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Burette
1. Clean the burette with tap water and then rinse with distilled water
2. Rinse the burette with a small quantity of the solution to be filled in the
burette and discard the solution into the sink.
3. Fill the burette with required solution using funnel, remove the funnel and
fill the nozzle of the burette with the solution.
4. When the burette reading is noted down, the burette should be at the
level of the eye to avoid parallax error.
Pipette
1. Clean the pipette with tap water and then rinse with distilled water
2. Rinse the pipette with a small quantity of the solution to be pipetted and
discard the solution in to the sink
3. Pipette out exactly 20mL of the solution into a clean conical flask. During
transferring the solution into a clean conical flask, when all the solution
from the pipette runs out, touch the tip of the pipette to the bottom of the
flask gently.
Conical Flask
1. Clean the conical flask with tap water and then rinse with distilled water.
Test solution
1 Test solution is provided in a small reagent bottle. Transfer the given test
solution into a clean 100mL volumetric flask using funnel, after complete
transfer of the test solution, add small amount (2-3 mL) of distilled water
into the reagent bottle and transfer this solution into the standard flask and
finally dilute the solution up to the mark using distilled water with utmost
care. Use this as test solution for estimation.
2. Test solution will be provided only one time.
1
Titration
1. During the addition of the solution from the burette, the conical flask must
be constantly rotated with one hand while the other hand controls the stop
cock of the burette.
2
CYCLE - I Experiment-1
Date:
Principle:
Hardness of water is due to the presence of calcium and magnesium salts in
water. Ehtylene diamine tetraacetic acid (EDTA) forms complexes with a
large number of cations including Ca2+ and Mg2+ ions depending upon pH of
the solution. Hence, it is possible to determine the total hardness of water
using EDTA solution. EDTA in the form of its sodium salt (H2Y2-) is more
often used in place of EDTA in complexometric titration for estimation of
metal ions because pure EDTA (H4Y) is sparingly soluble in water. EDTA
has six binding sites (the four carboxylate groups and the two amino groups)
providing six pairs of electrons. The resulting metal-ligand complex, in which
EDTA forms a cage-like structure around the metal ion, is very stable at
specific pH. All metal-EDTA complexes have a 1:1 stoichiometry. The H2Y2-
form complexes with metal ions as follows.
M + H2Y2- MY2- + 2H+ (1)
where, M is Ca2+ and Mg2+ present in water. Reaction (1) can be carried out
quantitatively at pH of 10 using Eriochrome Black T (EBT) indicator. EBT
forms a wine-red complex with M2+ ions which is relatively less stable than
the metal-EDTA complex. On titration EDTA first reacts with free M2+ ions
and then with the metal-EBT indicator complex. The end point of the reaction
is change of colour from wine red to steel blue.
Requirements
3
Apparatus: Burette, pipette, conical flask, standard flask and burette stand
Procedure
Titration I - Standardisation of EDTA
Pipette out 20 mL of the standard hard water containing 1mg/mL of calcium
carbonate (1000 ppm) into a clean conical flask. Add one test tube full of
ammonia buffer (NH4OH NH4Cl) solution to maintain the pH around 10. Add
three drops of Eriochrome Black T (EBT) indicator and titrate it against the
given EDTA solution taken in the burette. The end point is change of colour from
wine red to steel blue. Repeat the titration for concordant titre values. Let V 1 be
the volume of EDTA consumed.
Calculations:
4
drops of Eriochrome BlackT (EBT) indicator. Titrate this mixture against
standardized EDTA solution taken in the burette. The end point is the change of
color from wine red to steel blue. Repeat the titration as carried out earlier for
concordant titre value. Let V2 be the volume of EDTA consumed.
Calculations:
From Titration 1, we have the following relation:
Removal of hardness using ion exchange method: (This should be the first
step in the lab)
Arrange the ion exchange column on to a burette stand and place a clean funnel
on top of the column. Take 50 mL of the hard water sample in a beaker and
5
slowly pass the water sample through the ion exchange column. Place a clean
beaker under the column and collect water passing through the column over a
period of 15 minutes. Adjust the valve of the column to match the duration of
outflow.
