FORCED DRAFT TRAY DRYER

OBJECTIVE:

To study the drying characteristics of a solid under forced draft condition.

AIM:
 To calculate the rate of drying.
 To calculate the critical moisture content.
 To plot the graph of time vs moisture content.
 To plot the graph of time vs rate of drying.
 To plot the graph of moisture content vs rate of drying.
 To plot the graph of mass velocity of air vs rate of drying.

INTRODUCTION:
In many cases, drying of materials is the final operation in the manufacturing
process, carried out immediately prior to packaging or dispatch. Drying refers to
the final removal of water, and the operation often follows evaporation, filtration
or crystallization. Drying iscarried out for one or more of the following reasons:
 To reduce the cost of transport.
 To make a material more suitable for handling.
 To provide definite properties.
 To remove moisture this may otherwise lead to corrosion.

THEORY
Drying of solids is considered to occur in two stages, a constant rate period followed
bya falling rate period. In the constant rate period, the rate of drying corresponds to
the removal of water from the surface of the solid. The falling rate period corresponds
to the removal of water from the interior of the solid. The rate in either case is
dependent on:
 Flow rate of air
 The Solid characteristics
 Tray material.

The drying rate of a solid is a function of temperature, humidity, flow rate and
transport properties of drying gas. The rate of drying can be determined for a
sample of a substance by suspending it over an electronic balance in the duct.
The weight of the drying sample can then be measured as a function of time.
Let ws is mass of solid A is drying area, x is moisture content at any time t. Then
the rateof drying is given as:

1
 Where x is moisture content difference and t is time difference.
Rate of drying curve:
From the data obtained during such a test, a curve of moisture content as a
function of time can be plotted. This will be useful directly in determining the
time required for dryinglarger batches under the same drying conditions. Much
information can be obtained ifthe data are converted into rates of drying.
Determine the critical moisture contents, xc (this is the point at which falling rate
is start) from the above graph. xe is equilibrium moisture content (at this point
no more drying is possible).
In forced draft dryer we can show the effect of air flow rate on rate of drying.

 DESCRIPTION:
The set up consists of an insulated double wall chamber. Inside the chamber a
tray is attached directly to an electronic weighing balance, which is fitted on top,
outside the chamber. Air from a blower passes through a heating chamber is used
as drying agent. Flow control is fitted to regulate the airflow rate. Manometer is
provided to measure the air flow rate.

 UTILITIES REQUIRED:
 Electricity Supply: Single Phase, 220 V AC, 50 Hz, 5-15 Amp combined socket
with earth connection. Earth voltage should be less than 5 volts.
 Bench Area Required: 0.75 m x 2 m
 Drying solids: sand/asbestos/silica, feed Size: 5-10 mm

 EXPERIMENTAL PROCEDURE:
STARTING PROCEDURE:
 Prepare a mixture of known weight of sand and water (30% - 50% water).
 Note down the weight of sand only.
 Fill the tray with above prepare mixture.
 Ensure that switches given on the panel are at OFF position.
 Switch ON the main power supply.
 Switch ON of the blower and set the flow rate of air by adjusting the control
valve.
 Set the temperature of heater (ambient to 90ºC) by PID controller.
 Switch ON the heater.
 Wait till constant temperature achieves, put tray in the drying chamber.
 Note down the temperatures and manometer readings.
 Start the stopwatch.
 Record the above reading till three consecutive balance readings are

2
 unchanged.
 Repeat the experiment for different solid material.
 Repeat the experiment for different air flow rate.
 Repeat the experiment for different temperatures.
CLOSING PROCEDURE:
 When experiment is over switch OFF the blower.
 Switch OFF the main power supply.
 Remove the dry solid material from tray and clean the tray properly.

 OBSERVATION & CALCULATION:

DATA:

Area of the tray A = m2

Diameter of orifice do = 0.026 m
Diameter of pipe dp = 0.052 m
Coefficient of discharge Cd = 0.6
Acceleration due to gravity g = 9.81 m/s2
Density of water ρw = 1000 kg/m3
Density of air ρa =1.21 kg/m3

OBSERVATIONS:
o
T = C
ww = kg
ws = kg

OBSERVATION TABLE:

S.No. t (s) w (kg) R1 (cm) R2 (cm)

1
2
3

3
CALCULATIONS:

CALCULATION TABLE:1

Sr. No. t (min) ∆t (min) x x

1
2
3

Plot the graph of t vs x.

4
 CALCULATION TABLE: 2

S.No. N (kg/s m2) G (kg/s) t (s) x

1
2
3

Plot the graph of G vs. N

Plot the graph of t vs. N

Plot the graph determine xc.

xc = __________

 NOMENCLATURE:

Nom Column Heading Units Type

A Area of the tray m2 Measured
ao Area of orifice m2 Calculated
ap Area of pipe m2 Calculated
Cd Coefficient of discharge * Given
do Diameter of orifice m Given
dp Diameter of pipe m Given
G Mass flow rate of air kg/s Calculated
g Acceleration due to gravity m/s2 Given
N Rate of drying kg/s m2 Calculated
3
Qa Volumetric flow rate of air m /s Calculated
R Manometric difference m Calculated
T Temperature °C Measured
t Time min Measured
w Weight of sample at any time t kg Measured

5
 ws Weight of solid kg Measured
ww Weight of wet solid kg Measured
w* Equilibrium weight of sample kg Calculated
x Free moisture content * Calculated
xc Critical moisture content * Calculated
xt Initial total moisture content * Calculated
x* Equilibrium moisture content * Calculated
ρa Density of air kg/m3 Given
ρw Density of water kg/m3 Given
H Head loss m Calculated
t Time difference Min Calculated
x Moisture content difference * Calculated
R1,R Manometric reading at both points cm Measured
2

 BLOCK DIAGRAM:

6
 Liquid-Liquid Extraction (Number of Stages)

AIM
To find out the number of stages required for extraction of acetic acid (dispersed phase) by ethyl
acetate (continuous phase).
To establish equilibrium isotherm between concentration of acetic acid and ethyl acetate.

THEORY
Liquid - liquid extraction, sometimes call solvent extraction, is the separation of the constituents
of a liquid solution by contact with another insoluble liquid. If the substances constituting the
original solution distributes themselves differently between the two liquid phase a certain degree
of separation will results and this can be enhances by use of multiple contact or their equivalent in
the manner of gas absorption and distillation.
Extraction equipment may be operated batch wise or continuously. A quantity oil feed liquid may
be mixed with a quantity of solvent in an agitated vessel (separating funnel), after which a layer
are settled and separated. The extract is the layer of solvent plus extracted solute, and the raffinate
is the layer from which solute has been removed. The extract may be lighter or heavier than the
raffinate and so the extract may be shown coming from the top of the equipment in some cases
and from the bottom in others. The operation may be repeated if more than one contact is required
but when the quantities involved are large and several contacts are needed, continuous flow
becomes economical. Figure shows the separating funnel used in liquid - liquid extraction process
to separate the components of a mixture into two immiscible solvent phases of different densities.

