PRACTICAL NO : 1

DIFFERENTIAL DISTILLATION

AIM: To verify Rayleigh’s equation for batch distillation of methanol-water mixture.

THEORY:
In the case of a differential distillation, the vapour at any time is in equilibrium with the
liquid from which it rises but changes continuously in the composition. Thus, the
mathematical approach used must be differential. Assume that L mol of liquid in the still of
composition x mole-fraction A and that an amount dD mol of distillate is vaporized, of mol
fraction y* in equilibrium with the liquid.

The rate of depletion of liquid is equal to the rate of distillate output. The instantaneous rate of
depletion of a component in the liquid is therefore,
− =
0− =
Component balance of more volatile material
∗
0− = ( )
∗
0− = +
∗
( − ) =

= ( ∗ − )
On integration,

= ( ∗ − )

= ( ∗ − )

This is called Rayleigh Equation for differential distillation.

ℎ , =
=
=
=
PROCEDURE:
Collect the necessary glass-wares to prepare for the setup of the distillation
experiment shown in figure. Ensure the all glass-wares are clean & dry.
Weigh empty RB still & product receiver accurately & note them down. Now mix
100 ml of methanol and 80 ml of water, then measure weight and density (using sp.
gravity bottle) of resulting mixture. Stir well to ensure uniform mixing of the two
liquids. Transfer the same to the RB still. Connect all apparatus and get the set up
ready as shown in fig. Before switching on the electric heater, make sure that the
supply of cooling water to condenser is turned on.
Start the electric heater. Increase the heat supply slowly until mixture reaches its
bubble point. Observe the distillation operation in progress. Once ½ of mixture
distilled off, switch off the heater. Wait for the 10 min before turning off the cooling
water. Disconnect the product receiver & RB still and allow their contents to cool
down to room temperature covering their mouth with aluminium foil.
When cooled, weigh the still & product receiver and record the readings. Also
measure the density of distillate and bottom product (using SG bottle). Now proceed
further to prepare calibration curve to estimate mole fraction of Distillate and Bottom
from their respective densities.
Procedure for preparation of calibration curve:
Prepare different mixtures known volume of water-methanol system as follows.
Vol. of Water (ml) Vol. of Methanol (ml)
0 50
10 40
20 30
25 25
30 20
40 10
50 0

Determine the density of pure water & ethanol at room temperature. Convert the
volume fraction to mole fraction of ethanol. A plot of density vs. mole fraction is the
required calibration chart. If density is known mole fraction can be easily obtained
from the calibration chart.
OBSERVATION:

BEFORE COMMENCEMENT OF EXPERIMENT:

 Density of pure H2O = _________________ gm/ml
 Density of pure methanol = _________________ gm/ml
 Volume of H2O taken in RB flask = _________________ ml
 Volume of methanol taken in RB flask = _________________ ml
 Density of feed mixture(H2O + Methanol) = _________________ gm/ml

AFTER COMMENCEMENT OF EXPERIMENT:

 Volume of distillate (VD) = ___________________ ml
 Volume of bottom (VB) = ___________________ ml
 Density of distillate (ρD) = ___________________gm/ml
 Density of bottom (ρB) = ___________________ gm/ml

OBSERVATION TABLE (For Preparation of Calibration Curve):

 Mass of empty of SG bottle = gm.

Vol. of Vol. of Total volume Mole fraction Density of Mass of soln. (gm.)
Water Methanol of solution of Methanol Solution (After subtracting mass
(ml) (ml) (ml) (gm/ml) of empty SG bottle)
0 50
10 40
20 30
25 25
30 20
40 10
50 0

CALCULATION:
Moles of Feed, F
_ ∗ _ _ ∗ _
F= +
_ _

= ____________ gm-mol
Composition of Feed,

∗
( )
XF = XMethanol =

= _____________
(Note: Verify the same from the graph of Density Vs. XMethanol)

Find out the composition of Methanol in Distillate (From the graph)

