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_Chemistry_Chapter 1_SOLID STATES
Solids: A solid is a form of matter which possesses rigidity & hence possesses definite shape & definite volume.
General characteristics of solid:-
1. The constituent particles are closely packed . i.e. intermolecular distances are very small.
2. Intermolecular forces are strong
3. The constituent particles occupy fixed position & can oscillate about their mean position
4. They have definite shape , volume & mass
5. They have high density
6. They are incompressible & rigid
Classification of solids
Crystalline solids Amorphous solids
Define- A solid is said to be crystalline if its various
constituent particles are arranged in a definite
geometric pattern in three dimension so that there is
a long order,
A solid is said to be amorphous if there is no regular
arrangement of constituent particles so there is only
short range order of the constituent particles
Melting point- they have sharp melting point They melt over a range of temp.
Nature- These are true solids They are pseudo solids
Heat of fusion- they have definite & characteristic
heat of fusion
They do not have definite heat of fusion
Cleavage- they undergo a clean cleavage They undergo an irregular cut
Anisotropy- they are anisotropic in nature , means
value of physical properties show different when
measured along different direction
They are isotropic in nature , means value of any
physical properties would of any physical properties
would be same along all direction
Uses of Amorphous solids
1. Amorphous solids are widely used in inorganic glasses. Which found application in construction, house ware
& laboratory ware etc.
2. Rubber is used in making tyres , shoe-soles which is amorphous solid
3. A large no. plastics which are amorphous solids are being used in articles of everyday life.
4. Amorphous silica has been found to be the best material for converting sunlight into electricity ( in
photovoltaic cell )
MOLECULAR SOLID: - Molecules are the constituent particles of the molecular solids. Depending upon nature of
molecules they are further classified as.
NON POLOR MOLECULAR SOLIDS: - Those crystalline solids in which the constituent particles are either atoms (like
noble gases He, Neon etc.) or non- polar molecules like
etc. The forces holding these molecules together are dipole dipole forces of alt. location. These
intermolecular forces of attraction are comparatively stronger than London dispersion forces.
- They are soft
- They are non conductor of electricity
- Melting & boiling point are comparatively high than non-polar molecules,
- They also exists as gases or liquids at room temperature
HYDROGEN BOUNDED MOLECULAR SOLIDS:- The constituent particles of such molecules contain hydrogen atom
linked with highly electronegative atom small in size such as , O , N , e.g. In H
Nacl , zincblende , cu
Tetragonal Primitive , Body
centred
A=b c X==Y=90 White tin ,sn
,
Ti
, ca
Orthorhombic Primitive , Body-
centred , Face-
centred , End-
centred
A X=
Rhombic sulphur ,
Hexagonal Primitive A=b X=
Y=120
Graphite
ZNO , CDS
Rhombohedral Primitive A=b=c X= y
Calcite(Ca
HgS , (CINNABAR)
Monoclinic Primitive , end
centre
A X=y=90
Monoclinic.
Sulphur , N
s
.
lo
o
Triclinic Primitive a x
,cus
o ,
Number of atoms in a unit cell:-
I. PERIMITIVE CUBIC UNIT CELL:- Primitive cubic unit cell has atoms only at the corner , each atom of corner is
shared by eight adjacent unit cell. Thus only
= 1 atoms
II. BODY CENTRED CUBIC UNIT CELL:- In a body centred cubic unit cell:-
a. 8 corner x
= 1 atoms
b. 1 Body centre atoms = 1 x 1 = 1 atom.
c. Total no. of atoms per unit cell = 2 atoms
III. FACE-CENTRED CUBIC UNIT CELL:- In a face-centred cubic unit cell:-
a. 8 corners x
= 1 atoms.
b. 6 face centred atoms x
= 1 atoms.
b. 2 face centre atoms x
atoms per unit cell = 1 atom
c. Total no. of atoms = 2 atom
CLOSE PACKING IN CRYSTALS:-
1. CLOSE PACKING IN ONE DIMENSION:- There is only one way of arranging spheres in one- dimensional packed
structure , that is to arranged then in a row & touching each other. In one dimensional close packing
coordinates number is 2.
2. CLOSE PACKING IN TWO DIMENSION:- When the row are stacked over each
other , a two dimensional close packed structure is produced , which can be done in two different ways.
a. SQURE CLOSE PACKING IN TWO DIMENSION:- The spheres in the second row may be placed in such a
way that they are touching the spheres of the first row & are exactly above the sphere of first row .
