MODULE 5- WATER CHEMISTRY

Introduction

Water is one of the most abundant and widely distributed substances. Water is the second
most important substance (first being air) required to sustain human, animal and plant lives.
The uses of water are many and varied such as in the manufacture of paper, textiles, sugar
and in steam power plants apart from human consumption.

Sources of water
The sources of water are classified as surface water and underground water.

Surface water
1. Rain water: - The purest form of natural water usually contains dust particles and gases
dissolved from atmosphere such as O2, N2, and CO2 (Ammonium salts, H2S or H2SO4 may be
present in rain water in industrial areas)
2. River water: It usually rich in turbidity, suspended impurities of decaying organic
matter(vegetable and animal) sand & finely divided clay, micro-organisms & bacteria and
small amounts of mineral salts(mainly Ca2+, Mg2+, Na+, SO4-, Cl- etc) dissolved from top soil.
3. Lake water: It contains less of dissolved minerals but quite a high quantity of organic
matter.
4. Sea water: It is the most impure form of natural water. It contains on an average of about
3.5% of dissolved salts out of which about 2.6% is sodium chloride. Other salts present are
sulfates of sodium, bicarbonates of potassium, magnesium and number of other compounds.
5. Underground water: (From well, bore wells etc) Usually contains negligible amounts of
suspended and organic impurities but may contain applicable amounts of mineral
impurities(Ca2+, Mg2+, K+, Na+, Fe2+, Al3+, Mn2+, HCO3-, CO3-, SO42-, Cl-, NO3-, finely
divided clay etc)

Impurities in water- The major types of impurities found in water are,

1. Dissolved gases: The water contains mainly CO2 and oxygen as dissolved gases. Some
water may contain ammonia and sulfur compounds such hydrogen sulphide also as dissolved
gases which impart foul smell to water.

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2. Dissolved solids: The soluble salt impurities present in water include salts of calcium,
magnesium, sodium in various soluble salt forms. Oxides of manganese iron, lead and arsenic
may also present in water.
3. Suspended impurities: The suspended matter may be of inorganic or organic nature. The
inorganic materials include particles such as sand, clay silica, hydroxides of iron and
aluminium etc derived from the erosion of soil. Some of these particles have large size and
therefore settle down readily. Others are fine particles and colloidal in nature. Such particles
do not settle down easily. The organic suspensions are decaying vegetable matter and due to
microorganisms. These are also present in colloidal form. The presence of suspended matter,
particularly the colloidal particles impart turbidity to water.

Determination of total hardness of water

Hardness in water is caused by divalent metal ions such as calcium and magnesium. The
hardness in water is of two types, namely temporary hardness and permanent hardness.
Temporary hardness is due to the presence of bicarbonates of calcium and magnesium.
Temporary hardness can be removed by a simple physical process such as boiling. Permanent
hardness is caused by the presence of chlorides and sulfides of calcium and magnesium.
Permanent hardness requires chemical processes for softening.
Temporary hardness and permanent hardness added together gives total hardness.
Hardness is usually expressed in terms of dissolved calcium and magnesium salts calculated
as calcium carbonate equivalent. The reason for expressing hardness as CaCO3 equivalent is
due to the fact that its molecular mass is 40 + 12 + 48 = 100 (or equivalent weight is 50) and
it is the most insoluble salt that can be precipitated in water treatment.

Equivalentof CaCO3 = Mass of hardness producing material X Chemical equivalent of CaCO3

Chemical equivalent of hardness producing substance.

= ____Mass of hardness producing material X 50___

Chemical equivalent of hardness producing substance

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Units of hardness

Parts per million (ppm): It is the most commonly used unit of hardness. It is defined as the
number of parts of hardness causing substances (in terms of CaCO3) present in million
parts of water, mg per dm3 (liter) and grams per cubic meter numerically the same.

