation must be surrounded by maximum number of anions and vice versa.
(2) Anion-anion and cation–cation contact should be avoided
 There will 2 different kind of atoms, cation & anion, so there will be two different coordination number (C.N.).
C.N. of cation = no. of anions surroundings any cation.
C.N. of anion = no. of cations surrounding any anion.
Considering a minicube
Mini
Cube
a/2
Figure
Cation will lie at the centre of the body diagonal of the mini cube of side a/2.
1
r– + r+ = × (body diagonal of minicube)
2
1 a fcc 4
r+ + r– = × afcc = (r  r– )
3 3
2 2
Structure of some ionic compound :

(1) NaCl type of structure (Rock salt structure) :
Figure
rNa 
 Experimental r – = 0.51.
Cl
(i) Cl– ions form the FCC lattice while Na+ ion occupy all the octahedral void.
(ii) Effective number of ion per unit cell
(iii) Effective number of Cl– ion per unit cell = 4
Effective number of Na+ ion per unit cell = 4
(iv) Formula of unit cell Na4Cl4
Formula of ionic compound = NaCl
Effective number of formula unit (Z) = 4
Z M
(v) Density (d) = N  a3
A
 Here 2 a  4RCl–  as anion–anion are not in contact.

 2[rCl– + rNa+] = a
(vi) Coordination number :
Coordination number of Cl– = Number of Na+ ion touching it = 6.
Coordination number of Na+ = 6 [placed in octahedral void of Cl– ions].
Anion Cation
Figure
For Cl– :
Table : 11
a
Nearest Na+, 6
2
a
(Next)1 Cl–, 12
2
3
(Next)2 Na+ (B.C.), a 8
2
(Next)3 Cl–, a 6
Example : Halide of Li, Na, K and Rb, AgCl, AgBr, NH4Cl.

Note : Lattice of NaCl is FCC of Cl– in which all octahedral void are occupied by Na+.
or  FCC of Na+ in which octahedral void are occupied by Cl–.
(2) ZnS type (Zinc blende) (AB type) (4 : 4 coordination number compound) :
Figure
Zinc blende type :
(i) S2– ion form the FCC lattice.
 Zn2+ ion occupy alternate (non adjacent) four tetrahedral void.
Figure
(ii) Effective number of ion
Effective number of S2– ion per unit cell = 4.
Effective number of Zn2+ ion per unit cell = 4.
(iii) Formula of unit cell = Zn4S4
Formula of ionic compound = ZnS
rZn 2 
(iv) r 2 – = 0.3
S
so anion–anion contact is not there.
3
so [rZn2+ + rS2–]= a
4 FCC
 Z M 
(v) Density (d) =  3
 M = 97 gram/mole.
 NA  a 
(vi) Coordination number :

Coordination number of Zn2+ ions = 4.
Coordination number of S2– ions = 4.
Ex : ZnS, CuCl, CuBr, CuI, AgI.
For S2–
Table : 12
Type of neighbour Distance No. of neighbours Ions
3
Nearest a 4 Zn2+
4 FCC
a
(Next)1 12 S2–
2
11
(Next)2 a 12 Zn2+
4
(Next)3 a 6 S2–
19
(Next)4 a 12 Zn2+
11 FCC
(3) CaF2 [Flourite structure] [AB2 type]

Coordination number of compound
Figure
(i) Ca2+ ion form the FCC lattice.
 F– ion occupy all tetrahedral voids.
(ii) Coordination number of F– ion = 4  It occupy tetrahedral void.
 Coordination number of Ca2+ ion = 8
(iii) Effective number of Ca2+ ion = 4.
 Effective number of F– ion = 8.
(iv) Formula of unit cell = Ca4F8
 Formula of ionic compound = CaF2.
(v) Effective number of formula unit cell (Z) = 4.
 Z M 
(vi) Density =  
 NA  a3 
rF –
3a
(vii) 0.225 < r 2 < 0.414 ; [rCa2+ + rF–] =
Ca 4
Other examples : CaF2 , SrF2 , BaF2, BaCl2.
2+
For Ca
Table : 13
, Type of neighbour Distance No. of neighbours Ions
3
Nearest 8 F–
4
a
(Next)1 12 Ca2+
2
11
(Next)2 24 F–
16
(Next)3 a 6 Ca2+
For F—
Table : 14
Type of neighbour Distance No. of neighbours Ions
3
Nearest 4 Ca2+
4
a
(Next)1 6 F–
2
a
(Next)2 12 F–
2
11
(Next)3 16 – Ca2+
(4) Na2O [Sodium oxide] [A2B type]

 Anti-fluorite structure [4 : 8 coordination compound]   O2– ion  FCC lattice.
Na+  All the tetrahedral void.
rCs 
(5) CsCl type of structure [8 : 8 coordination compound] : r – ~ 0.93
Cl
(i) Cl– form simple cubic lattice.
 Cs+ ion occupies cubical void.
(ii) Effective number of ion :
 Effective number of Cs+ ion = 1.   Effective number of Cl– ion = 1.
(iii) Formula of ionic compound = CsCl. So Z = 1.
 Z M 
(iv) Density (d) =  3

 NA  a 
 anion–anion contact is not there so,
2[rCl– + rCs+] = 3 aSc
(v) Coordination number of Cs+ ion = 8.
(vi) Coordination number of Cl+ ion = 8.
Other example : CsCl, CsBr, CsI.
Note : On increasing pressure  Coordination number tends to increase.
On increasing temperature  Coordination number tends to decrease.
P T
4 : 4  6 : 6 ; 8 : 8  6 : 6
Other important structure :

(1) Spinel structure [AB2O4] : Spinel is an oxide consisting of two type of metal ions with the oxides ion
arranged in CCP layers in normal spinel one eight of the tetrahedral holes occupied by one type of metal ion and
one half of the octahedral holes occupied by another type of metal ion.
Ex : A spinel is formed by Zn2+, Al3+ and O2– with Zn2+ ion in the tetrahedral holes. The formula of the spinel is
ZnAl2O4.
(2) Perovskite structure [ABO3] : This structure may be described as a cubic lattice, with barium ions occupying
the corners of the unit cell, oxide ions occupying the face centers and titanium ions occupying the centres of the
unit cells.
Ex : BaTiO3 or MgTiO3.
(3) Lattice of diamond :
 ZnS types in which all S2– location and all Zn2+ location are occupied by C atoms.
So, Z = 8 atom per unit cell
4
aFCC = [dC – C]
3
dC – C = 2rC – C where rC – C is radius of C-atom.
 Packing efficiency = 34%.

 In crystal lattice of diamond, carbon atoms adopt FCC arrangement with occupancy of 50%
tetrahedral voids.
2 2
Note : (1) Distance between two plane in FCC or HCP arrangement is a or a = 2R = 2 R.
3 3
(2) If number of unit cell along one edge are ‘x’ then total number of unit cell in cube = x3.
e.g.
Figure
Number of unit cell along one edge = 2, then total number of unit cell in cube = 23 = 8.
Ex. A mineral having formula AB2 crystallize in the cubic close packed lattice, with the A atoms occupying the
lattice points. What is the co-ordination no. of A atoms? of the B atoms? what fraction of tetrahedral sites
is occupied by B atoms.
Ans. 8, 4, 100%.
It has fluorite (CaF 2) structure.
Ex. CsBr has b.c.c. structure with edge length 4.3 A. The shortest inter ionic distance in between Cs + and Br –
is:
(A) 3.72 (B) 1.86 (C) 7.44 (D) 4.3
Ans. (A)
3a 3  4. 3
Sol. r+ + r– = = = 3.72 Å .
2 2
Crystal imperfections / defects
Imperfections can be because of :-
- Conditions under which crystals have been developed,
- Impurities,
- Temp (because of thermal conductivity some atoms/ions can get displaced)
These imperfections can be
(a) Point defects - defects will be only at certain lattice positions.
(b) Line defects - If atoms/ions are misplaced/missing/replaced by some other ions along a line.
(c) plane (screw) defects - If atoms/ions are misplaced/missing/replaced by some other ions along a line
in a plane.
Point Defects :
1. Stoichiometric -The formula of compound remains same even after presence of these defects.
2.Non-stoichiometric -The formula of compound will get modified because of the presence of these defects.
(i) Stoichiometric defects :
(a) Schottkey (b) Frenkel (c) Interstitial
Missing ions pairs Cation Anion dislocated cation Cation Anion Interstitial entity
Cation Anion
Sc hottky defec t Frenkel defec t Interstitial defec t

Figure
Schottkey : When atoms/point are totally missing from the lattice.
net density of crystal will get decreased
exp < theoritical
  th –  exp 
% missing units =   th
  100 %

 
Frenkel : When atoms/ions displaced from normal lattice positions and are present in some interstitial
voids.Density remains same
Interstitial :
When some small foreign atoms are trapped in interstitial voids of the lattice without any chemical reaction.
Formula remains the same exp > theortical
(ii) Non-stoichiometric defects :
(a) metal excess or cation excess defect :-
- If no. of missing anion is more than no. of missing cations.
- To maintain electrical neutrality some electron are trapped at anionic vacancies.
Because of these extra e– the electrical and optical (colour) properties of the compound get modified.
So these locations of e–s are also known as color centres (F - centres) .
ZnO - white in color at room temperature.
- on heating some O2– ion get released in the form of O2 and e– are trapped at their locations.
Because of this it because yellow in color.
(b) metal deficiency (cation deficiency) defects :
- no. of missing cations should be more than no. of missing anions.
- oxidation no. of cation will get modified to maintain electrical neutrality.
Cation Anion Sr+ 2 replacing Na+
F-centre
Na+ Cl- Na+ Cl- Na+ Cl-
-e Na+ Cl- Na+ Cl- Sr+ 2 Cl- Na+ Cl-
Na+ Cl- Na+ Cl- Na+ Cl-
Metal excess Cation Vac anc y
Figure
Ex. Which of the following is incorrect
(A) The defect is known as schottky defect

(B) Density of compound in the defect decreases
(C) NaCl(s) is example which generally shows this defect
(D) Stoichiometry of compound will change slightly.
Ans. (D)
Ex. Ferrous oxide (FeO) is experimentally found to have the formula Fe0.93O.Find the %age of Fe ions in +3 state.
Fe0.93O
Sol.
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
Properties of Solids :
(i) Electrical Properties
(ii) Magnetic Properties
(i) Electrical Properties : Solids exhibit an amazing range of electrical conductivities, the range of electrical
conductivities from 10–20 to 107 ohm–1 m–1. Solids can be classified into three types on the basis of their
conductivities.
(1) Conductors : Metals are goods condcutors and have conductiveites in the order 107 (m)–1.
(2) Insulators : Those solids which have very low conductivities ranging from 10–20 to 10–10 (m)–1 are electrical
insulators e.g.; MnO, CoO; NiO, CuO, Fe2O3, TiO2.
(3) Semicondutors : Those solids which have intermideidate conductivities generally from 10–6 to 104 (m)–1
are termed as semicondcutors.
Intrinsic Semicondcutors : The conduction by pure subtances such as silicon and germanium is called
intrisic conduction and these pure substances exhibiting electrical condcutivity are called intrinsic semicodcutors.
Causes of Conductance in Solids :
1. In most of the solids, conduction is through electron movement under an electric field.
2. In ionic solids conduction is by movement of ions in molten state.
3. The magnitude of electrical conductivity strongly depends upon the number of electrons available to take part
in conduction process.
4. In metals, conductivity strongly depends upon the number of electrons available per atom. The atomic orbitals
form moleuclar orbitals which are too close in energy to each other so as to form a band.
5. If conduciton band is not completely filled or it lies very close to a higher unoccupied band, then electrons can
flow easily under an electric field thereby showing conductivity.
6. In case of insulators, the gap between valence band conduction band is too large, so electrons cannot jump
from valence band to conduction band and very small conductivity is observed.
7. In case of semiconductors, the gap between valence band and conduction band is small and therefore some
of the electrons may jump from valence band to conduction and some conductivity is observed.
8. Electrical conductivity of semiconductors increases, with increase in temperature. This is due to the fact that
with increase in temperature, large number of valence electrons from the valence band can jump to conduction
band. Pure substances like silicon and germanium that exhibit this type of conducting behaviour are called
interinsic semiconductors.
9. For partical purpose, the conductivity of pure silicon and germanium is too low at room temperature, therefore,
there is need to increase the conductance by doping.
Figure
Doping : The conductivity of silicon and germanium can be increases by adding apporpirate amount of suitable
impurity. The process is called doping.
Type of Semiconductors :
(1) n-Type Semiconductors : Metal excess compounds conduct electricity through normal electron conduction
mechanism and are therefore n-type semiconductors.
Creation n-Type Semicondcutor :
1. When siliconk is doped with small amont of group -15 elements such as P, As or Sb, its electrical condcutivity
increass sharply.
2. In pure silicon each silocn atom uses its four valence electrons for the formation of four covalent bonds with
the neighbouring silicon atoms.
3. When silcon is doped with some group-15 element, the some of the positions in the lattice are substituted by
atoms fo groups -15 elements have five valence electrons. After forming the four covalent bonds with silicon (or
anyother group-14 element such as germanium). one excess electron is left on them.
4. Since this electron is not involed in bonding it becomes delocalized and contributre to electrical
conduction. Silicon dped with group 15 element behaves as a n-type semconductor.
(2) p-Type Semiconductors : Metal deficient compounds conduct electricity through positive hole conduction
mechanism and are therefore p-type semiconductors.
Creation p-Type Semiconductor :
1. Electrical conductivity of silicon or germinum can alos be increases by doping with some group-13 element
such as B, Al or Ga.
2. Goup-13 elements have only three valence electrons. The combine with group-14 elements to form an electron
deficient bond or electron vacancy or a hole. These holes can move sthough the crystal like a positve charge
giving rise to electrical condcutivity.
3. Gorup-14 elements doped with group-13 elements behave as p-type semicondcutors. In the presence of
electricl field the holes move in direction opposite to that of electrons.
Application of n-type and p-type semicondcutiors.

1. Diode is a combination of n-type and p-type semicondcutors used as rectifier.
2. They are used for making transitors which contains n-p-n and p-n-p junctions to amplify radio and audio
singnals.
3. The solar cell is photo-diode used to convert light energy into electrical energy.
13-15 Compouds : The solid state materials are porudced by combination of elements of goups 13 and 15 the
compounds thus obtianed are called 13-15 compouds e.g. InSb, AlP GaAs.
12-16 Compounds : The solid state compounds are obtianed by combination of elements fof groups 12 and 16
the compounds are called 12-16 compouds e.g. ZnS, CdS, CdSe and HgTe.
Super Conductivity : The electrical resistance of metals is found to depend on temperature. Electrical resistance
decreases with decrease in temperature and becomes almost zero near the absolute zero. Materials in this
state are said to possess. superconductivity. The phenonmenon of superconductivity was first discovered by
kammerlingh Onners in 1913 when he found that mercury becomes superconducting at 4.0 K temperature.
Transition Temperature : The temperature at which a substance starts behaving as super-condcutor is called
transition temperature.
(ii) Magnetic Properties
Every substance has some magnetic properties associated with it. The origin of these properties lies in the
electrons. Each electron in an atom behaves like a tiny magnet.
Its magnetic moment originates from two types of motions.
(i) its orbital motion around the nucleus. (ii) its spin around its own axis.
Figure : Demonstration of the magnetic moment associated with

(a) an orbiting electron and (b) a spinning electron.
On the basis of their magnetic properties, substances can be classified into five categories:
(i) paramagnetic (ii) diamagnetic (iii) ferromagnetic (iv) antiferromagnetic and (v) ferrimagnetic.
(1) Paramagnetism : When substances which are attracted by the external magnetic field are called paramagnetic
substances and the phenomenon is called as paramagnetism. Atoms ion or molecules containing unpaired
electron show this property, eg. O2 Cu2+, Fe3+ etc. these substances lost their magnetism in the absence of
magnetic field.
(2) Diamagnetic materials : Those materials which are repelled by magnetic field are called diamagnetic materials
e.g. Cu+, TiO2, NaCl and C6H6. They do not have unpaired electrons.
(3) Ferromagnetism : When substances show permanent magnetism even in the absence of the magnetic field
this phenomenon is called as Ferromagnetism and such substances as called as Ferromagnetic substances
e.g. Fe Ni Co and CrO2.
This type of magnetism arise due to the spontaneous alignment of magnetic moments due to unpaired electron
in the same direction.
(4) Anti Ferro Magnetism : Substances which are expected to possess paramagnetism or ferro magnetism on
the basis of unpaired electrons but actually they possess zero net magnetic moment are called Anti-ferromatic
substances and the phenomenon is called as Anti-ferromagnetism. eg. MnO, Anti-ferromagnetism is due to the
presence equal number of magnetic moments in the opposite direction.
(5) Ferrimagnetism : Substances which are expected to possess large magnetism on the basis of unpaired
electrons, but actually have small magnetic momentum are called ferrimagnetic substances eg. Fe3O4, ferrites
of the formula M2+, Fe2O4 where M = Mg, Cu, Zn etc. Ferrimagnetism arises due to the unequal moments in
opposite direction resulting in same net magnetic moment. On heating these substance loss their magnetism
and convert in to paramagentic substance
Curie Temperature : The temperature at which a ferromagnetic substance loses its ferromagnetism and
becomes only paramagnetic. For iron the curie temperature is 1033 K and for nickel 629 K, for Fe3O4 850 K.
Below this temperature paramagnetic solid becomes ferromagnetic.
Domain : In solid state the metal ions of ferromagnetic substances are grouped together into small regions
called domains.
Effect of Temperature on Metal (Conductor) Semiconductor or Insulator :
1. The conductivity of semiconductors and insulators increases with increase in temperature
2. The conductivity of metal (conductors) decreases with increase in temperature.
Ex. What is a semiconductor? Name the two main types of semiconductors.
Ans. Substances whose conductance lies in between that of metals (conductors) and insulators are called
semiconductors. Two main types of semiconductors are n-type and p-type.
Ex. Explain the following with suitable examples:
(i) Ferromagnetism (ii) Paramagnetism (iii) 12-16 and 13-15 group compounds.
Ans. (i) Ferromagnetism : When substances show permanent magnetism even in the absence of the magnetic
field this phenomenon is called as Ferromagnetism and such substances as called as Ferromagnetic substances
e.g. Fe Ni Co and CrO2.
This type of magnetism arise due to the spontaneous alignment of magnetic moments due to unpaired electron
in the same direction.
(ii) Paramagnetism : When substances which are attracted by the external magnetic field are called paramagnetic
substances and the phenomenon is called as paramagnetism. Atoms ion or molecules containing unpaired
electron show this property, eg. O2 Cu2+, Fe3+ etc. these substances lost their magnetism in the absence of
magnetic field.
(iii) 13-15 Compouds : The solid state materials are porudced by combination of elements of goups 13 and 15
the compounds thus obtianed are called 13-15 compouds e.g. InSb, AlP GaAs.
12-16 Compounds : The solid state compounds are obtianed by combination of elements fof groups 12 and 16
the compounds are called 12-16 compouds e.g. ZnS, CdS, CdSe and HgTe.
MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. Calculate the number of formula units in each of the following types of unit cells :
(a) MgO in a rock salt type unit cell
(b) ZnS in zinc blende structure
(c) platinum in a face-centred cubic unit cell.
Sol. (a) 4 (the same as in NaCl)
(b) 4
(c) 4 (1 at the corner, 3 at the face-centres)
2. A mineral having the formula AB2 crystallises in the cubic close-packed lattice, with the A atoms occupying the
lattice points. What is the coordination number of the A atoms and B atoms ? What percentage fraction of the
tetrahedral sites is occupied by B atoms ?
Sol. C.N. of A atom = 8
C.N. of B atom = 4
tetrahedral sites occupied by atoms B = 100% (all tetrahedral voids are occupied).
3. (a) What is the C.N. of Cr atom in bcc structure ?
(b) Cobalt metal crystallises in a hexagonal closest packed structure. What is the C.N. of cobalt atom ?
(c) Describe the crystal structure of Pt, which crystallises with four equivalent atoms in a cubic unit cell.
Sol. (a) 8, (b) 12, (c) fcc or cubic close packed.
4. Titanium metal has a density of 4.54 g/cm3 and an edge length of 412.6 pm. In what cubic unit cell does titanium
crystallise? (Ti = 48)
zM
Sol. Density d =
a3N0
d = 4.54 g/cm3 , M = 48g mol–1 , Z = ? N0 = 6.023 × 1023 mol–1
If value of z is known, structure can be decided
dN0a3 4.54  6.023  1023  ( 412.6  10 –10 )3

z= = =4
M 48
Thus, titanium has face-centred cubic structure.
5. MgO has a structure of NaCl and TiCl has the structure of CsCl. What are the coordination numbers of
ions in each (MgO and TiCl).
Sol. C.N. of Na+ in NaCl = 6
C.N. of Cl– in NaCl = 6
hence C.N. of Mg2+ is also = 6
and that of O– – or O2– = 6 in MgO
We know in CsCl
C.N. of Cs+ = 8
C.N. of Cl– = 8
Hence, Ti+ and Cl– , in TiCl, have also C.N. 8 each.
6. A solid AB has the NaCl structure, If radius of cation A+ is 120 pm, calculate the maximum possible value of the
radius of the anion B–.
Sol. We know for the NaCl structure, for maximum of radius of B–, the ratio r+ / r– should be minimum for octahedral
void i.e. 0.414.
radius of cation/radius of anion = 0.414
rA 
rB – = 0.414
r  120
rB – = 0.A414 = = 290 pm.
0.414
7. The C.N. of the barium ion Ba2+, in BaF2 is 8. What must be the C.N. of F– ion ?
Sol. C.N.of barium ion tells us that it is surrounded by eight fluoride ions (charge 8 × (–1) = – 8). In order to balance
out the eight negative charges, we need four barium ion (charge 4 × (+2) = +8). Hence, the C.N. of F– ions must
be 4.
8. The radius of calcium ion is 94 pm and of oxide ion is 146 pm. Predict the crystal structure of calcium oxide.
r 94
Sol. The ratio r– = = 0.644
146
The prediction is an octahedral arrangement of the oxide ions around the calcium. Because the ions have equal
but opposite charges, there must also be an octahedral arrangement of calcium ions around oxide ions. Thus
CaO structure is similar to Rock Salt(NaCI) structure.
9. Sodium metal crystallises in body centred cubic lattice with cell edge = 4.29 Å. What is radius of sodium atom?
Sol. In ‘BCC’ structure
body diagonal = 4 × rNa = 3 a
 4 × rNa = 3  4.29
3
rNa =  4.29 = 1.86 Å
4
10. CsCI crystallises in a cubic that has a CI– at each corner and Cs+ at the centre of the unit cell. If (rCs+) = 1.69
Å and rCI – = 1.81 Å, what is value of edge length a of the cube?
Sol. We assume that the closest Cs+ to CI– distance is the sum of the ionic radii of Cs and Cl.
= 1.69 + 1.81 = 3.50 Å
a 3
This distance is one-half of the cubic diagonal =
2
a 3
 = 3.50 Å  a = 4.04 Å
2
11. Platinum (atomic radius = 1.38 Å) crystallises in a cubic closest packed structure. Calculate the edge length
of the face-centred cubic unit cell and the density of the platinum (Pt = 195).
a
Sol. r= (for fcc), a = 2 2 r = 3.9 Å
2 2
ZM 4  195
density = = = 21.83 g/cm3 .
a3 N0 ( 3.9  10 8 )3  6.023  10 23
12. Calculate the edge length of the unit cell of sodium chloride given density of NaCI is 2.17 × 103 kg m–3 and
molecular weight 58.5 × 10–3 kg mol–1.
Sol. NaCI is face-centred cubic lattice so that number of NaCI molecules in a unit cell (z) = 4.
zM
We know density d =
a3N0
where a = length of the unit cell

Mz 4  58.8  10 3
Volume = a3 = dN = = 1.79 × 10–28 m3
0 2.17  103  6.02  1023
a = 5.64 × 10–10 m
a = 5.64 Å = 564 pm.
13. The effective radius of an iron atom is 1.42 Å. It has a rock-salt structure. Calculate its density (Fe = 56).
Sol. Due to rock-salt (fcc) structure, number of atoms in a unit cell (z) = 4.
zM
Thus, d (density) = a = 2 2 r = 2 2 × 1.42 × 10–8 cm
a3N0
4  56
 d= = 5.743 g/cm3
6.02  10 23  ( 2 2  1.42  10 8 )3
14. In a CPS (close packed structure) of mixed oxides, it is found that lattice has O2– (oxide ions), and one-half of
octahedral voids are occupied by trivalent cations (A3+) and one-eighth of tetrahedral voids are occupied by
divalent cations (B2+). Derive formula of the mixed oxide.
Sol. Number of octahedral voids per ion in lattice = 1
1 1
Hence, number of trivalent cations (A3+) = 1 × 
2 2
number of tetrahedral voids per ion in lattice = 2
1 1
Hence, number of divalent cations (B2+) = 2 × 
8 4
Thus, formula is A1/2 B1/4O or A2BO4.
15. An element crystallises as face-centred cubic lattice with density as 5.20 g/cm3 and edge length of the side of
unit cell as 300 pm. Calculate mass of the element which contains 3.01 × 1024 atoms.
Sol. z = 4 in fcc lattice M = ?, d = 5.20 g/cm3
a = 300 pm = 3 × 10–8 cm
 a3 = 27 × 10–24 cm3
N0 = 6.02 × 1023
dN0 a3 5.20 g / cm3  6.02  10 23 mol1  27  10 24 cm3

 M= = 4 = 21.13 g mol–1
z
Thus, 6.02 × 1023 atoms have = 21.13 g
21.13
 3.01 × 1024 atoms have = × 3.01 ×1024 g = 105.65 g
6.02  1023
16. Calcium crystallises in a face-centred cubic unit cell with a = 0.556 nm. Calculate the density if it contained
0.1% Vaccancy defects.
zM
Sol. Thus, density can be determined using d=
a3N0
3.996  40
d(with Vaccance defect) = = 1.5448 g/cm3
(0.556  10 7 )3  6.02  1023
Type (I) : Very Short Answer Type Questions : [01 Mark Each]
1. Define the term ‘space lattice.’
2. What is the percentage of free space in bodycentred cubic crystal ?

