UNIT I DIFFUSION AND MASS TRANSFER

PART A

1. Define the term diffusion?

Diffusion is defined as it is the movement, under the influence of a physical stimulus
of an individual component through a mixture.

2. Name some classification of diffusion.

(i)
(ii)
(iii)
(iv)

Molecular diffusion
Eddy diffusion
Thermal diffusion (diffusion induced by temperature )
Pressure diffusion(diffusion induced by total pressure and not partial pressure)

3. State Ficks law of diffusion

Ficks first law of diffusion states that the flux (J) of diffusion is proportional to the
concentration gradient for the Z direction be expressed as
JA = -DAB CA/ Z
Where D AB is diffusivity or diffusion coefficient for component A.
ve sign indicates that the diffusion occurs in the direction of drop in concentration.
JA = -CDAB xA / Z

4. Molecular diffusion:
is caused by the movement of individual molecules through a substance by virtue of
their thermal energy.

5. Define mass flux.

The mass (or molar) flux of a given species is a vector quantity denoting the amount
of the particular species, in either mass or molar units, that passes per given increment of
time through a unit area normal to the vector. The flux of species defined with reference
to fixed spatial coordinates, NA is
N

A A

6. Define molecular diffusivity.

The ratio of the diffusive flux to the negative of the concentration of gradient is the
direction of diffusion is called molecular diffusivity.

7. Define Dew point temperature.

Dew point temperature is defined as the temperature at which vapor gas mixture
becomes saturated when cooled at constant pressure out of contact with the liquid.

8. Define Percentage humidity.

Percentage humidity is defined as the ratio of the actual humidity to the saturation
humidity.

9. Define mass transfer.

The transport of one constituent from a region of higher concentration to that of
lower concentration is called mass transfer.

10. What are the two bases is derived to derive relationships between flux and
velocity?
(i)
Relative to a stationary interface
(ii)
Relative to the phase as a whole.

11. Diffusivity-Explain
Ficks law proportionality, D AB, is known as mass diffusivity (simply as diffusivity)
or as the diffusion coefficient. D AB has the dimension of L 2 / t, identical to the
fundamental dimensions of the other transport properties: Kinematic viscosity, =
( / ) in momentum transfer, and thermal diffusivity, (= k / C ) in heat transfer.
Diffusivity is normally reported in cm2 / sec; the SI unit being m2 / sec. Diffusivity
depends on pressure, temperature, and composition of the system. Diffusivities of
gases at low density are almost composition independent, increase with the
temperature and vary inversely with pressure. Liquid and solid diffusivities are
strongly concentration dependent and increase with temperature.

12. Diffusivity in Gases

Pressure dependence of diffusivity is given by
D

AB

1
p

(for moderate ranges of pressures, upto 25 atm).

and temperature dependency is according to

3

D AB T 2
Diffusivity of a component in a mixture of components can be calculated using the
diffusivities for the various binary pairs involved in the mixture.

13. Eddy diffusion depends on the

Flow pattern, velocity, position in the flowing stream, physical properties, physical
mixing and eddies in the turbulent zone.

14. Diffusion can be caused by

Concentration gradient, activity gradient (reverse osmosis), temperature gradient
(heat transfer) and external forces (centrifugal forces).

15. The diffusivity depends on

Temperature, pressure and concentration gradient whether in liquid, gas or solid

solution and on the nature of the other constituents.

16. Define Eddy or turbulent diffusion.

When the diffusion process is processed by mechanical agitation, it is known as Eddy or
turbulent diffusion.

17. Define surface diffusion.

Surface diffusion is defined as it is a phenomenon accompanying adsorption of
solutes onto the surface of the pores of the solid.
PART B
1. Derive the expression for the steady state diffusion of gas A through a stagnant
film of non diffusing gas B.
2. Describe a method for estimation of diffusivity of a volatile solvent in to air.
3. Derive an expression for the molar flux under equimolal counter diffusion
clearly indicates the assumptions made.
4.

Determine the diffusivity of Co 2 (1), O 2 (2) and N 2 (3) in a gas mixture having
the composition: Co2 : 28.5 %, O2 : 15%, N 2 : 56.5%, The gas mixture is at 273 k
and 1.2 * 10 5 Pa. The binary diffusivity values are given as: (at 273 K)
D 12 P = 1.874 m 2 Pa/sec
D 13 P = 1.945 m 2 Pa/sec
D 23 P = 1.834 m 2 Pa/sec
5. Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25C.
Concentration of oxygen at planes 2 mm apart are 10 and 20 volume %
respectively. Nitrogen is non-diffusing.
(a) Derive the appropriate expression to calculate the flux oxygen. Define units
of each term clearly.
(b) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89 * 10 5
m 2/sec.
6. In a gas mixture of hydrogen and oxygen, steady state equimolar counter
diffusion is occurring at a total pressure of 100 kPa and temperature of 20C. If the
partial pressures of oxygen at two planes 0.01 m apart, and perpendicular to the
direction of diffusion are 15 kPa and 5 kPa, respectively and the mass diffusion flux
of oxygen in the mixture is 1.6 * 10 5 kmol/m 2.sec, calculate the molecular diffusivity
for the system.

7. A tube 1 cm in inside diameter that is 20 cm long is filled with Co 2 and H2 at a

total pressure of 2 atm at 0C. The diffusion coefficient of the Co 2 H2 system
under these conditions is 0.275 cm2/sec. If the partial pressure of Co2 is 1.5 atm at
one end of the tube and 0.5 atm at the other end, find the rate of diffusion for:
i)
ii)
iii)

steady state equimolar counter diffusion (N A = - N B)

steady state counter diffusion where N B = -0.75 N A, and
steady state diffusion of Co2 through stagnant H2 (NB = 0)

8. Calculate the rate of diffusion of butanol at 20C under unidirectional steady

state conditions through a 0.1 cm thick film of water when the concentrations of
butanol at the opposite sides of the film are, respectively 10% and 4% butanol by
weight. The diffusivity of butanol in water solution is 5.9 * 10 6 cm 2/sec. The
densities of 10% and 4% butanol solutions at 20C may be taken as 0.971 and 0.992
g/cc respectively. Molecular weight of Butanol (C 4 H 9 OH) is 74, and that of water
18.
9. Methane diffuses at steady state through a tube containing helium. At point 1 the
partial pressure of methane is p A1 = 55 kPa and at point 2, 0.03 m apart P A2 = 15
KPa. The total pressure is 101.32 kPa, and the temperature is 298 K. At this
pressure and temperature, the value of diffusivity is 6.75 * 10 5 m 2/sec.
i)
calculate the flux of CH 4 at steady state for equimolar counter
diffusion.
ii)
Calculate the partial pressure at a point 0.02 m apart from point 1.

UNIT II GAS LIQUID OPERATIONS

PART A
1. Define gas absorption
Gas absorption is an operation in which a gas mixture is contacted with
a liquid for the purpose of preferentially dissolving one or more
components of gas and to provide a solution of them in the liquid. For
eg., the gas from byproduct coke ovens is washed with water to
remove benzene and toluene vapors.

2. What are the properties of solvent used for Gas absorption?

gas solubility

volatility

corrosiveness

cost

viscosity

nontoxic & nonflammable & chemically stable

3. Brief on Various types of packings

Various types of packings are made of different types of materials of construction. Both
random and structured packings are commonly used. Examples of random packings as
shown in the Figures below - left and right - are Raschig rings, Pall rings, Berl saddles,
etc.

4. What are the Basic Requirements of Packings?

Briefly, the principal requirements of a packing material are:
1. chemically inert to the fluids
2. strong but without excessive weight
3. contain adequate passages (void volume) for both streams without
excessive liquid hold-up or pressure drop
4. provide good contact between the liquid and the gas. Aan important
measure here is the parameter 'a', having the unit m2/m3 or ft2/ft3, which
we will looked at in greater detail later (for example, see Table below)
5. reasonable in cost
5. Define absorption factor & indicate its significance.
The absorption factor A = L / mG is the ratio of the slope of the operating line to that of
the equilibrium curve.
For values of A less than unity, corresponding to convergence of the operating line and
equilibrium curve for the lower end of the absorber.
For values of A greater than unity, any degree of absorption is possible if sufficient trays
are provided.

