Q1. Discuss the critical state of the gas.

Derive the relationship between critical constants and

Vanerwaals constants (7 .5 M)
Ans. Critical state (also called a critical point) is a point in which the distinction between the liquid and gas (or
vapour) phases disappears, i.e., both phases have the same temperature, pressure and volume or density. The
critical point is characterized by the phase-state parameters Tcr, Pcr and Vcr (or cr), which have unique values for
each pure substance
At the critical point, the particles in a closed container are thought to be vaporizing at such a rapid rate that the density of liquid and
vapor are equal, and thus form a supercritical fluid. As a result of the high rates of change, the surface tension of the liquid
eventually disappears.
This liquid-vapor equilibrium curve has a top limit (labeled as C in the phase diagram in Figure 1), which is known as the critical
point. The temperature and pressure corresponding to this are known as the critical temperature and critical pressure. If you
increase the pressure on a gas (vapor) at a temperature lower than the critical temperature, you will eventually cross the liquidvapor equilibrium line and the vapor will condense to give a liquid.

Figure 1: Phase diagram for a single component system with critical point emphasized

This works fine as long as the gas is below the critical temperature.
Above the critical temperature, it is impossible to condense a gas into a liquid just by increasing the pressure. All you get is a highly
compressed gas. The particles have too much energy for the intermolecular attractions to hold them together as a liquid. The critical
temperature obviously varies from substance to substance and depends on the strength of the attractions between the particles. The
stronger the intermolecular attractions, the higher the critical temperature.
The Relationship between the van der Waals Parameters and the Critical Constants
If

then

At the critical point,

and
So, differentiating our expression for pressure with respect to volume at constant temperature

so that

Differentiating again gives

so that

Dividing these two expressions gives

and so

Substitution of this result into the expression that we obtained by differentiating once

gives

which, when rearranged, gives

Substitution of the expressions for the critical volume Vc and critical temperature Tc into the van der Waals equation
gives

and so

Thus Zc = 0.375, which is a compressibility factor at critical point. This value is approximately equal to the
experimental values and also proves the Law of Corresponding States. Since R is a gas constant, and the values of a
and b are different for different gases. They can be calculated in terms of critical-point quantities Pc and Tc from
equation (7, 8) by substituting Vc = 3 Tc R / (8 Pc) . a = 27 R2 Tc2 / ( 64 Pc) and b = R Tc / (8 Pc)
Q2. Derive the expression for the law of corresponding states. (7.5M)

Ans.

Ans. 5

Liquid Crystals
Ans. 1 Applications of Liquid Crystals
Liquid crystal technology has had a major effect many areas of science and engineering, as well as device technology. Applications for this
special kind of material are still being discovered and continue to provide effective solutions to many different problems.
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. Please refer to the LCD chapter for more detail.
Liquid Crystal Thermometers
As demonstrated earlier, chiral nematic (cholesteric) liquid crystals reflect light with a wavelength equal to the pitch. Because the pitch is
dependent upon temperature, the color reflected also is dependent upon temperature. Liquid crystals make it possible to accurately gauge
temperature just by looking at the color of the thermometer. By mixing different compounds, a device for practically any temperature range can
be built.
The "mood ring", a popular novelty a few years ago, took advantage of the unique ability of the chiral nematic liquid crystal. More important and
practical applications have been developed in such diverse areas as medicine and electronics. 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. [Collings, 140-142]
Optical Imaging
An application of liquid crystals that is only now being explored is optical imaging and recording. In this technology, a liquid crystal cell is
placed between two layers of photoconductor. Light is applied to the photoconductor, which increases the material's conductivity. This causes an
electric field to develop in the liquid crystal corresponding to the intensity of the light. The electric pattern can be transmitted by an electrode,
which enables the image to be recorded. This technology is still being developed and is one of the most promising areas of liquid crystal research.

Other Liquid Crystal Applications

Liquid crystals have a multitude of other uses. They are used for nondestructive mechanical testing of materials under stress. This technique is
also used for the visualization of RF (radio frequency) waves in waveguides. They are used in medical applications where, for example, transient
pressure transmitted by a walking foot on the ground is measured. Low molar mass (LMM) liquid crystals have applications including erasable
optical disks, full color "electronic slides" for computer-aided drawing (CAD), and light modulators for color electronic imaging.
As new properties and types of liquid crystals are investigated and researched, these materials are sure to gain increasing importance in industrial
and scientific applications.