3. What is the number of tetrahedral voids in a unit cell of a cubic close-packed structure ?
4. What is the percentage efficiency of packing in case of a simple cubic lattice?
5. Octahedral voids are larger than tetrahedral voids or not. Give reason.
6. Solid elements of group 13 or 15 impurities with group 14 elements are found to exhibit unusual electrical
properties. Why ?
7. What is doping ? Why is it done ?
8. Explain the term dislocation in relation to crystals.

9. What type of semiconductor is obtained when Si is doped with boron?
10. Given an example of antiferromagnetic solid.

Type (II) : Short Answer Type Questions : [02 Marks Each]
11. Classify the following solids on the basis of bonding considerations :
CO2, MgO, Al, H2, Si, Gd, Pb, AgCl.
12. (i) Name the type of crystal shown in .
(ii) What is the relationship between a, b and c ?

(iii) What is the relationship ,  and ?
Are they equal to 90º or not ?
(iv) Give one example of a crystalline Fig. solid having this type of crystal lattice.
13. Define the following terms in relation of crystalline solids :
(i) Unit cell (ii) Coordination number
Give one example in each case.
14. Explain how you can determine the atomic mass of an unknown metal if you know its mass density and the
dimensions of unit cell of its crystal.
15. Calculate the packing efficiency of a metal crystal for a simple cubic lattice.
16. The length of the unit cell edge of a body centred metal crystal is 352 pm. Calculate the radius of an atom of
a metal.
17. An element (atomic mass = 60) having facecentred cubic structure has a cell edge of 400 pm. What is its
density ? [NA = 6.023 × 1023 ]
18. Copper crystallizes in to an fcc lattice with , edge length of 3.61x10–8 c.m. Calculate the density of copper.
(Given : At. No. of Cu :63.5g/mol.,NA: 6.023 x 1023)
19. Explain the following terms with suitable examples : (i) Schottky defect (ii) Interstitial defect
20. In corundum, oxide ions are arranged in hcp arrangement and the Al3+ ions occupy two third of the octahedral
voids. What is the formula of corundum ?
Type (III) : Long Answer Type Questions: [03 Marks Each]
21. An element crystallized in the simple cubic structure. Its density is 8 g cm–3 and its 200 g contains 24 × 1023
atoms. Calculate the edge length.
22. An element crystallises in a structure having fcc unit cell with edge length of 200 pm. Calculate its density, if 200
g of this element contains 24 × 1023 atoms.
23. An alloy of Cu, Au and Ag is found to have Cu forming simple cubic strcture, Ag atom occupy edge centres and
Au is at body centre. What is the formula of alloy ? Explain.
24. (a) Diamond and solid rhombic sulphur both are covalent solids but the latter has very low melting point then
former. Explain why ?
(b) Out of SiO2(s), Si(s), NaCl(s) and Br2(l) which is best electrical conductor and why ?
(c) Sodium metal has bcc structure with edge length 4.29 Å. What is the radius of an atom ? What is length of
body diagonal of unit cell ?
25. Calcium metal crystallizes in face cented cubic lattice with length 556 pm. Calculate the density of metal if it
contains, (i) 0.5% Frenkel defects (ii) 0.2% Schottky defects.
26. Account for the following :
(i) Fe3O4 is ferrimagnetic at room temperature but becomes paramagnetic at 850 K.
(ii) Zinc oxide on heating becomes yellow.
(iii) Frenkel defect does not change the density of AgCl crystals.
27. Define the following deffects (i) Stoichiometric point defect (ii) Non-stoichiometric point defect
28. What is meant by (i) 12–16 compound and (ii) 13–15 compound ? Give example.
29. How do electrical resistivity of the following class of materials vary with temperature ?
Semiconductor,metallic conductor, insulator.
30. Explain the following terms with one suitable example of each :
(i) Ferromagnetism (ii) Paramagnetism
Type (IV) : Very Long Answer type Questions [2 + 3 = 5 Marks]
31. (a) In reference to crystal structure, explain the meaning of ‘coordination number’. What is the number of atoms
in a unit cell of (i) a face centred cubic structure ? (ii) a body centred cubic structure ?
(b) The density of lead is 11.35 g cm–3 and the metal crystallizes with fcc unit cell. Estimate the radius of lead
atom. (At. mass of lead = 207 g mol–1 and NA = 6.02 × 1023 mol–1).
32. (a) Chromium metal crystallises in a body centred cubic lattice. The length of the unit cell edge is found to be
287 pm. Calculate the atomic radius of chromium.
(b) Silver crystellies in fcc lattice. If the edge length of unit cell is 4.07 x 10–8 c.m. and density of crystel is 10.5
g/cm3., calaulate the atomic mass of silver. (NA = 6.02 x 1023 atom/mole)
33. (a) An element (atomic mass=60) having face-centred cubic unit cell has a density of 6.23 g cm–3. What is edge
length of unit cell ?
(b) A metal (atomic mass=50) has a body-centred cubic crystal lattice. The density of the metals is
5.91 g cm–3. Find out the volume of the unit cell. [NA = 6.023 × 1023 ]
34. (i) What type of close packing is shown in Fig. ?
(ii) What is coordination number of central sphere ?
(iii) What is free space in this packing ?
(iv) How many atoms are present in single unit cell having this type of packing ?
1
35. (a) In a mixed oxide of a compound, th of tetrahedral voids are occupied by cation ‘A’. half of octahedral voids
8
are occupied by cation ‘B’ whereas oxide ion froms cubic close packed structure.
What will be the formula of oxide ? Explain.
(b) Calculate the efficiency in body centrad cubic crystal.
36. (a) What are ‘point defects’ in crystals ?
(b) Copper has fcc structure. If its density is 8.92 g cm–3, calculate its radius if atomic weight of Cu is 63.5 g mol–1.
37. (a) How are the following properties of crystals affected by Schottky and Frenkel defects :
(i) Density (ii) Electrical conductivity
(b) With the help of suitable diagrams, on the basis of band theory, explain the difference between
(i) a conductor and an insulator.
(ii) a conductor and a semiconductor.
LEVEL # 1
Q.10 The most malleable metals (Cu, Ag, Au) have
Questions
based on
Types of crystal close - packing of the type-
(A) Hexagonal close - packing
Q.1 Which one is called pseudo solid - (B) Cubic close - packing
(A) CaF2 (B) Glass (C) Body - centred cubic packing
(C) NaCl (D) All (D) Malleability is not related to type of
packing
Q.2 Graphite is an example of -
Q.11 The maximum percentage of available volume
(A) Ionic solid that can be filled in a face centred cubic
(B) Covalent solid system by an atom is -
(C) Vander waal's crystal (A) 74% (B) 68% (C) 34% (D) 26%
(D) Metallic crystal Q.12 The rank (effective atoms per unit cell) of a
Q.3 Amorphous solids - cubic unit cell is 4. The type of cell as-
(A) Possess sharp melting points (A) Body centred (B) Face centred
(B) Undergo clean cleavage when cut with (C) Primitive (D) None of these
knife Q.13 An element occurring in the BCC structure
(C) Do not undergo clean cleavage when cut has 12.08 x 1023 unit cells. The total number
with knife of atoms of the element in these cell will be-
(D) Possess orderly arrangement over long (A) 24.16 x 1023 (B) 36.18 x 1023
(C) 6.04 x 10 23 (D) 12.08 x 1023
distances
Q.14 The space occupied by B.C.C. arrangement
Q.4 Wax is an example of - is approx -
(A) Ionic crystal (B) Covalent crystal (A) 50% (B) 68% (C) 74% (D) 56%
(C) Molecular crystal (D) Metallic crystal
Q.15 In a close pack array of N spheres, the
Q.5 Crystals which are good conductor of number of tetrahedral holes are-
electricity and heat are known as - (A) 4N (B) N/2 (C) 2N (D) N
(A) Ionic crystals Q.16 Transition metals, when they form interstitial
(B) Covalence crystals compounds, the non-metals (H, B, C, N) are
(C) Metallic crystals accomodated in-
(D) Molecular crystals (A) Voids or holes in cubic - packed structure
(B) Tetrahedral voids
Q.6 Iodine crystals are - (C) Octahedral voids
(A) Metallic solid (B) Ionic solid (D) All of these
(C) Molecular solid (D) Covalent solid
Questions
Q.7 W hich among the following will show based on
Mathematical analysis of Crystal
anisotropy- Q.17 Ferrimagnetism is in -
(A) Glass (B) Barium chloride (A)   (B) 
(C) Wood (D) Paper (C)  (D) none of these
Q.8 Which is covalent solid- Q.18 If a is the length of unit cell, then which one
(A) Fe2O3 (B) Diamond is correct relationship-
(A) For simple cubic lattice, Radius of metal
(C) Graphite (D) All
a
atom =
Questions 2
based on
Packing in Crystals & Voids (B) For bcc lattice, Radius of metal
Q.9 The arrangement ABC ABC ........... is 3a
atom =
referred to as - 4
(A) Octahedral close packing (C) For fcc lattice,Radius of metal
(B) Hexagonal close packing a
(C) Tetrahedral close packing atom =
2 2
(D) Cubic close packing (D) All
Q.19 The number of atoms present in a simple Q.27 The shaded plane abcd is referred to as -
cubic unit cell are- Z
(A) 4 (B) 3 (C) 2 (D) 1 b
Q.20 The number of atoms/molecules contained in
one face centred cubic unit cell of a a
monoatomic substance is-
(A) 4 (B) 6 (C) 8 (D) 12 Y
c
Q.21 In a body centred cubic arrangement, the d
number of atoms per unit cell is -
X
(A) 8 (B) 2 (C) 1 (D) 4
(A) rectangular plane of symmetry
Q.22 The fraction of total volume occupied by the (B) diagonal plane of symmetry
atoms in a simple cube is - (C) unit plane
(D) none of these
   
(A) (B) 2 (C) 2 (D)
4 8 6 6
Questions
based on
Ionic Crystals
Questions
C. No., Symmetry in Crystal
based on Q.28 The C.N. of a M2+ in MX2 is 8. Hence, C.N.
Q.23 6 : 6 of NaCl coordination changes to 8 : 8 of X– is -
coordination on - (A) 8 (B) 6
(A) applying high P (C) 4 (D) 2
(B) increase in temperature Q.29 The melting point of RbBr is 682ºC, while
(C) both (A) and (B) that of NaF is 988ºC. The principal reason
(D) no effect on coordination that melting point of NaF is much higher
than that of RbBr is that-
Q.24 The second order Bragg diffraction of X-rays (A) The two crystals are not isomorphous
with  = 1.0 Å from a set of parallel planes (B) The molar mass of NaF is smaller than
in a metal occurs at an angle 60º. The that of RbBr
distance between the scattering planes in the (C) The internuclear distance, r c + ra is
crystals is - greater for RbBr than for NaF
(A) 1.155 Å (B) 1.00 Å (D) The bond in RbBr has more covalent
character than the bond in NaF
(C) 2.00 Å (D) 1.7 Å
Q.30 A binary solid (A + B¯) has a rock salt
Q.25 The elements of symmetry in a crystal are- structure. If the edge length is 400 pm and
(A) Plane of symmetry radius of cation is 75 pm the radius of anion
(B) Axis of symmetry is -
(C) Centre of symmetry (A) 100 pm (B) 125 pm
(D) All (C) 250 pm (D) 325 pm
Q.31 Each unit cell of NaCl consists of 4 chloride
Q.26 A crystal may have one or more planes and
ions and -
one or more axes of symmetry but it
(A) 13 Na atoms (B) 4 Na ions
possesses -
(C) 6 Na atoms (D) 8 Na atoms
(A) Two centres of symmetry
Q.32 In the unit cell of NaCl lattice there are –
(B) One centre of symmetry
(A) 3Na+ ions (B) 6Na+ ions
(C) No centre of symmetry –
(C) 6Cl ions (D) 4 NaCl units
(D) None of these
Q.33 TiCl has structure similar to CsCl, the co-
Questions
ordination number of Ti+ is - based on
Defects in Crystal
(A) 4 (B) 6
(C) 10 (D) 8 Q.40 Structure shown here represents -
Questions
based on
Radius Ratio
Q.34 For tetrahedral co-ordination the radius ratio
(r+ /r¯) should be - Cation
(A) 0.414 - 0.732 (B) > 0.732 Anion
(C) 0.156 - 0.225 (D) 0.225 - 0.414
Q.35 The ratio of cations to anion in a closed pack

tetrahedral is - (A) Schottky defect
(A) 0.414 (B) 0.225 (B) Frenkel defect
(C) 0.02 (D) None (C) metal excess defect
(D) none of these
Q.36 The radius of the Na+ is 95 pm and that of
Cl – ion is 181 pm. Predict the co-ordination Q.41 Which of the following defect, if present,
number of Na+ lowers the density of the crystal-
(A) 4 (B) 6 (A) Frenkel
(C) 8 (D) Unpredictable (B) Schottky
(C) Edge dislocation
Q.37 The ionic radii of Rb+ and I¯ are 1.46 and (D) Constitution of F-centres.
2.16 Å. The most probable type of structure
exhibited by it is - Q.42 The yellow colour of ZnO and conducting
(A) CsCl type (B) NaCl type nature produced in heating is due to-
(C) ZnS type (D) CaF2 type (A) Metal excess defects due to interstitial
cation
Questions (B) Extra positive ions present in an
based on
Electrical & Magnetic Crystals
interstitial site
Q.38 One among the following is an example of (C) Trapped electrons
ferroelectric compound- (D) All
(A) Quartz (B) Lead chromate
(C) Barium titanate (D) Tourmaline Q.43 In antiflourite structure, the negative ions -
(A) Occupy tetrahedral voids
Q.39 Certain crystals produce electric signals on (B) Occupy octahedral voids
application of pressure. This phenomenon is (C) Are arranged in ccp
called - (D) Are arrange in hcp
(A) Pyro electricity (B) Ferroelectricity
(C) Piezoelectricity (D) Ferrielectricity Q.44 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
LEVEL # 2
Q.1 How many number of atoms are there in a Q.9 A solid XY has NaCl structure. If radius of X+
cube based unit cell having one atom on is 100 pm. What is the radius of Y – ion-
each corner and two atoms on each body (A) 120 pm
diagonal of cube - (B) 136.6 to 241.6 pm
(A) 8 (B) 6 (C) 4 (D) 9 (C) 280 pm
Q.2 An alloy of copper, silver and gold is found (D) Unpredictable
to have copper constituting the C.C.P. lattice. Q.10 How many atoms are there in a unit cell of
If silver atoms occupy the edge centres and Mg which forms hexagonal crystals, there
gold is present at body centre, the alloy has being a face-centred atom in each end of
a formula- the unit cell and 3 completely enclosed
(A) Cu4Ag2Au (B) Cu4Ag4Au atoms within the unit cell-
(C) Cu4Ag3Au (D) CuAgAu (A) 4 (B) 6
Q.3 The number of atoms/molecules contained (C) 12 (D) 8
in one face centred cubic unit cell of a mono Q.11 A solid is made of two elements X and Z.
atomic substance is- The atoms Z are in C.C.P. arrangement while
(A) 1 (B) 2 (C) 4 (D) 6 atoms X occupy all the tetrahedral sites.
Q.4 In a face centred cubic arrangement of A & What is the formula of the compound -
B atoms whose A atoms are at the corner of (A) XZ (B) XZ2
the unit cell & B atoms at the face centres. (C) X2Z (D) Unpredictable
One of the A atom is missing from one corner Q.12 Close packing is maximum in the crystal-
in unit cell. The simplest formula of (A) Simple cubic (B) Face centred
compound is- (C) Body centred (D) None of these
(A) A7B3 (B) AB3
Q.13 The vacant space in B.C.C. unit cell is -
(C) A7B24 (D) A7/8 B3
(A) 32% (B) 10%
Q.5 Which is/are amorphous solids - (C) 23% (D) 46%
(A) Rubber (B) Plastics
Q.14 The density of KCl is 1.9893 g cm –3 and the
(C) Glass (D) All
length of a side unit cell is 6.29082 Å as
Q.6 A solid has a B.C.C. structure. If the distance determined by X-Rays diffraction. The value
of closest approach between the two atoms of avogadro's number calculated from these
is 1.73 Å. The edge length of the cell is- data is-
3 (A) 6.017 × 1023
(A) 200 pm (B) pm (B) 6.023 × 1023
2
(C) 6.03 × 1023
(C) 142.2 pm (D) 2 pm (D) 6.017 × 1019]
Q.7 In a close packed array of N spheres, the Q.15 The unit cell cube length for LiCl (just like
number of tetrahedral holes are- NaCl structure) is 5.14 Å. Assuming anion-
N anion contact, the ionic radius for chloride
(A) (B) 4N
2 ion is-
(C) 2N (D) N (A) 1.815 Å (B) 2.8 Å
Q.8 In a face centred cubic cell, an atom at the (C) 3.8 Å (D) 4.815 Å
face centre is shared by- Q.16 At room temperature, sodium crystallizes in
(A) 4 unit cells a body centred cubic lattice with a = 4.24 Å.
(B) 2 unit cells The theoretical density of sodium (At. wt. of
(C) 1 unit cell Na = 23) is -
(D) 6 unit cells (A) 1.002 g cm –3 (B) 2.002 g cm –3
(C) 3.002 g cm–3 (D) None of these
Q.17 In a body centred cubic cell an atom at the Q.24 ZnS is -
body of centre is shared by- (A) Ionic crystal
(A) 1 unit cell (B) 4 unit cells (B) Covalent crystal
(C) 3 unit cells (D) 2 unit cells (C) Metallic crystal
(D) Vander Waals' crystal
Q.18 In a face centred cubic lattice the number of
nearest neighbour for a given lattice point Q.25 LiF is a/an-
are- (A) Ionic crystal (B) Metallic crystal
(A) 6 (B) 8 (C) Covalent crystal (D) Molecular crystal
(C) 12 (D) 14
Q.26 A solid having no definite shape is called-
Q.19 In a solid, oxide ions are arranged in CCP. (A) Amorphous solid (B) Crystalline solid
Cations A occupy one-sixth of the tetrahedral (C) Anisotropic solid (D) None of these
voids and cations B occupy one-third of the
Q.27 The mass of a unit cell of CsCl corresponds
octahedral voids. The formula of the
to-
compound is -
(A) 8Cs+ and 1Cl¯ (B) 1Cs+ and 6Cl¯
(A) ABO3 (B) AB2O3 +
(C) 1Cs and 1Cl¯ (D) 4Cs+ and 4Cl¯
(C) A2BO3 (D) A2B2O3
Q.28 Close packing is maximum in the crystal
Q.20 A solid AB has rock salt structure. If the
lattice of -
edge length is 520 pm and radius of A+ is 80
(A) Simple cubic (B) Face centred
pm, the radius of anion B– would be -
(C) Body centred (D) None of these
(A) 440 pm (B) 220 pm
(C) 360 pm (D) 180 pm Q.29 The structure of MgO is similar to NaCl. The
co-ordination number of Mg is -
Q.21 A binary solid (A+ B –) has a zinc blende
(A) 2 (B) 6
structure with B¯ ions constituting the lattice
(C) 4 (D) 8
and A + ions occupying 25% tetrahedral
holes. The formula of solid is - Q.30 Each unit cell of NaCl consists of 14 chlorine
(A) AB (B) A2B atoms and-
(C) AB2 (D) AB4 (A) 13 Na atoms (B) 14 Na atoms
(C) 6 Na atoms (D) 8 Na atoms
Q.22 A certain metal crystallises in a simple cubic
structure. At a certain temperature, it Q.31 Schottky defect is noticed in-
arranges to give a body centred structure. In (A) NaCl (B) KCl
this transition, the density of the metal- (C) CsCl (D) All
(A) Decreases Q.32 The structure of sodium chloride crystal is-
(B) Increases (A) Body centred cubic lattice
(C) Remain unchanged (B) Face centred cubic lattice
(D) Changes without a definite pattern (C) Octahedral
Q.23 For the structure given below the site marked (D) Square planar
as S is a- Q.33 A crystal of Fe3O4 is-
(A) Paramagnetic (B) Diamagnetic
(C) Ferrimagnetic (D) None of these
S
Q.34 A cubic crystal possesses in all ..... elements
of symmetry-
(A) 9 (B) 13
(C) 1 (D) 23
Q.35 The structure of sodium crystal is-
(A) Tetrahedral void (B) Cubic void
(A) Body centred cubic lattice
(C) Octahedral void (D) None of these
(B) Face centred cubic lattice
(C) Octahedral
(D) Square planar
Q.36 Extremely pure samples of Ge and Si are Q.45 NH4Cl crystallizes in bcc lattice with edge
non-conductors, but their conductivity length of unit cell equal to 387 pm. If radius of
increases suddenly on introducing ....... in
Cl– is 181 pm, the radius of NH4 will be -
their crystal lattice-
(A) As (B) B (A) 174 pm (B) 154 pm
(C) Both (A) and (B) (D) None of these (C) 116 pm (D) 206 pm
Q.37 The co-ordination number of a body centred Q.46 8 : 8 coordination number of CsCl change into
atom is- 6 : 6 on -
(A) 4 (B) 6 (A) Applying high P
(C) 8 (D) 12 (B) Increasing temperature
(C) Both A and B
Q.38 Which is ferromagnetic- (D) Can't be changed
(A) Ni (B) Co
(C) CrO2 (D) All Q.47 Point defect which lowers the density of
materials -
Q.39 Which of the following is ferroelectric compound (A) schottky (B) Frenkel
(A) BaTiO3 (B) K4[Fe(CN)6] (C) Both (D) None of these
(C) Pb2O3 (D) All.
Q.40 An example of body cubic is - Q.48 At low temperature O2 freezes to form crystalline
(A) Sodium (B) Magnesium solid. Which term best describer the solid -
(C) Zinc (D) Copper. (A) Ionic crystal (B) Covalent crystal
(C) Metallic crystal (D) Molecular crystal
Q.41 Sodium crysrallizes in cubic lattice with cell
edge a=4.29Å. What is the radius of Na atom - Q.49 Arrangement of Cl– in CsCl is -
(A) HCP (B) Simple cubic
(A) 1.86 Å (B) 6.81 Å
(C) FCC (D) BCC
(C) 8.61 Å (D) 2.94 Å
Q.50 The decreasing order of the size of void is -
Q.42 A binary solid x+ y– crystallizes in rock structure.
(A) Cubic > Octahedral > Tetrahedral > Trigonal
If the edge lenght is 400pm and radius of cation
(B) Trigonal > Tetrahedral > Octahedral > Cubic
75pm, the radius of anion will be -
(C) Trigonal > Octahedral > Tetrahedral > Cubic
(A) 325 pm (B) 250 pm
(D) Cubic > Tetrahedral > Octahedral > Trigonal
(C) 125 pm (D) 325 pm
Q.51 In Ax By atoms of A occupy each corner of the
Q.43 A mineral having the formula AB2 crystallize in
cube and atom of B occupy centre of each face.
cubic close packed lattice with the A atoms
The composition will be -
occupying the lattice points. The coordination
(A) AB3 (B) A2 B3 (C) A3B (D) A3B4
number of atoms of A, atoms of B and the
fraction of the tetrahedral sites occupied by B
Q.52 Among solids highest melting point is
are respectively -
established by -
(A) 2, 6, 75% (B) 8, 4, 100%
(A) Covalent solids (B) Amorphous solids
(C) 3, 1,25% (D) 6, 6, 50%
(C) Ionic solids (D) Molecular solid
Q.44 In Corundum, oxide ions are arranged in hcp

Q.53 Pink colour in non stoichiometric LiCl is due
arrangement and aluminium ion occupy two third
to -
of the octahedral holes. Its formula is -
(A) Cl– ions in lattice (B) Li+ ions in lattice
(A) Al2O3 (B) Al2O4
(C) e– in lattice (D) Both A and B
(C) Al3O4 (D) AlO2.
QUESTIONS FROM COMPETITIVE EXAMS.