From the water collected through the column, pipette out 20 mL into a clean
conical flask and repeat the EDTA titration as carried out above. Note down the
volume of EDTA consumed as V3.
Calculations:
From Titration 1, we have the following relation:
Result:
1. Total hardness of the water sample = X ppm
2. Residual hardness in the water sample = Y ppm
3. Hardness removed through the column = X Y ppm
6
Space for Calculations
7
CYCLE I Experiment-2
Date:
Principle :
From the emf of the cell involving saturated calomel electrode and metal
electrode dipped in its solution of 0.1 N electrolyte, electrode potential of the
metal electrode is readily calculated using the standard potential of calomel
electrode as;
Ecell = EM/M+ Ecalomel
8
EM/M+= EM/M+ 0.0595 Iog aMn+
n
Activity coefficient (c) 0.905 0.870 0.809 0.749 0.675 0.570 0.485 0.405
9
Apparatus: Digital potentiometer, copper electrode, zinc electrode, calomel
electrode, 100 mL beaker, burette, standard flask.
Procedure:
Calibrate the digital potentiometer with the help of the wires to display 1.018 V.
The metal electrode is sensitized by dipping in a small quantity of 1:1 nitric acid
containing a small quantity of sodium nitrite until effervescence occurs. Then the
electrode is washed well with distilled water. 50 mL of the given concentration of
the electrolyte solution is taken in a beaker and its corresponding metal electrode
is introduced. This is connected with the saturated calomel electrode (half-cell)
by means of a salt bridge. The metal electrode is connected to the positive
terminal of and the calomel electrode is connected to the negative terminal of the
potentiometer. The emf of the cell (Ecell) is measured and noted in Table 1. The
standard electrode potential [EM/M2+] is computed using Nernst equation (eqn.
no. 1).
In the Daniel cell, copper and zinc electrodes are immersed in the equimolar
solution of copper(II)sulfate and zinc(II)sulfate respectively. At the anode, zinc
is oxidized as per the following half-reaction:
10
Zn(s) Zn2+(aq) + 2e
At the cathode, copper is reduced as per the following reaction:
Cu2+(aq) + 2e Cu(s)
The overall reaction is:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Construct Daniel cell using the following concentrations of Copper and Zinc
solutions and record the voltage of the cells and enter into the Table 3.
Table 3: EMF of Daniel Cell observed from three different concentrations of
zinc and copper solutions
EMF
Metal Concentration Metal Concentration
observed
(N) (N)
(Ecell / V)
0.01 N 0.01 N
0.1 N 0.1 N
Result:
(a) The single electrode potential of zinc and copper systems are
___________ and ______________ respectively.
(b) Potentials (V) of Daniel cell: __________________
Evaluation of result:
11
CYCLE I Experiment-3
OBSERVATION AND CALCULATIONS
Titration-I
Burette: Potassium Permanganate solution (0.05 N)
Beaker: 20 mL of steel solution + one test tube dilute H2SO4
Electrodes: Indicator electrode (Pt) to red terminal and SCE to black terminal
Volume of
S. No. EMF (volt)
KMnO4 (mL)
1
2
3
4
5
6
7
8 Figure I: Plot of EMF vs volume of KMnO4
9 added (mL)
10
11
12
13
14
15
12
CYCLE I Experiment-3
Date:
Principle:
Potassium permanganate oxidizes ferrous ion (Fe2+) to ferric ion (Fe3+) in the
presence of acid as per the reaction:
5Fe+2 5Fe+3 + 5e
MnO4- + 8H+ + 5e Mn2+ + 4H2O
5Fe + MnO4- + 8H+ 5Fe+3 + Mn2+ + 4H2O
+2
The electrode potential (oxidation potential) in the titration depends upon the
concentration of Fe2+, Fe3+ and hydrogen ions.
