Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

MODULE 5

Water chemistry: Introduction, sources and impurities in water, Potable water; meaning and
specifications (as per WHO standards), Hardness of water, types, determination of hardness using
EDTA titration, numerical problems on hardness of water. Definition of Biological oxygen demand
(BOD) and Chemical Oxygen Demand (COD), determination of COD of waste water sample and
Numerical problems on COD.
Methods of Chemical Analysis:
Volumetric Analysis: Introduction, principles of titrimetric analysis, requirement of titrimetric
analysis, primary and secondary standards. Requirement of a primary standard solution, units of
standard solutions- Definition of normality, molarity, molality, mole fraction, ppm.
Instrumental methods of analysis: Introduction, Theory, Instrumentation and applications of
Colorimetry, Flame Photometry, Potentiometry, Conductometry (Strong acid with strong base,
weak acid with a strong base, mixture of strong acid and a weak acid with a strong base)

WATER CHEMISTRY
Sources of water:
1. Surface water: It is available on the surface of the earth either still form or in flowing from.
Example: rain water, river water, lake water and sea water.
2. Under ground water: It is developed by any type of well or spring from beneath the surface of
the ground whether the water flows from the well or spring by natural force or is withdrawn by
pumping, other mechanical device, or artificial process. Example: Springs, well and tube wells.

Impurities in water:
The major categories of impurities found in the water may be broadly classified into four categories.
1. Dissolved impurities
2. Suspended impurities
3. Dissolved gases
4. Organic matter
1) Dissolved impurities: Dissolved impurities mainly consist of soluble salts of Ca, Mg, Na. I.e.
bicarbonates, and chlorides, sulphates of Ca, Mg, and Na. In addition, small amount of nitrates,
nitrites, silicates, ammonium and ferrous salts are also present. These salts are derived from the rock
and soil with which the water is in contact. Thus the water which is in contact with limestone
contains CaCO3. Since the CO2 dissolved in water interacts with limestone.
CaCO3 + H2O + CO2 Ca (HCO3)2
Similarly water which is in contact with magnesite contains MgCO3.
MgCO3 + H2O + CO2 Mg (HCO3)2
In general ground water contains more dissolved salts than the surface water.
2) Suspended impurities: Suspended matter may be inorganic or organic in nature. The inorganic
materials include small particles of sand, clay, silica, hydroxides of iron and aluminium, derived
from the erosion of soil. Some of these have large particle size and therefore settle down readily.
Others are fine particles and colloidal in nature. These do not settle easily.
The organic suspended impurities are decaying vegetable matter and are due to microorganisms.
These are also present in the colloidal form. This causes turbidity of water.
3) Dissolved gases: Water contains mainly CO2 and O2, SO2, NH3 and oxides of nitrogen all of
which are derived from atmosphere.

Prof. Bhagya N P/Prof. Raveendra R S/Prof. Anil Kumara K V/Prof. Mutthuraju M Page 1
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

4) Organic matter: Organic impurities in water arise from the decay of vegetable matter. Mainly
organic acids and from farming, paper making and domestic and industrial waste .These include
detergents, fats, oils, solvents and residues from pesticides and herbicides. Water also contaminated
with sewage and human excreta

Portable water
Water that is safe enough to be consumed by human beings is called as potable water. The
word potable is a Latin word meaning drinkable. WHO’s guidelines for drinking-water
qualitywere set up in Geneva in the year 1993.

Water quality specification by WHO

Sl. No. Parameter Quantity

1. Copper 2 mg
2. Aluminum 0.2 mg/L
3. Lead <0.01 mg/L
4. Mercury <0.001 mg/L
5. Cadmium <0.003 mg/L
6. Antimony <0.005 mg/L
7. Arsenic <0.01 mg/L
8. Chloride < 250 mg/L
9. Fluoride < 1.5mg/L
10. Hardness < 200mg/L
11. Chlorine < 5 mg/L
12. Conductivity 250 µS/cm
13. Microorganisms 0 in 100 to 250 cm3

