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COS-ISO-00-OIN/OPS/CHEM/017
Rev. No. : 0 April 2006

OPERATION INFORMATION NOTE

Manual on Analytical Test


Procedures for Water and
Steam in Power Plants

CORPORATE OPERATION SERVICES

NTPC Limited

NTPC LIMITED
OPERATION & MAINTENANCE FORMAL DOCUMENTATION SYSTEM
OPERATION INFORMATION NOTE: COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0

Date: April, 2006

Manual on Analytical Test


Procedures for Water and
Steam in Power Plants

Approved for
Implementation by ..
E. D. (OS)
Date: ..
Enquiries to: Head of Corp. Operation Services

Manual on Analytical Test Procedures for Water and


Steam in Power Plants
INDEX
S.N.

Contents

I) Introduction
II) Superseded Documents
III) Coagulation Flocculation Jar Test
IV) Colour 6
V) Conductivity
VI) Corrosivity of Cooling Water (Coupon Test)
VII)
Crud (Colour Comparison Method)
VIII)
pH 17
IX) Oxidation Reduction Potential (ORP)
X) Turbidity (Nephelometric)
XI) Suspended and Total Dissolved Solids
(25mg/litre or Less of Total Solids)
XII)
Suspended and Total Dissolved Solids
(More than 25mg/litre of Total Solids)
XIII)
Alkalinity (Titration Method, 10 to 500mg/litre)
XIV)
Alkalinity due to Hydroxide
XV)
Aluminium
XVI)
Aluminium Atomic Absorption Method (Direct)
XVII)
Ammonia (Indophenol method, 10 to 500 micrograms/litre)
XVIII)
Ammonia
XIX)
Ammonia by ION Selective Electrode
XX)
Carbon Dioxide (Bicarbonate Titration Method)
XXI)
Carbon Dioxide (Direct Titration of Free Carbon Dioxide)
XXII)
Chloride (Mercuric Thiocyanate Method, 0.05 to 1.4mg/litre)
XXIII)
Chloride (Mercuric Thiocyanate Method, Modified, 2 to 100
micrograms/litre)
XXIV)
Chloride (Silver Nitrate Method, 5mg/litre or more)
XXV)
Chlorine Demand
XXVI)
Chlorine, residual (DPD Method, 0.02 to 4.0mg/litre)
XXVII) Chlorine, Residual (Starch Iodide Thiosulphate Method,
0.04mg/litre or more)
XXVIII) Copper (Neocuprine method, 2 to 1000 micrograms/litre Cu)
XXIX)
Copper (Atomic Absorption Spectrophotometry Method)
XXX)
Equivalent and Free Mineral Acidity
XXXI)
Fluoride (SPANDS DYE Method)
XXXII) Hardness (Total, Calcium and Magnesium)
XXXIII) Hydrazine
XXXIV) Iron (Bathophenanthroline Method)
XXXV) Iron (Ferrozine Method, 500 micrograms/litre and lees)
XXXVI) Atomic Absorption Method (Graphite Furnace)

Page No.
1
1
2
8
11
15
21
25
27
29
31
34
36
38
40
42
45
48
50
52
54
56
58
61
65
68
72
73
75
79
83
86
90
92
Contd.

Manual on Analytical Test Procedures for Water and


Steam in Power Plants
INDEX (Contd.)
S.N.

Contents

Page No.

XXXVII) Nickel (Glyoxime Method, 0.01 to 5.0mg/litre Ni)


XXXVIII) Atomic Absorption Method (Direct)
XXXIX) Manganese
XL)
Nitrate (Azodye Method)
XLI)
Nitrate Phenol Disulphonic Acid (PDA) Method
XLII)
Nitrate UV Spectrophotometric Method
XLIII)
Oil and Grease
XLIV)
Organic Matter (Potassium Permanganate Consumption Method)
XLV)
Oxygen, Dissolved (Indigo Carmine Method
less than-60 micrograms/litre)
XLVI)
Oxygen, Dissolved (Iodometric Method, 1.0 mg/litre or more)
XLVII)
Oxygen Demand Biochemical (Dissolved Oxygen Loss Method)
XLVIII) Oxygen Demand, Chemical (Potassium Dichromate Method
XLIX)
Phosphate (Amino Reduction Method, 0.1 to l0mg/litre)
L) Silica, Non Reactive (Hydrofluoric Acid method)
LI) Silica, Non-Reactive (Membrane Filtration Method)
LII)
Silica Reactive (Amino Reduction Method)
LIII)
Steam Purity (Sodium Tracer Method)
LIV)
Sulphate (Gravimetric Method)
LV)
Sulphate (Volumetric Method)
LVI)
Sulphite (Titration Method)
LVII)
Review

93
95
97
99
103
105
107
111

ANNEXURE-I Atomic Weight/Atomic Numbers of Various Elements


ANNEXURE-II Determination of Saturation Index Langelier) and Stability
Index (RYSNER) of Cooling Water
ANNEXURE-III Shelf Life and Storage of Reagents and Standards
ANNEXURE-IV Standard Specifications for Reagent Water
ANNEXURE-V Conversion Factor of Frequently used Chemicals to CaCO3
Equivalent

150

113
116
119
121
125
128
132
135
139
141
143
147
149

153
155
158
160

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

Manual on Analytical Test Procedures for Water and Steam in


Power Plants
I)

INTRODUCTION
Chemical analysis of water and steam is probably the most important tool for the
Chemist in the power plant. This is frequently required to ascertain the
constituents of water and steam which is working fluid of the unit. Manual on
analytical test procedures for water and steam in thermal power station was issued
in 1983. Based on experience gained in last two decades, some of the earlier
methods have been revised and a couple of new parameters have been included in
this revised manual. It is expected that the revised manual will be handy for the
working personnel of power station laboratories.

II) SUPERSEDED DOCUMENTS


Manual on Analytical Test Procedures for Water and Steam in Power Plants issued
in 1989.

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

III)

COAGULATION FLOCCULATION JAR TEST

1.0

SUMMARY OF METHOD
The coagulation - flocculation jar test is carried out to determine chemicals and
their dosages, and conditions required in order to reduce suspended, colloidal, and
non-settleable matter from water by chemical coagulation - flocculation, followed
by gravity settling to achieve optimum results. The variables to be investigated
are (i) chemical additives, (ii) pH, (iii) temperature and (iv) order of addition and
mixing condition.

2.0

APPARATUS

2.1

Multiple Stirrers - with continuous speed variation from about 20 to 150 rpm. The
stirring paddles should be of light gage, corrosion - resistant material, all of the
same configuration and size. An illuminated base is useful to observe the floc
formation.

2.2

Beakers - glass beakers, 1000 to 1500m1 capacity.

2.3

Reagent Racks - for introducing each test solution to all beakers simultaneously.
There should be at least one rack for each test solution or suspension. A typical
configuration is given in Fig-I.

3.0
3.1

REAGENTS
Water - conforming to specifications Type IV conforming to ASTM specification
D-1193.
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Manual on Analytical Test Procedure for Water and Steam in Power Plants
3.2

Prime Coagulants (l0g/litre)

3.2.1

Alum [A12(SO4)3.18H2O].

3.2.2

Ferric Sulphate [Fe2 (SO4)3.XH2O].

3.2.3

Ferric Chloride (FeCl3.6H2O).

3.2.4

Ferric Sulphate (FeSO4.7H2O).

3.2.5

Magnesium Carbonate (MgCO3.3H2O).

3.2.6

Sodium Aluminate (NaA1O2).

3.3

Coagulant Aids - activated silica, polyelectrolytes (anionic, cationic and neutral).

3.4

Oxidising Agents - Chlorine (C12), Chlorine dioxide (C1O 2), Potassium


permanganate (KMn04), Calcium hypo-chlorite [CaO(C1O).4H20], Sodium
hypochlorite (NaC1O).

3,5

Alkalis - calcium carbonate (CeC03), dolomitic lime (58% CaO, 40% MgO),
lime-hydrated (Ca(OH)2) magnesium oxide (MgO), sodium carbonate (Na 2CO3),
sodium hydroxide (NaOH).

3.6

Weighting Agents - bentonite, kaolin, Fuller's earth, other clays and minerals.

4.0

PROCEDURE

4.1

Place equal volumes (1000m1) of sample into each beaker (1500m1 capacity) and
record the temperature of the sample. Load the test chemicals in the reagent racks.
Final volume of each tube should be same after required make up.

4.2

Start the multiple stirrers at flash mix speed (approximately 120 rpm). Add the
test solutions or suspensions at predetermined dosage levels and sequence. Flash
mix for approximately 1 minute after the addition of chemicals. Record the flash
mix time and mixer speed (rpm).

4.3

Reduce the speed to the minimum required, to keep floc particles uniformly
suspended throughout the "slow mix" period. Slow mix for 20 minutes. Record
the mixer speed (rpm).

4.4

After the slow mix period, withdraw the paddles and observe settling of floc
particles. Record the time required for the bulk of the particles to settle.

4.5

After 15 minutes of settling, record the sample temperature and by means of a


pipette, withdraw supernatant liquor for conducting colour, turbidity, pH, nonreactive and/or colloidal silica and other required analysis.

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
5.0

INTERFERENCES

5.1

Temperature changes during test - Thermal or convection currents may occur,


interfering with the settling of coagulated particles.

5.2

Gas release during test - Floatation of coagulated floc may occur due to gas
bubble formation, caused by mechanical agitator, temperature increase or
chemical reaction.

5.3

Testing period - Biological activity or other factors may alter the coagulation
characteristics of water upon prolonged standing. Therefore, the period between
sampling and testing should be kept to a minimum.

6.0

NOTES

6.1

All polyelectrolytes are classified as anionic, cationic, or neutral, depending upon


their composition. A small dosage, under 1 ppm, may permit a reduction in the
dosage or complete elimination of the coagulant. In case the coolant aid is in
powdered form, prepare 0.1 % solution to provide proper dose. Always add
powdered aids to dissolving water rather than reverse.

6.2

It is recognized that reproducibility of results is important. To demonstrate


reproducibility, the so-called 3 and 3 procedure is suggested. In this procedure,
duplicate sets of 3 beakers each, are treated simultaneously with the same
chemical dosages in beakers 1 & 4, 2 & 5 and 3 & 6.

6.3

A suggested format for recording the results-is given below:


FORMAT FOR RESULTS RECORDING
STATION

LOCATION
SAMPLE

pH

TURBIDITY

COLOUR

TEMPERATURE

SAMPLE SIZE (ml)

NTPC Limited

DATE

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
S.No.

BEAKER N0.
1

6
1.

Chemicals,* mg/litre

Flash mix speed, rpm

3.

Flash mix time, minutes

4.

Slow mix speed, rpm

5.

Slow mix time, minutes

6.

Temperature, C.

7.

Time first floc, minutes

8.

Floc size, mm (approx.)

9.

Settling rate

10

Supernatent Tests :
a. Turbidity
b. pH
c.

Colour

d.

Non-reactive/colloidal Silica

Indicate order of addition of Chemicals:

The preferred sequence of addition of chemical is (a) alum ----- (b) chlorine and
------ (c) lime

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

IV)
1.0

COLOUR
SUMMARY OF METHOD
Sample colour is visually compared with a standard Chloroplatinate colour
solution. The unit of colour (Hazen unit) is that produced by l mg
platinum/litre in the form of the chloroplatinate ion.

2.0

APPARATUS

2.1

Nessler tubes - matched, 50m1 capacity, tall form.

2.2

pH meter.

3.0

REAGENTS

3:1

Water - conforming to specifications Type II.

3.2

Standard Stock Solution (colour of 500 units)


Dissolve 1.246g potassium chloroplatinate, K 2PtCl6, (equivalent to 500mg Pt)
and 1.00 g cobaltous chloride, CoCl2.6H20, (equivalent to about 250mg Co) in
water with 100m1 hydrochloric acid (sp gr 1.19) and dilute to 1 litre with
water.

3.3

Colour Standards
Prepare standards having colours of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60
and 70 units by diluting suitable volumes of standard stock solution (3.2) to 50
ml with water in Nessler tubes.

4.0

PROCEDURE

4.1

Place 50 ml of sample in a Nessler tube.

4.2

Compare the colour of the sample with standard colour by looking vertically
downwards against a white surface.

4.3

If the colour exceeds 70 units, dilute with water until the colour is within the
range of the standards.

4.4

If the sample is turbid, report as "apparent colour".

4.5

Measure the pH of the sample.

5.0

CALCULATIONS

5.1

Calculate colour unit (Hazen Units) by the following equation:


Colour unit = A x 50
B
Where:
A = estimated colour of the diluted sample.
B = milliliters of sample.

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
5.2

Report colour results in whole numbers and record as follows:


Colour Unit

Record to Nearest

1 -50

51 -100

101 -250

10

251 -500

20

5.3

Report Sample pH.

6.0

INTERFERENCES

6.1

Even a slight turbidity causes the apparent colour to be noticeably higher than
the true colour; therefore turbidity should be removed before measurement of
true colour.

6.2

The colour value of water is extremely pH dependent and invariably increases


as the pH of the water is raised. When reporting a colour value, specify the pH
at which colour is determined.

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

V) CONDUCTIVITY
1.0

SUMMARY OF METHOD
The conductivity cell is dipped in the sample contained in a beaker and the
conductivity is read directly from the conductivity meter.

2.0

APPARATUS

2.1

Conductivity meter.

2.2

Conductivity cells with cell constants from 0.01 to 10 cm-1.

2.3

Thermometer, accurate to 0.5C, when the instrument is not provided with


manual or automatic temperature compensation.

3.0

REAGENTS

3.1

Water -conforming to specifications Type I. In making up the potassium


chloride solution for cell constant determination, use water of conductivity
< 1.5 us/cm

3.2

Potassium Chloride (KC1) - Dry at 105C for 2 hours.

3.3

Potassium Chloride Reference Solution A (Conductivity of 97838


microsiemens/cm at 18C and 111342 microsiemens/cm at 25C) - Dissolve
74.2460g of potassium chloride in water and dilute to 1 litre at 20 2 0 C.

3.3

Potassium Chloride Reference Solution B (Conductivity of 11167


microsiemens/cm at 18C and 12856 microsiemens/cm at 25 C) - Dissolve
7.4365g of potassium chloride in water and dilute to 1 litre at2020 C.

3.4

Potassium Chloride Reference Solution C (Conductivity of 1220.5


microsiemens/cm at 180 C and 1408.8 microsiemens/cm at 25 0 C) - Dissolve
0.7440g of potassium chloride in water and dilute to 1 litre at 20+2 0 C.

3.5

Potassium Chloride Reference Solution D (Conductivity of 146.93


microsiemens/cm at 25oC) - Dilute 100m1 of reference solution C to 1 litre
with water at 202 0 C shortly before using.

4.0

PROCEDURE

4.1

Determination of Cell Constant

4.1.1

Rinse the conductivity cell with at least three portions of standard potassium
chloride solution.

4.1.2

Thermostat the reference standard at 18 or 250 C and measure conductivity in


accordance with the instrument manufacturer instructions.
Cell constant (A) = K1 + K2
Kx

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
Where:
K1

Conductivity of the reference standard potassium chloride


solution (microsiemens/cm) at the temperature of
measurement.
K2

Conductivity of water (microsiemens/cm), used to prepare the


reference solution, at the temperature of measurement.

Kx

Measured conductance (microsiemens/cm).

4.2

Measurement of Conductivity

4.2.1

Conductivity Below 10 microsiemens/cm.

4.2.1.1

Use a flow type conductivity cell. Adjust the sample stream to a proper flow
rate and bring the temperature to a steady value as near 25 C as possible Read
the temperature to the nearest 0.5oC.

4.2.1.2

If the conductivity meter is provided with a manual temperature compensator,


adjust this to the sample temperature value.

4.2.1.3

If an automatic temperature compensator is provided, no adjustment is


necessary but sufficient time must be allowed to permit equalization of
temperatures.

4.2.1.4

Read the conductivity. -

4.2.1.5

If the instrument has no means of temperature compensation, determine a


temperature correction to convert readings to 25C (see notes).

4.2.2

Conductivity Above 10 microsiemens/cm.

4.2.2.1

Either a flow-type, dip-type, or pipette-type cell may be used. If a flow-type


cell is used, proceed in accordance with 4.2.1.

4.2.2.2

If another type of cell is used, rinse the cell thoroughly several times with
water and then two or more times with the sample. Measure the conductivity
and the temperature (to the nearest 0.5C) on successive portions of the sample
until a constant value is obtained.

4.2.2.3

Proceed in accordance with 4.2.1.2, 4.2.1.3 and 4.2.1.5.

5.0

CALCULATIONS

5.1

Calculate the conductivity of the sample as follows:


Conductivity (K), microsiemens/cm = A x KX
Where:
A

cell constant.

KX

measured conductance of thesample, in microsiemens/cm.

6.0

PRECISION

6.1

Results obtained should not differ by more than 1% of the conductivity.


NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
7.0

INTERFERENCES

7.1

Exposure of a sample to the atmosphere may cause changes in conductivity


due to loss or gain of dissolved gases.

7.2

The carbon dioxide, normally present in the air, can drastically change the
conductivity of pure water. Contact with air should be avoided by using flow
through or inline cells.

8.0

NOTES

8.1

The unit of conductivity is siemens per centimeter. The conductance is


directly proportional to the cross-sectional area, A (cm2) and inversely
proportional to the length of the path, L (cm)
A
Conductance = K X ------L
The conductance measured between opposite faces of a centimeter cube, K, is
called specific conductivity.

8.2

Recommended cell constants for various conductivity ranges are given below:
Range of conductivity,

Cell constant,

(Microsiemens/cm)

(Cm-1 )

0.05 to 10

0.01 to 0.1

10 to 200

0.1 to 1

200 to 5000

1 to 10

5000 to 1000000

10 to 100

8.3

The conductivity of water and aqueous solutions depends strongly upon the
temperature. To avoid making a correction, it is necessary to hold the
temperature of the sample to 25 0.5C. If this cannot be done, the
temperature coefficient is determined by conductivity and temperature
measurements on the sample over the required temperature range. The
conductivity is plotted against temperature and from this curve a table of
temperature correction factors may be prepared, or the ratio of conductivity at
temperature, T, to conductivity at 25C may be plotted against temperature
and this ratio taken from the curve.

8.4

When using an instrument provided with a manual or automatic temperature


compensator, follow the manufacturers instructions to calibrate the
compensator or check its accuracy and applicability to the sample being
tested.

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

VI)

CORROSIVITY OF COOLING WATER (Coupon Test)

1.0

SUMMARY OF METHOD
Carefully prepared and weighed metal coupons are installed in contact with
flowing cooling water for a specified length of time. After removal from the
system, these coupons are examined, cleaned and reweighed. The corrosivity
and fouling characteristics of the water are determined from the difference in
weight, the depth and distribution of pits and the weight and characteristics of
the foreign matter on the coupons.

