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of Chemistry,
AIT
PART A
(Instrumental Experiments)
Dept. of Chemistry,
AIT
Volume of
Potential
3
K2Cr2O7 ( cm ) E (mV)
0.0
0.5
0.5
1.0
0.5
1.5
0.5
2.0
0.5
2.5
0.5
3.0
0.5
3.5
0.5
4.0
0.5
4.5
0.5
5.0
0.5
5.5
0.5
6.0
0.5
6.5
0.5
7.0
0.5
7.5
0.5
8.0
0.5
8.5
0.5
9.0
0.5
9.5
0.5
10.0
0.5
E
V
Volume
of K2Cr2O 7
Equivalence point
Volume of K2Cr2O7
K Cr O
N
FAS
0.5 ........
K Cr O
V
FAS
25 cm FAS.
25
X Equivalent weight of FAS
X 392 =
g
2
GRAPH
SHEET-1 NO.
Experiment 1
Potentiometric estimation of FAS using standard K2Cr2O7 solution
Theory: Redox titrations can be carried out potentiometrically using platinum-calomel electrode
combination. For the reaction,
Reduced form
Oxidized form + n electrons
The potential is given by Nernst equation,
0.0591
[Oxidized form]
E = E0 +
log
n
[ Reduced form ]
Where E is the standard potential of the system. The potential of the system is thus controlled by the
ratio of the concentration of the oxidized to that of the reduced species present. As the reaction
proceeds, the ratio and hence the potential changes more rapidly in the vicinity of the end point of the
titration. This may be followed potentiometrically and a plot of change in potential against volume
(titration curve) is characterized by a rapid increase in potential at the equivalence point. The rapid
increase in the potential at the equivalence point is explained as follows:
The reaction that takes place
in the3+determination of Fe 2+
2+
is Fe Fe + e
Cr2O72- + 14H+ + 6e 2Cr3+ + 7H2O
Prior to the equivalence point, the potential is determined by the Fe 3+/ Fe2+ system and the potential is
given by the equation,
Ecell = EFe
2+
=E
0.0591
log
= 0.75 V + 0.0591
log
[Fe3+]
[Fe2+]
[Fe3+]
[Fe2+]
The potential of the solution will be around 0.75 V (since the contribution to the potential by the
second term is negligible). At the equivalence point the potential is determined by both E 0Fe2+ and
E0Cr2O72- and is given by
2- 2-
1.33V +
0.0591
6
6
log
Cr O
Cr
Cr
/Cr
3+
And hence at equivalence point potential rises steeply. In the experiment, the potential of the cell is
determined with reference to saturated calomel electrode.
PROCEDURE:
Pipette out 25.0 cm3 of ferrous ammonium sulphate solution into a beaker. Add one test tube-full of
dilute sulphuric acid. Immerse the Platinum-calomel electrode assembly into the solution and connect
the electrodes to a potentiometer. Measure the potential. Fill the burette with standard potassium
dichromate solution. Add 0.5 cm3 of K2Cr2O7 to the beaker. Stir the solution carefully and measure the
potential after 10 seconds. Continue the procedure till the potential shows a tendency to increase
rapidly. Further take 6 more readings. Determine the end point by differential method i.e., by plotting
E/V against volume of potassium dichromate as shown in the figure. Calculate the normality of the
FAS solution and determine the amount of FAS in the given solution.
Result:
1. Equivalence Point
2. Normality of FAS =
=
3
********
3
Absorbance
A
B
S
O
B
A
N
C
E
5
10
15
20
Test Solution
63.54 mg of Cu
4.2 mg of CuSO4.5H2O=
63.54 4.2
249.54
= 1.069
mg of Cu
mg of Cu
cm3
mg of Cu
GRAPH
SHEET-1 NO.
Experiment 2
Colorimetric estimation of copper
Theory: When a monochromatic light of intensity I 0 is incident on a transparent medium, a part I a is
absorbed, a part Ir is reflected and the remaining part It is transmitted.
I0 = Ia + Ir + It
For a glass-air interface Ir is negligible. Therefore,
I0 = Ia + It
It / I0 = T, called the transmittance, log 1/T= log I0/It is called the absorbance or optical density A. The
relation between absorbance A, concentration c (expressed in mol lit -1) and path length t (expressed in
cm) is given by Beer - Lamberts law,
A = log I0/It = ct
Where
is the molar extinction coefficient and constant for a given substance at a given wavelength.
If the path length (cell thickness) is kept constant, then, A c. Hence a plot of absorbance against
concentration gives a straight line as shown in figure (calibration curve). The absorbance of the
colored solution is measured using a spectrophotometer at a wavelength where the absorbance is
maximum.
A series of standard solutions containing cupric ions is treated with ammonia to get deep blue
cuprammonium complex and is diluted to a definite volume.
Cu2+ + 4[NH3] Cu[NH3]42+
Deep blue
The absorbance of each of these solutions is measured at 620 nm since the complex shows maximum
absorbance at this wavelength. The concentration is plotted against absorbance to get a calibration
curve. A known volume of the test solution is treated with strong ammonia and diluted to the same
volume as above. The absorbance of this solution at 620 nm is measured and weight of Cu in the test
solution is determined from the calibration curve.
