Complexometric

Determination of
Hardness of Water
(EDTA Method)
1

Reaction:
Standard Hard
Standard
For example:
For example:
• Advantages of EDTA method: greater accuracy, convenience &
rapid procedure

• Significance of hardness determination: useful analytical test -

provides a measure of quality of water- particularly important
to industry - hard water while heating precipitates CaCO3 which
clogs boilers & pipes

11
 Determination of
Dissolved Oxygen (DO) in
Waste Water
What is dissolved oxygen and why is it
important? gains
• A water stream, both produces and consumes oxygen
• Gains oxygen from the atmosphere and from plants as a result of
photosynthesis
• Respiration by aquatic animals, decomposition, and various chemical
reactions consume oxygen
• Waste water from sewage treatment plants often contains organic
materials that are decomposed by microorganisms, which use oxygen in
the process
• The amount of oxygen consumed by these organisms in breaking down
the waste is known as the biochemical oxygen demand or BOD
• Oxygen is measured in its dissolved form as dissolved oxygen (DO)
• DO is used as an indicator of the health of a water body, where higher
dissolved oxygen concentrations are correlated with little pollution
 The Winkler or Iodometric Method
• Technique used to measure dissolved oxygen (DO)
• Uses titration to determine DO in the water sample

Theory:
In the Iodometric method, divalent manganese solution is added to the water
sample, followed by addition of strong alkali. DO rapidly oxidize an equivalent
amount of divalent manganese to higher valence states

In the presence of iodide ions in an acidic solution, the oxidized manganese reverts
to the divalent state, with the liberation of iodine equivalent of the original DO
content

The iodine is then titrated with a stranded solution of thiosulfate. The titration end
point can be detected visually with a starch indicator and interpreted in terms of
DO in mg/L unit
Reactions

MnO(OH)2
 12.0 12.0 12.0
12.1 12.1
12.0 12.0

x mL 0.005N Na2S2O3 = x x 0.04 mg of dissolved oxygen

RESULTS:
12.0 mL
(1) Volume of 0.005N Na2S2O3 solution required for 50 mL of given water sample = ____
9.6 mg/L
(2) Dissolved oxygen in the given water sample = ____
Iodometric Determination
of Cu in Brass Sample
Solution
IODINE TITRATIONS
 Iodometric titrations

Iodine titrations in which some oxidizing agent liberate I2 from an

I- solution and then liberated I2 is titrated with a standard solution
of reducing agent

2Cu(NO3)2 + 4KI = Cu2I2 + 4KNO3 + I2

2 +2
• Detection of the end point – using chemical Indicator

• In this titration a solution of starch is used as indicator

• Starch reacts with iodine in the presence of iodide to form an intensely blue-colored
complex, which is visible at very low concentrations of iodine
Aim: Estimation of Cu in brass sample using standard sodium
thiosulfate solution (Iodometric titration)
Theory 2Cu(NO3)2 + 4KI = Cu2I2 + 4KNO3 + I2

End point

blue color colorless

Procedure:
0.5g of brass is dissolved in 10mL conc. HNO3 and dilute it
upto 100 mL with distilled water in standard measuring flask.
Pipette 10 mL of this diluted alloy solution (test solution) into
a conical flask then add a few drops of dilute NH4OH solution
until a slight permanent precipitate remains. The precipitate is
redissolved by adding acetic acid drop by drop till the solution
becomes clear. Then about 5 mL of a 5% KI solution is added
and titrate the liberated iodine with 0.05N Na2S2O3 solution
from the burette using 1% starch solution as an indicator. The
end point is marked with the disappearance of blue color.
Repeat the titration 3-4 times.
OBSERVATIONS
Burette: 0.05 N Na2S2O3 Solution
Flask: 10 ml diluted alloy solution + NH4OH (dropwise till slight permanent Precipitation) + HAc (till
the precipitation dissolves) + 5% KI
Indicator: Starch solution (2-3 drop)
End point: Disappearance of Blue color

Observation table

Sr No Initial Burette reading Final Burette Difference (ml) Concurrent

(ml) reading(ml) Reading (ml)
1 0.0 9.2 9.2
2 0.0 8.2 8.2 8.2
3 0.0 8.2 8.2
4 0.0 8.0 8.0

Equations:
2Cu(NO3)2 + 4KI = Cu2I2 + 4KNO3 + I2
2CuSO4 + 4KI = Cu2I2 + 2K2SO4 +I2

I2 + 2Na2S2O3 = Na2S4O6 + 2NaI

(Sodium Tetrathionate)
2Na2S2O3 = I2 = 2CuSO4 = 2Cu

NaS2O3 = I = CuSO4 = 2Cu

Calculation:
1000 ml 1N Na2S2O3 = 63.57g of Cu = 249.57 g CuSO4·5H2O

1 ml 1N Na2S2O3 = 0.06357g of Cu = 0.24957 g CuSO4·5H2O

A ml of 0.05 N Na2S2O3 = 8.2 ml

Quantity of Copper in the given solution = A × 0.05 × 0.06357 ×100/10

= B = 0.26 g

% of Copper in the alloy = X × 100/W = 52%

Where W = weight of the alloy taken = 0.5 g

A = Constant Burette Reading and B = Quantity of Copper.