2.0

APPARATUS

2.1

Coupon Specimens - prepare coupons in accordance with section 4.0.

2.2

Insulating washer, screw, and nut -for attaching the coupon to the phenolic rod.
The insulating washer has a sleeve that fits into the coupon hole and around the*
screw.

2.3

Phenolic rod -use .a 152mm length of canvas based


13mm
outside
diameter phenolic rod attached at one end to a drilled pipe plug and having a
flat surface and a hole at the other end, suitable for attachment of the coupon.

3.0

REAGENTS

3.1

Water - conforming to specifications Type III.

3.2

Benzene.

3.3

Corrosion Inhibitor - specific for hydrochloric acid.

3.4

Hydrochloric Acid (1+4) - Mix 1 volume of concentrated hydrochloric acid (sp


gr 1.19) with 4 volumes of water.

3.5

Hydrochloric Acid (1+1.8, inhibited) - mix 357m1. of hydrochloric acid (sp gr


1.19) and 5.0 g of inhibitor. Dilute to 1 litre with water.

3.6

Isopropyl Alcohol.

3.7

Methyl orange Indicator (0.5g/litre) - Dissolve 0.05g of methyl orange in


water and dilute to 100m1.

3.8

Trichloroethylene.

3.9

Tripoli finely granulated, porous, of siliceous rock;' amorphous silica, soft,


porous, and free of sharp edges.

3.10

Trisodium phosphate (Na3P04.12H20).

3.11

Vapour phase Inhibitor paper.

4.0

COUPON PREPARATION

4.1

Prepare coupon from sheet metal.

4.2

Use a coupon size of 13 by 102 by 0.8mm.


NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
4.2.1

Shear 20 gage sheet metal of the type desired to the dimensions of 3 by


102mm.

4.2.2

Drill a 7mm hole with its center about 8mm from one end of the coupon.

4.2.3

Deburr all sharp edges on the coupon specimen using a file or emery belt and
deburr' the hole with an oversize drill.

4.2.4

Stamp identifying numbers on the small coupon area between the edge and the
mounting hole.

4.3

Cleaning of coupons (ferrous, copper, brass and cupronickel coupons) Remove oil by immersion in benzene. Dry. Immerse in hydrochloric acid
(1+4) for 30 minutes at room temperature. Remove acid from the coupon by
three rapid successive rinses in separate water baths; the last rinse water bath
shall contain methyl orange solution and must be kept neutral (yellow).
Rinse successively in isopropyl alcohol and benzene, and dry with a clean
cloth. Store in a desiccator.

5.0

PROCEDURE

5.1

Weigh the clean, dry coupon to the nearest 0.lmg.

5.2

Attach the coupon to the phenolic rod, using an insulating washer, the screw
and nut assembly.

5.3

Install the holder and coupon assembly in a suitable place.

5.4

Remove the coupon from the system at chosen intervals.

5.4.1

Use short time intervals (4 to 7 days) for the first time series to establish the
rate at which passivity occurs.

5.4.2

Use long time intervals (1 to 3 months) for the second time series to establish
the mean steady state corrosion rate.

5.5

Clean the ferrous coupons, prior to reweighing, with a plastic knife. Remove
oily and greasy deposits by soaking in trichloroethylene. Remove remaining
loose corrosion product by brushing with a soft bristle brush. Immerse in
inhibited hydrochloric acid (1+1.8) for 30 seconds at room temperature.
Remove the specimen from acid bath and rinse with water. Rub with granular
trisodium phosphate and then with tripoli. Rinse with water and then with
isopropyl alcohol. Dry between paper towels followed by warm air drying.

5.6

Clean the copper and copper alloy coupons, prior to reweighing, with a plastic
knife. Remove oily or greasy deposits by soaking in trichloroethylene.
Immerse the coupons in inhibited hydrochloric acid (1+1.8) for 30 seconds.
Rinse with water, then with isopropyl alcohol and finally with benzene. : Dry
between paper towels and place in a desiccator for 1 hour.

5.7

Reweigh each coupon to the nearest 0.lmg.

5.8

Subject a weighed blank coupon of the same material to the identical cleaning
procedure (5.5 and 5.6) used for the test specimens and reweigh to determine
the blank correction factor.
NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
5.9

Record the appearance of the cleaned, weighed coupon a protected",


'moderate localized', moderate pitting" or 'severe pitting'.

6.0

CALCULATIONS

6.1

Calculate the corrosion rate for each coupon as follows:


P = [H (W1-W2)/W1D] x 1.825 x 102
Where :

6.2

corrosion rate, millimeters per year (mmpy).

original thickness of the coupon, mm.

W1 =

original weight of the coupon, mg.

W2 =

final weight of the coupon, mg.

D =

exposure time, days.

In systems, where all variables are closely controlled, apply the following
equation which gives more precise corrosion rate. Calculate the corrosion rate
for a rectangular coupon as follows:
1
P = --------------------------------------------- x [(W1- W2)/W1.D] x 1.825 x 102
[(1/H) + (1/X) + (1/Y)]
Where:

6.3

corrosion rate, mmpy.

original thickness of coupon, mm.

original length of coupon, mm.

original width of coupon, mm.

W1

original weight of coupon, mg.

W2

final weight of coupon, mg.

exposure time, days.

Express the relationship between corrosion rate in grams per square meter per
day (g/m2d) and penetration in millimeters per year (mmpy) as follows:
mmpy = g/m2 d x (365/d)
Where:
d

density of the metal, kg/m3.

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
7.0

INTERFERENCES

7.1

Deviations in metal composition or surface preparation of the coupons may


influence the precision of the results.

7.2

The presence of different metals in close proximity to the coupon (within


76mm) even if they are insulated from the coupon, constitutes a source of
error in the results.

7.3

Deviations in the velocity and direction of flow past the coupons may
influence the precision of the results.

7.4

Results are directly comparable only for the water temperature to which the
coupon is exposed.

7.5

Crevices, deposits or biological growths may affect local corrosivity.

8.0

NOTES

8.1

The ferrous metal coupons, until ready for use, should be stored in desiccator
in separate envelopes made from vapour phase inhibitor - impregnated paper.

8.1.1

Non ferrous metal coupons should be stored in sealed plastic envelopes or


wrapped in plastic film.

8.2

Since the corrosion rate will be very high initially and then fall to a lower,
nearly constant rate, two time series are chosen. Short time interval is for 4 to
7 days and long time interval is for 1 to 3 months.

8.3

The interim period between removal of specimens and reweighing should be


kept to a minimum and in no case should it exceed 1 week. Protect the
specimen if it cannot be examined, cleaned and reweighed immediately after
removal, by storing as described in 8.1.

8.4

The specimen can be photographed...

8.5

Chemical analysis of the deposit may be performed, if required.

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VII)

CRUD (Colour Comparison Method)

1.0

SUMMARY OF METHOD
The sample is filtered through a membrane filter of uniform porosity of 0.45
micron and the coloration produced on the membrane filter is compared with
the standard Babcock & Wilcox Comparison Chart.

2.0

APPARATUS

2.1

Filter Holder, 47mm diameter.

2.2

Filtration Flask, 1 litre capacity.

2.3

Laboratory Vacuum pump or Aspirator.

2.4

Membrane Filter, 47mm diameter, 0.45-micron porosity.

3.0

PROCEDURE

3.1

Filter 1-litre of the sample through the membrane filter by applying vacuum.

3.2

Dry the membrane filter at room temperature and compare the coloration on
the membrane filter with the standard Babcock & Wilcox Comparison Chart.

4.0

CALCULATIONS

4.1

Determine the crud level in the sample from the matched colour of the
enclosed Babcock & Wilcox Comparison Chart.

5.0

The method is approximation only. For determining the exact crud level
weighment method to be adopted after passing adequate amount of water
through membrane using in-line filter holder.

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Figure 2 Iron Determinations by Membrane Filters

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Article I.
1.0

VIII)

pH

SUMMARY OF METHOD
The pH meter and associated electrodes are standardized against two reference
buffer solutions, which are close to the anticipated sample pH. The Sample
measurement is made under specified conditions and prescribed techniques.

2.0

APPARATUS

2.1

Laboratory pH meter together with its associated glass and reference


electrodes.

3.0

REAGENTS

3.1

Water - conforming to specifications Type I.

3.2

Borax Reference Buffer Solution (pH = 9.18 at 25 C) - Dissolve 3.80g of


sodium tetraborate decahydrate (Na2 B407.1OH20) in water and dilute to 1litre.

3.3

Phosphate Reference Buffer Solution (pH = 6.86 at 25C) - Dissolve 3.39g of


potassium dihydrogen phosphate (dried at 130C for 2 hours) (KH2PO4) and
3.53g of anhydrous disodium hydrogen phosphate (dried at 130C for 2 hours)
(Na2HPO4) in water and dilute to 1-litre.

3.4

Phthalate Reference Buffer Solution (pH = 4.00 at 25C) - Dissolve 10.12g of


potassium hydrogen phthalate (dried at 110C for 2 hours) (KHC8H4O4) in
water and dilute to 1-litre.

3.5

Tetraoxalate Reference Buffer solution (pH = 1.68 at 25C) - Dissolve 12.61g


of potassium tetroxalate dihydrate (KHC2H4H2C2O4.2H2O) in water and dilute
to 1 litre.

3.6

Sodium Bicarbonate - Sodium Carbonate Reference Suffer Solution (pH a


10.01 at 25C) - Dissolve 2.092g of sodium bicarbonate (NaHCO3) and 2.640g
of sodium carbonate (dried at 275C for 2 hours) (Na2CO3) in water and dilute
to 1-litre.

4.0

PROCEDURE

4.1

Switch on the pH meter, allow it to warm up thoroughly, and bring it to


electrical balance with the manufacturer's instructions.

4.2

Select two reference buffer solutions, the pH values of which are close to the
anticipated sample pH and if possible bracket the sample pH.

4.3

Standardize the pH meter with the above two (4.2) reference buffer solutions
in accordance with the manufacturer's instructions.

4.4

Wash the electrodes with water and fill the beaker (provided with a
thermometer) with water sample. Insert the electrodes into the beaker and
record the pH of the water sample when the drift is less than 0.02 units in 1minute.
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5.0

CALCULATIONS

5.1

Most pH meters are calibrated in pH units and the pH of the sample is


obtained directly by reading the meter scale.

5.2

Report the temperature of measurement to the nearest 1C.

5.3

Report the pH of the test solution to the nearest 0.01 pH units when the pH
measurement lies between 1.0 and 12.0.

5.4

Report the pH of the test solution to the nearest 0.1 pH units when the pH
measurement is less than 1.0 and greater than 12.0.

6.0

PRECISION

6.1

The precision of this method is 0.05 pH units for pH measurements between 1.0
and 12.0.

6.2

When the pH is less than 1.0 and greater than 12.0, the precision is 0.1 pH units.

6.3

In order to attain this precision the condition of the instrumentation and the
technique for standardization and operation is extremely important.

7.0

INTERFERENCES

7.1

The true pH of an aqueous solution is affected by the temperature, which can be


compensated automatically in many instruments or can be manually
compensated in most other instruments. The temperature compensation corrects
for the effect of the water temperature on the instrument, including the
electrodes, but does not correct for temperature effects on the chemical system
being monitored. It does not adjust the measured pH to a common temperature;
therefore, the temperature should be reported for each pH measurement.

7.2

The glass electrode reliably measures pH in nearly all aqueous solutions and in
general, is not subject to solution interference from colour, turbidity, colloidal
matter, oxidants or reductants.

7.3

The pH response of most glass electrodes is imperfect at both ends of the pH


scale. The indicated pH value of highly alkaline solutions will be too low. This
is minimized by the selection of proper glass electrode.

7.4

The-indicated pH value of strong aqueous solutions of salts and strong acids


having a pH less than 1, will often be higher than the true pH value. This is
termed the negative error and the pH indicated is somewhat greater than the true
pH.

7.5

The pH response of the glass electrode may be impaired by a few coating


substances such as oily materials and particulates. The electrodes can be
restored to normal by an appropriate cleaning procedure recommended by the
manufacturer.

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8.0

NOTES

8.1

The pH is the negative logarithm to the base ten of the conventional hydrogen
ion activity. It is derived from the electromotive force (emf) of the cell,
Reference electrode
pH =

| | solution

pHr

||

glass electrode

(E Er ) F
= --------------2.3026 RT

Where :
pHr

pH of the reference buffer.

emf obtained when the electrodes are immersed in


the sample.

Er

emf obtained when the electrodes are immersed in a


reference buffer solution.

Faraday constant.

Gas constant.

absolute temperature.

8.2

New glass electrodes and those which have been stored dry, shall be
conditioned and maintained as recommended by the manufacturer. It is
necessary to keep the immersible ends of the electrodes in water between
measurements. For prolonged storage, glass electrodes may be allowed to
become dry, but the junction and filling openings of reference electrodes
should be capped to decrease evaporation. Glass electrodes should be stored
as recommended by the manufacturer and reference electrodes in saturated
potassium chloride solution.

8.3

Both the saturated Calomel electrode and silver-silver chloride electrode are
satisfactory for measurement at room temperature. The silver-silver chloride
electrode is recommended for measurement at elevated temperatures where its
potential is more stable than that of the saturated calomel electrode.

8.4

Where emulsions of free oil and water are to be measured for pH, it is
necessary to clean the glass electrodes thoroughly after each measurement.
The cleaning is done by washing with soap or detergent and water, followed
by several rinse with water, after which, the lower third of the electrode is
immersed in hydrochloric acid (1+9) and finally washed thoroughly with
water.

8.5

If the sample contains sticky soaps or suspended particles, the cleaning is


done with a suitable solvent or by chemical treatment, to dissolve the
deposited coating. After cleaning with solvent the lower third is immersed in
hydrochloric acid (1+9) followed by thorough washing with water.

8.6

If glass electrode has failed to respond the treatment as described in 8.4, it is


immersed in chromic acid cleaning solution for several minutes. This drastic
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treatment limits the life of electrode and is used only as an alternative to
discarding it. After chromic acid treatment, the electrode is allowed to stand in
water overnight.
8.6.1

If the electrode fails to respond to chromic acid cleaning, it is immersed in a


20% solution of ammonium bifluoride (NH4HF2) for about 1-minute. This
treatment removes a portion of the bulb glass and should be used only as a last
resort. After the fluoride treatment the electrode is thoroughly rinsed with
water and conditioned, as is recommended for a new glass electrode.

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IX)

OXIDATION REDUCTION POTENTIAL (ORP)

1.0

INTRODUCTION
ORP provides a useful measurement of the oxidizing or reducing nature of a
particular water sample. It finds various applications like chlorination/ dechlorination process of water, monitoring cycle chemistry in power plants .
ORP is defined as the electromotive force between a noble metal electrode
and a reference electrode when immersed in a solution. The ORP electrodes
are inert and measure the ratio of the activities of the oxidized to the reduced
species present.

2.0

APPARATUS
Meter Most laboratory pH meters can be used for measurement of ORP by
substitution of an appropriate set of electrodes and meter scale. Readability to
1 mv is adequate. Most process pH meters can be used for ORP measurement
by substitution of an appropriate set of electrodes and meter scale. The choice
of process ORP analyzers is generally based on how closely the characteristics
of the analyzer match the requirement of the application. Typical factors
which may be considered are the types of signals which the analyzer can
produce to drive external devices, and the span range available. For remote
ORP measurements the potential generated can be transmitted to an external
indicating meter. Special shielded cable is required to transmit the signal.
Reference electrode A calomel, silver-silver chloride or other reference
electrode of constant potential shall be used. If a saturated calomel electrode is
used, some potassium chloride crystal shall be contained in the saturated
potassium chloride solution. If the reference electrode is of the flowing
junction type, a slow outward flow of the reference electrode solution is
desired. To achieve this, the solution pressure inside the liquid junction should
be some what in excess of that outside the junction. In non pressurized
applications this requirement can be met by maintaining the inside solution
level higher than that the outside solution level. If the reference electrode is
non flowing junction type, these outward flow and pressurization
considerations shall not apply.
Oxidation-Reduction Electrode A noble metal is used in the construction of
oxidation reduction electrodes. The most common metals employed are
platinum and gold; silver is rarely used. It is important to select a metal that is
not attacked by the test solution. The construction of electrode shall be such
that only the noble metal comes in contact with the test solution. The area of
the noble metal in contact with the test solution should be approximately 1
cm3
Electrode assembly A conventional electrode holder or support can be
employed for laboratory measurements. Many different styles of electrode
holders are suitable for various process applications such as measurements in
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an open tank, process pipe line, pressure vessel, or a high pressure sampling
line.
3.0

REAGENTS AND MATERIALS


Purity of reagents Reagent grade chemicals shall be used in all tests
Purity of water Water conforming to type-I or II
Aqua regia
- Mix 1 volume of con. Nitric acid (HNO 3, sp. gravity 1.18)
with three volumes of con. Hydrochloric acid (HCl, sp.gr 1.18)
Phthalate reference Buffer solution ( pH = 4.0 at 25 0C ) Dissolve 10.12 g of
potassium hydrogen phthalate ( KHC8H4O4) in water and dilute to 1 lit.
Phosphate reference Buffer solution ( pH = 6.86 at 25 0C ) Dissolve 3.39 g
of potassium dihydrogen phosphate ( KH2PO4) and 3.53 gm of anhydrous
disodium hydrogen phosphate ( Na2HPO4 ) in water dilute to 1 lit.
Chromic acid solution Dissolve about 5 gm of potassium dichromate
(K2Cr2O7) in 500 ml of concentrated sulphuric acid (H2SO4, sp.gr. 1.84)
Detergent - Use any commercially available low soda liquid or solid
detergent
Nitric acid ( 1 + 1 ) - Mix equal volumes of concentrated nitric acid ( HNO 3 ,
sp. Gr. 1.42 ) and water

4.0

Redox standard solution: Ferrous Ferric reference solution:


Dissolve 39.21 g of ferrous ammonium sulphate (Fe(NH 4)2(SO4).6H2O ),
48.22 gm of ferric ammonium sulphate ( FeNH 4 (SO4)2 .12H2O ) and 56.2 ml
of sulphuric acid ( H2SO4, sp.gr. 1.84 ) in water and dilute to 1 lit. It is
necessary to prepare the solution using reagent grade chemicals and the
solution to be stored in a closed glass or plastic container.
The ferrous-ferric reference solution is a reasonable oxidation-reduction
potential.
Potential of platinum electrode for several reference electrodes at 25 0C in
ferrous ferric solution
REFERENCE ELECTRODE

POTENTIAL EMF (mv)

Hg, Hg2Cl2 satd. KCL

+ 430 mv

Ag, AgCl, 1.00 M KCl

+ 439 mv

Ag, AgCl, 4.00 M KCl

+ 475 mv

Ag, AgCl, satd.