PROCEDURE:
Fill a burette
with the given copper sulphate solution (stock solution). Withdraw
5.0, 10.0, 15.0 and
3
20.0 cm3 of the copper
sulphate
solution
into
separate,
labeled
50
cm
volumetric
flasks from the
burette. Add 5 cm3 of ammonia solution to each of them and make up to the mark with ion exchange
water. Stopper the flasks and mix the solutions well.
To the test solution taken in a 50 cm 3 volumetric flask, add 5 cm3 of ammonia solution and
make up to
3
the mark with ion exchange
water.
Mix
well.
Prepare
a
blank
solution
by
diluting
5
cm
of
ammonia
solution in a 50 cm3 volumetric flask to the mark with ion exchange water and mixing well.
After 10 minutes, measure the absorbance of the solutions against blank at 620 nm using a
colorimeter. Draw a calibration curve by plotting weight of copper against absorbance. Using the
calibration curve determine the weight of copper in the test solution.
Note: Ammonia should be added to all the solutions including the test solution at the same time
Result:
The given test solution contains =
mg of Cu
********
Dept. of Chemistry,
AIT
cm3
Conductance
Volume of NaOH
cm3
-1cm-1
0.0
5.5
0.5
6.0
1.0
6.5
1.5
7.0
2.0
7.5
2.5
8.0
3.0
8.5
3.5
9.0
4.0
9.5
4.5
10.0
5.0
10.5
Conductance
-1cm-1
C
o
n
d.
.
V1
Volume of NaOH
cm3
Normality of NaOH = 1
Normality of HCl
Normality of CH 3COOH
x 36.5 =
V2
x 60
CH3COOH
GRAPH
SHEET-1 NO.
Experiment 3
Conductometric estimation of HCl and CH3 COOH in a mixture using standard NaOH
Theory:
The neutralization point in acid-base titrations is determined by a change in the color of the
indicator. Such a determination can also be carried out by conductometric titration. In conductometric
titrations, there is a sudden change in conductance of the solution near the neutralization point.
However, the change is not sharp and hence the neutralization point is determined graphically by
plotting conductivity against titre values. The principle underlying conductometric titrations is the
replacement of ions of a particular conductivity by ions of different conductivity during titration.
When hydrochloric acid is titrated against sodium hydroxide the following reaction occurs:
NaOH + HCl
NaCl + H2O
The addition of sodium hydroxide to hydrochloric acid decreases the conductance of the latter because
highly mobile H+ ion (mobility: 350 ohm-1m-1) are replaced by the less mobile Na + ion (mobility: 50
ohm-1m-1). This trend continues till all the H+ ions of HCl are replaced i.e., the acid is neutralized and
end point is reached. Further addition of NaOH raises the conductance steeply due to the presence of
free OH- ions (mobility: 198 ohm-1 m-1). A typical titration curve is shown in the figure.
PROCEDURE:
Fill a microburette with the standard NaOH solution. Pipette out 50 cm 3 of the given acid mixture into
a clean 100 cm3 beaker. Wash and immerse the conductivity cell into the beaker. Connect the cell to
the conductivity bridge and measure the conductance of the solution. Add 0.5 cm 3 NaOH solution
from the burette. Stir the solution gently and measure the conductance. Continue the measurement of
conductance after each addition of 0.5 cm3 of NaOH. The conductance initially decreases and then
rises moderately. Continue addition of NaOH. The conductance rises sharply. Continue taking
readings till the initial reading is observed.. Plot a graph of conductance versus volume of NaOH.
From the graph, find the neutralization points and the volumes required to neutralize the acids. From
this calculate the amount of HCl and acetic acid present in 1 liter mixture.
Result: 1. Normality of HCl
2. Weight of HCl
3. Normality of CH3COOH
4. Weight of CH3COOH
*******
7
I
n
Emission Intensity
(Candella)
e
n
s
i
t
y
5
10
15
20
Test Solution
ml (Say X)
g of NaCl (say Y)
g of Na
----------
(SayZ)
= Z x 1000 mg of Na
GRAPH
SHEET-1 NO.
Experiment 4
Flame photometric Estimation of Sodium
Theory
Sodium, potassium, calcium and lithium and other common elements impart characteristic s with the
Bunsen flame. The intensity of the emitted flame varies with the amount of element introduced. This
forms the basis of flame photometry.
When a solution containing a compound of the metal to be investigated is aspirated into a flame, the
following processes occur.
i) Solvent evaporates leaving behind a solid residue.
ii) Vaporization of the solid coupled with dissociation into its constituent atoms, which are
initially in the ground state.
iii) Some gaseous atoms get excited by the thermal energy of the flame to higher energy
levels.
The excited atoms which are unstable quickly emit photons and return to lower energy state i.e.
ground state. Flame photometry involves the measurement of emitted radiation.
Schematically it is represented as:
Evaporation
Vapourisation
Dissociation
M +X MX
MX
M (gas) + Gas
Thermal excitation
M (g) Flame emission, h
The relationship between the ground state and excited state populations is given by the Boltzmann
N1/No = (g1/go)e- E/kT where
equation:
N1 = Number of atoms in the excited state
No = Number of atoms in the ground state
g1/go = ratio of statistical weights for ground and excited states
E = Energy of excitation = h
k = the Boltzmann constant, T = Absolute Temperature
From the above equation, it is evident that the ratio N 1/No is dependent upon both the excitation
energy E and the temperature T. An increase in temperature and a decrease in E will both result in a
higher value for the ratio N1/No.
