"The difference between a successful person and others is not a lack of

strength, not a lack of knowledge, but rather in a lack of will."

~Vincent
Vincent T. Lombardi
 Experiment No. : 1
Estimation of Copper present in electroplating effluent by optical sensor
(colorimetry)

An optical sensor converts light rays into electronic signals

signals.. It measures the physical
quantity of light and then translates it into a form that is readable by an instrument. An optical
sensor is generally part of a larger system like colorimeter that integrates a source of light, a
measuring device and the optical sensor.
A photoelectric colorimeter (optical sensor) is an electrical instrument which
measures the amount ount of light absorbed using a photo cell. There are two types of
photoelectric colorimeters namely, single beam type and double beam type.Chemical analysis
through measurements of absorption of light radiation in visible region of the spectrum is
known as colorimetry.
Colorimetry is concerned with the determination of the concentration of a
substance by measurement of relative absorption of light with respect to the known
concentration of the substance.

Monochromatic radiation as it passes through an aabsorbing

bsorbing solution of thickness ‘b’ cm and
concentration c mol litre-1.
1. Because of interaction between the photon and absorbing analyte,
the radiant power of the beam decreases from Po to P (Figure 2).

The transmittance T of the solution is the fraction of of incident radiation transmitted by the
solution as shown in the equation 1.
T = P/Po ------------------------(1)
Transmittance T is always expressed as percentage transmittance.
The absorbance A of a solution is related to transmittance in the logar logarithmic
ithmic manner as
shown in equation 2.
A = -logT = log (Po/P) ---------------(2)
As the absorbance of the solution increases transmittance decreases. Reflection and scattering
losses can occur at walls of a typical glass cell containing solution as shown in figure 3.
In this example the light passes through following boundaries called interfaces air-glass,
air
glass-solution, solution-glass
glass and glass-air.
glass air. To compensate for these effects, the power of the
beam transmitted through a cell containing the aanalyte
nalyte solution (sample solution) is compared
with the identical cell containing only the solvent or reagent blank.

Beer-Lambert’s
Lambert’s law: As a monochromatic radiation passes through an absorbing solution of
thickness ‘b’ cm and concentration c mol L-1. The absorbance is directly proportional to the
path length ‘b’ and concentration of absorbing species ‘c’ expressed by equation 3,
A = log Po / P = abc ----------------------(3)
Where, Po = Incident radiant power
P = Transmitted radiant power
b = Path length of absorbing medium
a = Proportionality constant called absorptivity
A = Absorbance or Optical density ofsolution.

Because absorbance ‘A’ is a unitless quantity, the absorptivity must have the units that cancel
the units of ‘b’ and ‘c’. If for example, c has the units of g L-1 and b has the units of cm then
absorptivity has the units of L g-11 cm-1.
When we express the concentration in equation 3 in moles per liter and b in cm the
proportionality constant is called molar absorptivity and is given the special symbol ε
Thus,
A = εbc -------------------(4)
Where ε has the units of L mol-1 cm-1
The best way to determine whether
whe a complex solution obeys Beer-Lambert’s
Lambert’s law is to
prepare a series of standard solutions of desired range of concentrations and find out
absorbance (optical density) using a photoelectric colorimeter keeping constant path length.
Since the absorbance is directly proportional to the concentration, a plot of absorbance
against concentration gives a linear graph passing through the origin.
 Experiment No. : 2

Determination of Viscosity coefficient of lubricant (Ostwald’s viscometer)

Viscosity is the property of liquids, which 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
stationery while that at the axis of the tube moves faster than any other intermediate layers.
A slow moving layer exerts a friction on its nearest moving layer. This property of a liquid
by which it retards the motion between the successive layers of liquid is called Viscosity.
The co-efficient 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 at
unit distance apart. Viscosity is a temperature dependent property and hence the
measurements are carried out at constant temperature. The co-efficient of viscosity of a
liquid is given by Poiseuille’s formula.

η = π P r4 t /8 V l

Where V…….volume of liquid.

r …… radius of the capillary tube
t……..time of flow
P…….the pressure difference between the two ends of the tube
l……..length of the tube
η……..the co-efficient of viscosity of the liquid

If ‘t1’ and ‘t2’ are times required to flow for equal volumes of two different liquids through
the same length of capillary tube under identical conditions, then,

η1/η2 = P1.t1 / P2.t

The pressure of the liquid (P) = ρ g h

Since for the two liquids h & g are same. Therefore, P1/P2 = d1/d2

η1/η2 = d1 t1 / d2 t2
Where d1 & d2 are the densities of two liquids.

