Liquid state

B. R. Thorat
Govt of Maharashtra

ismail Yusuf
Arts, Science
and
Commerce
College,
Mumbai

Surface
tension

Introduction
method of determination of surface
tension drop number method
parachor value
applications of surface tension

Introduction
Surface tension is a fundamental property by which the gasliquid interfaces are
characterized. It is well surface phenomena.

Let us consider a
liquid in contact
with its vapor

Observation

Inertial molecules: A molecule in the bulk liquid is subjected to attractive forces from
all directions by the surrounding molecules. It is practically in a uniform field of force.
Molecule at surface: The molecule at the surface of the liquid, the net attraction
towards the bulk of the liquid is much greater than the attraction towards the vapor
phase, because the molecules in the vapor phase are more widely dispersed. This
indicates that the molecules at the surface are pulled inwards.

Effect of such field

The liquid surfaces to contract to minimum

areas, which should be compatible with the total
mass of the liquid.
The droplets of liquids or gas bubbles assume
spherical shape, because for a given volume, the
sphere has the least surface area.

The area of the surface is to be

extended, one has to bring more
molecules from the bulk of the
liquid to its surface

It requires expenditure of some energy because work has to be done in bringing the
molecules from the bulk against the inward attractive forces. The amount of work
done in increasing the area by unity is known as the surface energy.
If the molecules of a liquid exert large force of attraction, the inward pull will be
large. Therefore, the amount of work done will be large.
Surface energy is the amount of work done per unit area extended. Its unit is J/m 2
(which is equivalent to N/m). For example, the amount of work required to create 1 m 2
surface is about 72.8 x 10-3 J for water.

Defination

Surface tension is defined as the force at right angle to any line of unit length in the
surface. Therefore, surface tension = force/distance. It is expressed in N/m. Therefore,
it is apparent that the units of surface energy and surface tension are identical.

Effect of
temperature
When the temperature of liquid increases, inter molecular forces of attraction decreases
which result decrease in the inward pull functioning. Hence, surface tension decreases with
increase in temperature.
Theoretically, the value of surface tension should become zero at the critical
temperature, since at this temperature; the surface of separation between a liquid and its
vapor disappears. However, it has been observed that the meniscus disappears a few degrees
below the critical temperature for some liquids.

Surface tension also responsible for rise and fall of liquids in the capillary tube. The
greater surface tension of the liquid, higher is its capillary rise. Hence capillary rise is used to
measure the surface tension of liquid.

Water has natural tendency to be attracted to the surface of

glass. Capillary action is the result of adhesion (adhesive
force) and surface tension. Adhesion of water to the walls of
a vessel will cause an upward force on the liquid at the edges
and result in a meniscus which turns upward. The surface
tension acts to hold the surface intact, so instead of just the
edges moving upward, the whole liquid surface is dragged
upward.
In case of mercury, molecules are strongly
attracted by each other (cohesive force) than
the glass (adhesive force), therefore mercury
does not spread on the glass, and it has little
contact with glass surface, consequently
mercury level in the capillary falls down.

Surface tension of liquid was changes when other substances are dissolved in it. E.g.
Soaps and detergents lower the surface tension of water which improves the
spreading property of these substances. Even in the preparations of tooth pastes,
mouth washes, toilet creams and medical emulsions, detergents are added to
improve spreading property.

Method of determination of surface tension

The drop-weight method
du Noy ring method
Wilhelmy plate method
the maximum bubble pressure method
Parachor method

Parachor method
Sugden (1924) proposed the following equation to calculate
surface tension from the physical properties of the compound.

Parachor is a weak function of temperature for a variety of liquids over wide ranges of
temperature, and generally assumed to be a constant.
Escobedo and Mansoori (1996) have suggested that parachor is a function of temperature.
They proposed the following temperature-dependence for it.

Where,
is independent of temperature, but depends on the physical properties of the
compound, such as its critical temperature, pressure, normal boiling point and molar
refraction.
Estimation of surface tension using the parachor (additive method) data usually gives good
results. Its simplicity makes it a popular method for calculating surface tension.