To avoid the effect of the change in the hydrogen ion concentration, the titration
is usually carried out in large excess of an acid.
The oxidation potential of this redox system is given by
RT Fe 3
E E0 ln( 2 )
nF Fe
Connecting the redox electrode (Pt) with a saturated calomel electrode (SCE)
completes the necessary cell as indicated below:
13
Titration-II
Steel solution containing Fe(II) 20 mL + 20 mL (one test tube) 2.0 N H2SO4
In beaker, KMnO4 in burette
Vol. of
Sl. E E/V Average
KMnO4 EMF (Volt) V (mL)
No. (Volt) (Volt/mL) Volume (mL)
( mL)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
15
Carry out another titration in similar way but by adding 1 mL aliquots of KMnO4
initially and then 0.1 mL aliquots between the two volumes where the end point is
detected. Continue the titration beyond the end point as done above. The exact
end point is determined by differential method i.e. by plotting E/V vs. average
volume of KMnO4 added. Calculate the percentage of Fe(II) in the given solution
by calculations shown.
Calculations:
By stoichiometry, 5 moles of Fe(II) will need 1 mole of KMnO4 for complete
oxidation. Hence, 279.25 g Fe(II) will need 158.04 g of KMnO4
Result
Percentage of Fe (II) in the steel sample =
Evaluation of result
Sample Experimental value Actual Percentage of Marks awarded
number Value error
16
Space for calculations
17
CYCLE I Experiment-4
Measured
concentration
2+
of Ca (ppm)
2+
Prepared concentration of Ca (ppm)
Result
The amount of calcium present in the given water sample = ppm
Evaluation of result
Sample Experimental value Actual Percentage of Marks awarded
number Value error
18
DETERMINATION OF HARDNESS DUE TO CALCIUM IN A WATER SAMPLE
USING FLAME EMISSION PHOTOMETRY
Date:
Principle :
The estimation of calcium is based on the emission spectroscopy, which deals
with the excitation of electrons from ground state to higher energy state and
coming back to its original state with the emission of light. Trace amount of
calcium can be determined by flame emission photometry at a wavelength of 423
nm. The intensity of light at 423 nm is proportional to the concentration of the
element. After careful calibration of photometer with solution of known
composition, it is possible to correlate the intensity of a spectral line of unknown
solution with the amount of an element present that emits the particular radiation.
Reagents
1) Distilled water
2) Calcium stock solution 1000 ppm stock (Dissolve 2.497 g CaCO3 in 1-2 mL
conc. HCl and dilute to 1L accurately).
3) Prepare five different concentrations of calcium solution in the range of 20
ppm
200 ppm in 50 mL standard flasks by making up with distilled water.
4) Along with these solutions, prepare given unknown sample in another 50 mL
5) standard flask.
Apparatus:
Burette, graduated pipette, beakers, rubber Bulb, standard volumetric flasks (50 mL),
Flame photometer and accessories.
19
Procedure:
Setting the instrument for estimation of Calcium
1) Start the electrical supply and switch on the air supply. Stabilize the air and
the needle should be steady at the mark to maintain about 0.5 Kg/cm 2
pressure.
2) Switch on the gas and maintain the gas fuel mixture so that blue flame is
seen through the viewing window.
3) Adjust the flame so that the flame is seen as 5 cones each in two parallel
rows.
4) Follow the operating instructions of the instrument kept near to the
instrument..
5) Following the instructions seen on the screen, carry out calibration using the
five diluted solutions of calcium. Stop when CALIBRATION OVER display
comes.
6) Then select SAMPLE from the menu.
7) Each one of the solutions should be aspirated as sample and the
concentration reading displayed by the instrument should be noted down.
8) A plot should be made as prepared concentration vs displayed concentration.
9) Simultaneously record the concentration of calcium from the given unknown
by introducing unknown as sample and report the result.