Fig. Separating Funnel

UTILITIES REQUIRED
Beaker, Burette, Funnel, Separating funnel, Distilled Water, 15% Acetic Acid solution, Ethyl
Acetate, Phenolphthalein, 0.1 N NaOH solution, Stopwatch

EXPERIMENTAL
Experiments will be conducted to find out the number of stage required for the extraction of
acetic acid by ethyl acetate and consequently extraction isotherm will be plotted.

PROCEDURE
To find the number of stage required for complete extraction
Experiments were performed to find out number of stages required for maximum extraction
percentage in extraction of acetic acid by using ethyl acetate at equal volume ratio and extraction
time was kept constant for 2min.
 Take known amount (volume) of acetic acid solution having initial concentration Ci and
keep it in the separating funnel.
 Take same amount of ethyl acetate nd mix it with the acetic acid solution in the same
separating funnel.
 Mix it thoroughly for 2 min.
 Keep the separating funnel on the stand for the separation of two different layers.
 Separate the extract from the raffinate and 10 ml of the sample will be taken for titration.
 Titrate the sample with 0.1N NaOH with phenolphthalein indicator.
 Repeat the experiment by taking fresh solvent and same raffinate until acetic acid is
completely extracted.

Extraction isotherm
Extraction isotherm was plotted by assuming perfect equilibrium between the raffinate and
extract phase at each stage. Figure shows the systematic of the stage wise batch extraction
stream “S” (solvent) and “A” (aqueous) are mixed for the sufficient time with S/A ratio = 1. S0
and S1, S2 are Initial first and second stage concentration of solvent and that of aqueous phase
concentration are A0, A1 and A2 respectively.
𝐴2
Equilibrium concentration S2 and A2 are related as 𝑆2 = 𝑆1 − . It can be noted that here A0 =
𝑟
0
 A0
S0 A1
S1 1st stage S1

A1
T
S0 2nd stage S2

T A2

OBSERVATION
Observation table
Sr Feed Solvent Time Volume Volume of Sample Readings
No (ml) (ml) of extract Raffinate (ml) (ml)
(ml) (ml)

CALCULATION
R = volume of sample
V = burette reading
Total amount of acetic acid in sample
N1. V = N2. R
N2 = (N1.v)/R
For acetic acid normality = molarity
Mass of acetic acid raffinate = (V*N2*mol wt)/ 1000
𝑤𝑡. 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑
% 𝐸𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛 = ∗ 100
𝑖𝑛𝑡𝑖𝑎𝑙 𝑤𝑡 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑
Similar calculation were done for all stages of experiments performed.
Outlet equilibrium concentration are related as
First stage S1 = S0 – A1

Second stage S2 = S0 – A2

Calculation table
Sr. no Time % Extraction An (mole/lit) S2 (mole/lit)

From different values of Sn and An construct isotherm on normal graph

RESULTS AND CONCLUSION

 Liquid-Liquid Extraction (Effect of Phase ratio)

AIM
To study the effect of phase ratio on extraction of acetic acid (dispersed phase) by ethyl acetate
(continuous phase).
To establish equilibrium isotherm between concentration of acetic acid and ethyl acetate.

THEORY
Liquid - liquid extraction, sometimes call solvent extraction, is the separation of the constituents
of a liquid solution by contact with another insoluble liquid. If the substances constituting the
original solution distributes themselves differently between the two liquid phase a certain degree
of separation will results and this can be enhances by use of multiple contact or their equivalent in
the manner of gas absorption and distillation.
Extraction equipment may be operated batch wise or continuously. A quantity oil feed liquid may
be mixed with a quantity of solvent in an agitated vessel (separating funnel), after which a layer
are settled and separated. The extract is the layer of solvent plus extracted solute, and the raffinate
is the layer from which solute has been removed. The extract may be lighter or heavier than the
raffinate and so the extract may be shown coming from the top of the equipment in some cases
and from the bottom in others. The operation may be repeated if more than one contact is required
but when the quantities involved are large and several contacts are needed, continuous flow
becomes economical. Figure shows the separating funnel used in liquid - liquid extraction process
to separate the components of a mixture into two immiscible solvent phases of different densities.

Fig. Separating Funnel

UTILITIES REQUIRED
Beaker, Burette, Funnel, Separating funnel, Distilled Water, 15% Acetic Acid solution, Ethyl
Acetate, Phenolphthalein, 0.1 N NaOH solution, Stopwatch

EXPERIMENTAL
Experiments were conducted to examine the effect of phase ratio i.e feed to solvent ratio.

PROCEDURE
Effect of S/A (solvent to aqueous) ratio
Experiments will be performed for the extraction of acetic acid in water by using ethyl acetate as
solvent at different S/A ratio and extraction time will be kept constant.
 Take known amount (volume) of acetic acid solution having initial concentration Ci and
keep it in the separating funnel.
 Take same amount of ethyl acetate and mix it with the acetic acid solution in the same
separating funnel.
 Mix it thoroughly for 2 min.
 Keep the separating funnel on the stand for the separation of two different layers.
 Separate the extract from the raffinate and 10 ml of the sample will be taken for titration.
 Titrate the sample with 0.1N NaOH with phenolphthalein indicator.
 Repeat the experiment for different S/A ratio.

OBSERVATION
Observation table
Sr Feed Solvent Time Volume Volume of Sample Readings
No (ml) (ml) of extract Raffinate (ml) (ml)
(ml) (ml)
CALCULATION
R = volume of sample
V = burette reading
Total amount of acetic acid in sample
N1. V = N2. R
N2 = (N1.v)/R
For acetic acid normality = molarity
Mass of acetic acid raffinate = (V*N2*mol wt)/ 1000
𝑤𝑡. 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑
% 𝐸𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛 = ∗ 100
𝑖𝑛𝑡𝑖𝑎𝑙 𝑤𝑡 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑
Similar calculation were done for all stages of experiments performed.

Calculation table
Sr No. Time % Extraction A2 (mole/lit) S2 (mole/lit)

RESULTS AND CONCLUSION

 Liquid Liquid Extraction (Effect of Time)

AIM
To determine the effect of time on extraction efficiency and find out the optimum time for
maximum percentage of extraction.

THEORY
Liquid - liquid extraction, sometimes call solvent extraction, is the separation of the constituents
of a liquid solution by contact with another insoluble liquid. If the substances constituting the
original solution distributes themselves differently between the two liquid phase a certain degree
of separation will results and this can be enhances by use of multiple contact or their equivalent in
the manner of gas absorption and distillation.
Extraction equipment may be operated batch wise or continuously. A quantity oil feed liquid may
be mixed with a quantity of solvent in an agitated vessel (separating funnel), after which a layer
are settled and separated. The extract is the layer of solvent plus extracted solute, and the raffinate
is the layer from which solute has been removed. The extract may be lighter or heavier than the
raffinate and so the extract may be shown coming from the top of the equipment in some cases
and from the bottom in others. The operation may be repeated if more than one contact is required
but when the quantities involved are large and several contacts are needed, continuous flow
becomes economical. Figure shows the separating funnel used in liquid - liquid extraction process
to separate the components of a mixture into two immiscible solvent phases of different densities.

