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PHYSICAL CHEMISTRY

XII (ALL)
SOLID STATES
r - - - A
I " A SPECI ALLY DESI GNED KI T FOR LEARNI NG"
CONTENTS
THE KEY Basic principles oI subjects. An outline oIthe topics to be
discussed in class lectures.
THEATLAS Basic layout oI subject. Aroute map correlating diIIerent subtopics
in coherent manner
EXERCI SE I
PROFICIENCY TEST


Introductory problems to get Iirst hand experience oI problem
solving.
To check you newly acquired concepts.
EXERCI SE H A collection oI good problems.
EXERCI SE IIl Test your objective skill.
^ EXERCI SE IV A collection oI previous ten years JEE problems.
THE KEY
Crvstalline solids.
Crystalline solids are those whose atom, molecules or ions have an ordered arrangement extending over
a Long Range. example-(Rock salt, NaCl).
Amorphous solids.
Amorphous solids are those whose constituted particles are randomly arrange and have no ordered
long range structure, example: Rubber, Glass ect.
TYPES OF CRYSTALLINE SOLIDS.
Type oI Solid Intermolecular Iorces Properties Examples
Ionic Ion-Ion Iorces Brittle, hard high Melting NaCl, KC1, MgCl
2
Molecular
Dispersion
Iorces/Dipole-Dipole
/H-bond
SoIt, low melting non-
conducting
H
2
0, Br
2
, C0
2
, CH
4
Covalent
network
Covalent bonds Hard: High melting
C-Diamond Si0
2
Metallic Metallic bonds
Variable hardness and melting
point conducting
Na, Zn, Cu, Fe
SItiiW-iXc`e 3 Cx
*z
TYPES OF UNIT CELL.
Collection oI lattice points, whose repetition produce whole lattice is called a unit cell. The whole lattice
can be considered to be made by repetion oI unit cell.
i) Cf-odL is famed . W~teOKce
turet ` r r w e n si cs- .
1. Unit Cell:
(~) lest *f M
Zpace
(a thcc
c,/./-
pm
SJ&uri H.
CxTSUf. .
tv (Jyflt-f
,V S t~.
Crystal Systems Bravais Lattice
Unit Cell Parameters
Crystal Systems Bravais Lattice
Intercepts Crystal Angles
4 Cubic
Primitive, Face Centered,
Body Centered
a b c a p y 90
2 Orthorhombic
Primitive, Face Centered,
Body Centered, End Centered
a * b * c a p y '90
3 Rhombohedral Primitive a b c a P Y * 90
4 Monoclinic Primitive, End Centered a ` b a Y 90, P * 90
5 Triclinic Primitive a ` b a * p * Y * 90
6 Tetragonal Primitive, Body Centered a b c a p Y 90
t Hexagonal Primitive a b c a P 90, Y