There Is horizontal as well as vertical alignment of rows. We call this arrangement Of AAAA type
arrangement. Coordination number is 4 in this type of arrangement.
b. HEXAGONAL CLOSE PACKING IN TWO DIMENSION:- The
sphere in second row may be placed in the depression of
the first row. If we call first row as A , then second row is
of B type , then the spheres of third row again placed in
depression of second row but aligned with A. We call
this arrangement of ABABAB. Type. It is more efficient
as more space is occupied by spheres. Coordination
number is 6 in this type of arrangemeny.
3. CLOSE PACKING IN THREE DIMENSIONS: - All the structures are three dimensional structures. They can be
obtained by stacking two dimensional layers one over other
a. THREE DIMENSIONAL CLOSE PACKING FROM TWO DIMENSIONAL SQURE CLOSE PACKED LAYERS: - The
second square closed packed layer is placed over first square close packed layer such that the spheres of
upper layer are exactly above first layer. Similarly we place more layers one over the other. (AAAA.
Type). In this arrangement spheres of both the layers are perfectly aligned horizontally as well as
vertically. This type of arrangement is of AAAA. Type pattern. Coordination number is 6 & its unit cell
is primitive cubic unit
b. THREE DIMENSIONAL CLOSE PACKING FROM TWO DIMENSIONAL HEXAGONAL CLOSED PACKED
LAYERS:-This can be generated by placing layers.
i. PLACING SECOND LAYER OVER FIRST LAYER:- Two dimensional hexagonal close packed (A) is
placed & then another two dimensional hexagonal close packed layer is placed above it such
that the spheres of second layer are placed in depression of first layer. Since the spheres of
two layers are aligned differently. And we call the second layer as B.
TETRAHEDRAL VOIDS:- Sphere of the second layer is placed above the triangular void of first
layer. Thus void formed is called tetrahedral void. In other words , A void surrounded by four
spheres is called tetrahedral void.
OCTAHEDRAL VOID:- The triangular void is the second layer are above the triangular void in
the first layer. Such voids are surrounded by the six spheres & are called octahedral voids .
ii. PLACING THIRD LAYER OVER THE SECOND LAYER:- There are further two possibilities of
placing third layer:-
a. COVERING TETRAHEDRAL VOID:- Tetrahedral void of the second layer may be covered by
spheres of third layer. Thus spheres of third layer are exactly aligned with first layer. This
is a ABABType arrangement. This structure is called hexagonal close packed (HCP).
Coordination no 12
b. Covering octahedral void: The third layer may be placed above the second layer in such a
way that its sphere covers the octahedral void. In this manner spheres of third layer are
not aligned with first or second layer. This is ABCABC. Type arrangement. This structure
is called cubic close packed (ccp) or(fcc) structure. Coordination No.
COORDINATION NO:- The number of nearest neighbor of a particle Is called its coordination number.
Coordination no. of (bcc) structure is 8
Coordination no. of (fcc) , (HCP) , (CCP) is 12
Coordination no. of primitive unit cell 6
NUMBER OF VOIDS FILLED & FORMULA OF COMPOUND:-In a HCP or CCP structure , they are only two types of
voids:- TETRACHEDRAL & OCTAHEDRAL.
1. No. of octahedral voids:= No. of particles present in close packing
2. No. of tetrahedral voids:= 2 x No. of octahedral void
In case of ionic compounds, bigger ions (anions) are present in packing whereas smaller ions (cations) occupy the
voids. If the cations are small in size. , they may occupy tetrahedral voids, they may occupy octahedral voids.
1. In (CCP) total no. of voids per unit cell = 8(tetrahedral) + 4(octahedral)=12 voids.
2. In (HCP) total no. of voids per unit cell = 129(tetrah) + 6 (octahedral) = 18 voids.
PACKING EFFICIENCY:- If is the percentage of total space filled by the particles.
1. In (HCP) & (CCP) structure or (FCC) structure:-
x100
P.E =
[Packing efficiency =74%]
[Void percent =100-74 =26%]
2. In body centre cubic structure:-
x100
=
Packing efficiency = 68%
Void percent= 32%
3. In simple cubic lattice:-
x 100
=
Packing efficiency = 52.4%
Void percent= 47.6%
CALCULATING INVOLVING UNIT CELL DIMENSION:-
Density unit cell=
[d=
Z=number of atoms in unit cell.
M=molar mass
A= edge length of unit cell
Na=Avogadros number
D=density of unit cell.
IMPERFECTION IN SOLIDS: - any
departure from perfectly ordered
arrangement of constituent
particles in crystal is called
imperfection or defect.
