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Environmental Chemistry and Analysis Prof. M.S.

Subramanian













Indian Institute of Technology Madras
MODULE 2.2
Analysis of common ions at low
concentrations in water
Ultraviolet And Visible Spectrometry 1
Spectrophotometric instrumentation 2
Analysis by direct absorption 3
Nitrate determination 3
Analysis after formation of derivative 4
Chloride: Automated method using
mercuric thiocyanate and ferric nitrate
4
Fluoride: Zr-Alizarin lake method 5
Nitrite 5
Phosphate 5
Automatic procedures 5
Field Techniques 6
Flame photometry 6
Ion Chromatography 7
Examples Of The Use Of Other Techniques 11
Ammonia 12
Fluoride 13
Sulphate 13
Free chlorine (Residual chlorine) 14
Sulphide 14
Sample Collection and preservation 15
Spectrophotometric determination of H
2
S 15
Titrimetric method 15
Cyanide 16

Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
MODULE 2.2
Analysis of common ions at low concentrations in
water:
In this chapter the application of instrumental techniques to determine the
concentration of ions which are present in mg l
-1
concentration range are
discussed . One of the major advantages of the use of instrumental techniques is
that elaborate sample preparation is not necessary. However when it comes to
the analysis of ions at g l
-1
levels, a preconcentration step is needed inorder to
bring the concentration of the analyte ions within the working range of the
instruments. In that case the instrumental part becomes just one part of a more
complex analytical procedure. The analysis of ions present at g l
-1
concentration
level are discussed in the next chapter.
Ultraviolet And Visible Spectrometry:
This technique is based on Beer-Lambert law. That is at sufficiently low
concentrations of the absorbing species the above law is obeyed which can be
expressed mathematically as
A = cl
Where A = absorbance of radiation at a particular wavelength;

o
t
I
A log
I

=



= Intensity of incident radiation;
= Intensity of transmitted radiation;
= Molar absorptivity; l mol
o
I
t
I

-1
cm
-1

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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
C = Concentration of absorbing species (mol l
-1
);
l = Path length of light beam (cm)
There are many instruments which are used to measure the absorption of
light. These can range from sophisticated laboratory instruments which can
operate over the whole visible-ultraviolet range to portable colorimeters using
natural visible light, which are used as field instruments.
Natural water is colourless since none of the common ions present in
water absorb light in the visible region. The only ions which absorb in the
ultraviolet range above 200nm are nitrate and nitrite.
Since nitrate ions absorb at 220nm, it permits the concentrations of these
ions in water to be determined using spectrophotometer by direct absorption.
The concentration of ions such as chloride, fluoride and phosphate which
do not absorb in the visible region, can however be determined after converting
them into a suitable coloured species by chemical reactions. Nitrate and nitrite
also are converted into suitable coloured products, the absorbances of which can
be measured.
Spectrophotometric instrumentation:
The out line of a simple single-beam spectrophotometer is shown in fig.1.
Source
Monochro
mator
Sample
Detector
& read out