6. What is flooding?
With a large pressure difference in the space between trays, the level of liquid leaving a
tray at relatively low pressure and entering one of high pressure must necessarily assume
an elevated position in the downspouts.
7. Write note on HETP (Height Equivalent to a Theoretical Plate)
With a tray column, the vapours leaving an ideal plate will be richer in the more
volatile component than the vapour entering the plate by one equilibrium "step". When
packings are used instead of trays, the same enrichment of the vapour will occur over a
certain height of packings, and this height is termed the height equivalent to a theoretical
plate (HETP).
8. Write short note on Number of transfer units (NTU)
The number of transfer units (NTU) required is a measure of the difficulty of the
separation. A single transfer unit gives the change of composition of one of the phases
equal to the average driving force producing the change. The NTU is similar to the
number of theoretical trays required for trayed column. Hence, a larger number of
transfer units will be required for a very high purity product.
9. Write short note on height of a transfer unit (HTU)
The height of a transfer unit (HTU) is a measure of the separation effectiveness of the
particular packings for a particular separation process. As such, it incorporates the mass
transfer coefficient that we have seen earlier. The more efficient the mass transfer (i.e.
larger mass transfer coefficient), the smaller the value of HTU. The values of HTU can be
estimated from empirical correlations or pilot plant tests, but the applications are rather
restricted.
10. Define Tray efficiency.
Tray efficiency is the fractional approach to an equilibrium stage which is attained by a
real tray.
11. What is meant by desorption?
When a mass transfer occurs in the opposite direction as that of absorption i.e. from the
liquid to the gas, the operation is called desorption or stripping. These operations are used
for solute recovery or solute removal.
12. Define Overall tray efficiency.
EO = Number of ideal trays required / Number of real trays required
13. Define stage efficiency.
Stage efficiency is defined as the fractional approach to equilibrium which are real stage
produces.
14. Define Murphee efficiency.
Murphee efficiency is the fractional approach of one leaving stream to equilibrium with
the actual concentration in the other leaving stream.

EMG = yn - y n+1
y*n - y n+1
15. Define Permeability.
At the two faces of a membrane the equilibrium solubility of the gas in the polymer is
directly proportional to the pressure.
P = DA SA
P Permeability
DA - Diffusivity of A
S A - Solubility coefficient (or) Henrys law constant
PART B
1. Explain how the number of stages can be theoretically determined for an
absorber.
2. What are the types of typical tower packings used in packed bed absorbers? State
their principal requirements.
3. Discuss the concept of HTU and HETP in absorption operations.
4. Explain with neat sketches the various types of contactors available for gas-liquid
operations.
5. Explain the terms channeling and flooding velocity with reference to packed
towers. How are they checked for a controlled operation?
6. How will you choose a good solvent for absorption?
7. Discuss multi component gas absorption.

UNIT III VAPOUR LIQUID OPERATIONS

1. State Raoults law.
For an ideal solution, the equilibrium partial pressure P A* of a component at a
fixed temperature equals the product of its mole fraction in the liquid and the vapour
pressure (PVA) when it is pure at that temperature.
PA*= xA PVA
2. Define Relative volatility
It is the ratio of the vapor pressure of A to the vapor pressure of B at the same
temperature.
= y* (1- x)
x (1- y*)
3. Define distillation.
Distillation is a method of separating the components of a solution which depends
upon the distribution of the substances between a gas and liquid phase, applied to
cases where all components are present in both phases.

4. What is meant by Reflux ratio?

The molar ratio of the reflux to the distillate withdrawn from the column is the
reflux ratio.
R=L/D
5. Briefly explain the principle of Flash vaporization is used
Flash vaporization or equilibrium distillation, or single stage operation wherein a
liquid mixture is partially vaporized, the vapour allowed to come to equilibrium with
the residual liquid and the resulting vapour and liquid phases are separated and
removed from the apparatus.

Flash distillation (sometimes called "equilibrium distillation") is a single stage

separation technique. A liquid mixture feed is pumped through a heater to raise the
temperature and enthalpy of the mixture.
6. Define azeotropes.
In azeotrophic mixture, the equilibrium vapor composition is the same as that of the
liquid.
7. Explain the term Total reflux.
When R=L/D= the intercept will become zero. Therefore the enriching & stripping
line will coincide with the diagonal line. At this condition the number of plates will
be minimum. There will be no product stream in the column. All the vapors from the
top is condensed and return back to the column as reflux. This is known as total
reflux.
8. Distinguish between equilibrium distillation and differential Distillation.
In Equilibrium distillation the vapor and the liquid phases are at equilibrium.
In differential distillation different batches of the solution having differential
composition.
9. Write Rayleighs equation
ln(F/W) = xwxF dx/(y*- x)
F moles of charge of composition xF
W- moles of residual liquid of composition xw

10. Write Total Reflux

The total reflux condition represents operation with no product removal. All the
overhead vapor is condensed and returned as reflux. Consequently, the reflux ratio
(L/D) is infinite. This, in turn, makes the operating lines the 45 degree line (prove it to
yourself by setting D=0, and noticing that consequently L=V). With the operating
lines on the diagonal, they are as far as they can get from the equilibrium curve, so if
the number of plates is stepped off using the diagonal and the equilibrium curve, the
number of theoretical stages will be a minimum.
11. Define Minimum Reflux
The minimum reflux condition represents the theoretical opposite of total reflux -an infinite number of ideal separation stages. In this case, the intersection of the operating
lines lies on the equilibrium curve itself. Thus, the distance between the equilibrium
curve and the operating lines is at its minimum, the stepping triangles become very small,
there is no gap between the equilibrium curve and the intersection point, so you cannot
step past the feed point.

PART B
1. A liquid feed consisting of 1200g moles of mixture containing 30%
naphthalene and 70% dipropylene glycol is differentially distilled at 100
mmHG pressure and final distillate contains 55% of naphthalene. The VLE
data are
X
: 8.4
11.6 24.8 50.6 68.7 80.6
88
Y
: 22.3 41.6 62.9 74.8 80.2 84.4
88
(i) Determine the amount of distillate.
(ii) Determine the concentration of naphthalene in residue and distillate.
2. Write short notes on
(i)
Azeotropic distillation
(ii)
Molecular distillation
(iii)
Extractive distillation
3. i) Derive Rayleighs equation for batch distillation.
ii) Write short notes on Flash Distillation and its application.
4. A feed of 50 mole % hexane and 50 mole % octane is fed into a pipe still
through a pressure reducing valve and then into a flash disengaging
chamber. The vapor and liquid leaving the chamber are assumed to be in
equilibrium. If the fraction of the feed converted to the vapor is 0.5, find the
composition of the top and bottom products. The following table gives the
Equilibrium data for this system.
Mole fraction of
Hexane in liquid

1.00

0.69

0.40

0.192

0.045

0.00

Mole fraction of
Hexane in vapor

1.00

0.932

0.78

0.538

0.1775 0.00

5. A liquid mixture containing 40 mole % n-heptane and 60 mole % n-octane is

subjected to differential distillation at atmospheric pressure with 60 mole %
of liquid distilled. Compute the composition of the composited distillate and
the residue.
Take the relative volatility = 2.16
6. A binary mixture of benzene and toluene containing 40% of benzene is to be
distilled at 1 atm. Pressure to recover 95% of the benzene. Estimate the molal
percent of mixture to be distilled and the composition of the distillate
obtained if distillation is carried out (ii) Equilibrium distillation. (ii)
Differential distillation, Collecting all the distillate together.
The average relative volatility of Benzene to toluene is 2.16
7. Show that for a binary system Y= a X/ [1+(a-1)X] where a is the relative
volatility.
8. A liquid mixture containing 60 mole% benezene and rest toluene is
differentially distilled at 1 atm Pressure to yield a residue containing 30 mole
% benzene. Calculate the composition of the composited distillate and the
percentage vapourisation. The vapour- liquid equilibrium data as follows
Mole fraction of
benzene in liquid : 0.06

0.16

0.30

0.4

0.5

0.7

0.82 1.00

Mole fraction of
benzene in vapor : 0.13 0.30 0.45 0.06 0.72 0.83 0.92 1.00
9. A continuous fractionating column is to be designed for separating 4000kg/h
of liquid mixture containing equimolar mixture of methanol and water into
an overhead product containing 95% methanol and a residue containing 3%
methanol.
The feed is 30% vaporized. Calculate
(i)
molar flow rate of overhead and bottom product.
(ii)
The number of actual plates assuming overall tray efficiency of
0.7.
Use reflux ratio of 1.75 times minimum.
(iii)
Locate the feed tray
Equilibrium data:
Mole fraction
of methanol
in liquid

0.1

0.2

0.30

0.40

0.50

0.60 0.70

0.80

0.90

Mole fraction
of methanol
in vapour
0.417 0.579 0.669 0.729 0.78 0.825 0.879 0.915 0.959

10.
A mixture of 35 mole % A and 65 mole % B is to be separated in
afractinating column. The concentration of A in the distillate is 93 mole % and 96
mole % of all product A is in the distillate. The feed is half vapor and the reflux ratio
is to be 4.0. The relative volatility of A to B is 2.0 . Calculate the number of
theoretical plates in the column and locate the feed plate. The equilibrium relation
may be obtained using the following relation
y= x/1+ (-1)x.
11.
Explain in detail the method of estimation of number of stages by Mc CabeThiele method.