The unit of Viscosity in CGS system in Poise (Poise = dynes sec cm -2), where as SI unit of
viscosity is Pa. s . There is no unit for relative Viscosity
 Experiment No. : 3
Estimation of total hardness of water by EDTA method

Hardness is that characteristic of water which prevents lather formation with soap solution. It
is defined as the concentration of multivalent metallic cations in solution. There are two types
of hardness.

i) Temporary or Carbonate hardness: It is due to the presence of soluble salts of

carbonates & bicarbonates of calcium and magnesium, which can be removed merely by
boiling the water.

ii) Permanent or Non-carbonate hardness: It is due to the presence of soluble salts of

Chlorides, Sulphates and Nitrates of Ca & Mg that can be removed by chemical processes.
Other ions like Fe+3, Fe+2, Mn+2, Sr+2& Al+3 also cause hardness in negligible amounts. For
all the practical purposes hardness may be represented by the sum of calcium and magnesium
ions.

Total hardness of water is the algebraic sum of temporary and permanent hardness and it is
expressed in terms of CaCO3 equivalent because it is the most insoluble salt & its molecular
weight is 100, which makes the calculations easier.
The hardness of water is determined by complexometric titration using Std. EDTA (Ethylene
diamine tetra acetic acid) solution or disodium salt of EDTA as complexing or chelating
agent. The indicator used is Eriochrome Black-T (EBT) [Sodiun-1-(-1-hydroxy-2-
naphthylazo)-6-nitro-2-naphthol-4-sulphonate]. It is a blue coloured organic dye with two
ionisable phenolic hydrogen atoms. It is also called as metal ion indicator because it reacts
only with metal ions.
The EBT combines with few of Ca & Mg ions (M2+) present in water around pH 10 (Buffer
solution of NH4OH and NH4Cl is used to maintain the pH) and forms a weak wine red
coloured complex.
M+2 + EBT → [M-EBT]
Weak wine-red complex

During the titration with EDTA, all free hardness-causing ions are complexed.

M2+ + EDTA → [M-EDTA]

Finally, the EDTA disrupts the wine red complex because it is capable of forming a more
stable complex with hardness-causing ions. This action frees the Eriochrome Black-T and the
wine red colour changes to a distinct blue colour indicating the end point of the titration.

[M-EBT] + EDTA → [M-EDTA] + EBT

Colourless stable
 Experiment No. : 4
Estimation of iron in TMT bar by external indicator method
Thermo Mechanically Treated bars or TMT bars are manufactured by using a unique
technique that leaves them with a tough outer area and a soft inner core – this makes the TMT
bar strong but also flexible. The chemical composition of the TMT is as follows: Fe (98.9%),
C (0.13%), Si (0.11%), Mn (0.56%), S (0.03%), P (0.03%), Cu (0.10%), and Cr
(0.06%).TMT
TMT bars have now become the gold standard in construction and are used widely in
diverse projects, such as –Residential
Residential projects, Highrise residential buildings,
buildings Office /
industrial structures, Dams, Long span bridges and flyovers.
As an oxidant, dichromate has some advantages over permanganate, but, as it is less
powerful, its use is much more limited. It is obtainable in a state of high purity and can be
used as a primary standard. Solutions of dichromate in water are stable indefinitely. The half
reaction for the dichromate system is:

The most important application of dichromate is in its reaction with iron(II) in which it is
often preferred to permanganate..

and the total reaction is:

Unlike permanganate, dichromate titrations require an indicator. Three internal indicators

may be used for the titration of Fe2+ with K2Cr2O7. Those are diphenylamine,
diphenylbenzidine and diphenylamine sulfonate. The colour change for all three indicators is
green to violet. And the external indicator Potassium Ferricyanide is used as an external
indicator that forms a complex with Fe+2 ions. The reaction is as follows.

4Fe2+ + 3K3[Fe(CN)6] H+
Fe4 [Fe(CN)6]3 + 6K+
 Experiment No. : 5
Potentiometric estimation of FAS using standard K2Cr2O7 solution
A potentiometric titration may be defined as a titration in which the equivalence point is
detected by measuring the change in potential of a suitable electrode, which responds to the
change in concentration of the species. This method has number of advantages,
No indicator is required
Turbid, fluorescent, opaque or coloured solutions can be titrated
Mixture of solutions or very dilute solutions can be titrated.
The results are more accurate because the actual end point or equivalence point is determined
by means of graphs.
The electrode that responds to the change in concentration of the ion in the solution is called
the indicator electrode. (in this case Platinum electrode)
The indicator electrode (Pt-Electrode)
Electrode) is coupled with a Calomel electrode (a reference
electrode whose potential remains constant during titration)
titration) to measure the cell potential.
The titration of FAS solution with K2Cr2O7 solution in presence of H2SO4 is a redox
titration.
Fe2+ → Fe3+ + e-
Cr2O72- + 14H+ + 6e → 2Cr3+ + 7H2O
6Fe2+ + Cr2O72- + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O
The presence of both oxidized (Fe3+) & reduced (Fe2+) forms of the same substance in a
solution leads to the formation of a Redox electrode, developing an electrode potential at
platinumm electrode. Thus (Pt/ Fe3+, Fe2+) is the indicator electrode, whose electrode potential
is determined by Nernst’s equation & is given by,