Results
1. 10 ml of diluted solution required = 8.2 ml of 0.05 N Na2S2O3
2. Quantity of Copper in the given solution = 0.26 g
3. Percentage of Copper in the alloy = 52%.
Expt. No: 9

To study electro-deposition
of Cu on cathode
Electro-deposition or Electroplating
Electro-deposition cell – Electrolytic cell

H2

• Cathode - electrode to be coated/plated

• Anode - sacrificial anode or inert anode (platinum or graphite)
• Electrolyte
• DC power supply
 Reaction involved

Pt Pt
CuSO4 solution

At Cathode At Anode

Cu2+(aq) + 2e– → Cu(s) 4OH–(aq) → 2H2O(l) + O2(g) + 4e–

H+(aq) + 2e– → H2 2H2O(l) → 4H+(aq) + O2(g) + 4e–

Circuit Diagram

B
Conductometric titration
to determine the
strength of strong acid
by strong base
Conductometric titration
• Titration in which conductance measurement
are made use of in determining the end-point

• Method used to determine end point in acid-

base reactions, precipitation reactions or
complexation reactions

titrant

Conductometer

analyte
 Theory

σ
ρ
Depends on no. of free ions, charge & size of the ions, mobility
of the ions
Titration curve of a strong acid (HCl) with a strong base (NaOH)
• Before NaOH is added, the conductance is high due to the presence of highly
mobile H+

• When the NaOH is added, the conductance falls due to the replacement of H+ by
the added Na+ as H+ ions react with OH− ions to form un-dissociated water

• This decrease in the conductance continues till the equivalence point

• At the equivalence point, the

solution contains only NaCl

• After the equivalence point, the

conductance increases due to the Conductance
large conductivity of OH− ions

• You will get a titration curve - point

of intersection of the two lines
gives the point of neutralization
i.e. equivalence point
AIM: Conductometric titration to determine the strength of
strong acid (HCl) by strong base (NaOH)

Procedure:
• Rinse the conductivity cell with
double distilled water
• Pipette out 20 mL HCl (unknown NaOH
conc.) in a beaker and dip the
conductivity cell in it
• Add small amount of NaOH (0.1N)
from burette, stir and measure the
conductance
• Measure conductance after each HCl
addition
• Take at least five readings after
the end point
 Observation Table Plot Graph
Vol. of NaOH Conductance

(S)
added (V2, mL) (S)

End point

V2 mL
(mL)

Let, V2 be the volume of 0.1N (N2) NaOH

required to complete the neutralization (end
point volume from the graph) 20 mL (V1) of xN
(N1) HCl

Calculations:
N1V1 = N2V2 , N1 = N2V2/V1

Strength(g/L) = Normality × Eq.wt.

= N1 × 36.5
For example:
 Results:
Normality of HCl = _____ N
Strength of HCl = _____ g/L
Potentiometric Redox
Titration of Fe by
2+

standard Ce solution
4+
• A potentiometric titration belongs to chemical methods of
analysis in which the endpoint of the titration is monitored
with an indicator electrode that records the change of the
potential as a function of the amount (usually the volume)
of the added titrant of exactly known concentration

• Provide more reliable data than data from titrations that use
chemical indicators

• Particularly useful with colored or turbid solutions

Potentiometric redox titration of Fe2+ vs. Ce4+ solution
• The reference electrode used here is saturated calomel electrode (SCE). It consists
of mercury metal covered with a paste of Hg + Hg2Cl2↓ in contact with saturated
KCl solution and Pt Wire for electrical contact. The reduction potential of this
electrode is 0.244 V. This saturated calomel electrode functions as ANODE.