XD = _________________
Find out the composition of Methanol in Residue/Bottom (From the graph)
XB = _________________

Average Molecular Wt. of Bottom:-

MWBottom = {X ∗ (MW_methanol) + (1 − X ) ∗ _H2O}

= _________________ gm/gmol

Weight of Bottom Product (WB) = VB * ρB

= ____________ gm

Moles of Bottom Product (B) =

_

= _____________ gm/gmol

ln = __________________ ----------------(1)

Vapour-Liquid Equilibrium Data for Methanol-Water System:

Sr. x y* 1/(y*- x) Sr. x y* 1/(y*- x)
1. 6.
2. 7.
3. 8.
4. 9.
5. 10.
Draw the graph of 1/(Y*- X) Vs. X
From the graph calculate the area under the curve as:-

∫ ∗ = _______________ ----------------(2)

Moles of distillate D,
From material balance,

F = B+D
D= F- B
= __________ gm-mol (Theoretical)

From the experiment,

Composition of distillate XD = ______________

(From the graph of density vs. composition)

MWDistillate = {X (MW_Methanol) + (1 − X ) _H2O}

= ____________________ gm/mol
Moles of distillate:-
∗
D=

= __________________ gm-mol

(Note: Compare theoretical & practical values of D & give justification.)

CONCLUSION:
 PRACTICAL NO: 2
BATCH ADSORPTION

AIM: To verify the Freundlich adsorption isotherm.

APPARUTUS: Glass Beakers, Titration set, Conical flask, Filter paper, Weighing scale.
CHEMICALS: Charcoal (Adsorbent), Oxalic acid (H2C2O4.2H2O) (Adsorbate), Sodium-
Hydroxide soln., Phenolphthalein indicator.
THEORY:
The degree of adsorption of a solute (adsorbate) on the adsorbent depends on the chemical
nature of the adsorbent and the adsorbate, the specific surface area of the adsorbent, the
temperature and the concentration or the pressure of the adsorbate.
At constant temperature the relation between the amount adsorbed and concentration in a
limited concentration range may be represented by one of the three adsorption isotherms of
Freundlich, Langmuir, and BET (Brunauer Emmett and Teller).

Freundlich Isotherm:
X/M = kCe1/n
Where X = weight of adsorbate in gm, adsorbed by M gm of the adsorbent.
k, n = emperial constants.
Ce = equilibrium concentration.
X/M = weight of the adsorbate in grams, adsorbed by one gram of the
adsorbent
Freundlich equation can be linearized by taking the logarithmic form
Ln (X/M) = (1/n) Ln Ce +Ln K

Langmuir Isotherm:
In the contrary of frendlich isotherm, langmuir is based on a theoretical consideration
of the process of adsorption. These considerations are:
1. A maximum of monolayer will be adsorbed.
2. The adsorption surface is homogeneous with each site having the same affinity for
adsorption.
3. There are a finite number of site to which molecules can be absorbed.
4. There is a competition between solvent and solute molecules for the adsorption site.
5. Adsorption is a function of the number of adsorption site available and therefore the
rate of adsorption (or the occupation of these sites) will decrease with time.
PROCEDURE:
 Prepare 1N oxalic acid by dissolving 15.75gm oxalic acid in 250 ml
distilled water.
 Take four conical flasks. Prepare solutions as shown in table below.
 Flask No.  Vol. of 1 N Oxalic  Vol. of Water
Acid  (ml)
 (ml)
 1  10  90
 2  20  80
 3  40  60
 4  50  50
 Now, add 5 gm of charcoal to each conical flask. Keep contents of
conical flask well stirred for 15 to 20 min.
 Then filter out each and collect the filtrate. Take 10 ml of filtrate and
titrate it against 1N sodium hydroxide solution, after adding few drops
of phenolphthalein.
 Calculate the amount of acid absorbed in charcoal from normality of
the filtrate & plot a graph of ln(X/M) vs. lnC.
OBSERVATIONS:
Weight of charcoal taken in each flask = _____ gm
Equivalent weight of oxalic acid = _______ gm-eqvt./gm
Burrete: - 1 N NaOH Sol.
Indicator: - Phenolphthalein
End point: - colourless to pink