Choose the appropriate answer:
1. The number of unit cells in 58.5 g of NaCl is 9. In crystals structure of sodium chloride, the
[MP PMT 2000] arrangement of Cl– ions is [BHU 2002]
20
(1) 6 × 10 (2) 3 × 1022 (1) fcc (2) bcc
23 24
(3) 1.5 × 10 (4) 0.5 × 10 (3) both fcc and bcc (4) None of these
2. How many unit cells are present in a cube-shaped 10. Which of the following describes the hexagonal
ideal crystal of NaCl of mass 1.00 g? close packed arrangement of spheres?
[AIEEE 2003] [CETME 1995]
(1) 2.57 × 10 unit cells (2) 5.14 × 1021 unit cells
21
(1) ABC ABA (2) ABC ABC
(3) 1.28 × 1021 unit cells (4) 1.71 × 1021 unit cells
(3) ABABA (4) ABB ABBB
3. An element having bcc structure has 12.08 × 1023
unit cells. The number of atoms in these cells is 11. Bragg’s law is given by equation
[MP Engg 1994] [M.P.P.M.T. 1995, 2002]
23 23
(1) 12.08 × 10 (2) 24.16 × 10 (1) n  2 sin  (2) n  2d sin 
23
(3) 48.38 × 10 (4) 12.08 × 1022
1
4. An element (atomic mass = 100 g/mol) having bcc (3) 2 n  d sin  (4) n  d sin 
structure has unit cell edge 400 pm. Then, density of 2
the element is [CBSE 1996] 12. The second order Bragg diffraction of X-rays with
3 3
(1) 10.376 g/cm (2) 5.188 g/cm   1.00 Å from a set of parallel planes in a metal
(3) 7.289 g/cm 3
(4) 2.144 g/cm3 occurs at an angle of 60°. The distance between
the scattering planes in the crystal is
5. Ionic solids with Schottky defects contain in their
structure [CBSE 1994] [CBSE 1997]
(1) Equal number of cation and anion vacancies. (1) 0.575 Å (2) 1.00 Å
(2) Anion vacancies and interstitital anions (3) 2.00 Å (4) 1.15 Å
(3) Cation vacancies 13. The intermetallic compound LiAg crystallizes in a
(4) Cation vacancies and interstitial cations cubic lattice in which lithium and silver atoms have
6. In a solid lattice the cation has left a lattice site and co-ordination number of 8. To what crystal class
is located at an interstitial position, the lattice defect does the unit cell belong? [CBSE 1997]
is [AIIMS 1991] (1) Simple cubic (2) Face centred cubic
(1) Interstitial defect (2) Valency defect (3) Body-centred cubic (4) None
(3) Frenkel defect (4) Schottky defect
14. The ratio of close packed atoms to tetrahedral holes
7. A solid with high electrical and thermal conductivity in cubic close packing is [Pb. PMT 1998]
from the following is [CBSE 1994]
(1) 1 : 1 (2) 1 : 2
(1) Si (2) Li
(3) 1 : 3 (4) 2 : 1
(3) NaCl (4) Ice
8. If we mix a pentavalent impurity in a crystal lattice 15. In a metal ‘M’ having b.c.c. arrangement, edge
of germanium, what type of semiconductor formation length of the unit cell is 400 pm. The atomic radius
will occur? [CBSE 1996] of M is [CET Kuruskhetra 1998]
(1) p-Type (2) n-Type (1) 100 pm (2) 141 pm
(3) Both (1) and (2) (4) None of the two (3) 173 pm (4) 200 pm
16. Which of the following metal oxides is anti- 25. An ionic compound has a unit cell consisting of A
ferromagnetic in nature? [MP.PET 2002] ions at the corners of a cube and B ions on the
(1) MnO2 (2) TiO2 centres of the faces of the cube. The empirical
(3) VO 2 (4) CrO2 formula for this compound would be[AIEEE 2002]
17. Pick up the correct statement [CBSE 1998] (1) AB3 (2) A3B
(1) The ionic crystal of AgBr does not have Schottky (3) AB (4) A2B
defect 26. In a hexagonal close packed (hcp) structure of
(2) The unit cell having crystal parameters, a=b  c, spheres, the fraction of the volume occupied by the
spheres is A. In a cubic close packed structure, the
 =  = 90°,  =120° is hexagonal
fraction is B. The relation for A and B is
(3) In ionic compounds having Frenkel defect, the
[Kerala MEE 2000]
ratio r+/r– is high
(1) A = B (2) A > B
(4) The coordination number of Na+ ion in NaCl is 4
(3) A < B
18. Schottky defect in crystals is observed when (4) A is equal to the fraction is a simple cubic lattice
[CBSE 1998] 27. Coordination number of Na+ in NaCl is
(1) An ion leaves its normal site and occupies an [Manipal PMT 2002]
interstitial site (1) 3 (2) 4
(2) Equal number of cations and anions are missing (3) 5 (4) 6
from the lattice 28. A crystal lattice with alternate positive and negative
(3) Unequal number of cations and onions are ions has radius ratio 0.524, Its coordination number
missing from the lattice is [Manipal PMT 2002]
(4) Density of the crystal is increased (1) 3 (2) 4
19. The edge length of face centred unit cubic cell is (3) 6 (4) 12
508 pm. If the radius of the cation is 110 pm, the 29. When molten Zn is cooled to solid state, it assumes
radius of the anion is [CBSE 1998] HCP structure. Then the number of nearest
(1) 288 pm (2) 398 pm neighbours of Zn atoms will be
(3) 144 pm (4) 618 pm [CBSE PMT 2001]
20. Which of the following is not a crystalline solid? (1) 4 (2) 6
[CBSE 1998] (3) 8 (4) 12
(1) KCl (2) CsCl 30. The major binding force of diamond, silicon and
quartz is [Kerala M.E.E. 2002]
(3) Glass (4) Rhombic sulphur
(1) Electrostatic force (2) Electrical attraction
21. Potassium crystallizes with a [MP PMT 1998]
(3) Covalent bond force (4) Van der Waal’s force
(1) Face-centred cubic lattice
31. The inter-ionic distance for cesium chloride crystal
(2) Body-centred cubic lattice
will be [M.P.P.E.T. 2002]
(3) Simple cubic lattice (1) a (2) a/2
(4) Orthorhombic lattice
22. Which of the following is ferroelectric compound? (3) 3 a/2 (4) 2a / 3
[AFMC 1997] 32. A substance AxBy crystallizes in a face centred cubic
(1) BaTiO3 (2) K4[Fe(CN)6] (FCC) lattice in which atoms ‘A’ occupy each corner
of the cube and atoms ‘B’ occupy the centre of each
(3) Pb2O3 (4) None of these
face of the cube. Identify the correct composition
23. How many kinds of space lattices are possible in a of the substance AxBy. [IIT 2002]
crystal? [MP PMT 1998] (1) AB3 (2) A4B3
(1) 23 (2) 7 (3) A3B (4) Can’t be predicted
(3) 30 (4) 14 33. In a solid AB having NaCl structure, ‘A’ atoms
24. Example of unit cell with crystallographic dimensions occupy the corners of the cubic unit cell. If all the
a  b  c,     90,   90 is[AFMC 1998] face-centred atoms along one of the axes are
(1) Calcite (2) Graphite removed, then the resultant stoichiometry of the solid is
(3) Rhombic sulphur (4) Monoclinic sulphur (1) AB2 (2) A2B [IIT 2001]
(3) A4B3 (4) A3B4
34. The number of octahedral sites per sphere in fcc (1) AB3 (2) A3B [AIEEE 2006]
structure is [M.P.P.M.T. 2000] (3) AB (4) A2B
(1) 1 (2) 2 2+ –
45. The Ca and F are located in CaF 2 crystal,
(3) 4 (4) 8 respectively at face centred cubic lattice points and
35. The packing fraction for a body centred cubic is in [AIIMS 2006]
[M.P.P.M.T. 2000] (1) Tetrahedral voids
(1) 0.42 (2) 0.53 (2) Half of tetrahedral voids
(3) 0.68 (4) 0.82
(3) Octahedral voids
36. Which of the following crystals does not exhibit
Frenkel defect? [M.P.P.E.T. 2000] (4) Half of octahedral voids
(1) AgBr (2) AgCl 46. Which of the following statement is not correct ?
(3) KBr (4) ZnS [CBSE 2008]
37. Due to Frenkel defect the density of ionic solids (1) The number of Bravais lattices in which a crystal
[M.P.P.E.T. 2002] can be categorized is 14
(1) Decreases (2) Increases (2) The fraction of the total volume occupied by
(3) Does not change (4) Changes the atoms in a primitive cell is 0.48
38. Percentage of free space in a body centred cubic (3) Molecular solids are generally volatile
unit cell is: [CBSE 2008] (4) The number of carbon atoms in an unit cell of
(1) 28% (2) 30% Diamond is 4
(3) 32% (4) 34%
47. If ‘a’ stands for the edge length of the cubic systems
39. Semiconductors are derived from compounds of
simple cubic, body centred cubic and face centred
[Kerala MEE 2002]
cubic, then the ratio of radii of the spheres in these
(1) p-block elements (2) Lanthanides systems will be respectively,
(3) Actinides (4) Transition elements
40. With which one of the following elements silicon 1 3 1
(1) 1a: 3a : 2a (2) a: a: a
should be doped so as to give p-type of semiconductor 2 4 2 2
? [CBSE 2008]
(1) Boron (2) Germanium 1 1 1 3 2
(3) a: 3a : a (4) a: a: a
(3) Arsenic (4) Selenium 2 2 2 2 2
41. To get n-type doped semiconductor, impurity to be
added to silicon should have the following number 48. A compound contains two types of atoms X and Y.
of valence electrons [KCET 2001] It crystallizes in a cubic lattice with atoms X at the
(1) 1 (2) 2 corners of the unit cell and atoms Y at the body
(3) 3 (4) 5 centers. The simplest possible formula of this com-
pound is (DPMT 2009)
42. The appearance of colour in solid alkali metal halides
is generally due to [CBSE 2006] (1) X8Y (2) X2Y
(1) Interstitial positions (2) F-centres (3) XY (4) XY8
(3) Schottky defect (4) Frenkel defect 49. Copper crystallises in a face-centred cubic lattice
43. CsBr crystallises in a body centred cubic lattice. The with a unit cell length of 361 pm. What is the radius
unit cell length is 436.6 pm. Given that the atomic of copper atom in pm? (CBSE 2009)
mass of Cs=133 and that of Br = 80 amu and (1) 128 (2) 157
Avogadro number being 6.02 × 1023 mol–1, the density
(3) 181 (4) 108
of CsBr is [CBSE 2006]
(1) 4.25 g/cm3 (2) 42.5 g/cm3 50. Lithium metal crystallises in a body centred cubic
(3) 0.425 g/cm3 (4) 8.25 g/cm3 crystal. If the length of the side of the unit cell of
lithium is 351 pm, the atomic radius of the lithium will be
44. An ionic compound has a unit cell consisting of A
ions at the corners of a cube and B ions on the (CBSE 2009)
centres of the faces of the cube. The empirical (1) 240.8 pm (2) 151.8 pm
formula for this compound would be (3) 75.5 pm (4) 300.5 pm
BOARD LEVEL EXERCISE : HINT & SOLUTIONS

1. Space latice is the three demensional regular arrangement of atoms, ions or molecules represented by points
called lattice points.
2. In body-centred cubic crystal free space is 32%.
3. There are 8 tetrahedral voids in a unit cell of ccp structure.
4. Packing efficiency in a simple cubic lattice = 52.4%.
5. The size of octahedral void is larger than tetrahedral void because cation can occupy octahedral void if size of
cation is 0.414 times as large as anion whereas in tetrahedral voids it should be 0.225 times as large as anion.
6. It is because their presence leads to excess of electrons or leads to formation of positive holes which increase
electrical conductivity.
7. Doping is a process of adding impurities in a crystal lattice. It is done by adding calculated amount of impurity.
Addition of one boron atom per 105 silicon atoms increases the conductivity of silicon by 103 at room tempera-
ture.
8. Dislocations: A dislocation extends along lines and result from the imperfect orientation of planes with respect
to one another in the crystal.
9. p-type semiconductor
10. MnO is antiferromagnetic solid.
11. Molecular solids – CO2, H2 ; Ionic solids – MgO, AgCl

Covalent solids – Si ; Metallic solids – Gd, Al, Pb
12. (i) Triclinic (ii) a  b  c, (iii)    90º, (iv) CuSO4.5H2O

13. (i) Unit cell is the smallest portion of a crystal lattice which, when repeated in different directions, generates the
entire lattice.
e.g., primitive unit cells : simple cubic
centred unit cells : bcc, fcc, ecc
(ii) The number of spheres which are touching a given sphere is called the coordination number.
e.g., In simple cubic arrangement coordination number is : 6.
In bcc arrangement coordination number is : 8.
In hcp or fcc arrangement coordination number is : 12.
14. Given : Density, edge length, Perameter of simple cubic unit cell [½ Mark]
Asked : Atomic mass
Z  M / N0
Formulae : Density = 3 [½ Mark]
a  1030
Explanation : a pm = edge of the unit cell [½ Mark]

z = Number of atom present per unit cell
M = atomic mass
 Volume of the unit cell = (a pm)3 = a3 × 10–30 cm3.
15. In a simple cubic unit cell : Suppose the edge length of the unit cell = a and radius of the sphere = r.
1
Number of spheres per unit cell = × 8 = 1.
8
4 3
Volume of the sphere = r
3
Volume of the cube = a3 = (2r)3 = 8r3
4 3
 r 
3  
Fraction occupied, i.e., packing fraction = 3 = = 0.524.
8r 6
% of occupied volume = 52.4%.
16. Given : a = 352 pm. [½ Mark]
Asked : r = ?
3
Formulae : r = a (for bcc unit cell) [½ Mark]
4
Explanation : r = radius of an atom
a = edge length
3  352 1.732  352

Substitution & Calculation : r = = [½ Mark]
4 4
Ans. 152.416 pm. [½ Mark]

17. Given : M = 60 g mol–1, Z = 4, a = 400 pm = 400 × 10–10 cm, NA = 6.023 × 1023 [½ Mark]
Asked : d = ?
Z M
Formulae : d= [½ Mark]
NA  a3
Explanation : d = density
a = edge length
M = atomic mass
NA = Avagadro number
4  60
Substitution & Calculation : d = 23 [½ Mark]
6.023  10  ( 400  10 10 )
Ans.: 6.23 g cm–3 [½ Mark]

Z M 4  63 . 5
18. Density (d) = 3 = = 8.96 g/cm3
a  NA (3.61) 10 – 24  6.023 10 23
3
19. (i) Schottky defect : It occurs when the equal number of vacant cation and anion sites are found in lattice

structure. It decreases the density of the substance.
(ii) Interstitial defect : When some constituent particles (atom or molecules) occupy an interstitial site, the
crystal is said to have interstitial defect. This defect increases the density of the substance. For example, non-
ionic solids.
20. O2– ions are arranged in hcp,  number of O2– ions are equal to = 6
Al3+ ions occupy 2/3 of the octahedral voids.
2
No. of Al3+ ions =  6  Al 2 O6 Al2/3O1 Formula of corundum is Al
Al2O3.
3 3
6
21. Given : Z = 1 for simple cubic, M = 200 g, N = 24 × 10 atoms, d = 8 g cm , NA = 6.023 × 1023[½ Mark]
23 –3
Asked : a = ? [½ Mark]

Z M Z M
Formulae : d= ; a3 = [1 Mark]
NA  a3 dN
a = edge length
M = atomic mass
Z = Effective number of atoms
1 200
Substitution & Calculation : a3 =
8  24  1023
a3 = 10.41 × 10–24 cm3
a = 2.18 × 10–8 cm = 2.18 × 10–8 × 1010 pm = 218 pm. [ 1 cm = 1010 pm] [1 Mark]
Ans.: 218 pm.
22. Given : Z = 4 for fcc, M = 200 g, N = 24 × 1023 atoms, a = 200 pm = 200 × 10–10 cm = 2 × 10–8 cm.
[½ Mark]
Asked : d = ? [½ Mark]
Z M
NA  a3
a = edge length
M = atomic mass
Z = Effective number of atoms [½ Mark]
ZM 4  200
Substitution & Calculation :d = 
3
a N ( 200 )  10 30  24  10 23
3
4  200 1000
d =  24 23 = = 41.67 g cm–3 [1 Mark]
8  10  24  10 24
Ans.: 41.67 g cm–3
1 1
23. Cu forms sc  Cu = 8 × = 1 Ag at edge centres = 12 × = 3 Au at body centre = 1
8 4
Formula = Cu Ag3 Au
24. (a) It is due to strong covalent bonds in diamod whereas there are weak van der Waal’s forces of attraction in
S8 molecules. [1 M]
(b) Silicon is best conductor out of these because it is semiconductor whereas others are insulator in solid
state. [1 M]
(c) In bcc,4r = 3a [½ M]
3a 1.732  4.29Å 7.43

r =  ; r = Å = 1.857 Å
4 4 4
Body diagonal = 3a = 1.732 × 4.29 Å = 7.43 Å. [½ M]
25. (i) Frenkel defects have no effect on the density because number of atoms per unit cell remains the same.
Given : For fcc, Z = 4, Atomic weight of Ca = 40 g mol–1
a = 0.5506 nm = 0.556 × 10–7 cm, NA = 6.023 × 1023 [½ Mark]
Asked : d = ?
Z M
NA  a3
a = edge length
M = atomic mass
4  40 160 160
Substitution & Calculation : d = =  [1 Mark]
(0.556  10 7 )3  6.022  10 23 0.17  6.022  10 2 103.5
d = 1.5458 g cm–3 Ans.: 1.5458 g cm–3
(ii) Due to 0.2% Schottky defect, No. of atoms
0.2
– × 4 = 3.992 [½ Mark]
100
ZM 4  3.992
d = 3 = = 1.5427 g cm–3. [½ Mark]
a  NA (0.556  10 7 )3  6.022  10 23
26. (i) At 850 K ,Fe3O4 (magnetite) loses its alignment of magnetic moment is parallel and anti-parallel direction in

unequal numbers and become paramagnetic.
(ii) Zinc oxide is white in colour at room temperature. On heating it loses oxygen and turns yellow. (due to
formation of F - centre)
heating 1
ZnO   Zn2+ + O2 + 2e–
2
(iii) Due to Frenkel defect, no ions are missing from the crystal as a whole. Thus, there is no change in density.
27. Stoichiometric Defects :The compounds in which the number of positive and negative ions are exactly in the
ratios indicated by their chemical formulae are called stoichiometric compounds. The defects that do not
disturb the stoichiometry (the ratio of numbers of positive and negative ions) are called stoichiometric defects.
Non-Stoichiometric Defects :The defects which disturb the stoichiometry of the compound are called non-
stoichiometric defects. These defects are either due to the presence of excess metal ions or excess non-metal
ions.
28. (i) 12–16 Compound. A semiconductor formed by combination of group 12 and group 16 elements is called
12–16 compound e.g., ZnS, CdS, HgTe etc.
(ii) 13–15 Compound. A semiconductor formed by the combination of group 13 and group 15 elements is
called 13–15 compound e.g., AlP, InSb, GaAs etc.
29. In semiconductor, electrical resistivity decreases with increase in temperature. In metals, electrical resistivity
increases with increases in temperature and in insulators electrical resistivity decreases with increase in
temperature.
30. (i) Ferromagnetism : Materials which are strongly attracted by magnetic fields are called ferromagnetic

materials and the property thus exhibited is called ferromagnetism. only three elements (Fe, Co, Ni) show
ferromagnetism at room temperature.
(ii) Paramagnetism : Materials which are weakly attracted by magnetic fields are called paramagnetic materials
and the property thus exhibited is called paramagnetism. Paramagnetic substances contain unpaired electron.
e.g. TiO, CuO, O2 and VO2 etc.
31. (a) Coordination number : The number of nearest neighbours is a packing in a crystal structure is called
coordination number. [1 mark]
(b) Number of atoms in a unit cell of
(i) a face centred cubic structure is 4. (ii) a body centred cubic structure is 2. [½ + ½ = 1 marks]
(b) Given : Z = 4 for simple cubic, M = 207 g/mol, d = 11.35 g cm–3, NA = 6.023 × 1023 [½ Mark]

Asked : a = ?, r = ? [½ Mark]
Z M Z M a
Formulae : d= ; a3 = ; for fcc 4r = 2 a ; r = [1 Mark]
NA  a3 dN 2 2
a = edge length
M = atomic mass
r = Radius of an atom
Z M
Substitution & Calculation : Density (d) = (For fcc(z) = 4) [½ Mark]
a3  NA
4  207 828
11.35 = ; a3 =
a 3  6.02  10 23 11.35  6.023  10 23
1/ 3
 828  a
a =  23
 = 494.8 pm ; for fcc 4r = 2 a ; r =
 11.35  6.023  10  2 2
494.8
r = = 175 pm [1 Mark]
2 2
Ans.: 175 pm.
32. (a) Given : a = 287 pm. [½ Mark]
Asked : r = ? [½ Mark]
3
Formulae : For body centred cubic lattice, we have r = a [½ Mark]
4
Explanation : a = edge length
3 3 1.73  287 496 .51

Substitution & Calculation :r = a = × 287 = = = 124.1275 pm.[½ Mark]
4 4 4 4
Ans.: 124.1275 pm.
(b). Given : Z = 4, d = 10.5 g/cm3, a = 4.07 x 10–8 c.m, NA = 6.023 × 1023 [½ Mark]
Asked : M = ? [½ Mark]
Z M NA  a3  d
Formulae : d = 3 ; M = [1 Mark]
NA  a Z
a = edge length
M = atomic mass
d  a 3  NA 10.5  ( 4.07)3  10 24  6.02  10 23 4261 .564

Substitution & Calculation : M = = =
Z 4 40
= 106.5391 g/mol [1 Mark]
Ans.: 106.5391 g/mol
33. (a) Given : Z = 4 for simple cubic, M = 60 g/mol, d = 6.23 g cm–3 , NA = 6.023 × 1023 [½ Mark]
Asked : a = ?
ZM Z M
Formulae : d = 3
; a3 = [½ Mark]
NA  a dN
a = edge length
M = atomic mass
ZM 4  60 2400
Substitution & Calculation : a3 = N  d = = ×10–24
A 6.023  10 23  6.23 37.52
a3 = 64 × 10–24 cm3 ; a = (4 × 10–8 ×1010) pm = 400 pm [1 Mark]
Ans.: 400 pm.
(b) Given : M = 50 g mol–1, Z = 2, d = 5.91 g cm–3 , NA = 6.023 × 1023 [½ Mark]
Asked : V = a3 = ? [½ Mark]
Z M ZM
Formulae : d= ; Volume (V) = a3 = [1 Mark]
NA  a3 dN
a = edge length
M = atomic mass
ZM 2  50
Substitution & Calculation : d = 
NA  a3 a 3  6.023  10 23
2  50 100  10 23
a3 = = = 2.809 × 10–23 cm3 [1 Mark]
5.91 6.023  10 23 35.59
Volume = a3 = 2.809 × 10–23 cm3 Ans. 2.809 × 10–23cm3
34. (i) It is a hexagonal close packing
(ii) The coordination number is 12
(iii) Free space = 26%
(iv) Z = 6, There are six atoms in single unit cell having hexagonal close packing.
1 1
35. (a) Cations A = × 8 = 1 ; Cations B = × 4 = 2
8 2
1 1
O2– = 8 × + 6 × = 4 [ O2– forms cubic close packed structure]
8 2
AB2O4 is formula of mixed oxide.
4r
(b) In bcc, 4r = 3a a =
3
4 3
Volume of sphere = r ; Z = 2
3
4 3
Total volume occupied by all spheres = 2 × r
3
3
 4r 
Volume of cube = a = 
3 

 3
4 3
2
r
3 8 3 3 3 22
Efficiency = 100 × 444 3
r
= 100 ×   = 100 ×  = 68%
3 3
3 4 4 4 8 7
36. (a) Point defects. The defects which are caused by missing or misplaced atoms or ions in the crystal.
(b) Given : Z = 4, d = 8.92 g cm–3, M = 63.5 g mol–1, NA = 6.023 × 1023 [½ Mark]
Asked : a = ?, r = ? [½ Mark]
Z M Z M a
Formulae : d= 3 ; a3 = ; for fcc 4r = 2 a ; r = [1 Mark]
NA  a dN 2 2
a = edge length
M = atomic mass
ZM 4  63.5
Substitution & Calculation : d3 = N  d =
A 6.022  1023  8.92
254 .0
= × 10–23 = 4.728 × 10–23
53.716
d3 = 47.28 × 10–24
a = 3 47.28  10 8 x = (47.28)1/3
1 1
a = 3.616 × 10–8 × 1010 pm log x = log (47.28) = × 1.6746
3 3
a = 361.6 pm x = Antilog 0.558277
4r = 2a x = 3.616
a 361 .6 361.6
r = = r = = 127.86 pm [1 Mark]
2 2 2  1.414 2.828
Ans.: 127.86 pm
37. (a) (i) Schottky defect decreases the density of the crystal.
Frenkel defect does not change the density of the crystal.
(ii) Electrical conductivity of the crystal is increased in both Schottky and Frenkel defects.
(b) (i) In conductors the energy gap are very close or even overlapped by the conduction bands. Due to this
reason electron can flow very easily from valence to conduction band under an electronic field and shows
conductivity.
In insulator, the energy gap between the valence band and conduction band is too high so that electron can not
flow from valence band to conduction band. Therefore, no conduction is possible.
(ii) In semiconductor the energy gap between valence band and conductor band is small which make some of
the electron enable to jump from valence to conduction band and shows conductivity

LEVEL # 1
1. (B) 10. (B) 19. (D) 28. (C) 37. (B)

2. (B) 11. (A) 20. (A) 29. (C) 38. (C)
3. (C) 12. (B) 21. (B) 30. (B) 39. (C)
4. (C) 13. (A) 22. (D) 31. (B) 40. (A)
5. (C) 14. (B) 23. (A) 32. (D) 41. (B)
6. (C) 15. (C) 24. (A) 33. (D) 42. (D)
7. (B) 16. (D) 25. (D) 34. (D) 43. (C)
8. (D) 17. (C) 26. (B) 35. (B) 44. (C)
9. (D) 18. (D) 27. (B) 36. (B)
LEVEL # 2
1. (D) 12. (B) 23. (C) 34. (D) 45. (B)

2. (C) 13. (A) 24. (A) 35. (A) 46. (B)
3. (C) 14. (A) 25. (A) 36. (C) 47. (A)
4. (C) 15. (A) 26. (A) 37. (C) 48. (D)
5. (D) 16. (A) 27. (C) 38. (D) 49. (B)
6. (A) 17. (A) 28. (B) 39. (A) 50. (A)
7. (C) 18. (C) 29. (B) 40. (A) 51. (A)
8. (B) 19. (A) 30. (A) 41. (A) 52. (A)
9. (B) 20. (D) 31. (D) 42. (C) 53. (C)
10. (B) 21. (C) 32. (B) 43. (B)
11. (C) 22. (B) 33. (C) 44. (A)
QUESTIONS FROM COMPETITIVE EXAMS.
1. (3) 11. (2) 21. (2) 31. (3) 41. (4)

2. (1) 12. (4) 22. (1) 32. (1) 42. (2)
3. (2) 13. (3) 23. (4) 33. (4) 43. (1)
4. (2) 14. (2) 24. (4) 34. (1) 44. (1)
5. (1) 15. (3) 25. (1) 35. (3) 45. (1)
6. (3) 16. (1) 26. (1) 36. (3) 46. (2)
7. (2) 17. (2) 27. (4) 37. (3) 47. (2)
8. (2) 18. (2) 28. (3) 38. (3) 48. (3)
9. (1) 19. (3) 29. (4) 39. (1) 49. (1)
10. (3) 20. (3) 30. (3) 40. (1)
50. (2)
Solution & Colligative Porperties Boards / Medical
SOLUTION & COLLIGATIVE PROPERTIES

1. Introduction :
A solution is a homogeneous mixture of two or more substances which are chemically non-reacting. We come
across many types of solutions in our daily life. e.g., solid-liquid, liquid-liquid, gas-gas. In this chapter we will
learn several properties of solutions and their applications.
Solution : A homogeneous mixture of two or more substances is known as solution.