• The Indicator electrode is a platinum electrode which responds rapidly to oxidation-

reduction couples and senses the potential which depends upon the concentration
ratio of the reactants & products of redox reactions. Here, the Pt electrode is in
contact with a Ferrous-Ferric couple. This electrode functions as CATHODE.
• The cell potential is measured during the course of reaction and graphs are plotted

• From the graphs end point of the titration is located and concentration is calculated

Experiment Std. soln in burette

Requirements:
Indicator electrode (Pt)
Potentiometer, Platinum electrode, Saturated Ref. electrode (SCE)
calomel electrode (SCE), Ferrous ammonium sulfate Analyte solution
and 0.25 M Ceric ammonium sulphate (both
prepared in 2N H2SO4)
Procedure:

• Pipette out 25 ml of test solution (ferrous solution) in a clean 100 ml beaker, place
the platinum electrode & SCE in the solution, which creates a Fe+2/Fe+3 couple.
Connect the electrodes to the potentiometer and measure the EMF of the of the cell

• Add cerric sulfate from burette in small portions to the ferrous solution, stir it and
note the EMF
Fe2+ + Ce4+ → Fe3+ + Ce3+

• Continue the titration till a sudden inflextion in EMF occurs. Then take about 6 to 8
readings after inflexion

• Draw a graph of Ecell Vs volume of cerric sulfate added; the inflexion point gives an
approximate equivalence

• Differential graph is drawn by plotting ∆E/∆V (Y-axis) vs. volume of cerric sulfate (X-
axis) to get a sharp peak, which corresponds to the precise equivalence point of
titration

• From the titration curve, volume of cerric sulfate required is found out and
concentration of ferrous sulphate can be calculated
Observation table V Ce4+
(mL)

V1 E1

V2 E2 E2-E1 V2-V1

V3 E3 E3-E2 V3-V2

Graphs

End point

End point

Volume (mL) Volume (mL)

…….g/L
For example
 𝛥𝐸
E
𝛥𝑉
 5.1

0.051

0.051 N
5.1

0.051 x 392
19.992
pH-metric titration of acidic
water by standard base
Introduction
• The pH meter was invented in 1934 by the American chemist Arnold O. Beckman (1900-2004) to
measure the sourness of lemons.

• A simple and speedy device to measure the acidity and alkalinity of a fluid.

• pH: the logarithm of the reciprocal of hydrogen-ion concentration in gram atoms per litre;
provides a measure on a scale from 0 to 14 of the acidity or alkalinity of a solution (where 7 is
neutral and greater than 7 is more basic and less than 7 is more acidic)
 pH meter

+ 0.242 V.
Saturated calomel electrode (SCE) Glass electrode
Aim: To determine the amount of HCl in the given solution, using standard NaOH pH metrically

Requirements: Standard NaOH solution, standard buffer solution,

glass electrode, saturated calomel electrode (SCE), HCl solution (of
unknown conc.- analyte), pH meter

A = SCE
B = Glass electrode
C = Burette
D = pH Meter
E = Magnetic stirrer
F = Magnetic bead
 Spectrophotometry. Many substances dissolve to give coloured
solutions. The higher the concentration of solute, the more light
is absorbed and the less light is transmitted through the sample.
Spectrophotometry is a simple technique used to measure
absorbance of solutions.

About: When the solution contains a specific molecule that

absorbs light at a specific wavelength.

The intensity of light hitting the detector after

passing through a “blank” solution is measured –
this is a solution that is identical to the sample but
doesn’t contain the solute. This measurement is
called “I0”.

Then the intensity of light hitting the detector

after passing through the sample is measured. This
measurement is “I”.

What is a blank in spectrophotometry?

A blank is a sample containing everything except
for the significance analyte. The blank is a sample
of the solvent itself.
Isobestic point:

What are transmittance and absorbance?

Consider monochromatic light transmitted through a solution; with an

incident intensity of I0 and a transmitted intensity of I.

The transmittance, T, of the solution is defined as the ratio of the

transmitted intensity, I, over the incident intensity, I0:

and takes values between 0 and 1. However, it is more commonly

expressed as a percentage transmittance:
Experimental measurements are usually made in terms
of transmittance (T), which is defined as:

T = I / Io

where I is the light intensity after it passes through the sample and
Io is the initial light intensity. The relation between A and T is: or
The absorbance, A, of the solution is related to the transmittance
through the following relations:

or

A = -log T = - log (I / Io).

Absorption of light by a sample

The absorbance has a logarithmic relationship to the transmittance; with

an absorbance of 0 corresponding to a transmittance of 100%
and an absorbance of 1 corresponding to 10%
transmittance.

The Absorbance of a Solution

For each wavelength of light passing through the spectrometer, the intensity of the light
passing through the reference cell is measured. This is usually referred to as Io - that's I for
Intensity.
The intensity of the light passing through the sample cell is also measured for that
wavelength - given the symbol, I. If I is less than Io, then the sample has absorbed

some of the light (neglecting reflection of light off the cuvette surface). A simple bit of math
is then done in the computer to convert this into something called the absorbance of the
sample - given the symbol, A. The absorbance of a transition depends on two external
assumptions.