I. Point defect: - When the deviations or irregularities exist from the ideal arrangement around a point or
an atom in a crystalline substance. The defect is called defect.
a. STOICHIOMETRIC DEFECTS:-If imperfections in crystal are such that the ratio between the
cations & anions remains the same as represented by molecular formula. And the stoichiometry
of solid is not disturbed the defects are called stoichiometric defect
i. VACANCY DEFECT: - When in crystalline substance , some of the lattice sites are vacant ,
the crystal is said to have vacancy defect. It results in decrease, the crystal of substance.
This defects arises when a substances is heated.
ii. INTERSTITIAL DEFECT: - When some extra constituent particles are present in the
interstitial sites, the crystal is said to have interstitial defect. It results in increase in
density.
iii. FRENKEL DEFECT:- This defect is shown by ionic solids. The smaller ion (cation) is missing
from its lattice site & it occupies the interstitial site. This is called frenkel defect.
- Electrical neutrality maintained eg: AgBr, Agcl,AgI,Zns.
- Doesnt change the density of substance
- Also called dislocations defect
- This defect is combination of vacancy & interstitial defect.
iv. SCHOTTKY DEFECT:-This defect is also shown by ionic solids. The number of missing
anion & cation are equal.
- Electrical neutrality maintained eg:AgBr,Nacla,Kcl,Cscl
- Density of solid decrease
- This is basically vacancy defect
b. NON-STOICHIOMETRIC DEFECT: If as a result of the imperfections in the crystals, the ratio of
the cations to the anion becomes different from that indicated by the ideal chemical formula,
the defect are called non-stoichiometric defect
Metal excess defect: it is of further two types
1. By Anion vacancies: a negative ion may be missing from its lattice site, leaving a hole which is occupied by
an electron. So as to maintain electrical balance. Thus, the site containing the electrons thus trapped in
anion vacancies are called F-centeres, because they are responsible for imparting colour to the crystals.
- this defect is shown by Nacl, Kcl, Licl
- this defect is similar to schottky defect
2. By the presence of extra cations interstitial sites: Metal excess may also be caused by an extra cation
occupying the interstitial sites. Electrical neutrality sites, this defect is similar to Frenkel defect. This defect is
shown by Zno, Zns etc
c. IMPURITY DEFECT: If molten NaCl containing a little amount of SrCl
2
is crystallized, some of the
sites of Na
+
ions are occupied by Sr
2+
& each Sr
2+
ions replaces two Na
+
ions. It occupies the sited
of one ion & other site remains vacant. Thus cationic vacancies are equal to S
2
+ ions. Other
examples are CdCl
2
, AgCl.
Electrical properties: Depending upon the difference in electrical conductivities, the solids are classified into three
types.
1. Conductors: The solids which have conductivities in the range 10
4
to 10
7
ohm
-1
m
-1
are called conductors. And
those metals whose conductivity in the order of 10
7
ohm
-1
m
-1
are good conductors.
2. Insulators: The solids which have extremely low conductivities ie. Ranging from 10
-20
to 10
-10
ohm
-1
m
-1
are
called insulators. For e.g. wood, plastic, rubber, sulphur etc.
3. Semiconductors: These are the solids with conductivities in the intermediate range from 10
-6
to 10
4
ohm
-1
m
-1
CONDUCTION OF ELECTRICITY OF METALS ON THE BASIS OF BAND THEORY:-
BAND:-In case of metals, the atomic orbital of the metal atoms are so close in energy that they overtap to form a
large no. of molecular orbitals is called Band.
1. IN METAL: - If the valsance band is partially filled or it overtaps with the unoccupied
conduction band then electrons can easily flow under the influence of an applied electric
field. Hence metals conduct electricity in this way.
2. IN INSULATORS-: If the gap between filled valence band & the
unoccupied conduction band in large, electrons cannot jump from
valence band to conduction low conductivity & it behaves as an
insulator.
3. IN SEMICONDUCTOR-: In case of semiconductors, the gap b/w valence band & empty
conduction band is small. Therefore some electrons may jump to
conduction band & show some conductivity.
a. Conductivity of semiconductor rises with in temperature
b. Silicon & are called intrinsic semiconductors
DOPING: - The process of adding impurities to a crystalline substance so as to increase the
conductivity is called doping. Doping in intrinsic semiconductor cause electronic defect in them
(a) ELECTRON RICH IMPURITIES (n-type):- When the elements of group 14 (silicon, germanium) which are
tetravalent are mixed with small amount of group 15 elements (P, As) which are pentavalent 4
& makr
bond with 4 neighbour atoms but fifth electron is free & and delocalized in conductivity is due to negatively
charged electron because silicon is doped with negah (electron-rich) impurity. Thus it is called n-type
semiconductor.
