[Link] II sem G.B.
R Degree College
Liquid crystals (Mesomorphic state):
There are certain solids on heating undergo two sharp transformations.
1. They fuse sharply giving turbid liquid.
2. Then at higher temperature, they give clear liquid.
These changes are exactly reversed on cooling at same temperature. The turbid liquid show
anisotropy (different physical properties in different directions particularly optical property).
True liquid is isotropic (physical properties are same in all directions). Turbid liquids show
double refraction and interference which are characteristic property of crystals. Turbid liquid
is called “liquid crystal”. Liquid crystals obtained by heating or cooling are called
theromotropic liquid crystals. They do not have the properties of crystalline state but they are
more like liquids. Thus other names suggested are crystalline liquids and anisotropic liquids.
But these are also not satisfactory. The term “mesomeric state” (meaning intermediate form
in Greek) probably fits best. However the name liquid crystal is still in use in all literatures.
In general, substances like long chain organic molecules either terminating in groups like –
OR, -COOR or having groups like –CN, -N = N-, -C = C- in the middle show the above
behaviour.
Eg: Cholesteryl benzoate was the first solid discovered (1888) to have this property. It fuses
sharply at 145oC to give a turbid liquid and at 178oC it changes into clear liquid. The above
changes are reversed on cooling.
145oC 178oC
p-cholesteryl benzoate p-cholesteryl benzoate p-cholesteryl benzoate
(liquid crystal) (liquid)
(solid)
The temperature at which turbid liquid is formed is called transition point (Tp) and the
temperature at which clear solution is obtained is called melting point (MP). The substances
showing liquid crystal character is highly stable and do not decompose on heating. Some
examples showing mesomorphic state are indicated in table-15.4.
Therefore there are evidently 4 phases or 4 states of matter to be considered. They are
1. Solid. 2. Liquid. 3. Gas. 4. Mesomorphic state.
Mahima Jyothi
[Link] II sem G.B.R Degree College
Table-15.4: substances showing liquid crystal character.
Sl. Substance Transition Melting point
No
point (oC) (oC)
1. Anisaldazine 165 180
(CH3O-C6H4-CH=N-N=CH-C6H4-OCH3)
2 p-Azoxyanisole 116 135
(CH3O-C6H4-N-ON-C6H4-OCH3)
3 p-azoxyphenetole. 137 167
(C2H5O-C6H4-N-ON-C6H4-OC2H5)
4 Diethylbenzidine 115 120
(C2H5NH-C6H4-C6H4-NHC2H5)
5 Mercury-di-(p-ethoxybenzal-aminophenyl). 204 272
Hg(C6H4-N=CH-C6H4-OC2H5)2.
6 p-methoxycinnamic acid
(CH3O-C6H4-CH=CH-COOH) 170 186
Vapour pressure-temperatrue diagram:
M N
True Liquid
liquid C
crystal
V.P Crystalline
solid
B
O
A Vapour
Temperature
Fig-15.13.
The changes in states may be represented as follows.
solid liquid crystal Liquid Gas
In the Fig-15.13, curve AO is V.P curve of solid crystal. OB is V.P curve of liquid
crystal. BC is V.P curve of pure liquid. Point O is transition point and point B is melting point.
Both these points are triple points.
At point O, Solid Liquid crystal Vapour
At point B, Liquid crystal Liquid Vapour
Mahima Jyothi
[Link] II sem G.B.R Degree College
Curve OM shows the effect of pressure on transition point and curve BN shows the effect
of pressure on melting point of substance.
Classification of liquid crystals.
Further studies have shown that liquid crystals can be classified into two types.
1. Smectic (soap like in Greek) liquid crystals.
2. Nematic (thread like in Greek) liquid crystals.
Some substances are capable of existing in both forms.
Smectic liquid crystals:
Fig-15.14.
The smectic liquid crystals do not flow as normal liquids. They flow in layers as if different
planes or sheets are gliding over one another. The distribution of velocity in different layers is
different from that found in a true liquid. Therefore, the concept of viscosity is not applicable
to this type of liquid crystals. When spread over a clean glass surface, they form a series of
terraces or strata (Fig-15.14). The edges of these terraces often show a series of fine lines even
in ordinary light.
The existence of the layers suggests that the crystal lattice still exists through in somewhat
distorted form. However the spacing of the layers is different from that observed in the solid
state.
Smectic liquid crystals also give X-ray diffraction patterns like solid crystals, but it is in one
direction only. Thus, smectic phase has a complex internal structure. When viewed in
polarised light smectic phases appear to have fan like structure. They are always uniaxial and
are not affected by a magnetic field. A few examples yielding smectic phases when heated at
the transition point are given in table-15.5.
Table-15.5: Smectic liquid crystals.