+ 476 mv

KCl

Pt,H2 (p=1), H(a=1)

NTPC Limited

+ 675 mv

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5.0

Redox reference Quinhydrone Solutions Mix 1 Lit of pH 4 buffer solution


with 10 g of quinhydrone. Be sure that excess quinhydrone is used in each
solution so that solid crystals are always present. These reference solutions are
stable only for 8 hrs.
Nominal ORP of reference quinhydrone solutions
ORP , (mv)
Buffer solution, pH

6.0

--------------------

---------------------

Temperature 0 C

20

25

30

20

25

30

Reference electrode
Silver/silver chloride

268

263

258

92

86

79

Calomel

223

218

213

47

41

34

Hydrogen

470

462

454

295

285

275

Redox standard solution: iodide/Triodide Dissolve 664.04 g of potassium


iodide, 1.751 g of resublimed I2 , 12.616 g of boric acid and 20 ml. of 1 M
potassium hydroxide in water and dilute to 1 lit . This solution can be stored in
a plastic or glass container and stable up to one year.
Nominal Potential in mV of Platinum Electrode in Iodide/Tri iodide
standard solution
Reference electrode

25 0 C

25 0 C

30 0C

Ag, AgCl, satd KCl

220

221

222

Pt, H2 (p=1), H (a=1)

424

420

415

Hg, Hg2Cl2, satd KCL

176

176

175

Preparation
7.0

Electrode treatment Condition and maintain ORP electrodes as


recommended by manufacturer. If the assembly is in intermittent use, the
immersible ends of the electrode should be kept in water between
measurements. Cover the junctions and fill holes of reference electrodes to
reduce evaporation during prolonged storage.

8.0

ORP electrode cleaning:


It is desirable to clean the electrode daily. Remove foreign matter by a
preliminary treatment with a detergent. If this is insufficient use 1 + 1 nitric
acid. Rinse the electrode in water several times. Another method is to immerse
the electrode in chromic acid cleaning mixture at room temperature for several
minutes, then rinse with dilute hydrochloric acid, and then thoroughly rinse
with water.

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9.0

Standardization
Turn on meter according to manufacturers instructions. Check zero on meter
by shorting the input connection. The reading should be less than +/- 0.5 mV.
Checking the response of the electrode to standard redox solutions Wash the
electrodes with three changes of water or by means of a flowing steam from a
wash bottle. Use one or more of the above mentioned reference solutions to
check the response of the electrode. Fill the sample container with fresh redox
standard solution and immerse the electrodes. The reading should be within 30
mV of the value expected for the standard solution. The second reading should
not differ from the first by more than 10 mV.

10.0

Procedure
After the electrode / meter assembly has been standardized, wash the
electrodes with changes of water or by means of flowing water. Place the
sample in a clean glass beaker or sample cup and insert the electrodes. Provide
adequate agitation throughout the measurement period. Read the millivolt
potential of the solution allowing sufficient time for the system to stabilize.
Measure successive portions of the sample until readings on two successive
portions differ by no more than 10 mV. A system that is very slow to stabilize
probably will not yield a meaningful ORP.
Continuous determination of ORP of flowing streams
Process ORP analyzers with their rugged electrodes and electrode chambers
provide continuous measurements which are the basis for fully automatic
control. Make selection of the electrodes and electrode chamber to suit the
physical and chemical characteristics of the process material. Locate the
submersion-style electrode chamber so that fresh solution representative of the
process stream or batch continuously passes across the electrodes. Agitation
may be employed to make the stream/ batch more homogeneous. The ORP
value is usually displayed continuously and can be noted at any specific time.
Frequently the pH value is also recorded yielding a permanent record.

11.0

Report
Report the ORP value to the nearest 1 mV, interpolating the meter scale as
required. When considered appropriate, the temperature at which the ORP and
/ or pH were measured may also be reported.

12.0

Precision and Bias


Precision and bias of the measurement depends largely on the condition of the
electrode system and on the chemical system being measured. In the absence
of substances that coat or poison the electrode, the precision is +/- 10 mV.

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X)

TURBIDITY (Nephelometric)

1.0

SUMMARY OF METHOD
Turbidity is an expression of optical properties of a sample that causes light
rays to be scattered and absorbed rather than transmitted in straight lines
through the sample. The intensity of light scattered by the sample under given
conditions is compared with the intensity of light scattered by a standard
reference suspension under the, same conditions. The higher the intensity of
the scattered light, the higher the turbidity of the sample.

2.0

APPARATUS

2.1

Nephelometer - covering the range 0 to 1000 NTU.

2.2

Sample tubes. It must be clear, colourless glass and clean from both inside
and outside. Index marked so that repeated exact placements into the
instrument cuvette well for measurement can be made.

3.0

REAGENTS

3.1

Turbidity free water - water conforming to specifications Type I.

3.2

Stock Turbidity Suspension

3.2.1

Solution A - Dissolve 1.000g of Hydrazine Sulphate [(NH 2)2H2SO4] in


turbidity free water and dilute to 100 ml in a volumetric flask.

3.2.2

Solution B - Dissolve 10.00g Hexamethylene Tetramine [(CH2)6N4) in


turbidity free water and dilute to 100 ml in a volumetric flask.

3.2..3

In a 100m1 volumetric flask, mix 5.0ml solution A with 5.0 m1 Solution B.


Allow to stand for 24 hours at 25 +/ - 3 0C. Make up to the mark with turbidity
free water and mix well. The turbidity of this suspension is 400 NTU and this
stock solution to be prepared on monthly basis.

3.3

Standard Turbidity Suspension

3.3.1

Dilute l0.0m1 of stock turbidity suspension (3.2.3) to 100ml with turbidity


free water. The turbidity of this suspension is 40 NTU. Prepare weekly this
suspension.

3.4

Dilute Turbidity Standard

3.4.1

Dilute portions of the standard turbidity suspension (3.3.1) with turbidity free
water, as required. Prepare weekly. But pl. note that dilution below 4.0 NTU
should be prepared daily. (Standards below 1.0 NTU are difficult to prepare
accurately. Refer to specific manufacture instruction to determine if such a
standard is needed.)

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4.0

PROCEDURE

4.1

Calibrate the Nephelometer with standard turbidity suspension for each range,
in accordance with the manufacturer's instructions.

4.2

Replace the standard by the sample in the same tube after thoroughly washing
the tube with turbidity -free water or in an optically identical tube and record
the reading.
Turbidity less than 40 NTU
Shake the sample thoroughly to disperse the solids. Allow air bubble to
disappear, then proceed.
Turbidity exceeding 40 NTU
Dilute the sample with one or more equal volumes of reagent water until
turbidity is below 40 NTU after mixing and degassing. Then treat this less
than 40 NTU solution as above. The turbidity of the original sample can be
calculated based on dilution data and original sample volume.
After calibration check and adjustment, empty the cell of turbidity standard
and rinse the cell with the water to be tested. The measured NTU value of the
water sample to be determined using the instrument value and the appropriate
calibration curve.

5.0

CALCULATIONS

5.1

Report the result as nephelo turbidity units (NTU) as follows:


NTU

Report to nearest (NTU)

1.00 -10.0

0.1

10.0 40.0

1.0

40 100

5.0

100 400

10.0

400 1000

50.0

> 1000

100.0

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XI)

SUSPENDED AND TOTAL DISSOLVED SOLIDS


(25mg/litre or Less of Total Solids)

1.0

SUMMARY OF METHOD
Total solids are determined by evaporation, or the suspended and dissolved
solids are separated by filtration and individually determined. The suspended
solids are dried and weighed. The solution of dissolved solids is evaporated to
dryness using a dish provided with a constant level control. The residue is
dried and weighed.

2.0

APPARATUS

2.1

Sample Reservoir - A covered 20-litre container of corrosion resistant metal,


TFE fluorocarbon, polyethylene, or chemical resistant glass with necessary
tubular connections.

2.2

Automatic Evaporation Assembly - A dust shield, constant level device, heater


and evaporation dish.

2.3

Sampling Device - A cooling coil with overflow pipe and solenoid valve
suitable for sampling from a water source to a continuous sample evaporator.
(The cooling coil is necessary, only when, sample is above room temperature).

2.4

Membrane Filter Assembly - A borosilicate glass or stainless _steel funnel


with a flat, fritted base of the same material, and membrane filters (0.45
micron pore size) to fit.

2.5

Glass Petri Dish, 150mm diameter.

2.6

Evaporating Dish - A straight walled or round bottom platinum dish of 80 to


100 mm diameter and approximately 200 ml capacity.

3.0

REAGENTS

3.1

Chloroform or Benzene, purified.

4.0

PROCEDURE

4.1

Select a volume of sample sufficient to yield on evaporation a residue of


approximately 25mg.

4.2

Suspended Solids

4.2.1

Place the membrane filter in a petri dish and dry in an oven at 103 C for 15
minutes or in a vacuum desiccator for 30 minutes. Weigh the filter to the
nearest 0.1 mg.

4.2.2

Filter the sample through membrane filter (4.2.1) using the filtration assembly
and the vacuum pump or water aspirator. Wash the residue with chloroform or
benzene. Place the filter in the petri dish.

4.2.3

Place the petri dish in the oven at 103C for 30 minutes. Reweigh the filter and
record the weight of the residue on the filter.
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4.3

Total Solids and Dissolved Solids

4.3.1

Weigh a platinum dish that has been dried at 103C for 1 hour and cooled in a
desiccator. Using evaporation assembly start the evaporation of the selected
volume of the sample for total solids (4.1) or the filtrate from the suspended
solids determination (4.2).

4.3.2

When the evaporation is almost complete remove the dish from the assembly
and dry at 103C for 1 hour in an oven: Cool in a desiccator and weigh.
Record the weight of the residue.

5.0

CALCULATIONS

5.1

Calculate the result of each specific determination as follows:


Total Solids, mg/litre

W1
=. --------- x 1000
V

Suspended solids, mg/litre =

W2
---------- x 1000
V

Total dissolved solids, mg/litre =

W3
------------- x 1000
V

Where:
W1 =

grams of total solids.

W2

grams of suspended solids.

W3

grams of dissolved solids.

litres of sample used.

6.0

NOTES

6.1

Some evaporation residues readily absorb moisture, therefore rapid weighing


should be done.

6.2

Samples containing 25mg/litre or less of total solids on which only the total solids
content is, to be determined shall be immediately acidified with 0.2ml of
hydrochloric acid (sp gr 1.19) per litre of water. If suspended solids is to be
separately determined, the sample, regardless of total solids content, shall be
filtered, as soon as possible and then acidified

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XII)

SUSPENDED AND TOTAL DISSOLVED SOLIDS


(More than 25mg/litre of Total Solids)

1.0

SUMMARY OF METHOD
Total solids are determined by evaporation of an appropriate portion of the
sample and weighing the residue obtained. The suspended and dissolved
solids can be separated by filtration and then determined individually. The
suspended solids are dried and weighed and dissolved solids are determined
by weighing the residue, obtained by evaporating the filtered sample.

2.0

APPARATUS

2.1

Sample Reservoir - A chemical resistant container of 1 to 4-litre capacity,


having a valve controlled outlet.

2.2

Membrane Filter Assembly - A borosilicate glass or stainless steel funnel with


a flat, fritted base of the same material, and membrane filters (0.45 micron
pore size) to fit.

2.3

Glass Petri Dish, 150mm diameter.

2.4

Evaporating Dish - A straight wall or round bottomed platinum dish of 80 to


100mm diameter and approximately 200m1 capacity. A porcelain dish may be
substituted for the platinum dish.

2.4

Heater - Hot plate or steam bath for maintaining the temperature of the
evaporating sample near the boiling point.

3.0

REAGENTS

3.1

Chloroform or Benzene purified.

4.0

PROCEDURE

4.1

Measure a quantity of sample sufficient to yield, on evaporation,


approximately 25mg of residue.

4.2

Suspended Solids

4.2.1

Place the membrane filter in a petri dish and dry in an oven at 103 C for 15
minutes or in a vacuum desiccator for 30 minutes. Weigh the filter to the
nearest 0.1 mg.

4.2.2

Filter the sample through the membrane filter (4.2.1) using the filtration
assembly and the vacuum pump or water aspirator. Place the filter in the petri
dish.

4.2.3

Place the petri dish in the oven at 103C for 30 minutes. Reweigh the filter and
record the weight of the residue on the filter,

4.3

Total Solids and Dissolved Solids

4.3.1

Transfer the sample for total solids determination (4.1) or the filtrate from
suspended solid determination (4.2) to a sample reservoir.
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4.3.2.

Fill an evaporating dish (previously dried at 103 C for 1 hour and weighed) to
within 6.3mm of the top, with sample.

4.3.3

Evaporate the sample on a hot plate or steam bath. Periodically, add sample
from the reservoir to the dish until the reservoir is empty.

4.3.4

Dry the dish at 103C for 1 hour. Cool in a desiccator and weigh. Record the
weight of the residue in the dish.

5.0

CALCULATIONS

5.1

Calculate the result of each specific determination, as follows:


W1
---------- x 1000
V

Total Solids, mg/litre =

Suspended solids, mg/litre =

W2
-------- x 1000
V

W3
Total dissolved solids, mg/litre = --------- x 1000
V
Where :
W1

grams of total solids. W3 =

grams of dissolved solids

W2

grams of suspended solids, V=

litres of sample used.

6.0

NOTES

6.1

Some evaporation residues readily absorb moisture, therefore rapid weighing


should be done.

6.2

Suspended solids are defined as those solids, exclusive of gases and in nonliquid state, which are dispersed in water to give a heterogeneous mixture.
Dissolved solids (exclusive of gases) are dispersed in water to give a
homogeneous liquid and total solids is the sum of suspended and dissolved
solids.

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XIII)

ALKALINITY (Titration Method, 10 to 500mg/litre)

1.0

SUMMARY 0F METHOD
The sample is titrated with a standard acid solution to a designated pH and the
end point is determined using internal indicator.

2.0

RANGE
10 to 500 mg/litre as CaCO3.

3.0

REAGENTS

3.1

Water - conforming to specifications Type I.

3.2

Phenolphthalein Indicator Solution (5.0 g/litre) - Dissolve 0.5g of


phenolphthalein in 50m1 of ethyl alcohol (95%) and dilute to 100ml with
water.

3.3

Standard Hydrochloric Acid (0.02N) - Dilute 1.66m1 of hydrochloric acid (sp


gr 1.19) to 1 litre with water. For standardization - see notes.

3.4

Mixed Bromocresol Green - Methyl Red Indicator Solution -Dissolve 20mg of


methyl red and 100mg of bromocresol green (sodium salt) in either 100m1 of
water or 100m1 of ethyl alcohol (95%).

3.5

Methyl Orange Indicator Solution (0.5g/litre) - Dissolve 0.05g of methyl


orange in water and dilute to 100 m1.

3.6

Sodium Thiosulphate Solution (0.1N) - Dissolve 2.5g of sodium thiosulphate


(Na2S2O3.5H2O) in 50m1 of water, add 0.011g of sodium carbonate. Dilute to
100m1 and allow to stand for 24 hours. .

4.0

PROCEDURE

4.1

Phenolphthalein Alkalinity (P-Alkalinity)

4.1.1

Place 50m1 sample in a titration flask and add 2 drops of phenolphthalein


indicator.

4.1.2

Titrate over a white surface with 0.02N standard hydrochloric acid from a
pink colour to a colourless end point.

4.2

Total Alkalinity by Mixed Indicator

4.2.1

Add 3 drops of the mixed indicator to the solution in which the


phenolphthalein alkalinity has been determined.

4.2.2

Titrate over a white surface with 0.02N standard hydrochloric acid to the
required end point.
Above

pH 5.2
AT pH 5.0
pH 4.8
pH 4.6

Greenish blue
Light blue
Pink grey with bluish tinge
Light Pink

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4.3

Total Alkalinity (M-Alkalinity) by Methyl Orange

4.3.1

Add 2 drops of methyl orange indicator to the solution in which the


phenolphthalein alkalinity has been determined.

4.3.2

Titrate over a white surface with 0.02 N standard hydrochloric acid to the
required end point. (At pH 4.6 the colour changes to orange and at pH 4.0 to
pink).

4.4.0

Potentiometer Method Pipette 20 ml or a suitable aliquot of sample


into a 100-ml beaker and titrate with standard sulphuric acid to pH
8.3 then to pH 3.7, using a potentiometer. No indicator is required.

5.0

CALCULATIONS

5.1

Phenolphthalein Alkalinity, mg/litre as CaCO3 =

A x N x 50,000
V

5.2

M-Alkalinity (Total Alkalinity), mg/litre as CaCO3 =

B x N x 50,000
V

Where:
A

5.3

milliliters of standard hydrochloric acid to reach the


phenolphthalein end point.
B
=
total milliliters of standard hydrochloric acid to reach the
mixed indicator or methyl orange end point.
N
=
normality of hydrochloric acid.
V
=
milliliters of sample.
Alkalinity Relationship.
The following table gives the stoichiometric classification of the three
principal forms of alkalinity present in water.
Results of
Titration

Hydroxide
Carbonate
Bicarbonate
Alkalinity
(as Alkalinity
(as Alkalinity
(as
CaCO3)
CaCO3)
CaCO3)

P=0

P < 1/2 M
P = 1/2 M
P > 1/2 M
P=M

0
0
2P-M
M

2P
2P
2(M-P)
0

M-2P
0
0
0

Where :
P

Phenolphthalein Alkalinity.

M-Alkalinity (or total alkalinity).

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6.0

PRECISION

6.1

The precision of this method is l mg/litre as CaCO3.

7.0

INTERFERENCES

7.1

Free residual chlorine markedly affects the indicator colour response in some
water samples through its bleaching action. It can be removed by the addition
of sodium thiosulphate.

7.2

Natural colour or the formation of a precipitate during titration may mask the
colour change.

7.3

Salts of weak organic and inorganic acids also affect the titration.

8.0

NOTES

8.1

Reagent grade chemicals should be used for preparing the reagents.

8.2

Phenolphthalein indicator is used for alkalinity determination contributed by


hydroxide and half the carbonate. Indicators responding in the pH range 4-5
are used to measure the alkalinity contributed by hydroxide, carbonate and
stoichiometric relationship bicarbonate absence of significant radicals other
than bicarbonate carbonate, and bicarbonate. The between hydroxide, are
valid only in the concentration of weak acid hydroxide, carbonate or
bicarbonate.

8.3

The following pH values are suggested as the equivalence points for the
corresponding alkalinity concentration as calcium carbonate:
pH of 5.1 for total Alkalinities of about 30mg/litre, pH of 4.8 for 150mg/litre,
and pH of 4.5 for 500 mg/litre.

8.3.1

Indicators effective in these ranges which give the most reliable results are
mixed indicator for higher pH values and methyl orange for pH values below
4.6.