PROCEDURE:
1.
2.
3.
4.
5.
Transfer 5, 10, 15, and 20 ml of standard NaCl solution (which is prepared by weighing
accurately 2.542 g NaCl into a 1 litre volumetric flask and dissolving the crystals and
diluting the solution up to the mark with distilled water and mixwell. The solution gives
1 ppm/ml) into 50 ml standard volumetric flasks and dilute up to the mark with distilled water.
Place the distilled water in the suction capillary of the instrument and set the instrument to
read zero.
Place each of the standard solutions in the suction capillary and record the emission intensity.
Dilute the given test solution up to the mark and shake well and place the solution in the
suction capillary and record the emission intensity.
Draw a calibration curve by plotting the Emission intensity (y-axis) against volume of NaCl
solution (x-axis).
From the calibration curve, find out the volume of the given test solution and calculate
the amount of Na.
Result:
The test solution contains = -----------
mg of Na
********
9
pH
pH
pH
V
0.0
0.5
0.5
1.0
0.5
1.5
0.5
pH
V
Vol. of NaOH
Equivalence point
2.0
0.5
2.5
0.5
3.0
0.5
3.5
0.5
4.0
0.5
4.5
0.5
pH
5.0
0.5
pKa
5.5
0.5
6.0
0.5
6.5
0.5
7.0
0.5
7.5
0.5
8.0
0.5
8.5
0.5
9.0
0.5
9.5
0.5
10.0
0.5
Vol.of NaOH
cm
10
GRAPH
SHEET-2
NOS.
Experiment 5
Determination of pKa value of weak acid using pH meter
Theory: In the titration of an acid with a base, the pH of the solution increases gradually at first, then
more rapidly, until at the equivalence point, there is a very sharp increase in pH for a very small
quantity of added base. Beyond the equivalence point, the pH increases only slightly on addition of
excess base. The titration curve obtained by plotting changes in pH against volume of the base added.
Just as the pH is a measure of the hydrogen ion concentration, pK a is a measure of the dissociation
constant (Ka) of an acid. The pKa value of an acid can be calculated using Henderson -Hasselbalch
equation,
pH = pKa + log [salt]/[acid]
Where pKa = -log Ka
At half equivalence point, [salt] = [acid] and hence pH = pK a . Thus pH at half equivalence point
gives the pKa of the weak acid.
PROCEDURE:
Pipette out 25.0cm3 of the given weak acid into a beaker. Immerse a glass electrode - calomel
electrode assembly into the acid and connect the cell to a pH meter. Measure the pH of the acid. Fill a
microburette with the sodium hydroxide. Add NaOH with an increment of 0.5 ml to the beaker. Stir
the solution carefully and measure the pH after each addition. After the rapid increase in pH, take 6
more readings by adding NaOH.
Plot a graph of pH/V against V and determine the equivalence point. Plot a graph of pH (ordinate)
against the volume of sodium hydroxide added (abscissa). Determine the pH at half equivalence point.
This gives the pKa of the weak acid.
Result:
pKa value of the given weak acid =
********
11
Mark
A
Mark
B
Constant
temperature
bath
Trial 2
Trial 3
Average
Test liquid
(tl)
Water (tw)
Liquid no.
Lab temperature
dw = Density of water
w = Viscosity coefficient of water =
dl = Density of liquid
= -------------- g cm
-3
------------ millipoise
= -------------- g cm
-3
w dl tl
dw tw
12
Experiment 6
Determination of Viscosity coefficient of organic liquid by Ostwalds viscometer
Theory: Viscosity arises due to internal friction between moving layers of molecules. A liquid flowing
through a cylindrical tube of uniform diameter is expected to move in the form of molecular layers. A
layer close to the surface is almost stationary while that at the axis of the tube moves faster than any
other intermediate layer. A slow moving layer exerts a friction on its nearest moving layer. This
property of a liquid by which it opposes motion between layers is called viscosity. The coefficient of
viscosity is defined as the tangential force per unit area required to maintain a unit velocity gradient
between any two successive layers of a liquid situated unit distance apart. The
coefficient of viscosity of a liquid is given by Poiseuilles formula,
4
pr t
8v l
Where v = volume of the liquid, r = radius of the tube, l = length of the tube, p is the pressure
difference between the two ends of the tube, is the coefficient of viscosity of the liquid and t is the
time of flow. If equal volumes of two different liquids are allowed to flow through the same capillary
under identical conditions, then
t1 d1
=
. (1)
tw dw
The time (t1) taken by the test liquid to flow through a certain distance in the capillary is determined.
The time (tw) taken by a water to flow through the same distance is measured. Coefficient of viscosity
of the test liquid is calculated from the densities (d l and dw) of the test liquid and the water and the
coefficient of viscosity of the water. The viscosity measurement is carried out in Ostwalds
Viscometer shown in figure. Viscosity is a temperature dependent property and hence the
measurements are carried out at constant temperature.
PROCEDURE:
Fix the dry viscometer vertically to stand in a constant temperature bath (beaker containing water).
Transfer a known volume (say 10 cm 3) of water into the wider limb by clean pipette. Allow the
viscometer to stand for some time so that the liquid attains the bath temperature. Suck the water above
the upper mark A of the viscometer. Allow it to flow freely through the capillary. When the level of
water just crosses mark A, start a stop clock. Stop the clock when the water just crosses the lower
mark B. Note the time of flow in seconds (t w). Repeat to get agreeing values. Pour out the water, rinse
the viscometer with acetone and dry it. Repeat the experiment with exactly the same volume of the
liquid whose viscosity is to be determined and find the time of flow (t l seconds). Calculate the
coefficient of viscosity of the liquid using Eq. (1).