Determination of hardness of water by EDTA method

Principle: The total hardness of water sample could be determined by titrating against
ethylene diamine tetra acetic acid (EDTA). EDTA forms complexes with Ca2+ and Mg2+ ions.
EDTA has the structure,

HOOC – H2C CH2 - COOH

N – CH2 – CH2 – N

HOOC – H2C CH2 - COOH

It is commonly represented as H4Y. The ionization in solution is represented as

H4Y H2Y 2- + 2 H +

The anion formed in the ionization form complexes with metal ions, M2+ which can be given
as
M 2+ + H2Y 2- MY 2- + 2 H + where M2+ is a Ca2+ or Mg2+.

The total hardness of water can be determined by titrating known volume of water against
standard EDTA solution at a pH of 10 using eriochrome black- T indicator. The colour of the
free indicator at pH 10 is blue. Eriochrome black – T forms a wine red complex with M2+
ions. On titration, EDTA first gets complexed with the entire free M2+ indicator complex.
Thus the indicator gets freed and consequently gives colour change from wine red blue at the
equivalence point. Since the reaction involves the release of H+ ions, a buffer mixture to
maintain a pH of 10.

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The total hardness is determined by titrating known volume of water sample against EDTA.
To determine the temporary hardness, another sample of the same volume of water is boiled
to convert the bicarbonates to carbonates and the precipitated calcium carbonate is filtered
off. The filtrate, after cooling is titrated against EDTA in the same way. This gives the
permanent hardness. The difference between the total hardness and the permanent hardness
gives the temporary hardness.

Procedure
1. Total hardness:- Pipette out 25 ml of the sample of water into a clean titration flask, add 5
ml of NH3 – NH4Cl buffer solution and 3 - 4 drops of eriochrome black – T indicator. Titrate
against say 0.01 M EDTA till the colour changes from wine red to clear blue without any
reddish tinge. Let the volume of EDTA required be V1 ml.
2. Permanent hardness: Transfer 25 ml of the sample of water into a clear 500ml beaker
and boil gently for 20 – 30 minutes. Cool and filter it directly into a 250 ml conical flask.
Add 5 ml of buffer solution followed by 3 – 4 drops of eriochrome black – T indicator.
Titrate against standard say 0.01 M EDTA as described above. Let the volume of EDTA
required be V2 ml.

CALCULATIONS

1000 ml of 1 M EDTA = 100 g CaCO3 (Mol. Wt. of CaCO3 100 G)

1 ml of 1 M EDTA = (100 / 1000) g of CaCO3
or
V1 ml of 0.01 M EDTA = V1 X 0.01 X 100 g of CaCO3
1000
50 ml of water sample contains = V1 X 0.01 X 100 g of CaCO3
1000
106 (1 million) ml of water sample contain = V1 X 0.01 X 100 X 106 g of CaCO3
1000 X 50
= 40 X V1 g of CaCO3
Total hardness of water sample = 40 X V1 ppm CaCO3 equivalent.

Similarly permanent hardness = V2 X 0.01 X 100 X 106

1000 X 50
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 = 40 X V2 g of CaCO3

Temporary hardness = 40 (V1 – V2) ppm CaCO3 equivalent.

Biological oxygen demand (BOD)

Natural water contains dissolved oxygen (8.7 ppm or 8.7 mg / dm3) and the dissolved oxygen
(DO) is capable of oxidizing many of these pollutants particularly the organic wastes such as
dead plant matter and animal wastes. In this way the dissolved oxygen is consumed.
However, in running water such as streams and rivers there us continuous replenishment of
oxygen maintaining the DO level and hence the degradation is aerobic. The degradation
products are CO2 and water which are harmless. On the other hand, in stagnant waters such as
in lake and well waters, there is a gradual decrease in the DO level ultimately during
anaerobic (absence of air) degradation of organic waters releasing obnoxious gases such as
H2S, CH4 and NH3.
The amount of organic matter present in sample natural water is measured in terms of the
amount of dissolved oxygen required by micro organisms to oxidize the organic matter. This
is called the biological (or biochemical) oxygen demand (BOD). It is defined as the quantity
of oxygen required by micro organisms to oxidize the organic wastes present in one liter of
waste water over a five day period at 20˚C under aerobic conditions.