HARDNESS OF WATER:
Introduction: “Hardness is a measure of the concentration of multivalent cations”.
Hardness of water is caused by divalent metal ions such as Ca2+ and Mg2+. The hardness is derived
largely from contact of water with the soil and limestone. The hardness of water can be classified
into 2 types. i.e. 1) Temporary hardness and 2) Permanent hardness.
1) Temporary hardness: It is also called Carbonate hardness. It is caused due to the presence of
bicarbonates of Ca and Mg i.e. calcium bicarbonate [Ca (HCO 3)2] and magnesium bicarbonate [Mg
(HCO3)2]. Temporary hardness can be removed by physical treatment like boiling.
CaCO3 + H2O + CO2 Ca (HCO3)2
MgCO3 + H2O + CO2 Mg (HCO3)2
2) Permanent hardness: It is also called non-carbonate hardness. It is caused due to the presence
of chloride, sulphates of Ca and Mg i.e. calcium chloride, calcium sulphate and magnesium chloride,
magnesium sulphate. Permanent hardness can be removed by chemical treatment.
CaCl2 + 2Na-st Ca-st + 2NaCl
MgCl2 + 2Na-st Mg-st + 2NaCl
MgSO4 + 2Na-st Mg-st + Na2SO4
Units of Hardness: Hardness can be expressed in terms of ppm of CaCO3 i.e. 1ppm = 1 part of
CaCO3 equivalent hardness in 106 parts of water.

Prof. Bhagya N P/Prof. Raveendra R S/Prof. Anil Kumara K V/Prof. Mutthuraju M Page 2
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Determination of total hardness of water using standard EDTA:

The total hardness (Temporary + Permanent) of water is determined by EDTA method which
involves complexometric titration.
Principle:
EDTA is a complexing agent and hexadentate ligand with a molecular formula (HO 2C CH2)2 -N-
(CH2)2 – N – (CH2-CO2H) 2.
Structural formula is written as follows

HOOC-H2C CH2-COOH

N -CH2-CH2-N

HOOC-H2C CH2-COOH

It forms a stable water soluble complex with metal ions (Ca 2+ and Mg2+). Eriochrome black-T (EBT)
is used as the indicator. The end point being indicated by the change in the color from wine red to
clear blue. When added to the solution containing metal ions at the pH 10 maintained by adding
NH3- NH4Cl buffer solution, EBT forms a wine red colored complex with metal ions.
When the solution is titrated with EDTA, EDTA combines with free metal ions present in the
solution. At the end point EDTA dissociates the wine red colored metal – EBT complex and forms
stable blue colored metal-EDTA complex.
Procedure:
Preparation of Standard EDTA Solution: About 2.5 g of EDTA salt is accurately weighed and
transferred into a 250 ml standard flask. Few drops of NH3 are added, make up the solution to the
mark and shake well to get uniform concentration, molarity of EDTA is calculated.
Estimation of total hardness of water: Pipette out known volume of the water sample into a conical
flask .Add 5ml of NH3 - NH4Cl buffer solution and 3 - 4 drops of EBT indicator. Titrate with
standard EDTA solution till the colour changes from wine red to clear blue. Record the volume of
EDTA used (say V2 ml). This corresponds to the total hardness of the water sample.
Estimation of Permanent hardness:
Transfer known volume of the water into a beaker, boil gently for 1-2 hour, cool and filter into a 250
ml standard flask, make up to the mark. From this pipette out known amount of water into a conical
flask add 5ml of NH3 - NH4Cl buffer solution and 3 - 4 drops of EBT indicator. Titrate with standard
EDTA solution till the colour changes from wine red to clear blue. Record the volume of EDTA
used (say V1 ml). This corresponds to the Permanent hardness of the water sample.
Estimation of Temporary hardness
This can be determined by subtracting Permanent hardness from total hardness of water.
𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 − 𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠
Calculations
Strength of EDTA = M
Volume of water sample = V ml
Volume of EDTA consumed during total hardness = V2 ml
Volume of EDTA consumed during permanent hardness = V1 ml
Volume of EDTA consumed during temporary hardness = (V2 - V1) ml
1000ml of 1M EDTA = 100 g of CaCO3
1ml of 1M EDTA = 0.1g of CaCO3
𝑁 ∗ 𝑉2 ∗ 0.1 ∗ 106
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 =
𝑉
Prof. Bhagya N P/Prof. Raveendra R S/Prof. Anil Kumara K V/Prof. Mutthuraju M Page 3
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

𝑁 ∗ 𝑉1 ∗ 0.1 ∗ 106
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 =
𝑉

𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 − 𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠

Definition of BOD: Biological Oxygen Demand is an important measure of water quality. BOD
is defined as “The amount of oxygen required by microorganism to oxidize the organic matter in
a water sample over a period of 5 days under aerobic condition at 20 0C”.