Note: Dry the viscometer thoroughly before conducting the experiment with test liquid
********
13
Normality of FAS =
X 4
=
392
=
FAS
in burette
Final burette
reading
Initial burette
reading
Volume of
FAS run down
(cm3)
Trial 1
Trial 2
0.0
0.0
Trial 3
0.0
(say z)
Indicator
and color change
Ferroin
Bluish green to
reddish brown
cm3 (say y)
cm3 (say x)
cm3
= 8 g of oxygen
8 x - y z
g of oxygen
1000
1000
8(x y)z
g of oxygen
25
14
Experiment 7
Determination of chemical oxygen demand (COD) of waste water - redox titration
Theory: Chemical oxygen demand is a measure of the oxygen equivalent of organic and inorganic
materials in a water sample that can be oxidized by a strong chemical oxidant. This parameter is
important for industrial waste studies. COD is expressed as mg of oxygen required to oxidize
impurities present in 1000 cm3 of waste water.
The oxidizable constituents of waste water include straight chain aliphatic compounds,
aromatic hydrocarbons, straight chain alcohols, acids, pyridine and other oxidizable materials. Straight
chain compounds and acetic acid are oxidized more effectively in presence of silver ions (added as
silver sulphate) as catalyst. However, the silver ions become ineffective in presence of halide ions
(present in waste water) owing to the precipitation of silver halide. This difficulty is overcome by
treating the waste water with mercuric sulphate before the analysis for COD. Mercuric sulphate binds
the halide ions and makes them unavailable.
A known volume of the waste water sample is treated with known excess of acidified
potassium dichromate. Unreacted dichromate is titrated against standard ferrous ammonium sulphate
solution using ferroin indicator. A blank titration without the water sample is performed. COD of the
water sample is determined from the difference in the titre values.
This is a redox titration
PROCEDURE:
Preparation of standard solution of FAS (Mohrs salt)
Weigh out accurately about 4.0 grams of ferrous ammonium sulphate into a 250 cm 3 volumetric flask.
Add one test-tube full of dilute sulphuric acid and swirl the flask to dissolve the crystals. Dilute the
solution up to the mark with ion exchange water. Mix the solution well. Calculate the normality of
ferrous ammonium sulphate.
Back titration: Pipette out 25.0 cm3 of the waste water sample into a 250 cm 3 conical flask. Add 10.0
cm3 of standard potassium dichromate using a pipette followed by one-test-tube full of 1:1 sulphuric
acid (containing silver sulphate and mercuric sulphate) Add 2-3 drops of ferroin indicator and titrate
against the ferrous ammonium sulphate solution until the solution turns from bluish green to reddish
brown.
Blank titration: Pipette out 10.0 cm3 of potassium dichromate solution. Add one test-tube full of 1:1
sulphuric acid followed by 2-3 drops of ferroin indicator and titrate against the ferrous ammonium
sulphate solution till the solution turns from bluish green to reddish brown.
Result:
1. Normality of FAS =
2. COD of the given waste water sample = ------------ mg of oxygen per litre
********
15
Trial 1
Final burette
reading
Initial burette
reading
Volume of Na2S2O3
run down (cm3)
0.0
Trial 2
Trial 3
0.0
0.0
Disappearance
of blue color
Indicator color
change
Starch towards
the end point
g
0.2
(say y)
cm3 (say x)
g of Cu (say a)
a 100
w
16
Experiment 8
Determination of percentage of copper in brass - iodometric titration
Theory: Brass is an alloy of copper and zinc. It also contains small amounts of tin, lead and iron. The
percentage composition of a typical brass alloy is Cu: 50-90 % Zn: 20-40 % Sn : 0-6 % Pb: 0 - 2 % Fe
: 0 - 1%
The amount of copper present in brass can be determined iodometrically. A solution of brass is made
by dissolving the sample in minimum amount of nitric acid. Excess nitric acid is destroyed by boiling
with urea. The solution is treated with ammonia to remove any mineral acid and acidified with acetic
acid. Then potassium iodide is added. The potassium iodide reduces cupric ions to cuprous ions
liberating equivalent amount of iodine. And cuprous iodide is precipitated.
2Cu2+ + 4KI
Cupric
Cuprous iodide
The liberated iodine is titrated against sodium thiosulphate using starch as indicator towards the end
point.
2+ 2I 2S2O32- + I2 S4O6
Thiosulphate
Tetrathionate
Starch forms a blue complex with iodine. The end point is detected by a sharp disappearance of the
blue color. The volume of sodium thiosulphate required is a measure of the amount of copper present.
Note: i) Brass solution should not contain mineral acids as they would oxidize iodine to iodic acid and also
decompose sodium thiosulphate (hence the solution is neutralized with aqueous ammonia and acidified with
acetic acid) .
ii) Starch is invariably added near the end point when the concentration of iodine is low. At high iodine
concentrations a water insoluble starch- iodine complex is formed which results in error in the end point.
PROCEDURE:
Dilute the given Brass solution in 250 cm3 volumetric flask up to the mark with ion exchange water.