Chemical oxygen demand

BOD refers to biologically oxidizable impurities and does not account for non – oxidizable
and other slowly oxidizable impurities. A faster method for determining the amount of
oxygen required to oxidize both the biologically oxidizable and biologically non – oxidizable
but chemically oxidizable organic and inorganic wastes is by evaluating the chemical oxygen
demand, COD.
It is defined as the amount of oxygen consumed in the chemical oxidation of organic and
inorganic wastes present.
The principle of the method is the oxidation of organic matter using chemical oxidizing
agents such as acidified potassium dichromate in the presence of a catalyst such as silver
sulphate (which catalyst the oxidation of organic matter) and mercuric sulphate (which forms
a complex with chloride ions present in water thus preventing its inference).
A typical reaction representing the oxidation of organic matter is given below.

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 Ag2SO4
3 CH2O + 16 H + + 2 Cr2O7 2- 4Cr 3+ + 3 CO2 + 11 H2O
HgSO4
Experimental method
Principle: The method consists of addition of excess standard solution of potassium
dichromate acidified with sulphuric to a known volume of effluent sample and back titrating
the excess potassium dichromate against a standard solution of ferrous ammonium sulphate.
COD values are also expressed in mg / dm3.
Method: To a measured volume of waste water sample taken in a flask, add 10cm3 of 0.25 N
K2Cr2O7 solution followed by 30cm3 of 6N H2SO4. Add 1g of Ag2SO4 followed by 1g of
Hg2SO4. Attach a reflux condenser and reflux the contents for 2 hours. Cool and titrate the
excess of K2Cr2O7 against ferrous ammonium sulphate solution using ferroin as indicator till
the bluish green colour turns sharply to reddish brown. Let the volume of titrant required be
‘a’ cm3. Perform a blank titration taking the same amount of water in place of waste water.
Let the volume required be ‘b’ cm3.

Calculations
Volume of K2Cr2O7 required for the sample = (b-a) cm3
COD of the sample = N x (b-a) x 8 g / dm3
V
= N x (b-a) x 8000 mg / dm3
V
Where N = Normality of ferrous ammonium sulphate
V = Volume of waste water sample.

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 Methods of Chemical Analysis
Volumetric Analysis

Titration is a quantitative chemical analysis. It is used to determine an unknown

concentration of a known substance in a sample. The basic principle of the titration is the
following: A solution – a so called titrant or standard solution – is added to sample to be
analyzed. The titrant contains a known concentration of a chemical which reacts with the
substance to be determined. The titrant is added by means of a burette. A burette is a device
which allows to exactly measure the quantity (volume) of the titrant added. Due to the
chemical reaction taking place in the sample to be analysed, the characteristics of the sample
changes.
This change of the characteristics can be detected either by a so called color indicator or a
sensor:
• A color indicator changes its color as soon as all the substance contained in the
sample has reacted with the titrant added.
• A sensor shows a significant change in the signal measured as soon as all the
substance contained in the sample has reacted with the titrant added.

The concentration of the substance contained in the sample can then be calculated based on
the volume of the titrant which was required to add until all the substance had reacted.

Volumetric Titrimetry
• The gradual addition of a solution of accurately known concentration to another
solution of unknown concentration until the chemical reaction between the two
solutions is complete is called as titration.
• Volumetric methods of analysis are based on the measurement of the amount of
reagent that combines with the analyte. The terms volumetric analysis specifically
involves the determination of the volume of the reagent solution needed for a
complete reaction.
• Volumetric titrimetry: methods that require that a reagent solution of known
concentration, standard solution or titrant, be used.

For a successful titrimetric analysis, the requirements are as follows

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 • The titrant should either be a standard or should be standardized.
• The reaction should proceed to a stable and well defined equivalence point.
• The equivalence point must be able to be detected.
• The titrant’s and sample’s volume or mass must be accurately known.
• The reaction must proceed by a definite chemistry. There should be no complicating
side reactions.
• The reaction should be nearly complete at the equivalence point. In other words,
chemical equilibrium should favour the formation of products.
• The reaction rate should be fast enough to be practical.