Definition of COD: It is defined as “The amount of oxygen required for the complete oxidation
of both organic & inorganic matter present in 1 litre of waste water using strong oxidizing agent”.
DETERMINATION OF COD OF WASTE WATER:
Characteristics of COD:
1) The unit of COD is mg/dm3 or ppm.
2) In general COD > BOD since both biodegradable and non biodegradable organic load are
completely oxidized.
Principle: In this method, the given samples of water containing organic and inorganic
impurities are oxidized by K2Cr2O7 in acidic media in the presence of catalyst Ag2SO4 and
HgSO4.(Added to prevent the interference the chloride and silver ions). The unreacted K2Cr2O7
is titrated against FAS solution in the presence of a redox indicator, ferroin which shows its color
change in the oxidized (bluish green) and reduced states (reddish brown).

𝐾2 𝐶𝑟2 𝑂7 + 𝐻2 𝑆𝑂4 → 𝐾2 𝑆𝑂4 + 𝐶𝑟2 (𝑆𝑂4 )3 + 𝐻2 𝑂 + 3(𝑂)

3(𝑂) + Ø𝐶𝐻𝑂 → 2𝐶𝑂2 + 𝐻2 𝑂

Procedure: Preparation of standard solution: Standard FAS solution is prepared by adding
dilute H2SO4 (Added to prevent hydrolysis of FAS) to a known weight of FAS salt.
1. Pipette out known amount of the waste water into a clean conical flask.
2. Add 10 ml of K2Cr2O7 and 10 ml 1:1 H2SO4 into a conical flask.
3. Add 1 g of Ag2SO4 followed by 1 g of HgSO4 and warm if necessary.
4. Titrate with standard FAS solution using ferroin as indicator till color changes from
bluish green to reddish brown.
5. Note down the volume of FAS consumed as ‘V1’ ml.
Perform the blank titration with distilled water. Note down the volume as ‘V2’ ml.
Calculations
Strength of FAS = N
Volume of FAS consumed during blank titration = V2 ml
Volume of FAS consumed during back titration = V1 ml
Volume of FAS consumed = (V 2 - V1) ml

𝑁 × (𝑉2 − 𝑉1 ) × 8 × 1000
𝐶𝑂𝐷 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = 𝑚𝑔/𝑙𝑡 𝑜𝑓 𝑂2
𝑉

Prof. Bhagya N P/Prof. Raveendra R S/Prof. Anil Kumara K V/Prof. Mutthuraju M Page 4
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Methods of Chemical Analysis

Volumetric Analysis
Chemical analysis can be broadly classified into
1. Qualitative analysis
2. Quantitative analysis
Identification of elements/radicals/ions/compounds is called as qualitative analysis.
Determination of exact quantity of the constituents present in the substance is called as quantitative
analysis.
The quantitative analysis can be further classified into:
1. Gravimetric analysis.
2. Volumetric or titrimetric analysis.

Gravimetric analysis: It is a process of measuring the amount of an analyte by its mass.

Volumetric analysis: is a process used to determine the volume of a solution of known

concentration, which is required to react quantitatively with the measured volume of the solution of
a substance, whose concentration is to be determined.

Procedure of volumetric analysis.

1. A solution of known concentration called as a titrant is taken in a calibrated burette.
2. A known volume of solution that needs to be analysed called as titrand is pipette out into a
conical flask.
Water Chemistry, Chemical Analysis, and Instrumental Method of Analysis.
3. Titrant is added to the conical flask in small quantity using burette until the reaction is complete
between titrant and the titrand, which is called equivalence or end point.
4. To find out the equivalence point, an indicator is used, which changes the colour of the solution
at the equivalence point.
5. The volume of titrant added corresponding to the indicator colour change at the end point is
noted.
6. By knowing the volume and concentration of the titrant and the volume of the titrand,
concentration of the titrand or analyte is calculated using the formula.

(NV) titrant = (NV) titrand

Principles of titrimetric analysis

The reagent of unknown concentration reacts with a chemical of known concentration in
the presence of an indicator to show the end point of a reaction. Volume of the reagent
consumed is measured and the concentration of the analyte is calculated using the formula:
N1V1 = N2V2

Where N1 and N2 are the normality of titrant and titrand respectively. V1 and V2 are the
volumesof titrant and titrand respectively.