Solute : The substance present in smaller amount in a solution is called solute.
Solvent : The substance present in larger amount in a solution is called solvent.
Binary solutions : Those solutions which contain two components are called binary solutions, e.g., salt
solution, benzene and toluene.
Miscible liquids : Those liquids which mix with each other and form homogeneous mixture are called miscible
liquids.
Immiscible liquids : Those liquids which do not mix with each other are called immiscible liquids.
Alloys : Solid solutions of the two or more metals are called alloys. One of them can be a non-metal also.
The concentration of a solution can be expressed by different concentration terms which are described as
follows.
2. Types of Solutions :
S.No. Solute Solvent Types of Solutions Examples
Solid Solutions
1 Solid Solid Solid in solid All alloys like brass, bronze, an alloy of copper and gold, etc.
2 Liquid Solid Liquid in solid Amalgam of mercury with Na, CuSO4.5H2O. FeSO4.7H2O
3 Gas Solid Gas in solid Solution of H2 in Pd, dissolved gases in minerals.
Liquid Solutions
4 Solid Liquid Solid in liquid Sugar solution, salt solution, I2 in CCl4
5 Liquid Liquid Liquid in liquid Benzene in toluene, alcohol in water.
6 Gas Liquid Gas in liquid CO2 in water, NH3 in water etc.
Gaseous Solutions
7 Solid Gas Solid in gas Iodine vapours in air, camphor vapours in N2.
8 Liquid Gas Liquid in gas Water vapours in air, CHCl3 vapours in N2.
9 Gas Gas Gas in gas Air (O2 + N2)
3. Concentration Terms :
3.1 % Concentration
weight of solute (g)
 % w/w =
weight of solution (g) × 100
 It does not change on changing temperature.
Ex. 10% w/w urea solution = 10 gm of urea is present in 100 gm of solution.
= 10 gm of urea is present in 90 gm of water.
 % wt/vol. (w/v)
% w/v = wt. of solute/100 mL of solution
gram of solutes
% w/v = volume of solution in mL  100
 It changes on changing temperature.
Ex. 10% (w/v) urea solution. = 10 gm of urea is present in 100 mL of solution.
But not 10 gm of urea present in 90 ml of water
for dilute solution : volume solution = volume solvent.
% v/v
If both solute & solvent are liquids = volume in (mL) of solute per 100 mL of solution.
Ex. 10% v/v alcohol ethanol aq solution = 10 ml of ethanol in 100 ml of solution.
 10 ml of C2H5OH in 90 ml of H 2O
3.2 Strength of solution in g/L
Weight of solute (in gram) per litre (1000 mL) of solution.
Ex. 10% (w/v) sucrose solution, then specify its concentration in g/L
100 mL .......... 10 g
10
 1000 mL ........  1000 = 100 g/L
100
Ex If we have 6% w/w urea solution with density 1.060 g/mL, then calculate its strength in g/L ?
Solution 6 g urea is present in 100 gm solution.
100
6 g in mL
1.060
100
mL  6 gm.
1.060
6
 1000 mL = 100 × 1.060 × 1000 = 10.6 × 6 = 63.6
3.3 Molarity = No. of moles of solute per litre of solution.
Let n = No. of moles of solute
N = No. of moles of solvent
V = volume of solution
n W 1000
M = V (in L) =  M  x V (in mL )
 
no. of moles of solute = molarity x volume ( in L)
no. of m. moles of solute = molarity x volume ( in mL)
If V1mL of C1 molarity solution is mixed with V 2 mL of C2 molarity solution (same substance or solute)
 Cf (V1+V2) = C1V1 + C2V2
 C1V1  C 2 V2  Total moles
Cf =  V  V
 =
Total volume
 1 2 
 It changes on changing temperature.
3.4 Molality = No. of moles of solute per kg(1000 g) of solvent.
Let w gram of solute (Molar mass = Mg/mole) is dissolved in 'W' gram of solvent.
w 1000
molality =   x W ( g )
M
 
moles 1000
molality = W (g)of solvent
 It does not change on changing temperature.

Ex If 20 ml of 0.5 M Na2SO4 is mixed with 50 ml of 0.2 M H2SO4 & 30 ml of 0.4 M Al2(SO4)3 solution.
Calculate [Na+], [H+], [SO42–], [Al3+]. [Assuming 100% dissociation]
moles
Solution Molarity = = 10 m. moles of Na2SO4
volume
 20 m. moles of Na+
20
(i)  [Na+] = = 0.2 M
100
(ii) [H+]=?
10 m. moles H2SO4
20 m. moles H+
20
[H+] = = 0.2 M
100
10  10  36 56
(iii) [SO42–] = = = 0.56 M
100 100
24
(iv) [Al3+] = = 0.24 M
100
 Derive a relationship between molality & molarity of a solution in which w gm of solute of molar
mass M g/mol is dissolved in W g solvent & density of resulting solution = 'd' g/ml.
say 1 L solution taken,
mass of 1 lit solution = (1000 d) g
moles of solute = (molarity)
mass of solute = (molarity) x m
mass of solvent = W = 1000 d – (molarity) × m
(molarity )  1000
 molality = 1000 d  molarity  M.Wt [Where no.of moles of solute = molarity]
Ex Calculate molality of 1.2 M H 2SO4 solution ? If its  = 1.4 g/mL

1.2  1000
Soluiton Molality = 1000  1.4  1.2  98 = 0.936
3.5 Normality
no. of equivalent s of solute
No. of equivalents per litre of solution =
volume of solution (in L )
 No. of equivalents = normality  volume (in L)
(Normality = n-factor  molarity)
Molar mass
 Equivalent mass =
n  factor
Mass of the species Mass of the species
 No. of equivalent = = Molar mass
equivalent mass
n  factor
'n' - factor
(i) For oxidizing/reducing agents :
no. of e– involved in oxidation/reduction half reaction per mole of oxidising agent /reducing agent .
e.g. : 5e– + 8H+ + MnO4–  Mn2+ + H2O n- factor = 5
(ii) For acid/ base reactions :
no. of H+ ions displaced/ OH – ions displaced per mole of acid/ base.
e.g. : NaOH n - factor = 1 H2SO4 n - factor = 2
(iii) For salt:
n = Total charge on cations.
or
total charge on anions
e.g. : Al2(SO4)3 n - factor = charge on the cation = 2 x 3 = 6
3.7 Mole Fraction :
For binary mixture
moles of solute n
Xsolute = total moles in solutions =
nN
moles of solvent N
XSolvent = Total moles in solutions =
nN
Xsolute + XSolvent = 1
3.8 ppm (Parts Per Million).
wt. of solute (in g)
(a) ppm (w/w) = wt. of solution (in g) × 106 = 1 million
wt. of solute (in g)

(b) ppm (w/v) = vol. of solution (in mL ) × 106
moles of solute
(c) ppm (moles/moles) = moles of solution × 106
Table : 1
Ex If we have 10 molal urea solution, Calculate mole fraction of urea in this solution & also calculate
% w/w of urea (MW = 60).
Solution 10 moles urea in 1000 g of water
10 10
X urea = 1000 = 65.55 = 0.1526
10 
18
10  60
% w/w weight of urea = x 100 = 37.5%
10  60  1000
* Note : For dil. aq. solution molality  molarity
molarity  1000
molality = 1000  d  molarity  m  (1 g/ml)
Ex Calculate molarity of CaCO 3(aq.) solution which has concentration of CaCO 3 = 200 ppm.
Solution 200 g of CaCO 3 in 106 g of water.
200
 2 moles of CaCO 3 in 103 liters of water. (density =1g/mL)
100
2
So molarity = = 2 × 10–3 M.
103
4. Solubility : Solubility of a substance is its maximum amount that can be dissolved in a specified amount of
solvent (generally 100 g of solvent) at a specified temperature to form a saturated solution.
Solubility of one substance into another depends on
(i) nature of the solute and solvent. (ii) Temprature (iii) Pressure
4.1 Solubility of a solid in a liquid :
Like dissolves like: Polar solutes dissolve in polar solvents and non polar solutes in non-polar solvents.
Sodium chloride and sugar dissolve readily in water, naphthalene and anthracene do not. On the other hand,
naphthalene and anthracene dissolve readily in benzene but sodium chloride and sugar do not.
Dissolution : When a solid solute is added to the solvent, some solute dissolves and its concentration increases
in solution. This process is known as dissolution.
Crystallisation : Some solute particles in solution collide with the solid solute particles and get separated out
of solution. This process is known as crystallisation.
At equilibrium, rate of dissolution is equal to rate of crystallisation. At this stage the concentration of solute in
solution will remain constant under the given conditions, i.e., temperature and pressure. Such a solution is said
to be saturated with the given solute.
Solute + Solvent Solution
Saturated solution : A solution in which no more solute can be dissolved at the same temperature is called
saturated solution.
Unsaturated solution : It is a solution in which more amount of solute can be dissolved at the same temperature.
4.2 Effect of temperature on solubility of a solid in a liquid
Consider the equilibrium: Solute + Solvent Solution. By Le Chatelier's Principle:
If above process is exothermic i.e. H < 0, then as T increases, solubility decreases.
If above process is endothermic i.e. H > 0, then as T increases, solubility increases.
4.3 Effect of pressure on solubility of a solid in a liquid (no effect)
Pressure does not have any significant effect on solubility of solids in liquids. It is so because solids and liquids
are highly incompressible and practically remain unaffected by changes in pressure.
5. Solubility of gases in liquids :
5.1 Factors Affecting Solubility of Gas In Liquid :
(i) Nature of gas (ii) Nature of liquid (iil) Temperature (iv) Pressure
5.2 Henry Law (effect of pressure on solubility of gases in liquids) :
Statement : The solubility of a gas in a liquid at a given temperature is directly proportional to the pressure at
which it is dissolved.
Let x = Mole fraction of gas at a given temperature as a measure of its solubility.
p = Partial pressure of gas in equilibrium with the solution.
By Henry's Law: xp or px

p
That is; p = KH x or x= K , where KH = Henry law constant.
H
5.3 Characteristics of Henry law constant (KH).

(i) Unit same as those of pressure: torr or bar.
(ii) Different gas have different value of KH for the same solvent.
(iii) The KH value of a gas is different in different solvents and it increase with the increase in temperature.
p
(iv) Higher the value of KH of a gas, lower will be its solubility. Since, X = K .
H
Plot of p Vs X is a straight line passing through the origin with slope equal to KH .
Plot of p Vs X for solution of HCl in cyclohexane.

Note : If a mixture of gases is brought in contact with solvent each constituent gas dissolves in proportion to its partial
pressure. It means Henry's law applies to each gas independent of the pressure of other gas.
Ex 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 of 298 K and 5 atm
pressure is : [JEE - 2009]
–4 –5 –4
(A*) 4 × 10 (B) 4.0 × 10 (C) 5.0 × 10 (D) 4.0 × 10–6
Solution PN = KH × x N2
2
1
x N2 = × 0.8 × 5 = 4 × 10–5 per mole
105
In 10 mole solubility is 4 × 10–4 .
5.4 Effect of temperature :
Solubility of gases in liquids decreases with rise in temperature.
Explaination: When dissolved, the gas molecules are present in liquid phase and the process of dissolution
can be considered similar to condensation and heat is evolved in this process. We have learnt that dissolution
process involves dynamic equilibrium and thus must follow Le Chatelier's principle. As dissolution of gases in
liquids is an exothermic process, the solubility should decrease with increase of temperature.
Note : KH values for both N2 and O2 increase with increase of temperature indicating that the solubility of gases
increases with decrease of temperature. It is due to this reason that aquatic spcies are more comfortable in cold
wasters rather than warm water.
5.5 Application of Henry's law :
Several application in biological and industrial phenomena.
(i) To increase the solubility of CO2 in soft drinks and soda water the bottle is sealed under high pressure.
(ii) Scuba divers must cope with high concentrations of dissolved gases while breathing air at high pressure
underwater. Increased pressure increases the solubility of atmosphere gases in blood. When the divers come
towards surface, the pressure gradually decreased. The release the dissolved gases and leads to the formation
of bubbles of nitrogen in the blood. This blocks capillaries and creates a medical condition known as bends,
which are painful and dangerous to life. To avoid bends, as well as, the toxic effects of high concentrations of
nitrogen in the blood, the tanks used by scuba divers are filled with air diluted with helium (11.7% helium, 56.2%
nitrogen and 32.1% oxygen).
(iii) At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low
concentrations of oxygen in the blood and tissues of people living at high altitudes or climbers. Low blood
oxygen causes climbers to become weak and unable to think clearly, symptoms of a condition known as
anoxia.
5.6 Limitation of Henry's law :
Henry’s law is valid only under following condition.
(i) The pressure of gas is not too high.
(ii) The temperature is not too low.
(iii) The gas should not undergo any chemical reaction with the solvent.
(iv) The gas should not undergo dissociation in solution.
6. Vapour Pressure of a pure liquid or pure solid :
6.1 The origin of saturated vapour pressure: The evaporation of a liquid
Some of the more energetic particles on the surface of the liquid move fast enough to escape from the attractive
forces holding the liquid together. They evaporate. The diagram shows a small region of a liquid near its surface.
Note: evaporation only takes place on the surface of the liquid. That's quite different from boiling which happens
when there is enough energy to disrupt the attractive forces throughout the liquid. That's why, if you
look at boiling water, you see bubbles of gas being formed all the way through the liquid.
If you look at water which is just evaporating in the sun, you don't see any bubbles. Water molecules are simply
breaking away from the surface layer. Eventually, the water will all evaporate in this way.
The evaporation of a liquid in a closed container: Evaporation and Condensation
Now imagine what happens if the liquid is in a closed container. Common sense tells that water in a sealed
bottle doesn't disappear over time. But, there is still constant evaporation from the surface. Particles continue to
break away from the surface of the liquid - but this time they are trapped in the space above the liquid.
As the gaseous particles bounce around, some of them will hit the surface of the liquid again, and be trapped
there. This is called as condensation. There will rapidly be an equilibrium set up in which the number of particles
leaving the surface is exactly balanced by the number rejoining it. At equilibrium, rate of evaporation becomes
equal to the rate of condensation.
In this equilibrium, there will be a fixed number of the gaseous particles in the space above the liquid. When
these particles hit the walls of the container, they exert a pressure. This pressure is called the saturated
vapour pressure (or just vapour pressure) of the liquid.
Suppose,we take 10 gram liquid in a chamber. Initially, there are no molecules in the gaseous phase. Thus, no
pressure is exerted on the mercury and the level of mercury in both columns is equal. Suppose, after vapourization
of 5 gram of the liquid vapour-liquid equillibrium is established. Now, molecules in the gaseous phase exert
pressure on the mercury and level of mercury in the column attached to the chamber decreases.
Note: From the figure, we can see that, Vapour Pressure of the liquid = h mm Hg.
Note: Volatile solids (like Iodine) also evaporate and have a vapour pressure at any given tempratre, just like
liquids.
6.2 Important Points related to vapour pressure :
(1) Definition of vapour pressure :The partial pressure of vapours in equilibrium with pure solid or pure liquid at a
given temperature.
At eq. the rate of evaporation = rate of condensation
e.g. H2O(l) H2O(g)
eq
Kp = pH2O,g
Hence V.P is equilibrium constant (KP) of the reaction, liquid vapours.
(2) Since vapour pressure is an eqlibrium constant. so it's value is dependent only on
(a) Nature of liquid. (b) Temperature of the given liquid
(3) The value of a liquid's vapour pressure depends on the magnitude of the intermolecular forces in the liquid. The
smaller the intermolecular fores, higher the vapour pressure becuase loosely held molecules escape more
easily into vapour phase.
(4) At higher temperature, more molecules from the liquid have enough KE to escape from the surface of the liquid.
That will increase the saturated vapour pressure.
Vapourization (liquid to vapour) is always endothermic. It needs heat to convert the liquid into the vapour.
According to Le Chatelier, increasing the temperature of a system in a dynamic equilibrium favours the endothermic
change. That means that increasing the temperature increases the amount of vapour present, and so increases
the saturated vapour pressure.
The dependence of vapour pressure with temperature is given by Clausius-Clapeyron equation
p  Hv  1 1 
ln  2      
 p1  R  T2 T1  , where Hv = molar enthalpy of vapourisation of the given liquid,
p2 = vapour pressure of the liquid at T2 and p1 = vapour pressure of the liquid at T1 .

(5) Vapour pressure of a liquid does not depend on :
(i) On the amount of liquid taken.
(ii) On surface area of the liquid
(iii) On volume or shape of the container
(6) Partial pressure of vapours: If vapours of a liquid are present in a gaseous mixture then,
Pr essure of vapours
Partial pressure of vapours of the liquid = Total pressure
Saturation: A gas or gaseous mixture is said to be saturated with the vapours of a liquid if the partial pressure
of the liquid vapours is equal to its (saturated) vapour pressure.
(7) (a) Saturated (Equillibrium) Vapour pressure of water, at a given temprature, is called aqueous tension.
The value of aqueous tension is different at different temprature.
Partial pressure of water vapour at given temperature
(b) Relative Humidity (R.H.) = Vapour pressure of water at the same temperature × 100%
(8) Saturated vapour pressure and boiling point:

A liquid boils when its saturated vapour pressure becomes equal to the external pressure on the liquid. When
that happens, it enables bubbles of vapour to form throughout the liquid. If the external pressure is higher than
the saturated vapour pressure, these bubbles are prevented from forming, and we just get evaporation at the
surface of the liquid.
If the liquid is in an open container and exposed to normal atmospheric pressure, the liquid boils when its
saturated vapour pressure becomes equal to 1 atmosphere. This happens with water when the temperature
reaches 100°C. But at different pressures, water will boil at different temperatures. For example, at the top of
Mount Everest the pressure is so low that water will boil at about 70°C.
(a) Boiling point : The boiling point is the temperature at which the vapour pressure of a liquid is equal to the
external pressure.
(b) At boiling temperature, vapour pressure of the pure liquid i.e. Pº = Pext
(c) At normal boiling point, vapour pressure of the pure liquid i.e. Pº = 1atm
(9) Saturated vapour pressure and solids: Sublimation
Solids can also lose particles from their surface to form a vapour, except that in this case we call the effect
sublimation rather than evaporation. Sublimation is the direct change from solid to vapour without going through
the liquid stage.
The forces of attraction in many solids are too high to allow much loss of particles from the surface. However,
there are some solids which easily form vapours.
Naphthalene (used in "moth balls") has quite a strong smell. Molecules must be breaking away from the surface
as a vapour, because otherwise we wouldn't be able to smell it.
Solid carbon dioxide never forms a liquid at atmospheric pressure and always converts directly from solid to
vapour. That's why it is known as dry ice.
(10) If partial pressure of vapours of a liquid is increased beyond the saturated (equillibrium) vapour pressure value
(Pº), its vapours begin to condense till their partial pressure becomes equal to the saturated vapur pressure.
(11) If the partial pressure of vapour is less than v.p. of liquid, the liquid (if present) will vaporize till
(a) its v.p. is attained or
(b) the liquid completely gets vaporized
(12) If a volatile solid/ liquid is brought in contact with a gas (or vaccuum), vapours of that solid/ liquid occupy the gas
phase till the gas phase becomes saturated with that solid /liquid vapours.
Ex The vapor pressure of water at 80º C is 355 torr. A 100 ml vessel contained watersaturated oxygen at
80º C, the total gas pressure being 760 torr. The contents of the vessel were pumped into a 50.0 ml,
vessel at the same temperature. What were the partial pressures of oxygen and of water vapor, what
was the total pressure in the final equilibrated state ? Neglect the volume of any water which might
condense.
Ans. PO2 = 810mm Hg, PH2O = 355 mm Hg , Ptotalal = 1165 mm Hg
Solution In 100 ml vessel which contained water - saturated oxygen, the pressure of O2 gas = 760 – 355 =
405 torr when the contents of this vessel were pumped into 50 ml vessel, at the same temperature, the
pressure of oxygen gets doubled i.e. PO2 = 810 torr..
But pressure of water vapour will remain constant, as some vapour in this 50 ml vessel, gets condensed.
So PH2O = 355 torr & Total pressure = 810 + 355 = 1165 torr..
7. Vapour Pressure of liquid-liquid solution: volatile solute + volatile solvent
7.1 Statement of Raoult's law ( for volatile liq. mixture ): In solution of volatile liquids, the partial vapour
pressure of each component is directly proportional to its mole fraction
pA  xA
pA = xAPAº
pA = Partial vapour pressure of component A
xA = Mole fraction of component ‘A’ in solution.
PAº = Vapour pressure of pure component ‘A’ at given temprature
Derivation of total pressure over solution using Raoult’s law and Dalton’s law:
Let A, B be to two volatite liquids in a closed container as shown.
A
x x
x
x
x B
x x
x
A+ B
XA
XB
pA  xA
pA = xAPAº
Similarly, for liquid B we have, pB  xB ; pB = xBPBº
Total pressure over the solution PT , according to Dalton's law is
PT = pA + pB = xAPA0 + xBPB0
Determinig composition of vapour phase:
Let, yA = mole fraction of A in vapour phase above the solution and
yB = mole fraction of B in vapour phase above the solution
Now, we have
pA = yA PT .....Daltion's law of partial pressure for a gaseous mixture
pA = xAPAº ...........Raoult's law
Thus, pA = yA PT = xA PAº
Also, pB = yBPT = xBPBº
y A PT y bPT
xA + xB = 1 = 
PA0 PB0
1 y A yB
Thus, P = 0  0
T PA PB
Graphical Representation of Raoult's Law:

pA= xAPAº & pB = xB PBº
PT = xAPAº + xB PBº
PT = xAPAº + (1 – xA) PBº = ( PAº – PBº ) xA + PB0
PT = (1 – xB) PAº + xBPBº = ( PBº – PAº ) xB + PA0
This represents equation of straight line. PT v.s. x
Note: if PAº > PBº , A is more volatile than B. B.P. of A < B.P. of B
7.2 Application of Raoult’s Law:
(1) Phase Diagrams of Two-Component Ideal Solutions: Bubble And Dew Points
The compositions of the liquid and vapour that are in mutual equilibrium are not necessarily the same. Common
sense suggests that the vapour should be richer in the more volatile component. This can be easily derived from
Raouls’s Law.
1 y A yB y 1 yA
= 0
 0 = A0 
PT PA PB PA PB0
PA0 PB0
PT 
PA0  ( PB0  PA0 ) y A
From the above equation, the plot of PT with respect to y is a curve instead of a straight line. We can superimpose
this curve on the diagram for graphical representation of Raoult’s Law to get following phase diagrams.
(A) Pressure versus Composition Phase Diagram (At constant T): P vs. x and y
In this kind of phase diagram the temperature has a fixed value. The mole fraction of one component is plotted
on the horizontal axis and the pressure is plotted on the vertical axis. If A is more volatile than B, then we get
following diagram.
Explaination:
(i) On horizontal-axis we have plotted both x and y that is both liquid composition and vapour composition.
(ii) The lower curve (Dew Point Curve) represents the total pressure as a function of the composition i.e. mole
fraction in the vapor phase at equilibrium with the liquid phase. It is plotted using PT vs. yA equation:
PA0 PB0
PT 
PA0  ( PB0  PA0 ) y A
(iii) The upper curve i.e. Bubble Point Curve (a straight line in the case of an ideal solution) represents the total
pressure as a function of composition i.e. mole fraction in the liquid. It is plotted using PT vs. xA equation:
PT = ( PAº – PBº ) xA + PB0
(iv) The area between these two curves is vapour-liquid equilibrium region. Vapours cannot exist above the
bubble point curve and liquid can not exist below the dew point curve.
(v) Suppose, initially the pressure over the solution is very high so that no vapour exist above the liquid. As we
gradually decrease the pressure, a point (Bubble point) comes when we cross the Bubble-Point curve and first
bubble of vapour starts forming. Hence, the name bubble point curve. Now we have entered the vapour-liquid
equilibrium region. On further decreasing the pressure, a point (Dew Point) comes when we cross the Dew-Point
curve when almost all the liquid has evaporated into vapour i.e. only the last drop of liquid (Dew) remains.
Beyond this point no liquid exists in the system.
Ex (a) A liquid mixture of benzene and toluene is composed of 1 mol of benzene and 1 mol of toluene.
If the pressure over the mixture at 300K is reduced, at what pressure does the first bubble form?
(b) What is the composition of the first bubble formed.
(c) If the pressure is reduced further, at what pressure does the last trace of liquid disappear?
(d) What is the composition of the last drop of liquid?
(e) What will be the pressure, composition of the liquid and the composition of vapour, when 1 mol of
the mixture has been vaporized? Given PT0 = 40mmHg, PB0 = 100mmHg
Ans. (a) 70 mmHg, (b) xb = 5/7 (c) P = 400/7 = 57.14 mm
Solution (a) P = XAPA0 + XBPB0 = 0.5 x 40 + 0.5 x 100 = 70
0.5 x 40 2 5
(b) YA = = YB =
70 7 7
(c) at last trace of liquid YA = 0.5 YB = 0.5
1 YA YB 0 .5 0.5
= 0 + 0 = +
P PA PB 40 100
400
P=
7
YA PA0 X A 40 5 2
(d) YA =  0.5 = XA = XB =
P 400 / 7 7 7
(e) Let x mole of B be present in liquid phase.
Mole of A Mole of B
Liquid 1-x x
Vapour x 1-x
P = 40 (1 – x) + 100 x
1 YA YA 1 x 1 x 100 x  (1  x )40
= 0 + P  = + = 40 x 100
P PA B P 40 100
So p2 = 40 x 100 ; p = 20 10
20 10 = 40 (1 – x) + 100x = 40 + 60x
20 10  10 10  2
x= =
60 3
(B) Temperature versus Composition Phase Diagrams i.e. T vs x and y diagram
(i) In this type of phase diagram the pressure is held fixed. The
mole fraction of one component is plotted on the horizontal axis
and the boiling temperature is plotted on the vertical axis.
(ii) The upper curve (Dew-Point curve) gives the boiling temperature
at the given pressure as a function of the mole fraction in the
vapor phase, and the lower curve (Bubble-Point curve) gives the
boiling tempera ture at the given pressure as a function of the
mole fraction in the liquid phase.
Note: If a liquid has a high vapour pressure at a particular
temperature, it means that its molecules can escape easily from
the surface. The liquid with the higher vapour pressure at a particular
temperature is the one with the lower boiling point. If A is more
volatile than B, then we get following diagram.
(2) Distillation:
(i) The compositions of the liquid and vapour that are in mutual equilibrium are not necessarily the same.
Common sense suggests that the vapour should be richer in the more volatile component.
(ii) In a simple distillation, the vapour over a boiling mixture is withdrawn and condensed in a separate container.
The liquid collected in the new container is called condensate and the liquid remaining in the original container
is called distillate. The condensate has higher mole fraction of the more volatile component than the original
mixture. The distillate has higher mole fraction of the less volatile component than the original mixture. This is
the principle of distillation and is used to separate a more volatile liquid from a less volatile liquid.
(iii) In fractional distillation, the boiling and condensation cycle is repeated successively to get a condensate
which gets richer in the more volatile component after each cycle.
Ex An equimolar mix of benzene & toluene is prepared the total V.P. of this mix as a fraction of mole
fraction of benzene is found to be PT = 200 + 400 Xben.
(a) Calculate composition of vapours of this mix. [ Assume that the no. of moles going into vapour phase
is negligible in comparsion to no. of moles present in liq. phase ].
(b) f the vapour above liq in part A are collected & are condensed into a new liqiuid calculate composition
of vapours of this new liq.
Solution (a) P0Beazene= 600 mm of Hg
P0Toloune = 200 mm of Hg
1 1
PT = × 600 + × 200 = 400 mm of Hg
2 2
Pbenz = xben ' Pºben = ybenPT.
1/ 2  600 3 1
ybenzene = = = 75% ; yToloune = = 25%
400 4 4
75% 25%
condensate
( Liq. formed after
(b) condensation of
vapours. distillate ( rem. liq.)
3 1 3 / 4  600
PT = × 600 + × 200 = 500  yben = = 0.9 = 90%
4 4 500
yToluene = 0.1 = 10%
7.3 Limitaions of Raoult’s Law: Raoult's Law only works for ideal solutions. Very dilute solutions obey Raoult's
Law to a reasonable approximation.
(1) IDEAL SOLUTIONS :

Those solutions which obey Raoult's law are called ideal solutions. When the forces of attraction between A —
A, B — B is similar to A — B, then A and B will form ideal solution.
Properties of ideal solution :

(i) Raoult's law is obeyed
(ii) Hmix = 0, i.e., there should not be enthalpy change when components of ideal solutions are mixed.
(iii) Vmix = 0, (1L + 1L = 2L) i.e., there should not be change in volume on mixing. e.g.; n-hexane and n-heptane;
ethyl bromide and ethyl iodide; benzene and toluene; chlorobenzene and bromobenzene form ideal solutions.
(2) NON _ IDEAL SOLUTIONS :
Those solutions which do not obey Raoult's law are called non-ideal solutions.
When the forces of attraction between A — A, B — B is different from A — B then 'A' and 'B' form non-ideal
solutions. For these solutions :
(i) Raoult's law is not obeyed. (ii) Hmix  0 ; (iii) Vmix  0.
Types of Non-Ideal Solutions:
(A) NON-IDEAL SOLUTIONS SHOWING POSITIVE DEVIATION FROM RAOULT’S LAW :
(i) In this case, partial pressure of each component A and B is higher than that calculated from Raoult's law, and
hence total pressure over the solution is also higher than if the solution were ideal, as shown in figure.
(ii) Boiling point of such a solution is relatively lower than the boiling points of both A and B.
P0A > P0B
Note: Dashed lines represent vapour pressures and total pressure corresponding to ideal solution
Examples: water and ethanol, chloroform and water, ethanol and CCI4, methanol and chloroform, benzene and
methanol, acetic acid and toluene, acetone and ethanol, methanol and H2O, C2H5OH + cyclohexane.
Explaination: The fact that the vapour pressure is higher than ideal in these mixtures means that molecules
are breaking away more easily than they do in the pure liquids. That is because the intermolecular forces
between molecules of A and B are less than they are in the pure liquids.
You can see this when you mix the liquids. Less heat is evolved when the new attractions are set up than was
absorbed to break the original ones. Heat will therefore be absorbed when the liquids mix. The enthalpy change
of mixing is endothermic.
(B) NON-IDEAL SOLUTIONS SHOWING NEGATIVE DEVIATION FROM RAOULT’S LAW :
(i) In this case, partial pressure of each component A and B is lower than that calculated from Raoult's law, and
hence total pressure over the solution is also lower than if the solution were ideal, as shown in figure.
(ii) Boiling point of such a solution is relatively higher than the boiling points of both A and B.
P0A > P0B
Note: Dashed lines represent vapour pressures and total pressure corresponding to ideal solution
Examples: chloroform and acetone, chloroform and methyl acetate, H2O and HCI, H2O and HNO3, acetic acid
and pyridine, chloroform and benzene.
Explaination:These are cases where the molecules break away from the mixture less easily than they do from
the pure liquids. New stronger forces must exist in the mixture than in the original liquids.
You can recognise this happening because heat is evolved when you mix the liquids - more heat is given out
when the new stronger bonds are made than was used in breaking the original weaker ones.
7.4 Azeotropic Mixtures : Very large deviations from ideality lead to a special class of mixtures known as azeotropes,
azeotropic mixtures, or constant-boiling mixtures.
Azeotropes : Liquid mixtures which distill over without changes in composition are called constant boiling
mixtures or Azeotropes or Azeotropic mixtures.
A boiling liquid mixture at the azeotropic composition produces a vapour of exactly the same composition, and
the liquid does not change its composition as it evaporates. Two types of azeotropes are known.
(1) Minimum Boiling Azeotropes : Non-ideal solutions showing large positive deviation from Raoult's law form
minimum boiling azeotropes which boil at temperature lower than boiling point of its components A and B. e.g.:
water and benzene, chloroform and methanol.
The figures below show the Temprature vs. composition (at constant pressure) phase diagram on the left side
and Pressure vs. composition (at constant temprature) phase diagram for a minimum-boiling azeotropic mixture
chloroform and methanol.
Note: The detailed values in the diagram are not important. Only the qualitative shape of the diagram is important.
At the lowest point in the temperature vs. composition phase diagram, the concentration in the vapour phase is
the same as the concentration in the liquid phase (y = x ). This concentration is known as the azeotropic
composition. At this point, the mixture boils at a constant temperature and without change in composition.
(2) Maximum Boiling Azeotropes : Non-ideal solutions showing large negative deviation from Raoult's law
form maximum boiling azeotropes which boil at temperature higher than the boiling point of its components A
and B respectively. e.g.: mixture of HCl and H2O.
On left side, temprature versus composition phase diagram and on right side, pressure versus compostion
diagram is shown for maximum boiling azeotrope.
(3) Separation of Azeotropic Mixtures

When the azeotropic composition has been reached, the condensate has the same composition as the azeotropic
liquid. The vapour phase is not richer in any component than the liquid phase. Thus, azeotropic mixtures can’t
be separated beyond the azeotropic composition using distillation.
7.5 Completely Immiscible Liquids and Steam Distillation
For mixture of two completely immiscible liquids, each liquid exerts its own vapor pressure, independent
of the other, and the total vapor pressure is the sum of the separate vapour pressures of the two components
in the pure state at the given temperature.
(1) Immiscible Liquids :
When two liquids are mixed in such a way that they do not mix at all then both liquids constitute two different
phases. Hence, mole fraction of each liquid is one in it's own phase.
(i) PT = pA + pB
(ii) pA = PA0 xA But, xA = 1. Thus, pA = PA0
(iii) pB = PB0 xB But, xB = 1. Thus, pB = PB0
PA0 nA PA0 WA MB n A RT nBRT
(iv) PT = PA0 + PB0 (v) = n (vi)  (v)PA0 = ; PB0 =
PB0 B PB0 M A WB V V
where nA and nB are the numbers of moles of each component present in the vapor phase.
(vi) To express the ratio of A to B in the vapor in terms of the actual weights w A and wB, the numbers of
moles must be multiplied by the respective molecular weights M A and MB ; hence,
(2) Steam DIstillation: The boling point of a solution of two immiscible liquids is less than the individual boiling
points of both the liquids. This concept is used in steam distillation.
(i) A system of two immiscible liquids will boil when the total vapor pressure P is equal to the atmospheric
pressure. The boiling point of the mixture is thus lower than that of either constituent.
(ii) Further, since the total vapor pressure is independent of the relative
amounts of the two liquids, the boiling point, and hence the composition
of the vapor and distillate, will remain constant as long as the two layers
are present.
A liquid (generally organic) that is immiscible with water, and that has a
higher boiling point than water can be boiled (distilled) at a much lower
temperature by passing steam through it. In this way, the organic liquid
can be purified from impurities using steam distillation.
8. Colligative properties & constitutional properties :

 Colligative properties :
The properties of the solution which are dependent only on the total no. of particles or total concentration
of particles in the solution & are not dependent on the nature of particle i.e. shape, size, neutral /charge
etc. of the particles.
Constitutional Properties :
Properties which are dependent on nature of particles are constitutional properties like electrical
conductance.
There are 4 colligative properties of solution.
 P 
1. Relative lowering in vapour pressere  
 P 
2. Elevation in b.p. (T b)
3. Depression in freezing pt. (T f)
4. Osmotic pressure
8.1 Abnormal Colligative Properties :
Vant – Hoff correction
For electrolytic solutes the No. of particles would be different then the No. of particles actually added,
due to dissociation or association of solute.
The actual extent of dissociation/association can be expressed as a correction factor known as vant
Haff factor (i).
moles of particles in solution after dissociation / association
Vant – Hoff factor : i = moles of solute dissolved
 If solute gets associated or dissociated in solution then experimental / observed / actual value of
colligative property will be different from theoretically predicted value so it is also known as abnormal
colligative property.
This abnornality can be calculated in terms of Vant-Hoff factor.
exp/ observed / actual / abnormal value of colligative property

i= Theoretical value of colligative property
exp . / observed no. of particles or concentration Theoretical molar mass of subs tan ce
= =
Theoritical no. of particles or concentration exp erimental molar mass of the subs tan ce
i > 1 dissociation
i < 1 association
Case - I : Electrolyte dissociates

Relation between i &  (degree of dissociation) :
Let the electrolyte be AxBy
AxBy (aq.)  xAy+ + yBx–
t=0 C 0 0
teq C(1 – ) xC yC
Net concentration = C – C + xC + yC = C [1 + ( x+y –1) ] = C [1 + ( n –1) ].
n=x+y
= no. of particles in which 1 molecule of electrolyte dissociates
C [1  (n  1) ]
i=
C
i = 1 + ( n – 1) 
e.g. NaCl (100% ionised), i = 2. ; BaCl2 (100% ionised), i = 3. ; K4[Fe(CN)6] (75% ionised), i = 4.
Case - II : Electrolyte associates
Relation between degree of association  & i.
nA  A n.
t=0 C 0
C
teq C ( 1– )
n
C 1 
 C – C +  C [ 1 +   1  ]
n n 
1 
i = 1 +   1 
n 
dimerise n = 2 ; trimerise n = 3 ; tetramerise n = 4.
1 1
e.g. CH3COOH 100% dimerise in benzene, i = ; C6H5COOH 100% dimerise in benzene, i =
2 2
8.2 Relative lowering in vapour pressure (RLVP) :
Vapour Pressure of a solutions non-volatile solute in a volatile solvent
Vapour Pressure of a solution of a non volatile solute ( solid solute ) is always found to be less than the vapour
pressure of pure solvent .
Reason : Some of the solute molecules will occupy some surface area of the solutions so tendency of the
solvent particles to go into the vapour phase is slightly decreased hence Pº > PS, where Pº is vapour pressure
of pure solvent and PS is vapour pressure of the solution.
0
P Ps
solution of non-volatile solute

Pure solvent in volatile solvent
Lowering in VP = P 0 – PS = P and
P
Relative lowering in Vapour Pressure =
P0
Raoult's law (For non–volatile solutes): The vapour pressure of a solution of a non-volatile solute is equal to the
vapour pressure of the pure solvent at that temperature multiplied by its mole fraction.
OR Relative Lowering in Vapour Pressure = mole fraction of the non volatile solute in solutions.
PS  x solvent P 0  (1  x solute )P 0
P 0 - Ps n
RLVP = 0 = xSolute =
P n  N
where n = number of moles of non-volatile solute and N = number of moles of solvent in the solution.
P0 nN N
 0 = = 1+
P - Ps n n
N P 0 - Ps Ps
= –1= 0
n P 0 P - Ps
P 0 - Ps n
0 =
P N
P 0 - Ps w M w M w 1000 M
= × = × × 1000 = × ×
Ps m W m W 1000 m W 1000
P 0 - Ps M
= ( molality ) ×
Ps 1000
where w and W = mass of non-volatile solute and volatile solvent respectively

m and M = molar mass of non-volatile solute and volatile solvent respectively
P 0 - Ps i.n P 0 - Ps M
If solute gets associated or dissociated ; = that is = i × (molality) ×
Ps N Ps 1000
Ex Calculate wt of urea which must be dissolved in 400 gm of water so final solutions has V.P. 2% less than
V.P. of pure water :
Solution Let V.P be V. of water
P0 – Ps = .02 V
Ps = 0.98 V
0.02 w 18
 = × ; where w = weight of urea.
0.98 60 400
2  60  400
w= gm.
18  98
Ex 10 gm of a solute is dissolved in 80 gm of acctone V.P. of this sol = 271 mm of Hg. If V.P. of pure
acctone is 283 mm of Hg. Calculate molar mass of solute.
P 0 - Ps w M
Solution = ×
Ps m W
283 - 271 10 58
 = × , m = 163 gm/mol.
271 m 80
Ex-12 V.P. of solute containing 6 gm of non volatile solute in 180 gm of water is 20 Torr/mm of Hg. If 1 mole of
water is further added in to the V.P. increses by 0.02. Torr calculate V.P of pure water & molecular wt.
of non volatile solute.
P 0 - Ps w M
Solution = ×
Ps m W
Pº-20 6 18
 = ×
20 m 180
Pº-20.02 6 18
= ×
20.02 m 198
 Pº = 20.22 Torr.
m = 54 gm/mol.
Ex-13
What is the final volume of both container.
Solution i1C1 = i2C2

0.1 2 0.1 1
= .
100  x 100 – x
200 – 2x = 100 + x.
x = 33.3 ml.
Ex-14 If 0.1 M solutions of K4 [ Fe ( CN ) 6 ] is prepared at 300 K then its density = 1.2 gm/mL . If solute is 50%
dissociated calculate P of solutions if P of pure water = 25 mm of Hg. (K = 39, Fe = 56)
P 0 - Ps w M
Solution =i ×
Ps m W
P 0 - Ps im  M
=
Ps 1000
 3  0.1 1000  18
=  
 1000  1 . 2 – 1. 2  368  1000
P0
= 1 + 7.12 × 10–3
Ps
Ps = 24.82 mm of Hg
p = 25 – 24.82 = 0.18 mm of Hg
8.3 Ostwald–Walker Method :
ΔP P
Experimental or lab determination of relative lowering of vapoure pressure i.e. 0 or P
P s
dry air
Ps P
anhydrous CaCl2
(dehydrating agent)
solution solvent
(i) Initially note down the weights of the solution set, solvent set containers & of dehydrating agent before start
of experiment.
(ii) Note down the same weights after the experiment is complete.
Loss of wt of solution containers  Ps.
Loss of in wt of solvent containers  (P – Ps)
gain in wt of dehydriating agent  P.
P 0 - Ps loss in wt. of solvent

= loss in wt. of solution
Ps
P 0 - Ps loss is wt. of solvent w M M

= = × = ( molality ) ×
Ps gain is wt . of dehydrating agent m W 1000
Suppose, dry air was passed through a solution of 5 gm of a solute in 80 gm of water & then it is passed through
pure water. Loss in weight of solution was 2.50 g & loss in weight of pure water was 0.04 g. Then,
to find molecular weight of the solute, we have
P 0 - Ps loss in wt. of solvent

= loss in wt. of solution
Ps
P 0 - Ps 0.04 w M 5 18
= = × =  . Thus. m = molecular weight of the solute = 70 g/mol.
Ps 2.50 m W m 80
Ex
If same volume solution of different solute is used then what is order of (a) vapour pressure (b) moles of
solute (c) molar mass of solute.
Ans. PA  1 gm. ; PA – PB  0.5 gm, PB  0.5 gm.
PC – PB  1 gm ; PC  1.5 gm.
PC > PA > PB ; nC < nA < nB . ; MC > MA > MB.
8.4 Elevation in Boiling point of a solution of non-volatile solute in volatile solvent (Tb)
Boiling point: The temprature at which vapour pressure of a liquid becomes equal to the external pressure
present at the surface of the liquid is called b.p of liquid at that pressure.
Normal Boiling Point: The boiling temprature when Pext = 1 atm = 760 mm of Hg is called normal boiling point
of the liquid (Tb).
H2O() H2O(g) H = +ve
Kp = PH2O( g)/ eq.
 K p2  H  1 1
    
ln  K  R  T1 T2 
 p1 
 P2   H vap.   1 1
ln   =  
 R  T  T  (Claussius – Clapeyron equation)
 P1    1 2
lnP1 P
1/T
T
Elevation of Boiling point of any solution :

Since V.P. of solution is smaller than V.P. of pure solvent at any temp. hence to make it equal to Pext. we have to
increase the temp. of solution by greater amount in comparision to pure solvent.
Formula for Elevation of Boiling Point
Tb = Kb × molality
Note: (i) If solute gets associated/dissociated then ΔTb = i × Kb × molality
ΔTb K
(ii) Units of Kb:   Thus units of Kb = K kg mol–1
molality mol/kg
(iii) Kb is dependent on property of solvent and known as molal elevation constant of solvent
2 2
RTb M RTb
Kb = =
1000  Hvap 1000  L vap
where, Hvap is molar enthalpy of vaporisation

LVap is Latent Heat of Vapourisation in cal/gm or J/gm
M is molecular mass of the solvent in gram
R = 2 cal mol–1 cal–1 or 8.314 J ....
Tb = b.p. of pure liquid solvent (in kelvin)
Kb = K kg mol–1
 H vap 
Lvap =  M 

 
(iv) Kb = elevation in bp of 1 molal solution.
(v) elevation in boiling point is proprtional to the lowering of vapoure pressure i.e. ΔTb  P
Calculate Kb of water if Lvap = 540 Cal/gm Tb = 100ºC
2  373  373
 Kb = = K kg mol–1 = 0.52 K k/gm
1000  540
Extra Information (Not for Boards)
Pext.
for pure solvent for solution
P
Ps
As only solvent particles are going into vapours, we haveHvapourisation of solvent = Hvapourisation of solution
 Tsolution > Tpure solvent
Vapour is always pure solvent
Ssolution (more entropy

more randomness)
Ssolvent
ΔH vapourisat ion
Svapourisation =
Tbp
H
Svapourisation of pure solvent = T
b,solvent
H
Svapourisation of solution
= T
b, solution
Thus, Svapourisation of pure solvent > Svapourisation of solution ; because Tb, solvent Tb, solution.
Due to presence of solute, it is difficult to vapourise the solution (because relative lowering of vapour pressure
occurs), that is it is difficult to boil the solution so there is elevation in boiling point with respect to pure solvent.
1 atm
Liquid
Psolv
Pressure (atm)
Solid
Psoln
Gas
fpsolv
fpsoln bpsolv bpsoln
Tf Tb
Temperature (ºC)
Phase diagram for a pure solvent and a solution of a nonvolatile solute. Because the vapor pressure of the
solution is lower than that of the pure solvent at a given temperature, the temperature at which the vapor
pressure reaches atmospheric pressure is higher for the solution than for the solvent. Thus, the boiling point of
the solution is higher point of the solution is higher by an amount Tb .
Ex A solution of 122 gm of benzoic acid is 1000 gm of benzene shows a b.p. elevation of 1.4º. Assuming
that solute is dimerized to the extent of 80 percent (80ºC) calculate normal b.p. of benzene. given molar
enthalpy of vap. of benzine = 7.8 Kcal/mole.
H
122  1000   1  
Solution Tb – Ti = × Kb 1   n  1  0.8 H H
122  1000   
1  H H
 Kb   0.8
 2 
H
Tb – Ti = Kb × 0.6
2
RTb
Kb =
1000  L vap.
2
2  Tb  78
Kb =
1000  7.8  1000
0.4  2 2
1.4 = Tb
105
Tb = 418.33 K
Ex 1 Lit. of aq. solution of urea having density = 1.060 gm/mL is found to have Tb = 0.5ºC, If temp. of this
solution increase to 101.5ºC then calculate amount of water which must have gone is vapour state upto
this pt. given Kb = 0.5 K kg mol–1 for water
Solution mass of solution = 1.060 × 103 = 1060 gm
1060 M
0.5 = 0.5 ×  1060 × 60 = M
1060 60
1 Lit solution = 1060 gm
(Mass of water) i = 1000 gm
urea = 60 gm
Tb = (molality)i × Kb
60 1000
(Molality)i  3 = 60  W
water
1000
W water = gm.
3
1000 2000
mass of water vaporised = 1000 – = gm = 666.67 gm
3 3
8.5 Depression in freezing point of a solution of non-volatile solute in volatile solvent (Tb)
Freezing point : Temprature at which vapour pressure of solid becomes equal to v.p of liq. is called freezing
point of liquid or melting point of solid.
vacuum
Hsub = + ve
Hsub > Hvap.
ice cube
Hsub = Hfusion + Hvap.
H2O(s) H2O (g) , Kp = PH2O (g) /eq. = V.P. of solid
Formula for Depression of freezing point
Tf = Kf x Molality
2 2
RTf RTf M
Kf = molal depression constant = =
1000  L fusion 1000  Hfusion
where, Hfusion is molar enthalpy of fusion
Lfusion is Latent Heat of fusionin cal/gm or J/gm
M is molecular mass of the solvent in gram
 Hfusion
Lfusion =  
 M 
2  273  273
For water Tf = 273 K & LFusion = 80 cal/g. Thus, Kf = = 1.86 K kg mol–1
1000  80
Note: (i) Depression in freezing point is proprtional to the lowering of vapoure pressure i.e. Tf  P
(i) If solute gets associated/dissociated then Tf = i × Kf × molality
ΔTf K
(iii) Units of Kf:   Thus units of Kf = K kg mol–1
molality mol/kg
(iv) At freezing pt or below it only solvent molecules will freeze not solute molecules (solid will be of pure solvent)
(v) Kf = depression in freezing point of 1 molal solution.
H fusion
(vi) SFusion =
T f . p.
Ssolution
[More entropy
Spure solvent more randomness]
S pure solvent Ssolution
Ssolid
Solution is only pure solvent.
SSoution > Ssolvent because freezing point of solution < freezing point of solvent
Ex Van’t Hoff factors of aqueous solutions of X, Y, Z are 1.8, 0.8 and 2.5. Hence, their (assume equal
concentrations in all three cases)
(A) b.p. : X < Y < Z (B*) f. p. Z < X < Y
(C) osmotic pressure : X = Y = Z (D) v. p. : Y < X < Z
Solution As van’t Hoff factor increases RLVP increases i.e., V.P. decreases y > x > z
Elevation in b.p. increases i.e., b.p. increases y < x < z
Depresion in f.p increases i.e., f.p decreases y>x>z
Osmotic pressure increases so y < x < z.
Ex 1000 gm H2O have 0.1 mole urea and its freezing point is – 0.2ºC and now it is freezed upto – 2ºC then
how much amount of ice will form.
Solution It is assume that solute do not freeze and do not vapourise
TF = 0.2 = Kf 0.1 × 1000 .......(i)