fig.1 block diagram of a single beam spectrophotomer
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
For absorption in the visible region, a tungsten lamp is used as a source and
that for absorption in uv region hydrogen lamp is used. The light of the desired
wavelength is isolated using diffraction monochromator. Normally for all
absorption measurements 1 cm cells are used and for all uv absorption
measurements cells made of quartz are used. Different types of detectors such
as photocell, photomultiplier or photodiode array detectors are used in the
absorption measurements.
Analysis by direct absorption:
Nitrate determination:
This method is useful only for screening water samples that have low
organic matter contents, i.e., uncontaminated natural waters and potable water
supplies.The calibration curve follows Beer's law upto 11
ppm. Measurement of uv absorption at 220nm enables rapid determination of
nitrate. Because dissolved organic matter also may absorb at 220 nm and
does not absorb at 275 nm, a second measurement made at 275 nm, may
be used to correct the value. The extent of this empirical correction is
related to the nature and concentration of organic matter and may vary from one
water to another. This method is therefore not recommended if a significant
correction for organic matter absorbance is required, although it may be useful in
monitoring levels within a water body with a constant type of organic
matter. Sample filtration is intended to remove possible interference from
suspended particles. Acidification with 1N HCl is designed to prevent interference
from hydroxide or carbonate concentration upto 1000 ppm as CaCO
-
3
NO
-
3
NO
-
3
NO
-
3
NO
3
. Chloride
does not interfere in the determination. However organic dissolved matter,
surfactant, , and Cr(VI) do interfere.
-
2
NO
3
Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
Analysis after formation of derivative:
Chloride: Automated method using mercuric thiocyanate and
ferric nitrate:
Thiocyanate ion is liberated from mercuric thiocyanate solution by the
formation of soluble mercuric chloride. In the presence of ferric ion, free
thiocyanate ion, forms a highly coloured ferric thiocyanate complex
(max=470 nm) the absorbance of which is proportional to the chloride
concentration.
The interference due to particulate matter can be overcome by filtration or
centrifugation before analysis.
The method is applicable to potable, surface, and saline waters, and
domestic and industrial waste waters. The concentration range of chloride that
can be measured is 1 to 200 ppm.
Fluoride: Zr-Alizarin lake method:
This SPANDS Colorimetric method is based on the reaction
between fluoride and a coloured zirconium-alizarine lake. Fluoride reacts with the
Zirconium alizarin lake, dissociating a portion of it into a colourless complex
anion (ZrF
6
2-
). As the amount of fluoride increases, the colour of zirconium dye
lake becomes progressively lighter.
The reaction between fluoride and zirconium ions is influenced
greatly by the acidity of the reaction mixture. If the proportion of acid in the
reagent is increased, the reaction can be made almost instantaneous. The
absorbance measurements can be done at 570nm and concentrations can be
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
determined with calibration graph. Both the standards and samples should be
kept for one hour before absorption measurements.
Nitrite:
Nitrite is determined through formation of a purple azo dye produced
at pH 2.0 to 2.5 by coupling diazotised sulfanilamide with
N-(1-naphthyl)-ethylenediaminedihydrochloride. The absorbance of the resulting
purple azo dye can be measured at 543 nm using a spectrophotometer. Beer's
law is obeyed upto 25 g
-
2
NO
-1
. Higher Concentration of can be determined by
diluting the sample. Free chorine and the following ions which form precipitates
under test conditions such as Sb
-
2
NO
3+
,Au
3+
, Bi
3+
, Fe
3+
, Pb
2+
, Hg
2+
, Ag
+
interfere .
Cupric ion may cause low results by catalysing decomposition of the diazonium
salt.
Phosphate: The procedure for phosphate involves the addition of a mixed
reagent (sulphuric acid, ammonium molybdate,ascorbic acid, antimony
potassium tartrate) to a known volume of sample, diluting to volume, shaking and
leaving for 10 min. A blue phosphomolybdenum complex is produced and the
absorbance is measured at 880 nm.
The concentration is calculated using a predetermined calibration graph
derived from standard solution treated in the same way.
Automatic procedures: have been developed for most of the ions listed in
the previous paragraph.
Instead of mixing reagents for each analysis, streams of each reagent
(segmented by air bubbles to diminish mixing effects) in narrow-bore tubes are
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
mixed by combining the flows at a T-junction or within a mixing cell. A sample is
introduced from an automatic sampler as a continuous flow into the reaction
stream. The combined flow is then led into a spectrophotometer and the
absorption measured. The flows of all the reagents and samples are produced
from a multi-channel peristaltic pump.
Field Techniques:
Field techniques are very important and they give immediate
measurement of ion concentration. Using the automated procedures described
above unmanned field stations can be set up. Otherwise portable instruments
can be used to perform the analysis at the site.
Flame photometry:
This technique is used in water analysis for determining the concentration
of alkali and alkali metal ions such as sodium, potassium and calcium. The
following diagram (fig 2) shows the basic components of a flame photometer.
Monochromator
Detector
& read out
Nebuliser & burner
sample
solution
in
flame
lens