Requirement for titrimetric analysis.

1. The analyte must react completely and rapidly with the other reagent in stoichiometric
proportion.
2. There must be an alteration in the physical or chemical property of the solution at the

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

equivalence point, which can be detected by an indicator or by measuring the potential difference
or current etc.
Standard Solution: A solution of known concentration is called as standard solution.
Primary standards: Any compound in which total amount of impurities does not exceed
0.01to 0.02% is considered as primary standards.
Conditions for primary standard
 Easily available in pure and dry form.
 Safely stored.
 Easy to detect the impurities present in it.
 Should have high relative molecular mass.
 Readily soluble in a suitable solvent.
Requirements of primary standard solution.
 Has a high level of purity
 Has low reactivity (high stability)
 Has a high equivalent weight (to reduce error from mass measurements)
 Is not likely to absorb moisture from the air (hygroscopic), to reduce
changes in mass in humid versus dry environments
 Is nontoxic
 Is inexpensive and readily available
Secondary standard: is used for standardization after finding its exact concentration by
titration against a standard solution of primary standard.

Units of Concentration of Solution

1. Mole fraction (X) “It is the ratio of the number of moles of solute and the total number
ofmoles of solute and solvent”.
2. Parts per million (ppm) “It is defined as the parts of a component per million parts of
the solution. It is widely used when a solute is present in trace quantities”. It can also be
expressedas milligrams per litre (mg/L).
3. Molarity (M) “is the number of moles of solute per litre of solution”. Unit is
mol/L
4. Molality (m) “Molality of any solution is represented as the number of moles of solute
present per kg of solvent per litre of solution”. Unit is mol/kg.
5. Normality (N) “is the number of gram equivalent weight of solute per litre of solution”.
Unit is gram equivalent/ L.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

INSTRUMENTAL METHODS OF ANALYSIS

Introduction:
Analytical chemistry deals with the quantitative and qualitative characterization of a
materials.it cover a wide variety of fields like environmental science, agricultural science,
biomedical and clinical chemistry, solid state research and electronics, oceanography,
forensic research and space research. Analytical chemist is an integral part of the R and D
sections of any industry.
Chemical analysis of a matter is of two types.
1) Qualitative analysis
2) Quantitative analysis
COLORIMETRIC METHOD

Introduction: this method is useful to determine the concentration of unknown solution. The
concentration of the unknown solution is determined by measuring the absorbance of the light
w.r.t known concentration. The instrument name is Photoelectric Colorimeter

Theory: Theory of the colorimeter is explained by Beer – Lambertz Law.

When a monochromatic light is passed through a solution, a part of light is absorbed by the
solution. The absorbance depends on the concentration of the solution and the path length of
the light through the solution.
Beer-Lambert’s law: Absorbance is directly proportional to concentration and thickness.
A = € ct
€ = molar absorption co-efficient A = Absorbance of light, T = Path length, C = Concentration of the
solution
Lambert’s Law: The intensity of the monochromatic light decreases exponentially as the thickness
of the medium increases arithmetically
Beer’s Law: The intensity of the monochromatic light decreases exponentially as the concentration
of the medium increases arithmetically

Instrumentation: The instruments is used to measure the absorbance of a solution is called

photoelectric colorimeter. It consists of
Source: tungsten bulb or lamp is used as a light source
Filter: It is a device to provide desired wavelength range
Sample cell: Sample is hold in glass cell
Photocell: Converts the emitted light into electrical signal.
When light is allowed to fall on the sample cell at particular wavelength. The blank solution
is taken in the sample cell and placed in the path of light beam. Its absorbance is adjusted to
zero. Then the analyte solution I placed in the path of light and its absorbance is measured. A
plot of absorbance against standard concentrations of analyte is used to find the unknown
concentration of analyte in the samples.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Applications:
 In quantitative analysis: large number of metal ions, anions and cations
compounds can be determined by in this method
 Photometric Titration i.e. equivalence point can also be determined
 Determination of the composition of
colored complex For example:
Procedure: Pipette out 2, 4, 6,
8, 10 ml of standard copper
sulphate solution into 25 ml
standard flask. Add 2.5 ml of
ammonia solution into each of
them and make up to the mark
with distilled water and shake
well. Set the filter to 620 nm.
Adjust the initial reading to
zero by using blank solution in
the sample tube. Measure the
absorbance for each standard flask solution and plot graph of absorbance v/s concentration of
copper sulphate.