Mix well.
Estimation of copper:
Pipette out 25 ml of above prepared brass solution into a clean conical flask Add aqueous
ammonia drop wise until a pale blue precipitate. [Cu(OH) 2, is formed] Dissolve the precipitate by
adding test tube of dilute acetic acid. Add one test-tube-full of 10 % KI. Titrate the liberated iodine
against standard sodium thiosulphate solution till the mixture turns straw yellow. Add 1dropper starch
indicator and continue the titration till the blue color just disappears and a white precipitate is left
behind. Repeat the titration for concordant values.
Result:
Percentage of copper in Brass = ----------
********
1
7
Dept. of Chemistry,
AIT
X 4
Normality of K2Cr2O7 =
=
Equivalent mass of K2Cr2O7
49
=
K2Cr2O7
in burette
Trial 1
Trial 2
(say y)
Trial 3
K3[Fe(CN) 6]
(External)
Final burette
reading
Initial burette
reading
0.0
0.0
0.0
No blue or green color
with indicator
Volume of
K2Cr2O7 run
down (cm3)
Weight of haematite ore in 250 cm3 of the given solution (w) =
1.6 g
g of Fe (say a)
10a
w
X 100
=
18
PROCEDURE:
Preparation of standard solution of K2Cr2O7:
Experiment 9
Cr2O72-
Mercurous chloride
Fe2+ Fe3+ + e 6
+ 14H+ + 6e 2Cr3+ + 7H2O
2-
........(1)
........(2)
Weigh out accurately about 1.0 g of potassium dichromate crystals and transfer it into a 250 cm 3
volumetric flask. Dissolve in ion exchange water, make up to the mark and mix well. Calculate the
normality of potassium dichromate.
Estimation of Iron:
Pipette out 25.0 cm3 of the haematite solution into a clean conical flask. Add T T of concentrated
HCl and heat the solution to boiling. Add stannous chloride to the hot solution drop wise till the
yellow solution just turns colorless. Add 2 drops in excess to ensure complete reduction. Cool, and
rapidly add T T of mercuric chloride followed by 2 T T ion exchange water. A silky white
precipitate of mercurous chloride is formed.
Place a number of drops of freshly prepared potassium ferricyanide indicator on a wax paper. Add a
few cm3 of potassium dichromate from the burette to the conical flask and mix well. Using a clean
glass rod withdraw a drop of the solution from the flask and bring it in contact with a drop of the
indicator on the wax paper. The color of the indicator turns deep blue. Add 1 cm 3 of the potassium
dichromate and again bring a drop of the titrated solution in contact with a fresh drop of the indicator.
If the blue color develops, continue the titration by adding increments of 1 cm 3 at a time and testing as
above till a drop of the mixture fails to produce a blue color with the indicator (clean the glass rod
after every test).
Repeat the titration with another 25.0 cm 3 of the haematite solution. In the next trial, add most of the
potassium dichromate required at a stretch and then titrate drop wise. Mix the contents of the flask
after every addition and test a drop of the titrated mixture with a drop of the indicator as described
above till the color of the indicator drop fails to develop blue or green color. Repeat for agreeing
values.
Note: (i) SnCl2 should be added drop wise to the hot solution (ii) Mercuric chloride should be added rapidly in
cold condition. A large excess stannous chloride reduces mercuric chloride to mercury (grey precipitate).
Formation of a grey precipitate on the addition of HgCl 2 indicates that a large excess SnCl 2 has been added in
which case the trial has to be discarded. (iii) Potassium ferricyanide forms a blue precipitate with Fe(II).
Hence, the titration has to be stopped when the titrated solution just fails to produce a color with the indicator.
Result:
1. Normality of K2Cr2O7 = ------------ 2. Percentage of Fe in the haematite ore sample = ------------
********
1
9
Dept. of Chemistry,
AIT
Molarity of EDTA =
X 4
=
372
=
EDTA in burette
Trial 1
Final burette
reading
Initial burette
reading
Volume of EDTA
run down cm3
0.0
Trial 2
Trial 3
0.0
(say z)
Indicator &
color change
Eriochrome
Black T
0.0
Wine red to
blue
Calculations
Volume of EDTA required to react with 25.0 cm3 of water sample =
cm
(say x)
x cm of z M EDTA
1000 1
g of CaCO3
=
=
(say a)
ppm of CaCO3
ppm of CaCO3
20
Experiment 10
Determination of total hardness of water - complexometric titration
Theory: Hardness of water is due to the presence of dissolved salts of calcium and magnesium. The
total hardness is determined using ethylenediaminetetraacetic acid (EDTA) and is expressed in terms
of parts per million (ppm) of CaCO3. EDTA is a hexadentate ligand and forms complexes with Ca 2+
and Mg2+ ions. The molecule represented as H 4Y has two easily replaceable hydrogen atoms. EDTA
has the structure
HOOC - CH2
CH2 - COOH
N - CH2 -CH2 - N
HOOC - CH2
CH2 - COOH
H2Y2- + 2H+
The anion formed in the above ionization forms complex with metal ion M 2+ which can be
represented as:
M2+ + H2Y2MY2- + 2H+
where M2+ is Ca2+ or Mg2+.