Where Eo is the standard potential of the system

Before the equivalence point, the ratio of determines the potential. During titration, as
K2Cr2O7 solution is added continuously [Fe3+] goes on increasing & [Fe2+] goes on
decreasing with the gradual change in electrode potential. Nearer to the end point the ratio
Fe3+ to Fe+2 increases rapidly as [Fe2+] becomes almost negligible.
When Fe2+ ions are completely oxidized to Fe3+ ions by K2Cr2O7 solution, the redox
electrode, Pt/ Fe3+, Fe2+ ceases to function but the presence slight excess of K2Cr2O7 forms
another redox electrode Pt/ Cr2O72-, Cr3+. Beyond the equivalence point, the potential is
determined by Pt/ Cr2O72-, Cr3+ system. Thus, an abrupt increase in the potential of the
solution in the vicinity of the equivalence point is observed.
 Experiment No: 6
Conductometric estimation of an acid mixture

Conductometric titration is a method of analysis based on the change in conductivity of

the solution with the addition of the titrant.

Advantages of conductometric titrations are,

1. Prior knowledge of strength of acids and bases is not required unlike volumetric
titrations.
2. Indicators are not required.
3. No keen observation is required for end point detection as it is determined graphically.
4. Conductometric titrations are very useful in dilute solutions, coloured solutions, and
different types of acid base titrations, precipitation type titrations and solubility studies.

Upon adding a strong base (NaOH) to a mixture of strong acid (HCl) against and weak
acid(CH3COOH), the following reactions occur sequentially.

HCl + NaOH NaCl + H2O

CH3COOH + NaOH CH3COONa + H2O

First, the conductance falls on adding the strong base to the mixture until the
strong acid is fully neutralized; then rises as the weak acid is converted to its salt: a strong
electrolyte and finally rises more steeply as the alkali is introduced in excess.
Conductance: Conductance is the reciprocal of resistance and is expressed in siemens
(S).

Conductivity: The resistance (R) of a solution in contact with the cell in which electrodes
are l cm apart and have area of cross section A cm2 is directly proportional to the distance
between the two electrodes and inversely proportional to the area of cross section of
either electrode.
Rαl/A
R=ρl/A
Where ρ is called the resistivity of solution.
Therefore, conductivity κ = 1 / ρ = l / RA

Specific conductivity: Specific conductivity is the conductance of a solution in contact

with a cell in which the electrodes are unit distance (l =1 cm) apart and have unit area (A
= 1 cm2) each. It is expressed in S cm-1.

κ = 1 / R = Specific conductivity
Equivalent conductivity (Λeq) : Equivalent conductivity of an electrolyte is defined as
the conductance of volume of a solution containing one gram equivalent mass of the
electrolyte placed between two electrodes, which are at a unit distance apart.
Molar conductivity (Λm): Molar conductivity of an electrolyte is defined as the
conductance of volume of a solution containing one gram mole of the electrolyte placed
between two electrodes, which are at a unit distance apart.
Cell Constant: Cell Constant is defined as the ratio of the distance between the electrodes
to the area of either electrode.
Cell Constant = l /A
 Experiment No. : 7
Determination of Chemical Oxygen Demand(COD) of industrial waste
water sample

The Chemical oxygen demand (COD) test is used to estimate the amount of organic
matter in the wastewater. It measures both the biologically oxidisable and biologically
non-oxidisable organic matter present in the sewage sample. It is an important and
quickly measured parameter for industrial waste water analysis and water treatment
plants. This test allows the measurement of a waste in terms of the total quantity of
oxygen required for oxidation of waste matter to carbon dioxide and water. A measured
quantity of the sample is refluxed with a known excess of std. Potassium dichromate
solution that acts as an oxidizing agent in acid medium. The excess of potassium
dichromate remaining after the reaction is titrated with ferrous ammonium sulfate to
determine the amount of K2Cr2O7 consumed and the oxidisable organic matter is
calculated in terms of oxygen equivalent. The reaction between FAS and K2Cr2O7 may be
represented as follows:

6Fe+2 + Cr2O72- + 14H+ 6Fe3+ + 2Cr3+ + 7H2O

The interference caused by chlorides can be eliminated by the addition of mercuric

sulfate to the sample prior to the addition of other reagents.

6Cl- + Cr2O72- + 14H+ 3Cl2 +2Cr3+ + 7H2O

Hg2+ + 2Cl- HgCl2

Addition of silver sulfate (Ag2SO4) catalyses the oxidation of straight chain aliphatic and
aromatic compounds.