Basic Concepts of Standardization Process

• Standardization: The process by which the concentration of a solution is determined.

• Standard Solution: A solution of accurately known concentration.
• Primary Standard: a high purity compound used to prepare the standard solution or to
standardize the solution with.
• Secondary Standard: a second material used as a substitute for a suitable primary
standard. This standard solution should always be standardized using a primary
standard.

Requirements of Primary Standards

A primary standard in metrology is a standard that is sufficiently accurate such that it is not
calibrated by or subordinate to other standards. Primary standards are defined via other
quantities like length, mass and time. Primary standards are used to calibrate other standards
referred to as working standards.

A primary standard is typically a reagent which can be weighed easily, and which is so pure
that its weight is truly representative of the number of moles of substance contained. Features
of a primary standard include:

1. High purity
2. Stability (low reactivity)
3. Low hygroscopicity (to minimize weight changes due to humidity)
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 4. High equivalent weight (to minimize weighing errors)[3]
5. Non-toxicity
6. Ready and cheap availability

Some examples of primary standards for titration of solutions

• Sodium chloride for standardisation of silver nitrate solutions
• Sodium carbonate for standardisation of aqueous acids: hydrochloric, sulfuric
acid and nitric acid solutions (but not acetic acid)

Units of Standard Solutions

The concentrations of standard solutions are normally expressed in units of moles per litre
(mol/L, often abbreviated to M for molarity), moles per cubic decimetre (mol/dm3),
kilomoles per cubic metre (kmol/m3) or in terms related to those used in particular titrations.

1. Normality (N) is defined as the number of mole equivalents per liter of solution.
Normality = number of mole equivalents/1 L of solution

2. Molarity (M) is defined as the number of moles of solute per liter of solution.
Molarity = moles of solute/liters of solution

3. Molality (m) is defined as the number of moles of solute per kilogram of solvent.
molality = moles of solute/kilograms of solvent.

Molarity is a measurement of the moles in the total volume of the solution,

whereas molality is a measurement of the moles in relationship to the mass of the solvent.

Mole fraction
The ratio of the number of moles of one component of a solution or other mixture to the total
number of moles representing all of the components is called as mole fraction.

Formula:

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 xi = mole fraction
ni = amount of a constituent in moles
ntot= total amount of all constituents in a mixture in moles

ppm
This is a way of expressing very dilute concentrations of the substances. One ppm is
equivalent to 1 milligram of substance dissolved per liter of water (mg/l). ppm is obtained by
dividing the mass of the solute by the mass of the solution, then multiplying by 1,000,000.

Instrumental Method of Analysis

COLORIMETRY

Introduction
The variation of the color of a system with change in concentration is the basis of
colorimetry. In colorimetry, the concentration of a substance is determined by measurement
of the relative absorption of light with respect to a known concentration of the substance.

Principle
Optical methods of analysis involve the absorption of radiations such as UV, visible
and infrared. On passing these radiations through a sample, a part of it is absorbed resulting
in a decrease in intensity of the incident radiation. Hence this principle can be used to identify
and quantify a substance. The basic law which relates the light absorbed with the chemical
analysis is the Beer- Lamberts law.

Lamberts law
The relation between the incident, absorbed and transmitted lights with thickness of
the cell is expressed in the form of Lamberts law. It is stated as “When a monochromatic
light passes through a transparent medium, the rate of decrease in intensity with the
thickness of the medium is proportional to the intensity of the light.

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Mathematically it can be expressed as
- dI = kI
dt Where k is proportionality constant.
ie.,
- dI = kdt
I
Integrating this equation and substituting I = I0 when t = 0,
ln I0 = kt
It
It = I0 e-kt
This equation shows the exponential decrease in intensity of transmitted light with the
increase in thickness of the medium.

