EFFECT OF TEMPERATURE AND PRESSURE ON LATTICE

CRYSTAL

 With increase in temperature increases atomic vibrations

coordination number of ions decrease, e.g upon heating to
760K, the CsCl type structure having 8:8 to NaCl type 6:6.

 With increase in temperature the structure of crystal get

disordered e.g. upon heating at 9700C the Co-Cr-Mo-C changes
from face-centered-cubic (FCC) to Hexagonal-close-packed (HCP).

 With increase in pressure the coordination number of ions

increases, ions come closer to each other. This gives closed
packed (more compact) structure e.g. Graphite has coordination
number of 3 and that of Diamond of 4.

 High pressure phases have more ordered structures.

 The crystal structure symmetry is conserved during the

compression.
 SIO2

The polymorphs that have the name quartz: α-quartz (low quartz) and β-quartz
(high quartz). Both α-quartz and β-quartz have structures based on helical
arrangements of SiO4 tetrahedral with the “ridgepole” of one tetrahedron
connected to the “keel” of the next tetrahedron in the spiral.

β-quartz is hexagonal with both 6-fold and 3-fold screw rotation axes. The α-
quartz structure is a distorted version of the β-quartz structure such that all of the
screw-rotation axes are 3-fold.

β-tridymite is hexagonal and has these layers stacked in a hexagonal closest

packing arrangement with a mirror plane between the layers and a repeat every
other layer.

β-cristobalite is cubic and has its layers stacked in a cubic closest packing
arrangement with an offset between the layers and a repeat every third layer.

α-tridymite (orthorhombic) and α-cristobalite (tetragonal) have structures that

are distorted versions of the β-forms that occur at lower temperatures and have
lower symmetry.

At 1 bar pressure, the change from α-quartz to β-quartz occurs very rapidly and
reversibly at 573°C. Indeed, it is not possible to “quench” β-quartz; β-quartz exists
only at temperatures above 573°C. Because the change from α- to β-quartz occurs
without the breaking of any bonds, this change is called a displacive
transformation.

β -quartz should change to β-tridymite at temperatures above 867°C (at 1 bar

pressure). This change involves the breaking of bonds and, therefore, is called a
reconstructive transformation
 WITH INCREASING PRESSURE AND TEMPERATURE

573
o
C

Tetrahedron Trigonal Hexagonal

870
o
C

1470o
C

Orthorhombic
α -cristobalite (tetragonal)

β-cristobalite ( cubic)
 ZnO

Structurally, ZnO has a non- cento symmetric wurtzite crystal structure

with polar surface. The wurtzite structure off ZnO can be considered to
be composed of interpenetrating hexagonal close packed (hcp) sub
lattices of cation (Zn) and anion (O) displaced by the length of cation-
anion bond.

With increasing temperature (300k) and pressure the ZnO (wurtzite)

change to zinc blende face-centered cubic (fcc).The rock salt or
Rochelle salt structure (NaCl) is obtained at relatively high pressure of
(88.6k bars)

Cubic rocksalt Face-

Hexagonal- Face-centered
centered
close packed cubic(cubic)
cuccubiccubic(cubic)
 SnO2 (Rutile structure)

The Sn-O bonds increases the lattice parameter and produce

asymmetry in the rutile tin-oxygen octahedron with anneheling
temperature the atomic bond length between the oxygen atom shared
by adjacent octahedral decreased, contracting the lattice and increasing
symmetry.

Here are different paths from the rutile-type structure(Body centered

cubic) to the pyrite-type structure depending on the temperature and
pressure conditions. The effect of heating at these phase transitions is
not determined for SnO2 material very well, but it seems that heating is
effective above the temperature of 800oC

8000C

Rutile CUBIC CUBIC

TETRAGONAL
 NH4I

The effect of pressure of high pressure on ammonium halogenide NH 4I

shows the remarkable patterns of the pressure induced phase
transitions they undergo. At room temperature the ammonium
halogenide have Cs-CL-type cubic structures with deuterium
(Hydrogen) distributed randomly over all the possible states which
corresponds to orientational disorder of ammonium ion and thus
undero ordered-disordered phase transition.

Ordered-disordered