Fig. Separating Funnel

UTILITIES REQUIRED
Beaker, Burette, Funnel, Separating funnel, Distilled Water, 15% Acetic Acid solution, Ethyl
Acetate, Phenolphthalein, 0.1 N NaOH solution, Stopwatch

EXPERIMENTAL
Experiments were conducted to find out the number of stage required for the extraction of acetic
acid by ethyl acetate and consequently extraction isotherm were plotted.

PROCEDURE
Experiments will be performed to find out optimum time required for maximum extraction
percentage in extraction of acetic acid by using ethyl acetate at equal volume ratio.
 Take the known amount (volume) of acetic acid solution having initial concentration Ci
and keep it in the separating funnel.
 Take same amount of ethyl acetate and mix it with the acetic acid solution in the same
separating funnel.
 Mix it thoroughly for 2 min.
 Keep the separating funnel on the stand for the separation of two different layers.
 Separate the extract from the raffinate and 10 ml of the sample will be taken for titration.
 Titrate the sample with 0.1N NaOH with phenolphthalein indicator.
 Repeat the experiment for different time.

Material Balance
Figure shows stream “S” (solvent) and “A” (aqueous) are mixed for the sufficient time with S/A
ratio “r”. Initial and final concentration of solvent is S1 and S2 and that of aqueous is A1 and A2.
𝐴2
Equilibrium concentration S2 and A2 are related as 𝑆2 = 𝑆1 − . It can be noted that here A1 =
𝑟
0

A1
S1 A1
S2
S/AS=1 r Time =2min

A2

T
OBSERVATION
Observation table
Sr Feed Solvent Time Volume Volume of Sample Readings
No (ml) (ml) of extract Raffinate (ml) (ml)
(ml) (ml)

CALCULATION
R = volume of sample
V = burette reading
Total amount of acetic acid in sample
N1. V = N2. R
N2 = (N1.v)/R
For acetic acid normality = molarity
Mass of acetic acid raffinate = (V*N2*mol wt)/ 1000
𝑤𝑡. 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑
% 𝐸𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛 = ∗ 100
𝑖𝑛𝑡𝑖𝑎𝑙 𝑤𝑡 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑
Similar calculation were done for all experiments performed at different time.
Further applying material balance find the concentration S2 which is related with A2 by equation
S2 = S1 – A2

Calculation table
Sr. no Time % Extraction A2 (mole/lit) S2 (mole/lit)

RESULTS AND CONCLUSION

 Water Cooling Tower
Objective:
To study mass transfer operation in water cooling tower for different flow and thermodynamic
conditions.

Aim:
To calculate the tower characteristic of water cooling tower for various liquid and air flowrates.

Introduction:
Water from condensers and heat exchangers is usually by an air stream in spray ponds or in cooling
towers using natural draft or forced draft by flow of the air. Mechanical draft towers are of the forced
draft type, where the air is blown into the tower by a fan at the bottom. The forced draft materially
reduces the effectiveness of cooling.

Theory:
Water may be cooled by the air as long as its temperature is above the wet bulb temperature of the
entering air. Markel’s theory is used which is based on enthalpy potential difference as the driving force.
For mass transfer operation:
Each particle of water is assumed to be surrounded by a film of air and the enthalpy difference between
the film and the surrounding air provides the driving force for the cooling process. In the integrated
from Markel’s equation can be written as:
𝑇5
𝐾𝑎 𝑉 𝑑𝑇
= ∫
𝐿 𝑇0 ℎ𝑊 − ℎ𝑎

Tower characteristic can be evaluated numerically by:

𝑇5
𝐾𝑎 𝑉 𝑑𝑇 (𝑇5 − 𝑇6 ) 1 1 1 1
= ∫ = ∗( + + + )
𝐿 ℎ𝑊 − ℎ𝑎 4 ∆ℎ1 ∆ℎ2 ∆ℎ3 ∆ℎ4
𝑇6

1 1 1 1 1
if = ( ∆ℎ + ∆ℎ + ∆ℎ + ∆ℎ )
∆ℎ 1 2 3 4

Then the above equation becomes:

𝐾𝑎 𝑉 (𝑇5 − 𝑇6 ) 1
= ∗
𝐿 4 𝛥ℎ
ℎ𝑤1 = 𝑇6 + 0.1(𝑇5 − 𝑇6 )
ℎ𝑤2 = 𝑇6 + 0.4(𝑇5 − 𝑇6 )
ℎ𝑤3 = 𝑇5 + 0.4(𝑇5 − 𝑇6 )
ℎ𝑤4 = 𝑇5 + 0.1(𝑇5 − 𝑇6 )
ℎ𝑎1 = ℎ1 + 0.1(𝐿⁄𝐺 )(𝑇5 − 𝑇6 )
 ℎ𝑎2 = ℎ1 + 0.4(𝐿⁄𝐺 )(𝑇5 − 𝑇6 )
ℎ𝑎3 = ℎ2 − 0.4(𝐿⁄𝐺 )(𝑇5 − 𝑇6 )
ℎ𝑎4 = ℎ2 − 0.1(𝐿⁄𝐺 )(𝑇5 − 𝑇6 )
𝐾𝑎 𝑉
Where is tower characteristics also called mass transfer coefficient group. Δh is summation
𝐿
of reciprocal of enthalpy difference. Hw1 – Hw2 are enthalpy of water, ha1-ha4 are enthalpy
of air. L/G is liquid to air flow ratio. H1-h2 are enthalpy of air at wet bulb temperature.
The carrying of liquid the gas stream is termed as liquid entrainment. This may be due to a high
rate of air flow. This should be avoided to get better performance.
Description:
The set-up consists of tower which is forced draft counter current type. Fan is provided at the
bottom of the tower. There is an orifice meter mounted with its taps connected to a manometer
to measure the flow rate of air. Butterfly valve is given to control the air flow rate. Nozzles are
provided for distribution of water on the packing. Rotameter is given to control the water flow
rate. A water tank at the bottom fitted with level gauge is provided. Magnetic pump is provided
for circulation of hot water. Temperature sensors are provided to measure the dry bulb and wet
bulb air temperatures. The cooling tower is packed with aluminium expanded wire mesh.
Experimental procedure:
1. Starting procedure:
 Close all the valves V1 – V5
 Ensure that switches given on the panel are at OFF position
 Open the valve V1 and fill the water
 Connect electric supply to the set up
 Set the desired water temperature in the DTC by operating the increment or
decrement and set button of DTC
 Open by pass valve V3 and switch ON the pump
 Switch ON the heater and wait till desired temperature achieves
 Switch ON the blower
 Allow hot water to flow through cooling tower and adjust the flow rate by
rotameter and control valve V2
 Allow air to flow through cooling tower and adjust the flow rate by control valve
V4 provided in pipe line
 At steady state(constant water temperature) record the temperatures
 Record the flow rate of water and manometer reading
 Repeat the experiment for different air flow rates
 Repeat the experiment for different water temperature
2. Closing Procedure:
 When experiment is oven switch OFF the heater
 Switch OFF the pump and blower
 Switch OFF main power supply
 Drain the water tank by open the valve V5
Observation and calculation:
3. Data
Cross sectional area a 0.0225 m2
Diameter of orifice do 0.026 m
Diameter of pipe dp 0.052 m
Coefficient of discharge Cd 0.64
Acceleration due to gravity g 9.81 m/s2
Density of water ρw 1000 kg/m3
Density of air ρa 1.21 kg/m3