(b) ELECTRON DEFICIT IMPURITIES(p-type):- When the elements of group 14 such as (silicon , germanium)
which are tetravalent are mixed with small amount of group 13 elements (Al or Ga) which are Gi- valent , p-
type semiconductor are formed. Atoms of gr 13 can share only 3
I. PARAMAGNETIC SUBSTANCES: - Substances which are weakly attracted by external magnetic field. This
property is shown by those substances whom atom, molecule or ion contain unpaired electrons. For ex.
.
II. FENOMAGNETISM: - Substances which are weekly repelled by external magnetic field. Those substances
which have fully-filled orbitals or no- unpaired electron show this type of property. The magnetic moment
possesd by an electron with spin in one direction cancelled by that with spin in opposite direction. For ex.
Benzene, Nacl,
etc.
III. FENOMAGNETISM: - Substances which are strongly attracted by an magnetic field are called
Fenomagnetism. Once they magnetized, they do not lose their magnetic character even if they are no longer
in contact with the magnetic field for ex. Fe , Ni, CO .
IV. ANTIFENOMAGNETISM: - Substances which posses zero net magnetic moment are called
antifenomagnetism. Their domains are oppositely oriented & cancel out each others magnetic moments.
For ex. MNO.
V. FENIMAGNETISM: - These substances are weakly attracted by magnetic field as compared to fenomagnetic
substances. These substances lose ferrimagnetism on heating & become paramagnetic. For ex.
.
NUMERICALS
TYPE 1- Based on calculation of particles per unit cell & formula of compounds
Q1. A cubic is made up of two elements x & Y. ATOM Y are at comers and x at the centre. What is the formula
of compound?
ANS- No. of y atoms in unit cell(present at corner) = 8x
= 1
No. of x atoms in unit cell (present at body centre =1
There fore formula of compound is xy
Q2. A compound is made up of two elements A & B. atoms A are at corner position & atom B are at face-
centred position. What is formula of compound?
ANS- No. of A atoms in unit cell (present at corner) =8x
= 1
No. of B atoms in unit cell (present at face centre) =
x 6 = 3
Therefore, formula of compound is A
Q3. A compound is made up of three elements M,N and o in such a way that M atom are at corner, N atom at
the centre of body & o . Atoms a present at the centre of each face, then find the formula of compounds?
ANS- No. of M atom in unit cell (present at corners) = 8x
=1
No. of N atoms in unit cell (present at body centre) =1
No. of o atoms in unit cell (at face centre ) =
x 6 = 3
Therefore formula of compound in MN
.
TYPE II- Number of voids filled & formula of compound
Q1. A compound is formed by two elements x & y. atoms of elements y make CCP & those of elements x occupy
octahedral voids. What is the formula of compounds?
ANS-Suppose, total no. of atoms in compound = n; Then y=n
Octahedral voids = n = no. of atoms in CCP
Also, octahedral voids are occupied by x atoms = n
Ratio of x:y = n:n = 1:1
Hence, formula of compound is xy
Q2. Atoms of element B form help lattice & those of elements A occupy 2/3
rd
of tetrahedral voids . what is
formuls of compound ?
ANS- Let, total no. of atoms (B) in hep= n
Also, A occupy 2/3
rd
of tetrahedral void=
x 2n =
Ratio of A:B =
: n =
: 1 =4:3
Hence , the formula of compound
.
Simple
a=d
Relationship b/w nearest neighbour
distance(d) & edge (a) of unit cell
Relationship b/w atomic radius (r) & edge (a)
of unit cell.
Face centre Body centre Simple Fce Bcc
=0.707a =0.866a =0.353a 0.433a
TYPE III- Relationship b/w nearest neighbor (d). edge (a) & radius of atom (r) of the unit cell for pure elements.
Q1. Chromium metal crystallizes in a BCC lattice. The length of unit cell edge is 287 pm. Calculate atomic radius ?
ANS- for body centred cubic lattice r =
Given, a = 287 pm
R=
; R=124.12pm
Q2. The edge length of a face centred cubic unit cell of aluminium is 404 pm. Calculate the radius of aluminium
atom?
ANS- Given, edge length a = 404 pm.
For fee cubic lattice r =
R=
; R= 142.8 pm
Q3. Silver crystallizes in face centred cubic (FCC) unit cell. If the radius of silver atom is 145 pm , what is the
length of each side of unit cell.
ANS- Radius =145pm
Edge length = a = ?