20
Space for calculations
21
CYCLE II Experiment-5
22
ESTIMATION OF NICKEL IN A NI-PLATED MATERIAL FOR CORROSION
PROTECTION BY COLORIMETRY
Date:
Principle:
Dimethylglyoxime reacts with nickel ions and forms a pink colored Ni(dmg) 2
complex in alkaline medium. Nickel forms a brown-red, water soluble oxidized
nickel-dimethylglyoxime complex with potassium ferricyanide in alkaline medium
as shown in the scheme below. The absorption spectrum of the oxidized complex
shows absorption maximum at a wavelength of 440 nm (Figure 1). After drawing
calibration graph the determination of nickel concentration in a given unknown
sample can be done by colorimetry applying Beer-Lambert law.
Solutions required
23
Procedure:
In five 100 mL standard volumetric flasks add 1.00 mL of dimethylglyoxime
solution by a pipette followed by 1,00 mL of potassium ferricyanide solution
through a burette. Then add 1.00, 2.00, 3.00, 4.00, and 5.00 mL of the steel
containing nickel(II) solution from a burette to the flask. All flasks are shaken well
and made up to 100 mL mark with 1N NaOH solution. Allow the flasks to rest for
15 minutes after the addition of all the reagents for the complete complex
formation. Then the absorbance of the formed brown-red solution can be
measured at 440 nm against the distilled water blank. Set the colorimeter to this
wave length range using appropriate filters. Record the absorbance of each one
of the solutions using water as blank and enter in Table-1. Prepare the unknown
sample in a similar way and record its absorbance also. Draw a calibration graph
taking concentration of nickel (II) as X-axis and absorbance readings as Y-axis
and a straight line that passes through the origin is obtained as shown in Figure
From the calibration plot, measure the concentration of nickel (II) in the unknown
sample is calculated.
Result
Concentration of Nickel in the steel sample = .. ppm (mg/L)
Evaluation of result
24
Space for Calculations
25
CYCLE II Experiment-6
Titration I :
Standardization of Sodium Thiosulphate
Concordant value
Calculations:
V1N1 = V2N2
N2 = V1N1/V2
= ..N
=N
26
DISSOLVED OXYGEN (DO) ANALYSIS IN WATER BY WINKLERS METHOD
Date:
Principle:
Dissolved oxygen is an important factor in corrosion. Oxygen is poorly
soluble in water. The solubility of oxygen decreases with increase in conc. of the
salt under a pressure of one atmosphere, the solubility is less in saline water.
The estimation of dissolved oxygen in water is useful in studying corrosion effect
of boiler feed water and in studying water pollution. Dissolved oxygen is usually
determined by Winklers method. It is based on the fact that dissolved oxygen
oxidized potassium iodide (KI) to iodine. The liberated iodine is titrated against
standard sodium thiosulphate solution using starch indicator. Since dissolved
oxygen in water is in molecular state. It as such cannot oxidize KI. Hence
Manganese Hydroxide is used as an oxygen carrier to bring about the reaction
between KI and Oxygen. Manganese hydroxide, in turn, is obtained by the action
of NaOH on MnSO4.
27
Titration : II
Calculations :
V1N1=V2N2
N1= V2 X N2/V1
= .
Amount of dissolved oxygen (ppm) = normality equivalent weight of O21000mg/L
of the given water sample.
= .N 8 1000mg/L
= ------------------ ppm.
28
Reagents:
Standard Potassium dichromate, sodium thiosulphate solution, potassium iodide
solution, Alkali Iodide solution: (KI + NaOH in water), conc. H2SO4, Manganese
sulphate, starch solution as indicator
PROCEDURE:
The burette is washed and rinsed with sodium thiosulphate solution. Then the
burette is filled with given sodium thiosulphate solution. 20 mL of 0.01N
potassium dichromate solution is pipette out into a clean conical flask. To this 5
mL of sulphuric acid and 10 mL of 10% potassium iodide are added. This is
titrated against sodium thiosulphate solution, when the solution become straw
yellow colour, starch indicator is added and then the titration is continued. The
end point is disappearance of bluish brown colour. The titration is further
repeated twice or thrice to get the concordant value.