120
Simple Cubic
a b c
a p y 90
k Z F
Tetragonal
a b * c
a p y 90
Orthorhombic
a p y 90
Monoclinic
a * b * c
a y 90, P * 90
Triclinic
a * b * c
KS
Hexagonal Primitive
a b * c
a p 90, y 120
^Bansal Classes Solid State
TKere a 4 c c c w / r* Iwit cell-
( U S t y l e T t e o d b * v s * t a * ` o j It, c a I c * ~
[2j
;.; Primitive or simple cubic (PS/SC) unit cell: Spheres in one layer sitting directly on top oI those in
previous layer, so that all layers are identical. Each sphere is touched by six other, hence coordination
number is 6. 52 oI available space occupied by spheres.
Example: Polonium crystallises in simple cubic arrangement.
Z 1 ; C.N. 6
P J /
|
A i c v n 5
o n l y
C c r a - n e ` .
Oj. I i `Cel A- -
1.2 Body Centered cubic (BCC) unit cell: Spheres in one layer sit in the depression made by Iirst layer in
a-b-a-b manner. Coordination number is 8, and 68 oI available space is occupied by atoms.
Example: Iron, sodium and 14 other metal crystallises in this manner.
C o ` V w ` t o A T \ 0 . \ - IA0. Of nearest Ye j bours ~
f f c f r cm cdcm KctS dn a u- ceM-
-p I e e ? ! 2
3cc - Bcc
\-ACP CC p I I C Ua-S i 2.
1.3 Face centered cubic (FCC) unit cell:
Examples: Al, Ni, Fe, Pd all solid noble gases etc.
Z 2 ; C.N.
H c P e x p
C
t U t ( Xv\ I t t P
CvJoccm.
(3) a * , p l u 3 `
e a c h ` x - e . O I C x v W
..
2. Density oI cubic crystals:
7 T P O F PACKING.
Z 4 ' C N 12
A t - A ADOP4 C o h e i r s ,
j
!
I 1 ' c W o o c-yv' ` b - o o o p p
` C . C t k ? ` TWIT y .
fei p `
3. Closest packing oI atoms: This is the most eIIicient way oI packing 74 oI available space is occupied
by spheres and coordination number is 12.
(i) Hexagonal close pack (A-B-A-B) tvpe packing. Each layer has hexagonal arrangement oI touching
sphere and 3
rd
layer is similar (exactly on top) oI Iirst layer.
(ii) Cubic close pack (A-B-C-A-B-C). AB layers are similar to HCP arrangement but third layer is oIIset
Irom both A and B layers. The Iourth layer is exactly on top oI Iirst layer. irVgaox`s LcAIt'Cg.
( ? ) P Hd t a Cc AVA' CVS
C*) riJM-
' . A I ~ CUoY-I)
" V`IOk void a
YCA cow
F CC
( o o o r
efftcXfncvl t
V- VJaCo`vvA Spwcc
[OQ - [OO Pl~
- (OOfl-PF~
voi d ' b'
sL
TOVSLV \M
c t excs. 1 M
p o s s i b l e - -
(uWc


r-.S* /
`
a
/
2
J l
feBansal Classes
C l ) E I j - HO. (Di a I e ` (V
i J J , , , , , A u / n / h c c i ` -
Exploded view Hexagonal close-packed
( a) structure ( " &) ` y u ` A e 1 ( d l
l b ~ S * " e 2 -- 2. BCC
( ? ` t - 4 R- c
, , T W iVI) M ^ ^
F`ct cI i on 04
J
Uil u v ,
Cubic close-packed ' 0-j C`t OvU' . -
s t r u c t u I e
`
Exploded view
C C ) s
A
Solid State dQ
3
( a ) V i J l J ` o .
I T 2 x V s
[3j
16
Hexagonal primitive unit cell
r

LY
l a ye r A
l a ye r B
. . . . . l a ye r A
c t p q c \ A \
:
C P
MS ' I T
u J b i
r
c d p A & O e c p
C
c 12-
S`V`V ScI SleoAK
9"
a2r
` 4 - i P ' ' d ` c I t b ` ` l a d v v p i t w of.
1M l o u j e s 1 V\ S ` v e H e x u o c t y I R d n I I o ` s - r v i S
ci A alth U fU laea", r.No. 0(2.
T y p e s oI v o i d s C
c
P-; - ffenefiutfes Fee s obi:-fnfct fbu plcrtfisu-
T e t r a h e d r a l v o i d Ire spV\*t oI j(l I a y e * o v \ K e
X dSvXT CNo ` i z
Q x -p- n - e T s c s i V l a ` o ? `
S U b i ' t C r u t C e l t . . .
Te t r a he dr a l voi d
.


i
i
T e t r a h e d r a l `
f

v o i d
f


Nu mb e r o I t e t r a he dr a l v o i d s p e r F C C uni t cel l
4.2 Octahedral void
Tc p j o w s H( CJ t mu I a J i \ x h A s c w d *0oUs c x S ` d
0 \ o " V \ a a v K ` ' C a l U n e , C - N O . g r C e t - H )
j V. (J / L
1
- ` - "
1
' V N.I Q
Ai l U o i d e Q v\
TVs !s I - r p
C W - p r e S e ' w i r & I "
Tfub/oxJ OA b o d w I
OC5t
5.
Octahedral void
mMi
.... . ` i i
,,
Octahedral
Wf
void
* I