Advantages:
 Can be determine the concentration of the colored solution
 It is very simple method
 Colorimeter gives most accurate value
 Used for lower concentration

FLAME PHOTOMETRY

Introduction: Elements impart characteristic color with Bunsen flame. The flame photometry is
based on the measurement of intensity of the light emitted when a metal is introduced into a flame.
The intensity of the emitted light tells about the concentration of the element present.
Theory: A photoelectric flame photometer is a device used in inorganic chemical analysis to
determine the concentration of certain metal ions, among them sodium, potassium, lithium and
calcium that are easily excited to higher energy levels at a relatively low temperature flame.

The excited metal atoms are not stable and they return to ground state by emitting radiation that is
proportional to the concentration of metal ions in solution an di measured by flame photometer.
Instrumentation: It consist of
Source of flame: A Burner in the flame photometer is the source of flame. It can be maintained in at
a constant temperature.
Optical system: The optical system consists of convex mirror and convex lens. The convex mirror
transmits the light emitted from the atoms. Convex mirror also helps to focus the emissions to the
lens. The lens helps to focus the light on a point or slit.
Filters: The reflections from the mirror pass through the slit and reach the filters. Filters will isolate

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

the wavelength to be measured from that of irrelevant emissions.

Photo-detector: The intensity of radiation emitted by the flame is measured by photo detector.
Here the emitted radiation is converted to an electrical signal with the help of photo detector. These
electrical signals are directly proportional to the intensity of light.

Air is passed through atomizer and sample in drawn through capillary tube, the solution mix with the
air as mist. The mist passes into the flame and burns. The radiation emitted pass through the lens and
then filter which transmits only radiation characteristics of the element. The detector displays the
emission intensity. Plot a graph emission intensity against volume of NaCl and find the
concentration of unknown NaCl solution.

Applications: It is used in the quantitative determination of metals in solution, especially alkali &
alkaline earth in the given sample.

For example: Flame photometric estimation of sodium

Prepare 1ppm NaCl solution by weighing
2.52g of sodium chloride and dissolved
one liter of distilled water.
Transfer 2, 4, 8, 10ml of standard NaCl solution
into different standard flask. Set the instrument
to zero by using distilled water and hundred by using pure NaCl solution. Measure the emission
intensities for other standard solutions. Draw a calibration curve by plotting the emission intensity
(Y axis) and concentration of NaCl in ppm (X axis). From the curve find out concentration of NaCl
and calculate the amount of Na.

POTENTIOMETRIC TITRATION

Aim: Determination of the weight of ferrous ammonium sulphate and ferrous iron in the given
solution by potentiometric titration method.

Theory: In this titration the amount of substance in the solution is determined by measuring the
emf between two electrodes that are dipped into the solution. When the metal M is immersed in the
solution containing its own ions Mn+ ions, the electrode potential is given by Nernst equation,
E=Eo+ 0.0591log [Mn+]
n

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

From this equation the potential of the electrode is directly proportional to the concentration of the
ionic species present in the solution.
Instrumentation: A potentiometer consists of a indicator electrode (e.g.: Platinum) and an
saturated reference electrode (E.g.: Calomel electrode), stirrer & potentiometer to measure the
potential values.
Emf of the solution can be measured by combining reference electrode with indicator electrode.
The electrode which responds to the change in the concentration of the ion in the solution is called
indicator electrode & reference electrode is one whose potential is constant. A known volume of the
analyte is taken in beaker and its potential is measured. The titrant is added in increments of 0.5ml
and potential is measured each time. Near the equivalence point there is a sharp increase in the
potential. The end point is determined by plotting changein potential against volume of the titrant.

Application:
1. Estimation of concentration of the ionic species present in the given solution.
2. Coloured solution can also be titrated
3. Acid-base titration can also be done in this method.
4. In this method Oxidation-reduction titrations can also be carried out.
5. Precipitation reactions can also be carried out potentiometrically.
For example:
Procedure: Pipette out 25cm3 of FAS solution into a 50 cm3 beaker. Add one test tube full of
dil H2SO4. Immerse Pt. & calomel
electrodes into the solution, & connect the electrodes to a Potentiometer.
Fill the burette with K2Cr2O7 solution.
Add K2Cr2O7 solution from the
burette with increment of 0.5cm3, stir
well and measure the potential after
each addition. Continue the titration
till the potential indicates a rapid
jump with a drop of titrant.
Plot the graph of ∆E/ ∆V v/s vol. of
K2Cr2O7.