1000
0 .1 wt. of solvent 0 .2
TF = 2 = Kf × 1000 .......(ii) on dividing = .
wt. of solvent 1000 2
weight of remaining H2O is 100 gm and weight of ice is 900 gm.
Ex If boiling point of an aqueous solution is 100.1ºC. What is its freezing point? Given latent heat of fusion
and vaporization of water are 80 cal g–1 and 540 cal g–1 respectively.
Solution For a given aqueous solution
Tb = Kb × molality ; Tf = Kf × molality
Tb K b' RTb2 1000 lf

 = = × RTf2 .
Tf K f' 1000 lv
Tb Tb2  lf
Tf = T 2  lv
f
Tb = 100 + 273 = 373 K.
Tf = 0 + 273 = 273 K.
lf = 80 cal g–1.
lv = 540 cal g–1.
0. 1 373  373  80
 Tf = 273  273  540 .
 Tf = 0.362.  Tf = 0.0 – 0.362.= – 0.362ºC.
Ex A 0.001 molal solution of a complex reprsented as Pt(NH3)4Cl4 in water had a freezing point depression
of 0.0054ºC. Given Kƒ for H2O = 1.86 molality–1. Assuming 100% ionisation of the complex, write the
ionisation nature and formula of complex.
Solution Let n atoms of Cl be the acting as ligand. Then formula of complex and its ionisation is :
[Pt(NH3)4Cln]Cl(4 – n)  [Pt(NH3)4Cln]+(4 – n) + (4 – n) Cl–
1 0 0
0 1 (4 – n)
Thus particles after dissocation = 4 – n + 1 = 5 – n
and therefore, van't Hoff factor (i) = 5 – n
Now Tƒ = K'ƒ × molality × van't Hoff factor
0.0054 = 1.86 × 0.001 × (5 – n)
 n = 2.1  2 (integer value)
Thus complex and its ionisation is : [Pt(NH3)4Cl2]Cl2  [Pt(NH3)4Cl2]2+ + 2Cl–
Ex Depression of freezing point of 0.01 molal aq. CH3COOH solution is 0.02046°. 1 molal urea solution
freezes at – 1.86°C. Assuming molality equal to molarity, pH of CH3COOH solution is :
(A) 2 (B*) 3 (C) 3.2 (D) 4.2
Solution For urea
Tf 1.86
Tf = kf × m or kf = = = 1.86
m 1
Now for CH3COOH
0.02046
Tf = i kf m so i= = 1.1
1.86  0.01
Now i=1+ so  = 1.1 – 1 = 0.1
Now CH3COOH CH3COO– + H+
C 0 0
C – C C C
[H+] = C = 0.01 × 0.1 = 0.001 so pH = 3.
8.6 Osmosis & Osmotic pressure :
Diffusion : Spontaneous flow of particles from high concentration region to lower concentration region is
known as diffusion.
H2O
Cu2+ Blue
Ex.
Saturated
Uniform
CuSO4 (Solution)blue
Figure
Osmosis :
The spontaneous flow of solvent particles from solvent side to solution side or from solution of low
concentration side to solution of high concentration side through a semipermeable membrane (SPM) is
known as osmosis.
Semipermeable Membrane(SPM): A membrane which allows only solvent particles to move across it.
(a) Natural : Semi permeable membrane
Animal/plant cell membrane formed just below the outer skins.
(b) Artificial membranes also : A copper ferrocyanide.
Cu2[Fe(CN)6] & Silicate of Ni, Fe, Co can act as SPM.
Ex.
Figure
Conclusion : After some time in (A) grape or egg will shrink and in (B) grape or egg will swell.
Ex In which soluton side complex [Cu(NH 3)4]2+ will form and deep blue colour will obtain.
Solution In neither of side colour complex will form. No solute particle passes through SPM.
Osmotic Pressure :
h
---------------------------
Solvent
Solution
SPM
Figure
The equilibrium hydrostatic pressure developed by solution column when it is seperated from solvent by
semipermeable membrane is called osmotic pressure of the solution.
 = gh ;  = density of solution
g = acceleration due to gravity ; h = eq. height
1 atm = 1.013 x 105 N/m 2
Figure
Definition : The external pressure which must be applied on solution side to stop the process of osmosis
is called osmotic pressure of the solution.
C1 > C2 particle movement.
Pext. = (1 – 2)
Pext. must be applied on the higher concentration side.
Reverse Osmosis :
If the pressure applied on the solution side is more than osmotic pressure of the solution then the solvent
particles will move from solution to solvent side. This process is known as reverse osmosis.
Berkely : Hartely device/method uses the above pressure to measure osmotic pressure.
Vant – Hoff Formula (For calculation of osmotic pressure)
   concentration (molarity)
T
 = CST C – mol/lit.
S = ideal solution constant  = atm. R – 0.082 lit.atm. mol–1 K–1
= 8.314 J mol–1 K–1 (exp value) T – kelvin
= R (ideal gas) constant
n
 = CRT = RT (just like ideal gas equation)
V
In ideal solution solute particles can be assumed to be moving randomly without any interactions.
 C = total concentration of all types of particles.
= C1 + C2 + C3 + s.................
(n1  n 2  n3  .........)
=
V
Ex Calculate osmotic pressure of 0.1 M urea aqueous solution at 300 K ,
Solution R = 0.082 lit atm K–1
 = CRT
 = 0.1 x 0.082 x 300
 = 2.46 atm.
Ex If 10 gm of an unknown substance (non-electrolytic) is dissolved to make 500 mL of solution,
then osmotic pressure at 300 K is observed to be 1.23 atm find molecular weight ?
10  1000
Solution 1.23 = x 0.082 x 300
M  500
20 0.082
M= x x 300  400 gm/mol
1.23 100
Ex If 6 gm of urea, 18 gm glucose & 34.2 gm sucrose is dissolved to make 500 mL of a solution at
300 K calculate osmotic pressure ?
Solution molecular weight of urea = 60 gm , Glucose = 180gm , Sucrose = 342 gm
 = C x 0.082 x 300
0.3  1000  0.082  300
=
500
 14.76 atm
MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. A 6.90 M solution of KOH in water has 30% by weight of KOH. Calculate density of solution.
Sol. Let V = 1 lt , then moles of solute = 6.9
wt of solute = 6.9 × 56 gm
Msolute 6.9  56
%= M × 100 So, =  100 = 30 ; d = 1.288 gm/litre
solution d  1000
2. 10 ml of sulphuric acid solution (sp. gr. = 1.84) contains 98% by weight of pure acid. Calculate the volume of 2.5
M NaOH solution required to just neutralise the acid.
98
Sol. Wt of solute = 10 × 1.84 × gm
100
18.4 98
So moles of solute = × = 0.184
98 100
n = 2 × 0.184
H
2.5  V
2 × 0.184 =
1000
V = 147.2
3. A sample of H2SO4 (density 1.8 g mL–1) is labelled as 74.66% by weight. What is molarity of acid ? (Give answer
in rounded digits)
Sol. Let V = 1lt = 1000 ml
So mass of solution = 1800 gm
74.66
So mass of solute = 1800 × gm
100
18  74 .66
So molarity = moles of solute in 1lt = = 13.71 M Ans.
98
4. The density of 3M solution of Na2S2O3 is 1.25 g mL–1. Calculate.
(a) the % by weight of Na2S2O3 (b) mole fraction of Na2S2O3
Ans. (a) 37.92 (b) 0.065
Sol. (a) msolution = 1000 × 1.25 = 1250 gm
mass of Na2S2O3 = 3 × 158 = 474
474
% (w/w) = × 100 = 37.92
1250
3
(b) XNa2S2O3 = = 0.065.
3  43.11
5. Calculate Molality of aqueous urea solution which has X urea = 0.2
1000 X1 1000  0.2
Sol. molality = (1 – X )m = = 13.88.
1 2 0.8  18
6. If 200 mL of 0.1 M urea solution is mixed with 300 mL of 0.2 M Glucose solutions at 300 K calculate
osmotic pressure
Ans. 3.94 atm
C1V1  C 2 V2
Sol. Cnet = V1  V2
Now  = Cnet RT
p = (0.04 + 0.12) × 0.0821 × 300 = 3.94 atm.
7. A 500 gm liquid consist of 15 gm ethane at any temp. T, at a pressure = 2 atm. Find Pressure of gas required
to dissolve 30 gm gas in 300 gm liquid.
Ans. P2 = 6.66 atm.
Type (I) : Very Short Answer Type Questions : [01 Mark Each]
1. Distinguish between molarity and molality.
2. Why is ether not miscible in water?
3. State Raoult's law for a binary solution containing volatile components.
4. What are the values of Ptotal, H, V for negative deviation from ideality? Give one example.
5. What are maximum boiling azeotropes ? Give one example.
6. What is Henry law ?
7. What is expected value of van't Hoff factor for K3[Fe(CN)6] in dilute solution ?
8. In the determination of molar mass of A+B– using a colligative property, what may be the value of van't Hoff factor
if the solute is 50% dissociated ?
9. Define molal elevation constant or ebullioscopic constant?
10. Which has the highest freezing point :