29
RESULT :
Evaluation of result
Sample Experimental value Actual Percentage of Marks awarded
number Value error
30
CYCLE II Experiment-7
Observations and calculations
Ostwald Viscometer
Eflux time for pure water (t0) = sec.
3.
r = relative viscosity
sp= specific viscosity
Intrinsic viscosity of the given polymer (from the graph) =
31
ESTIMATION OF THE MOLECULAR WEIGHT OF A POLYMER BY OSTWALD
VISCOMETER
Date:
Principle:
When a polymer is mixed with a solvent, the solvent enters into the
polymer matrix and swelling of polymer coils takes place. This expanded polymer
coil disintegrates and moves out of polymer matrix and dissolves in the solvent.
The apparent volume occupied by the expanded coil is referred to as the
`Hydrodynamic Volume of the polymer molecule in the solution under flow. The
viscosity of a polymer solution is a direct measure of hydrodynamic volume of the
polymer, which in turn is a measure of its molecular weight. The viscosity of a
polymer is more in a good solvent than in a poor solvent. In a particular solvent,
molecular weight of the polymer is directly proportional to viscosity of the
solution. MarkHouwink equation relates the molecular weight and intrinsic
viscosity of the polymer solution as follows.
= KM
where K, are constants (depends on the nature of polymer, solvent and
temperature)
32
Observations and calculations
= KM
Molecular weight of the given polymer (M) =
33
20
15
sp
/C
10
0
0 0.1 0.2 0.3 0.4
Concentration (C g/mL)
Rinse the Ostwald viscometer with a little amount of water. Fill it with 20 mL pure
water and keep it in a constant temperature thermostat maintained at 30 C for
34
10 to 15 minutes so that solvent attains the temperature of water bath (30 C). By
keeping the upper mark of the small reservoir of viscometer parallel to eyes,
allow the solvent to flow down to the lower mark and note down time in seconds. This
is known as the Eflux time. Repeats the same experiment for 3 times to get the
average Eflux time for water( t0).
Evaluation of result
CYCLE II Experiment-8
35
WATER PRESERVATION THROUGH SMART MATERIALS (HYDROGEL)
Date:
Principle:
Hydrogels are polymeric cross-linked network structures obtained from a
class of synthetic and/or natural polymers which can absorb and retain significant
amount of water due to the presence of hydrophilic groups or domains (Scheme
1). Water is brought into the network through the process of osmosis and quickly
is absorbed into the central part of the polymer network. This is mainly due to the
affinity of these functional groups towards water (e.g., due to the
protonation/deprotonation as a result of changes in pH and temperature) and
leading to a reversible change in the swelling degree as shown in Scheme 1.
Figure 1: Bulk hydrogels with specific functional groups (FG) the different
solvation water depending on environmental conditions (e.g., pH, or
temperature) leads to large reversible changes in the degree of swelling.
Hydrogels find applications mainly in tissue engineering, pharmaceutical, and
biomedical and agricultural fields. Due to their high water absorption capacity and
36
biocompatibility they are now being used in wound dressing, drug delivery,
sanitary pads as well as trans-dermal systems, dental materials, implants,
injectable polymeric systems, ophthalmic applications, hybrid-type organs.
Table-1
Sl. No. Wt. of polymer taken, Wt. of polymer Amount of
g after swelling, water
g absorbed, mL
1 Wd1 Ws1
2 Wd2 Ws2
3 Wd3 Ws3
Average
Table-2
Sl. No. Wt. of polymer Amount of Wt. of Amount of
taken, g ionic polymer after water
compound swelling, g absorbed,
added mL
1 Wd1 Ws1
2 Wd2 Ws2
3 Wd3 Ws3
Average
Table-3
37
Sl. No. Wt. of polymer Amount of Wt. of Amount of
taken, g neutral polymer after water
compounds swelling, g absorbed,
added mL
1 Wd1 1.0 Ws1
2 Wd2 1.0 Ws2
3 Wd3 1.0 Ws3
Average
Procedure
Part-A:
----Eq.1
38
Part-B
Part-C
A small amount of dry polymer material is placed in the beaker (0.5 g, note down
the exact weight of the polymer taken) and then 1 % sucrose solution (prepared
by adding 1 g of sucrose in 100 mL of deionized water) is poured into the beaker.