8.4

To standardize 0.02N hydrochloric acid, weigh accurately 0.088 0.001 g of


sodium carbonate (previously dried in a platinum crucible at 250 0C for 4
hours) and transfer to a 500m1 conical flask. Add 50m1 of water to dissolve
the carbonate and add 2 drops of 0.1% solution of methyl red in alcohol.
Titrate with hydrochloric acid to the first appearance of a red colour, and boil
the solution carefully until the colour is discharged. Cool to room temperature
and continue the titration. Repeat the process of boiling and titration until a
faint red colour is obtained that is not discharged on further heating.

8.5

Sulphuric acid can also be used in place of hydrochloric acid for titration.

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XIV)

ALKALINITY DUE TO HYDROXIDE

1.0

SUMMARY OF METHOD
The sample is treated with a solution of strontium chloride to precipitate
dissolved carbonates and phosphates and the hydroxide ion is titrated with a
standard hydrochloric acid solution using phenolphthalein indicator.

2.0

REAGENTS

2.1

Water - conforming to specifications type III.

2.2

Hydrochloric acid (0.02N) - Dilute 1.66m1 of hydrochloric acid (sp gr 1.19)


to 1 litre with water. For standardization - see notes.

2.3

Phenolphthalein Indicator Solution (5.0g/litre) - Dissolve 0.5g of


phenolphthalein in 50m1 of ethyl alcohol (95%) and dilute to 100m1 with
water.

2.4

Strontium Chloride Solution (4.5g/litre) - Dissolve 4.5g of strontium chloride


(SrC12.6H2O) in water and dilute upto to 1 litre.

3.0

PROCEDURE

3.1

Transfer 100m1 of the sample to a 500 ml conical flask.

3.2

Add quickly, while swirling the flask, 1 ml of strontium chloride solution for
each milligram of carbonate or phosphate ion in the sample aliquot, plus a 4ml
excess.

3.3

Stopper the flask loosely, boil the contents for a few seconds, and then cool to
room temperature.

3.4

Add 4 drops of phenolphthalein indicator solution and quickly titrate with


standard hydrochloric acid to a colourless end-point.

4.0

CALCULATIONS

4.1

Calculate the concentration of hydroxide ion, in mg/ litre, as follows:


N x V1 x 17000
Hydroxide ion, mg/litre as OH =--------------------------------------V
Where:

4.2

normality of standard hydrochloric acid.

V1

milliliters of standard hydrochloric acid.

milliliters of sample.

Calculate the concentration of hydroxide ion, in mg/litre as CaCO3, as


follows:
Hydroxide ion, mg/litre as, CaCO3 = B X 2.94
Where:
B = hydroxide ion, mg/litre as OH.
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5.0

PRECISION

5.1

The single operator precision of the method can be expressed as follows:


S

0.05 mg/litre.

Where S = single operator precision.


6.0

INTEREFENCES

6.1

Aluminium, carbonates, chromates, phosphates, silicates, and some organic


matter affect the sample titration.

6.2

The effects of carbonates and phosphates are eliminated by the addition of


strontium chloride in excess.

7.0

NOTES

7.1

Reagent grade chemicals should be used for preparing the reagents.

7.2

To standardize 0.02N hydrochloric acid, weigh accurately 0.088 0.001g of


sodium carbonate (previously dried in a platinum crucible at 250C for 4
hours) and transfer to a 500m1 conical flask. Add 50m1 of water to dissolve
the carbonate and add 2 drops 0.1% solution of methyl red in alcohol. Titrate
with hydrochloric acid to the first appearance of a red colour, and boil the
solution carefully until the colour is discharged. Cool to room temperature and
continue the titration. Repeat the process of boiling and titration until a faint red
colour is obtained that is not discharged on further heating.

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XV)

ALUMINIUM

1.0
1.1

SUMMARY OF METHOD
Aluminium is complexed with ferron (8-hydroxy-7-iodo-5-quinoline
sulphonic acid) and its concentration is determined colorimetrically at a wavelength of 370nm.
Orthophenanthroline is added to greatly minimize the iron interference and its
simultaneous determination at a wavelength of 520nm.
RANGE
0.00 to 2.00 mg/litre Al.
APPARATUS
Spectrophotometer for use at 370 and 520nm.
Matched pair of l0 mm cells.
REAGENTS
Water - conforming to specifications Type II.
Aluminium Standard
Solution (l ml = 0.010mg A1) - Dissolve 1.769g of
aluminium potassium sulphate [AlK(SO4)2.12H20] in water. Add 10 ml of
hydrochloric acid (sp gr 1.19) and dilute to 1 litre with water (solution A).
Dilute 100m1 of solution A to 1 litre with water.
Iron Standard Solution (l ml = 0.010mg Fe) - Dissolve 0.7022g of ferrous
ammonium sulphate [FeSO4(NH4)2 SO4.6 H2O] in 50m1 of water and 20m1 of
Sulphuric acid (sp gr 1.84). Dilute to 1 litre with water (solution B). Dilute
100 ml of Solution B to 1 litre with water.
Ferron- orthophenanthroline Reagent - Add 0.5g of ferron and 1.0g
orthophenanthroline to 1 litre of water. Stir for at least 2 hours. If any solids
settle out, decant the clear supernatent liquid for use.
Hydroxylamine Hydrochloride Solution (10%) - Dissolve 100g of
hydroxylamine hydrochloride in 500m1 water. Add 40m1 of hydrochloric acid
(sp gr 1.19) and l g of beryllium sulphate (BeSO 4) and dissolve. Dilute to 1
litre with water.
Sodium Acetate (275g/litre) - Dissolve 275g of sodium acetate trihydrate
(NaC2H3O2.3H2O) in water and dilute to 1 litre with water.
CALIBRATION
Aluminium Curve
To eleven 100m1 volumetric flasks, add respectively 0.0, 2.0, 4.0, 6.0, 8.0,
10.0, 12.0, 14.0, 16.0, 18.0 and 20.Om1 of standard aluminium solution (4.2, l
ml = 0.010 mg A1). Dilute to 100m1 with water.
Using the procedure described in section 6.0, develop the colour and measure
the absorbance of each standard at 370nm.
Prepare a calibration curve by plotting the absorbance against the
concentration.

2.0
3.0
3.1
3.2
4.0
4.1
4.2

4.3

1.4

4.5

4.6
5.0
5.1
5.1.1

5.1.2
5.1.3

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5.2
5.2.1

5.2.2
5.2.3
6.0
6.1
6.2
6.3
6.4
7.0
7.1
7.2

7.3

Iron Correction Curve


To nine 100m1 volumetric flasks, add respectively 0.0, 5.0, 10.0, 15.0, 20.0,
25.0, 30.0, 35.0 and 40.0m1 of standard iron solution (4.3, l ml = 0.010 mg
Fe) Dilute to 100m1 with water.
Using the procedure described in section 6.0 develop the colour and measure
the absorbance of each standard at 370 and 520nm.
Prepare calibration curves by plotting absorbance against concentration of
iron at the two specified wavelengths.
PROCEDURE
Place 25 ml sample into a beaker or flask, and add 2.0 ml of hydroxylamine
hydrochloride solution. Allow to stand for 30 minutes.
Add 5.0 m1 of ferron-orthophenanthroline solution and mix.
Add 2m1 of sodium acetate solution and allow to stand for 10 minutes.
Measure the absorbance at 370 and 520 nm against the zero standard prepared
by adding the reagents (6.2, 6.3) to 25m1 of water.
CALCULATIONS
Designate the absorbance measurement at 370nm as A.
Using the iron correction curve locate the absorbance value measured at 520
nm. At the same iron concentration read the corresponding absorbance at 370
nm. Designate this value as B.
A minus B is the corrected absorbance. Using the aluminium calibration
curve, find the aluminium concentration corresponding to the corrected
absorbance.

8.0
8.1

PRECISION
The precision of this method may be expressed as follows:
So
=
0.035
Where
So = single operator precision in mg/litre of aluminium.

9.0
9.1
9.2

INTERFERENCES
Each mg/litre of iron increases the aluminium reading by about 0.01 mg/litre.
Several other metals and anions cause interference, but only manganese, lead,
cobalt and fluoride show sufficiently pronounced effects to require correction.
Orthophosphate upto 5mg/litre and residual chlorine up to 5mg/litre do not
interfere. Natural colour and turbidity interfere and a correction is usually
required.

10.0

NOTES

10.1
10.2

Reagent grade chemicals should be used for preparing the reagents.


Filter the sample at the time of collection through a 0.45 micron filter and
perform the analysis as soon as possible after sample collection.
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XVI)

ALUMINIUM (ATOMIC ABSORPTION METHOD)

1.1

Principle
The aluminium content of the sample is determined by atomic absorption
spectrophotometers. For dissolved aluminium the filtered sample may be
directly aspirated to the atomizer. For total recoverable aluminum, a
pretreatment with conc. HCl is carried out, prior to aspiration of the sample.
This method is applicable in the range from 5 to 100 mg/l of aluminium.
However, the concentration range will vary with the sensitivity of the
instrument used.

1.2

Apparatus

1.2.1

Atomic Absorption Spectrophotometer with nitrous oxide-acetylene flames,


hollow-cathode lamp or electrode less discharge lamp for use at 309.3 nm.
NOTE Use nitrous oxide with strict adherence to manufacturers directions.
Improper sequencing of gas flows at start up and shut down of instrument can
produce explosion from flash back.

1.2.2

Standard Volumetric Glass wares

1.3

Reagents

1.3.1

Hydrochloric Acid concentrated (11 N).

1.3.2

Nitric Acid concentrated (16 N) and dilute (1:499).

1.3.3

Potassium Chloride Solution


Dissolve 250 g of KCl in water and dilute to 1 000 ml in a volumetric flask.

1.3.4

Stock Aluminium Solution


Dissolve 8.791 g of aluminium potassium sulphate, AlK(SO 4)2.12H2O in
water and dilute to 1 000 ml with water in a volumetric flask (1 ml = 500 g
of Al).

1.3.5

Standard Aluminium Solution


Dilute 10.0 ml of stock aluminium solution to 1000 ml with water in a
volumetric flask (1ml = 5.0 g of Al)
NOTE Fresh standard aluminium solution to be prepared after a week.

1.4
1.4.1

Procedure
Calibration
Prepare a reagent blank and sufficient standards containing 0 to 60 mg/l of
aluminium by diluting suitable volumes of standard aluminium solution with
nitric acid (1:499) to 100 ml in volumetric flasks. Add 2 ml of KCl solution to
each of the volumetric flasks. Aspirate the reagent blank and carry out zero
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63adjustment. Aspirate sequentially the standard solutions and measure the
absorbance at 309.3 nm.
1.4.2

Determination of Aluminium
Add 0.5 ml of concentrated nitric acid to 100 ml of the sample taken in a 250ml beaker. (If total recoverable aluminium is to be determined, use 100 ml of
the sample obtained after a pretreatment as given below. Add 5 ml of
concentrated hydrochloric acid to 100ml of the sample taken in a 250-ml
beaker. Heat on a hot plate to reduce the volume to about 50 ml and filter the
sample through 0.45m membrane. Transfer quantitatively the contents of the
beaker to a 100ml volumetric flask. Make up to the mark in volumetric flask.)
Add 2ml of KCl solution to this. Prepare a reagent blank with 100ml of water.
Rinse the atomizer by aspirating water containing 1.5 ml conc HNO 3/l.
Aspirate the reagent blank and carry out zero adjustment. Aspirate the sample
solution and measure the absorbance at 309.3 nm. From the absorbance data,
determine the micrograms of aluminium present in 100 ml of the final
solution.

1.5

Calculations
Aluminium, g/l = M
V
Where
M = mass of aluminium present in g in 100 ml of the final solution, and
V = volume of the sample in ml.

1.6

Precision and Accuracy


The relative standard deviation reported in the literature for aluminium in the
4.5mg/l concentration range is 4.2 percent.

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XVII)

AMMONIA (Indophenol method)

1.0

SUMMARY OF METHOD
The sample is reacted with hypochlorite and phenol in the presence of a
manganous salt to produce an intense blue compound, the intensity of which
is measured spectrophotometrically at a wavelength of 630nm.

2.0

RANGE
10 to 500 micrograms/litre as N.

3.0

APPARATUS

3.1

Spectrophotometer for use at 630nm. .

3.2

Matched pair of 10 mm and 50 mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type I.

4.2

Phenolate Reagent Solution - Dissolve 2.5g of sodium hydroxide and 10 g of


phenol in 100 ml of water. Prepare every week.

4.3

Hypochlorous Acid Solution - Add 10 ml of a 5% commercial bleaching


powder solution to 4 ml of water. Adjust the pH to 6.5 to 7.0 with
hydrochloric acid (check with a narrow range pH paper). Prepare every week.

4.4

Manganous Sulphate Solution - Dissolve 0.050 g of manganous sulphate


(MnSO4.H2O) in 100 ml of water.

4.5

Ammonia Nitrogen Standard Solution (l ml = 0.5 micro-gram N) - Dissolve


0.3819g of anhydrous ammonium chloride (NH 4C1), previously dried at 1050
C for I hour, in water and dilute to 1 litre. Dilute 5.0 m1 of this solution to 1
litre.

5.0

CALIBRATION

5.1

Transfer 0.0, 1.0, 5.0, 10.0, 15.0 and 20.0ml of the standard ammonia nitrogen
solution. (1ml =0.5 microgram N) to 25ml volumetric flasks,

5.2

Add 0.05ml of manganous sulphate solution and mix.

5.3

Add 0.5ml of hypochlorous acid. solution and add immediately but slowly
0.6m1 of Phenolate solution. Dilute to 25m1 with water.

5.4

Measure the absorbance of each standard at 630nm against the zero standard
(blank).

5.5

Prepare a calibration curve by plotting absorbance versus micrograms of


ammonia nitrogen.
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6.0

PROCEDURE

6.1
6.2

Place 10ml (or other suitable volume containing not more than 10 micrograms
ammonia nitrogen) of the sample in a 25m1 volumetric flask.
Proceed in accordance with section 5.0 .(5.2 to 5.4).

7.0

CALCULATIONS

7.1

Calculate the ammonia concentration in microgram/ litre of nitrogen in the


sample, as follows:

Ammonia, micrograms/litre as. NH3

A x 1000
-----------------------------V

Where:
A = micrograms of ammonia, nitrogen observed from toe calibration curve.
V =
7.2

milliliters of sample.

Calculate the ammonia concentration, in micrograms/ litre of ammonia in the


sample, as follows:
Ammonia, microgram/litre as NH3 = B X 1.22
Where B =

ammonia nitrogen, micrograms/litre.

8.0

INTERFERENCES

8.1

More than 500 mg/litre of alkalinity, more than 100 mg / litre of acidity,
colour and turbidity interfere.
These interferences can be removed by distillation prior to analysis.

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XVIII) AMMONIA by Nesselers Reagent


1.0

SUMMARY OF METHOD
The sample is reacted with Nessler's reagent (KZHgI4) to produce a reddish
brown colloidal compound, the intensity of which is measured
spectrophotometrically at a wavelength of 425nm.

2.0

RANGE
0.1 to 2mg/litre as N.

3.0

APPARATUS

3.1

Spectrophotometer for use at 425nm.

3.2

Matched pair of 10 mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type I.

4.2

Ammonia Nitrogen, standard solution (l ml = 0.01mgN) - Dissolve 4.718g of


ammonium sulphate [(NH4)2SO4] (previously dried at 100C for 1 hour) in
water and dilute to 1 litre. Dilute 10 ml of this solution to 1 litre.
Nessler Reagent- Dissolve 100g of anhydrous mercuric iodide (HgI 2) and 70 g
of anhydrous potassium iodide (KI) in a small volume of water; add this
mixture slowly, with stirring, to a cooled solution of 160g of sodium
hydroxide in 500m1 of water. Dilute the mixture to 1 litre. Store the solution
in dark for 5 days and filter twice through a fritted glass crucible before using.
This reagent has a shelf life of 1 year, if stored in dark.

4.4

Reagents For Sample Turbidity/Cloudiness Removal

4.4.1

Sodium Hydroxide Solution (250g/litre) - Dissolve 250g of sodium hydroxide


in water and dilute to 1 litre.

4.4.2

Zinc Sulphate Solution (100g/litre) - Dissolve 100g of zinc sulphate


(ZnSO4.7H2O) in water and dilute to 1 litre.

4.4.3

Sodium Potassium Tartarate Solution (300 g/litre) - Dissolve 30g of sodium


potassium tartarate tetrahydrate in 100m1 of water.

4.4.4

Disodium Dihydrogen Ethylenediamine tetraacetate solution (500g/litre) Dissolve 50g of disodium dihydrogen ethylenediamine tetraacetate dihydrate
in water containing 10g of sodium hydroxide. Gently heat to complete
dissolution. Cool and dilute to 100m1.

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5.0

CALIBRATION

5.1

Prepare a series of standards by diluting 0.0, 1.0, 3.0, 5.0, 8.0 and l0.0m1 of
standard ammonia nitrogen solution (l ml = 0.01 mg N) to 50m1 in Nessler
cylinders.

5.2

Add l ml of Nessler reagent, mix and allow to stand for 20 minutes.

5.3

Measure the absorbance of each standard (5.1) at 425nm against the zero
standard (blank) using l0mm matched pair of cells.

5.4

Prepare a calibration curve by plotting absorbance versus milligrams of


ammonia nitrogen.

6.0

PROCEDURE

6.1

Place 50ml sample (or other suitable volume diluted to 50ml) containing not
more than 0.lmg of ammonia nitrogen in a Nessler cylinder.

6.2

Add l ml of Nessler reagent, mix, and allow to stand for 20 minutes.

6.3

Measure the absorbance of the sample at 425nm against the reagent blank
prepared by taking 50 ml of water in a Nessler cylinder and following the step
6.2.

7.0

CALCULATIONS

7.1

Calculate the ammonia concentration in mg/litre of nitrogen in the sample, as


follows:
Ammonia nitrogen, mg/litre as N

A x 1000
-----------------------V

Where:

7.2

milligrams of ammonia nitrogen observed


from the calibration curve.

milliliters of sample.

Calculate the ammonia concentration, in mg/litre of ammonia in the sample,


as follows:
Ammonia, mg/litre as NH3 = B x 1.22
Where B = Ammonia nitrogen, mg/litre as N.

8.0

PRECISION

8.1

The precision of this method at ammonia nitrogen levels up to 0.50mg/litre is


0.04.

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9.0

INTERFERENCES

9.1

Glycerine, hydrazine, and some amines will react with Nessler's reagent to
give the characteristic yellow colour in the time required for the test.

9.2

Residual chlorine must be removed prior to ammonia determination with


sodium arsenite (NaAsO2) solution (1 g/litre). One milliliter of this solution
will remove l mg/litre of residual chlorine from the 500ml sample.