(a) 1M glucose (b) 1M NaCl (c) 1M CaCI2 (d) 1M AlF3?
11. A 10% solution of urea is isotonic with 20% solution of 'x' at same temperature. Calculate molecular weight of x.
12. A person suffering from high blood pressure should take less common salt, why?
Type (II) : Short Answer Type Questions : [02 Marks Each]
13. What type of non-idealities are exhibited by cyclohexane-ethanol and acetone-chloroform mixture? Give reasons
for your answer.
14. Calculate the molality of K2CO3 solution which is formed by dissolving 2.5 g of it in one litre of solution. Density
of solution is 0.85 g ml–1. (At. wt. of K = 39, C = 12,O = 16)
15. An electrolyte AB is 50% ionised in aqueous solution. Calculate the freezing point of 1molal aqueous solution.
16. 5 g of compound 'A' was dissolved in 100 g of water at 303 K. The vapour pressure of the solution was found to
be 4.16 kilopascal. If the vapour pressure of pure water is 4.24 kPa at this temperature, what is the molecular
mass of 'A' ?
17. When fruits and vegetables are dried and placed in water, they slowly swell and return to original form, why?
Does an increase in temperature accelerate the process ? Explain.
18. The normal freezing point of nitrobenzene (C6H5NO2) is 278.82 K. A 0.25 molal solution of a certain solute in
nitrobenzene causes a freezing point depression of 2 degrees. Calculate the value of Kf for nitrobenzene.
Type (III) : Long Answer Type Questions: [03 Marks Each]
19. Urea forms an ideal solution. Determine the vapour pressure of an aqueous solution containing 10 per cent by
mass of urea at 40°C. (Vapour pressure of pure water at 40°C = 55.3 mm Hg) .
20. State Raoult's law. If T is the elevation in boiling point of a solvent and m is no. of moles of solute per kilogram
of solvent, what is the relationship between T and m ?
21. An aqueous solution of 3.12 g of BaCl2 in 250 g of water is found to boil at 100.0832°C. Calculate the degree of
dissociation of BaCI2. Given that the value of Kb(H2O)=0.52 K/m.
22. 18 g of glucose (molar mass 180 g mol–1) is present in 500 cm3 of its aqueous solution. What is the molarity of
the solution? What additional data is required if the molality of the solution is also required to be calculated?
23. Define Osmotic pressure and Arrange the following solutions in increasing order of osmotic pressure :
(a) 34.2 g L–1 of sucrose (b) 60 g L–1 of urea (c) 90 g L–1 of glucose (d) 58.5 g L–1 of NaCI.
24. The vapour pressure of water is 12.3 kPa at 300 K. Calculate the vapour pressure of a one molal solution of a
non-volatile, non-ionic solute in water.
25. (a) What are non-ideal solutions ?
(b) What role does the molecular interaction play in deciding the vapour pressure of solutions (i) alcohol and
acetone (ii) chloroform and acetone?
Type (IV) : Very Long Answer Type Questions: [05 Mark Each]
26. Explain giving examples the term ‘colligative molality’. Why do we sometimes get abnormal molecular masses
of the substances using colligative properties of the solution? The freezing point depression of 0.1 molal solution
of benzoic acid in benzene is 0.526 K. For benzene Kf is 5.12 K kg mol–1. Calculate the value of van’t Hoff factor
for benzoic acid in benzene. What conclusion can you draw about the molecular state of benzoic acid in
benzene?
27. 2.82 g of glucose (molar mass = 180) is dissolved in 30 g of water. Calculate the (i) molality of the solution
(ii) mole fractions of (a) glucose (b) water.
28. An aqueous solution freezes at 272.4 K, while pure water at 273 K. Determine the (i) molality of the solution
(ii) boiling point of solution (iii) lowering of vapour pressure of water at 298 K. (Given Kf = 1.86 K kg mol–1,
Kb = 0.512 K kg mol–1 and vapour pressure of pure water is 23.757 mm Hg)
LEVEL # 1
Q.10 5.85 g of NaCl are dissolved in 90 g of
Questions Different concentration terms of water. The mole fraction of NaCl is -
based on
a solution (A) 0.1 (B) 0.01
(C) 0.2 (D) 0.0196
Q.1 The molarity of a glucose solution containing
Q.11 The molality of 15% (wt./vol.) solution of
36 g of glucose per 400 mL of the solution is-
H 2 SO 4 of density 1.1 g/cm 3 is
(A) 1.0 (B) 0.5 (C) 2.0 (D) 0.05
approximately-
Q.2 A molal solution is one that contains one (A) 1.2 (B) 1.4 (C) 1.8 (D) 1.6
mole of a solute in -
Q.12 10 mL of concentrated H 2 SO 4 (18M) is
(A) 1000gm of the solution
diluted to one litre. The approximate strength
(B) 1000c.c. of the solution
of the dilute acid is -
(C) 1000c.c of the solvent
(A) 18 M (B) 180 M
(D) 1000gm of the solvent
(C) 0.18 M (D) 1.8 M
Q.3 Molarity of a solution relates the-
Q.13 2.3 g of C2H5OH (mol. wt. 46) are dissolved
(A) Moles of solute and solvent
in 500 mL of water. The molarity of the
(B) Moles of solute and mass of solution
solution is -
(C) Volume of solute and volume of solvent
(A) 0.01 (B) 0.1 (C) 0.05 (D) 2.0
(D) Volume of solution and moles of solute
Q.14 The number of moles present in 2 litre of 0.5
Q.4 The units of mole fraction of a compound in
M NaOH is-
solution are-
(A) 2 (B) 1 (C) 0.1 (D) 0.5
(A) mol kg –1 (B) mol litre –1
(C) g litre –1 (D) None of these Q.15 3.0 molal NaOH solution has a density of
1.110 g/ml. The molarity of the solution is-
Q.5 Which of the following is correct-
wt. (A) 2.9732 (B) 3.05
(A) mole = molarity x Vin l = (C) 3.64 (D) 3.0504
mol. wt.
(B) milli mole = molarity x Vin mL Q.16 A solution contains one mole of alcohol and
wt.
= x 1000 four moles of water. What are the mole
mol. wt. fractions of water and alcohol-
(C) Moles and millimoles of reactants react
(A) 1/4, 4/1 (B) 4/1, 1/4
according to stoichiometric ratio of
(C) 4/5, 1/5 (D) 1/5, 4/5
balanced chemical equation
(D) All Q.17 The mole fraction of NaCl in a solution
containing 1 mole of NaCl in 1000 g of water
Q.6 The hardness of water is usually expressed
is -
in-
(A) 0.0177 (B) 0.001
(A) ppm (B) g/litre
(C) 0.5 (D) 0.244
(C) Mol/litre (D) None
Q.18 In the aqueous solution of sulphuric acid the
Q.7 Density of water is 1g/mL. The concentration
mole fraction of water is 0.85. The molality of
of water in mol/litre is-
the solution is-
(A) 1000 (B) 18 (C) 0.018 (D) 55.5
(A) 8.9 m (B) 0.19 m
Q.8 How many grams of NaOH will be needed to (C) 9.8 m (D) 15 m
prepare 250 mL of 0.1 M solution-
Q.19 1000 gram aqueous solution of CaCO 3
(A) 1 g (B) 10 g (C) 4 g (D) 6 g
contains 10 gram of carbonate. Concentration
Q.9 How many grams of glucose should be of solution is -
dissolved to make one litre solution of 10%(w/v) (A) 10 ppm (B) 100 ppm
glucose- (C) 1000 ppm (D) 10,000 ppm
(A) 10 g (B) 180 g (C) 100 g (D) 1.8 g
Q.20 Equal volumes of 0.1 M AgNO3 and 0.2 M Q.28 The relative lowering in vapour pressure is-
NaCl are mixed. The concentration of NO3– 1
ions in the mixture will be- (A)  Xsolute (B) 
X solute
(A) 0.1 M (B) 0.05 M (C) = Xsolute (D)  m
(C) 0.2 M (D) 0.15 M
Q.29 The boiling point of C6H6 , CH3OH , C6H5NH2
Q.21 H2O2 solution used for hair bleaching is sold and C6H5NO2 are 800C , 650C , 1840C and
as a solution of approximately 5.0 g H2O2 2120C respectively. Which will show highest
per 100 mL of the solution. The molecular vapour pressure at room temperature-
weight of H2O2 is 34. The molarity of this (A) C6H6 (B) CH3OH
solution is approximately- (C) C6H5NH2 (D) C6H5NO2
(A) 3.0 (B) 1.5 (C) 0.15 (D) 4.0 Q.30 An aqueous solution of methanol in water
has vapour pressure –
Q.22 All of the water in a 0.20 M solution of NaCl
(A) Equal to that of water
was evaporated and 0.150 mol of NaCl was
(B) Equal to that of methanol
obtained. What was the original volume of
(C) More than that of water
the sample ? (D) Less than that of water
(A) 30 mL (B) 333 mL
(C) 750 mL (D) 1000 mL Q.31 When a substance is dissolved in a solvent,
the vapour pressure of solvent decreases. This
Q.23 25 mL of 3.0 M HNO3 are mixed with 75 mL brings -
of 4.0M HNO3. If the volumes are additive, (A) An increase in b.pt. of the solution
the molarity of the final mixture would be- (B) A decrease in b.pt of a solution
(A) 3.25 M (B) 4.0 M (C) An increase in f.pt of the solvent
(C) 3.75 M (D) 3.50 M (D) none
Q.24 10 gram of glucose are dissolved in 150 gram Q.32 Boiling point of water is defined as the
of water. The mass % of glucose is- temperature at which –
(A) 5% (B) 6.25% (A) Vapour pressure of water becomes equal
(C) 93.75% (D) 15% to that of atmospheric pressure
(B) Bubbles are formed
Q.25 If 100 ml of 1.0 M NaOH solution is diluted (C) Steam comes out
to 1.0 L, the resulting solution contains- (D) None of the above
(A) 1 mole of NaOH
(B) 0.1 mole of NaOH Questions Raoult’s laws-ideal & Non-ideal
(C) 10.0 mole of NaOH based on solution
(D) 0.05 mole of NaOH Q.33 A solution of sulphuric acid in water
exhibits -
Questions Vapour pressure & Relative (A) Negative deviations from Raoult’s law
based on lowering in vapour pressure (B) Positive deviations from Raoult’s law
(C) Ideal properties
Q.26 If P0 and Ps are the vapour pressures of the (D) The applicability of Henry’s law
solvent and solution respectively and n1 and
Q.34 Binary liquid mixtures which exhibit positive
n2 are the mole fractions of the solvent and deviations from Raoult’s law boil at .....
solute respectively, then- temperature than the expected b.pt -
(A) Ps = P0n1 (B) Ps = P0n2 (A) Lower (B) Higher
(C) P0 = Psn2 (D) Ps = P0 (n1/n2) (C) Same (D) Can’t be said
Q.27 Vapour pressure of a solvent containing Q.35 Which of the following is not correct for ideal
nonvolatile solute is - solution -
(A) More than the vapour pressure of a solvent (A) Raoult's law is obeyed for entire
(B) Less than the vapour pressure of solvent concentration range and temperatures
(C) Equal to the vapour pressure of solvent (B) Smix = 0
(D) None of these (C) Vmix = 0
(D) Hmix = 0
Q.36 Which one of the following liquid-pairs shows Q.44 Azeotropic mixture of water and HCl boils at
a positive deviation from Raoult's law- 381.5 K. By distilling the mixture it is possible
(A) Acetone-chloroform to obtain-
(B) Benzene-methanol (A) Pure HCl only
(C) Water-Hydrochloric acid (B) Pure water only
(D) Water-nitric acid (C) Neither HCl nor water
(D) Both water and HCl in pure state
Q.37 Which of the following conditions is not
correct for ideal solution-
(A) no change in volume on mixing Questions
Elevation in B.P. & depression in F.P.
based on
(B) no change in enthalpy on mixing
(C) it obey's Raoult's law Q.45 Which of the following is not a colligative
(D) Ionisation of solute should occurs to a property -
small extent (A) T f (B)  (C) T b (D) Kb
Q.38 When a crystal of the solute is introduced Q.46 Solute when dissolved in water -
into a super saturated solution of the solute- (A) Increases the vapour pressure of water
(A) The solute dissolves (B) Decreases the boiling point of water
(B) The excess solute crystallises out (C) Decreases the freezing point of water
(C) The solution becomes unsaturated (D) All of the above
(D) The solution remains super saturated Q.47 The elevation of boiling point method is used
Q.39 An ideal solution is that which- for the determination of molecular weight of -
(A) Shows positive deviation from Raoult's (A) Non-volatile and soluble solute
law (B) Non-volatile and insoluble solute
(B) Shows negative deviation from Raoult's (C) Volatile and soluble solute
law (D) Volatile and insoluble solute
(C) Has no connection with Raoult's law Q.48 Which statement is correct for the boiling
(D) Obeys Raoult's law point of solvent containing a dissolved solid
Q.40 Which does not influence the solubility of a substance-
solid in a liquid solvent- (A) Boiling point of the liquid is depressed
(A) Nature of solute (B) Boiling point of the liquid is elevated
(B) Nature of solvent (C) There is no effect on the boiling point
(C) Temperature (D) The change depends upon the polarity of
(D) Pressure the liquid
Q.41 When one mole of non-volatile solute is Q.49 In cold countries, ethylene glycol is added
dissolved in three moles of solvent, the vapour to water in the radiators of cars during
pressure of the solution relative to the vapour winters. It results in -
pressure of the pure solvent is - (A) Lowering in boiling point
1 1 3 (B) Reducing viscosity
(A) (B) (C) (D) 1 (C) Reducing specific heat
3 4 4
(D) Lowering in freezing point
Q.42 Solutions distilled without change in
composition at a temperature are called- Q.50 The molal elevation/depression constant
(A) Amorphous depends upon-
(B) Azeotropic mixture (A) Nature of solvent (B) Nature of solute
(C) Ideal solution (C) Temperature (D) H solution
(D) Super saturated solution Q.51 An example of colligative property is -
Q.43 Which pair shows a contraction in volume on (A) Freezing point
mixing along with evolution of heat- (B) Boiling point
(A) CHCl3 + C6H6 (B) H2O + HCl (C) Vapour pressure
(C) H2O + HNO3 (D) All (D) Osmotic pressure
Questions Q.59 The correct relationship between the boiling
based on Osmotic Pressure points of very dilute solutions of AlCl3 ( t1)
and CaCl 2 (t 2 ), having the same molar
Q.52 The passing of particles through
concentration is-
semipermeable membrane is called -
(A) t1 = t2 (B) t1 > t2
(A) Osmosis (B) Electrodialysis
(C) t2 > t1 (D) t2  t1
(C) Electrophoresis (D) Electroplating
Q.60 0.5 M solution of urea is isotonic with-
Q.53 In the case of osmosis, solvent molecules
(A) 0.5 M NaCl solution
move from-
(B) 0.5 M sugar solution
(A) Higher vapour pressure to lower vapour
(C) 0.5 M BaCl2 solution
pressure
(D) 0.5 M solution benzoic acid in benzene
(B) Higher concentration to lower
concentration Q.61 Which salt may show the same value of Vant
(C) Lower vapour pressure to higher vapour Hoff factor (i) as that of K4Fe(CN)6 in very
pressure dilute solution state-
(D) Higher osmotic pressure to lower osmotic (A) Al2(SO4)3 (B) NaCl
pressure (C) Al(NO3)3 (D) Na2SO4
Q.54 If mole fraction of the solvent in a solution Q.62 Which compound corresponds Vant Hoff
decreases then- factor (i) to be equal to 2 in dilute solution-
(A) Vapour pressure of solution increases (A) K2SO4 (B) NaHSO4
(B) b.pt decreases (C) Sugar (D) MgSO4
(C) Osmotic pressure increases Q.63 In which of the following , the Vant Hoff factor
(D) All are correct (i) is equal to one-
Q.55 Two solutions have different osmotic (A) NaCl (B) KNO3
pressures. The solution of higher osmotic (C) Urea (D) All
pressure is called- Q.64 The Vant Hoff factor (i) for a dilute aqueous
(A) Isotonic solution solution of glucose is -
(B) Hypotonic solution (A) zero (B) 1.0
(C) Isotopic solution (C) 1.5 (D) 2.0
(D) Hypertonic solution
Q.65 Vant Hoff factor (i)-
Q.56 According to Boyle-Vant Hoff law for (A) Is less than one in case of dissociation
solutions, the osmotic pressure of a dilute (B) Is more than one in case of association
solution is - normal molecular mass
(A) Inversely proportional to its volume (C) i = observed molecular mass
(B) Directly proportional to its volume
observed molecular mass
(C) Equal to its volume (D) i = normal molecular mass
(D) None of the above
Q.57 Which solution will show maximum elevation Q.66 In case of electrolyte which dissociates in
in b.pt - solution the Vant Hoff's Factor -
(A) 0.1 M KCl (B) 0.1 M BaCl2 (A) > unity (B) < Unity
(C) 0.1 M FeCl3 (D) 0.1 M Fe2(SO4)3 (C) = Unity (D) can be > or < 1
Q.67 Which one of the following salts would have
Questions Colligative properties of
the same value of the Vant Hoff factor (i) as
based on electrolytes, Vant Hoff’s Factor that of K3 [Fe(CN)6].
Q.58 W hich of the following 0.1 M aqueous (A) NaCl (B) Na2SO4
solutions will have the lowest freezing point- (C) Al2(SO4)3 (D) Al(NO3)3
(A) Potassium sulphate(B) Sodium chloride
(C) Urea (D) Glucose
LEVEL # 2
Q.1 Select correct statement - Q.8 Consider following solutions -
(A) b.p. of 1 molal NaCl solution is twice I : 1 M aq. glucose
that of 1 molal sucrose solution II. : 1 M aq. sodium chloride
(B) b.p. elevation of 1 molal glucose solution III. : 1 M benzoic acid in benzene
is half of the 1 molal KCl solution IV. : 1 M ammonium phosphate
(C) b.p. is a colligative property Select incorrect statement -
(D) All of the above (A) all are isotonic solutions
(B) III is hypotonic of I, II, IV
Q.2 Total vapour pressure of mixture of 1 mol
(C) I, II, IV are hypertonic of III
volatile component A(pºA = 100 mmHg) and
(D) IV is hypertonic of I, II, III
3 mol of volatile component B (pºB = 60
mmHg) is 75 mm. For such case - Q.9 The relationship between osmotic pressure
(A) there is positive deviation from Raoult's at 273 K when 10 g glucose (P1) 10 g urea
law (P2) and 10 g sucrose (P3) are dissolved in
(B) boiling point has been lowered 250 ml of water is -
(C) force of attraction between A and B is (A) P1 > P2 > P3 (B) P3 > P1 > P2
smaller than that between A and A or (C) P2 > P1 > P3 (D) P2 > P3 > P1
between B and B Q.10 The osmotic pressure of a solution of benzoic
(D) All the above statements are correct acid dissolved in benzene is less than
Q.3 At a given temperature, total vapour pressure expected because -
in Torr of a mixture of volatile components A (A) Benzoic acid is an organic solute
and B is given by (B) Benzene is a non-polar solvent
P = 120 – 75 XB (C) Benzoic acid dissociates in benzene
hence, vapour pressure of pure A and B (D) Benzoic acid gets associated in benzene
respectively (in Torr) are - Q.11 Assuming each salt to be completely
(A) 120, 75 (B) 120, 195 dissociated which of the following will have
(C) 120, 45 (D) 75, 45 highest osmotic pressure-
Q.4 Van't Hoff factors of aqueous solutions of X, (A) Decimolar Al2(SO4)3
Y, Z are 1.8, 0.8 and 2.5. Hence their - (B) Decimolar BaCl2
(A) b.p. : Y < X < Z (C) Decimolar Na2SO4
(B) f.p. : Z < X < Y (D) A solution obtained by mixing equal
(C) osmotic pressure : X = Y = Z volumes of (B) and (C) and filtering
(D) v.p. : Y < X < Z Q.12 Which one of the following pairs of solution
Q.5 Decimolar solution of potassium ferricyanide, can we expect to be isotonic at the same
K3[Fe(CN)6] has osmotic pressure of 3.94 temperature-
atm at 27ºC. Hence percent ionisation of the (A) 0.1 M urea and 0.1 M NaCl
solute is - (B) 0.1 M urea and 0.2 M MgCl2
(A) 10% (B) 20% (C) 30% (D) 40% (C) 0.1 M NaCl and 0.1M Na2SO4
(D) 0.1 M Ca(NO3)2 and 0.1 M Na2SO4
Q.6 An aqueous solution of urea containing 18 g
urea in 1500 cm 3 of solution has a density of Q.13 For a solution containing non-volatile solute,
1.052 g/cm 3. If the molecular weight of urea the relative lowering of vapour pressure is
is 60, then the molality of solution is- 0.2. If the solution contains 5 moles in all,
(A) 0.2 (B) 0.192 (C) 0.064 (D) 1.2 which of the following are true ?
I. Mole fraction of solute in the solution is 0.2
Q.7 2.56 g of sulphur in 100 g of CS2 has depression
II. No. of moles of solute in the solution is 0.2
in f.p. of 0.010º, Kf = 0.1º (molal)–1. Hence,
III. No. of moles of solvent in the solution is 4
atomicity of sulphur is -
IV. Mole fraction of solvent is 0.2 -
(A) 2 (B) 4 (C) 6 (D) 8
(A) I, IV (B) II, III (C) I, III (D) II, IV
Q.14 A complex containing K+, Pt (IV) and Cl– is Q.24 A molal solution is one that contains one
100% ionised giving i = 3. Thus, complex is - mole of a solute in-
(A) K2 [PtCl4] (B) K2[PtCl6] (A) 1000 gram of the solvent
(C) K3[PtCl5] (D) K[PtCl3] (B) One litre of the solvent
(C) One litre of the solution
Q.15 If pKa = – log Ka = 4, and Ka = C2 then van't
(D) 22.4 litres of the solution
Hoff factor for weak monobasic acid when
C = 0.01 M is - Q.25 One among the following is an incorrect
(A) 0.01 (B) 1.02 (C) 1.10 (D) 1.20 statement-
(A) Molality of a solution is dependent on the
Q.16 pH of 1M HA (weak acid) is 2. Hence van't
temperature
Hoff factor is -
(B) Molarity of a solution is dependent on the
(A) 1.2 (B) 1.02 (C) 1.1 (D) 1.01
temperature
Q.17 In which case van't Hoff factor is maximum ? (C) Normality of 0.5 M aqueous solution of
(A) KCl, 50% ionised H2C2O4.2H2O is 1 N
(B) K2SO4 40% ionised (D) Molality of a solution relates moles of
(C) FeCl3, 30% ionised solute and mass of solvent
(D) SnCl4, 20% ionised
Q.26 Molality of the solution is-
Q.18 If 18 gram of glucose (C 6H 12O6) is present (A) The number of moles of the solute
in 1000 gram of an aqueous solution of dissolved per kilogram of solvent
glucose it is said to be- (B) The number of gram mole of the solute
(A) 39.2 gram (B) 1.1 molal dissolved per ml of the solution
(C) 0.5 molal (D) 0.1 molal (C) The number of grams of the solute
Q.19 What is the molarity of H2SO4 solution that dissolved per kilogram of solvent
has a density of 1.84 gm/cc at 350C and (D) The number of moles of the solute
contains 98% by weight- dissolved per litre of the solution
(A) 4.18 M (B) 8.14 M Q.27 An azeotropic solution of two liquids has
(C) 18.4 M (D) 18 M boiling point lower than either when it -
Q.20 In order to prepare 100 cm 3 of 0.250 M (A) shows a negative deviation from Raoult's
barium chloride solution the amount of law
BaCl 2.2H 2O required will be- (B) shows a positive deviation from Raoult's
(A) 0.250 moles law
(B) 0.0025 moles (C) shows no deviation from Raoult's law
(C) 2.5 moles (D) is saturated
(D) 6.1 gram of BaCl2.2H2O Q.28 A molar solution represents a solution of
Q.21 25 mL of 3 M HCl were added to 75 mL of molarity equal to–
0.05 M HCl. The molarity of HCl in the (A) 1 (B) 2
resulting solution is approximately- (C) 3 (D) None
(A) 0.055 M (B) 0.35 M Q.29 1000 g aqueous solution of CaCO3 contains
(C) 0.787 M (D) 3.05 M 10 g of calcium carbonate. Concentration of
Q.22 0.2 mole of HCl and 0.1 mole of CaCl2 were solution is-
dissolved in water to have 500 ml of solution, (A) 10 ppm (B) 100 ppm
the molarity of Cl¯ ions is- (C) 1000 ppm (D) 10000 ppm
(A) 0.04 M (B) 0.8 M (C) 0.4 M (D) 0.08 M Q.30 The osmotic pressure of 10%(w/v) aqueous
Q.23 When 5.0 gram of BaCl2 is dissolved in water solution of urea (1) is related to that of
to have 10 6 gram of solution. The 10%(w/v) aqueous solution of glucose (2)
concentration of solution is - as -
(A) 2.5 ppm (B) 5 ppm (A) 1 = 2 (B) 1 > 2
(C) 5M (D) 5 gm L –1 (C) 1 < 2 (D) 1 = 1 – 2
Q.31 Cryoscopic constant of a liquid is - Q.38 The freezing point of 1 molal NaCl solution
(A) Decrease in freezing point when 1 gram assuming NaCl to be 100% dissociated in
of solute is dissolved per kg of the solvent water is-
(B) Decrease in the freezing point when 1 (A) – 1.86 0C (B) – 3.720C
mole of solute is dissolved per kg of the (C) + 1.86 0C (D) + 3.72 0C
solvent
Q.39 The molar freezing point constant for water is
(C) Is the elevation for 1 molar solution
1.86 0C/mole. If 342 gm of cane sugar
(D) Is a factor used for calculation of elevation
(C12H22O11) is dissolved in 1000 gram of
in boiling point
water, the solution will freeze at-
Q.32 If the vapour pressure of solutions of two (A) – 1.86 0C (B) 1.86 0C
liquids are less than those expected from 0
(C) – 3.92 C (D) 2.420C
ideal solution they are said to have-
Q.40 100 ml of liquid A and 25 ml of liquid B is
(A) Negative deviation from ideal behaviour
mixed to give a solution which does not obey
(B) Positive deviations from ideal behaviour
Raoult's law. The volume of the solution -
(C) Ideal behaviour
(A) will be 125 ml
(D) Positive deviation for lower conc. and
(B) can be > or < than 125 ml
negative deviations for higher
(C) can be greater than, equal to or less than
concentration
125 ml
Q.33 A solution of benzoic acid dissolved in (D) will be less than 125 ml
benzene will show a molecular mass closer
Q.41 A binary solution of ethanol and n-heptane is
to -
an example of -
(A) 122 (B) 244 (C) 61 (D) 366
(A) Ideal solution
Q.34 The osmotic pressure of the solution having (B) Non ideal solution with +ve deviation
concentration 0.05 M . (C) Non ideal solution with – ve deviation
(A) Increases with increase in temperature (D) Un predictable behaviour
(B) Does not change with change in
Q.42 H2O and perchloric acid (b.p. 383 K ) form
temperature
constant boiling mixture at 71.6% of perchloric
(C) Decreases with increase in temperature
acid. The boiling point of the solution at this
(D) Initially decreases and then increases with
composition is -
rise in temperature
(A) > 373 but < 383 K (B) < 373 K
Q.35 Pure benzene freezes at 5.450C at a certain (C) > than 383 K (D) = 373 K
place but a 0.374 m solution of tetra
Q.43 10 gram of solute with molecular mass 100
chloroethane in benzene freezes at 3.550C.
gram mol-1 is dissolved in 100 gram solvent
The Kf for benzene is -
to show 0.3 0C elevation in boiling point. The
(A) 5.08 K. kg mol –1 (B) 508 K kg mol –1
value of molal ebullioscopic constant will be-
(C) 0.508 K kg mol –1 (D) 50.8 0C kg mol –1
(A) 10 (B) 3
Q.36 At certain Hill-station pure water boils at (C) 0.3 (D) Unpredictable
99.7250C. If Kb for water is 0.5130C kg mol –1.
Q.44 If the observed and theoretical molecular
The boiling point of 0.69 m solution of urea
mass of NaCl is found to be 31.80 and 58.50,
will be-
then the degree of dissociation of NaCl is-
(A) 100.079 0C (B) 1030C
0
(A) 83.96% (B) 8.39%
(C) 100.359 C (D) Un predictable
(C) 90% (D) 100%
Q.37 The freezing point of a 0.05 molal solution
Q.45 When mango is placed in dilute aqueous
of a non-electrolyte in water is -
solution of hydrochloride acid, it-
(Kf = 1.860C/mol) -
(A) Shrinks (B) Swells
(A) – 1.86 0C (B) – 0.93 0C
0
(C) Bursts (D) Nothing happens
(C) – 0.093 C (D) 0.930C
Q.46 In certain solvent, phenol dimerizes to the Q.54 A 0.01 M solution of glucose in water freezes
extent of 60%. Its observed molecular mass at – 0.0186 0C. A 0.01 M solution of KCl in
in that solvent should be- water is freezes at temperature-
(A) > 94 (B) = 94 (A) higher than – 0.01860C
(C) < 94 (D) Unpredictable (B) 00C
Q.47 Two liquids A and B form an ideal solution. At (C) 0.0186 0C
300 K the vapour pressure of a solution of 1 (D) lower than -0.0186 0C
mole of A and x moles of B is 550 mm. If the Q.55 The osmotic pressure of 0.2 molar solution
vapour pressures of pure A and B are 400 of urea at 300 K
mm and 600 mm respectively, then x is - (R = 0.082 litre atm mol –1 K –1) is -
(A) 1 (B) 2 (C) 3 (D) 4
(A) 4.92 atm (B) 1 atm
Q.48 Equal volume of 1M urea and 1M glucose (C) 0.25 atm (D) 27 atm
are mixed. The mixture will have-
Q.56 A liquid is in equilibrium with its vapour at its
(A) Same osmotic pressure
boiling point. On the average the molecules
(B) Lower osmotic pressure
(C) Higher osmotic pressure in the two phase have equal-
(D) None of these (A) Inter-molecular forces
(B) Potential energy
Q.49 For dilute solution Raoult's law states that- (C) Total energy
(A) The lowering of vapour pressure is equal (D) Kinetic energy
to the mole fraction of the solute
(B) The relative lowering of vapour pressure Q.57 The hard shell of an egg is dissolved in acetic
is equal to the mole fraction of the solute acid and then egg was subsequently placed
(C) The relative lowering of vapour pressure in saturated solution of NaCl
is proportional to the amount of solute in (A) The egg will shrink
solution (B) The egg will become harder
(D) The vapour pressure of the solution is (C) The egg will swell
equal to the mole fraction of the solvent (D) No change in the size of egg
Q.50 An azeotropic solution of two liquids has Q.58 All form ideal solutions except-
boiling point lower than either of them when it- (A) C2H5Br and C2H5I
(A) Shows a negative deviation from Raoult's (B) C6H5Cl and C6H5Br
law (C) C6H6 and C6H5.CH3
(B) Shows no deviation from Raoult's law (D) C2H5I and C2H5OH
(C) Shows positive deviation from Raoult's
law Q.59 The substance A when dissolved in solvent
(D) Is saturated B shows the molecular mass corresponding
to A3. The vant Hoff's factor will be-
Q.51 The molal elevation constant is the ratio of
(A) 1 (B) 2 (C) 3 (D) 1/3
the elevation in BP to-
(A) Molarity Q.60 Which statement is incorrect about osmotic
(B) Molality pressure (), volume (V) and temperature (T)-
(C) Mole fraction of solute 1
(D) Mole fraction of solvent (A)   if T is constant
V
Q.52 The osmotic pressure of solution increases if- (B)   T if V is constant
(A) Temperature is decreased (C)   V if T is the constant
(B) Solution constant is increased (D)  V is constant if T is constant
(C) Number of solute molecules are increased Q.61 The osmotic pressure of a solution is given
(D) Volume is increased by the relation-
Q.53 A 5% solution of can sugar is isotonic with RT CT
(A)  = (B)  =
0.877 % of X. The molecular weight of C R
substance X is - RC 
(A) 58.98 (B) 119.96 (C)  = (D) = RT
T C
(C) 95.58 (D) 126.98
Q.62 Blood cells retain their normal shapes in Q.68 The osmotic pressure of equimolar solutions
solutions which are- of urea, BaCl2 and AlCl3 will be in the order-
(A) isotonic to blood (A) AlCl3 > BaCl2 > Urea
(B) hypotonic to blood (B) BaCl2 > AlCl3 > Urea
(C) hypertonic to blood (C) Urea > BaCl2 > AlCl3
(D) all of these (D) BaCl2 > Urea > AlCl3
Q.63 The osmotic pressure of a dilute solution is Q.69 Which of the following is a colligative property-
given by- (A) Change in free energy
(A) P = P0X (B) V = nRT (B) Dipole moment
P P0  P (C) Heat of vaporisation
(C) P = P0N2 (D) = (D) Osmotic pressure
P0 P0
Q.64 Osmotic pressure of a solution increases by- Q.70 Which of the following statements is correct
(A) Decreasing the temperature for the boiling point of solvent containing a
(B) Increasing the volume dissolved solid substance-
(C) Increasing the number of molecules of (A) Boiling point of the liquid is depressed
the solute (B) Boiling point of the liquid is elevated
(D) None of the above (C) There is no effect on the boiling point
Q.65 The solution having same osmotic pressure (D) The change depends upon the polarity of
are called- the liquid
(A) Equivalent solutions
(B) Ideal solutions Q.71 The vapour pressures of pure A and B at
(C) Equimolar solutions given temperature are 108 and 36 bar
(D) Isotonic solutions respectively what is the mole fraction of B in
the vapour phase of the solution containing
Q.66 A property which depends primarily on the equimolar mixture of A and B -
number of molecules of a system and not on (A) 0.25 (B) 0.5
their nature is known to be- (C) 0.75 (D) 0.66
(A) Constitutive (B) Additive
(C) Colligative (D) None of the above
Q.67 The values of observed and theoretical
molecular masses of certain electrolyte XY
are 65.4 and 114.45 respectively. The
electrolyte XY in the solution has dissociation
to the extent of -
(A) 75% (B) 80%
(C) 50% (D) 90%
QUESTIONS FROM COMPETITIVE EXAMS
Choose the appropriate answer:

1. Which of the following 0.1 M aqueous solution will 8. Molal depression constant depends upon
have lowest freezing point? [MLNR 1990] (1) Nature of the solute [Pb CET 1991]
(1) Potassium sulphate (2) Sodium chloride (2) Nature of the solvent
(3) Urea (4) Glucose (3) Vapour pressure of solution
2. Molality is expressed in [CBSE Med 1990] (4) Heat of solution
(1) Gram/litre 9. Mole fraction of glycerine C3H5(OH)3 in solution
(2) Litre/moles containing 36 gm of water and 46 gm of glycerine is
(3) Mole/litre (1) 0.46 (2) 0.40
(4) Mole/kg (3) 0.20 (4) 0.36 [CPMT ’91]
3. The freezing points of equimolar aqueous solution 10. The molecular mass of sodium chloride as determined
will be highest for [IIT 1990] by osmotic pressure method is :
[Haryana CET Sample Paper 1992]
 
(1) C H N H Cl (2) Ca ( NO 3 ) 2 (1) Equal to 58.5
6 5 3
(2) Greater than 58.5

(3) La ( NO 3 ) 3 (4) C 6 H12 O 6
(3) Less than 58.5
4. Osmotic pressure of a solution is 0.0821 atm at
temperature of 300 K. The concentration of solution (4) None of the information is correct
in moles/litre will be [Roorkee 1990] 11. The molarity of pure water is [KCET 1993]
(1) 0.33 (2) 0.066 (1) 55.6 (2) 50
–2
(3) 0.3 × 10 (4) 3 (3) 100 (4) 18
5. Which is not a colligative property? 12. Which of the following liquid pairs will show positive
deviation from Raoult’s Law? [MPCEE 1993]
(1) T f (2) 
(1) Water-hydrochloric acid
(3) Tb (4) Kb [Pb CET ’91] (2) Water-nitric acid
6. The relative lowering in vapour pressure is (3) Acetone chloroform
proportional to the ratio between the number of (4) Benzene methanol
(1) Solute molecules to solvent molecules 13. The law which states that the mass of a gas dissolved
(2) Solute molecules to the total number of molecules in given mass of the solvent at any temperature is
in solution directly proportional to the pressure of the gas above
the solution is [PMT 1998]
(3) Solvent molecules to the total number of
molecules in solution (1) Joule’s law (2) Boyle’s law
(3) Henry’s law (4) Charle’s law
(4) Solvent molecules to the total number of ions in
solution [CBSE 1991] 14. Increasing the temperature of an aqueous solution
will cause [IIT 1993]
7. 500g tooth paste sample has 0.2 g fluoride ion
concentration. What is the concentration of fluoride (1) Decrease in molarity
in terms of ppm level? [AIIMS 1991] (2) Decrease in molality
(1) 250 (2) 200 (3) Decrease in mole fraction
(3) 400 (4) 1000 (4) Decrease in % (w/w)
15. The molal freezing point for water is 1.86° C/m. 22. A 0.2 molal aqueous solution of a weak acid (HX) is
Therefore the freezing point of 0.1 m NaCl solution 20 percent ionised. The freezing point of this solution
in water is expected to be [MLNR 1994] is (Given Kf = 1.86°C kg mol–1 for water)
(1) –1.86°C (2) –0.186°C (1) –0.45° (2) –0.90°C
(3) –0.372°C (4) +0.372°C (3) –0.31°C (4) –0.53°C [IIT ’95]
16. At 25°C the highest osmotic pressure is expected 23. 0.1 M NaCl and 0.1 M CH3COOH solutions are
by 0.1 M solution is [CBSE 1994] kept in separate containers. If their osmotic pressure
(1) CaCl2 (2) KCl are P1 and P2 respectively then what will be the
correct statement? [CPMT 1996]
(3) Glucose (4) Urea
(1) P1 > P2 (2) P1 = P2
17. Which of the following salts will have the same value
of Van’t Hoff factor (i) as that of K4[Fe(CN)6] (3) P1 < P2 (4) P1 = P2 = 0 atm
[CBSE 1994] 24. Azeotropic mixture of HCl and H2O has
(1) Al2(SO4)3 (2) NaCl [AFMC 1997]