After 5 min the swollen polymer was separated by using a filter paper and note
down the weight of the gel. By weighing the gel, one can find the swollen
capacity of the polymer using the given equation.
39
Result
Swelling index of the polymer material with deionized water = _____________
Swelling index of the polymer material with ionic impurities = _____________
Swelling index of the polymer material with neutral impurities = _____________
Students are informed to bring their choice of materials (any neutral or ionic) to
carry out the experiments on their own to answer the above questions. Answers
for these questions are very important to use these hydrogel materials in an
efficient way with recoverability.
Date:
Principle:
Definition of Aniline point (AP): AP is the lowest temperature at which the
sample is homogeneous i.e. completely miscible with equal volume of aniline.
Mixed Aniline point (MAP): MAP is the minimum equilibrium solution
temperature of a mixture of two volume of aniline, one volume of sample and one
volume of n-heptane of specific purity.
Aniline point (AP) is characteristic of petroleum fractions that indicate the
degree of aromaticity of hydrocarbon mixtures. Lower the aniline point, the
higher the aromatics content in the fuel oil. The higher the aromatics content, the
lower the cetane number of the fuel. The aniline point can thus be used to
indicate the probable ignition behaviour of a diesel fuel.
Procedure:
Clean and dry the U tube and arrange the apparatus desired. Now add 5 mL of
distilled aniline and 5 mL of given sample in the U tube, it will form two layers.
Arrange the apparatus with stirrers in such way that liquid in U tube and the
water in the beaker are stirred simultaneously. Switch on the heater to heat the
water at a controlled rate, so there is no much difference in temperature of
paraffin bath and U tube.
The minimum temperature at which two layers give a single phase is noted as
aniline point. Now stirring of U tube mixture is stopped, and mixture is allowed to
cool. Temperature at which two layers are formed is also considered as aniline
point.
41
For mixed aniline point the above procedure is repeated by taking 2.5 mL of
sample, 2.5 mL of n-heptane and 5 mL of aniline.
Observations:
Result:
(1) Aniline point of the given sample = --------------
(2) Mixed Aniline point of the given sample = --------------
Evaluation:
42
ESTIMATION OF SULPHATE IN EFFLUENT BY TDS-CONDUCTIVITY METHOD
Date:
Principle
Electrolyte solutions conduct electricity due to the presence of ions in solution. In
case of precipitation titration between BaCl2 and Na2SO4, the conductance
decreases slowly due to the replacement of Na ion by SO42- upto the
equivalence point. After the equivalence point the conductance increases rapidly
due to the excess addition of BaCl2 which remains in solution as Ba2+ and Cl-.
This makes detection of neutralization point easy from the conductance trend
plotted as a graph. This is the principle is used in the estimation of SO 42- from an
effluent sample.
Apparatus required
TDS-Conductivity bridge, conductivity cell, burette, pipette, volumetric flasks,
glass rod and 100 mL beaker.
Chemicals required
BaCl2, Na2SO4, unknown sulphate solution and distilled water.