UNIT IV EXTRACTION OPERATIONS

PART A
1. Define Liquid Extraction
Liquid extraction produces separation of the constituents of a liquid solution by contact
with another insoluble liquid.
2. Define differential heat of adsorption.
Differential heat of adsorption is defined as the heat liberated at constant temperature
when unit quantity of vapour is adsorbed upon a large quantity of solid already
containing adsorbate, such a large quantity of solid is used that the adsorbate
concentration is unchanged.
3. Write note on the Terminologies used in extraction
Certain terms are commonly used when describing extraction processes. The solution to
be extracted is called the feed, the liquid used in contacting is the solvent. The enriched
solvent product is the extract and the depleted feed is called the raffinate.
4. Liquid - Liquid Equilibrium

5. Define
Plait
Point

The plait point point is located near the top of the two-phase envelope, at the inflection
point. It represents a condition where the 3-component mixture separates into two phases,
but the phases have identical compositions.
6. How to select the solvent for extraction
The choice of the solvent should be done based on the following parameters
Selectivity -- compare the equilibrium ratio of solute in each phase
Distribution Coefficients -- y/x at equilibrium; large values preferable
Insolubility -- solvent should not be soluble in carrier liquid
Recoverability -- consider constraints (i.e. azeotropes)
Density -- must be different so that phases can be separated by settling
Interfacial Tension -- if too high, liquids will be difficult to mix
Chemical Reactivity -- solvent should be inert and stable
Viscosity, Vapor Pressure, Freezing Point -- low values make storage easier
Safety -- toxicity, flammability
Cost
7. Define Leaching
Leaching is the preferential solution of one or more compounds from a solid mixture by
contact with a liquid solvent. Percolation of the liquid through a fixed bed of the solid.
8. Give some examples of Leaching
the metals industry for removing mineral from ores (acid solvents)
the sugar industry for removing sugar from beets (water is solvent)
the oilseeds industry for removing oil from soybeans, etc. (hexane or similar
organic solvents)
9. Define Decoction.
Decoction refers specifically to the use of the solvent at its boiling point.
10. State the principle of ion exchange.
Chemical reactions between an electrolyte in solution and an insoluble electrolyte
with which the solution is contacted.
Positively charged ions (cations) of a solution which are capable of diffusing
through the pores will exchange with the Na+ ions of such a mineral(Na2O)
11. Define the term Distribution Coefficient.
This is the ratio y* / x at equilibrium.
X = concentration of A in the liquid, mole fraction
Y* = y in equilibrium with x, mole fraction
Y = concentration of A in the gas, mole fraction
12. Define elution.

When the soluble material is largely on the surface of an insoluble solid and is merely
washed off by the solvent, this operation is called elution.
13. What is lixiviation?
Synonym for leaching refers specifically to the leaching of alkali from wood ashes.
14. Write any two applications of leaching?
(i)
Copper minerals are dissolved from their ores by leaching with
sulfuric acid or ammonical solutions
(ii)
Gold is separated from its ores with aid of sodium cyanide solutions.
15. Define Integral heat of adsorption.
The Integral heat of adsorption at any concentration X of adsorbate adsorbent
combination minus the sum of the enthalpies of unit weight of pure solid adsorbent
and sufficient pure adsorbed substance to provide the required concentration X, all at
the same temperature.

PART B
1.
How will you select the appropriate solvent for extraction operations?
2.
Explain briefly the various types of contacting devices available for liquid-liquid
extraction operation.
3.
A solution containing 20 mass per cent of acetone in water is to be extracted using
monochlorobenzene (MCB) containing 0.5% acetone by weight by counter current
extraction process. MCB and water may be considered to be immiscible within the
operating range. The equilibrium data are as follows:
Kg of acetone
Per Kg of water 0.0258 0.0739 0.1605 0.267
Kg of acetone
Per Kg of MCB 0.0288 0.0704 0.156 0.237
i)
Compute minimum solvent ratio to obtain a raffinate containing 1% acetone.
ii)
What are the suitable extractors for this operation.
3) 1000 kg/hr of the water dioxane solution containing 20% dioxane
is to be continuously and counter currently extracted with benzene at 25C to recover
80% dioxane. Water and benzene are essentially insoluble and the equilibrium
distribution of dioxane between them are as follows:
wt% of dioxane in water (100 x) 5.1 18.9 25.2
wt% of dioxane in benzene (100 y) 5.2 22.5 32.0
Determine the number of stages required if the solvent rate is 1.5 times the minimum
benzene is used. Benzene is free from dioxane.
4)
An aqueous solution C is to be extracted with pure solvent B to recover the
solute. The equilibrium data in terms of weight % of solute in the two layers are given
below.

Aqueous layer : 2 8 15 20
Solvent layer : 8 22 35 45
5) A feed 20% by weight of solute is to be treated in two consecutive cross current
cascades using aqueous solution is to solvent ratio 1.8. Calculate
(i) Concentration of final farrinate
(ii) Amount of raffinate
(iii) % recovery of solute
(iv) Amount of solovent to be used for a single stage extraction to obtain the
same final concentration.
(v) Water and solvent are immiscible with each other.

UNIT V SOLID FLUID OPERATIONS

PART A
1. Define Adsorption
Adsorption is a process that occurs when a gas or liquid solute accumulates on the
surface of a solid or, more rarely, a liquid (adsorbent), forming a molecular or atomic film
(the adsorbate). It is different from absorption, in which a substance diffuses into a liquid
or solid to form a solution.
2. Give some examples of Adsorbents
Adsorbents are usually porous solids, and adsorption occurs mainly on the pore walls
"inside" particles. Examples of adsorbents include:
activated carbon (adsorbs organics)
silica gel (adsorbs moisture)
activated alumina (adsorbs moisture)
zeolites and molecular sieves
synthetic resins
3. What are the steps involved in adsorption?
1. solute diffuses through the fluid to an area near the solid particle surface
2. solute diffuses into the pores of the particle
3. solute diffuses to the pore wall
4. solute adsorbs to the pore wall surface
4. Write note on Adsorption Equilibrium

the

Adsorption equilibrium data is typically

plotted in the form of an adsorption
isotherm (i.e. at constant temperature)
with the mass adsorbed on the y-axis and
mass in the fluid on the x-axis. The
shape of the curve is significant and
factors heavily into design. "Favorable"

isotherms permit higher solid loadings at lower solution concentrations. These tend to
start out steep and level out. Isotherms which start out flat are "unfavorable", since they
only work well at high concentrations of solute. Usually, as temperature increases the
amount adsorbed decreases (permitting thermal regeneration).
The Freundlich isotherm describes physical adsorption from liquids and can also be used
for the adsorption of hydrocarbon gases on activated carbon. It is a two parameter model,
of the form

Maybe the best known is the Langmuir isotherm, given by

which assumes that the number of adsorption sites is fixed and that adsorption is
reversible.
5. Breakthrough Curves
Adsorption is a transient process. The amount of material adsorbed within a bed depends
both on position and time. Consider the time dependence. As fluid enters the bed, it
comes in contact with the first few layers of absorbent. Solute adsorbs, filling up some of
the available sites. Soon, the adsorbent near the entrance is saturated and the fluid
penetrates farther into the bed before all solute is removed. Thus the active region shifts
down through the bed as time goes on.