Beer’s law
This law is stated as “The intensity of the transmitted light decreases
exponentially as the concentration of the medium increases arithmetically”.
Mathematically, this maybe expressed as,
It = I0 e-k’c, Where ‘c’ is the molar concentration of the sample solution.
Combining equations for Beer’s law and Lambert’s law, equation for Beer-Lambert’s law
can be written as
It = I0 e-kk’ct,
It = I0 e-Kct,
It = I0 e-Єct, Where Є is called as molar absorption coefficient, is a constant for a given
substance at a given wavelength.
From the above equations we can write as
Log I0 = Єct
It
This equation is referred to as Beer-lamberts law.
The ratio Log I0 = A, the absorbance of the medium or optical density D.
It
The ratio It
= T, called transmittance.
I0
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The above equation becomes
A = Є ct = Log I0 = log 1 / T
It
If the path length of the cell is kept constant, then, absorbance A is proportional to the
concentration ‘c’.

Instrumentation: – Photoelectric colorimeter

The essential parts of a photoelectric colorimeter are a light source, a light filter, a
container for the solution, a photo cell to receive the transmitted light and some means for
measuring the response of the photocell. The block diagram is shown below.

Source Filter Sample Photocell Recorder

The function of the filters is to isolate any desired spectral region by filtering off the
undesired radiations. Optical filters consist of either thin films of gelatin containing different
colored glass. The filter allows radiations of a definite wavelength range to pass through it
and reach the sample.

Applications
1. In quantitative analysis: - Colorimetric estimation of copper
When cupric ions are treated with ammonia solution, it gives deep blue colored
cuprammonium complex. The absorbance is measured at 620 nm (λmax) since the complex
shows the maximum absorbance at this wavelength. When absorbance of known solutions is
plotted against concentration, a straight line will be obtained. From this unknown solution
concentration can be obtained by measuring the absorbance of unknown solution.
Cu 2+ + 4 NH3 Cu [NH3]42+
Deep blue

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Procedure:
Take known volumes of standard copper sulphate (2, 4, 6,8,10 etc ml) in separate standard
flasks. Add 5 ml of ammonia in to each of these flasks and make up to the mark with ion
exchange water. Stopper the flasks and mix the solutions well. To the given test solution add
5 ml ammonia and make it up to the mark with ion exchange water. Stopper the flask and mix
the solution well. Measure the absorbance of the solutions against blank at 620 nm using
colorimeter. Draw the calibration curve by plotting concentration of copper against
absorbance. Using the calibration curve determine the concentration of copper in the test
solution.

Absorbance Concentration of unknown sample

Concentration of Cu 2+

POTENTIOMETRY
Potentiometric titration is very important application of emf measurement.
Theory
The potential of an electrode is given by Nernst equation
E = Eo + 0.0591 log[Mn+]
n
Thus, the potential of an electrode depends upon the concentration of the ion to which it is
reversible. The potentiometric titration is applicable mainly in the determination of endpoint
of various types of titrations such as neutralization and redox.
Suppose a known volume of the analyte is titrating with a standard solution of the titrant,
neutralization or redox reaction take place. During the titration, initially the change in
potential will be small. At the equivalence point, there will be a steep rise in the potential.
Beyond the equivalence point, there will be no significant change in the potential. By plotting
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a graph of change in potential against volume of titrant added, the equivalence point can be
determined.

∆E Equivalence point
∆V

Vol. of K2Cr2O7 (in ml)

Instrumentation
Potentiometer consists of a reference electrode, an indicator electrode and a potential
measuring device. The indicator electrode responds rapidly to the changes in the
concentration of the analyte i.e. the solution under study. A simple arrangement of
potentiometric titration is given below.

To
Potentio
meter

A C B

A Reference electrode (saturated calomel electrode)

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B Indicator electrode
C Mechanical stirrer
The solution to be titrated is taken in the beaker. A known volume of analyte is taken and its
potential is determined. The titrant is added in increments of 0.5 ml and EMF is measured
each time. At the approach of equivalence point, the EMF tends to increase rapidly; few more
readings are taken beyond the end point. Thus the changes in potential at different volumes of
titrant are recorded.