Observation table:
S.No T1 T2 T3 T4 T5 T6 R1(cm) R2 QW
(°C) (°C) (°C) (°C) (°C) (°C) (cm) (LPH)

Calculation:
𝑅1 − 𝑅2 𝜌𝑤
𝛥𝐻 = ( − 1) (𝑚)
100 𝜌𝑎
𝜋 2 2
𝑎𝑜 = 𝑑 (𝑚 )
4 𝑜
𝜋
𝑎𝑝 = 𝑑𝑝2 (𝑚2 )
4
𝑎𝑝 𝑎𝑜 𝑚3
𝑄𝑎 = 𝐶𝑑 √2𝑔∆𝐻 ( )
√𝑎𝑝2 − 𝑎𝑜2 sec

𝑘𝑔
𝑀𝑎 = 𝑄𝑎 𝜌𝑎 ( )
sec
𝑄𝑊 𝜌𝑊 𝑘𝑔
𝑀𝑊 = ( )
1000 ∗ 3600 sec
𝑀𝑎 𝑘𝑔
𝐺= ( )
𝑎 (𝑠𝑒𝑐 ∗ 𝑚2)
𝑀𝑤
𝐿= (𝑘𝑔/ sec 𝑚2)
𝑎
𝐿
𝑅=
𝐺
𝑇𝑤1 = 𝑇6 + 0.1(𝑇5 − 𝑇6 )(°𝐶)
𝑇𝑤2 = 𝑇6 + 0.4(𝑇5 − 𝑇6 ) (°𝐶)
 𝑇𝑤3 = 𝑇5 + 0.4(𝑇5 − 𝑇6 ) (°𝐶)
𝑇𝑤4 = 𝑇5 + 0.1(𝑇5 − 𝑇6 )(°𝐶)
Tw1 to Tw4 are called characteristic temperature of water.
To calculate the characteristic enthalpy of water (hw1) at temperature Tw1, (hw2) at temperature
Tw2, (hw3) at temperature Tw3,(hw4) at temperature Tw4.
hW1=…………………... (KJ/kg water)
hW2=…………………... (KJ/kg water)
hW3=…………………... (KJ/kg water)
hW4=…………………... (KJ/kg water)
To calculate the property of air (h1) at temperature T2 (from psychrometric chart)
h1 = ……………………. (KJ/kg dry air)
ℎ2 = ℎ1 + 𝑅(𝑇5 − 𝑇6 )(KJ/kg dry air) (Also, can be taken from psychrometric chart at T4)
ℎ𝑎1 = ℎ1 + 0.1 ∗ 𝑅(𝑇5 − 𝑇6 )(KJ/kg dry air)
ℎ𝑎2 = ℎ1 + 0.4 ∗ 𝑅(𝑇5 − 𝑇6 )(KJ/kg dry air)
ℎ𝑎2 = ℎ2 − 0.4 ∗ 𝑅(𝑇5 − 𝑇6 )(KJ/kg dry air)
ℎ𝑎4 = ℎ2 − 0.1 ∗ 𝑅(𝑇5 − 𝑇6 )(KJ/kg dry air)
∆ℎ1 = ℎ𝑤1 − ℎ𝑎1 (KJ)
∆ℎ2 = ℎ𝑤2 − ℎ𝑎2 (KJ)
∆ℎ3 = ℎ𝑤3 − ℎ𝑎3 (KJ)
∆ℎ4 = ℎ𝑤4 − ℎ𝑎4 (KJ)
1 1 1 1 1
=( + + + )
∆ℎ ∆ℎ1 ∆ℎ2 ∆ℎ3 ∆ℎ4
(𝑇5 − 𝑇6 )
𝑇𝐶 = ( ∗ ∆ℎ)
4

Calculation Table:
SR.NO Tc R

To plot the graph of TC Vs R

 Adsorption Study

Objective

The aim of this experiment is to study the adsorption of acetic acid by solid adsorbent
activated carbon and then test the validity of certain adsorption isotherm.

Principle and Theory

Adsorption is a process that uses special solids to remove substances from either
gaseous or liquid mixtures. It is an industrially important process occurs with the attachment
of the gas particles onto a solid surface. The special solids that gas or liquid particles
attached are called adsorbent. The substances adsorbed are called adsorbate. Adsorption is a
phenomenon occurs at the surface; the molecules are taken up by the surface. It should not
be confused with absorption. Adsorption and absorption are two different processes: the
molecules are taken up by the volume in absorption, not by surface i.e. the solute is
dissolved in the bulk material in absorption. Adsorption can be classified into two different
groups depending on the type interaction between the adsorbed molecule and the solid
surface.

 Physisorption ;Physisorption is caused mainly by intermolecular forces(Van der

Waals) and electrostatic forces between adsorbate molecule and the atoms which
compose adsorbent surface. It will occur when the intermolecular attractive forces
between and adsorbent and adsorbate are greater than those existing between
molecules of the adsorbate itself.

 Chemisorption; Chemisorption is the result of chemical interaction between

adsorbate and adsorbent. The adsorbate sticks to the solid by the formation of a
chemical with the surface. This interaction is much stronger than physisorption.
Unlike in physisorption only monolayer adsorption is observed.

Activated carbon is basically amorphous carbon based material exhibiting a high degree of
porosity and interparticulate surface area. large surface area of activated carbon provides
excellent adsorbent characteristics. The surface area per gram of material can range 500 to
2000 m2. Because of its good adsorption properties they are useful in many industrial
processes. Filtration, purification, deodorization, decolorization and separations are the
examples of processes.

Adsorption Equilibrium ;

A large majority of adsorption operate through equilibrium adsorption of mixture. The

amount of gas or liquid adsorbed, na by mass, per gram of solid, ms, depends on the
specific surface area of the solid, the equilibrium solute concentration in the solution on,
Ceq (pressure for gas phase adsorption), the temperature, and the nature of the molecules
involved. For the given system at constant temperature it is possible to write the adsorption
isotherm equation as follows

𝑞𝑒𝑞 = 𝑛𝑎 ⁄𝑚 𝑠 = 𝑓(𝐶𝑒𝑞 )……………………(1)

Where qeq is the amount of adsorbate per unit mass of adsorbent.

The most common way of getting information about a given system is to take experimental
measurements, at constant temperature, of the amount of adsorbate on the surface as a
function of concentration(or pressure) and then draw a plot of qeq (the amount of adsorbate
per unit mass of adsorbent) versus Ceq (the equilibrium solute concentration). Such a graph is
called an adsorption isotherm.