J....
.
A n oc t a he dr a l v o i d at t he c e n t r e
o I a n e d g e i n a F C C uni t cel l .
Radius ratio
Oc t a h e d r a l
v o i d
A n o c t a h e d r a l v o i d at t he b o d y
c e n t e r e d p o s i t i o n i n F C C uni t cel l
T-c-P,
(
a
) (b)
5.1 Radius ratio Ior co-ordination number 3
(TriangularArrangement): r

r - J f r
2 - y 3
- ` T - 0 . 1 5 5
Solid State
[41
5.2 Radius ratio Ior coordination number 4
(Tetrahedral arrangement): r

r

B . /


J
H
D i D i
4
V 2
V 3 - V 2
V 5
0.225
5.3 Radius ratio Ior coordination number 6:
(Octahedral Arrangement) or
Radius ratio Ior coordination number 4
(Square plannar arrangement)
' 2'a
Top v i e w oI oct ahedr al a r r a nge me nt
5.4 Radius ratio Ior coordination number 8 :
(Body centered cubic crystal)
r r
V 2
r
V 2 - 1 0 . 4 1 4
r

r
r V3 r
a/3-1 0.732
6. Types oI ionic structures
6.1 Rock salt structure: (NaCl) Larger atom Iormic ccp
arrangement and smaller atom Iilling all octahedral voids.
Ro c k salt s t r uct ur e
<!l Bansal Classes Solid State
[5j
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.
i

(b)
*

(II)
*

(b)
*
Zinc blende (sphalerite) structurer(ZnS) Larger
atom Iormic ccp arrangement and smaller atom Iilling
halI oI alternate tetrahedral voids
Fluorite structure: (CaF,,) Ca
2
Iorming ccp
arrangement and F~ Iilling all tetrahedral voids.
AntiIluorite structure :(Li
2
0) O
2
ion Iorming ccp
and Li

taking all tetrahedral voids.


Zi nc bl ende s t r uct ur e
o
0 '

P
Fluorite structure
Ant i I l uor i t e s t r uct ur e
Cesium halide structure: (CsCl) CI at the corners
oI cube and Cs

in the center
Ce s i um chl or i de s t r uct ur e
Corundum Structure: (A1
2
0
3
) O
2
Iorming hep andAl
3
Iilling 2/3 octahedral voids.
Rutile structure: (Ti0
2
) O
2
Iorming hep while Ti
4
ions occupy halI oI the octahedral voids.
Pervoskite structure: (CaTi0
3
) Ca
2
in the corner oI *
cube O
2
' at the Iace center and Ti
4
at the centre oI cube.
Pe r vos ki t e s t r uct ur e
Spinel and inverse spinel structure: (MgAl
2
0
4
)0
2
~ Iorming Iee, Mg
2
Iilling 1/8 oI tetrahedral voids
and Al
3
taking halI oI octahedral voids. In an inverse spinel structure, O
2
" ion Iorm FCC lattice, A
2
ions
occupy 1/8 oI the tetrahedral voids and trivalent cation occupies 1/8 oI the tetrahedral voids and 1/4 oI
the octahedral voids.
Crystal deIects:
Point deIects: When ions or atoms do not hold the theoretical position, this is called point deIect. Point
deIects are oI two types:
Stoichiometric defects.
Schottky deIect: Due to missing oI ions Irom lattice point in pairs.
Frenkel deIect: It is caused due to the creation oI lattice vacancy as a result oI misplaced ion in
interstitial site.
Schottky deIect common in ionic solid with high coordination number. NaCl, KC1, KBr
Frenkel deIect:- Solid with low coordination number ZnS, AgBr.
Non-Stoichiometric defects. Ratio oI positive and negative ion diIIer Irom that indicated by chemical
Iormula.
Metal-excess deIect :
A negative ion replaced by electron. (F-centre)
Extra metal ion present in lattice and electron also present in interstitial site.
Metal-deIiciency deIect caused by: Cation missing Irom lattice point, electroneutrality maintained by
metal ions with higher oxidation state as Fe
0 94
0.
^Bansal Classes Solid State
THE ATLAS
fe Bansal Classes Solid State
m