(1) 48% HCl (2) 82.2% HCl
(3) Al(NO3)3 (4) Na2SO4
(3) 36% HCl (4) 20.2% HCl
18. 12 g of urea is dissolved in 1 litre of water and 68.4g
of sucrose is also dissolved in 1 litre of water. The 25. Which is not affected by temperature?
lowering in the vapour pressure of first case is [AIIMS 1997]
(1) equal to second [EAMCET 1995] (1) Normality (2) Molality
(2) greater than second (3) Molarity (4) Formality
(3) less than second 26. If all the following four compounds were sold at the
(4) double the second same price, which would be the cheapest for
preparing antifreeze solution for a car radiator?
19. Isotonic solutions have same [AFMC 1995]
[AMU 1997]
(1) Molar concentration (2) Molality
(1) CH 3OH (2) C2H 5OH
(3) Normality (4) None of these
(3) C2H4(OH)2 (4) C3H5(OH)3
20. Which of the following statements is true?
27. The vapour pressure of a solvent decreases by
[Orissa JEE 2003] 10 mm mercury when a non-volatile solute is added
(1) The relative lowering in vapour pressure of a to the solvent. The mole fraction of the solute in the
solution is equal to the mole fraction of the solute. solution is 0.2. What should be the mole fraction of
the solvent if the decrease in vapour pressure is to
(2) Passage of solute molecules towards solution
be 20 mm mercury? [CBSE 1998]
side through semipermeable membrane is
osmosis (1) 0.8 (2) 0.6
(3) Boiling point of solution is always lower than (3) 0.4 (4) None of these
that of the solvent. 28. A 5% solution of cane sugar (molar mass = 342) is
(4) Boiling point of a liquid is the temperature at which isotonic with 1% solution of a substance X. The molar
its vapour pressure becomes equal to 200 mm. mass of X is [CBSE 1998]
21. An elevation in b.p. of a solution of 10g of solute (1) 171.2 (2) 68.4
(molar mass = 100) in 100 g of water is Tb . The (3) 34.2 (4) 136.2
equllioscopic constant for water is 29. A sugar syrup of weight 214.2 g contains 34.2g of
[CBSE 1995] sugar. The molal concentration of solution is
(1) 0.55 (2) 5.5 [IIT 1998]
(1) 10 (2) 10 Tb
(3) 55 (4) 0.1
(3) Tb (4) Tb /10
30. Which has highest boiling point at 1 atm pressure? 38. Depression in freezing point is directly proportional to
[MP PMT 1998] [Tamil Nadu CET 2001]
(1) 0.1 M NaCl (2) 0.1 M Sucrose (1) Mole fraction of the solution
(3) 0.1 M BaCl2 (4) 0.1 M Glucose (2) Molarity of the solution
31. An aqueous solution freezes at –0.186°C (Kf = 1.86, (3) Molality of the solution
Kb = 0.512). What is the elevation in boiling point?
(4) Molality of the solvent
[MP PMT 1998]
39. Which of the following aqueous solutions will have
(1) 0.186 (2) 0.512
least freezing point? [Kerala EEE 2001]
(3) 0.86 (4) 0.0512
(1) 0.1 m urea (2) 0.1 m sucrose
32. The osmotic pressure of 1M solution at 27°C is
(3) 0.1 m acetic acid (4) 0.1 m CaCl2
(1) 2.46 atm [CPMT 1999]
40. 250 mL of Na2CO3 solution contains 2.65 grams of
(2) 24.63 atm (3) 1.21 atm the carbonate. If 10 mL of the solution is diluted to
(4) 12.16 atm one litre, what is the concentration of the resultant
33. Which of the following does not show positive solution ? (Molar mass of Na2CO3 = 106)
deviation from Raoult’s Law? [MP PMT 2000] [EAMCET 2001]
(1) Benzene-chloroform (1) 0.1 M (2) 0.001 M
(2) Benzene-acetone (3) 0.01 M (4) 10–4 M
(3) Benzene-ethanol 41. Colligative properties of the solutions are those
(4) Benzene-carbon tetrachloride properties which depend on the
34. Depression in freezing point for 1M urea, 1M glucose (1) Shapes of the particles [Kerala PMT 2002]
and 1M NaCl are in the ratio. (2) Nature of the solvent
[Haryana CET 2000] (3) Nature of the particles only
(1) 1 : 2 : 3 (2) 3 : 2 : 2 (4) Number of the particles only
(3) 1 : 1 : 2 (4) None of these 42. Colligative properties are used for the determination
35. For determination of the molar mass of colloids of [Kerala CET 2002]
polymers and proteins which colligative property is (1) Molar mass (2) Equivalent mass
used? [CBSE 2000] (3) Arrangement of molecules
(1) Diffusion pressure (4) Melting and boiling points
(2) Atmospheric pressure 43. 2.5 litre of 1 M NaOH solution is mixed with a
(3) Osmotic pressure 3.0 litres of 0.5 M NaOH solution. The molarity of
(4) Turgor pressure the resulting solution is [CBSE 2003]
36. To 500 cm3 of water, 3.0 × 10–3 kg of acetic acid is (1) 0.80 M (2) 1.0 M
added. If 23% of acetic acid is dissociated what will (3) 0.73 M (4) 0.50 M
be depression in freezing point? Kf for water is 1.86 44. What is the Van’t Hoff factor when benzene vapour
K kg mol–1 and density of water is 0.997 g cm–3. pressure falls from 165 mm to 162 mm on addition
[IIT 2000] of 6g of CH3COOH to 3 moles of benzene
(1) 0.186 K (2) 0.228 K [UPSEAT 2002]
(3) 0.372 K (4) 0.556 K (1) 0.56 (2) 0.325
37. The volume of water to be added to 100 cm3 of (3) 2 (4) 0.07
0.5 N H2SO4 to get decinormal solution is : 45. If liquids A and B form an ideal solution
[KCET 2001] (1) The free energy of mixing is zero
(1) 100 cm3 (2) 450 cm3 (2) The free energy as well as the entropy of mixing
are each zero.
(3) 500 cm3 (4) 400 cm3
(3) The enthalpy of mixing is zero
(4) The entropy of mixing is zero [AIEEE 2003]
–1
46. If a 0.2 molal aqueous solution of a weak acid HX, (1) 200 g mol (2) 250 g mol–1
the degree of ionisation is 0.3. Taking Kf for water (3) 300 g mol–1 (4) 350 g mol–1
as 1.85, the freezing point of the solution will be
nearest to [AIEEE 2003] 52. 1.00 g of a non-electrolyte solute (molar mass 250
g mol–1) was dissolved in 51.2 g of benzene. If the
(1) –0.260°C (2) +0.180°C freezing point depression constant, Kf of benzene is
(3) –0.480°C (4) –3.60°C 5.12 K kg mol–1, the freezing point of benzene will
47. Formation of solution from two components can be be lowered by [CBSE 2006]
considered as : (1) 0.2 K (2) 0.4 K
(i) Pure solvent  Separated solvent molecules; H1 (3) 0.3 K (4) 0.5 K
(ii) Pure solute  Separated solute molecules; H 2 53. A solution of acetone in ethanol [CBSE 2006]
(1) Obeys Raoult’s law
(iii) Separated solvent and solute molecules ; H 3 .
Solution formed will be ideal if (2) Shows a negative deviation from Raoult’s law
(3) Shows a positive deviation from Raoult’s law
 H1  H 2  H3
(1) Hsol 
(4) Behaves like a near ideal solution
 H1  H 2  H3
(2) Hsol  54. During osmosis, flow of water through a
semipermeable membrane is [CBSE 2006]
 H3  H1  H 2
(3) Hsol 
(1) From solution having lower concentration only
 H3  H1  H 2 [CBSE 2003]
(4) Hsol  (2) From solution having higher concentration only
48. What is the effect of the addition of sugar on the (3) From both sides of semipermeable membrane
boiling and freezing points of water? with equal flow rates
[Kerala CET 2003] (4) From both sides of semipermeable membrane
with unequal flow rates
(1) Both boiling and freezing points increase
55. Density of a 2.05 M solution of acetic acid in water
(2) Both boiling and freezing points decrease
is 1.02 g/mL. The molality of the solution is
(3) Boiling point decreases and freezing point
increases (1) 2.28 mol kg–1 [AIEEE 2006]
–1
(4) Boiling point increases and freezing point (2) 0.44 mol kg (3) 1.14 mol kg–1
–1
decreases (4) 3.28 mol kg
49. The volume of water to be added to N/2 HCl to 56. 18 g of glucose (C6H12O6) is added to 178.2 g of
prepare 500 cm3 of N/10 solution is water. The vapour pressure of water for this aqueous
solution at 100°C is [AIEEE 2006]
[Karnataka CET 2003]
3 (1) 76.00 Torr (2) 752.40 Torr
(1) 45 cm (2) 400 cm3
(3) 759.00 Torr (4) 7.60 Torr
(3) 450 cm3 (4) 100 cm3
57. Which of the following aqueous solutions has the
50. During depression in freezing point in a solution, the highest boiling point? (DPMT 2009)
following are in equilibrium [IIT 2003]
(1) 0.1 M KNO3 (2) 0.1 M Na3PO4
(1) Liquid solvent and solid solvent (3) 0.1 M BaCl2 (4) 0.1 M K2SO4
(2) Liquid solvent and solid solute 58. A 0.0020 m aqueous solution of an ionic compound
(3) Liquid solute and solid solute Co(NH3)5(NO2)Cl freezes at –0.00732°C. Number
(4) None of these of moles of ions which 1 mol of ionic compound
produces on being dissolved in water will be
51. A solution containing 10 g per dm3 of urea (molecular
(kf = – 1.86°C/m) (CBSE 2009)
mass = 60 g mol–1) is isotonic with a 5% solution of
a nonvolatile solute. The molecular mass of this (1) 2 (2) 3
nonvolatile solute is [CBSE 2006] (3) 4 (4) 1
BOARD LEVEL EXERCISE : HINT & SOLUTIONS

1. Molarity is defined as number of moles of solute dissolved per litre of solution.
Molality is defined as number of moles of solute dissolved per kilogram of solvent.
2. Ethers are not miscible with water because they cannot form H-bonds with water.
3. The vapour pressure of each component is directly proportional to mole fraction of each component.
4. pTotal < pA ºxA + pB ºxB, H= – ve, V = – ve, e.g., CHCI3 and Acetone.
5. Maximum boiling azeotropes are those which boil at higher temperature than boiling point of each component
in pure state, e.g. H2O and HCI.
6. Henry law deal with effect of pressure on the solubility of gas.

Statement :
The solubility of a gas in a liquid at a given temperature is directly proportional to the pressure at which it is
dissolved.
Let X = Mole fraction of gas in liquid at a given temperature as a measure of its solubility.
p = Partial pressure of gas in equilibrium with the solution.
Then according to Henry's law.
Mathematically, p = KHX
where KH = Henry law constant.
7. i= 4 because
K3 [Fe(CN)6] )  3K+ + [Fe(CN)6]3–
i–1 i–1
8. =  0.5 =  i = 1.5.
n 1 2 1
Given  = 0.5
Asked i = ?
i–1
Formulae : = [½ Mark]
n 1
Explanation :  = degree of dissociation, i = van't Hoff factor
Substitution & Calculation : [½ Mark]

i–1
0.5 =  i = 1.5.
2 1
Ans. van't Hoff factor is 1.5
9. Molal elevation constant is defined as elevation in boiling point when molality of solution is equal to 1.
10. (a) 1 M glucose solution has highest freezing point because it has lowest Tf.
11. Given 10% solution of urea is isotonic with 20% solution of 'x'
urea = x
Asked Molecular weight of x (M) = ?

Formulae : urea = x [½ Mark]
C1RT = C2RT
Explanation : C1 = concentration of urea solution, C2 = concentration of x solution
Substitution & Calculation [½ Mark]
10 1000 20 1000
× × RT = × × RT
60 100 M 100
m = 0.0213
Ans. Molecular weight of x is 120 g mol–1
12. Common salt contains Na+ and Cl– ions which increase osmotic pressure of blood, therefore, increase blood
pressure.
13. Ideal solutions are those solutions which follow (i) Raoult’s law (ii) Hmix = 0 (iii) Vmix = 0 (iv) Force of attraction
between A – A, B – B and A – B are of same order.
Non-ideal solutions do not follow (i) Raoult’s law (ii) Hmix  0 (iii) Vmix  0
It is because force of attraction between A – B and B – B.
Cyclohexane-ethanol mixture shows positive deviation from Raoult’s law because forces of attraction between
cyclohexane and ethanol are less than in pure cylcohexane as well as in pure ethanol. Acetone-chloroform
mixture shows negative deviation from Raoult’s Law because forces of attraction between acetone and chloroform
are higher than that of pure acetone and pure chloroform.
14. Given Mass of solute (K2CO3 ) = 2.5 g
Volume of solution = 1000 ml
Density of solution = 0.85 g ml–1.
Asked Molality of solution (m) = ?
WB 1000
Formulae : m= M × W [1 Mark]
B A
Explanation : m = molality of solution, W B = Mass of solute, MB = Molecular weight solute
W A = Mass of solvent in grams
Calculation : Mass of solute = 2.5 g [½ Mark]
Mass of solution = volume × density = 1000 ml × 0.85 g ml–1 = 850 g
Mass of solvent = (850 – 2.5) 847.5 g.
Substitution in formulae : [½ Mark]
2.5 1000
m= ×
138 847.5
m = 0.0213
Ans. molality of solution is 0.0213
15. Given  = 0.5
Molality of solution (m) = 1m
Asked freezing point of solution. = ?
Formulae : Tf = i × Kf × m [1 Mark]

Explanation : Tf = Depression in freezing point
i = van’t hoff factor
Kf = cryoscopic constant
m = Molality solution
Calculation of i
[½ Mark]
n=2
i 1 i 1
= 0.5 = , i = 1.5
n 1 2 1
Substitution 1.5 × 1.86 × 1 = 2.79 K [½ Mark]
Freezing point of solution = 273 × 2.79 = 270.21 K
Ans. Freezing point of solution = 270.21 K
16. Given Mass of solute (A) = 5g
Mass of solvent (water) = 100 g
vapour pressure of the solution = 4.16 kilopascal
vapour pressure of solvent = 4.24 kPa
Asked molecular mass of solute = ?
WB
PA0 – PA MB
Formulae : = xB = W [1 Mark]
PA0 A  WB
MA MB
Explanation : PA0 = vapour pressure of pure solvent
PA = vapour pressure of solution
xB = Mole fraction of solute
W B = Mass of solute
MB = Molecular weight solute
W A = Mass of solvent
MA = Molecular weight of solvent
Substitution & Calculation [1 Mark]
5 5
4.24 – 4.16 MB 0.08 MB 0.08  MB 100 5
= 100 5  = 100 5  MB + 0.08 × = M × 4.24
4.24  4.24  18 B
18 MB 18 MB
0.40 8 21.20 20.80 8
 M + = M  MB = 18
B 18 B
20.80  18
 MB = = 46.8 g mol–1. Ans. molecular mass of 'A' is 46.8 g/mol
8
17. When fruits and vegetables that have dried are placed in water, osmosis takes place, i.e., water molecules
pass through semipermeable membrane present in cell-walls, therefore, they swell. If temperature is increased,
osmosis will be faster.
18. Given Normal freezing point of nitrobenzene (C6H5NO2) = 278.82 K
molality of solution = 0.25 m
Freezing point depression = 2 degrees
Asked Cryoscopic constant = ?
Formulae : Tf = Kf × m [1 Mark]
Explanation : Tf = Freezing point depression
Kf = cryoscopic constant
m = molality of solution
2 = Kf × 0.25
2
Kf = = 8 K kg mol–1.
0.25
Ans. cryoscopic constant (Kf) of nitrobenzne is 8 K kg mol–1
19. Given 10 per cent by mass of urea solution means 10 g urea is dissolved in 100 g of solution
Mass of solute (urea) = 10 g
Mass of solvent (water) = 90 g
vapour pressure of pure solvent 55.3 mm Hg
Asked vapour pressure of solution = ?
PA0 – PA WB / MB
Formulae : 0 = W [1 Mark]
PA A  WB
MA MB
Explanation : PA0 = vapour pressure of pure solvent, PA = vapour pressure of solution

W B = Mass of solute, MB = Molecular weight solute, W A = Mass of solvent
MA = Molecular weight of solvent
PA0 – PA 10 / 60 1
= 90 10 =
PA0  31
18 60
PA 1 PA 1 30
1– =  =1– =
PA0 31 PA0 31 31
55.3  30 1659
PA = = = 53.51 mm Hg.
31 31
Ans. vapour pressure of solution is 53.51 mm Hg.
20. (a) In solution of volatile liquids, the partial vapour pressure of each component is directly proportional to its
mole fraction
pA  xA
pA = pAº xA
pA = Partial vapour pressure of component A
xA = Mole fraction of component ‘A’ in solution.
pAº = Vapour pressure of pure component ‘A’.
(b) The difference in boiling point of solution Tb and pure solvent Tbº is called elevation of boiling point which is
directly proportional to number of moles of solute in a given amount of solvent.
Tb = Tb – Tbº ; Tb  m
m = Molality ; Tb = Kbm
21. Given Mass of solute (BaCl2) = 3.12 g
mass of solvent (water) = 250 g
Boiling point of solution = 100.08320C
Boiling point of pure solvent = 1000C
Asked Degree of dissociation = ?
WB 1000
Formulae : Tb = iKb × M × W [1 Mark]
B A
Explanation : Tb = Elevation of boiling point, i = van’t hoff factor, Kb = Molal Elevation constant
W B = Mass of solute, MB =Molecular mass of solute, W A = Mass of solevent
3.12 1000
Substitution (100.0832 – 100) = i × 0.52 × × [1 Mark]
208 250
3.12 1000
0.0832 = i × 0.52 × ×
208 250
0.0832  208 17.30
i= = = 2.66.
4  3.12  0.52 6.489
Calculation of  [1 Mark]
n=3
i 1 2.66  1 1.66
= = = = 0.83.
n 1 3 1 2
Ans. Degree of dissociation ()is 0.83.
22. Given Mass of solute (glucose ) = 18 g
Molar mass of solute (glucose) = 180 g mol–1
Volume of solution = 500 cm3
Asked Molarity of solution (M) = ?
WB 1000
Formulae : M= M × [1 Mark]
B Volume of solution in cm3
Explanation : M = molarity of solution, W B = Mass of solute, MB = Molecular weight solute
18 1000
M= × = 0.2 mol L–1. Ans. Molarity of solution is 0.2 mol L–1.
180 500 cm3
Density of solution is required if the molality of solution is also to be calculated.
23. Osmotic pressure is the extra pressure which must be applied on solution side so as to preven the flow of
solvent molecules into solution when both are separated by semipermeable membrane. [½ Mark]
Given (a)Mass of sucrose in 1 litre = 34.2 g
(b)Mass of urea in 1 litre = 60 g
(c)Mass of glucose in 1 litre = 34.2 g
(d)Mass of NaCl in 1 litre = 34.2 g
Asked Osmotic pressure () = ?
Formulae :  = iMRT = 1 [½ Mark]
Explanation : = Osmotic pressure, M = molarity of solution, i = van’t hoff factor
T = Temperature, R = gas constant
Calculation of osmotic pressure
34.2
(a) sucrose = 1 × RT = 0.1 RT [½ Mark]
342
60
(b) urea =1× RT = RT [½ Mark]
60
90
(c) glucose = 1 × RT = 0.5 RT [½ Mark]
180
58.5
(d) NaCl = 2 × RT = 2 RT [½ Mark]
58.5
Ans. The osmotic pressure of (a) < (c) < (b) < (d).
24. Given Molality of solution = 1m
vapour pressure of solvent = 12.3 kPa
Asked Vapour pressure of solution = ?
PA0 – PA
Formulae : = xB [1 Mark]
PA0
Explanation : PA0 = vapour pressure of pure solvent
PA = vapour pressure of solution
xB = Mole fraction of solute
Calculation of xB
m 1 18
xB = 1000 = 1000 = 1018 [1 Mark]
m 1
MA 18
Substitution in formulae [1 Mark]
PA0 – PA PA 18
 1 – = xB =
PA0 PA0 1018
PA 18 PA 18 1000
1– =  =1– =
12.3 1018 12.3 1018 1018
12.3  1000 12300

PA = = = 12.08 kPa.
1018 1018
Ans. Vapour pressure of solution is 12.08 kPa.
25. (a) Non-ideal solutions are those solutions which
(i) do not follow Raoult's law (ii) Hmix  0. (iii) Vmix  0.
(iv) The force of attraction between A — A and B — B is not equal to A — B.
(b) (i) In alcohol and acetone, force of attraction is less than in alcohol and alcohol molecules as well as in
acetone and acetone molecules therefore, vapour pressure increases.
(ii) In chloroform and acetone, force of attraction increases due to intermolecular H-bonding therefore, vapour
pressure decreases.
26. The colligative properties like elevation in boiling point and depression in freezing point depend upon number of
independent particals in solution this is called colligative property
We get abnormal molecular mass if solute either undergoes association or dissociation.
Numerical problem
Given Molality of solution = 0.1 m
Freezing point depression = 0.526 K
Cryoscopic constant of benzne = 5.12 K kg mol–1
Asked Van’t hoff factor = ?
Formulae : Tf = i × Kf × m [1 Mark]
Explanation : Tf = Freezing point depression, Kf = cryoscopic constant
m = molality of solution, i = Van’t hoff factor
0.256 = i × 5.12 × 0.1
0.256 1 1
i= = Ans.Since van’t hoff factor of solution is , benzoic acid exists as dimer in benzene.
0.512 2 2
WB 1000 2.46 1000

27. (b) xH = M × = × = 0.615 M.
2O B vol. of solution in ml 40 100
Given Mass of solute (glucose ) = 2.82 g
Molar mass of solute (glucose) = 180 g mol–1
Mass of solvent = 30 g
Asked (i) molality of the solution = ?
(ii) mole fractions of (a) glucose & (b) water
Calculation of molility of solution
WB 1000
Formulae : m = M × W [1 Mark]
B A
Explanation : m = molality of solution, W B = Mass of solute
MB = Molecular weight solute, W A = Mass of solvent
Substitution [1 Mark]
2.82 1000
m= × = 0.52 m Ans. Molality of solution is 0.52 m
180 30
Calculation of mole fraction of glucose
nglu cos e
Formulae : xglucose = [1 Mark]
nglu cos e  nH2O
Explanation : xglucose = mole fraction of glucose
nglucose = mole of glucose
nH2O = mole of water
Substitution [½ Mark]
2.82
180
2.82 30 = 0.0093 Ans. Mole fraction of glucose 0.0093

180 18
Calculation of mole fraction of glucose
Formulae : x H2O = 1 – xglucose [1 Mark]
Explanation : xglucose = mole fraction of glucose
x H2O = mole fraction of water
Substitution [½ Mark]
x H2O = 1 – 0.0093 = 0.9907 Ans. Mole fraction of glucose 0.9907
28. Given Freezing point of solution = 272.4 K
Freezing point of pure solvent = 273 K
Molal elevation constant of water = 0.512 K kg mol–1
Cryoscopic constant of water = 1.86 K
Vapour pressure of pure solvent = 23.757 mm Hg.
Asked (i) Molality of solution = ?
(ii) Boiling point of solution
(iii) Lowering of vapour pressure of water
Calculation of Molality
Formulae : Tf = Kf × m [1 Mark]
Explanation : Tf = Depression in freezing point
Kf = Cryoscopic constant
m = Molality
Tf = 273 – 272.4 = 0.6 K  0.6 K = 1.86 × m
m = 0.322 mol/kg
Ans. Molality of solution is 0.322 m
Calculation of Boiling point of solution
Formulae : Tb = Kb × m [1 Mark]
Explanation : Tb = Elevation in boiling point, Kb = Molal elevation constant, m = Molality
Tb = 0.512 × 0.322 = 0.165 K Ans. Boiling point of solution is (373 + 0.165) = 373.165 K
Calculation of lowering of vapour pressure
PA0 – PA
Formulae : = xB [1 Mark]
PA0
Explanation : PA0 = Vapour pressure of pure solvent
PA = Vapour pressure of soltuion
xB = Mole friction of solute
Calculation of xB [½ Mark]
m
0.322
xB = m  1000 =
18 55 .87
Substitution in formulae [½ Mark]
PA 0.322 PA 0.322 55.55
1– =  =1– =
PA0 55.87 23.757 55.87 55.87
23.757  55.55
PA = = 23.62 mm of Hg.
55.87
Ans. Vapour pressure of the solution is 23.62 mm of Hg.
LEVEL # 1
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. B D D D D A D A C D D C B B A C A C D B
Q.No. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. B C C B B A B C B C A A A A B B D B D D
Q.No. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans. B B D C D C A B D A D A A C D A D A B B
Q.No. 61 62 63 64 65 66 67
Ans. A D C B C A D
LEVEL # 2
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. B D C A,B B B D A C D A D C B C D C D C D
Q.No. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. C B B A A A B A D B B A B A A A C B A B
Q.No. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans. B C C A B A C A B C B C A D A D A D D C
Q.No. 61 62 63 64 65 66 67 68 69 70 71
Ans. D A B C D C A A D B A
QUESTIONS FROM COMPETITIVE EXAMINATIONS

Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 1 4 4 3 4 2 3 2 3 3 1 4 3 1 3 1 1 1 1 1
Q.No. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 3 1 1 4 2 1 2 2 1 3 4 2 4 3 3 2 4 3 4 2
Q.No. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58
Ans. 2 1 3 1 3 3 1 4 2 1 3 2 3 4 1 2 2 1
IMPORTANT NOTES

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CONTENTS

Board Level Exercise 30 – 31

Question For Competative Exams 38 – 40

2. SOLUTION & COLLIGATIVE PROPERTIES

Board Level Exercise 77 – 78

Question For Competative Exams 88 – 91

Illustration of parameters of a unit cell

Square unit cell :

(a) Body centered (B.C.) : B.C.C  Body centered cubic.

(b) Face centered (F.C.) :

(c) End centered (E.C.) :

Hexagonal a=bc S Graphite, ZnO, CdS, Mg, PbI2,

Mass of unit cell  ZM 

Type of neighbour Distance No. of neighbours

Type of neighbour Distance No. of neighbours

(B) Arrangement of hexagonal closed packed sheets :

Unit cell : a = 2r = b;  = 120º

(i) Relation between a, b, c and R :

(iv) Coordination number, (CN) = 12

Ex. In a ccp structure, the :

0.414 2 a 0.414 2  3.61

Type of void Coordination Ex.of ionic

0.732  r+/r– < 1 cubical void 8 Caesium chloride

NOTE : In ionic compounds for maximum stability.

Structure of some ionic compound :

 Here 2 a  4RCl–  as anion–anion are not in contact.

Example : Halide of Li, Na, K and Rb, AgCl, AgBr, NH4Cl.

(vi) Coordination number :

(3) CaF2 [Flourite structure] [AB2 type]

(4) Na2O [Sodium oxide] [A2B type]

Other important structure :

 Packing efficiency = 34%.

Sc hottky defec t Frenkel defec t Interstitial defec t

-e Na+ Cl- Na+ Cl- Sr+ 2 Cl- Na+ Cl-

Na+ Cl- Na+ Cl- Na+ Cl-

Metal excess Cation Vac anc y

(A) The defect is known as schottky defect

Application of n-type and p-type semicondcutiors.

Figure : Demonstration of the magnetic moment associated with

dN0a3 4.54  6.023  1023  ( 412.6  10 –10 )3

where a = length of the unit cell

dN0 a3 5.20 g / cm3  6.02  10 23 mol1  27  10 24 cm3

2. What is the percentage of free space in bodycentred cubic crystal ?

4. What is the percentage efficiency of packing in case of a simple cubic lattice?

7. What is doping ? Why is it done ?

8. Explain the term dislocation in relation to crystals.

10. Given an example of antiferromagnetic solid.

12. (i) Name the type of crystal shown in .

(ii) What is the relationship between a, b and c ?

Q.35 The ratio of cations to anion in a closed pack

Q.44 In Corundum, oxide ions are arranged in hcp

QUESTIONS FROM COMPETITIVE EXAMS.

BOARD LEVEL EXERCISE : HINT & SOLUTIONS

11. Molecular solids – CO2, H2 ; Ionic solids – MgO, AgCl

12. (i) Triclinic (ii) a  b  c, (iii)    90º, (iv) CuSO4.5H2O

Explanation : a pm = edge of the unit cell [½ Mark]

3  352 1.732  352