INORGANIC CHEMISTRY (CHM 361)

CASE STUDY:
COORDINATION COMPUNDS IN METALLURGY PROCESSES:
EXTRACTION OF GOLD BY CYNIDATION

GROUP MEMBERS:
BIL NAME STUDENT ID
1. MOHAMMAD FAIZ BIN JAMAL 2016337807
2. ILYANA BINTI AMRAN 2016562461
3. NAJIHAH BINTI MOHD TAHIR 2016936353
4. NUR SYUHADA BINTI AHMAD TERMIZI 2016726471

GROUP:
A4AS1205_D

LECTURER’S NAME:
MADAM FARIESHA FARHA BINTI RAMLI
 1. Briefly explain the imperfection of solid which include the following:

1.1 Point Defects

Point defects are localised disruptions in an otherwise perfect arrangement of atoms in a

crustal lattice structure. A point defect involves a single atom or pair of atoms, and thus is
different from extended effects such as dislocations and grain boundaries. Point defects
include vacancies, self-interstitial atoms, interstitial impurity atoms, and substitution atoms.
Point defects can appear in a small area of the crystal, not exceeding several inter-nuclear
distances.

1.2 Stoichiometry Defects

Schottky Defects

This is a defect which mainly arises if some of the lattice points are unoccupied. Such
points which are unoccupied have been given name lattice vacancy or ‘holes’. The figure
exhibits Schottky defect of crystals when existence of two holes, one due to a missing positive
ion and the other due to missing ion in crystal lattice is there. It is also found that this defect is
general observed in strong ionic compounds having a high coordination number and the radius
ratio r/R is not far below unity. Examples are cesium chloride and sodium chloride. Although
both type of defects probably characterize crystals of non-stoichiometric compounds, the
Schottky defects are more important.

Frenkel Defect

Frenkal defect generally arises when an ion occupies and interstitial position between
lattice points.

This figure shows an example of Frenkel defect. It show that an positive ions occupy interstitial
positions being smaller than negative ions. It is clear that one of the positive ions occupies a
position in interstitial space rather than at its own appropriate site in the lattice due to which a
‘hole’ is created n the lattice as shown in the figure. This type of defect mostly appears in those
compounds where positive and negative ions differ largely in their radii and coordination
number is low.

Vacancy
A vacancy is a point defect where an atom is missing from its normal site in the crystal
structure. The vacancy disrupts the regular arrangement of atoms, and causes a local increase
in the strain energy owing to the minor misalignment in the atom positions. Vacancies in
aerospace alloys are formed during solidification and processing. During cooling and
solidification, the atoms, which are randomly spaced when the metal is molten, arrange
themselves to form an ordered crystalline pattern at the freezing point. Not all the atomic sites
are filled during freezing, which occurs over a narrow temperature range (typically less than 1
°C) and, thereby, vacancies are created. Vacancies are created by the displacement of the
atoms because lattice points in the crystal structure are left unoccupied by atoms of the base
metal (or substitutional element). Vacancies are also created when materials operate at high
temperature.

Interstitial

An interstitial defect is formed when a foreign (solute) atom is positioned in the crystal structure
at a point that is normally unoccupied. The defect is formed when a solute atom such as an
alloying or impurity element sits within a gap between the crystal lattice points of the base
metal (solvent). An interstitial atom is usually smaller than the solvent atoms located at the
lattice points, but is larger than the interstitial site it occupies. Consequently, the surrounding
crystal structure is distorted. An interstitial defect is often formed in metal alloys when the size
of the solute atom is less than about 85% of the size of the host metal atom. In many cases,
the solute atoms are less than half as small as the base metal. Carbon in iron (steel) is one
example of an element that is interstitial. This defect can be of two types which is self-interstitial
defect and interstitial defect.

Non-Stoichiometric Defect: Metal Excess and Metal Deficiency

Non-stoichiometric defects are either due to the presence of excess metal ions or deficiency
of metal ions.

Metal Excess defects: Cations are in excess.

a) Metal excess defect due to anionic vacancies:

Occurs due to absence of anions from its original lattice site in crystals.

b) Metal excess defect due to presence of extra cations at interstitial sites-

Due to extra cations released by compound on heating.

Metal Deficiency defect: Due to a smaller number of cations than anions.

a) Cation vacancies:

Cations may be missing from their lattice sites. The extra negative charge may be balanced
by some metal ion having two positive charges. Ex. FeO (Ferrous oxide)

b) Extra anions occupying interstitial sites:

The extra anions may be occupying interstitial sites. The extra negative charge is balanced by
some metal ion having extra charges. Ex. ZnO

Differentiation between Vacancy and Schottky defect.

Vacancy Defect Schottky Defect

 Formed due to a missing atom from its
normal sites or some of lattice sites in
the crystal structure is vacant.
 Vacancy defect occur in non-ionic
crystals due to imperfect packing
during crystallization.
 Loss of one atom in its lattice sites.
Increasing in temperature, the number
of vacancy defects also increase.
 Vacancies can move by exchanging
positions with their neighbours.
 Occurs when oppositely charged
atoms (cation and anion) leave their
corresponding lattice sites and
create a pair of Vacancy defects.
 Schottky defects occur in ionic
crystals where the size of anion is
almost same with the size of the
cation
 One Schottky defect leads to the
formation of two vacancies where the
number of missing cations and
anions are equal
 The cation and anion atoms
permanently leave the crystal.
 Factor Interstitial defect Frenkel defect
Diagram

Definition An interstitial defect is formed Frenkel defect occur when an

when a foreign (solute) atom is
positioned in the crystal
structure at a point that is
normally unoccupied.
Density Increase in density of the
substance
Type of crystal Occur in non-ionic crystal
atom or smaller ion(usually
cation) leaves its place in the
lattice, creating a vacancy,
and becomes an interstitial
by lodging (accommodation)
in a nearby location.
No change in density
Occur in ionic crystal

Differentiation of Interstitial and Frenkel defect

References:
1. https://www.sciencedirect.com/topics/materials-science/point-defect
2. https://www.britannica.com/science/vacancy#ref161573
3. http://www.sciencehq.com/chemistry/stoichiometric-defects.html
4. http://www.minaprem.com/materials-science/defects/interstitial-defect-point-defect-
defects-in-solid/
5. https://chemistryonline.guru/imperfection-solids/
6. https://www.embibe.com/study/non-stoichiometric-defects-
concept?entity_code=KTSD16
7. https://amazingsolids.wordpress.com/2013/06/15/non-stoichiometric-defects/
8. www.minaprem.com/materials-science/defects/schottky-defect-point-defect-in-ionic-
crystal/
9. http://www.minaprem.com/materials-science/defects/vacancy-point-defect-defects-in-
solid/