OBSERVATION TABLE:
Volume Volume
Volume Burette
of pipette
Flask of reading Ni Nf X X/M Ce=Nf
Oxalic out for
No. water B.R. (N) (N) (gm) (N)
Acid titration
(ml) (ml)
(ml) (ml)
1 10 90
2 20 80
3 40 60
4 50 50
SAMPLE CALCULATION:
For Flask-1:
Vol. of Oxalic Acid =10 ml
Vol. of Water =90 ml
Initial Concentration of Oxalic Acid in Flask (Ni)
Ni = (1 N x Vol. of Oxalic Acid) / 100

Final Concentration of Oxalic Acid in Flask @ equilibrium (Nf)

Ce = Nf = (1 N NaOH sol. x B.R.) / Volume pipette out for titration

Amount of Oxalic Acid adsorbed on Charcoal in gms.

.
X = ((Ni – Nf) * *
/

=
X = ___ gm
Mass adsorbed per gm of adsorbent can be given as
X/M = ___/ 5 gm
Similarly for all flasks, results are tabulated as follows.
Flask No. ( / ) e
1
2
3
4

Now, Plot ln(X/M) Vs. ln Ce

From the graph, we can find out freundlich parameters as
n = slope of line = ________
k = exp (Intercept) = ________
RESULT:

CONCULSION:
 PRACTICAL NO-

VAPOUR – LIQUID EQUILIBRIUM

AIM- To construct Vapour liquid equilibrium for given system

Determination of Vapor-Liquid Equilibrium

One of the most common chemical engineering operations is the separation of two or more compounds
based on differences in boiling points. At a given pressure a pure compound boils at a very well defined
temperature. Mixtures of compounds boil at temperatures intermediate between the two pure compound
boiling points; the exact temperature depends upon the composition of the mixture. Unlike the pure
compounds in which the vapor and liquid have the same composition, boiling mixtures will have a different
composition in the liquid phase than in the vapor phase. Note that for a boiling mixture, the vapor and
liquid phases are at the same temperature. A plot of this behavior is a VLE (Vapor-Liquid Equilibrium)
envelope, as shown in Figure 1. This difference in composition between the vapor and liquid phases
becomes the basis for separating the compounds. The industrial separation device is the distillation column.

Not all VLE curves are as simple as that shown in Figure 1 and under certain circumstances, the boiling
point of the mixture can be above or below those of the pure components when the mixture forms an
azeotrope. Figure 2 is such a VLE curve. Complete separation by simple distillation is then not possible,
which is why ethanol cannot be easily separated from water by distillation.

VLE - Furan / Carbon Tetrachloride

(1 atm)

180
160
Temp ( F )

140
120
100
80
0 0.2 0.4 0.6 0.8 1
Mole Fraction Furan
 VLE - Ethanol /Toluene

240
230
220
210
Temp (F)

200 y, vapor phase

190
180
170
x, liquid phase
160
150
0 0.2 0.4 0.6 0.8 1
Mole Fraction Ethanol

PROCEDURE

Make-up a 50% v/v CH3OH/H20 mixture.