The fluid emerging from the bed will have little or no solute remaining -- at least until the
bulk of the bed becomes saturated. The break point occurs when the concentration of the
fluid leaving the bed spikes as unadsorbed solute begins to emerge. The bed has become

ineffective. Usually, a breakpoint composition is set to be the maximum amount of solute

that can be acceptably lost, typically something between 1 and 5 percent.
As the concentration wave moves through the bed, most of the mass transfer is occurring
in a fairly small region. This mass transfer zone moves down the bed until it "breaks
through". The shape of the mass transfer zone depends on the adsorption isotherm
(equilibrium expression), flow rate, and the diffusion characteristics. Usually, the shape
must be determined experimentally. .
6. Define Drying
Drying is a unit operation in which a liquid is separated from a solid by supplying heat,
resulting in evaporation of the liquid.
Drying is defined as the process of removal of moisture from a substance.
7. Define: Equilibrium moisture content.
Equilibrium moisture content can be defined as the moisture content of a substance when
at equilibrium with a given partial pressure of the vapour.
8. Discuss on the various methods of Drying
Direct Convective Drying: Drying is established through direct contact between the
product and the gas heating medium. Material reaches steady state temperature near gas
wet bulb temperature.
Indirect Conductive Drying: Drying is established from a heated surface in contact with
the product. The heating medium and product are separated by a wall. Material reaches
steady state temperature near liquid boiling point for constant rate drying.
Radiant Drying: Heat transfer is established by radiation from an energy source. There
is no contact from a heated surface or medium and the product.
9. Write short note on Drying Process.
Constant Rate Drying
Energy is used for (surface) evaporation only evaporation rate is primarily controlled by
the rate of heat transfer from the energy source
Falling Rate Drying
Energy is used for evaporation and product heat up, while the evaporation rate decreases.
Drying is now diffusion rate limited. Drying is controlled by the rate of diffusion of
moisture to the particle surface. The falling rate drying is influenced by the residence
time, particle temperature, particle size, porosity and vapor concentration surrounding the
particle.
10. Define Bound moisture
Bound moisture is defined as the moisture contained by a substance which exerts an
equilibrium vapour pressure less than that of pure liquid at the same temperature.
11. Define Unbound moisture
Unbound moisture is defined as it is the moisture contained by a substance which exerts
an equilibrium vapour pressure equal to that of pure liquid at the same temperature.

12. Define Free moisture

Free moisture is defined as it is the moisture contained by a substance in excess of the
equilibrium moisture.
13. What is freeze drying?
The substances which cannot be heated even at moderate temperatures, are frozen by
exposure to very cold air and placed in a vacuum chamber, where the moisture sublimes
and is pumped off by steam-jet ejectors or mechanical vacuum pumps. This phenomenon
is known as freeze drying.
14. What are the advantages of a screen- conveyor dryer?
(i) handle variety of solids continuously with a very gentle action
(ii) cost is reasonable
(iii) steam economy is high.
15. What is heat of wetting? Give examples.
When an adsorbent solid is immersed in a pure liquid, the evolution of heat, known as the
heat of wetting.
PART B
1. Name the principal adsorbents in commercial use and their properties.
2. Explain multistage counter current adsorption. Give some applications.
3. Distinguish between the two types of adsorption phenomena bringing out their
essential features.
4. Explain briefly on Adsorption isotherm and adsorption hysterisis.
5. Explain the various regimes of drying.
6. Explain the operations of various driers.

ANNA UNIVERSITY QUESTIONS, NOV/DEC 2006

1. State Ficks law of diffusion
Ficks first law of diffusion states that the flux (J) of diffusion is proportional to the
concentration gradient for the Z direction be expressed as
JA = -DAB CA/ Z
Where D AB is diffusivity or diffusion coefficient for component A.
ve sign indicates that the diffusion occurs in the direction of drop in concentration.
JA = -CDAB xA / Z
2. Define mass transfer coefficient. How mass transfer coefficient and diffusivity
are related in film theory?
According to film theory, mass transfer coefficient and diffusivity are related as K c = DAB
/ f where Kc is the mass transfer coefficient , D AB is the diifusivity and f is the film
thickness.
3. State Raoults law.
For an ideal solution, the equilibrium partial pressure P A* of a component at a
fixed temperature equals the product of its mole fraction in the liquid and the vapour
pressure(PVA) when it is pure at that temperature.
PA*= xA PVA
4. Define NTU & HTU
Number of transfer units (NTU)
The number of transfer units (NTU) required is a measure of the difficulty of the
separation. A single transfer unit gives the change of composition of one of the phases
equal to the average driving force producing the change.
Height of a transfer unit (HTU)
The height of a transfer unit (HTU) is a measure of the separation effectiveness of the
particular packings for a particular separation process.
5.
The vapor pressures of A and B are 200 mm Hg and 400 mm Hg. The total
pressure is 760 mm Hg. Estimate the relative volatility.
Relative volatility is the ratio of the vapor pressure of A to the vapor pressure of B at
the same temperature.
Relative volatility = 200 /400 = 0.5

6.
Define external Reflux ratio. How is it related with internal reflux ratio?
The molar ratio of the reflux to the distillate withdrawn from the column is the reflux
ratio.
R=L/D
7. Define critical solution temperature
The lower critical solution temperature (also known as the LCST) is the critical
temperature below which a mixture is miscible in all proportions. It can also be seen as
the shared minimum of the concave up spinodal and binodal curves. The LCST is in
general pressure dependent, with increased pressure generally increasing the LCST.
The upper critical solution temperature (also known as the UCST) is the critical
temperature above which a mixture is miscible in all proportions. It can also be seen as
the shared maximum of the concave down spinodal and binodal curves. The UCST is in
general dependent on pressure, and in polymer mixtures on polymer degree of
polymerization and polydispersity.
8. Define Decoction
A decoction is a method of extraction by boiling of dissolved chemicals, or herbal or
plant material, which may include stems, roots, bark and rhizomes.
9. Adsorption Hysteresis
Adsorption is a transient process. The amount of material adsorbed within a bed depends
both on position and time. Consider the time dependence. As fluid enters the bed, it
comes in contact with the first few layers of absorbent. Solute adsorbs, filling up some of
the available sites. Soon, the adsorbent near the entrance is saturated and the fluid
penetrates farther into the bed before all solute is removed. Thus the active region shifts
down through the bed as time goes on.

The
fluid
emerging from the bed will have little
or no
solute remaining -- at least until the bulk of the bed becomes saturated. The break point
occurs when the concentration of the fluid leaving the bed spikes as unadsorbed solute
begins to emerge. The bed has become ineffective.

10. Recommend the correct choice of driers for

a) Drying granular materials - Fluid Bed Dryer
b) Drying fruit juices - Spray Dryer

ANNA UNIVERSITY QUESTIONS, NOV/DEC 2007

1.

Differentiate between two fluxes JA and NA

A more general flux relation which is not restricted to isothermal, isobaric system
dy A
could be written as J A C DA B
, using this expression, NA could be written
dZ
as
N

C DA B

dy A
y
dZ

The mass (or molar) flux NA of a given species is a vector quantity denoting the amount
of the particular species, in either mass or molar units, that passes per given increment of
time through a unit area normal to the vector. The flux of species defined with reference
to fixed spatial coordinates, NA is
N

A A

Relation among molar fluxes:

For a binary system containing A and B,
dy A
N A C DA B
y AN
dZ
N A J A y AN
J A N A y AN

or

State the assumptions of Reynolds analogy

Reynolds postulated that the mechanisms for transfer of momentum, energy and mass are
identical. Accordingly,
2.

kc

Cp

f
2

Here h is heat transfer coefficient

f is friction factor
is velocity of free stream
The Reynolds analogy suggests a very simple relation between different transport
phenomena. This relation is found to be accurate when Prandtl and Schmidt numbers are
equal to one. This is applicable for mass transfer by means of turbulent eddies in gases. In

this situation, we can estimate mass transfer coefficients from heat transfer coefficients
or from friction factors.
State Kremer- Brown- Souder Equation and its significance
3.
The equation has been the tool for obtaining the maximum allowable vapor velocity in
vapor-liquid separation vessels (variously called flash drums, knockout drums, knockout
pots, compressor suction drums and compressor inlet drums). It has also been used for
the same purpose in designing trayed fractionating columns, trayed absorption columns
and other vapor-liquid contacting columns.
A vapor-liquid separator drum is a vertical vessel into which a liquid and vapor mixture
(or a flashing liquid) is fed and wherein the liquid is separated by gravity, falls to the
bottom of the vessel, and is withdrawn. The vapor travels upward at a design velocity
which minimizes the entrainment of any liquid droplets in the vapor as it exits the top of
the vessel.

where:
V = maximum allowable vapor velocity, m/s
L = liquid density, kg/m
V = vapor density, kg/m
k = 0.107 m/s (when the drum includes a de-entraining mesh pad)
4.

Draw the operating line for cocurrent absorption operation.

When do the operating lines of stripping and rectifying sections coincide with
diagonal in McCabe Thiele method?
At total reflux condition the operating lines of stripping and rectifying sections coincide
with diagonal in McCabe Thiele method
The total reflux condition represents operation with no product removal. All the overhead
vapor is condensed and returned as reflux. Consequently, the reflux ratio (L/D) is infinite.
This, in turn, makes the operating lines the 45 degree line (prove it to yourself by setting
D=0, and noticing that consequently L=V). With the operating lines on the diagonal, they
are as far as they can get from the equilibrium curve, so if the number of plates are
stepped off using the diagonal and the equilibrium curve, the number of theoretical stages
will be a minimum.
5.