Radius of FCC unit cell r =
145 =
A= 145x2x1.414
A = 410.06pm
Edge length = 410.06pm
TYPE IV- Calculation of density of a cubic crystal from its edge.
Q1. Silver forms CCP lattice & x-ray studies of its crystal shows that the edge length of its unit cell is 408.6pm.
Calculate density of silver. (atomic mass = 107.9 m)
SOLUTION= P =
For fee unit cell (CCP is equivalent to FCC) ; Z=4
M=107.9gmo
A=408.6pm
=408.6x
P=
Density= 10.5g
Q2. An element body centred cubic structure with a cell edge of 288pm. The density of element is 7.2 gc
.[Motar mass of Nacl is 58.5 gmo
Volume of unit cell =
= (288x
2.39x
Volume of 208g of element
V=
= 28.88
No. of unit cells=
=
=12.08x
unit cell
As we now, is BCC, each unit cell have 2 atoms, thus,
Total no. of atoms is 208g = 2x12.08x
=24.16x
atoms.
Q3. Copper crystallizes with FCC unit cell. If the radius of copper atom is 127.8 pm , calculate the density of
copper . (Atomic mass =63.5m)
ANS- r=127.8 pm = 127.8x
cm
A=2r = 2x1.414x 127.8 x
A = 4.725x
M=63.55 GMO
Na = 6.022x
mo
D=
D=8.936
Q4. Calculate the value of anogadros number from following data:- density of Nacl=2.165g
. Distance b/w
N
in a Nacl is =281 pm
ANS- A unit cell of Nacl contains 4 Nacl unit, Z =4
M = 58.5 GAMO
P = 2.165
D = 281 PM
EDGE LENGTH (A) = 2R = 2X 281
=562 PM
P=
2.165=
NA = 6.09X
ASSIGNMENT
Q1. Crystalline solids anisotropic in nature; comment
Q2. How do metallic & ionic substances differ in conductivity?
Q3. Graphite is a good conductor of electricity .why?
Q4. What type of interactions hold the molecules together in polar molecular solids?
Q5. Stability of a crystal is related to magnitude of its melting point. How?
Q6. Name the parameters which characterizes a unit cell.
Q7. What is the number of atom in a unit cell of:
a. Body centred unit cell
b. Face centred unit cell
Q8. A compound is formed by element x and y in cubic structure where y atoms are at corners & x atoms are at
two opposite faces. Write the formula of compound.
Q9. Calculate the no. of atoms in a cubic based unit cell having one atom at each corner & two atoms on each
body diagonal.
Q10. Distinguish b/w hexagonal & monoclinic unit cell
Q11. In a compound p ions are arranged in HCP & ions occupy two third of octahedral voids. What is formula
of compound?
Q12. A solid is made up of two elements P &Q .Atoms are in CCP arrangement while atoms P occupy all
tetrahedral voids. What is the formula of compound?
Q13. Tunster crystallizes in body centred cubic unit cell. If the edge of the unit cell is 316.5 pm, what is the
radius of tunster atom?
Q14. Silver crystallizes in face-centred unit cell. Each side of the unit cell has a length of 409 pm. What is radius
of silver atom?
Q15. Density of Li atoms is0.53g/
)
Q17. The edge length of NACE unit cell is 564 pm. What is density of NACL in g/
. (M=58.5)
Q18. What is meant by doping in a semiconductor?
Q19. What are n-type semiconductors?
Q20. What is meant by intrinsic semiconductor?
Q21. Name the elements with which silicon should be doped to give the n-type semi-conductor.
Q22. Explain the following term with suitable examples of each:-
a. Fenomagnetism
b. Antifenomagnetism.
Q23. Explain the following term with suitable examples
a. Schottky defects
b. Femimagnetism
Q24. Give reason for the following:-
Copper is conducting as such while copper sulphate is conducting only in molten state or in aqueous
solution.
Q25. Write the Bohis magnetour.
[TEST PAPER]
Q1. Define crystalline solids with examples. Also write its properties. 3
Q2. Why glass is considered as super liquid. 1
Q3. Calculate the efficiency of packing in case of simple cubic unit cell. 2
Q4. Briefly explain what do you understand by F centres. With example. 3
Q5. Copper crystal has a face-centred cubic lattice structure. Atomic radius of copper is 128 pm. Calculate the
density of copper. (M=63.5). 2
Q6. Silver crystallizes in face centred cubic unit cell. Each side of this unit cell has a length 400pm. Calculate
the radius of silver atoms. 1
Q7. Give reason for the following:- 3
a)