Applications-Redox titrations

Redox titrations
Titrations involving oxidizing agents (K2Cr2O7 or KMnO4) and reducing agents (like
ferrous salt) can be followed potentiometrically by using platinum indicator electrode. On
adding K2Cr2O7 from the burette, EMF of the cell will increase first slowly, but at the
equivalence point, there will be sudden jump in potential, since change in the ratio of
Fe2+ / Fe3+ ions concentration, is quite rapid at the equivalence po0int.

When ferrous ammonium sulphate reacts with potassium dichromate in the presence of acid
medium, the following reactions take place.

Fe 2+ ---------> Fe 3+ + e –

Cr207 2-+ 14 H+ + 6 e – ----------> 2Cr 3+ + 7H2O

Prior to the equivalence point the potential is determined by the Fe 3+/ Fe2+system and the
potential is given by the equation,

E cell = Eo + 0.0591 log ([Fe 3+] / [Fe 2+])

At the equivalence point the potential is observed is maximum, due to the complete oxidation
of Fe2+ to Fe3+

Beyond the equivalence point the potential is determined by Cr2072-/ Cr3+system given by the
equation,

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 E cell = E⁰ + 0.0591 log ([Cr 6+] / [Cr 3+])

Thus an abrupt increase in the potential of the solution in the vicinity of the equivalence point
is observed.

CONDUCTOMETRIC TITRATIONS

Theory
Electrolytic conductivity is a measure of the ability of a solution to carry an electric current.
Electrolyte solution obey ohms law,
E = IR
Where, E is the applied potential, I is the current and R is the resistance.
The reciprocal of the resistance is called the conductance C = I / R. It is
expressed in ohm -1 or Siemens(S).
The resistance of any conductor is directly proportional to the area of cross section of
the conductor.
R = S (l/a), where S is specific resistance or resistivity of the conductor.
Therefore conductance, C = 1 / R = (1/S) (a/l)
= k (a/l)
Where, k is the specific conductance or conductivity of the electrolyte solution. When a=1,
l = 1, then C=k or specific conductance is the conductance of an electrolyte solution, when
two electrodes are kept between 1 m apart & area of cross section 1 m2 . The unit of k in SI
unit is Sm-1

Instrumentation
Conductometer consists of two platinum electrodes and a conductance measuring device. The
two electrodes have unit area of cross section and are placed unit distance apart. The
assembly responds rapidly to the changes in the concentration of the analyte (the solution
under study). A simple arrangement of conductometric titration is given below.

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 To
Conduct
ometer

Stirrer Pt-Electrode

Applications:
(a) Acid-base titrations

(i) Strong acid with a strong base

Eg: Titration of dilute HCl against NaOH

During the titration i.e. HCl with NaOH, the reaction taking place is
(H+ + Cl- ) + (Na+ + OH-) Na+ + Cl- + H2O
The highly conducting H+ ions of HCl initially present in the solution are replaced by the OH-
ions of NaOH to form nearly non-conducting water molecules. Hence conductivity of the
solution decreases progressively till the equivalence point is reached. On further addition of
sodium hydroxide solution the conductivity of the solution will rises due to the addition of
highly mobile OH- ions.

Conductance
( in Ohm-1 cm-1) Equivalence point

Volume of NaOH in ml

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(ii) Weak acid with a strong base

Eg: Titration of CH3COOH against NaOH

Initially the conductance is low due to the feeble ionization of acetic acid. On the addition of
base the conductance increases slowly due o the formation of CH3COONa which is an
electrolyte. This increase in conductance continues raise up to the equivalence point. Beyond
the equivalence point, conductance increases more rapidly with the addition of NaOH due to
the highly conducting OH – ions

(iii) Mixture of Strong acid and weak acid with a strong base

In the titration of a mixture of a weak acid (CH3COOH) and a strong acid (HCl) with a strong
base (NaOH), the conductance decreases upon adding NaOH to acid mixture due to the
substitution of highly mobile H+ ions (mobility: 350 ohm-1m-1) by the less mobile Na+ ions
(mobility: 50 ohm-1m-1). This trend continues till all the H+ ions of HCl are replaced by Na+
ions i.e, till the strong acid is neutralised.