6.

What is the temperature range of steam distillation

Steam distillation is a special type of distillation (a separation process) for temperature

sensitive materials like natural aromatic compounds. For example, the boiling point of
bromobenzene is 156 C and the boiling point of water is 100 C, but a mixture of the
two boils at 95 C. Thus, bromobenzene can be easily distilled at a temperature 61 C
below its normal boiling point.
Steam distillation can be used to extract some natural products - for example, to extract
eucalyptus oil from eucalyptus, citrus oils from lemon or orange peel, and to extract oils
used in perfumes from various plant materials.

7.

Show the effect of temperature on the extraction system

Lixiviation
8.
Lixiviation is the process of separating soluble from insoluble substances by dissolving
the former in water or some other solvent. lixiviation is the process of leaching alkaline
salts from ashes by pouring water on them.
9.

Adsorption Isotherm

Adsorption equilibrium data is typically

plotted in the form of an adsorption
isotherm (i.e. at constant temperature)
with the mass adsorbed on the y-axis and
the
mass in the fluid on the x-axis. The
shape of the curve is significant and
factors heavily into design. "Favorable"
isotherms permit higher solid loadings at
lower solution concentrations. These
tend to start out steep and level out.
Isotherms which start out flat are "unfavorable", since they only work well at high

concentrations of solute. Usually, as temperature increases the amount adsorbed

decreases (permitting thermal regeneration).

10.

What are funicular and pendular states of drying

In the first falling rate period after the critical point, the liquid/vapor meniscus retreats
into pores of the body. The moisture still exerts its full vapor pressure and is transferred
mainly by capillarity, as liquid is in the funicular state.
In the second falling rate period moisture is held in the finest capillaries and
evaporation occurs inside the body at the boundary between the funicular (continuous
liquid) and pendular (isolated pockets of liquid) regions. Transport in pendular region
occurs by evaporation-condensation mechanism. The drying rate decreases sharply and
takes place in all inner portions of the material.

IMPORTANT 16 MARKS QUESTIONS

1. Determine the diffusivity of Co 2 (1), O 2 (2) and N 2 (3) in a gas mixture having
the composition: Co2 : 28.5 %, O2 : 15%, N 2 : 56.5%, The gas mixture is at 273 k
and 1.2 * 10 5 Pa. The binary diffusivity values are given as: (at 273 K)
D 12 P = 1.874 m 2 Pa/sec
D 13 P = 1.945 m 2 Pa/sec
D 23 P = 1.834 m 2 Pa/sec
Calculations:
Diffusivity of Co 2 in mixture
D 1m

y 2
D 12

where y 2
y 3

Therefore

y 3
D 13

y2
y2 y3

0.15
0.21
0.15 0.565

0.565
0.79
0.15 0.565

y3
y2 y3

D 1m P

1
0.21
0.79

1.874 1.945

= 1.93 m 2.Pa/sec
Since P = 1.2 * 10 5 Pa,

1.93

D 1m

1.2 * 10

1.61 * 10 5 m 2 sec

Diffusivity of O 2 in the mixture,

D 2m

y 1
D 21

Where y 1

y 3
D 23
y1

y1 y3

0.285
0.335
0.285 0.565

(mole fraction on-2 free bans).

and

y 3

y3
y1 y3

0.565
0.665
0.285 0.565

and
D 21 P = D 12 P = 1.874 m 2.Pa/sec
Therefore
D 2m P

1
0.335 0.665

1.874 1.834

= 1.847 m 2.Pa/sec
D 2m

1.847
1.2 * 10 5

1.539 * 10 5 m 2 sec

By Similar calculations Diffusivity of N 2 in the mixture can be calculated, and is found to

be, D 3m = 1.588 * 10 5 m 2/sec.
2. Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25C.
Concentration of oxygen at planes 2 mm apart are 10 and 20 volume %
respectively. Nitrogen is non-diffusing.
(c) Derive the appropriate expression to calculate the flux oxygen. Define units
of each term clearly.
(d) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89 * 10 5
m 2/sec.
Solution:
Let us denote oxygen as A and nitrogen as B. Flux of A (i.e.) N A is made up of two
components, namely that resulting from the bulk motion of A (i.e.), Nx A and that
resulting from molecular diffusion J A:
N A Nx A J A ---------------------------------- (1)

From Ficks law of diffusion,

D AB

dCA

----------------------------------------- (2)

dz

Substituting this equation (1)

N A Nx

D AB

dCA
dz

----------------------------- (3)

Since N = N A + N B and x A = C A / C equation (3) becomes

NA NA NB

CCA

D AB

dCA
dz

Rearranging the terms and integrating between the planes between 1 and 2,
dz

cD

AB

C A2

A1

dC A

N AC C A N A N B

-------------- (4)

Since B is non diffusing N B = 0. Also, the total concentration C remains constant.

Therefore, equation (4) becomes
dC A
z
C
C A 2
A
1
CD AB
N AC N AC A

C C A2
1
ln
NA
C C A1

Therefore,
NA

CD AB
z

ln

C C A2
C C A1

---------------------------- (5)

Replacing concentration in terms of pressures using Ideal gas law, equation (5) becomes
NA

D AB P t
RTz

ln

P t P A2
P t P A1

--------------------------- (6)

where
D AB = molecular diffusivity of A in B
P T = total pressure of system
R = universal gas constant
T = temperature of system in absolute scale
z = distance between two planes across the direction of diffusion

P A1 = partial pressure of A at plane 1, and

P A2 = partial pressure of A at plane 2
Given:
D AB = 1.89 * 10 5 m2/sec
P t = 1 atm = 1.01325 * 10 5 N/m 2
T = 25C = 273 + 25 = 298 K
z = 2 mm = 0.002 m
P A1 = 0.2 * 1 = 0.2 atm (From Ideal gas law and additive pressure rule)
P A2 = 0.1 * 1 = 0.1 atm
Substituting these in equation (6)
NA

1.89 * 10 5 1.01325 * 10 5 ln 1 0.1

8314 298 0.002
5

1 0. 2

= 4.55 * 10 kmol/m .sec

3. Methane diffuses at steady state through a tube containing helium. At point 1 the
partial pressure of methane is p A1 = 55 kPa and at point 2, 0.03 m apart P A2 = 15 KPa.
The total pressure is 101.32 kPa, and the temperature is 298 K. At this pressure and
temperature, the value of diffusivity is 6.75 * 10 5 m 2/sec.
iii)
calculate the flux of CH 4 at steady state for equimolar counter diffusion.
iv)
Calculate the partial pressure at a point 0.02 m apart from point 1.
Calculation:
For steady state equimolar counter diffusion, molar flux is given by
N

Therefore;
NA

D AB
RT z

p A1 p A 2

--------------------------- (1)

6.75 * 10 5
55 15 kmol
8.314 * 298 * 0.03
m 2 . sec
kmol
3.633 * 10 5
m 2 sec

And from (1), partial pressure at 0.02 m from point 1 is:

3.633 * 10 5

6.75 * 10 5
55 p A
8.314 * 298 * 0.02

p A = 28.33 kPa
4. In a gas mixture of hydrogen and oxygen, steady state equimolar counter
diffusion is occurring at a total pressure of 100 kPa and temperature of 20C. If the
partial pressures of oxygen at two planes 0.01 m apart, and perpendicular to the
direction of diffusion are 15 kPa and 5 kPa, respectively and the mass diffusion flux

of oxygen in the mixture is 1.6 * 10 5 kmol/m 2.sec, calculate the molecular diffusivity
for the system.
Solution:
For equimolar counter current diffusion:
D AB
p A1 p A2 ------------------------ (1)
NA
RTz
where
N A = molar flux of A (1.6 * 10 5 kmol/m 2.sec):
D AB = molecular diffusivity of A in B
R = Universal gas constant (8.314 kJ/kmol.k)
T = Temperature in absolute scale (273 + 20 = 293 K)
z = distance between two measurement planes 1 and 2 (0.01 m)
P A1 = partial pressure of A at plane 1 (15 kPa); and
P A2 = partial pressure of A at plane 2 (5 kPa)
Substituting these in equation (1)
D AB