Place the mixture in a 1000 cm3 3-necked round-bottomed flask set up for simple distillation using a heating
mantle. Place a few anti-bump granules in the flask and heat until steady boiling occurs. Collect the sample
of distillate and place in stoppered sample bottle. Label sample vapour condensate 1. Take sample of
residual liquid from flask similarly and label liquid 1. Record still head temperature. Continue
distillation and take 5 more samples of distillate and liquid in still as before. You should aim to
take samples when the still head temperature is 65, 72, 79, 86, 93, 100 deg cent. Ensure that
samples are taken over the full distillation temperature range (65oC to 100oC)

In this experiment, you will determine the vapor-liquid equilibrium envelope (at atmospheric pressure) for
binary mixture made from two of the following compounds:

Water, Methanol and Ethanol

Analysis of the vapor and liquid samples will be done using the measuring density of the distillate and
bottom. The first task will be to build a calibration curve for the test solution. Note: this can be done while
the initial charge is heating in the still. You should use at least 10 (and preferably about 15) composition
samples to develop the calibration curve. Before you come to lab, you should make up a table showing the
volumes (or weights) of each of your two compounds you will use to make the individual calibration
samples. The procedure for preparation of calibration curve is described in previous experiment

Construction of a proper VLE curve requires the use of mole fractions for composition, not mass
fractions.

OBSERVATIONS
Mass of methanol taken:

Mass of water taken :

Temperatures at sample taken:

Sr. Temperature Density of Density of Mole Mole

No Distillate Residue Fraction of Fraction of
Distillate Residue
1 65
2 72
3 79
4 86
5 93
6 100
 Psychometric Calculation

Aim: To determine following properties of ambient air using Psychometric Chart.

Absolute Humidity
Molar Humidity,
% Relative Saturation
Dew Point
Humid Volume
Enthalpy

Observation:

Dry Bulb Temp. of Air :_________

Wet Bulb Temp. of Air : _________

Calculation:
▪ Absolute Humidity:

▪ Molar Humidity:

▪ Partial Pressure of H2O:

▪ % Relative Saturation

▪ Humid Volume:
▪ Enthalpy :

Dew Point:
 ION EXCHANGE

Aim- To study the water softening process by Ion Exchange Method

Introduction
Ion Exchange processes are used for the removal of color, organics, nitrates and hardness. Both
column tests and isotherms can be used to determine the capacity of ion exchange resins for a
given application. Ion Exchange is similar to adsorption processes and are common to water and
wastewater treatment.
All natural waters contain, in various concentrations, dissolved salts which dissociate in water to
form charged ions. Positively charged ions are called cations; negatively charged ions are called
anions. Ionic impurities can seriously affect the reliability and operating efficiency of a boiler or
process system. Overheating caused by the buildup of scale or deposits formed by these impurities
can lead to catastrophic tube failures, costly production losses, and unscheduled downtime.
Hardness ions, such as calcium and magnesium, must be removed from the water supply before it
can be used as boiler feed water. For high-pressure boiler feed water systems and many process
systems, nearly complete removal of all ions, including carbon dioxide and silica, is required. Ion
exchange systems are used for efficient removal of dissolved ions from water.

Ion exchangers exchange one ion for another, hold it temporarily, and then release it to a regenerant
solution. In an ion exchange system, undesirable ions in the water supply are replaced with more
acceptable ions. For example, in a sodium zeolite softener, scale-forming calcium and magnesium
ions are replaced with sodium ions.

CLASSIFICATIONS OF ION EXCHANGE RESINS

Ionizable groups attached to the resin bead determine the functional capability of the resin.
Industrial water treatment resins are classified into four basic categories:

• Strong Acid Cation (SAC)

• Weak Acid Cation (WAC)
• Strong Base Anion (SBA)
• Weak Base Anion (WBA)

SAC resins can neutralize strong bases and convert neutral salts into their corresponding acids.
SBA resins can neutralize strong acids and convert neutral salts into their corresponding bases.
These resins are utilized in most softening and full demineralization applications. WAC and WBA
resins are able to neutralize strong bases and acids, respectively. These resins are used for
dealkalization, partial demineralization, or (in combination with strong resins) full
demineralization.
SAC resins derive their functionality from sulfonic acid groups (HSO 3¯). When used in
demineralization, SAC resins remove nearly all raw water cations, replacing them with hydrogen
ions, as shown below:

The exchange reaction is reversible. When its capacity is exhausted, the resin can be regenerated
with an excess of mineral acid.