CONDUCTOMETRIC TITRATION
Conductance is ease with which current flows through the solution. It is reciprocal of resistance.
C=1/R = Ω-1 or mho or siemen
Theory:
The Conductance of the solution is explained by considering ohm’s law.
According to ohm’s law the current flowing through the conductor is directly proportional to
voltage and inversely proportional to the resistance.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

I= or E = I R
The resistance of the any conductor is directly proportional to the length of
inversely proportional to the area of cross section of the conductor
Therefore R = S (l/a) where S is specific resistance
Therefore C = 1/R = 1/S (a/l), K (a/l), K = specific conductance
It is defined as the conductance of the solution present between two parallel electrodes of 1cm2
area of cross section and 1cm apart.
The conductance of the solution is depends on mobility of the ion and number of the ion.
There are three type’s namely specific conductance, equivalence conductance, and molar
conductance.
Specific conductance (K) is the conductance of the solution present between two parallel
electrodes of 1cm2 area of cross section and 1cm apart.
K = 1/R (l/a) K = Siemen m-1
Equivalence conductance (λ) is the conductance of the solution when 1g equivalent weight of
solution is placed between two electrodes of area 1cm2 at 1cm apart.
Molar conductance (µ) is the conductance of the solution when 1g molecular weight of solute
is placed between two electrodes of area 1cm2 at 1cm apart

Instrumentation: It consists of two platinum electrodes each of unit area of cross section
placed at unit distance apart. The electrodes are dipped in the electrolytic solution taken in a
beaker. It is connected to a conductometer to measure the conductance. The conductance is
measured after the addition of the titrant at intervals of 0.5 ml.

Application of Conductometric titration

It is used in the estimation of acids and bases present in the sample solutions. The possible
combinations and condauctance responses are explained below,
Strong acid v/s strong base
HCl v/s NaOH
If the strong acid like HCl is titrated
against a strong base such
As NaOH, the conductance first decreases
due to replacement
of fast moving H+ ions by slow moving
Na+ ions
HCl + NaOH NaCl + H2O
After the neutralization point, conductivity
rapidly rises with further addition of
NaOH because of continuous addition of
fast moving
OH- ions. A plot of conductance against the volume of base added is shown in the figure. The
point of intersection of two curves gives the neutralization point.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Weak acid v/s Strong base

Consider the titration of acetic acid
against NaOH.
The conductance of the acid will be initially
low since acetic
acid is a weak electrolyte. When NaOH is
added to the acid,
the salt formed is highly ionized and
the conductance increases.
On complete neutralization of the acid,
further addition of base
leads to an increases in the number of mobile OH - ions.
Hence the conductance increases sharply.
CH3COOH+ NaOH CH3COONa + H2O
A plot of conductance against the volume of base added is shown in the figure. The point of
intersection of two curves gives the neutralization point.

Mixture of strong acid and weak acid v/s strong base

HCl, CH3COOH v/s NaOH
the strong acid like HCl is titrated
against a strong base such as NaOH, the
conductance first decreases due to
replacement of fast moving H+ ions by
slow moving Na+ ions
HCl + NaOH NaCl + H2O
The weak acid do not get neutralized initially
because of the well known common ion effect.
In the presence of excess of H+ ions, the ionization
of the weak acid is suppressed and hence, weak acid
like CH3COOH ionizes gradually after the first end point and the available H+ ions are neutralized
giving the second end point. Because of common ion effect dissolution of acetic acid is
suppressed. Hence it does not provide H+ ions which required for neutralization.
After the neutralization point of HCl, CH3COOH, conductivity rapidly rises with further
addition of NaOH because of continuous addition of fast moving OH- ions. A plot of
conductance against the volume of base added is shown in the figure. The point of
intersection of two curves gives the neutralization point.

Advantages:
 Mixture of acid can be titrated
 Indicators are not used
 Very weak acids can be titrated
 Can be used with colored solution

Prof. Bhagya N P/Prof. Raveendra R S/Prof. Anil Kumara K V/Prof. Mutthuraju M Page 12