9.3

Turbidity in the sample can be removed as follows:


Add l ml of Zinc sulphate solution to 100 m1 sample and mix. Add sodium
hydroxide solution to raise the pH to about 10.5 (check with a pH paper).
Allow to settle and filter through whatman No.40 filter paper. To prevent
cloudiness add 2 drops of sodium potassium tartarate solution or disodium
dihydrogen ethylenediamine tetraacetate.

10.0

NOTES

10.1

Reagent grade chemicals should be used for preparing the reagents.

10.2

The Nesseler reagent should give the characteristic colour with ammonia
within 10 minutes after addition, and should not produce a precipitate with
small amounts of ammonia (0.04mg in 50 m1 volume). The solution may be
used without 5 day storage if it is filtered 'through a 0.45 - micron membrane
filter shortly before use.

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XIX) AMMONIA BY ION SELECTIVE ELECTRODE


1.0

Scope
This test method is applicable to the measurement of ammonia in reagent and
effluent water.

2.0

Summary of Test Method


The sample is made alkaline with sodium hydroxide to convert ammonium
ion to ammonia. The ammonia thus format diffuses through a gas-permeable
membrane of an ion selective electrode (ISE) and alters the pH of its internal
solution which, in turn, is sensed by a pH electrode. The potential is measured
by means of a pH meter of an ISE meter. If the pH meter is used, the ammonia
content is determined from a calibration curve; if the ISE meter is used, the
ammonia content is read directly from the meter.

3.0

Interferences
1

Volatile amines are positive interferences.

Mercury, if present, forms ammonia complexes, thus causing negative


interference.

4.0

Organic compounds that form ammonia readily (within 5 min) under


alkaline conditions are a positive interference. In general, this should not
be a problem because the interfering concentrations may to be greater than
100 mg/L. Among the inorganic compounds, hydrazine sulfate has yielded
a reading of 0.2 mg/L of NH3 as N when its concentration was 100 mg/L
as N.
Apparatus
1 Electrode, gas-sensing, ammonia, incorporating and internal reference
electrode and a diffusion-type membrane.
2

Meter, one of the following:


pH Meter, digital or expanded millivolt scale, accurate to 0.1 mv.
ISE Meter, with direct-reading concentration scale.

5.0

Electrode Holder, for mounting the electrode at 200 to the vertical.

Stirrer, magnetic, with TFE-fluorocarbon-coated stirring bars.

Heat Barrier, 6-mm thick cork board placed underneath the beaker to
insulate the ample solution from heat generated by the magnetic stirrer.

Reagents
1

Ammonia, Solution, Stock (1000 mg NH3 as N/L) Dry reagent-grade


ammonium sulfate ((NH4) 2SO4) for 1 h at 1000C. Accurately weigh 4.718
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2
3

4
5
6.0

g and dissolve in water in a 1-L volumetric flask. Dilute to volume with


water. This solution is stable for at least three months.
Ammonia, Solution, Intermediate (100 mg NH3 as N/L) Pipette 100 ml
of the 1000-mg/L standard solution to a 1-L volumetric flask and dilute to
volume with water. This solution is stable for one month.
Ammonia, Solution, Working (10, 1 and 0.1 mg NH3 as N/L)
Quantitatively transfer 100, 10, and 1 ml of the 100-mg/L standard
solution into separate 1-L volumetric flasks. Dilute each to volume with
water. Prepare these solutions daily before use.
Ammonium Chlo9rice Solution (5.4 g/L) Dissolve 5.4 g of ammonium
chloride (NH4Cl) in water and dilute to 1 L. This solution is used only for
soaking the electrode.
Sodium Hydroxide Solution (400 g/L) dissolve 400 g of sodium
hydroxide (NaOH) in water. Cool and dilute to 1 L.

Calibration
1

pH Meter Refer to the manufacturers instruction manual for proper


operation of the pH meter. Prepare calibration curves using a minimum of
three standard solutions (see15.3), bracketing the expected concentrations
of the samples.

Treat the standards as directed in 1 and measure the potential of each


standard and record in millivolts. The standards and the sample must be at
the same temperature, preferably about 250C.

3. Using semilogarithmic graph paper, plot the concentration of ammonia


nitrogen in milligrams per litre on the log axis against the corresponding
electrode potential, in millivolts, on the linear axis.
4. Check the Calibration curve every 3 h when analyzing a series of samples.
5. ISE Meter Refer to the manufacturers instruction manual for proper
operation of the meter. Prepare calibration curves with three standard
solutions (see 15.3), bracketing the expected concentrations of the
samples.

7.0

6. Check the calibration curve every 3 h when analyzing a series of samples;


otherwise, calibrate daily.
Procedure
1
2
3

Sample Treatment:
Transfer 100 ml of the sample (or an aliquot diluted to 100 ml) to 150-ml
beaker. The sample temperature must be the same as that of the standards
used in calibration
Add the stirring bar and mix on the magnetic stirrer. Do not mix so rapidly
that air bubbles are drawn into the solution.
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4

5.
6
7.

8.
9.
10
8.0

Immerse the electrode into the sample, positioning it at an angle 200 to the
vertical, making sure that no air bubbles are trapped on the membrane of
the electrode. All precautions recommended by the manufacturer should
be observed to ensure accurate measurements.
Add 1.0 ml of NaOH solution (see 15.5) to the sample. The NaOH
solution should be added just prior to measurement because ammonia may
be lost to the atmosphere from a stirred alkaline solution
Check the pH of the sample with pH paper. The pH must be greater than
11.0. If less than 11.0, add additional NaOH solution (see 15.5) in 0.1-ml
increments until the pH of the solution exceeds 11.0.
When the electrode comes to equilibrium, measure the electrode potential
of the ammonia nitrogen concentration as directed below.
Note 3 The time required for the electrode to come to equilibrium is
dependent on the ammonia content of the sample. For concentrations
above 0.5 mg/L, the response time is about 30 s.
Sample Measurement Determine the ammonia nitrogen concentration by
means of a pH meter of a specific-ion meter.
pH Meter Record the observed potential in millivolts and convert to
milligrams per litre of ammonia nitrogen by means of the calibration curve
(see 17.2).
ISE Meter Record the concentration reading directly from the
logarithmic scale as milligrams of ammonia nitrogen per litre.

Calculations
Report the ammonia nitrogen content in milligrams per litre. If necessary
calculate for dilution of original sample.

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XX)

CARBON DIOXIDE (Bicarbonate Titration Method)

1.0

SUMMARY OF METHOD
Carbon dioxide concentration is determined from measured values of pH and
bicarbonate ion.

2.0

APPARATUS

2.1

pH meter.

3.0

REAGENTS

3.1

Water - conforming to specifications Type, I.

3.2

Hydrochloric Acid, Standard (0.04N) - Dilute 3.42 m1 of hydrochloric acid


(sp gr 1.19) to 1 litre with water and standardize with sodium carbonate (dried
at 250C for 4 hours) using methyl red indicator.

3.3

Methyl Red Indicator Solution (5g/litre) - Dissolve 0.5g of methyl red in 100
m1 of 95 % ethanol.

4.0

PROCEDURE

4.1

Determine the pH of the sample.

4.2

Place 50m1 or less of sample water containing no more than 80mg of


bicarbonate ion into a 200m1 beaker.

4.3

If the pH of the sample is above 8.3, titrate with 0.04N hydrochloric acid to
this pH value using the pH meter for end-point detection.

4.4

Continue to titrate to pH 4.5

4.5

Record the milliliters of hydrochloric acid required to titrate to pH 8.3 as V1


and milliliters required to titrate from pH 8.3 to pH 4.5 as V2.

5.0

CALCULATIONS

5.1

Calculate the bicarbonate ion concentration using the following equation:


2440 X (V2-Vl)
Bicarbonate (HC03), mg/litre = ------------------------V
Where:
V
=
volume of sample in milliliters.
V1

milliliters of hydrochloric acid required for titrating to


pH 8.3.

V2

milliliters of hydrochloric acid required for titrating


from pH 8.3 to 4.5.
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5.2

Calculate the free carbon dioxide concentration in mg/ litre by using the
following equation for waters with pH values from 6 to 9:
Free CO2, mg/litre as CO2 = 1.60 X 10 (6 .0-pH) X mg HCO3 / litre

5.3

Calculate free CO2 concentration in mg/litre as CaCO3 as follows:


Free CO2, mg/litre as CaCO3 = A x 1.14
Where:
A

concentration of CO2, mg/litre as CO2.

6.0

PRECISION

6.1

Precision of the bicarbonate determination is approximately l mg/litre for


bicarbonate ion concentrations below 100 mg/litre and 2 mg/litre in the 100 to
200 mg/ litre bicarbonate ion range. Precision of carbon di-oxide
measurement will be proportional to the fractional relationship between
bicarbonate ion and carbondioxide values determined.

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XXI)

CARBON DIOXIDE (Direct Titration of Free Carbon Dioxide)

1.0

SUMMARY OF METHOD
Free carbon dioxide is reacted with sodium hydroxide to form sodium
bicarbonate. The end point of the reaction is detected electrometrically or by
means of a pH colour indicator.

2.0

APPARATUS

2.1

pH meter.

3.0

REAGENTS

3.1

Water - conforming to specifications Type I.

3.2

Phenolphthalein Indicator Solution (5g/litre) - Dissolve 0.5 g of


phenolphthalein in 100m1 of a 50% solution of ethyl alcohol in water.

3.3

Sodium Hydroxide solution, Standard (0.04N) - Dissolve 1.6g of sodium


hydroxide in approximately 100 m1 of water, add 0.l g of barium hydroxide
and dilute to 1 litre with water. Allow the carbonate to settle and standardize
against the 0.04N hydrochloric acid.

3.4

Sodium Bicarbonate Solution (l g/litre) - Dissolve 0.l g of anhydrous sodium


bicarbonate in 50 ml water and dilute to 1 litre. Prepare just before use.

3.5

Hydrochloric Acid, standard (0.04N) - Dilute 3.42 m1 of hydrochloric acid


(sp.gr 1.19) to 1 litre with water and standardize with sodium carbonate (dried
at 250 C for 4 hours) using methyl red indicator.

3.6

Methyl Red Indicator solution (5g/litre) - Dissolve 0.5g of methyl red in 100
m1 of 95% ethanol.

4.0

PROCEDURE

4.1

Place 100m1 of sample in a 250m1 beaker and add 5 drops of phenolphthalein


indicator solution.

4.2

If the sample remains colourless, titrate rapidly with standard sodium


hydroxide solution until the first faint pink colour is detectable in the solution.

4.2.1

Alternatively, titrate the sample to pH 8.3 using a pH meter to detect the end
point.

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5.0

CALCULATIONS

5.1

Calculate the free carbondioxide content of the water in mg/litre using the
following equation:
Free CO2, mg/litre as CO2 = V x N x 440
Where V = milliliters of sodium hydroxide required to titrate 100 ml of
sample.
N = normality of sodium hydroxide solution.

5.2

Calculate free CO2 concentration in mg/litre as CaCO3 as follows:


Free CO2, mg/litre as CaC03 = A x 1.14
Where:

A = concentration of CO2, mg/litre as CO2

6.0

PRECISION

6.1

Under the most favourable conditions, precision is approximately 10% of the


indicated carbondioxide content.

7.0

INTERFERENCES

7.1

Cations or anions which affect the carbonate equilibrium or precipitate or


consume the reactant preferentially affect the accuracy. Aluminium, iron,
chromium and copper are examples of metal ions that may yield erroneous
results.

7.2

Abnormal results also may be obtained in the presence of ammonia, amines,


phosphate, borate, sulphide and nitrate.

7.3

Excessive dissolved solids also, will introduce error.

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XXII)

CHLORIDE (Mercuric Thiocyanate Method)

1.0

SUMMARY OF METHOD
The sample is treated with ferric ammonium sulphate and mercuric
thiocyanate solutions. The chloride ion reacts with mercuric thiocyanate to
release the thiocyanate ion which combines with ferric ion to form red ferric
thiocyanate. The intensity of the colour is measured at a wavelength of
463nm.

2.0

RANGE
0.05 to 1.4mg/litre as C1.

3.0

APPARATUS

3.1

Spectrophotometer for use at 463nm.

3.2

Matched pair of 50mm cells.

4.0

REAGENTS

4.1

Water -

4.2

Ferric Alum Solution - Dissolve 5.0 g of ferrous ammonium sulphate

conforming to specifications Type II.

[Fe (NH4)2 (SO4)2.6H20] in 20m1 of water. Add 38m1 of nitric acid (sp gr
1.42) and boil to oxidise the iron and remove the oxides of nitrogen. Dilute to
100 ml with water.
4.3

Mercuric Thiocynate Solution Dissolve 0.30 g of mercuric thiocyanate (Hg


(CNS)2] in 100 ml of absolute methanol in an amber bottle. Allow to stand for
24 hours before using. This solution has a shelf life of 4 weeks.

4.3

Standard Sodium Chloride Solution (l ml = 0.0l mg chloride) - Dissolve


1.649g of Sodium Chloride (dried at 600C for 1 hour) in water and dilute to 1
litre (solution A). Dilute 10.0 m1 of solution A to 1 litre with water.

5.0

CALIBRATION

5.1

Prepare a series of standards by diluting 0, 0.5, 2.5, 5.0, 7.5, 10 and 14m1 of
the standard sodium chloride solution (1ml = 0.01mg chloride) to 100 ml with
water in volumetric flasks.
Proceed in accordance with section 6.0.
Prepare a calibration curve by plotting absorbance versus the concentration of
chloride in mg/litre.
PROCEDURE
Place 25m1 of sample in a 50ml glass stoppered cylinder.
Add 5.0 ml of ferric alum solution and 2.5ml of mercuric thiocyanate solution,
mix thoroughly and allow to stand for 10 minutes.

5.2
5.3
6.0
6.1
6.2

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6.3

7.0
7.1
7.2

8.0
8.1

9.0
9.1
9.2
9.3
9.4
10.0
10.1
10.2
10.3

10.4

10.5

Measure the intensity of colour at 463m, against the reagent blank, prepared
by using 25 m1 of water and following step 6.2, using 50 mm matched
absorption cells.
CALCULATIONS
Read the concentration of chloride ion in mg/litre directly from the calibration
curve prepared in accordance with section 5.0:
Calculate the chloride concentration in mg/litre as CaC03 as follows:
Chloride, mg/litre as CaCO3, = A x 1.41
Where A =
chloride concentration, mg/litre as Cl.
PRECISION
The precision of this method may be expressed as follows:
Sr = 0.054 X
So = 0.013 X
Where:
Sr =
overall precision, mg/litre.
So =
single operator precision, mg/litre.
X =
concentration of chloride ion determined, mg/litre.
INTERFERENCES
Bromides, iodides, cyanides, thiosulphate, hydrazine and nitrites interfere.
Morpholine concentrations greater than 6mg/litre may interfere.
Colour may also interfere depending upon its spectral absorbance.
Boric acid upto 13000mg / litre does not interfere.
NOTES
Reagent grade chemicals should be used for preparing all the reagents.
Mercuric salts are very poisonous. Due precautions should be observed when
using these salts. In the preparation of mercuric thiocyanate solution, a slight precipitate may
form and settle out after 24 hours. Only the clear, supernatent liquid must be
used.
Soak all new glassware in hot nitric acid (1+19) for several hours and in water
(halide free) between tests. Discard all glassware that appear etched or
scratched.
For best results, the temperatures of the standard solutions should be within
1.0 oC of the reagent blank, and the samples.

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XXIII)

CHLORIDE (Mercuric Thiocyanate Method, Modified, 2 to


100 micrograms/litre)

1.0

SUMMARY OF METHOD
A solution of lead nitrate is added to the sample followed by addition of
phosphate buffer. The resulting precipitation of lead phosphate co precipitates
the Chloride in the sample. The sample resulting precipitation of lead
phosphate is centrifuged and the supernatant liquid discarded. The precipitate
is dissolved in a ferric iron-mercuric thiocyanate reaction medium and the
Chloride is determined spectrophotometrically at 463nm.

2.0

RANGE
2 to 100 micrograms/litre as Cl.

3.0

APPARATUS

3.1

Spectrophotometer for use at 463nm

3.2.

Matched pair of 50mm Cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

Ferric Nitrate Solution - Dissolve 8.09 of ferric nitrate [Fe(NO 3)3.9H2O] in


about 400ml of water and add 58.5m1 of nitric acid (sp gr 1.42). Dilute to I
litre with water.

4.3

Lead Nitrate Solution - Dissolve 20g of lead nitrate [Pb(N0 3)2] in water and
dilute to 1 litre.

4.4

Mercuric Thiocyanate Solution - Dissolve 0.30 gm of mercuric thiocyanate


[Hg(SCN)2] in 100ml of methanol. Store in amber bottle. Allow to stand for
24 hours before using.

4.5

Standard Sodium Chloride Solution (l ml = 1 microgram of Chloride) Dissolve 1.649g of sodium chloride (dried at 600C for 1 hour) in water and
dilute to 1- litre (Solution A). Dilute 100m1 of Solution A to 1 litre (Solution
B). Finally dilute 10.0 m1 of Solution B to 1 litre. This solution should be
prepared fresh before use.

4.6

Sodium Phosphate Solution - Dissolve 16.7g of sodium dihydrogen phosphate


(NaH2PO4.H2O) and 16.2g of disodium hydrogen phosphate (Na 2HPO4.7H2O)
in water and dilute to 1 litre.

5.0

CALIBRATION

5.1

Prepare a series of standards by diluting 0, 1.0, 5.0, 10.0, 15.0, and 25.0 m1 of
Standard Sodium Chloride Solution (l ml = 1 microgram of chloride) to 250
m1 in 250 ml glass stoppered bottles.

5.2

Proceed in accordance with Section 6.0 (6.2 to 6.7).

5.3

Prepare a calibration curve by plotting absorbance versus concentration of


Chloride in mg/litre.
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6.0

PROCEDURE

6.1

Place 250 ml sample in a clean 250m1 glass stoppered bottle.

6.2

Add 5.0 ml of the lead nitrate solution to the bottle. Cap the bottle and mix.
Allow to stand for 2 minutes.

6.3

Add 5.0m1 of sodium phosphate solution and mix. Allow to stand for 5
minutes.

6.4

Centrifuge the capped bottle solution at 1500 rpm for 6 minutes. Decant the
supernatent liquid immediately after centrifuging.

6.5

Add 15.0 m1 of ferric nitrate solution and mix to dissolve the precipitate.

6.6

Add 1.0 m1 of mercuric thiocyanate solution and mix. Dilute to 25 m1 with


water. Allow to stand for 10 minutes.

6.7

Measure the absorbance, against reagent blank prepared by taking 250 m1


instead of sample and repeating the steps 6.2 to 6.6, at 463nm using 50mm
matched cells.

7.0

CALCULATIONS

7.1

Read the concentration of chloride in micrograms/litre directly from the


calibration curve prepared in accordance with Section 5.0.