Strong acid cation exchangers function well at all pH ranges. These resins have found a wide range
of applications. For example, they are used in the sodium cycle (sodium as the mobile ion) for
softening and in the hydrogen cycle for decationization.

Weak acid cation exchange resins derive their exchange activity from a carboxylic group (-
COOH). When operated in the hydrogen form, WAC resins remove cations that are associated
with alkalinity, producing carbonic acid as shown:

These reactions are also reversible and permit the return of the exhausted WAC resin to the
regenerated form. WAC resins are not able to remove all of the cations in most water supplies.
Their primary asset is their high regeneration efficiency in comparison with SAC resins. This high
efficiency reduces the amount of acid required to regenerate the resin, thereby reducing the waste
acid and minimizing disposal problems.

Weak acid cation resins are used primarily for softening and dealkalization of high-hardness, high-
alkalinity waters, frequently in conjunction with SAC sodium cycle polishing systems. In full
demineralization systems, the use of WAC and SAC resins in combination provides the economy
of the more efficient WAC resin along with the full exchange capabilities of the SAC resin.

SBA resins derive their functionality from quaternary ammonium functional groups. Two types of
quaternary ammonium groups, referred to as Type I and Type II, are used. Type I sites have three
methyl groups:
In a Type II resin one of the methyl groups is replaced with an ethanol group. The Type I resin has
a greater stability than the Type II resin and is able to remove more of the weakly ionized acids.
Type II resins provide a greater regeneration efficiency and a greater capacity for the same amount
of regenerant chemical used.

When in the hydroxide form, SBA resins remove all commonly encountered anions as shown
below:

As with the cation resins, these reactions are reversible, allowing for the regeneration of the resin
with a strong alkali, such as caustic soda, to return the resin to the hydroxide form.

Weak base resin functionality originates in primary (R-NH2), secondary (R-NHR'), or tertiary (R-
NR'2) amine groups. WBA resins readily re-move sulfuric, nitric, and hydrochloric acids, as
represented by the following reaction:

Procedure
Take known quantity of cation exchange resin and anion exchange resin and fill in respective
columns. Pass known quantities of water through each bed and measure the hardness of water
before and after passing through the columns.

The hardness of water is measured by EDTA complexometric method.

Reagents:
Buffer solution: 10 pH solution of ammonium hydroxide
0.01M EDTA tetra sodium solution
Erichrome Black T indicator
Determination of total hardness
1. Pipette 50 ml water into a conical flask.
2. Add 2 ml buffer solution followed by 3 drops of Eriochrome Black T indicator solution.
3. Titrate with 0.01 M EDTA until the solution turns from wine red to sky blue with no hint of red
(save the solution for colour comparison).
4. Repeat the titration to obtain two concordant results.
OBSERVATIONS

Volume of Resin Taken:

Observation Table

For Tap Water

Sample B.R before passing through resin B.R after passing through resin column
No column

For RO treated Water

Sample B.R before passing through resin B.R after passing through resin column
No column

Calculations

1 ml of 1Molar EDTA = 100 mg of CaCO3

 Drying of Solids – Tray Dryer
Objectives

Experimental determination of the rate of drying curve for solid, at constant drying conditions
(constant air flow, temperature and humidity).The experiment is carried out in a batch dryer and
heat is supplied by direct contact with heated air at atmospheric pressure.

Important Definitions

• Humidity of an air-water vapor mixture (H):

H = Mass of Water (kg)  Mass of Dry Air (kg)

• Moisture content of a solid (X):

X = Mass of Water (kg)  Mass of Dry Solid (kg)

• Equilibrium Moisture Content of a Solid (Xe): Is the final moisture content of a solid after
being brought into contact with a stream of air (having humidity “H” and temperature “T”)
long enough, for equilibrium to be reached. Is expressed in the same way as X.