The total hardness of water can be determined by titrating a known volume of water against
standard EDTA solution at a pH of 10 using eriochrome black-T as indicator. The color of the free
indicator at pH 10 is blue. Eriochrome black-T forms a wine red complex with M 2+ which is relatively
less stable than MY2-. On titration EDTA first reacts with free M 2+ ions and then with the M2+indicator complex. The latter gives a color change from wine red to blue at the equivalence point.
Such indicators are referred to as metal-ion indicators. Since the reaction involves the release of H +
ions, a buffer mixture (NH3 - NH4Cl) is used to maintain a pH of 10. The free acid (EDTA) is only
sparingly soluble; hence the more soluble disodium salt, Na 2H2Y, is used for preparing the reagent.
PROCEDURE:
Preparation of a standard solution of disodium salt of EDTA: Weigh accurately about 2.0 g of
disodium salt of EDTA crystals using an analytical balance. Transfer the crystals carefully into a
funnel placed over a 250 cm3 volumetric flask and find the weight of the emptied weighing bottle.
Add ion exchange water through the funnel to ensure that all the crystals run down into the flask. Add
test tube of NH3. Wash the funnel with ion exchange water and remove the funnel. Dissolve the
crystals by gently swirling the flask. Dilute with ion exchange water and make up to the mark. Stopper
and invert the flask several times to give a homogeneous solution. Calculate the molarity of EDTA.
Determination of total hardness of water sample Using a pipette transfer 25.0 cm3 of the given
water sample into a clean conical flask. Add 2 cm 3 of NH3 - NH4Cl buffer and 1-2 drops of
eriochrome black-T indicator. Titrate against EDTA till the color of the solution changes from wine
red to blue. Repeat the experiment for agreeing values.
Result:
1. Molarity of EDTA =
2. Total hardness of the given water sample = ----------
ppm of CaCO3
********
2
1
Dept. of Chemistry,
AIT
Molarity of EDTA =
X 4
=
372
EDTA in
burette
Trial 1
Final burette
reading
Initial burette
reading
0.0
Trial 2
Trial 3
0.0
(say z)
Indicator &
color change
Patton &
Reeders
indicator
0.0
Volume of EDTA
run down (cm3)
Wine red to
blue
cm3 (say y)
10a 100
Percentage of CaO in the cement sample
22
Experiment 11
Result:
1. Molarity of EDTA = -----------2. Percentage of Calcium oxide in the given cement sample = -----------
********
23
Burette
readings
Trail 1
Trail 2
V2 ml
Trail 3
Trail 1
0.0
0.0
Trail 2
Trail 3
Final burette
reading
Initial
burette
reading
0.0
0.0
0.0
0.0
Volume of
HCl run
down in cm3
CALCULATION:
Alkalinity of water is expressed as parts of equivalent CaCO 3 per million parts of water.
1000 ml 1N HCl = 50 g of CaCO3
1 ml 1N HCl = 50 mg of CaCO3
Estimation of Phenolphthalein alkalinity (P):
V1 ml 0.1N HCl = V1 x 0.1 x 50 mg of CaCO3
( say a)
24
Experiment 12
-
-2
Determination Of Alkalinity (OH , CO3 & HCO3) of water sample using standard
HCl Theory:
The acidity of water sample is its capacity to neutralize a base where as its alkalinity
is measure of its capacity to neutralize acids. Natural water may be acidic or alkaline
depending upon the source of water and the extent and nature of pollutants from industry and
municipal sanitary disposal. If highly alkaline water is used in boiler for steam generation
leads to precipitation of sludge, deposition of scales, and cause caustic embrittlement.
Knowledge of kind of alkalinity present in water and their magnitudes is important. In
calculating the amount of lime and soda needed for water softening. In maintaining a pH
range where acids produced by hydrolysis of salts like MgCl 2, FeCl 2 etc. and coagulants
[Al2(SO4)3, Fe2 (SO4)3,] may be effectively neutralized. In corrosion control, and in internal
conditioning of boiler-feed water. Caustic alkality of industrial waste has to be neutralized
before discharging them into rivers or other receiving waters. Water containing in excess of
alkaline earth concentrations are not suitable for irrigation purposes. The alkalinity of water
sample may be determined volumetrically by titrating it with a standard acid to an arbitrary
pH using an indicator. At the end point, when the color changes from pink to colorless, the pH
is lower to about 8.3. the volume of acid(V 1ml) used up to this point corresponds to the
complete neutralization of hydroxides and conversion of all the carbonate into bicarbonates.
-
OH + H
Co3
-2
H2O (i)
+
+ H HCO3 (ii)
The alkality measured upto this point is called Phenolphthalein Alkalinity . Beyond the
phenolphthalein alkalinity end point, titration is continued using methyl orange indicator.
-
OH + HCO3
Co3
-2
+ H2O
25
( say b)
= b x 40 mg of CaCO3
Water
sample
1
Carbonate
(ppm)
0
2P
2P
2(M-P)
0
Bicarbonate
(ppm)
M
0
M-2P
0
0
Hydroxide (ppm)
Carbonate (ppm)
2P-M =
2(M-P) =
Bicarbonate (ppm)
0
26
PROCEDURE:
Dilute the hydrochloric acid given in 250 ml volumetric flask up to the mark with ion
exchange water and mix well.
Pipette out 25 ml water sample into a conical flask. Add one drop of phenolphthalein
indicator. Titrate against std. HCl until the pink color just disappears. Record the volume of
acid consumed as V1 ml. to the same solution add 2-3 drops of methyl orange indicator and
titrate further until the color changes from yellow to orange red. Record the additional
volume consumed as V2 ml. repeat the procedure two more time to get concurrent readings.