Compound Transition Melting
point (oC) point (oC)
Ethyl-p-azoxybenzoate 114 121
Ethyl-p-azoxycinnamate 140 249
n-octyl-p-azoxycinnamate 90 175
Mahima Jyothi
[Link] II sem G.B.R Degree College
Nematic liquid crystals:
They show behaviour nearer to that of normal liquids. They flow normally than smectic
liquid crystals. Their viscosity however is rather low compared to that of liquids. Thus,
nematic liquid crystals have liquid characters and yet turbid and anisotropic. This type is
therefore regarded less truly anisotropic than the smectic type.
In polarised light substances in nematic phase appear to have thread like structures. They
are uniaxial but are affected by strong magnetic field. When viewed in the direction of lines
of magnetic field, it looks quite clear. When magnetic field is cut off, the liquid phase appears
turbid again. Some of the examples for nematic liquid crystals are shown in table-15.6.
Table-15.6: Nematic liquid crystals.
Compound Transition Melting
point (oC) point (oC)
p-azoxyanisole 116 135
p-azoxyphenolate 137 167
p-methoxycinnamic acid 170 186
anisaldazine 165 180
dibenzalbenzidine 234 260
Compounds exhibiting both smectic and nematic characters:
Certain substances like higher cholesteryl esters from capretate to myristate, show on heating
three phase transformations instead of two. They change to smectic phase first and then at
higher temperature convert into nematic phase and at still higher temperature convert into clear
liquids. They have two transition points and one melting point.
Eg:
72oC 78oC 83oC
Cholesteryl myristate Smectic phase Nematic phase True liquid
(Solid)
Some compounds show two smectic phases, one nematic phase and one liquid phase (3
transition points and one melting point).
Eg: ethylanisal-p-aminocinnamate.
83oC 91oC 118oC 139oC
Solid Smectic phase-I Smectic phase-II Nematic phase True liquid
This type of liquid crystals having some smectic and some nematic characters are called
“Cholesteryl liquid crystals”.
Eg: Cholesteryl benzoate.
145oC 178oC
Cholesteryl benzoate Liquid crystal True liquid
(Solid)
Molecular arrangement in liquid crystals:
Turbid liquids were considered to be heterogeneous like emulsion, but it is not true. Turbid
liquids are homogeneous and turbidity is a simple optical effect as shown by ‘Lehmann’.
Mahima Jyothi
[Link] II sem G.B.R Degree College
In smectic state, the molecules are arranged in nearly parallel layers (Fig-15.15a). The layers
are held at regular distances from one another but the molecules within each layer are not
regularly spaced. The anisotropic properties such as double refraction can thus be readily
understood.
(a) (c)
(b)
Fig-15.15. Molecular arrangements in liquid crystals.
In nematic state, the arrangement of the molecules is still parallel but now there are no layers.
The arrangement is irregular and the molecules now have greater freedom of motion (Fig-
13.15b). This arrangement would still lead to difference in properties in different directions.
i.e. lead to anisotropic character.
The molecular arrangement in normal clear liquid is shown in fig-13.15c. The molecules
are now moving completely at random and consequently there is no scope for double refraction
or any anisotropy. It is completely isotropic in nature.
Uses: Most of the industrial lubricants exist more or less in the mesomorphic (liquid crystal)
state. In fact their functioning as lubricants is almost entirely due to their existence in this state.
The proteins and fats which are important constituents of food also exist or get changed into
this state before digestion and are therefore easily assimilated in the body.
This state is believed to play an important role in nutritional and other processes.
Differences between smectic and nematic liquid crystals.
Smectic liquid crystals Nematic liquid crystals
1 They do not flow like normal liquid. They flow like normal liquid.
2 Concept of viscosity is not applicable. Viscosity is low compare to normal liquid.
3 Molecules are arranged nearly in Molecules are not arranged inparallel layers.
parallel layers.
4 The arrangement of molecules is The arrangement of molecules is irregular
regular and freedom is less for free and freedom is more for free movement.
movement.
5 They are not attacked by magnetic They are attacked by magnetic field.
field.
6 In polarised light, they have fan like In polarised light, they have thread like
structure. structure.
Applications of liquid crystals in LCDs and thermal sensing
➢ Liquid crystals are everywhere. They are used in all kinds of display devices
including computer monitors and laptop screens, TVs, clocks, visors, and
navigation systems. Each pixel in a monitor is an assembly of liquid crystals controlled
by its own electromagnetic field.
Mahima Jyothi
[Link] II sem G.B.R Degree College
➢ In short, LCDs are lit by a backlight, and pixels are switched on and off electronically
while using liquid crystals to rotate polarized light.
➢ Liquid Crystal Displays The most common application of liquid crystal technology is
liquid crystal displays (LCDs.) This field has grown into a multi-billion dollar
industry, and many significant scientific and engineering discoveries have been made.
➢ Thermal sensing
Special liquid crystal devices can be attached to the skin to show a "map" of
temperatures. This is useful because often physical problems, such as tumors, have a
different temperature than the surrounding tissue. Liquid crystal temperature sensors
can also be used to find bad connections on a circuit board by detecting the
characteristic higher temperature.
Mahima Jyothi
