Atomic imperfections / point defect
When deviations exist from the regular arrangement
around an atom or a group of atom in a crystalline substance the defects are
called point defects.
Types of point defects
(A) Stoichiometric defects If
imperfection in the crystal are such that the ratio between the cations and the
ratio between the cations and anions remains the same as represented by the
molecular formula, the defects are called Stoichiometric defects (for CSIR-NET
Coaching in Chemistry, JAM Coaching in Chemistry
These are 2 types
1.
Schottky defects In an ionic crystal of A+ B-
types equal number of cations and anions are missing from their lattice site so
that the electrical neutrality is maintained it is called schottky defects. The
schottky defects containing one pair of holes due to missing of one cation and
one anion is shown in Fig
Compound exhibiting schottky defects have
- High coordination number
- Small difference in size of cation and anions
Examples are NaCl, KCl, KBr, and
CsCl
As a result of this defect, the density of solid
decreases
2. Frenkel defect if an ion is missing from its lattice site (causing a
vacancy or a hole these) and it occupies the interstitial site electrical
neutrality as well as stoichiometry of the compound are maintained. This type
of defect is called Frenkel defect
→ Frenkel defects is a hybrid type
of defect as it a combination of schottky defect and interstitial defects.
→ The Frenkel defects in which one
cation is missing from the lattice site and is occupying the interstitial site
is shown in fig
Types of compounds exhibiting
compounds which have Low
coordination number
Frenkel defects are found in silver
halides due to small size of Ag+ ion.
Effect on Density
Since no ions are missing from the
crystal as a whole, therefore density of the solid remains unchanged.
Non-Stoichiometric defects
If, as a result of the imperfections
in the crystal, the ratio of the cations to the anion becomes different from
that indicated by the ideal chemical formula, the defects are called
non-stoichiometric defects.
E.g. It is difficult to prepare
ferrous oxide with the ideal composition, FeO what is actually obtain is Feo,
95O or FexO where x = 0.93 to 0.96 These are 2 types
(A) Metal excess
(i) By anion Vacancies
A negative ion may be missing from
its lattice site, leaving a hole which is occupied by an electron for maintain
the electrical balance (electrical neutrality)
The electrons thus trapped in the
anion vacancies are called F-centers because they are responsible for imparting
colour in the crystals (F- farbe which is a German word for colour)
Eg. When NaCl is heated in an of Na
vapour, the excess of Na atoms deposit on the surface of NaCl crystal. Cl-
ion then diffuse to the surface where they combine with Na atoms which become
ionized by losing electrons. These electron defuse back into the crystal and
occupy the vacant sites created by the Cl- ions.
These electrons absorb some energy
of the white light giving yellow colour to NaCl
Similarly excess of Li in LiCl
makes it pink and excess of K in KCl makes it violet.
This defect is similar to schottky
defect and is found in crystals having schottky defects.
(ii) By the presence of extra
cation in the interstitial sites
Metal excess may also be caused by
an extra cation occupying the interstitial site. Electrical neutrality is
maintained by an electron present in another interstitial site. This defect is
similar to frenkel defect and is found in crystal having frenkel defects.
Eg. When Zno is heated, it loses
oxygen and turns yellow due to the following reach
Zno→Zn2+ +
O2 + ze-
The excess of Zn2+ ion
thus formed get trapped into the vacant interstitial sites and the electrons in
the neighboring interstitial sites
Crystals with either type of metal
excess defect contain some free electrons. Hence such materials acts as
semiconductors.
(B) Metal deficiency
This defect occurs when the metal
shows variable valiancy i.e. Transition metals. The defects usually occurs due
to the missing of a cation from its lattice site and presence of cation having
higher charge (eg. +2 instead of 1) in the adjacent lattice site.
Ex. FeO , Fes and NiO
The above mentioned topic is essential for CSIR-NET Coaching in Chemistry. It is also a hot topic for JAM
Coaching in Chemistry
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