This whole procedure is repeated for different samples of water.
RESULT: Alkalinity of water sample is
i) Hydroxide =.. ppm
ii) Carbonate =.. ppm
iii) Bicarbonate =.. ppm
********
27
OUTLINE OF PROCEDURES
INSTRUMENTAL EXPERIMENTS:
Experiment 1: Determination of pKa value of a weak acid:
Pipette out 25cm3 of the given weak acid into a clean beaker. Immerse the glass electrode- calomel electrode assembly
into the acid. Connect the electrodes to a pH meter and measure the pH. Add NaOH from a microburette in increments
of 0.5 ml and measure the pH until there is a sharp rise in the pH. Take 4 more readings. Plot the graph of pH/V
Versus Volume of NaOH and pH Versus Volume of NaOH. From the graph report the pKa value of the given weak acid.
pH
pH
V
pKaa
volume of NaOH
Equivalence point
V ol. of NaOH
Half eq.point
C
o
n
d.
.
V1
V2
Volume of NaOH
28
equivalence point
Volume of K2Cr2O7
l = w t 1 d1 =
t w dw
dw = Density of water
d
= Density
of liquid
---------- millipoise
y
Volume of NaCl
y
Volume of KCl
29
VOLUMETRIC EXPERIMENTS:
Experiment 7: Determination of COD of waste water sample
Weigh out about 4.0 g of FAS crystals into a funnel placed over a 250ml standard flask. Add 1 test tube of dil.H 2SO4
and dissolve the crystals. Dilute the solution up to the mark. Shake well.
N FAS
Weight of FAS 4
Equivalent weight of FAS ( 392)
From the titre value calculate the percentage of copper in the given brass sample.
Experiment 9: Determination of percentage of iron in haematite
Weigh out about 1.0 g of K2Cr2O7 crystals into a funnel placed over a 250ml standard flask. Add ion exchange water.
Dissolve the crystals, and dilute the solution up to the mark. Shake well.
N K2Cr2O7
Weight of K2Cr2O7 4
Equivalent weight of K2Cr2O7 ( 49)
Weight of EDTA 4
Molecular mass of EDTA (372)
30
Weight of EDTA 4
Molecular mass of EDTA (372)
31
VIVA VOCE
(The questions given below are only model questions. The students are expected to learn the principle
behind each experiment.)
INSTRUMENTAL EXPERIMENTS:
initially, when dichromate is added from the burette, Fe2+ is oxidized to Fe3+. As more and dichromate is
added, the concentration of oxidized species (Fe3+) increases and the concentration of reduced species
(Fe2+)decreases. Hence the second factor in the Nernst eqn. increases and potential increases. At equivalence
point once all the ferrous ions are oxidized to ferric ions, the potential increases sharply because the potential
is now due to both ferrous/ ferric system and dichromate / chromic system beyond this, there is no change in
potential because redox reaction is complete.
4. What are the electrodes used in the potential metric estimation of FAS?
The electrodes used in the determination of FAS potential metrically are calomel electrode (reference
electrode) and Platinum electrode ( indicator electrode)
5. What is an indicator electrode?
The electrode whose potential is dependent upon the concentration of the ion to be determined is
termed as indicator electrode. Example: Platinum electrode.
6. Name the reaction that occurs during the titration?
Reaction between FAS and K2Cr2O7 is a redox reaction, in acidic medium is given below:
6FeSO4 + 7H2SO4 + K2Cr2O7
3Fe2(SO4)3 + K2SO4 + Cr2(SO4)3 + 7H2O
33
Dept. of Chemistry,
AIT
A series of standard solutions of copper are treated with an optimum amount of NH 3 solution and diluted to
a definite volume. The absorbance of the standard samples is measured at 620nm using a colorimeter and the
absorbance are plotted against concentration to get the calibration curve. A known volume of the test
solution is also treated with the same optimum amount of ammonia and diluted to the same volume. The
absorbance of the sample is measured at 620nm. Then, the concentration of copper in the test solution is
evaluated using the calibration curve.
20. Why is ammonia added to copper sulphate solution?
Why is the same amount of ammonia added in colorimetric determination of copper?
Ammonia is added to get Cuprammonium sulphate [Cu(NH 3)4]SO4 (dark blue complex) same amount of
ammonia is added to nullify the absorbance due to a any coloring impurities present in ammonia.
I= E / R
3. What is conductance?
The reciprocal of resistance is called the conductance.
4. What is the unit of conductance?
The unit of conductivity is ohm-1m-1.
5. What is a conductivity cell or what is a cell?
A cell is a device, which produces an electromotive force and delivers an electric current as the result of a
chemical reaction.
34
Dept. of Chemistry,
AIT
k 1000
c
and
=kV
Dept. of Chemistry,
AIT
Evaporation of
3.
4.
Dept. of Chemistry,
AIT
salt
[ acid ]
10.
Explain the pH
scale. pH ranges from
0 - 14
if pH of the solution lies between 0 to < 7 then solution is acidic.
if pH of the solution is 7 then solution is neutral.
if pH of the solution lies between >7 to 14 then the solution is basic.
salt
because,
pH pKa log
acid
l
37
Dept. of Chemistry,
AIT
Dept. of Chemistry,
AIT
VOLUMETRIC EXPERIMENTS:
Dept. of Chemistry,
AIT
4. Why is ammonium hydroxide added to the brass solution in determination of copper in brass?
Brass solution is treated with dilute ammonium hydroxide to neutralize the mineral acids.