1. The absorbance is directly proportional to the concentration (c) of the solution of the
sample used in the experiment. (Beer’s Law)

2. The absorbance is directly proportional to the length of the light path (l), which is
equal to the width of the cuvette. (Lambert's law)

The constant ϵ is called molar absorptivity or molar extinction coefficient and

is a measure of the probability of the electronic transition. On most of the diagrams
you will come across, the absorbance ranges from 0 to 1, but it can go higher than
that. An absorbance of 0 at some wavelength means that no light of that particular
wavelength has been absorbed. The intensities of the sample and reference beam
are both the same, so the ratio Io/I is 1 and the log10of 1 is zero.
The Beer-Lambert Law

You will find that various different symbols are given for some of the terms in the equation -
particularly for the concentration and the solution length.

The Greek letter epsilon in these equations is called the molar absorptivity - or sometimes
the molar absorption coefficient. The larger the molar absorptivity, the more probable the
electronic transition. In uv spectroscopy, the concentration of the sample solution is
measured in mol L-1 and the length of the light path in cm. Thus, given that absorbance is
unitless, the units of molar absorptivity are L mol-1 cm-1.

Limitations of the Beer-Lambert law

The linearity of the Beer-Lambert law is limited by chemical and
instrumental factors. Causes of nonlinearity include:

• deviations in absorptivity coefficients at high concentrations

(>0.01M) due to electrostatic interactions between molecules in
close proximity
• scattering of light due to particulates in the sample
• fluoresecence or phosphorescence of the sample
• changes in refractive index at high analyte concentration
• shifts in chemical equilibria as a function of concentration
• non-monochromatic radiation, deviations can be minimized by using
a relatively flat part of the absorption spectrum such as the
maximum of an absorption band
• stray light
 Figure 3 (a): Absorption spectra
of Rhodamine B solutions with different concentrations in
water (b) Calibration curve of Rhodamine B in the water at
measured at λmax.
Result:

1. The straight-line natures group of concentration vs absorbance at λmax 510 nm which

confirms the Beer-Lambert’s Law.

2. From the graph the concentration of unknown Co2+solution = ……. ??? M

Estimation of COD of
Waste Water
 Theory
• Chemical Oxygen Demand (COD) is a measure of oxygen required to
oxidize organic matter and inorganic chemicals such as ammonia &
nitrate in waste water samples

• COD can be measured by performing a laboratory test on the water

sample using a strong chemical oxidant under specific conditions of
temperature and for a particular period of time

• Commonly used oxidant in COD assays is potassium dichromate, which

used in combination with boiling sulfuric acid

• COD is expressed in mg/L or ppm

• COD is often used as a quality parameter to assess the extent of organic

pollutants in municipal and industrial waste water

• High COD level => greater amount of oxidizable organic matter in water
 COD Measurement
• Indirect titration method/ back titration

• COD is measured by the oxidation of organic pollutants using a strong

oxidizing agent (Potassium dichromate) under acidic conditions

• The reaction of potassium dichromate with organic compounds is given by:

H2SO4

• In the process of oxidation, dichromate is reduced to Cr3+

• Amount of Cr3+ is determined after complete oxidation, and is used as an
indirect measure of the organic contents of the water sample

• For all organic matter to be completely oxidized, an excess amount of

dichromate must be present

• Once oxidation is complete, the amount of excess dichromate must be

measured
• To do so, the excess potassium dichromate is titrated with ferrous ammonium
sulfate (FAS) until all of the excess oxidizing agent has been reduced to Cr3+

• The oxidation-reduction indicator Ferroin is added during this titration step

• Once all the excess dichromate has been reduced, the Ferroin indicator
changes from blue-green to wine-red color

• The amount of FAS added is equivalent to the amount of excess dichromate

added to the original sample

• A blank sample is created by adding all reagents (e.g. acid and oxidizing
agent) to a volume of distilled water

• COD is measured for both the sample and the blank, and the two are
compared

• The oxygen demand in the blank sample is subtracted from the COD for the
original sample to ensure a true measurement
10 10 10

10 10

10 a

10
10
10

10
10

10 b
 10

10

10
Procedure

0.1N

Distilled water

0.1N

using
Ferroin indicator
0 20.1 20.1
0 20 20 20
0 20 20

a mL
 ^

0.1N

Waste water

0.1N

using
Ferroin indicator
0 12.1 12.1
0 12.2 12.2 12.1
0 12.1 12.1

b mL