The Freundlich isotherm

It applies over a limited range of concentrations and is somewhat better for liquid –solid
systems. It has the form of

𝑞 = 𝐾′(𝐶)1/𝑛 ……………………(2)

In Eqn (2) K’ and n are constants.

The Langmuir Isotherm

The theory of Langmuir is restricted to cases where only one layer of molecule can be
adsorbed on the surface. As mentioned before, in the case of chemisorption monolayer
adsorption is usually observed. The monolayer adsorption is distinguished by the fact that
amount adsorbed reaches a maximum value at moderate concentrations (corresponding a
complete coverage of the surface of the adsorbent by a layer of adsorbed molecules which is
one molecule thick only), and remains constant with further increase in concentration. The
equation of Langmuir as derived for the chemisorption of gases is:

𝜃 = ( KC) /(1+KC) (3)

where,

𝜃 : Fraction of the solid surface covered by the adsorbed molecules

K: Adsorption equilibrium constant

C: Initial concentration

Langmuir isotherm equation can be written for the gas adsorption by replacing C by P, also
note that

𝜃 = q / qm (4)

Where qeq is the amount of adsorbate per unit mass of adsorbent and qmeq is the amount of
adsorbate per unit mass of adsorbent required to form a monolayer.

Hence Eqn 3 takes the form of

q / qm = K.( C) /(1+K . C) (5)

C / q = C / qm + 1/(K . qm ) (6)

Chemical: Activated carbon, Acetic acid, Sodium Hydroxide, Phenolphthalein, Hydrochloric

acid, Potassium Hydrogen phthalate.
Experimental procedure

In this experiment, it is important to measure the acetic acid concentration accurately. To

avoid any error the NaOH solution must be titrated with standard 0.1M HCL solution and
then can be titrated with the acetic acid solution.

1. Take 0.3 g of activated carbon into 4 clean stoppered 125ml conical flasks.
2. Add 40 ml of 0.25M acetic acid (Stock Solution) to the first flask and shake. Then add
40ml to other flasks having concentration of 0.20M, 0.15M and 0.10M
3. Shake each flask periodically over 30 minutes noting the room temperature. Then
filter out the solution through a filter paper (to completely remove charcoal particles).
It is important that the equilibrium acetic acid concentration be accurately determined,
4. Pipet out 10mL portion of each filtrate add a few drops of phenolphthalein indicator
and titrate with 0.1 M NaOH. Record the volume of NaOH used.

Data Analysis

The Langmuir isotherm

Calculate the no. of acetic acid molecules adsorbed per gram of charcoal (q) at the
corresponding initial acid concentration (C). Plot C / q against C, slope will give 1/qm
and intercept will give value of 1/qmK. Determine the surface area per gram of
charcoal assuming that one adsorbed acetic acid molecule occupies an area of 21x 10-
10
m2 .

Estimate the value of the equilibrium constant K.

The Freundlich isotherm

By plotting log-log graph of q versus C, value of K’ and n can be calculated.

 ADSORPTION IN PACKED BED

 OBJECTIVE:
To study the adsorption in a packed bed for a solid liquid system.
 AIM:

 To plot the breakthrough curve of adsorption for a given system.

 To calculate the length of unused bed for the given system.

 INTRODUCTION:
A substantial number of unit operations of chemical engineering are concerned with
the problem of changing the compositions of solutions & mixtures through methods
not necessarily involving chemical reactions. One of the well-known operations for
solid liquid contacting is adsorption. The colored material which contaminates
impure cane sugar solutions can be removed by contacting the liquid solutions with
activated carbon, where upon the colored substances are retained on the surface of
the solid carbon.
In adsorption the molecules distribute themselves between two phases, one of
which isa solid while the other can be the liquid or gas. Adsorption suffers from one
drawback, that the capacity of the adsorbent for the adsorbate in question is
limited. At intervals, the adsorbent has to be removed from the process and
regenerated, that is, restored to its original condition. For this reason, in its early
applications in industry, the adsorption unit was considered to be more difficult to
integrate with a continuous process.

 THEORY:
Adsorption is the selective transfer of an adsorbent solute from a fluid phase to a
batch of rigid particles. The usual selectivity of an adsorbent between solute and
carrier fluid or between different solutes makes it possible to separate certain solutes
from the carrier or from one another.
It occurs when molecules diffusing in the fluid phase are held for a period of time
by forces emanating from an adjacent surface. The surface represents a gross
discontinuity in the structure of the solid, and atoms at the surface have a residue of
molecular forces which are not satisfied by surrounding atoms like those in the body
of the structure.
These residual or Vander Waals forces are common to all surface and the only
reason that certain solids are designated "adsorbents" is that they can be

1
 manufactured in a highly porous form, giving rise to a large internal surface. Few

fixed beds have internal probes that would permit measurement of profiles such as
concentration profile. However, these profiles can be predicted and used in

calculatingthe curve of concentration versus time for fluid leaving the bed. The type
of curve is called break through curve.

Length of unused bed can be calculated as:

Where L, θS, θB and LUB are total length of bed, ideal time, break point time and length
ofunused bed.
θB can be calculated from the above graph, it is the time where some minimum
concentration shows. θS can also calculate from the above graph, it is determined in
a way that the areas of the shaded portions are equal.

 DESCRIPTION:
The set-up consists of three borosilicate columns having different diameters &
lengths. For flow of fluid a pump & rotameter is provided. At the inlet of column,
valves are provided to feed only one column at a time. Valves are provided at the
bottom of columns & liquid tanks to drain out after running the apparatus. Filters are
provided before the column drain valves to prevent the charcoal from drain.

 UTILITIES REQUIRED:

2
  Electrical Supply: Single Phase, 220 V AC, 50 Hz, 5-15 Amp combined
socketwith earth connection.
 Water Supply (Initial fill).
 Floor Drain Required.
 Floor Area Required: 1.5 m x 1m.
 Colorimeter or Spectrophotometer.
 Chemicals:-

Activated charcoal : 2 kg
KMnO4 : 15 gm

 EXPERIMENTAL PROCEDURE:
STARTING PROCEDURE:
 Prepare 20 liter of colored liquid by dissolving known amount of KMnO4 in 20
liters of water.
 Close all the valves V1-V10.
 Ensure that switches given on the panel are at OFF position.
 Fill colored liquid in the feed tank.
 Keep activated charcoal in all the columns.
 Connect electric supply to the set-up.
 Open the valve V3 of the column-1.
 Partially open the by-pass valve V2.
 Switch ON the pump.
 Open and adjust the flow control valve V1 and by pass valve V2.
 Simultaneously start the stop watch.
 Collect samples from out let of column-1 after a time intervals.
 Note down the time.
 Measure the optical densities of the samples.
 Run the experiment till the change in color of outlet liquid becomes almost stable.
 Close the valve V3.
 Now open the valve V4 of the column-2.
 Simultaneously start the stop watch.
 Collect samples from outlet of column-2 after a time intervals.
 Note down the time.
 Measure the optical densities of the samples.
 Run the experiment till the change in color of outlet liquid becomes almost stable.
 Close the valve V4.
 Now open the valve V5 of the column-3.
 Simultaneously start the stop watch.
 Collect samples from outlet of column-3 after a time intervals.
 Note down the time.
 Measure the optical densities of the samples.
 Run the experiment till the change in color of outlet liquid becomes almost stable.
 Close the valve V5.