7.2

Calculate the chloride concentration in microgram/ litre as CaCO3 as follows:


Chloride, micrograms/litre as CaCO3 = A x 1.41
Where: A =

chloride concentration, micrograms/litre as C1.

8.0

INTERFERENCES

8.1

See mercuric thiocyanate method (Section 9.0) for the determination of


Chloride.

9.0

NOTES

9.1

See mercuric thiocyanate method (Section 10.0) for the determination of


chloride.

9.2

Lead nitrate is very toxic. Due precautions should be observed when using
this chemical.

9.3

2 microgram / litre chloride represents 0.006 absorbance with respect to a


reagent blank when using 50mm matched cells.

9.4

For standard method of further low level determination of Cl, PO 4 and SO4 in
high purity water, ASTM D-5542 -94 may be referred.

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XXIV)
1.0

CHLORIDE (Silver Nitrate Method, 5mg/litre or more)


SUMMARY OF METHOD
The sample is adjusted to a pH of 8.3 and titrated with silver nitrate solution
using potassium chromate indicator to a brick red colour.

2.0

RANGE
Validated for a concentration range of 8.0 to 250 ppm of Cl.

3.0

REAGENTS

3.1

Water - conforming to specifications Type II.

3.2

Standard Silver Nitrate Solution (0.025N) - Dissolve 4.247g of silver nitrate


(dried to constant weight at 40C) in water and dilute to 1 litre. Standardize
against standard sodium chloride solution.
Standard Sodium Chloride Solution (0.025N) - Dissolve 1.461g of sodium
chloride (dried at 600C for 1 hour) in water and dilute to 1 litre.

3.3
3.4

Hydrogen Peroxide (30%).

3.5

Phenolphthalein Indicator Solution (10g/litre) - Dissolve l g of


phenolphthalein in 100m1 of ethanol (95%), methanol or isopropyl alcohol.

3.6

Potassium Chromate Indicator Solution (5%) - Dissolve 50g of potassium


chromate (K2CrO4) in 100 ml of water, and add silver nitrate until a slight red
precipitate is produced. Allow to stand for 24 hours in dark. Filter and dilute
to 1 litre.

3.7

Sodium Hydroxide Solution (10g/litre) - Dissolve l0 g of sodium hydroxide in


water and dilute to 1 litre.

3.8

Sulphuric Acid Solution (1+19) - Mix 1 volume of sulphuric acid (sp gr 1.84)
with 19 volumes of water.

4.0

PROCEDURE

4.1

Place 50 m1 of sample into a 125 ml conical flask.

4.2

If Sulphite is present, add 0.5 ml of hydrogen peroxide solution and mix for 1
minute,

4.3

Adjust the pH to the phenolphthalein


endpoint (pH 8.3), using sulphuric
acid solution, or sodium hydroxide solution.

4.4

Add 1 ml of potassium chromate indicator and mix.

4.5

Titrate with standard silver nitrate solution to a brick red (or pink) colour
which persisted through out the sample when illuminated with a yellow light.

4.6

Repeat 4.1 to 4.5 using 25m1 of sample diluted to 50ml with water.

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5.0

CALCULATIONS

5.1

Calculate the chloride ion concentration in the sample, in milligrams per litre,
as follows:
Chloride, mg/litre as Cl =

(V1-V2) x N x 70906
-------------------------------V

Where:

5.2

V1 =

milliliters of standard silver nitrate solution for the sample (4.1).

V2 =

milliliters of standard silver nitrate solution for the sample (4.6).

N =

normality of standard silver nitrate solution.

V =

milliliters of sample (4.1).

Calculate the chloride concentration in mg/litre as CaC03 as follows:


Chloride, mg/litre as CaC03 = A x 1.41
Where:
A =

6.0

chloride concentration, mg/litre as Cl.

PRECISION
The precision of this method may be expressed as follows:
ST =
So =
Where:
ST =
So =
X =

0.013X + 0.70
0.007X + 0.53
overall precision, mg/litre.
Single operator precision, mg/litre.
Concentration of Chloride ion determined, mg/litre.

7.0

INTERFERENCES

7.1

Bromide, iodide, and sulphide are titrated along-with the chloride.

7.2

Orthophosphate and polyphosphate interfere, if present, in concentrations


greater than 250 and 25mg/litre, respectively.

7.3

Sulphite and objectionable colour or turbidity must be eliminated.

7.4

Compounds which precipitate at pH 8.3 may interfere.

8.0

NOTES

8.1
8.2

Reagent grade chemicals should be used for preparing all the reagents.
If the titration requires more than 25m1 of silver nitrate in 4.5, use a smaller
sample size.
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XXV)

CHLORINE DEMAND

1.0

SUMMARY OF METHOD
A chlorinating solution of known concentration is applied in increasing
increments of chlorine concentration to a series of portions of the individual
sample of water to be tested. The residual chlorine is determined at succeeding
intervals of time.

2.0

APPARATUS

2.1

pH meter.

3.0

REAGENTS

3.1

Water - conforming to specifications Type III.

3.2

Calcium Hydroxide Solution (10.7g/litre) - Weigh 10.7g of 100% hydrated


lime [Ca(OH)2] and suspend in water. Dilute to 1 litre.

3.3

Calcium Hypochlorite Solution (l ml = 0.5 to 100mg available Chlorine) Dissolve 145g of calcium hypochlorite (70% available chlorine, by weight) in
water and make up to 1 litre. Allow to settle and decant the supernatent
solution containing approximately 100 mg available chlorine per ml. Dilute
with water to give 0.5 to 100 mg of available chlorine per ml. Standardize
prior to use in accordance with 3.4.

3.4

Chlorine Water (l ml = 0.5 to 3mg available chlorine) - Pass gaseous chlorine


through water until the solution contains 0.5 to 3.0 mg available chlorine per
ml. For standardization add l0ml of chlorine water to a flask containing l0ml
of acetic acid (1+1) and l0ml of potassium iodide solution (5%). Titrate with
0.l0N sodium thiosulphate solution using starch indicator.
V1 x 3.546
Available Chlorine, mg/litre
=
-----------------V
(V1 is milliliters of 0.10 N sodium thiosulphate solution used in the titration
and V is milliliters of chlorine water taken for titration.)

3.5

Hydrochloric Acid (1+1) - Mix


1.19) and water.

equal volumes of hydrochloric acid (sp gr

4.0

PROCEDURE

4.1

Establishing Test Conditions

4.1.1

Ascertain the range of pH, time of chlorine contact, and the chlorine
application concentration to achieve the objective of Chlorination from past
experience, from literature survey, by experimentation, or from plant
conditions.
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4.1.2

Determine the pH of each test and additions of chlorinating solutions such that
there is not less than five equal increments of the chlorine application
concentrations.

4.1.3

In each of a series of clean 1 litre glass containers, place a 500 ml portion of


the sample.

4.2

Trial Chlorination

4.2.1

To the first of the series of 500 ml portions of the samples, add the maximum
anticipated amount of chlorinating solution. Determine the pH of the solution.

4.2.2

Adjust the pH (see notes).

4.2.3

Allow the chlorinated sample to stand for a minimum predetermined time.


Determine total and free available residual chlorine. Withdraw successive
samples at selected time intervals to cover the estimated range of minimum to
maximum contact times.

4.3

Chlorination

4.3.1

On the basis of information obtained by the trial chlorination, add desired


increments of chlorinating solution to separate 500 m1 portions of the sample.
Determine the pH of each portion.

4.3.2

Adjust the pH (see notes)

4.3.3

Allow each portion of chlorinated sample to stand for a predetermined time.


Withdraw a portion of the sample and determine the total residual chlorine.

5.0

CALCULATIONS

5.1

Calculate the chlorine dosage, in mg/litre, for each increment of chlorinating


solution as follows:
Chlorine dosage, mg/litre = 2AB
Where:

5.2

A =

milliliters of chlorinating solution added to 500 m1 of sample.

B =

milligrams
of
available
of the chlorinating solution.

chlorine

per

milliliter

Determine the chlorine consumed, mg/litre, for each increment of chlorine


application as follows:
On log-log graph paper, plot, for a given chlorine application, temperature,
and pH, the chlorine consumed versus the contact time in hours. Determine
the value of the chlorine consumed at the intercept of the line with the coordinate corresponding to a contact time of 1 hour. Designate the value of this
intercept as K. Determine the slop of the line and designate as n. The straight
lines for each chlorine application at each temperature and pH are of the
general form:
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DT = KT t n
Where :
DT = Chlorine consumed at a given temperature. t = contact time in hours.
KT = Chlorine consumed after l hour, mg/litre at a given temperature.
n

= Slope of curve.

The chlorine consumed can be interpolated between test values by use


of the above expression.
6.0

NOTES

6.1

Chlorine requirement is the amount' of chlorine required to achieve under


specified conditions the objectives of chlorination. Chlorine consumed is the
amount of chlorine expressed in mg/litre, determined as the difference
between the calculated concentration of chlorine applied at zero time
and the residual concentration measured at any selected interval of time
thereafter.

6.2

When the anticipated chlorine requirement is less than 600mg/litre, use the
chlorinating solution which is to be used in ultimate plant treatment. When the
anticipated chlorine requirement is 600 mg/litre or more, use the appropriate
hypochlorite solution.

6.3

pH Adjustment

6.3.1

If the pH of the chlorinated sample is higher than the desired range, add
hydrochloric acid (1+1) to the chlorinated sample until the pH of sample
reaches the upper limit of the desired range.

6.3.2

If the pH of the chlorinated sample is lower than the desired range, discard
the sample and proceed with another series of sample portions, as follows: add
sufficient calcium hydroxide solution to bring the pH of the unchlorinated
sample portion to the midpoint of the desired pH range.

6.3.3

If the chlorinating solution is chlorine water, add an additional 0.l ml of


calcium hydroxide solution for each milligram of available chlorine to be
applied to the sample.

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XXVI)
1.0

CHLORINE RESIDUAL (DPD Method, 0.02 to 4.0mg/litre)


SUMMARY OF METHOD
In the absence of iodide ion, free chlorine reacts with para-amino
diethylaniline (NN-Diethyl-p-Phenylene Diamine abbreviated as DPD) to
produce a red colour. Stepwise colour change is carried out to identify
monochloramine, dichloramine, and nitrogen trichloride. The individual
fractions are determined by titration with ferrous ammonium sulphate.

2.0

RANGE
Upto 4 mg/litre with minimum detection limit of 18 micrograms/litre.

3.0

REAGENTS

3.1

Water - conforming to specifications Type III, further treated to be free of


chlorine demand (see notes).

3.2

DPD Reagent - Dissolve 0.115g DPD sulphate, [NH 2C6H4


N(C2H5)2).H2SO4.5H2O), in 50m1 of
water containing 8m1 of sulphuric
acid (1+3) and 0.2g of EDTA disodium salt. Dilute to 100m1 and store in a
brown coloured glass bottle. Prepare fresh after every two weeks or discard it
when discoloured.

3.3

Phosphate Buffer Solution - Dissolve 2.4g disodium-hydrogen phosphate


(Na2HPO4) and 4.6 of potassium, dihydrogen phosphate (KH2PO4) in 50ml of
water. Add l0ml of EDTA disodium salt (8 g/litre) and make up to 100m1.
Add 1 drop of mercuric chloride (20 mg/litre).

3.4

Sodium Arsenite Solution- Dissolve 0.5 g sodium. arsenite (NaAsO2) in 100


m1 of water.

3.5

Potassium Iodide, crystalline.

3.6

Potassium Iodide solution (5g/litre)- Dissolve 0.5g of potassium iodide in


water and dilute to 100m1. Store in a brown coloured glass bottle. Discard
when yellow colour develops.

3.7

Ferrous Ammonium Sulphate Solution (1m1=1mg chlorine)- Dissolve 1.106g


of ferrous ammonium sulphate [FeSO4(NH4)2SO4.6H2O] in water containing l
ml of sulphuric acid (1+3) and make up to 1 litre. Standardize against
potassium dichromate. (for standardization see notes). .

3.8

Potassium Dichromate Standard Solution (0.003N) - Dissolve 0.147g of


potassium dichromate (K2Cr2O7), previously dried at 103C for 2 hours, in
water and dilute to 1 litre.

3.9

Phenanthroline - Ferrous Sulphate Indicator Solution - Dissolve 1.48g of 1, 10


- phenanthroline monohydrate and 0.70g of ferrous sulphate (FeSO4.7H2O) in
100 m1 of water.
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4.0

PROCEDURE

4.1

Free Chlorine

4.1.1

Place 5.0 m1 of DPD solution and 5.0m1 of phosphate buffer in a 250m1


titration flask.

4.1.2

Add 100 ml of sample and mix.

4.1.3

Titrate with ferrous ammonium sulphate solution until the red colour is
discharged.

4.1.4

Record the volume of ferrous ammonium sulphate in ml used in the titration


as A.

4.2

Monochloramine (NH2C1)

4.2.1

To the solution after titration for free chlorine (4.1) add 2 drops of potassium
iodide solution (5g/litre) and continue the titration.

4.2.2

Record the total volume of ferrous ammonium sulphate in ml as B. For free


chlorine + monochloramine)

4.3

Dichloramine (NHC12)

4.3.1

To the solution after titration for monochloramine (4.2) add about l g of


potassium iodide and mix rapidly to dissolve, and allow to stand for 2
minutes.

4.3.2

Continue titration with ferrous ammonium sulphate.

4.3.3

Record the total volume of ferrous ammonium sulphate in ml as C (for free


chlorine + monochloramine + dichloramine).

4.4

Nitrogen Trichloride (NC13)

4.4.1

Place a small crystal of potassium iodide in a 250m1 titration flask, add


100m1 of sample and mix.

4.4.2

Transfer the contents (4.4.1) to another flask containing 5m1 each of buffer
solution and DPD solution.

4.4.3

Titrate rapidly with ferrous ammonium sulphate solution.

4.4.4

Record the volume of ferrous ammonium sulphate in ml as D.

4.5

Total Available Chlorine

4.5.1

Place 1g of potassium iodide in a 250m1 titration flask, add 100m1 of sample


and mix.

4.5.2

Transfer the contents (4.5.1) to another flask containing 5 m1 each of buffer


solution and DPD solution and allow to stand for 2 minutes.

4.5.3

Titrate with ferrous ammonium sulphate solution and record the volume in ml
as V1.

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5.0
5.1

CALCULATIONS
Total available, chlorine, mg/litre as Cl =
Where:
V1 =
V =

5.2

V1
------------- x 100
V

milliliters of ferrous ammonium sulphate used for total available


chlorine.
milliliters of sample,

The following table may be used to determine various constituents:

C-D

TITRE VALUE

NC1 3 -ABSENT

NC1 3 -PRESENT

Free Chlorine

Free Chlorine

B-A

NH 2 C1

NH 2 C1

C-B

NHC1 2

NHC1 2 +1/2 NC1 3

Free chlorine+1/2 NC1 3

2 (D-A)

NC1 3
NHC1 2

C-D

6.0

INTERFERENCES

6.1

Copper and dissolved oxygen interfere in measurement, however, this is


suppressed by using ETDA in phosphate buffer.

6.2

Nitrite nitrogen up to 5mg/litre does not interfere.

6.3

For accurate results, careful pH control is essential. At the proper pH of 6.2 to


6.5, the red colour produced may be titrated to sharp colourless endpoints. ,

6.3.1

The titration should be carried out as soon as the red colour is formed in each
step.

6.3.2

Too low a pH in the first step will tend to make the monochloramine show in
the free-chlorine step and the dichloramine in the monochloramine step.

6.3.3

Too high a pH may cause dissolved oxygen to give a colour.

6.4

Oxidising manganese gives a colour leading to erroneous measurement. To


correct for this, place 5.0m1 buffer solution, one small crystal of potassium
iodide and 0.5 m1 sodium Arsenite solution in a titration flask. Add 100m1-of
sample and mix. Add 5.0 m1 of DPD solution, mix and titrate with standard
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ferrous ammonium sulphate until red colour is discharged. Subtract the
reading from 'A' as given in the procedure or from 4.5 as the case may be.
7.0

NOTES

7.1

Reagent grade chemicals should be used for preparing the reagents.

7.2

For preparing chlorine demand free water, add approximately 20mg/litre of


available chlorine to type III reagent grade water. Allow the chlorinated water
to stand about 1 week in the absence of sunlight until no residual chlorine
remains.

7.3

For standardizing ferrous ammonium sulphate (1.106g/ litre), place 25m1 of


0.003N potassium dichromate in a 500 ml titration flask and dilute to about
250 ml. Add 20 ml of sulphuric acid (sp gr 1.84) and allow the solution to
cool. Titrate with ferrous ammonium phenanthroline-ferrous sulphate
indicator.
Calculate the strength of ferrous ammonium sulphate solution as follows:
Strength (g / litre) of ferrous ammonium sulphate solution,
=

V1 X N1
--------------V

x 392

Where:
V1 =

milliliters of potassium dichromate solution.

N1 =

normality of potassium dichromate solution.

V =

milliliters of ferrous ammonium sulphate solution.

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XXVII) CHLORINE, RESIDUAL (Starch Iodide Thiosulphate Method)


1.0

SUMMARY OF METHOD
The sample is treated with potassium iodide at a pH between 3.0 and 4.0. The
librated iodine which is stoichiometrically proportional to the total chlorine
present is titrated with standard solution of sodium thiosulphate.

2.0

RANGE
0.04mg/litre or more, as Cl

3.0

REAGENTS

3.1

Water - conforming to specifications Type III, further treated to be free of


chlorine demand (see notes).

3.2

Acetic Acid, glacial (99.5%).

3.3

Potassium Iodide, crystalline.

3.4

Sodium Thiosulphate Standard Solution (0.1N)- Dissolve 25g of sodium


thiosulphate (Na2S203.5H20) in 500m1 of freshly boiled and cooled water, and
add 0.ll g of sodium carbonate (Na2C03). Dilute to 1 litre and allow to stand
for 24 hours. Standardize against potassium dichromate (see notes).

3.5

Sodium Thiosulphate Standard solution (0.01N)- Dilute 25m1 of 0.1N sodium


thiosulphate solution (3.4) to 250 m1 in a volumetric flask.

3.6

Starch Indicator Solution - Make a paste of l g of soluble starch and mix into 1
litre of boiling water. Add 20 g of potassium hydroxide, mix, and allow to
stand for 2 hours. Add 6 m1 glacial acetic acid, mix, and add sufficient
hydrochloric acid (sp gr 1.19) to adjust the pH to 4.0 (check. with a narrow
range pH paper). This has a shelf life of 1 year.

4.0

PROCEDURE

4.1

For residual chlorine concentrations of l0 mg/litre or less, use a 200 m1


sample, and for concentrations above l0 mg/litre, use proportionately less
sample.