Fig2. Outline of a flame photometer
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
The liquid sample to be analysed is sprayed under controlled conditions
into the flame where the water evaporates, leaving behind the inorganic salts as
minute particles. These salts decompose into constituent atoms or radicals and
may become vapourised. The vapours containing the metal atoms are excited by
thermal energy of the flame and this causes electrons of the metallic atoms to be
raised to higher energy levels. When these excited electrons fall back to their
original positions, they give off discrete amounts of radiant energy. The emitted
radiation is passed through the monochromater where the desired region
isolated. A photocell and an amplifier are then used to measure the intensity of
isolated radiation. Normally for alkali metals a propane-compressed air mixture is
used as a fuel.
A linear concentration range (for sodium and potassium 1 to 10 mg l
-1
and
for calcium 10-50 mg l
-1
) is within the range expected for environmental water
samples.The method is simple and sample preparation is not needed. However
care has to be taken that the calibration of the instrument and analytical
measurements are performed quickly after each other.
Ion Chromatography:
The major application of this instrument is for inorganic anions in
environmental analysis. This is a kind of ion-exchange chromatography used for
the separation of inorganic and some organic cations and anions using a
conductivity detector after suppressor column. The schematic diagram of an ion
chromatograph is shown in fig 3a.
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
Na2SO4
H2SO4
H2SO4
bath solution
2Na
+
CO3
2-
Eluate containing
Na
+
,CO
3
2-
,HCO
3
-
,+
analyte anions
SO4
2-
2H
+
H2CO3
Sulfonated
polyethylene
hollow fiber
Eluate containing
CO
2
,H
2
O,H
+
+
analyte anions
Fig 3b Micro membrane suppression









Eluent
reservoir
Pump
Sample injection
Separator column
micro membrane
suppressor
column
conductivity
detector
Fig 3a Schematic diagram of
ion chromatograph


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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
The stationary phase is a pellicular material, the particles consisting of an
impervious central core surrounded by a thin outer layer (about 2m thick)
incorporating cation-or anion-exchange sites. The thin layer contributes to faster
rates of exchange that results in higher efficiencies. For the separation of anions,
mobile phases containing solutions of electrolytes such as Na
2
CO
3
or NaHCO
3
are used. For the separation of cations, HCl solution is used as mobile
phase.The detection of low concentration of ionic solutes in the presence of high
concentrations of eluting electrolyte is not possible.
Unless the latter is removed. This is achieved by using a micro membrane
suppressor column (fig 3b) immediately after the separator column, which
converts the electrolyte into unionised water, leaving the solute ions as the only
ionic species in the mobile phase.
The reactions for the separation of inorganic anions on an-ion-exchange
column in the form using sodium hydrogen carbonate as mobile phase
are summarised in the following equation.
-
3
HCO
Separator Column:
n n
3 3 3 n
n 2 3
3 4 4
n (Res N R HCO ) x (Res N R ) x nHCO
wherex F ,Cl ,NO ,SO ,PO etc.
+ +

+ +
=
i i
3

.............................(1)

Suppressor reactions:

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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras


The most wide spread method of achieving low back ground conductivity is
by the use of "micromembrane suppressor" as illustrated in fig.3b. The effluent
flows between two semi-permeable membranes which separate it from the
counterflow of sulphuric acid. The migration of each ion is determined by the
relative concentrations of the ions in the two liquids, the ion moving into the
solution of lower concentration.
For the analysis of anions in environmental water samples which are found at mg
l
-1
concentrations by this technique, the sample has to diluted before injection.
This along with the filtration of the water sample is often the only sample
preparation necessary for carrying out the analysis. It takes only a few minutes
for the analysis of common anions that are present in water as shown in fig.4.