Procedure
Calibration of TDS-Conductivity meter:
Place a freshly prepared 0.01 N KCl solution (given in bottle) in a 100 mL beaker
and dip the conductivity cell in this solution and connect to the TDS-Conductivity
meter. Press CAL button and complete the internal calibration of the instrument
Standardization of BaCl2:
Standard flask A contains Na2SO4 which after making up to 50 mL will result in a
solution containing 0.96 mg/mL of sulphate ions. Pipette out 20 mL of this
solution and add 20 mL of distilled water to it in a 100 mL beaker. The
conductivity cell is dipped into the beaker and connected to TDS conductivity
meter. Fill the burette with BaCl2 solution (Solution B). Record the conductivity of
the sulphate solution as 0th reading. Add 0.5 mL portion of known concentration
8.5
8.0
Conductance (mhos)
7.5
7.0
6.5
6.0
5.5 V2 mL
5.0
0 2 4 6 8 10 12 14
BaCl2 added (mL)
Fig. Model graph-2 for TDS-Conductometric estimation of unknown sulphate sample solution
44
of BaCl2 into the beaker, stir with glass rod and note down the conductance.
Continue the addition of BaCl2 (0.5 mL each time) and note the conductance
after each addition. Continue the titration beyond the equivalence point for about
3mL. The conductance will decrease till complete precipitation of BaSO 4 and
then starts increasing on continuing the addition of BaCl2. A graph is now drawn
by plotting conductance Vs volume of BaCl2 added and the intersection point
from the graph gives the volume of BaCl2 required for precipitating the sulphate
from the known sample.
Estimation of unknown sulphate in the given solution:
Make up the unknown sulphate solution given in standard flask B up the 50 mL
mark. Pipette out 20 mL of this solution into a 100 mL beaker and add 20 mL
distilled water to it. Dip the conductivity cell and repeat the above procedure with
the unknown sulphate solution and determine the amount of BaCl2 required for
precipitating the unknown sulphate in the sample.
From the two titrations carried out, calculate the amount of sulphate present in
the effluent sample.
Calculations:
A)Standardization of BaCl2:
45
Result
Evaluation of result
Sample Experimental value Actual Percentage of Marks awarded
number Value error
46
EXPERIMENT-11
Lab scale production of biodiesel from plant seeds
(demo experiment)
Biodiesel is a mixture of mono alkyl ester of long-chain fatty acids obtained by
transesterification of vegetable oils or animal fats (triglycerides) with alcohol in
presence of base. It can be used in diesel engines, alone or blended with fossil
diesel. A pure biodiesel fuel is referred as B100. Biodiesel blends are referred as
BXX where XX indicates the amount of biodiesel in the blend, eg. B20 refers to
20% by volume of biodiesel and 80% by volume of fossil diesel. Since biodiesels
are biodegradable and its spills cause little or no threats they referred as bio-
diesel.
Principle
Vegetable oils and animal fats are comprised of complex mixtures of triglycerides
and other minor components, such as free fatty acids (FFAs), gums, waxes, etc.
Triglycerides are esters of glycerol with three chains of aliphatic or olefinic FFAs
of variable length (12-24 carbons).
47
Although vegetable oils occupy a prominent position in the development of
alternative fuels, there have been many problems associated with using it directly
in a diesel engine. Two of the problems are the high viscosity (about 11-17 times
higher than diesel fuel) and lower volatilities of vegetable oils, which causes the
formation of deposits in engines due to incomplete combustion and incorrect
vaporization characteristics. Triglycerides must be converted to simple esters to
achieve desirable flow properties and combustion characteristics for use in diesel
engines. Different ways have been considered to reduce the high viscosity of
vegetable oils:
Dilution of 25 parts of vegetable oil with 75 parts of diesel fuel
Microemulsions with short chain alcohols such as ethanol or methanol,
Thermal decomposition, which produces alkanes, alkenes, carboxylic acids and
aromatic compounds,
Catalytic cracking, which produces alkanes, cycloalkanes and alkylbenzenes,
and
Transesterification with methanol or ethanol.
Among the many ways and procedures to convert vegetable oil into a diesel-like
fuel, transesterification process was found to be the most viable oil modification
process. This is an attractive alternative (or extender) to petro-diesel fuel due to
well-known advantages.
Biodiesel has been produced by transesterification of triglyceride to methyl esters
with methanol in the presence of catalysts as illustrated by reaction scheme 1.