1.6 * 10 5

8.314 293 0.01

15 5

Therefore, D AB = 3.898 * 10 5 m 2/sec

5. A tube 1 cm in inside diameter that is 20 cm long is filled with Co 2 and H2 at a
total pressure of 2 atm at 0C. The diffusion coefficient of the Co 2 H2 system
under these conditions is 0.275 cm2/sec. If the partial pressure of Co2 is 1.5 atm at
one end of the tube and 0.5 atm at the other end, find the rate of diffusion for:
iv)
v)
vi)

steady state equimolar counter diffusion (N A = - N B)

steady state counter diffusion where N B = -0.75 N A, and
steady state diffusion of Co2 through stagnant H2 (NB = 0)

i) N A C D AB

dy

dz

N A N B

Given
NB = - NA
Therefore N A C D AB

dy

dz

(For ideal gas mixture C A

B

D AB

dz

pA
where pA is the partial pressure of A; such that p A + p
RT

= P)

d p A RT
dz
For isothermal system, T is constant
Therefore N A D A B

dCA

Therefore N A

D AB d p A
RT

Z2

(i.e.)
N

d z

dz

RT z

d pA

RT

Z1

D AB

P A2

D AB

p A1 p A2

P A1

---------------------------------- (1)

where Z = Z 2 Z 1
Given: D AB = 0.275 cm 2/sec = 0.275 * 10 4 m 2 /sec ; T = 0C = 273 k

0.275 * 10 4
1.5 * 1.01325 * 10 5 0.5 * 1.01325 * 10 5
A
8314 * 273 * 0.2
k mol
6.138 * 10 6
m 2 sec

Rate of diffusion = N A S, Where S is surface area

Therefore rate of diffusion = 6.138 * 10-6 * r 2
= 6.138 * 10 6 * (0.5 * 10 2) 2
= 4.821 * 10 10 k mol/sec
= 1.735 * 10 3 mol/hr.
ii) N A C D AB

dy

dz

N A N B

given: N B = - 0.75 N A
Therefore N A C D AB

dy

C D AB
N A 0.25 y

dz

dy

dz

N A 0.75 N A

0.25 y

dy

C D AB

d z C D AB

dy

dz

1 0.25 y

for constant N A and C

Z2

d z CD AB

Z1

y A2

dy

y A1

1 0.25 y

A
A

dx
1
a b x b ln a b x

4 CD AB

1
y
ln 1 0.25 y A y A2
A1
0
.
25

1 0.25 y A 2

ln
1 0.25 y A 1 ---------------------------------- (2)

N A z C D AB

Given:
C

p
2 * 1.01325 * 10 5

0.0893 K mol m 3
RT
8314 * 273

A1

A2

p A1

1.5
0.75
2
0.5

0.25
2

P
p A2

P
Substituting these in equation (2),
NA

4 * 0.0893 * 0.275 * 10 4 1 0.25 * 0.25

ln 1 0.25 * 0.75
0 .2
kmol
7.028 * 10 6
m 2 sec

Rate of diffusion = N A S = 7.028 * 10 6 * * (0.5 * 10 2) 2

= 5.52 * 10 10 kmol/sec
= 1.987 * 10 3 mol/hr.
iii) N A CD AB

dy

dz

N A N B
dy

Given: N B = 0 ,Therefore N A CD AB
Z2

N A d z CD AB
Z1

y A2

NA

1 y

ln

1 y

A2

A1

0.0893 * 0.275 * 10 4
0.2
kmol
1.349 * 10 5
m 2 . sec

y A1 1 y A

CD AB
Z

dy

dz

1 0.25
ln 1 0.75

Rate of diffusion = 1.349 8 10 5 * * (0.5 * 10 2) 2 = 1.059 Kmol / sec = 3.814 mol/hr

6. Calculate the rate of diffusion of butanol at 20C under unidirectional steady
state conditions through a 0.1 cm thick film of water when the concentrations of
butanol at the opposite sides of the film are, respectively 10% and 4% butanol by
weight. The diffusivity of butanol in water solution is 5.9 * 10 6 cm 2/sec. The
densities of 10% and 4% butanol solutions at 20C may be taken as 0.971 and 0.992

g/cc respectively. Molecular weight of Butanol (C 4 H 9 OH) is 74, and that of water
18.
Calculations
For steady state unidirectional diffusion,
NA

D AB
z

x A1 x A2
x B, lm

where C is the average molar density.

avg

Conversion from weight fraction the Mole fraction:

x

A1

A2

0.1 74

0.026

0.1 74 0.9 18
0.04 74
0.04 74 0.96 18

0.010

Average molecular weight at 1 & 2:

1
19.47 kg Kmol
0.9 18
1

18.56 kg Kmol
0.04 74 0.96 18

M1

M2

0.1 74

1 M 1 2

M2

avg

0.971 19.47 0.992 18.56

2

= 0.0517 gmol / cm 3
= 51.7 kmol/m 3
x B,lm

(i.e.)

x B 2 x B1

ln x B 2 x B1

x B,lm

1 0.01

1 x A2 1 x A1
1 x A2

ln

1 x A1

1 0.026
1 0.01
ln

1 0.026

0.016
0.982
0.0163
D AB
x A1 x A2

2 M avg
x B, lm

Therefore N A

5.9 * 10 6 * 10 4 * 51.7
2

0.1 * 10
kmol
4.97 * 10 7
m 2 sec
gmol
1.789
m 2 .hr .
g
1.789 * 74
2
m . hr .
g
132.4
m 2 . hr .

0.026 0.010
0.982

7. Explain in detail the method of estimation of number of stages by Mc CabeThiele method.

The graphical McCabe-Thiele Method can be used to determine the number of ideal
stages and feed tray location. To do this, you make a plot showing the equilibrium curve,
feed line, and operating lines for the rectifying and stripping sections (all on the same
axes), and then find answers by graphical construction.
A standard (beginner) distillation problem provides you with xF, q, xD, xB, and RD;
although not necessarily directly. You may need to use the overall material balances to
find some of the compositions; to calculate the q factor from temperature and
composition data; and/or determine the reflux ratio based on the limiting minimum value.
Once you have these values, the solution procedure is:
1.
2.
3.
4.
5.
6.

Plot the equilibrium curve.

Calculate the slope q/(q-1) of the feed line.
Plot the feed line using x=xF and the slope.
Calculate the y-intercept of the rectifying line xD/(RD+1).
Plot the rectifying line using (xd,xd) and the intercept.
Draw the stripping line connecting the intersection of the rectifying and feed lines
and the point (xb,xb).
7. Correct for stage efficiency by drawing the "effective" equilibrium curve between
the equilibrium curve and the operating lines.
8. "Step off" equilbrium stages.
The number of stages is found graphically by constructing triangles on the diagram. You
can start from either the top or the bottom. From a product composition on the operating
line (either (xd,xd) or (xb,xb)) move horizontally to the equilibrium curve, then vertically
back to the operating line, horizontally to the equilibrium curve, etc., constructing
triangles along the way. Always make the steps between the equilibrium curve and the
lower of the two operating lines (the rectifying line in the top half of the column, the
stripping line in the bottom half -- if you're looking for the bottom line, the switchover
point will be clear). The number of triangles you draw is the number of stages in your

column. If you are using the equilibrium curve to step from, you are determining ideal
stages.
If you don't want to draw, you can do the same thing, iteratively solving for the various
equation intersections. You'll need to be pretty careful with your "bookkeeping" if you try
this.
To apply Murphree tray efficiencies, construct an effective equilibrium curve between the
equilibrium and operating curves, and step using the effective curve to determine actual
separation stages. Remember that a partial reboiler or partial condenser is by definition an
ideal stage, so you use the ideal equilibrium curve (not the effective) for these stages.
The optimum feed tray is the triangle with one corner on the rectifying line and one on
the stripping line. Putting the feed anywhere else increases the number of stages needed
to make the separation. To visualize this, notice that the closer the operating line is to the
equilibrium curve, the smaller the stepping triangles become. Introducing the feed at the
intersection of the rectifying and stripping lines maximizes the size of the triangles and so
leads to the fewest steps.
When analyzing existing distillation systems, the actual feed entry point may not be at the
optimum (the tray where the operating lines intersect). In this case, the tray stepping
should switch from the rectifying line to the operating line at the actual feed tray location.
8. Enthalpy-Concentration Method or PONCHAN SAVARIT METHOD
Distillation calculations can be performed graphically on an enthalpy-concentration (Hx)
diagram. This approach is sometimes called the Ponchon-Savarit Method. Working on
the Hx diagram is more general than a McCabe-Thiele construction, because it takes
direct account of the thermal effects and does not require an assumption of equimolal
overflow.
The very shape of the Hx diagram provides a clue as to the importance of the energy
balances. If the dew point and bubble point lines are more or less straight and roughly
parallel, it indicates that the latent heat of vaporization is basically constant with respect
to composition. This is the prerequisite for assuming equimolar overflow, and so the
energy balances may be neglected. If the saturation curves show significant changes in
curvature or separation, it suggests that to assume equimolar overflow will introduce
error.
Points for the feed and product can be located on the Hx diagram; for our purposes we'll
call them the F, D, and B points. The coordinates are their composition and enthalpy. If
the products are saturated liquid, as is the case for total condensers without subcooling
and for partial reboilers, these points will lie on the bubble point curve on the Hx
diagram.