Drop-weight method
A drop is allowed to form slowly at the end of a
tube having a fine capillary inside it. Then it is
slowly released and collected in a container.
Several drops (e.g., 100 drops, at the rate of one
drop in about 200 micro-second) are collected in
the same manner and the weight of the liquid is
measured. From this weight, the average weight
of a drop is calculated. The classical instrument
for carrying out this measurement in the laboratory
is Stalagmometer.
Principle: As the size of the drop at the tip of the
tube grows, its weight goes on increasing. It remains
attached to the tube due to surface tension, which
acts around the circumference of the tube in the
upward direction. When the downward force due
to gravity acting on the drop becomes slightly
greater than the surface tension force, the drop
detaches from the tube.
Surface
tension

This equation is known as Tates law

Calculate surface
tension
Alternative method:
A liquid whose surface tension is known is used as a reference liquid. Highly-purified water
or an ultrapure organic liquid may be used for this purpose. The surface tension is calculated
from the following equation.
This equation does not gives good result, therefore it can be
modified as -

Corrections in Tates
law

Corrections need to be applied because only a portion of the drop (the larger portion) falls
from the tube. A significant amount of liquid (up to 40%) may remain attached to the tip of
the tube. A correction factor is known as Harkins-Brown factor. The modified equation is Harkins-Brown factor,

The correction factor can be quite large. Since the value of V can differ from liquid to
liquid, Harkins-Brown factor may differ from one liquid to another, even when the same
tip is used. Therefore, the ratio of correction factors in the relative method may not be
unity.
Precautions
The liquid should either completely wet the tip or do not wet it at all. In the latter case, the
internal radius of the tip should be used as r0.
The tip must be very clean. The presence of a very small amount surface active substance
can cause significant error in the measurement.

Applications of surface tension

Applications
Flow in capillaries and porous media is affected by DST. This finds
importance in enhanced oil recovery where aqueous foams are often used
to increase the sweep-efficiency in carbon dioxide flooding.
In bioprocessing systems, DST affects the rate of water-oxygenation by
influencing the mass transfer coefficient.
DST is also important in metal and textile processing, pulp and paper
production, and pharmaceutical formulations.
An important application of dynamic surface tension is for lung
surfactants, where the dynamic tension under constant or pulsating area
conditions controls the health and stability of the alveoli.
In the formulation of pesticides, if the aqueous spray has a low DST, it
can be dispersed into smaller droplets, which will spread more easily on
the leaves. For these reasons, surfactants are used as pesticide spraying
aids known as adjuvants

Viscosity

Introduction
coefficient of viscosity
relative viscosity
Ostwald viscometer method
for viscosity determination

The behavior of a fluid in flow is very much related to two intrinsic properties of the
fluid: density and viscosity. Viscosity is a quantitative measure of a fluids resistance to
flow.
In everyday terms (and for fluids only), viscosity is "thickness" or "internal friction".
Thus, water is "thin", having a lower viscosity, while honey is "thick", having a higher
viscosity. Put simply, the less viscous the fluid is, the greater its ease of movement
(fluidity) describes a fluid's internal resistance to flow and may be thought of as a measure
Viscosity
of fluid friction.
All real fluids (except super fluids) have some resistance to stress and therefore are viscous,
but a fluid which has no resistance to shear stress is known as an ideal fluid or inviscid
fluid

An intrinsic property is a property that an

object or a thing has of itself, independently of
other things, including its context.
An extrinsic (or relational) property is a
property that depends on a thing's relationship
with other things.

Consider the flow of liquid through a narrow pipe. All parts of the liquid do not flow with
the same velocity.
A thin layer, immediately in contact with the wall of
tube, is almost stationary. Each succeeding thin layer of
the liquid moves with gradually increasing velocity
which become maximum as the centre of the tube is
approached.
The resistance that one part of a liquid flowing with a certain velocity
offers to another part of the liquid flowing with a different velocity is
known as viscosity.
It may be defined as the force of friction between two layers of
liquid moving past one another with
different velocities.
Consider a cylindrical liquid layer of area A cm2 which moves over another similar layer at
a distance of s cm with velocity difference of v cm/sec. The tangential force of friction (F)
required maintaining a constant velocity difference is given as -

Where, is a constant at a given temperature and is known as coefficient of viscosity,

which depends upon the nature of the liquid.