5. Name the compound formed when ammonium hydroxide is added to brass solution.
When ammonium hydroxide is added to brass solution a pale blue precipitate of cupric hydroxide is formed.
6.
9. Why does the color of brass solution turn brown upon the addition of potassium iodide solution?
Blue solution of brass turns brown on addition of potassium iodide solution due to the liberation of iodine.
10. What is the composition of the white precipitate left at the end point in the determination of copper in
brass?
A white precipitate of cuprous iodide is left at the end of the titration in estimation of copper in brass.
11. Write the reaction involved in estimation of percentage of copper in brass.
2Cu2+ + 4KI
Cu2I2
+ 4K++ I2
Cupric
Cuprous iodide
The liberated iodine is titrated against sodium thiosulphate using starch as indicator.
+ 2 I+ I2
2S2O32S4O62thiosulphate
tetrathionate
12. Mention the difference between the iodometric and iodimetric titration?
Iodometric titration is the titration carried out with liberated iodine. Iodimetric
titration is the titration carried out with standard solution of iodine.
40
Dept. of Chemistry,
AIT
Hg2Cl2 + SnCl4
7. Name the indicator used in the determination of percentage of iron in haematite ore?
Potassium ferricyanide K3Fe(CN)6 is used as an external indicator.
8. What is the color of K3Fe (CN) 6 with ferrous ion?
Potassium ferricyanide produces an intense deep blue color with ferrous ion due to the formation
of ferroferricyanide complex.
9. Explain the color of the indicator drop before the end point and at the end point?
Before the end point, the indicator forms a blue complex with ferrous ions. At the end point, all the ferrous
ions are oxidized to ferric ions. The indicator fails to give blue color with a drop of the titrated solution at
the end point.
10. Why can potassium ferricyanide not be used as an internal indicator in the analysis of haematite ore?
Potassium ferricyanide combines irreversibly with ferrous ions to form a deep blue colored
ferroferricyanide complex. This blue color persists throughout the titration; hence end point cannot be
determined.
11. What is the reaction that takes place during the titration?
Acidified potassium dichromate oxidizes ferrous ion to ferric ion and itself gets reduced to chromic ion.
12. Explain the calculation of equivalent weight of potassium dichromate?
2-
Cr2 O7
14H 6e 2Cr
7H 2 O
Six electrons are required to reduce one molecule of dichromate to chromic ion,
molecular mass (294)
49 6
Dept. of Chemistry,
AIT
CH2COOH
NCH2CH2 N
HOOC-CH2
CH2COONa
NCH2CH2 N
CH2--COOH
NaOOC-CH2
EDTA (H4Y)
CH2--COOH
CH2COOH
N CH2CH2 N
HOOC-CH2
ethylene moiety
CH2--COOH
CH2COOH
N
HOOC-CH2
Diamine moiety
CH2--COOH
CH2COOH
NCH2CH2 N
HOOC-CH2
CH
25. What will happen to the pH of the solution if buffer is not added? Justify your answer.
If buffer is not added, the pH decreases. During the titration, the hydrogen in EDTA are replaced by the
metal ions in water. And hydrogen ions are liberated. This causes decrease in pH.
26. What is volumetric analysis?
Determination of the concentration of a solution by titration against a standard solution using a suitable
indicator is called volumetric analysis.
43
3.
44
Dept. of Chemistry,
AIT
6. Explain why Eriochrome Black-T (EBT) indicator cannot be used in the estimation of CaO in
cement solution?
Eriochrome Black T enables estimation of both calcium and magnesium ions. When Patton
Reeders indicator is used, calcium can be estimated in the presence of magnesium.
7. Give the IUPAC name of Patton and Reeders indicator?
IUPAC Name: 2-hydroxy-1-(2-hydroxy-4-sulpho-1-naphthylazo)-3-naphthoic acid.
-2
At = Am.o = Ah + Ac + Ab
Since the aim of the experiment is to determine total alkalinity, methyl orange is used as indicator in this
experiment.
3. Mention an indicator other than methyl orange that can be used to determine the alkalinity of water
Phenolphthalein can be used as an indicator in acid base titrations.
4. Write the reactions that take place during the titration
NaCl + H2O (for hydroxides )
NaOH + HCl
Na2CO3 + HCl
NaHCO3 + NaCl (for carbonates)
NaHCO3 + HCl
NaCl + H2O + CO2 (for bicarbonates)
...(1)
... (2)
... (3)
45
12. What are the possible combinations of ions causing alkalinity in water?
a) Only hydroxide b) Only carbonate c) Only bicarbonate d) Hydroxide and carbonate e) Carbonate
and bicarbonate together
13. The possibility of hydroxide and bicarbonate is not possible. Why?
The possibility of hydroxide and bicarbonate ions together is ruled out, because they combine
instantaneously to form carbonate. Thus hydroxide and bicarbonate ions cannot exit together. On the
basis of same reasoning, all the three hydroxide carbonate and bicarbonate ions cannot exit
together.
OH- + HCO3-
CO3-2 + H2O
********
********
46
Graph sheets
6 no.s