Overall Enthalpy Balance

The steady-state enthalpy balance for a distillation column is:

F*h;F = D*h;D + Q;C + B*h;B - Q;R
One of the tools of graphical solution is the notion of colinearity. This has been used
before if you have used lever arm principles. For an adiabatic process, the feed and
products will be colinear on an Hx diagram. Thus, it is useful to redefine our distillation
system to be adiabatic, by bringing the condenser and reboiler inside the system
boundary. Rearranging the enthalpy balance gives:
F*h;F = D*(h;D + 'quot(Q;C,D)) + B*(h;B - 'quot(Q;R,B))
If we then define:
h;Dp = h;D + 'quot(Q;C,D)
h;Bp = h;B - 'quot(Q;R,B)
The enthalpy balance becomes:
F*h;F = D*h;Dp + B*h;Bp
Substituting from the overall material balance:
(D+B)*h;F = D*h;Dp + B*h;Bp
h;F = 'quot(D*h;Dp, D+B) + 'quot(B*h;Bp, D+B)
After this modification, the system is adiabatic, so a line can be drawn through the feed
point, F, and the points (xD, hDp) and (xB, hBp). This line represents the system enthalpy
balance, and so is called the overall enthalpy line. Remember: for a given separation only
one of the reboiler and condenser duties is independent. So, you will probably want to
pick one duty and then construct the line through the feed point to determine the other
duty.

Reflux Ratio
As before, the reflux ratio can be determined from the L/V ratio, and for this formulation
is given by:
R;D = 'quot(h;Dp - H;y1,H;y1 - h;D)
where hD is the enthalpy of the overhead product, Hy1 the enthalpy of the vapor entering
the condenser, and hDp the adjusted enthalpy of the overhead. Notice that this represents
the ratio of distances on the Hx diagram: the numerator is the vertical distance between
the hDp point and the dew point saturation curve, while the denominator is the distance
between the saturation curves.
A calculation often begins by using the overhead product composition and temperature to
obtain hDand Hy1. These in turn are used with the reflux ratio to get hDp. Then the overall
enthalpy line is drawn from hDp through the feed point, and the intersection with xB gives
hBp.

Summary of Procedure
1. Obtain enthalpy-composition diagram
2. Fix the feed point F, and product points D and B using stream compositions and
enthalpies
3. Use the overhead product enthalpy and the reflux ratio to find the adjusted
enthalpy of the overhead. Plot it as point D', on a vertical line with point D.
4. Construct the overall enthalpy line from point D' through the feed point. It
intersects a vertical line drawn through point B at point B'.
5. Plot point V1. For a total condenser, the composition entering the condenser is the
same as the overhead product, so this point will be vertically above point D on the
saturated vapor curve.
6. Follow the tie line from point V1 to the saturated liquid curve. This intersection
will be point L1.
7. Construct an operating line connecting points D' and L1. The intersection of the
operating line with the saturated vapor curve will be point V2.
8. Repeat the two preceding steps until one of the V or L points is to the left of the
overall enthalpy line. Once it is crossed, construct operating lines using points Li
and B'.
9. When xi is less than xB, construction is finished.
The number of stages can be read as the number of complete triangles.

Limiting Conditions
At total reflux, operating lines are vertical (infinite slope). This can be used to determine
the minimum number of stages. Not that operating curves are not required to do this -only the endpoint compositions.
While doing constructions on the yx diagram, a "pinch" was defined as the intersection
point between the equilibrium curve and the operating curve. On an Hx diagram, there
isn't an equilibrium curve -- it has expanded to a region, and each point from the xy
equilibrium curve is represented by a tie line. The "pinch point" also expands, resulting in
a single line where the operating and tie lines overlap.
Minimum reflux still corresponds to a pinch at the feed conditions, so to determine the
minimum reflux a line must be constructed so that the overall enthalpy line coincides
with the tie line that runs through the feed point.

9. Convective Mass Transfer Coefficient

In the study of convective heat transfer, the heat flux is connected to heat transfer
coefficient as
Q A q h t s t m -------------------- (1)
The analogous situation in mass transfer is handled by an equation of the form
N A k c C As C A -------------------- (2)
The molar flux N A is measured relative to a set of axes fixed in space. The driving force
is the difference between the concentration at the phase boundary, CAS (a solid surface or
a fluid interface) and the concentration at some arbitrarily defined point in the fluid
medium, C A . The convective mass transfer coefficient kC is a function of geometry of the
system and the velocity and properties of the fluid similar to the heat transfer coefficient,
h.

Significant Parameters in Convective Mass Transfer

Dimensionless parameters are often used to correlate convective transfer data. In
momentum transfer Reynolds number and friction factor play a major role. In the
correlation of convective heat transfer data, Prandtl and Nusselt numbers are important.
Some of the same parameters, along with some newly defined dimensionless numbers,
will be useful in the correlation of convective mass-transfer data.The molecular
diffusivities of the three transport process (momentum, heat and mass) have been defined
as:
Momentum diffusivit y

Thermal diffusivit y

----------------------------- (3)

k
C p --------------------------- (4)

and
Mass diffusivit y D AB --------------------------- (5)

It can be shown that each of the diffusivities has the dimensions of L 2 / t, hence, a ratio of
any of the two of these must be dimensionless. The ratio of the molecular diffusivity of
momentum to the molecular diffusivity of heat (thermal diffusivity) is designated as the
Prandtl Number
Cp
Momentum diffusivit y

Pr

Thermal diffusivit y

------------------------ (6)

The analogous number in mass transfer is Schmidt number given as

Momentum diffusivit y

Sc

Mass diffusivit y
D AB
D AB -------------- (7)

The ratio of the molecular diffusivity of heat to the molecular diffusivity of mass is
designated the Lewis Number, and is given by
Thermal diffusivit y

k
Le

Mass diffusivit y
D AB
C p D AB ------------- (8)

Lewis number is encountered in processes involving simultaneous convective transfer of

mass and energy.
Let us consider the mass transfer of solute A from a solid to a fluid flowing past the
surface of the solid. The concentration and velocity profile is depicted. For such a case,
the mass transfer between the solid surface and the fluid may be written as
N A k c C As C A ---------------------- (1 a)
Since the mass transfer at the surface is by molecular diffusion, the mass transfer may
also described by

dC

D AB

dy

y 0

------------------------- (9)

When the boundary concentration, CAs is constant, equation (4.9) may be written as
N

d C A C As

D AB

dy

---------------------- (10)

y 0

Equation (1a) and (10) may be equated, since they define the same flux of component A
leaving the surface and entering the fluid
k

C A s

D AB

d
C
dy

As

y 0

---------(11)

This relation may be rearranged into the following form:

kc
D AB

d C A C As d y

C A C A

-------------------- (12)
y 0

Multiplying both sides of equation(12) by a characteristic length, L we obtain the

following dimensionless expression:
kc L
D AB

d C A C As d y

C A S

C A L

y 0

----------------- (13)

The right hand side of equation (13) is the ratio of the concentration gradient at the
surface to an overall or reference concentration gradient; accordingly, it may be
considered as the ratio of molecular mass-transport resistance to the convective masstransport resistance of the fluid. This ratio is generally known as the Sherwood number,
Sh and analogous to the Nusselt number Nu, in heat transfer.
10. Types of reboilers

The most critical element of reboiler design is the selection of the proper type of reboiler
for a specific service. Most reboilers are of the shell and tube heat exchanger type and
normally steam is used as the heat source in such reboilers. However, other heat transfer
fluids like hot oil or Dowtherm (TM) may be used. Fuel-fired furnaces may also be used
as reboilers in some cases.
Commonly used heat exchanger type reboilers are:

Image 1: Typical steam-heated kettle reboiler for distillation towers

Kettle reboilers
Image 1 depicts a typical steam-heated kettle reboiler. Kettle reboilers are very simple
and reliable. They may require pumping of the column bottoms liquid into the kettle, or
there may be sufficient liquid head to deliver the liquid into the reboiler. In this reboiler
type, steam flows through the tube bundle and exits as condensate. The liquid from the
bottom of the tower, commonly called the bottoms, flows through the shell side. There is
a retaining wall or overflow weir separating the tube bundle from the reboiler section
where the residual reboiled liquid (called the bottoms product) is withdrawn, so that the
tube bundle is kept covered with liquid.