• Free Moisture Content of a solid: Is the moisture above the equilibrium moisture content.
Is the only moisture that can be removed by drying under the given drying conditions.
• Critical Moisture Content of a solid (Xc): Is the solid moisture content attained, during the
drying process, when the entire surface of the solid is no longer wetted.

Experimental Determination of the Rate of Drying Curve

The rate of drying “R” is defined as the mass of liquid evaporated by unit time and by unit of
exposed surface area for drying. It can be mathematically expressed by

S dX
R = − ⎯ ⎯⎯⎯ (1)
A dt
Where

R = drying rate (kg H2O/m2 s)

S = weight of dry solid (kg)

A = exposed surface area for drying (m2)

X = solid moisture content (kg H2O/kg dry solid)

t = time (s)

To experimentally determine the rate of drying for a given material (case study sand), a sample is
placed in a dryer and under constant drying conditions, the loss in weight of moisture during the
drying process is determined at constant time intervals.
With the data obtained from the batch experiment, a plot of the solid moisture content “X” versus
time can be made (Figure 1). From this plot, the rate of drying curve can be obtained by measuring
the slopes of the tangents drawn to the curve, which give the values of dX/dt at given values of t.
The drying rate “R” is calculated for each point using equation (1). The drying rate curve is
obtained by plotting R versus the solid moisture content “X” as in figure 2.
The plot of the rate of drying curve can presents several shapes but generally the two major points
– constant and falling rate period – are present. At time zero the initial moisture content of the
solid is shown at point A or A’ depending on the solid temperature. At point B the surface
temperature as attained its equilibrium value and the constant rate period starts. This period
continues as long as the water is supplied to the surface as fast as it evaporates. At point C, the
solid critical moisture content “Xc” is attained. At this point there is no insufficient water on the
surface to maintain a continuous film of water and the first falling rate period starts. The wetted
area of the solid continually decreases until the surface is totally dry at point D. At this point begins
the second falling rate period, that continues until the equilibrium moisture content of the solid is
reached, at point E.
Figure1: solid moisture content “X” versus time for constant drying conditions

Figure2: drying rate “R“ versus solid moisture content “X” for constant drying conditions
Experimental Procedure –

1. Open the drying chamber and take out the trays. Measure the surface area of the trays
2. Switch ON the fan and adjust the predetermined velocity (flow rate) of air using the
regulator and measure it with the help of digital anemometer
3. Switch on the heaters and adjust the power input to them at predetermined value using the
regulator and measure it with the help of digital voltmeter and ampere meter provided on
the control panel
4. Prepare the samples whose drying characteristics are to be determined by taking about 2-3
kg of material (usually find sand) and adding about 10 % of solvent (usually water)
5. Fill all the three trays with equal amount of prepared sample and spread the material evenly
throughout the cross section of the tray
6. After achieving a fairly high and stable temperature. Open the door of the drying chamber
and place the trays in the tray rack carefully with the help of cotton cloth.
7. Note down the decrease in weight displayed on the digital weighing scale after an interval
of 5 minutes.
8. After certain time no loss of weight is observed for prolonged period of time, switch OFF
the heaters as well as weighing scale. Take out the trays after they are cooled.

Observations

Weight of dry solid = kg

Weight of added water =………….. kg

Initial moisture content =………….. %

Total sample weight (tray + solid + water) = . kg

o
Air temperature = C

Air velocity = . m/s

Surface area = 921.55 cm2

Observation Tables
Time (s) Weight of solid (kg)
 Time (s) . X (kg H2O/kg dry solid) . dX/dt . R (kg/s m2)

Calculations
 • Plot experimental X versus time t

• Plot experimental R versus experimental X

Practical Formulas

W − Ws

X = ⎯⎯⎯⎯⎯⎯ I

Ws

Ws dX

R = − ⎯⎯ ⎯⎯ II

A dt

where

W = weight of total solid (kg)

Ws = weight of dry solid (kg)

Result- Critical moisture content at constant drying conditions is ----------------