Coefficient of viscosity of a liquid is the force in

dynes-sec/cm2 required to maintaining a
difference of velocity of 1 cm/sec between two
parallel layers of liquid held over one another at
a distance of 1 cm.
The reciprocal of coefficient of viscosity of a liquid is called as fluidity which is depending on
the convention used, measured in reciprocal poise (cmsg1), sometimes called the rhe.

Units of viscosity
CGS unit of viscosity is called as poise. Still the more convenient units of viscosity
are centipoises, and millipoise. The SI unit of viscosity is kg/m.sec.

Several methods exist for characterizing the solution viscosity, or more specifically, the
capacity of the solute to increase the viscosity of the solution. That capacity is quantified by
using one of several different measures of solution viscosity. The most common solution
viscosity terms are:

is solution viscosity, 0 is viscosity of pure liquid, c is concentration.

Determination of viscosity: Ostwald

viscometer method
It consist of a special U-shaped tube with
bulbs in each limb. There are marking in
one of the limb. All we do to measure the
relative viscosity is to measure the times of
flow for equal volumes of water and the
liquid under examination through the same
capillary.
1- pure water and 2-liquid under study
Where is called the viscosity coefficient, t is the time of
flow of liquid, V is the volume of the liquid, and L is the
distance travelled by the liquid during time t.

h
Viscosity of liquid

The density of water can be separately determined by means of a pyknometer at constant

temperature.

Determination of unknown composition

Using an Ostwald viscometer, we can also calculate
the unknown composition of a mixture. The
viscosities of mixtures of different known
compositions are measured and a graph is plotted
with viscosity against the compositions of the
different mixtures. From the graph, the composition
of the unknown mixture corresponding to the
viscosity can be determined.

Applications of Viscosity
To reduce friction between the two moving surfaces which are in
contact, a drop or two of some oil is introduced between the two
contact surfaces.
The oil enters into the depressions in the contact surfaces and form
a thin layer so that direct contact between the surfaces is prevented.
Now, the viscous force of the oil in between the surfaces (lubricant)
reduces the friction between the two moving surfaces because the fluid
friction is always less than the friction between the solid surfaces.
However a good viscous lubricant can only reduce friction, but
cannot completely eliminate the friction.
Generally, for high speeds and low pressures, highly viscous oils
such as Mobil oil, grease, etc. are used.
For low speeds, oils of lower viscosity are used. It may be
interesting to note that air also acts as a sort of lubricant in reducing
friction.
The friction between two metallic surfaces in vacuum is found to
be greater than that in air.

Liquid
crystals

Introduction
classification and structure
of
thermotropic
phases
(nematic,
smectic
and
chlolesteric phases)
applications of liquid crystals

Introduction
Liquid crystals (LCs) are matter in a state that has properties between those of
conventional liquid and solid crystal.
The liquid crystal may be flow like liquid, but its molecules may be oriented in a crystal like
way.
Liquid crystal materials may not always be liquid crystal phase.

The liquid crystals can be divided into thermotropic, lyotropic and metallotropic phases.
Thermotropic and lyotropic liquid crystals consist of organic molecules.
Thermotropic liquid crystals exhibit a phase transition into the liquid crystal phase as
temperature changed while lyotropic exhibit phase transitions as a function of both
temperature and concentration of the liquid crystal molecules in a solvent (typically
water).

Organic
molecul
es

Metallotropic liquid crystals are composed of both

organic and inorganic molecules; their liquid
crystal transition depends not only on temperature
and concentration, but also on the inorganicorganic composition ratio.

Examples

Thermotropic liquid crystals

Thermotropic phases are those that occur in a certain temperature range. If the
temperature rising is too high, thermal motion will destroy the delicate cooperative ordering
of the liquid crystal phase, pushing the material into a conventional isotropic liquid phase.
In contrast to the high temperature, at too low T, most liquid crystal materials will form a
typical crystal.