Image 2: Typical horizontal thermosyphon reboiler

Thermosyphon reboilers
These do not require pumping of the column bottoms liquid into the reboiler. Natural
circulation is obtained by using the density difference between the reboiler inlet column
bottoms liquid and the reboiler outlet liquid-vapor mixture to provide sufficient liquid
head to deliver the tower bottoms into the reboiler. Thermosyphon reboilers are more
complex than kettle reboilers and require more attention from the plant operators.
There are many types of thermosyphon reboilers. They may be vertical or horizontal and
they may also be once-through or recirculating. Some fluids being reboiled may be
temperature-sensitive and, for example, subject to polymerization by contact with high
temperature heat transfer tube walls. In such cases, it is best to have a high liquid
recirculation rate to avoid having high tube wall temperatures which would cause
polymerization and, hence, fouling of the tubes. The thermosiphon reboiler depicted in
Image 2 is a typical steam-heated recirculating thermosiphon reboiler.
Relative volatility of feed to reboiler must be considered before designing thermosyphon
reboilers.

Image 3: A forced recirculating fired heater reboiler

Fired reboiler
Fired heaters (furnaces) may be used as a distillation column reboiler. A pump is required
to circulate the column bottoms through the heat transfer tubes in the furnace's

convection and radiant sections. Image 3 depicts a fired heater being used in a
configuration that provides recirculation of the column bottoms liquid. However, with
some relatively minor changes inside the bottom section of the distillation column, a fired
heater can also be used in once-through configuration.
The heat source for the fired heater reboiler may be either fuel gas or fuel oil. Coal would
rarely, if ever, be used as the fuel for a fired heater reboiler.

Image 4: Typical steam-heated forced circulation reboiler for distillation towers

Forced circulation reboilers

This type of reboiler uses a pump to circulate the column bottoms liquid through the
reboilers. Image 4 depicts a typical steam-heated forced circulation reboiler.
It should be noted steam is not the only heat source that can be used. Any fluid stream at
a high enough temperature could be used for any of the many shell and tube heat
exchanger reboiler types.
11. Steam Distillation
Steam distillation is a purifying technique used to distill a mixture of immiscible
substances. The solution boils at lower temperature than either of the separate
components (below 100 oC), a factor that causes substances to codistill and prevent
decomposition of unstable or high boiling point substances; furthermore, because the
substances are immiscible, the distillate will be divided into layers; the desired product
can then be isolated using a separatory funnel. Steam distillation is often used in
isolationg liquids from natural sources

12. Liquid - Liquid Extraction

Liquid extraction produces separation of the constituents of a liquid solution by contact
with another insoluble liquid. If the components of the original solution distribute
differently between the two liquids, separation will result. The component balances will
be essentially identical to those for leaching, but there are two major differences that
complicate the calculations:

the carrier phase is a liquid, not a solid, so the physical separation techniques will
change, and
two distinct phases develop, so the simplicity of uniform solution is lost.

Common applications of liquid extraction include: the separation and purification of lube
oils, separation of penicillin from fermentation broth, etc. Extraction is driven by
chemical differences, not by vapor pressure differences, and so can be used in situations
when distillation is impractical. For instance, it can be used to separate materials with
similar boiling points (so that distillation is impractical) or mixtures containing
temperature sensitive compounds.
Distillation and evaporation produce finished products; liquid extraction generally does
not. The products are still mixtures, although with new compositions, and these must be
separated to obtain final products. Secondary separation often requires distillation or
evaporation. The overall process cost thus must be considered when choosing extraction.
Extraction may become economical for dilute aqueous solutions when evaporation would
require vaporization of very large amounts of water.

Terminology

Certain terms are commonly used when describing extraction processes. The solution to
be extracted is called the feed, the liquid used in contacting is the solvent. The enriched
solvent product is the extract and the depleted feed is called the raffinate.
Extraction processes may be be single stage, multistage crosscurrent, or countercurrent.
Cocurrent extraction offers no advantages over a single stage (convince yourself of this!).
This class will primarily be concerned with countercurrent systems.

Equilibrium
Extraction calculations
require an understanding
of ternary equilibrium. You
probably should refresh
your memory on how
ternary diagrams are read
and used. I would
anticipate that you learned
this in your material
balance course.
One new term that may not
be familiar is the plait
point. This point is located
near the top of the twophase envelope, at the
inflection point. It
represents a condition
where the 3-component
mixture separates into two phases, but the phases have identical compositions. (Compare
this with an azeotropic mixture of liquid and vapor.)
There are two main classes of liquid-liquid equilibrium that occur in extraction. A Class I
system is the one I expect you are familiar with; it has one immiscible pair of compounds
and produces the familiar envelope. Class II mixtures have two pair of immiscible
compounds, and so the two-phase envelope crosses the triangular diagram like a bridge.
Class I mixtures are the most common and are
preferable -- so if you can pick a solvent to get
a Class I, you usually want to do so. Classes
can change with temperature, so that is also a
concern.
Solvent Selection

One of the key decisions when designing an extraction process is the choice of the
solvent to be used. Issues include:

Selectivity -- compare the equilibrium ratio of solute in each phase

Distribution Coefficients -- y/x at equilibrium; large values preferable
Insolubility -- solvent should not be soluble in carrier liquid
Recoverability -- consider constraints (i.e. azeotropes)
Density -- must be different so that phases can be separated by settling
Interfacial Tension -- if too high, liquids will be difficult to mix
Chemical Reactivity -- solvent should be inert and stable
Viscosity, Vapor Pressure, Freezing Point -- low values make storage easier
Safety -- toxicity, flammability
Cost

13. Types of Adsorption

Depending on the nature of attractive forces existing between the adsorbate and
adsorbent, adsorption can be classified as:
i) Physical adsorption
ii) Chemical adsorption
i) Physical adsorption (Physisorption)
In physical adsorption, the forces of attraction between the molecules of the adsorbate
and the adsorbent are of the weak van der Waals' type. Since the forces of attraction are
weak, the process of physisorption can be easily reversed by heating or decreasing the
pressure of the adsorbate (as in the case of gases).
ii) Chemical adsorption (Chemisorption)
In chemisorption, the forces of attraction between the adsorbate and the adsorbent are
very strong; the molecules of adsorbate form chemical bonds with the molecules of the
adsorbent present in the surface.
Adsorption is generally accompanied by release of energy, that is, most adsorption
processes are exothermic in nature. Adsorption is a spontaneous process; therefore its free
energy change is negative (DG<0). However, the entropy change associated with
adsorption is generally negative because the adsorbate molecules lose their translation
freedom when they get attached to the surface of the adsorbent. Therefore, in order for
DG to be negative, the enthalpy change (DH) must be sufficiently negative, such that,
(DG=DH-TDS)<0. This explanation accounts for exothermic adsorption processes. In
cases, where endothermic adsorption occurs as in the case of hydrogen adsorption on
glass, the entropy change DS is sufficiently positive such that DG remains negative.
Enthalpy of adsorption, which is the enthalpy change for the adsorption of one mole of an

adsorbate on an adsorbent surface, is usually in the range of 20 kJ/mole to 40kJ/mole

while for chemisorption, the values are an order of magnitude high, that is, 200 kJ/mole
to 400 kJ/mole.
Comparison between Physisorption and Chemisorption

14. Rate of drying curve

Figure 1 represents a typical drying curve for virtually any product. Drying occurs in
three different periods, or phases, which can be clearly defined.
The first phase, or initial period, is where sensible heat is transferred to the product and
the contained moisture. This is the heating up of the product from the inlet condition to
the process condition, which enables the subsequent processes to take place. In some
instances, pre-processing can reduce or eliminate this phase. For example, if the feed
material is coming from a reactor or if the feed is preheated by a source of waste energy,
the inlet condition of the material will already be at a raised temperature.
The rate of evaporation increases dramatically during this period with mostly free
moisture being removed.
During the second phase, or constant rate period, free moisture persists on the surfaces
and the rate of evaporation alters very little as the moisture content reduces. During this
period, drying rates are high, and higher inlet air temperatures than in subsequent drying
stages can be used without detrimental effect to the product. There is a gradual and
relatively small increase in the product temperature during this period.
Interestingly, a common occurrence is that the time scale of the constant rate period may
determine and affect the rate of drying in the next phase.
The third phase, or falling rate period, is the phase during which migration of moisture
from the inner interstices of each particle to the outer surface becomes the limiting factor
that reduces the drying rate.