CLOSING PROCEDURE:

3
 When experiment is over, stop the supply of feed by close the valve V1.
 Switch OFF the pump.
 Switch OFF the main power supply.
 Drain the columns by open the valve V6, V7 and V8.
 Drain the feed tank by open the valve V9.
 Drain the product tank by open the valve V10.
 Remove the charcoal by open the filter cups of the columns properly.

4
 OBSERVATION & CALCULATION:

DATA:

Length of column L1 =1m

Length of column L2 = 0.5 m
Length of column L3 = 0.3 m

5
 OBSERVATIONS:

F= LPH

O.D.F =

OBSERVATION TABLE: (select the column-1/ column-2/ column-3)

Sr.No. θ (min) O.D.

CALCULATIONS: (For column-1/column-2/column-3)

CF = [From O.D. vs C graph value of C corresponding to O.D.F]

C= [From O.D. vs C graph value of C corresponding to O.D.]

CALCULATION TABLE:

S.No. θ (min) O.D. C C/CF

6
 NOMENCLATURE:

Nom Column Heading Units Type

C Concentration of samples * Calculated
CF Concentration of feed * Calculated
F Flow rate of the feed LPH Measured
L1 Length of the column-1 m Given
L2 Length of the column-2 m Given
L3 Length of the column-3 m Given
LUB1 Length of unused bed of column-1 m Calculated
LUB2 Length of unused bed of column-2 m Calculated
LUB3 Length of unused bed of column-3 m Calculated
O.D. Optical density of samples * Measured
O.D.F Optical density of feed * Measured
Θ Time min Measured
ΘB Break point time min Calculated
Θs Ideal time min Calculated

7
 BLOCK DIAGRAM:

8
 ! " # $ % & ' # (

) * + , - . / , 0 1 * 2 1 3 4 , 5 * 6 * 7 3 * , 4 3 / . 3 / 1 3 8

& 9 (

) * = 4 > = - > 4 , 1 , 0 1 3 4 , 1 * 7 . 3 / 5 6 ? 7 * 3 . 5 7 7 1 3 1 6 , 4 5 3 7 > * @ 3 4 , 1 + 4 6 . . 5 7 7 1 3 1 6 , 4 5 3 5 6 > 1 ,

: ; <

, 1 A 2 1 3 4 , - 3 1 + 8

) * 2 > * , , 0 1 3 4 , 1 * 7 . 3 / 5 6 ? = - 3 B 1 8

: ; :

C % D E F G $ % & E C (

H 6 A 4 6 / = 4 + 1 + I , 0 1 . 3 / 5 6 ? * 7 A 4 , 1 3 5 4 > + 5 + , 0 1 7 5 6 4 > * 2 1 3 4 , 5 * 6 5 6 , 0 1 A 4 6 - 7 4 = , - 3 5 6 ?

2 3 * = 1 + + I = 4 3 3 5 1 . * - , 5 A A 1 . 5 4 , 1 > / 2 3 5 * 3 , * 2 4 = J 4 ? 5 6 ? * 3 . 5 + 2 4 , = 0 8 K 3 / 5 6 ? 3 1 7 1 3 + , * 7 5 6 4 >

3 1 A * B 4 > * 7 @ 4 , 1 3 I L , 0 1 * 2 1 3 4 , 5 * 6 * 7 , 1 6 7 * > > * @ + 1 B 4 2 * 3 4 , 5 * 6 I 7 5 > , 3 4 , 5 * 6 * 3 = 3 / + , 4 > > 5 M 4 , 5 * 6 8

K 3 / 5 6 ? 5 + = 4 3 3 5 1 . * - , 7 * 3 * 6 1 * 3 A * 3 1 * 7 , 0 1 7 * > > * @ 5 6 ? 3 1 4 + * 6 + N

·
) * 3 1 . - = 1 , 0 1 , 3 4 6 + 2 * 3 , 4 , 5 * 6 = * + , 8

·
) * A 4 J 1 4 A 4 , 1 3 5 4 > A * 3 1 + - 5 , 4 O > 1 7 * 3 0 4 6 . > 5 6 ? I 7 * 3 1 P 4 A 2 > 1 + * 4 2 2 * @ . 1 3 + I

. / 1 + , - 7 7 + I 7 1 3 , 5 > 5 M 1 3 + 8

·
) * 2 3 * B 5 . 1 . 1 7 5 6 5 , 1 2 3 * 2 1 3 , 5 1 + I + - = 0 4 + A 4 5 6 , 4 5 6 5 6 ? 7 3 1 1 7 > * @ 5 6 ? 6 4 , - 3 1 * 7 + 4 > , 8

·
) * 3 1 A * B 1 A * 5 + , - 3 1 Q @ 0 5 = 0 A 4 / * , 0 1 3 @ 5 + 1 > 1 4 . , * = * 3 3 * + 5 * 6 I 7 * 3 1 P 4 A 2 > 1 I , 0 1

. 3 / 5 6 ? * 7 = * 4 > ? 4 + * 3 O 1 6 M 1 6 1 2 3 5 * 3 , * = 0 > * 3 5 6 4 , 5 * 6 8

R > A * + , 4 > > . 3 / 5 6 ? 2 3 * = 1 + + 1 + 5 6 B * > B 1 , 0 1 3 1 A * B 4 > * 7 @ 4 , 1 3 O / B 4 2 * 3 5 M 4 , 5 * 6 I L , 0 - + 3 1 S - 5 3 1

, 0 1 4 . . 5 , 5 * 6 * 7 0 1 4 , 8

) 0 1 3 * , 4 3 / . 3 / 1 3 5 + 4 , / 2 1 * 7 5 6 . - + , 3 5 4 > . 3 / 1 3 1 A 2 > * / 1 . , * 3 1 . - = 1 * 3 A 5 6 5 A 5 M 1 , 0 1 > 5 S - 5 .

A * 5 + , - 3 1 = * 6 , 1 6 , * 7 , 0 1 A 4 , 1 3 5 4 > O / O 3 5 6 ? 5 6 ? 5 , 5 6 . 5 3 1 = , = * 6 , 4 = , @ 5 , 0 4 0 1 4 , 1 . ? 4 + 8 ) 0 1

. 3 / 1 3 5 + A 4 . 1 - 2 * 7 > 4 3 ? 1 3 * , 4 , 5 6 ? = / > 5 6 . 1 3 @ 0 5 = 0 + > * 2 1 + + > 5 ? 0 , > / + * , 0 4 , , 0 1 . 5 + = 0 4 3 ? 1 1 6 .