Ferroin (Ferrous 1,10-phenanthroline sulfate) is an excellent one to indicate when all

dichromate has been reduced by ferrous ions. It gives a very sharp red colour change that
is easily detected in spite of the blue colour produced by Cr3+ formed on reduction of the
dichromate. Blank titration is performed to obtain true measure of the organic matter
present in the sample.
 Experiment No. : 8
Determination of pKa of vinegar using pH sensor (Glass electrode)
pH sensor is one of the most important tools for measuring pH and is commonly used
in water quality monitoring. This type of sensor is capable of measuring alkalinity and acidity
in water and other solutions.

The Henderson-Hasselbalch
Hasselbalch equation is useful for estimating the pH of a buffer solution and
finding the equilibrium pH in an acid-base
acid reaction. A simple buffer solution consists of a
solution of an acid and a salt of the conjugate base of the acid. For example, the acid may be
acetic acid and the salt may be sodium acetate. The Henderson
Henderson–Hasselbalch
Hasselbalch equation relates
the pH of a solution containing a mixture of the two components to the acid dissociation
constant, Ka, and the concentrations of the species in solution.
The formula for the Henderson––Hasselbalch equation is:
pH = pKₐ + log([A⁻]/[HA]).
The ionization constants of strong
trong acids and strong bases can be easily calculated with the
help of direct methods. However, the same methods cannot be used with weak acids and
bases since the extent of ionization of these acids and bases are very low (weak acids and
bases hardly ionize).
ze). Therefore, in order to approximate the pH of these types of solutions,
the Henderson-Hasselbalch
Hasselbalch Equation is used.
The equation can be used to determine the amount of acid and conjugate base needed to make
a buffer solution of a certain pH. A weak acid has a pKa value in the approximate range -2 to
12 The Henderson-Hasselbalch
Hasselbalch equation relates pKa and pH. However, it is only an
approximation and should not be used for concentrated solutions or for extremely low pH
acids or high pH bases.

A weak
ak acid, like acetic acid dissociates partially in its aqueous solution

The equilibrium constant of dissociation of the acid is known as dissociation constant of

the acid Ka is given by

The solution is considered to be very dilute and activity of water in very dilute solution
is assumed to be 1
Taking - log on both sides
pH=pKa +log [CH3COO-]
[CH3COOH]
When exactly half of the acid undergoes dissociation, the value of [A]/[HA] becomes 1,
implying that the pKa of the acid is equal to the pH of the solution at this point.
in water and a strong acid has a pKa value of less than about -2.
 Experiment No. : 9
Estimation of Sodium present in soil/effluent sample using flame
photometry
Flame Photometry is used in the determination of alkali metals (Li, Na, K, Ca, Mg, etc) as
they are excited by the relatively low excitation energy of the flame. Na and K are more
frequently determined because of their importance in biological systems and water analysis.
In this method of analysis, the solution of the sample under test is atomized and finally spread
into the flame. The following events occur in rapid succession,

i) Evaporation of the solvent leaving a solid residue.

ii) Vaporization of solid with dissociation into its constituent atoms, which initially will
be in the ground state.

iii) Some atoms may be excited by the thermal energy of the flame to higher levels, and
attain a condition in which they radiate energy.

The excited atoms emit light at a specific wavelength characteristic of the element. The
intensity of light is proportional to the concentration of the element and is read directly from
the flame photometer. The sample is spread through a capillary tube into a mixing chamber,
where it is combined with air and gas, which is combusted in a burner attached to the
photometer. Na emit light of differing wavelength during this heating process. The emission
from the different metal ions can be separated and its intensity is measured by placing various
filters between the flame and the photocell. The intensity of the color varies with the
concentration of the metallic ions in the solution. The flame photometric method is also
applicable to natural surface and ground waters, drinking water, precipitation and wastewater.

Consider Eo represents the ground state in which the electrons of a given atom are at their
lowest energy level and E1, E2, E3, etc., represent higher or excited energy levels.
Transitions between two quantised energy levels, say from Eo to E1 correspond to the
absorption of radiant energy, and the amount of energy absorbed (ΔE) is determined by
Bohr’s Equation,

Where c = velocity of light, h = Plank’s constant, ν = frequency, λ = wavelength of the

radiation absorbed
 I
H
K L
J

D
F E
B

M A

A: Air B: Atomizer C: Sample D: Gas, E: mixing

chamber
F: Burner G: Flame H: Lens system I: Filter J: Detector
K: Amplifier and signal processor L: Digital display M: Drain
Figure 1. Flame photometer
Evaporation
M + X- M + X- MX solid
solution Mist

Vaporization

Thermal excitation Dissociation

Mo(gas) M(gas) + X(gas)
MX
Gas

Flame emission
hv