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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras

0 2
NO2
-
1.2 ppm
NO3
-
1.4 ppm
SO4
2-
1.1 ppm
Cl
-
Br
-
1.4 ppm
4 6 8 12 14 10
1.0 ppm
Time (Min)

Fig 4 Separation of ions in environmental water
Although ion chromatography is quite commonly used for the analysis of
anions in water, some common cations (Na
+
, K
+
, NH
4
+
, Ca
2+
, Mg
2+
) also are
being analysed using both the ion suppression system and also conventional
chromatographs with conductivity detection.
Examples Of The Use Of Other Techniques:
The most widely used methods covered so far are only for the analysis
common ions. There are however, a few frequently used methods which have
not been covered. For example the analysis of species such as ammonia,
fluoride and sulphate, free chlorine, sulphide and cyanide which have not been
discussed previously are described here.

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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
Ammonia:
In environmental water ammonia is the only alkaline gas commonly
found. The ammonia could be determined by a simple acid-base titration
provided it is isolated from solution. This may be done by addition of magnesium
oxide to ensure that the sample is slightly alkaline. Ammonia is then distilled off
into known excess acid. By tiltrating the excess acid with standard alkali, the
ammonia concentration can be determined.
Ion selective electrodes (i.e. an electrode whose potential measured with
respect to a reference) respond in a linear manner to the logarithm of the activity
of analyte over a four to six order of magnitude range of activity. Electrodes do
not consume unknown samples, and they introduce negligible contamination.
Response time is seconds or minutes. Since the electrodes respond only to the
activity of the uncomplexed ions, the ligands must be absent or masked.
In order to know the concentrations, an inert salt is often used to bring all
the standards and samples to a high constant ionic strength. If the activity
coefficients remain constant, the electrode potential gives concentrations directly.
Commercial electrodes are available for the detection of anions (e.g. for halides,
NO
3
-
, CN
-
, SCN
-
, S
2-
); cations (e.g. for H
+
,Na
+
,K
+
,Ca
2+
,Cd
2+
,Cu
2+
,Pb
2+
) and
gases (e.g. NH
3
,O
2
,CO
2
,NO
2
).
In the ammonia selective electrode which is a gas sensing type, the
ammonia diffuses through a permeable membrane and causes a pH change in a
small volume of internal solution which is sensed by a glass electrode. Before
taking the measurement, concentrated sodium hydroxide solution is added to
samples and standards which serves to increase the pH to above 11 so that all
ammonia is in the unprotonated form and provides a constant ionic strength.
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
Fluoride:
Fluoride ion can be estimated, based on potentiometric measurements
with a membrane electrode consisting of a single crystal of europium doped
lanthanum fluoride, LaF
3
. The purpose of Eu doping is to improve electrical
conductivity. The membrane is cut as a 1-mm thick disc, a few mm in diameter,
the disc is sealed into the end of a rigid plastic tube, filled with an equimolar
solution of KCl and NaF, into which dips an AgCl electrode. A reference
electrode (saturated calomel electrode) is inserted into the test solution along
with the fluoride electrode. The potential difference is measured. Fluoride
concentration down to 10
-6
M can be measured. This electrode shows extremely
high specificity to the analyte ion, the only pretreatment necessary being the
addition of buffer solution to maintain constant pH and ionic strength.
Alternatively fluoride can be determined by spectrophotometry or by ion-
chromatography both of which have been discussed already. Fluoride reacts with
zirconium-alizarin lake to form colourless ZrF
6
2-
and the dye. The colur of the dye
lake becomes progressively weak with increase in amount of F
-
.
To the sample solution is added drop of sodium arsenite solution to
remove residual chlorine if any. Then enough of zirconyl-alizarin reagent is
added.The solution is thoroughly mixed and absorbance measurement were
done at 570 nm after keeping the samples and standards for 1 hr.
Sulphate:
Ion chromatography is the only instrumental method for the direct
determination of sulphate. Sulphate may be precipitated either with Ba
2+
or
2-aminoperimidinium salts. The precipitate may be weighed for a direct
determination of the sulphate as a gravimetric method. Other methods using
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
insoluble salt precipitation are indirect, estimating the excess of the cation after
precipitation of the sulphate. Excess barium may be determined by titration with
EDTA or by atomic absorption.Excess 2-aminoperimidinium ions may be
estimated by visible spectrophotometry.
Free chlorine (Residual chlorine):
The effectiveness of chlorination of raw water for public water supply
can be checked by estimating free or residual Cl
2
in water samples. Free
available Cl
2
consists of Cl
2
,HOCl, and HClO
2
. Free Cl
2
reacts instantly with N,
N-diethyl phenylene diamine (DPD) indicator to form a red colour. This colour is
discharged by the addition of ammonium iron(II) sulphate solution.
The water sample is treated with DPD reagent solution and titrated
with standard ferrous ammonium sulphate solution until it becomes colourless.
The amount of free chlorine in the water sample can be determined from the
volume of ammonium iron (II) sulphate consumed.
Sulphide:
The major effluents containing sulfide in significant quantities are
tannery wastes, sulphide dye liquors, oil refinery wastes, viscose rayon wastes,
septic sewage and ammonical gas liquor.
Two methods namely colorimetric and titrimetric methods are used.
The colorimetric procedure is simple to carryout, rapid, sensitive and applicable
to sulphide concentrations of 0.2 to 20 ppm. Titrimetric procedure, though is
applicable to samples containing more than 1 ppm sulphide, it is generally used
for samples of higher concentration and containing more interferences.
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
Sample Collection and preservation:
Sample should be collected with least aeration as sulfide is
volatilised and oxygen destroys sulphide. Samples have to be preserved by the
addition of zinc acetate solution.the pH of the solution should be adjusted to > 9
by the addition of sodium hydroxide. The sample should contain representative
porportion of suspended solids.
Spectrophotometric determination of H
2
S :
In this method the absorbing solution used contains CdSO
4
and
NaOH. The precipitated cadmium sulphide on acidification releases S
2-
ions
which interacts with FeCl
3
and -diethylphenylene diamine to give a dye ethylene
blue which can be measured at 670 nm. Beer's law is obeyed from 0.1 to 10 ppm
S
2-
. Gases like SO
2
, O
3
, NH
3
do not interfere.
Titrimetric method:
This procedure measures total sulphides excepting acid insoluble
metallic sulphides.
To the Sulphide in acetate solution is added a known excess of iodine
solution which is later acidified. The excess iodine is back titrated with standard
thiosulphate solution using starch as indicator. Knowing the amount of the
standardised iodine consumed, and the volume of sample taken, the amount of
sulphide present in the water sample can be calculated.
..(4)

2 2
H S I 2H 2I S
+
+ + +
2
2 2 3 4 6
I S O 2I S O
2
+ +

.(5)
1 ml 0.05N I
2
=0.85mg H
2
S
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Environmental Chemistry and Analysis Prof. M.S.Subramanian













Indian Institute of Technology Madras
Cyanide:
This method is applicable to all types of industrial effluents, domestic
waste waters, polluted waters, raw and treated waters.
The cyanide in the sample is distilled and absorbed in alkali. CN
-
in the
alkaline distillate on treatment with bromine water is converted to cyanogen
bromide (CNBr) which reacts with p-phenylenediamine reagent to form a red dye.
The absorbance of the dye is measured at 530nm and the concentration of the
cyanide can be read from a calibration graph.
Most of the simple cyanides M(CN)
x
are readily converted to HCN by
acid distillation. The complex cyanides such as alkali ferri and ferrocyanides are
not converted to HCN during distillation. Acid cuprous chloride and /or
magnesium chloride are added to the sample which converts the complex
cyanide to simple cyanides which are then converted to HCN by distillation.
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