5 + > * @ 1 3 , 0 4 6 , 0 1 A 4 , 1 3 5 4 > 7 1 1 . 1 6 . 5 + * 3 . 1 3 , * = * B 1 / , 0 1 A 4 , 1 3 5 4 > - 6 . 1 3 ? 3 4 B 5 , / 8 T 4 , 1 3 5 4 >

, * O 1 . 3 5 1 . 1 6 , 1 3 + , 0 1 . 3 / 1 3 4 6 . 4 + , 0 1 . 3 / 1 3 3 * , 4 , 1 + I , 0 1 A 4 , 1 3 5 4 > 5 + > 5 7 , 1 . - 2 O / 4 + 1 3 5 1 +

* 7 5 6 , 1 3 6 4 > 7 5 6 + > 5 6 5 6 ? , 0 1 5 6 6 1 3 @ 4 > > * 7 , 0 1 . 3 / 1 3 8 U 1 4 , 5 6 ? * 2 , 5 * 6 + 5 6 = > - . 1 + , 1 4 A I ? 4 + I * 5 > I

, 0 1 3 A 4 > * 5 > I 4 6 . 4 - P 5 > 5 4 3 / O 5 * A 4 + + O - 3 6 1 3 + / + , 1 A 8


       
                      

    
      

 W # E D X (

Y
* 6 + 5 . 1 3 4 3 * , 4 3 / = * 6 , 5 6 - * - + = * - 6 , 1 3 Z = - 3 3 1 6 , . 3 / 1 3 7 1 . @ 5 , 0 4 6 * 6 2 * 3 * - + A 4 , 1 3 5 4 > 0 4 B 5 6 ?

4 > > A * 5 + , - 3 1 4 + - 6 O * - 6 . A * 5 + , - 3 1 8 R + , 0 5 + A 4 , 1 3 5 4 > 1 6 , 1 3 + , 0 1 . 3 / 1 3 I 5 , 5 + 7 5 3 + , 0 1 4 , 1 . , *

, 0 1 . 3 / 5 6 ? , 1 A 2 1 3 4 , - 3 1 8 H , @ 5 > > , 0 1 6 2 4 + + , 0 3 * - ? 0 , 0 1 > 1 6 ? , 0 * 7 . 3 / 1 3 4 , 6 1 4 3 > / , 0 1 @ 1 , Z

O - > O , 1 A 2 1 3 4 , - 3 1 4 6 . , 0 1 * 3 1 , 5 = 4 > > / 4 , , 0 1 1 6 . * 7 , 0 1 . 3 / 1 3 I , 0 1 A 4 , 1 3 5 4 > + 0 4 > > O 1

. 5 + = 0 4 3 ? 1 . 4 + . 3 / A 4 , 1 3 5 4 > 6 1 4 3 > / 4 , , 0 1 @ 1 , O - > O , 1 A 2 1 3 4 , - 3 1 8

R + + - A 2 , 5 * 6 + N

·
* 0 1 4 , > * + + 1 + 7 3 * A , 0 1 . 3 / 1 3 8

·
U 1 4 , 5 + 4 2 2 > 5 1 . , * , 0 1 A 4 , 1 3 5 4 > * 6 > / 7 3 * A , 0 1 4 5 3 I 6 * , O / = * 6 . - = , 5 * 6 7 3 * A , 0 1 . 3 / 1 3

+ 0 1 > > 8

·
R > > , 0 1 A * 5 + , - 3 1 2 3 1 + 1 6 , 5 + 7 3 1 1 A * 5 + , - 3 1 8

·
) 0 1 3 1 5 + 6 * 1 B 4 2 * 3 4 , 5 * 6 * 7 A * 5 + , - 3 1 5 6 , 0 1 2 3 1 > 5 A 5 6 4 3 / 0 1 4 , 5 6 ? 2 1 3 5 * . 8

K 3 / 5 6 ? 2 3 * = 1 1 . + 4 , 4 = * 6 + , 4 6 , @ 1 , O - > O , 1 A 2 1 3 4 , - 3 1 - 6 , 5 > . 1 + 5 3 1 . 4 A * - 6 , * 7 @ 4 , 1 3 0 4 +

O 1 1 6 3 1 A * B 1 . 8 ) 0 1 1 6 , 1 3 5 6 ? 4 5 3 5 + 4 + + - A 1 . , * O 1 \ ] ] ^ + 4 , - 3 4 , 1 . I + * 5 , + , 1 A 2 1 3 4 , - 3 1

6 1 1 . + , * O 1 3 4 5 + 1 . + * 4 + , * . 1 = 3 1 4 + 1 , 0 1 3 1 > 4 , 5 B 1 + 4 , - 3 4 , 5 * 6 8 ) 0 5 + @ * - > . 1 6 4 O > 1 , 0 1 4 5 3 , *

4 O + * 3 O A * 5 + , - 3 1 7 3 * A , 0 1 @ 1 , + * > 5 . 7 1 1 . 8 H 6 , - 3 6 , 0 1 1 P 5 , 5 6 ? 4 5 3 5 + A * 3 1 + 4 , - 3 4 , 1 . , 0 4 6 , 0 1

1 6 , 1 3 5 6 ? * 6 1 8

_ * 3 = * 6 , 5 6 - * - + . 3 / 1 3 4 , + , 1 4 . / + , 4 , 1 * 2 1 3 4 , 5 6 ? = * 6 . 5 , 5 * 6 + I

- = -
a b ` e a b `
g f f

\ j

c d c d

h h h h h i

) 0 5 + 4 + + - A 1 , 0 4 , , 0 1 . 3 / ? 4 + 7 > * @ k 4 6 . . 3 / + * > 5 . + 7 > * @ _ . * 6 * , = 0 4 6 ? 1 O 1 , @ 1 1 6 . 3 / 1 3

5 6 > 1 , 4 6 . * - , > 1 , 8 T 4 + + O 4 > 4 6 = 1 + = 4 6 4 > + * O 1 2 1 3 7 * 3 A 1 . * 6 , 0 1 * B 1 3 4 > > ? 4 + 4 6 . + * > 5 . +

1 6 , 3 4 5 6 A 1 6 , 5 6 , 0 1 1 P 0 4 - + , ? 4 + + , 3 1 4 A 8

) 0 1 3 1 S - 5 3 1 . + * > 5 . + 7 > * @ 3 4 , 1 I 5 6 > 1 , A * 5 + , - 3 1 = * 6 , 1 6 , l m 4 6 . * - , > 1 , A * 5 + , - 3 1 l n 4 3 1

6 * 3 A 4 > > / + 2 1 = 5 7 5 1 . I 4 6 . , 0 1 1 B 4 2 * 3 4 , 5 * 6 3 4 , 1 4 6 . * - , > 1 , ? 4 + 7 > * @ 4 3 1 = 4 > = - > 4 , 1 . 8

_ * 3 O 4 , = 0 . 3 / 1 3 @ 5 , 0 4 . 3 / A 4 + + A * 7 + * > 5 . + I 4 A 4 + + O 4 > 4 6 = 1 * 6 > / ? 5 B 1 + 4 + 6 4 2 + 0 * , 4 ,