4.2

Place 5 m1 or other required volume of glacial acetic acid in a 500 m1


titration flask in order to reduce the pH of the sample between 3.0 to 4.0.(To
be checked before hand with narrow range pH paper)

4.3

Add l g of potassium iodide followed by required amount of the sample to be


titrated. Mix well.

4.4

Titrate with sodium thiosulphate solution using starch as indicator.

4.5

Carry out a blank determination using water instead of sample:


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5.0

CALCULATIONS

5.1

Calculate the concentration of residual chlorine in mg/litre as C1, as follows:


Residual Chlorine, mg/litre as C1 =

(V1- V2) X N X 35.45


---------------------------------------V

Where:
V1 =

milliliters of sodium thiosulphate (0.01N) used in the titration for


the sample.

V2 =

milliliters of sodium thiosulphate (0.01N) used in the blank


titration.

N =

normality of sodium thiosulphate solution.

V=

milliliters of sample.

6.0

INTERFERENCES

6.1

Free available chlorine cannot be determined quantitatively when organic


matter is present that rapidly and continuously consume free available
chlorine.

6.2

Manganic manganese, in concentration as low as 1.0 mg/litre, liberates iodine


from iodide at a pH of 4.0.

6.3

Ferric iron, ferricyanide, and nitrites, in concentrations up to 1000mg/litre do


not interfere at a pH of 4.0.

6.4

Excessive colour and turbidity also interfere.

7.0

NOTES

7.1

Reagent grade chemicals should be used for preparing the reagents.

7.2

A suggested method for preparation of chlorine demand free water is to add


approximately 20mg/litre of available chlorine to Type III reagent grade water.
Allow the chlorinated water to stand about 1 week in the absence of sunlight
until no residual chlorine remains.

7.3

Test should be made as soon as possible after collection of the sample (not
more than 5 minutes) because the residual chlorine may diminish with time,
due to chlorine demand of the-sample.

7.4

For standardizing sodium thiosulphate solution (0.1N), pulverize 2g of


potassium dichromate, transfer to a platinum dish, and dry at 120C for 4
hours. Cool in a desiccator. Weigh accurately 0.21+0.0lg of the dried
potassium dichromate, and transfer to a 500m1 glass stoppered
conical flask. Add 100m1 of water, swirl to dissolve, remove the
stopper, and quickly add 3 g of potassium iodide, 2g of sodium
bicarbonate add 5 m1 of hydrochloric acid (sp gr 1.19): Stopper the flask
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quickly. and allow to stand for 10 minutes in dark. Titrate with sodium
thiosulphate solution until the solution is yellowish-green. Add 2m1 of starch
solution (10g/litre) and continue the titration to the disappearance of the blue
colour.
Calculate the normality of the sodium thiosulphate solution, as follows:
N=

W
--------------------0.04904 x V

Where:
N =

normality of sodium thiosulphate solution.

W =

grams of potassium dichromate used.

V =

milliliters of sodium thiosulphate solution required for titration of


the solution.

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XXVIII) COPPER (Neocuprine method, 2 to 1000 micrograms/ litre Cu)


1.0

SUMMARY OF METHOD
The copper (II) is reduced to Cu (I) with hydroxylamine-hydrochloride. The
pH of the aqueous phase is adjusted to 5 with sodium acetate buffer. The
cuprous ion is then reacted with neocuprine (2, 9 - dimethyl -1, 10 phenanthroline) and the yellow complex extracted either with chloroform or
isoamyl alcohol. The intensity of colour, when extracted with chloroform, is
measured at 457nm and at 454nm when extracted with isoamyl alcohol.

2.0

RANGE
20 to 1,000

micrograms/litre Cu (l0 mm cell).

2 to 150 micrograms/litre Cu (50 mm cell).


2 to 100 micrograms/litre Cu (100 mm cell).
3.0

APARATUS

3.1

Spectrophotometer for use at 454 and 457nm.

3.2

Matched pairs of l0 mm, 50 mm & 100 mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type I.

4.2

Copper Stock Solution (200mg/litre) - Place 0.200g electrolytic grade copper


in a 250m1 beaker, add 3m1 of water and 3ml of nitric acid (sp gr 1.42).After
the metal has completely dissolved, add l ml sulphuric acid (sp gr 1.84) and
evaporate on a hot plate to nearly dryness. Dissolve the residue in water and
dilute to 1 litre.

4.3

Copper Standard Solution (2mg/litre) - Dilute 100m1 of copper stock solution


(4.2) to 1 - litre. Again dilute 100 m1 of this diluted solution to 1 litre.

4.4

Hydrochloric Acid (sp gr 1.19).

4.5

Hydroxylamine Hydrochloride Solution (20%) - Dissolve 40 g of


hydroxylamine hydrochloride (NH2OH.HC1) in water and dilute to 200 m1.
Remove traces of copper from this solution by treating with neocuprine
solution and extracting with chloroform or isoamyl alcohol.

4.6

Neocuprine Solution (1 g/litre) - Dissolve 0.l g of neocuprine in 50 m1 of


isopropyl alcohol. Dilute to 100 m1 with water.

4.7

Sodium Acetate Solution (275g/litre) - Dissolve 55g of sodium acetate


trihydrate (NaC2H3O2.3H2O) in water and dilute to 200 m1. Remove traces of
copper from this solution by treating with hydroxylamine hydrochloride,
neocuprine and extracting with chloroform or isoamyl alcohol.
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4.8

Chloroform Solvent - Mix 9 volumes of chloroform (CHCl3) with one volume


of isopropyl alcohol.

4.9

Isoamyl Alcohol, copper free.

4.10

Isopropyl Alcohol, copper free.

5.0

CALIBRATION

5.1

Prepare a series of standards (at least five concentrations) to cover the


expected range of copper concentrations by diluting appropriate volumes of
copper standard solution (4.3, l ml = 2 micrograms Cu) as follows:

5.1.1

Place the required volumes of copper standard solution (4.3) in 250m1


separatory funnels.

5.1.2

Add 0.4 ml hydrochloric acid (sp gr 1.19) to each funnel and add water to
make 200m1.

5.1.3

Prepare a blank (zero standard) by diluting 0.4 m1 hydrochloric acid (sp gr


1.19) to 200 m1 with water.

5.1.4

Proceed in accordance with section 6.0 (6.2 to 6.7) and measure the
absorbance of each individual standard.

5.1.5

Use the organic liquid from the blank as a reference solution for the initial
spectrophotometer setting.

5.1.6

Prepare a calibration curve by plotting the absorbance of the standards against


the copper' content in micrograms.

6.0

PROCEDURE

6.1

Transfer 200 ml of acidified (with 0.4m1 hydrochloric acid, sp gr 1.19) and


unfiltered sample (for total. copper) or 200m1 of filtered (through 0.45 micron
filter) and acidified sample (for dissolved copper) into a 250m1 separatory
funnel.

6.2

Add l ml of hydroxylamine hydrochloride solution and mix.

6.3

Add l0 ml of sodium citrate solution and mix.

6.4

Add 10 m1 of neocuprine solution and shake the funnel and contents for 1
minute.

6.5

Add 20 m1 of chloroform solvent shake vigorously for at least 1 minute and


allow to stand for 5 minutes.

6.6

Transfer the organic layer into a dry 50 m1 Erlenmeyer flask and add 20 ml of
isopropyl alcohol to clear the solution. Make upto 50 m1 with chloroform
solvent or isolamyl alcohol depending on the extractant used.

6.7

Measure the absorbance of the organic solution (6.6) at 457 nm (when


chloroform solvent is the extractant) using a mixture of 25 m1 of chloroform
solvent and l0 ml of isopropyl alcohol as a reference solution for initial
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spectrophotometer setting or at 454 nm (when isoamyl alcohol is the
extractant) using a mixture of 25 m1 of isoamyl alcohol and l0 ml of isopropyl
alcohol as a reference solution.
6.8

Carry out a blank determination on 200m1 of water, with all reagents and
extracting in the same manner as for the sample.

7.0

CALCULATIONS

7.1

Calculate the concentration of copper in micrograms per litre in the sample, as


follows:
Copper, micrograms/litre, as Cu = W X 1000
V
Where:
W =

micrograms of copper determined in accordance with sections 5.0


and 6.0.

V =

milliliters of sample used.

8.0

PRECISION

8.1

The overall precision of this method may be expressed as follows:


ST =

0.008 X + 0.9

Where:
ST =

overall precision.

X =

determined concentration of copper, micrograms/litre.

9.0

INTERFERENCES

9.1

Cr interferes when its conc. exceeds 5 times of Cu. The interference from
organic matter, sulphide, cyanide and chromium can be eliminated by as
follows:
If the interfering substances are present add 1 ml of con.HNO 3. Evaporate the
sample to dense white sulphur trioxide fumes on a hot plate. Repeat the
treatment with 5 ml of con.HNO3 and 5 ml of H2O2 and evaporate the solution
to complete dryness. Dissolve the residue with 80 ml of water, boil, cool and
filter. Adjust the pH within 4 to 6 with dropwise addition of ammonium
hydroxide. Add 0.2 ml of hydrochloric acid and dilute to 100 ml. If no
interfering substance is present, just boil the acidified sample and cool.

10.0

NOTES

10.1

Reagent grade chemicals should be used for preparing the reagents.

10.2

A polythene bottle must be used for sample collection. Hydrochloric acid (sp
gr 1.19) should be added to the filtered sample for total recoverable copper
immediately at the time of collection. The volume of acid should be sufficient
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to neutralize the sample to pH 4 (using narrow range pH paper) and then add
2.0 m1 for each litre of sample.
10.3

Soak all new glassware in hot nitric acid (1+9) for several hours. To ensure the
conditioning of glassware, rinse it with water and run a copper determination
(blank) on copper free water. Repeat until the copper value is less than 4
micrograms per litre. After carrying out the test, always rinse the glassware
with organic solvent, followed by water. Always keep the glassware soaked in
nitric acid (1+9) until used again. Discard any glassware that appears etched
or scratched.

10.4

If the sample contains more than maximum concentration of copper specified


in the range, a smaller size sample should be diluted to 200m1 with. copper
free water containing 0.4m1 of hydrochloric acid (sp gr 1.19) per 200 m1 of
solution.

10.5

Normally, 2m1 of neocuprine solution is sufficient in a test. 4 m1 of the


reagent should be used when the sample contains more than 100 micrograms
of copper or when it is high in heavy metal ions.

10.6

The blank determination made for calibration in section 5.0 compensates for
copper in both the reagents and 200 m1 of water. When the test water contains
less than 10 micrograms/litre of copper, it is important (in 6.7) to compensate
only for the copper in the reagents and not to include the few micrograms per
litre of copper found in copper free water.
The reagent blank is found, by extracting the copper, from two 200 m1
aliquots of copper free water. In one aliquot the normal values of reagents i.e.
hydrochloric acid, hydroxylamine hydrochloride, sodium acetate and
neocuprine solution are used and in the other aliquot twice the normal values
of reagents are used. The organic extract from the normal blank is used as
reference solution for initial spectrophotometer setting and the blank obtained
from double reagents is measured against the normal blank. The correct value
for copper is found in the unknown sample (6.7) by subtracting from it the
value for the reagent blank.

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XXIX) COPPER (Atomic Absorption Spectrophotometry Method)


1.0

SUMMARY OF THE METHOD


Copper is determined by an atomic absorption spectrophotometer used in
conjunction with a graphite furnace. A sample is placed in a graphite tube,
evaporated to dryness, charred and atomized. Since graphite furnace uses the
sample much more efficiently than flame atomization, the detection of low
concentration of elements in small sample volume is possible. The absorption
signal generated during atomization is recorded and compared with standards.
Dissolved copper is determined on a filtered sample with no pretreatment.
Total recoverable copper is determined following acid digestion and filtration.
Because chloride interferes with furnace procedure of some metals, the use of
hydrochloric acid in any digestion/solubilization process is to be avoided. If
suspended material is not present, this digestion and filtration may be omitted.

2.0

APPARATUS
Atomic Absorption Spectrophotometer , for use at 324.7nm with background
correction. The manufacturers instruction should be followed for all
instrumental parameters.
Copper cathode lamp: A single element lamp is preferred but multielement
lamps may be used.
Graphite furnace : It must be capable of reaching temperatures sufficient to
atomize the element of interest.
Graphite tubes : It should be compatible with the furnace device. Pyrolytically
coated graphite tubes are recommended.
Data storage and reduction device: This shall be utilized for collection,
storage, reduction and problem recognition. Automatic sampling is
recommended.
Inject a measured aliquot of sample into the furnace device following the
direction as provided by the particular instrument manufacturer.

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XXX)

EQUIVALENT AND FREE MINERAL ACIDITY

1.0

SUMMARY OF METHOD

1.1

Equivalent Mineral Acidity - The sample is passed through a column


containing strong acid cation resin in hydrogen form and effluent produced is
titrated with a standard solution of sodium hydroxide using screened methyl
orange as indicator.

1.2

Free Mineral Acidity - The sample is titrated with a standard solution of


sodium hydroxide using screened methyl orange as indicator.

2.0

REAGENTS

2.1

Water - conforming to specifications Type II.

2.2

Strong Acid cation Resin, Bead Type.

2.3

Hydrochloric Acid (2N)-Dilute 166m1 of hydrochloric acid (sp gr 1.19) to 1


litre with water.

2.4

Sodium Hydroxide Solution (0.02N) - Dissolve 0.8g of sodium hydroxide in


water and dilute to 1 litre. For standardization (see notes).

2.5

Screened Methyl Orange Indicator Solution - Dissolve 0.02g of methyl orange


in a mixture of 28 m1 of methylated spirit and 25 m1 of water. (Solution A).
Dissolve 0.28g xylene cyanol FF in a mixture of 25m1 of methylated spirit
and 25m1 of water (Solution B). Mix Solution A and Solution B.

3.0

PROCEDURE

3.1

Equivalent Mineral Acidity (EMA)

3.1.1

Transfer 50m1 of strong acid cation resin into a cation column. Backwash
with water maintaining 50 percent expansion of the bed. Continue
backwashing until the effluent is clear.

3.1.2

Pass 250 m1 hydrochloric acid (2 N) at a rate of 3 to 4 m1 per minute. Rinse


with water until the effluent is alkaline to screened methyl orange.

3.1.3

Pass sample through the column. Reject first 50m1 and collect 100m1 sample
in a 500 m1 conical flask.

3.1.4

Add 2-3 drops of screened methyl orange indicator and titrate with standard
sodium hydroxide solution till the sample turns smoky grey.

3.2

Free Mineral Acidity (FMA)

3.2.1

Place 100m1 of sample in a 500 m1 conical flask.

3.2.2

Add 2-3 drops of screened methyl orange indicator and titrate with standard
sodium hydroxide solution till the sample turns smoky grey.

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4.0

CALCULATIONS

4.1

Calculate the equivalent mineral acidity, mg/litre as CaCO3, as follows:


V1 X N X 50,000
EMA, mg/litre as CaCO3 = ----------------------V
Where:

4.2

V1

milliliters of standard sodium hydroxide solution.

normality of sodium hydroxide solution.

milliliters of sample.

Calculate the free mineral acidity, mg/litre as CaCO3 as follows:


FMA, mg/litre as CaCO3 =

V2 X N X 50,000
----------------------V

Where:
V2 =

milliliters of standard sodium hydroxide solution.

N =

normality of sodium hydroxide solution.

V =

milliliters of sample.

5.0

NOTES

5.1

Reagent grade chemicals should be used for preparing the reagents.

5.2

For standardization of 0.02N sodium hydroxide solution place 0.19 + 0.005g


of potassium hydrogen phthalate (dried at 120C for 2 hours) in a 500 m1
conical flask. Add 100 m1 of water and 3 drops of phenolphthalein indicator
(1% solution in ethanol) and titrate with sodium hydroxide solution.
Calculate the normality of sodium hydroxide solution as follows:
N

W
----------------(0.20423xV)

Where:
N =

normality of sodium hydroxide solution.

W =

grams of potassium hydrogen phthalate.

V =

milliliters of sodium hydroxide solution consumed in the titration.

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XXXI) FLUORIDE (SPANDS Dye Method)


1.0

SUMMARY OF METHOD
The fluoride is distilled from the sample as hydrofluorosilicic acid which is
then treated with SPANDS dye. Decrease in the color-intensity of SPANDS
dye which is proportional to the concentration of fluoride is measured at a
wavelength of 570nm.

2.0

RANGE
0.00 to 1.40 mg/litre as F.

3.0

APPARATUS

3.1

Distillation Assembly - consisting of a 1-litre round bottom borosilicate


boiling flask, an adaptor with a thermometer opening, a connecting tube, a
condenser, and a thermometer reading to 200C.

3.2

Spectrophotometer for use at 570 nm.

3.3

Matched pair of l0mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type I.

4.2

Zirconyl Acid Reagent - Dissolve 0.133g of Zirconyl chloride octahydrate


(ZrOC12.8H2O) in about 25 m1 of water. Add 350 m1 of hydrochloric acid (sp
gr 1.19) and dilute to 500m1 with water.

4.3

SPANDS solution - Dissolve 0.958 g of SPANDS reagent (Sodium 2 (Parasulphophenylazo) - 1,8 - dihydroxy - 3,6 - naphthalene disulphonate] in
water and dilute to 500 m1.

4.4

Acid Zirconyl - SPANDS Reagent - Mix equal volumes of Zirconyl acid


reagent and SPANDS solution.

4.5

Reference Solution - Add l0 ml of SPANDS solution (4.3) to 100 m1 of water.


Dilute 7m1 of hydrochloric acid (sp gr 1.19) to l0 ml and add to the diluted
SPANDS solution. Alternatively, 0.00 mg F standard (Zero Standard) can be
used for instrument adjustment.

4.6

Sodium Fluoride Standard Solution (l ml = 0.0lmg F) - Dissolve 0.2210 g of


sodium fluoride (NaF) in water and dilute to 1 litre. Dilute 100m1 of this
solution to 1 litre with water. Store in borosilicate glass or polythene bottle.

4.7

Sodium Arsenite Solution - Dissolve 2g of sodium arsenite (NaAs02) in water


and dilute to 1 litre.

4.8

Sulphuric Acid (sp gr 1.84).

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5.0

CALIBRATION

5.1

Prepare a series of standards in the range from 0 to 1.40 mg/litre by diluting


standard sodium fluoride solution (l ml = 0.01 mg F) to 50 m1 with water in a
volumetric flask.

5.2

If the sample to be analyzed contains free chlorine, add 2 drops of sodium


arsenite solution to each standard.

5.3

Proceed in accordance with section 6.0 (6.2.1, 6.2.3 and 6.2.4).

5.4

Prepare a calibration curve by plotting absorbance versus the concentration of


fluoride in mg/litre.

6.0

PROCEDURE

6.1

Distillation

6.1.1

Place 400 m1 of water in the distillation flask and add 200 m1 of sulphuric
acid (sp gr 1.84). Assemble the apparatus and heat the solution to 180C.
Discard the distillate.