Solitary wave propagation in liquid crystals

A high intensity laser beam injected in a liquid crystal can produce a local reorientation of the director molecules.
In this way the light produces it's own waveguide and the laser light will not diffract but stays confined in a narrow
beam. The soliton application can lead to an addressable liquid crystal waveguide to switch light between several
optical fibers.

Hollow liquid crystal fibers

Hollow optical fibers have already proved their use. If we fill them with liquid crystals gives they can give
interesting controllable behavior to the optical fibers.

Optically addressed liquid crystal displays

In optically addressed liquid crystal displays, the strong electric field of a non-visible wavelength with high intensity
is used to switch the molecules in stead of an externally applied voltage.

Liquid crystal solar cell

A new and promising application using liquid crystals is the liquid crystal semiconductor. Liquid crystals are organic
molecules similar to polymers. In polymers containing conjugated systems (alternating single and double bond) the
creation of a higher and lower pi-bond leads to the creation of a band gap simular to semiconductors. The use of
such a liquid crystal in a device simular to the Grtzel cell can lead to new types of solar cells.
Colloids and surface chem
Ans 1. Adsorption is the phenomenon of accumulation of large number of molecular species at the surface of liquid
or solid phase in comparison to the bulk. The process of adsorption arises due to presence of unbalanced or
residual forces at the surface of liquid or solid phase. These unbalanced residual forces have tendency to attract
and retain the molecular species with which it comes in contact with the surface. Adsorption is essentially a surface
phenomenon.

Ans 7.
Gold No.:

Ans 8.
Electrophoresis is a separations technique that is based on the the mobility of ions in an electric field. Positively charged ions
migrate towards a negative electrode and negatively-charged ions migrate toward a positive electrode.For safety reasons one
electrode is usually at ground and the other is biased positively or negatively. Ions have different migrationrates depending on their
total charge, size, and shape, and can therefore be separated. Instrumentation An electrode apparatus consists of a high-voltage
supply, electrodes, buffer, and a support for the buffer such as filter paper, cellulose acetate strips, polyacrylamide gel, or
a capillary tube. Open capillary tubes are used for many types of samples and the other supports are usually used for biological
samples such as protein mixtures or DNA fragments. After a separation is completed the support is stained to visualize the
separated components.
Resolution can be greatly improved using isoelectric focusing. In this technique the support gel maintains a pH gradient. As a protein
migrates down the gel, it reaches a pH that is equal to its isoelectric point. At this pH the protein is netural and no longer migrates, i.e, it is
focused into a sharp band on the gel.

Schematic of zone electrophoresis apparatus

Dialysis is the separation of colloids from dissolved ions or molecules of small dimensions, orcrystalloid, in a solution. A colloid is
any substance that is made of particles that are of an extremely small size: larger than atoms but generally have the size of 10 -7 cm
ranging to 10-3cm. A crystalloid is a substance that has some or all of the properties of a crystal or a substance that forms a true
solution and diffuses through a membrane by dialysis. Dialysis is a process that is like osmosis. Osmosis is the process in which
there is a diffusion of a solvent through a semipermeable membrane.

Introduction
In 1861, chemist Thomas Graham used the process of dialysis, a process used to separate colloidal particles from dissolved ions or
molecules. Thomas Graham is also responsible for developing Graham's Law. Dialysis is possible because of the unequal rates of
diffusion through a semipermeable membrane. A semipermeable membrane is a membrane that lets some molecules to pass
through it while not letting others. Examples of semipermeable membranes include parchment and cellophane.

Figure 2: Graphic showing the diffusion of solutes across a membrane during dialysis. Image used with permision from wikipedia
(Potcherboy)
Another way to think of a semipermeable membrane is to think of a net like object that traps larger objects, but lets smaller object
pass through because they can pass through the holes in the net.

Video 1: Osmotic Pressure Dialysis Tubing

When a colloidal mixture is places in a semipermeable membrane, which is then placed in an aqueous solution or pure water,
dissolved ions and small molecules are allowed to pass through this membrane. This causes colloidal particles to stay in the
membrane, because these particles are unable to pass through the small pores of the membrane.

What is the rate of dialysis ?