* 6 1 2 * 5 6 , . - 3 5 6 ? , 0 1 . 3 / 5 6 ? = / = > 1 4 6 . 4 6 5 6 + , 4 6 , 4 6 1 * - + . 3 / 5 6 ? 3 4 , 1 ? 5 B 1 6 O / N

u w

= -
t p q o

s r s

h h h h h i y

u v

-
|  ‚
{ {

}  €

=
ƒ

h h h h h i „

} ~


       
                      

    
V      

 ‡ ‰

†
* A 1 , 5 A 1 + ‡ ˆ 5 + = 4 > > 1 . 3 4 , 1 * 7 . 3 / 5 6 ? 8

# Š $ D & ‹ % & E C (

) 0 1 + 1 , Z - 2 = * 6 + 5 + , + * 7 4 > * 6 ? 3 1 + * > B 5 6 ? = / > 5 6 . 3 5 = 4 > + 0 1 > > + > 5 ? 0 , > / 5 6 = > 5 6 1 . , * @ 4 3 . , 0 1 * - , > 1 , 8

) 0 1 + 0 1 > > 5 + 7 5 , , 1 . @ 5 , 0 , @ * O 3 4 = J 1 , + 7 * 3 + - 2 2 * 3 , 8 R 5 3 7 3 * A 4 O > * @ 1 3 2 4 + + 1 + , 0 3 * - ? 0 4

0 1 4 , 5 6 ? = 0 4 A O 1 3 + 1 3 B 1 + , 0 1 2 - 3 2 * + 1 * 7 . 3 / 5 6 ? 4 ? 1 6 , 8 R 6 4 3 3 4 6 ? 1 A 1 6 , 5 + 2 3 * B 5 . 1 . 7 * 3

3 * , 4 , 5 6 ? , 0 1 . 3 / 1 3 + 0 1 > > = * 6 6 1 = , 1 . @ 5 , 0 1 > 1 = , 3 5 = A * , * 3 4 6 . 4 3 1 . - = , 5 * 6 ? 1 4 3 O * P 8 _ > * @

= * 6 , 3 * > B 4 > B 1 4 6 . O / Z 2 4 + + B 4 > B 1 4 3 1 7 5 , , 1 . , * 3 1 ? - > 4 , 1 , 0 1 4 5 3 7 > * @ 8

% & Œ & % & # Š #  G & D # F (

† † Y Y “
> 1 = , 3 5 = 5 , / - 2 2 > / N 5 6 ? > 1  0 4 + 1 I ] ‘ R I ’ ] U M I R A 2 T @ 5 , 0 1 4 3 , 0

Ž ; < 

y y „ y

= * 6 6 1 = , 5 * 6 8

_ > * * 3 R 3 1 4 ” 1 S - 5 3 1 . N A P \ 8 ’ A 8

Ž ; :

† †
* > 5 . A 4 , 1 3 5 4 > 1 1 . + Z ’ A A j N J ?

Ž ; •

i „ y

– ‹ # D & 9 # C % — Œ D E $ # F G D # (

˜ ™ š ˜ › œ  š ž Ÿ ¡ ¢ š £

) 4 J 1 J 6 * @ 6 4 A * - 6 , * 7 , 0 1 + * > 5 . A 4 , 1 3 5 4 > 4 6 . @ 1 5 ? 0 5 , 8

; < ; <
¤

* @ A 5 P J 6 * @ 6 4 A * - 6 , * 7 @ 4 , 1 3 5 6 , 0 1 + * > 5 . 4 6 . @ 1 5 ? 0 , 0 1 @ 1 , + * > 5 . 8

; < ; :
¤

6 + - 3 1 , 0 4 , + @ 5 , = 0 1 + ? 5 B 1 6 * 6 , 0 1 2 4 6 1 > 4 3 1 4 , ¥ _ _ 2 * + 5 , 5 * 6 8

; < ; • 
¤

†
1 , , 0 1 2 3 1 0 1 4 , 5 6 ? , 1 A 2 1 3 4 , - 3 1 7 * 3 4 5 3 8

; < ; ¦
¤

†
@ 5 , = 0 ¥ , 0 1 A 4 5 6 2 * @ 1 3 + - 2 2 > / 8

; < ; §
¤

†
@ 5 , = 0 ¥ , 0 1 0 1 4 , 1 3 L @ 4 5 , , 5 > > , 0 1 + 1 , 2 * 5 6 , , 1 A 2 1 3 4 , - 3 1 5 + 4 3 3 5 B 1 . 8

; < ; Ž
¤

” - 6 , 0 1 O > * @ 1 3 4 6 . + 1 , , 0 1 7 > * @ 3 4 , 1 * 7 4 5 3 O / 4 . ¨ - + , , 0 1 B 4 > B 1 ‘ m 8

; < ;
¤ ¤

_ 5 > > , 0 1 7 1 1 . 0 * 2 2 1 3 @ 5 , 0 @ 1 , + * > 5 . 8

; < ; ©
¤

†
, 4 3 , , 0 1 . 3 / 1 3 5 6 3 * , 4 3 / A * , 5 * 6 8

; < ; ª
¤

R > > * @ , 0 1 @ 1 , + * > 5 . , * 7 > * @ , 0 3 * - ? 0 , 0 1 . 3 / 1 3 O / + , 4 3 , 5 6 ? , 0 1 + = 3 1 @

; < ; < «
¤

= * 6 B 1 / * 3 4 6 . 3 * , 4 , 5 6 ? 0 4 6 . @ 0 1 1 > A 4 6 - 4 > > / 8

R , + , 1 4 . / + , 4 , 1 3 1 = * 3 . , 0 1 A 4 6 * A 1 , 1 3 3 1 4 . 5 6 ? 8

; < ; < <

¤


       
                      

    
     

 * , 1 . * @ 6 , 0 1 4 5 3 , 1 A 2 1 3 4 , - 3 1 4 , 5 6 > 1 , 4 6 . * - , > 1 , 8

; < ; < :
¤

” 1 2 1 4 , , 0 1 1 P 2 1 3 5 A 1 6 , 7 * 3 . 5 7 7 1 3 1 6 , 4 5 3 7 > * @ 3 4 , 1 + 8

; < ; < •
¤

” 1 2 1 4 , , 0 1 1 P 2 1 3 5 A 1 6 , 7 * 3 . 5 7 7 1 3 1 6 , 4 5 3 5 6 > 1 , , 1 A 2 1 3 4 , - 3 1 8

; < ; < ¦
¤

Î ž Ï › œ  š ž Ÿ ¡ ¢ š £

0 1 6 1 P 2 1 3 5 A 1 6 , 5 + * B 1 3 + @ 5 , = 0 ¥ _ _ , 0 1 O > * @ 1 3 I 0 1 4 , 1 3 4 6 . . 3 / 1 3 8

; : ; < Ð
¤

†
@ 5 , = 0 ¥ _ _ , 0 1 A 4 5 6 2 * @ 1 3 + - 2 2 > / 8

; : ; :
¤

Y
> 1 4 6 , 0 1 . 3 / 1 3 2 3 * 2 1 3 > / 8

; : ; •
¤

! Š # D ' — % & E C — Œ $ G Œ — % & E C (

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