If the addition of NaOH is continued, the conductance increases moderately, as the weak
acid, CH3COOH is converted into its salt, CH3COONa.
CH3COO-H+ + Na+OH- ---------> CH3COO-Na+ + H2O

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If the addition of NaOH is further increased, then the conductance increases steeply due to
the presence of free OH- ions (mobility: 198 ohm-1 m-1). The equivalence points are obtained
by plotting a graph of conductance versus volume of NaOH added.

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FLAME PHOTOMETRY

Sodium, Calcium, Potassium and Lithium and other common elements impart
characteristic colours to the Bunsen flame by emission of light radiations. The
intensity of the coloured 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 changes occur.

(i) Solvent evaporates leaving behind the salt in the flame.

(ii)The salt goes to the vapour state and in the vapour state, salt dissociates into constituent
atoms

(iii)Some gaseous atoms get excited by the thermal energy of the flame to higher energy
levels

iv) The excited atoms which are unstable, quickly emit photons and return to lower energy
state ie, ground state

The relationship between the ground state and excited state populations is given by the
Boltzmann equation

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From the above equation, it is evident that the ratio N1/No is dependent upon the
excitation energy, ΔE and the temperature T. An increase in temperature and a
decrease in ΔE will result in a higher value for N1/No

MX (SOLUTION) MX (MIST) MX (SOLID) MX (GAS)

ABSORBS HEAT hγ
M (GAS) + X (GAS) M* (GAS) M (GAS)
(GROUND STATE) (EXCITED STATE) (GROUND STATE)

Instrumentation:

1. Fuel and oxidants: Fuel and oxidant are required to produce the flame such that
the sample converts to neutral atoms and they get excited by heat energy.

2. Nebulizer: Converts sample solution to fine droplets, which then gets mixed with
compressed air and gets converted to aerosol.

3. Burner: A homogenous flame of stable intensity is produced and the sample when
sprayed produces excited atoms.

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 4. Monochromators: Filters and monochromators are needed to isolate the light of
specific wavelength from remaining light of the flame. In practice Li, Na, k & Ca,
Mg are analyzed. Eg: For Sodium (Na) 589nm- Golden yellow radiation, Potassium
- 767nm range radiation.

4. Detector: Detects the photo response created from the emitted radiation (400nm to
700nm) and send it to display units.

5. Recorders and display: Converts the light signal into an electrical signal
proportional to the emitted light intensity, and gives the digital read out.

Application: Flame Photometric Estimation of Sodium

• Transfer 2, 4, 6, 8, 10 mL of given standard NaCl solution in to 25 mL standard flasks

and dilute up to the mark with distilled water and shake well for uniform
concentration.
• To the given unknown solution also, add distilled water and shake well
• Place the suction capillary of the instrument in distilled water and set the instrument
to zero.
• Place the suction capillary in the NaCl solution and set the instrument to 100
• Place each of the standard solution in contact with the suction capillary and read the
flame emission intensity for 2, 4, 6, 8,10mL solutions respectively (rinse the suction
capillary with distilled water between each reading) using sodium filter of
wavelength589nm
• Place the suction capillary in the test solution and record the flame emission intensity.
• Draw a calibration curve by plotting the emission intensity versus volume of NaCl
solution
• From the calibration curve, find out the volume of the given test solution and from
which, calculate the amount of sodium in the water sample.

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 heat heat
NaCl ---------> NaCl(g) ---------> Na+(g) + Cl-(g) (atoms)

Heat hγ
Na+(g) -------------------> Na+(g) -----------------> Na+(g)
(GROUND STATE) (EXCITED STATE) (GROUND STATE)

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