Dialysis is not a quick process; the rate of dialysis depends on the speed of the unequal diffusion rates between the crystalloids and
the colloids and the differences in particle size. The rate of dialysis can be changed through heating, or if the crystalloids are
charged, thenapplying an electric field, called electrodialysis. Electrodialysis is the type of dialysis in which electrodes are placed
on the sides of the membrane. In this way, positive ions can pass through one side of this membrane while the negatively charged
ions can pass through the other side of the membrane. This causes acceleration in the process of dialysis.

example of dialysis in our world

Hemodialysis is a method in which kidney failure is treated with the process of dialysis. In hemodialysis, blood is removed, purified
through dialysis, and returned to the bloodstream. In kidney failure, there is a retention of salts and water, urea, and metabolic acids.
The patient is then connected to a dialysis machine, which is also called a hemodialyzer. The blood flows through small channels
made of semipermeable membranes. The dissolved substances like urea and salts pass through a sterile solution. Compounds like
sugar and amino acids are added to the sterile solution. The dialysis solution is on the other side of the membranes, and the
molecules flow through the membranes. The molecules diffuse from a higher concentration to low concentration area. The
concentrations of molecules needed to be removed from the blood are zero in the dialysis fluid.
Ans 9. colloid is one of the three primary types of mixtures, with the other two being a solution and suspension. A colloid is a
solution that has particles ranging between 1 and 1000 nanometers in diameter, yet are still able to remain evenly distributed
throughout the solution. These are also known as colloidal dispersions because the substances remain dispersed and do not settle

to the bottom of the container. In colloids, one substance is evenly dispersed in another. The substance being dispersed is referred
to as being in the dispersed phase, while the substance in which it is dispersed is in the continuous phase.

Properties of Colloids
To be classified as a colloid, the substance in the dispersed phase must be larger than the size of a molecule but smaller than what
can be seen with the naked eye. This can be more precisely quantified as one or more of the substance's dimensions must be
between 1 and 1000 nanometers. If the dimensions are smaller than this the substance is considered a solution and if they are
larger than the substance is a suspension.

Classifying Colloids
A common method of classifying colloids is based on the phase of the dispersed substance and what phase it is dispersed in. The
types of colloids includes sol, emulsion, foam, and aerosol.
1. Sol is a colloidal suspension with solid particles in a liquid.
2. Emulsion is between two liquids.
3. Foam is formed when many gas particles are trapped in a liquid or solid.
4. Aerosol contains small particles of liquid or solid dispersed in a gas.

Figure 1: Examples of a stable and of an unstable colloidal dispersion.Image used with permission from Wikipedia.
When the dispersion medium is water, the collodial system is often referred to as a hydrocolloid. The particles in the dispersed
phase can take place in different phases depending on how much water is available. For example, Jello powder mixed in with water
creates a hydrocolloid. A common use for hydrocolloids is in the creation of medical dressings.