In transesterification, the triglyceride in vegetable oil reacts with an alcohol to
form a mixture of glycerol and fatty acid esters, called biodiesel. There are
different processes that can be applied to synthesize biodiesel: (i) base-catalyzed
transesterification, (ii) acid-catalyzed transesterification, (iii) integrated acid-
catalyzed pre-esterification of free fatty acids (FFAs) and base-catalyzed
transterification, (iv) enzyme-catalyzed transesterification, (v) pyrolysis, and (vi)
supercritical alcohol transesterification. At present, the most common way to
48
produce biodiesel is to trans-esterify triglyceride in vegetable oil or animal fats
with an alcohol in the presence of an alkali or acid catalyst (Base catalysis is
preferred to acid catalysed routes using sulphuric or sulfonic acids, which are
more corrosive with lower activities).
Transesterification
Chemicals required
1) Vegetable oil (soybean, peanut, cottonseed, coconut, or other oil of your
choice).
2) Sodium hydroxide, NaOH or KOH pellets
3) Methanol or ethanol absolute
Apparatus required
1) Magnetic stirrer with hot plate
2) Magnetic stir bar
3) 250 mL Erlenmeyer flask
4) 2 - 100 mL or 150 mL beakers
5) 50 mL graduated cylinder
6) Thermometer
7) Separatory funnel
PROCEDURE:
NOTE: Critical to these processes is the need for water-free triglycerides;
any water in the transesterification reaction may result in the production of
free fatty acids, thus complicating the separation of product layers and/or
contamination of the final product. So be sure to clean and dry glassware
for this experiment. Although soap is very similar in chemical structure to
biodiesel, the carboxylate salt can be corrosive inside an engine.
3) When all of the NaOH is dissolved, pour the 100 mL of oil into the
methoxide solution while continually stirring. At first the mixture will
become cloudy, but should soon separate into two layers. Stir for 15-30
minutes on high stirring.
4) Transfer the content of the flask into 250 mL separatory funnel. The
mixture will separate into different layers. The glycerol will fall to the
bottom, and the methyl ester (biodiesel) will float to the top. Since about
75% of the separation occurs within the first hour, you will be able to see
immediate progress. Allow the experiment to sit for about an hour.
5) Open the stopcock of the separatory funnel and drain the lower layer into
a 100 mL beaker. This solution contains glycerin, unreacted methanol,
unreacted sodium hydroxide, a trace of water and salts. In a commercial
process, the glycerin and methanol can be collected for reuse. In this
experiment, it will be disposed in a waste container. Make sure not to get
any biodiesel in the glycerol.
7) The top layer in the separatory funnel should be the biodiesel. It will be
contaminated with traces of methanol, glycerin, unreacted sodium
hydroxide, and some soap which is a byproduct of the reaction. (Soap is
the sodium salt of a fatty acid.)
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8) Wash the biodiesel by adding 10 mL of tap water to the separatory funnel.
Gently swirl the mixture for about 1 minute to dissolve the methanol,
glycerin, sodium hydroxide, and any soap. Do not shake the mixture
vigorously as an emulsion may form.
9) Allow the mixture to separate. Drain off and discard the bottom layer.
NOTE: If an emulsion forms, add 0.2 g of sodium chloride and swirl
the mixture for 1 to 2 minutes. Allow the mixture to stand. Two
layers should form. Drain off the lower layer and discard it.
10) Determine the mass and the volume of the biodiesel. Use the IR
spectrometer to identify the products. The biodiesel may hard to compare,
since most of oils are comprised of different length carbon chains.
Comparing to known spectra can easily identify the biodiesel and glycerol.
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PREPARATION OF SOME IMPORTANT REAGENTS AND SOLUTIONS
3. EBT - Indicator
Dissolve 0.4 gm of solid EBT indicator in 100 mL of methanol (or) ethanol.
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9. 1:5 Orthophosphoric acid
Add 1 mL of orthophosphoric acid to 5 mL of distilled water.
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