Thermotropic liquid crystals

Nematic phase

Molecules have no
positional order
(free to move in
space), but they
have long range
orientational
order.

Smectic phases

Well-defined layers that

can slide over one another

Chiral phases

Twisting of the molecules

perpendicular to the
director,
with
the
molecular axis parallel to
the director

Nematic phase
One of the most common liquid crystal phase is the nematic, where the molecules have no
positional order (free to move in space), but they have long range orientational order.
Therefore, the molecules flow just like in a liquid, but they all point in the same
direction.
Most nematics are uniaxial. Some liquid crystals are biaxial nematics, meaning that in
addition to orienting their long axis, they also orient along a secondary axis.

Smectic phases
The smectic phases, which are found at lower temperature, form well-defined layers that
can slide over one another in a manner similar to that of soap.
The smectics are thus positionally ordered along one direct ion in the smectic A phase, the
molecules are oriented along the layer normal, while in the smectic C phase they are tilted
away from the layer normal. These phases are liquid-like within the layers.

Chiral phases
The chiral nematic phase exhibits chirality. This phase is often called the cholesteric phase
because it was first observed for cholesterol derivatives. This phase exhibits a twisting of the
molecules perpendicular to the director, with the molecular axis parallel to the director.
The chiral pitch, p, refers to the distance over which the liquid crystal molecules undergo
a full 360 twist but, the structure of the chiral phase repeats itself every half-pitch, since in
this phase directors at 0 and 180 are equivalent.

Lyotropic liquid crystals

A lyotropic liquid crystal consists of two or more components that exhibit liquidcrystalline properties in certain concentration ranges.
In the lyotropic phases, solvents molecules fill the space around the compounds to provide
fluidity to the system.
In contrast to thermotropic liquid crystals, these lyotropics have another degree of freedom
of concentration that enables them to induce a variety of different phases. The lyotropic
liquid crystals are composed of cubic, hexagonal, lamellar, reverse hexagonal phase, etc

Applications of liquid crystals

Applications of liquid crystals

Display applications
By virtue of their fluid nature, LCs can be easily processed into thin films, yet they retain the
optical properties of crystalline materials such as the ability to rotate plane polarized light.
In addition, the orientation of the molecules in liquid crystal films can be modulated on a
relatively short time scale using a low electric field. Because the birefringence in a liquid
crystal phase is a function of the angle formed by plane-polarized light and the director n, it
can effectively function as an ON/OFF light shutter between crossed polarizers under the
influence of an electric field.

Temperature sensors
Chiral nematic (cholesteric) liquid crystals reflect light with a wavelength proportional to
the magnitude of pitch. Because the pitch is dependent upon temperature, the color reflected
also is dependent upon temperature. Thus, cholesteric LCs make it possible to accurately
gauge temperature just by looking at the color. By mixing different cholesteric LCs, a device
for practically any temperature range can be built. This property has been exploited for
practical applications in diverse areas including medicine, packing industry and electronics.
Cholesteric liquid crystals as fever strips are in use as disposable thermometers.

Columnar fluid phases as a promising media for modern applications

Columnar (Col) mesophases is driven by favorable - interactions between the aromatic
cores. Columnar mesophase offers a one-dimensional pathway for the electronic charge
migration, where the central aromatic core is the conducting unit, with external peripheral
chains as the insulating mantle. This LC state is of great importance because it allows the
possibility to combine different physical properties (optical, conductive) with orientational
control of the molecular order, self healing of structural defects and ease of processability.
Most importantly all these properties can be tailored by careful molecular engineering. Thus,
Col LC phases can be used as promising media for various device applications such as (a)
field effect transistor; (b) Photovoltaic or solar cells; (c) gas sensors and (d) organic light
emitting diodes. Currently the solar cells used for the direct conversion of light into electricity
by the photovoltaic effect are fabricated from inorganic semiconductors; in particular they are
based on the single or polycrystalline silicon cells. On the other hand, organic thin-film solar
cells having single crystalline material are also promising flat-plate photovoltaic technology.

Other applications

Thank
you