Table 1: Examples of Colloids

Dispersion Medium

Dispersed Phase

Type of Colloid

Example

Solid

Solid

Solid sol

Ruby glass

Solid

Liquid

Solid emulsion/gel

Pearl, cheese

Solid

Gas

Solid foam

Lava, pumice

Table 1: Examples of Colloids

Dispersion Medium

Dispersed Phase

Type of Colloid

Example

Liquid

Solid

Sol

Paints, cell fluids

Liquid

Liquid

Emulsion

Milk, oil in water

Liquid

Gas

Foam

Soap suds, whipped cream

Gas

Solid

Aerosol

Smoke

Gas

Liquid

Aerosol

Fog, mist

An easy way of determining whether a mixture is colloidal or not is through use of the Tyndall Effect. When light is shined through a
true solution, the light passes cleanly through the solution, however when light is passed through a colloidal solution, the substance
in the dispersed phases scatters the light in all directions, making it readily seen. An example of this is shining a flashlight into fog.
The beam of light can be easily seen because the fog is a colloid.
Ans 10. Langmuir adsorption isotherm is based on the following assumptions.
i) Adsorption does not proceed beyond monolayer coverage.
ii) All the sites available on the adsorbent surface are equivalent and the surface is perfectly uniform, that is flat.
iii) The ability of a gas molecule to get adsorbed at a particular site is independent of the occupation of neighboring sites. This
implies that there is no interaction between adjacent adsorbed molecules.
iv) A dynamic equilibrium exists between the adsorbed molecules and the free gas molecules.
Initially, since the surface is completely bereft of any gas molecules, every molecule of the gas that strikes the surface of solid may
get adsorbed. After some time, only those gas molecules may get adsorbed which strike the part of the surface that is not already
covered. This means, that initially the rate of adsorption is high and then decreases as less surface is available for adsorption.
Since a dynamic equilibrium exists between the adsorbed molecules and the free gas molecules, it implies that the adsorbed
molecules also undergo desorption, probably due to thermal agitation. When the rate of adsorption equals the rate of desorption,
dynamic equilibrium is attained.
If q is the fraction of the total available surface covered with gas molecules, at any instant, then (1-q) is the fraction of the surface of
the solid which is empty. From kinetic theory of gases, it is known that the rate at which gas molecules collide per unit area of a
surface is directly proportional to the pressure of the gas. The rate of adsorption depends on both the pressure of the gas and
fraction of surface available for adsorption. Hence,
Rate of adsorption = Ka (1-q) P ..(3)
Rate of desorption = Kd (q) ..(4)

At equilibrium, the rate of adsorption is equal to the rate of desorption i.e.,

Ka (1-q) P = Kd (q)

Now, the extent of adsorption (x/m) is proportional to the fraction of surface covered. Therefore,

This is the equation which describes the Langmuir adsorption isotherm. Here a and K are the Langmuir parameters and are
characteristic of a particular system at a particular temperature.
At very high pressure, the Langmuir isotherm acquires the limiting form.

At very low pressure,

i.e., the extent of adsorption is proportional to pressure.

The parameters a and K can be determined by taking the inverse form of equation 7.

A plot of m/x against 1/P gives a straight line with slope and intercept equal to 1/a and K/a respectively.
Langmuir isotherm shows that at low pressures of the adsorbate, the extent of adsorption is linear and at high pressure the extent of
adsorption is a constant. This form of isotherm is shown in figure 7.4.

fig 7.4 - Langmuir adsorption isotherm

v) Effect of temperature
Most adsorption processes are exothermic; hence adsorption decreases with increasing temperature. This is especially true for
physisorption. For chemisorption, extent of adsorption initially increases with temperature and then decreases. The plot of extent of
adsorption versus temperature T at a constant pressure is called the adsorption isobar. How the extent of adsorption (x/m) varies
with temperature for physisorption and chemisorption as shown in figures 7.5 (a) and 7.5 (b).

fig 7.5(a) - Physical adsorption at a given pressure

fig 7.5(b) - Chemical adsorption at a given pressure

In chemisorption, the initial increase of x/m with temperature is due to the fact that like chemical reactions, chemisorption also
requires activation energy.
(vi) Activation of adsorbent
Activation of an adsorbent implies enhancing the adsorptive powers of an adsorbent. This is done by either increasing the specific
area of the adsorbent by breaking the solid adsorbent into fine pieces or activating the surface of the adsorbent by specific
treatments. How charcoal is activated is already discussed in the section pertaining to nature of the adsorbent.

Ans 11.
Ans 12. Kinetic Property: ( Brownian movement )
In 1827 botanist Robert Brown observe the movement of plant spores floating in water.The molecules of the dispersion
medium constantly colloid with the colloidal particles thereby passing kinetic energy to them. The continuous rapid zig-zag motion of
the colloidal particle in the dispersion medium is called Brownian movement. This is due to the bombardment of colloidal particles by
molecules of the dispersion medium. the particle motion depends on the size of the particle and viscosity of the dispersion medium.
This phenomenon was latterly found in the case of colloidal solution, when observed ultra-microscopically. It is otherwise known as
Brownian motion or Pedesis.

Optical property: ( Tyndall effect )

A British physicist John Tyndall in 1869 first observed this phenomenon and hence it is known as Tyndall effect.

A beam of light is passed through a true solution, the light beam is not visible in this case. But in the case of colloidal solution
light beam is visible. This is due to the colloidal particles absorb light energy and then emit it in all directions. It illuminates the path
of the beam. This phenomenon of illuminated beam formed by the particles is called Tyndall effect. The amount of scattering
depends on the frequency of the light and density of particles. It is otherwise known as Tyndall scattering.
Example:
Illumination of light beam from projector in smoke filled theater's.

Visible beam of headlights in fog.

In 1909, Freundlich gave an empirical expression representing the isothermal variation of Adsorption of a quantity
of gas adsorbed by unit mass of solid adsorbent with pressure. This equation is known as Freundlich Adsorption
Isotherm or Freundlich Adsorption equation.

Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p and k, n are constants whose
values depend upon adsorbent and gas at particular temperature.
Explanation of Freundlich Adsorption equation
At low pressure, extent of adsorption is directly proportional to pressure (raised to power one).

At high pressure, extent of adsorption is independent of pressure (raised to power zero).

Therefore at intermediate value of pressure, adsorption is directly proportional to pressure raised to power 1/n
.Here n is a variable whose value is greater than one.

Using constant of proportionality, k, also known as adsorption constant we get

The above equation is known as Freundlich adsorption equation.

Plotting of Freundlich Adsorption Isotherm
As per Freundlich adsorption equation

Taking log both sides of equation, we get,

The equation above equation is comparable with comparable with equation of straight line, y = m x + c where, m
represents slope of the line and c represents intercept on y axis.
Plotting a graph between log(x/m) and log p, we will get a straight line with value of slope equal to 1/n and log k
as y-axis intercept.

log(x/m) vs. log p graph

Limitation of Freundlich Adsorption Isotherm
Experimentally it was determined that extent of adsorption varies directly with pressure till saturation pressure Ps
is reached. Beyond that point rate of adsorption saturates even after applying higher pressure. Thus Freundlich
Adsorption Isotherm failed at higher pressure.

Ans 4.

Solid State

Ans2
Ans 3. Semiconductors are mainly classified into two categories: Intrinsic and Extrinsic.
Intrinsic Semiconductor
An intrinsic semiconductor material is chemically very pure and possesses poor conductivity. It has equal numbers of negative
carriers (electrons) and positive carriers (holes). A silicon crystal is different from an insulator because at any temperature above
absolute zero temperature, there is a finite probability that an electron in the lattice will be knocked loose from its position, leaving
behind an electron deficiency called a "hole".

If a voltage is applied, then both the electron and the hole can contribute to a small
current flow.The conductivity of a semiconductor can be modeled in terms of the
band theory of solids. The band model of a semiconductor suggests that at
ordinary temperatures there is a finite possibility that electrons can reach the
conduction band and contribute to electrical conduction.The term intrinsic here
distinguishes between the properties of pure "intrinsic" silicon and the dramatically
different properties of doped n-type or p-type semiconductors.

Extrinsic Semiconductor
Where as an extrinsic semiconductor is an improved intrinsic semiconductor with a small amount of impurities added by a process,
known as doping, which alters the electrical properties of the semiconductor and improves its conductivity. Introducing impurities into
the semiconductor materials (doping process) can control their conductivity.
Doping process produces two groups of semiconductors: the negative charge conductor (n-type) and the positive charge conductor
(p-type). Semiconductors are available as either elements or compounds. Silicon and Germanium are the most common elemental
semiconductors. Compound Semiconductors include InSb, InAs, GaP, GaSb, GaAs, SiC, GaN. Si and Ge both have a crystalline
structure called the diamond lattice. That is, each atom has its four nearest neighbors at the corners of a regular tetrahedron with the
atom itself being at the center. In addition to the pure element semiconductors, many alloys and compounds are semiconductors. The
advantage of compound semiconductor is that they provide the device engineer with a wide range of energy gaps and mobilities, so
that materials are available with properties that meet specific requirements. Some of these semiconductors are therefore called wide
band gap semiconductors.

Ans 6.

Ans 7 A space lattice is an array of points showing how particles (atoms, ions or molecules) are arranged at
different sites in three dimensional spaces.
A crystal is a three dimensional design in which identical points form a 3-dimensional network of cells each
representing the unit and through which whole crystal can be built up. The lattice points can be connected by a
regular network of lines in various ways. Thus the lattice is broken up into a number of unit cells. This is done by
connecting the points by a regular network of lines as shown in figure on next page.
The unit cell may be defined as, the smallest repeating unit in space lattice which, when repeated over again,
results in a crystal of the given substance.
Therefore space lattice of a crystal has been likened to a wall-paper on which a single pattern is continuously
repeated. Each unit cell requires two vectors a and b for its description. A three dimensional space lattice can be
similarly divided into unit cells described by three vectors. The exact location of particles in a unit cell can be
obtained by X-ray diffraction.