6.1.2

Cool the solution to below 100 oC, add slowly 300 m1 of sample, mix
thoroughly and distill at 180C.

6.1.3

Stop the distillation when the volume of distillate reaches 300m1.

6.2

Analysis

6.2.1

Place 50 m1 of the distillate (or sample, if distillation not required) in a 100


m1 polythene bottle.

6.2.2

If the sample contains free chlorine, add 1 drop of sodium arsenite solution for
each 0.l mg of chlorine present. Add 2 drops of sodium arsenite solution in
excess.

6.2.3

Add 10.0 m1 of acid Zirconyl - SPANDS reagent and mix.

6.2.4

Measure the absorbance against reference solution (4.5) at 510 nm using l0


mm matched absorption cells.

7.0

CALCULATIONS

7.1

Calculate the concentration of fluoride in the sample, in mg/litre, directly from


the calibration curve prepared in accordance with section 5.0.

7.2

Calculate the fluoride concentration in mg/litre as CaC03, as follows: Fluoride


concentration, mg/litre as CaCO3 = A X 2.63
Where:
A = Fluoride concentration, mg/litre as F:

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8.0

PRECISION

8.1

The precision of this method was found to be 0.089 at a concentration of


0.81mg/litre of F.

9.0

INTFRFERENCES

9.1
9.1.1

In sample distillation, the following interferences may be experienced:


Aluminium in excess of 300 mg/litre, colloidal silica in excess of 400 mg/litre,
and silica as silicate in excess of 300 mg/litre will retard fluoride recovery.
Fluoride in excess of 3.0 mg/litre will hold up in the condenser to a certain
extent causing low results and act as a positive interference for subsequent
samples of lower fluoride content. In such cases, the condenser should be
flushed with 300 to 400 m1 of water and added to the distillate.
Chloride concentrations greater than 2500 mg/litre may distil over and act as
an interference in the subsequent colour reaction. To eliminate chloride
interference, add silver sulphate (Ag2S04) to the distillation mixture (6.1.2) at
a rate of 5 mg/litre of chloride.
Samples containing oily matter should be extracted initially with a suitable
solvent to remove the oily material and then warmed on a steam bath to
remove traces of the solvent.
The Table 1 lists the interferences of various constituents on the SPANDS
procedure.
TABLE 1

9.1.2

9.1.3

9.1.4

9.2

Concentration o Interfering Substances Causing 0.l mg/litre Error at 1:0 mg


F/litre.
a. Residual chlorine must be removed with arsenite reagent.
b. Colour and turbidity must be absent.
No.

Constituent

Concentration (mg/litre)

Type of Error

1.

Alkalinity (as CaCO3)

5000

Negative

2.2

Aluminium (A1+3)

0.1*

Negative

3.33 3

Chloride (CI-)

7000

Positive

4.44 4

Iron (Fe+3)

10

Negative

Positive

16

Positive

200

Positive

5.5 5
6.66

7.7

Hexametaphosphate(NaPO3)6
.
Phosphate (PO4-3)
Sulphate (SO4-2)

* Immediate reading. Tolerance increases with time; after 2 hours 3.0.


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10.0

NOTES

10.1

Reagent grade chemicals should be used for preparing all the reagents.

10.2

Distillation (6.1) may be omitted without loss of precision if the concentration


of interfering substances are below the values given in Table 1 (9.2).

10.3

The SPANDS solution (4.3) is stable indefinitely if stored in a well sealed


bottle protected from sunlight.

10.4

A new standard curve (5.0) should be prepared whenever a new batch of


SPANDS reagent is prepared.

10.5

The distillation temperature (6.1.2) should not exceed 180C.

10.6

The acid water distillation solution (6.1.1) may be used repeatedly until the
build up of interfering materials equal the concentration given in section 9.0.

10.7

The 50m1 distillate or sample (6.2.1) should contain less than 0.028 mg of
fluoride. If fluoride is more than 0.028 mg, a smaller aliquot diluted to 50 m1
should be used.

10.8

If interference from the aluminium is suspected, a correction may be made by


delaying the absorbance reading (6.2.4). A delay of 2 hours will provide self
correction of 3.0 mg/litre of aluminium.

10.9

The use of reference solution (4.5) permits the analyst to adjust the instrument
so that the meter reading of the blank may be used on the optimum portion of
the meter scale, 0.0 to 0.8 absorbance units.

10.9.1

Instrument can also be adjusted to some convenient point using the 0.00 mg F
standard. The fixed reading of 0.80 absorbance is suggested.

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XXXII) HARDNESS (TOTAL, CALCIUM AND MAGNESIUM)


1.0

SUMMARY OF METHOD
For the determination of total hardness the sample pH is adjusted to 10 with
ammonium chloride - ammonium hydroxide buffer solution and then titrated
with EDTA (ethylene diamine tetraacetic acid or its sodium salt) using
Eriochrome Black-T as indicator. For calcium hardness determination, the
sample pH is adjusted to 12 to 13 with sodium hydroxide and then titrated
with EDTA using ammonium purpurate as indicator. Magnesium is
determined by difference.

2.0

RANGE
1 to 1000mg/litre of Ca plus Mg expressed as Ca.

3.0

REAGENTS

3.1

Water - conforming to specifications Type II.

3.2

Buffer Solution - Dissolve 67.6g of ammonium chloride in 200 m1 of water.


Add 570 m1 of ammonium hydroxide (sp gr 0.90) and mix. Add 5.0 g of
magnesium salt of EDTA and dilute to 1 litre with water.

3.3

Sodium Hydroxide Solution (8% w/v).

3.4

Ammonium Purpurate - Mix thoroughly 1.0g of ammonium purpurate with


200 g of sucrose.

3.5

Eriochrome Black-T - Dissolve 0.4g


of
Eriochrome
100m1 of water. This solution has a shelf life of 1 week.

Black-T

in

Alternatively a dry powder mixture of 0.5g of Eriochrome Black-T and 100g


of sodium chloride can be used. This mixture has a shelf life of 1 year.
3.6

Calcium Standard Solution (l ml = 0.4mg Ca) Suspend 1.000g of calcium


carbonate (dried at 180C for 1 hour) in 600m1 of water and dissolve with a
minimum of dilute hydrochloric acid. Dilute to 1 litre with water.

3.7

EDTA standard Solution (0.01M, l ml = 0.4mg Ca or 0.243 mg Mg) - Dissolve


3.72 g of Na2EDTA
dihydrate [dried overnight over sulphuric acid (sp gr
1.84) in a desiccator] in water and dilute to 1 litre. Standardize against
standard calcium solution (3.6).

4.0

PROCEDURE

4.1

Total Hardness (Ca plus Mg)

4.1.1

Pipet 50.0 m1 of sample into a titration flask and adjust the pH to 7-10 by the
dropwise addition of ammonium hydroxide (sp gr 0.90).

4.1.2

Add l ml of buffer solution.


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4.1.3

Add 4 to 5 drops of Eriochrome Black T indicator or approximately 0.2g of


powdered indicator.

4.1.4

Titrate with EDTA standard solution. The end point will be indicated by
colour change from pink to clear blue.

4.1.5

Record the volume of EDTA solution required in the titration.

4.1.6

Determine a reagent blank correction by similarly titrating 50.0 m1 of water


including all added reagents.

4.2

Calcium Hardness

4.2.1

Pipet 50.0 m1 of sample into a titration flask and add l ml of sodium


hydroxide solution.

4.2.2

Add 0.2 g ammonium purpurate indicator and mix.

4.2.3

Titrate with EDTA standard solution. The endpoint will be indicated by colour
change from pink to purple.

4.2.4

Record the volume of EDTA solution required to titrate the calcium.

4.2.5

Determine a reagent blank correction by similarly 50.0m1 of water including


all added reagents.

5.0

CALCULATIONS
V1 x M
------------------------- x 10,000
V

5.1

Total hardness, mg/litre as CaCO3 =

5.2

V2 x M
Calcium hardness, mg/litre as CaCO3 = ------------------------- x 10,000
V
Magnesium hardness, mg/litre as CaCO3 = Total hardness, mg/litre as CaC03
minus calcium hardness, mg/ litre as CaCO3.
Where:
V1

= milliliters of standard EDTA solution. required for magnesium plus


calcium (4.1.5) minus the blank determination (4.1.6).

V2

= milliliters of standard EDTA solution required for calcium (4.2.4)


minus the blank determination (4.2.5).

= milliliters of sample taken.

= molarity of standard EDTA solution.

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6.0

PRECISION

6.1

The precision of this method for calcium (13 to 88 mg/ litre as Ca) may be
expressed as follows:
Sr =

0.006 X +0.62

So =

0.006 X +0.51

Where:

6.2

Sr

overall precision.

So

single operator precision.

determined concentration of calcium, mg/litre


as Ca.

The precision of this method for magnesium (2.5 to 36 mg/ litre, as Mg) may
be expressed as follows:
ST =

0.017 X + 0.85

So =

0.002 X + 0.70

Where:
ST =

overall precision.

So =

single operator precision.

X =

determined concentration of magnesium, mg/litre as Mg.

7.0

INTERFERENCES

7.1

EDTA reacts with several metallic ions. The interference due to these ions can
be minimized by addition of hydroxylamine and cyanide. Metal
concentrations as high as 5mg/litre Fe, l0mg/ litre Mn, l0 mg/litre Cu, l0
mg/litre Zn and l0 mg/litre Pb can be tolerated when hydroxylamine and
cyanide are added.

7.2

In the titration of total hardness the higher oxidation states of manganese


above 2 reacts rapidly with the indicator to form discoloured oxidation
products. Hydroxylamine hydrochloride reagent is used to reduce manganese
to divalent state. The divalent manganese interference can be eliminated by
addition of one or two small crystals of potassium ferrocyanide.

7.3

In the presence of aluminium concentrations in excess of l0 mg/litre, the blue


colour which indicates that the end point has been reached will appear and
then on short standing will revert to red.

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7.4

In the titration of calcium, ammonium purpurate reacts with strontium but not
with magnesium or barium. In the presence of strontium, the endpoint is slow
and the titration is not strictly stoichiometric. Barium does not titrate as
calcium, but affects the indicator in some unknown way so that no endpoint or
a poor endpoint is obtained. Barium can be removed by precipitation with
sulphuric acid.

8.0

NOTES

8.1

Reagent grade chemicals should be used for preparing the reagents.

8.2

If total recoverable calcium and magnesium concentration are being


determined, acidify the sample with nitric acid (sp gr 1.42) to a pH of 2 or less
(check with the help of narrow range pH paper) immediately at the time of
collection; normally about 2 m1/litre is required.

8.3

If dissolved calcium and magnesium concentrations are being determined,


filter the samples through a 0.45 micron membrane filter and acidify the
filtrate with nitric acid (sp gr 1.42), 2 m1/litre.

8.4

The upper and lower limits of concentration given in range (3.0) may be
extended either by dilution or use of micro apparatus.

8.5

The titration of the sample with EDTA should be completed within 5 minutes
of the buffer addition. If more than 15 m1 titrant is required, take a smaller
sample aliquot and repeat the test.

8.6

Fluorescein methylene iminodiacetic acid indicator can be used in place of


ammonium purpurate used in the titration of calcium. The end point will be
indicated by a colour change from deep green to purple.
This indicator is prepared by grinding 0.2g of fluorescein methylene
iminodiacetic acid and 0.12g of thymol-phthalein with 20 g of potassium
chloride to 300 to 425 micron size.

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XXXIII)
1.0

HYDRAZINE (p-Dimethylamino Benzaldehyde Method)


SUMMARY OF METHOD
The sample is reacted with a solution of para-dimethyl aminobenzaldehyde to
produce a yellow colour. The intensity of the colour is measured
colorimetrically at a wavelength of 458nm.

2.0

RANGE
4 to 100 micrograms/litre N2H4.

3.0

APPARATUS

3.1

Spectrophotometer suitable for measurement at 458nm.

3.2

Matched pairs of l0 mm and 50 mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

Hydrazine standard solution (l ml = 100 microgram N2H4) - Dissolve 0.328g


of hydrazine dihydro chloride (N2H4.2HCl) in 100 m1 of water and l0 ml of
hydrochloric acid (sp gr 1.19). Dilute to 1 litre with water.

4.3

Hydrochloric Acid (sp gr 1.19).

4.4

Hydrochloric Acid (1+9) - Mix 1 volume of hydrochloric acid (sp gr 1.19)


with 9 volumes of water.

4.5

Hydrochloric Acid (1+99) Mix 1volume of hydrochloric acid (sp gr 1.19)


with 99 volumes of water.

4.6

Para Dimethylaminobenzaldehyde Solution - Dissolve 4.0 g of pdimethylaminobenzaldehyde in 200m1 of methyl alcohol and 20m1 of
hydrochloric acid (sp gr 1.19). Store in a dark bottle, out of direct sunlight.

5.0

CALIBRATION

5.1

Prepare a series of hydrazine standards by making appropriate dilutions of the


hydrazine solution. (1 ml = 100 micrograms N 2H4) with hydrochloric acid
(1+99), so that a 50m1 aliquot of each dilution will contain the desired
quantity of hydrazine (0.2 to 5.0 micrograms).

5.2

Pipet 50m1 portions of the hydrazine standard solutions as prepared in section


5.1 into 100 m1 cylinders and proceed in accordance with section 6.0 (6.36.4).

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5.3

Prepare a calibration curve by plotting transmittance against micrograms of


hydrazine.

6.0

PROCEDURE

6.1

Place 5.0 m1 of hydrochloric acid (1+9) into a 100m1 cylinder.

6.2

Transfer a portion of the sample, to the above cylinder (6.1) that will contain
approximately 0.20 to 5.0 micrograms of hydrazine and make the final
volume to 50m1 with water.

6.3

Add l0.0ml of p-dimethylaminobenzaldehyde solution, mix and allow to stand


for 10 minutes.

6.4

Measure the transmittance of the solution at 458nm by adjusting the


spectrophotometer at 100% transmittance with the blank, prepared by adding
10.0 m1 of p-dimethylaminobenzaldehyde to 50 m1 of water.

7.0

CALCULATIONS

7.1

Calculate the hydrazine concentration in micrograms per litre as follows:


W x 1000
Hydrazine, micrograms/litre = ---------------------------------V
Where:

8.0

W =

micrograms of hydrazine found in accordance with section 6.0.

V =

milliliters of sample.

PRECISION
The precision of this method may be expressed as follows;
So =

(0.99 X + 0.041)/ V

St =

(1.08 X + 0.081)/V

Where:
So =

single operator precision expressed in mg/litre of hydrazine.

St =

overall precision expressed in mg/litre. of hydrazine:

X =

concentration of hydrazine determined in mg/litre.

V =

milliliters of sample taken for test.

9.0

INTERFERENCES

9.1

The hydrazine content may be diminished by oxidising agents collected with


the sample or absorbed by it prior to testing.

9.2

Colours, that absorb in the prescribed wavelength, also, interfere.


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10.0

NOTES

10.1

Reagent grade chemicals should be used for preparing the reagents.

10.2

The purity of hydrazine dihydrochloride may be checked by iodimetric


methods.

10.3

Para-dimethylaminobenzaldehyde
reagent
obtained
from
different
manufacturers produce different intensities of colour in solution. It is
necessary that each new supply of reagent be tested on standard solutions
before using with previously determined calibration curves.

10.4

The sample should be analyzed as quickly as possible after collection since


hydrazine undergoes auto-oxidation, as well as, oxidation by oxidising agents.
Such agents may be in the sample or may enter the sample from the
atmosphere. If it is suspected that oxidation of the hydrazine in the sample is
occurring in the interval between collection and analysis or if the sample is
not to be analyzed immediately then the sample is to be collected under acid
by placing 5.0 m1 of hydrochloric acid (1+9) in a 50m1 volumetric flask, and
collecting sufficient sample to make total volume to 50 m1.
When the sample is collected under acid, the step 6.1 of section 6.0 should be
deleted and in step 6.2 hydrochloric acid (1+99) to be used, instead of water
for dilution.

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XXXIV)
1.0

IRON (Bathophenanthroline Method)


SUMMARY OF METHOD
Iron is reduced with hydroxylamine hydrochloride and then reacted with
bathophenanthroline (4,7- diphenyl - 1, 10 phenanthroline). The red ferrous
complex is extracted with n-hexyl or isoamyl alcohol and the intensity of the
colour is measured at 533nm.

2.0

RANGE
4 to 80 micrograms/litre Fe with 100mm cell.
10 to 160 micrograms/litre Fe with 50mm cell.

3.0

APPARATUS

3.1

Spectrophotometer for use at 533nm.

3.2

Matched pair of 50mm and 100mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

Alcohol, n-Hexyl or Isoamyl.

4.3

Alcohol, Methyl, ethyl or Isopropyl.

4.4

Bathophenanthroline Solution (0.835g/litre)bathophenanthroline in 100m1 of ethyl alcohol.

4.5

Hydrochloric Acid (1+1) - Mix equal volumes of hydrochloric acid (sp gr


1.19) and water.

4.6

Hydroxylamine Hydrochloride Solution (10%)

4.7

Iron Standard Solution (l ml = 1 microgram Fe) - Dissolve 0.1000g of pure


iron in l0ml of hydrochloric acid (1+1) and l ml of bromine water. Boil to
remove excess bromine. Add 200m1 of hydrochloric acid (1+1), cool, and
dilute to 1 litre with water (solution A). To l0ml of solution A add 12m1 of
hydrochloric acid (1+1) and dilute to 1 litre with water.

4.8

Hydrochloric Acid (1+9) - Mix 1 volume of hydrochloric acid (sp gr 1.19)


with 9 volumes of water.

4.9

Ammonium
Hydroxide (1+1) - Mix equal volumes of ammonium
hydroxide (sp gr 0.90) and water.

5.0

CALIBRATION

5.1

Prepare a series of standards (at least five.


concentrations) to cover the
expected range of iron concentrations by diluting appropriate volumes of Iron
standard solution (4.7, l ml = 1 microgram Fe) as follows:
NTPC Limited

Dissolve

0.0835g

of

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5.1.1

Place the required volumes of Iron standard solution (4.7) in 125m1


separatory funnels.

5.1.2

Add water to make 50m1.

5.1.3

Add 2.0 m1 of hydroxylamine hydrochloride solution and mix.

5.1.4

Add 3.0 m1 of bathophenanthroline solution and shake for 30 seconds.

5.1.5.

Add ammonium hydroxide (1+1) dropwise with mixing until a distinct


turbidity forms. Add hydrochloric acid (1+9) dropwise with mixing until 1
drop clears the solution. Allow to stand for 1 minute.

5.1.6

Proceed in accordance with section 6.0 (6.5 to 6.8).

5.1.7

Simultaneously carry out a blank determination containing no added iron


using 50m1 of water and all reagents.

6.0

PROCEDURE

6.1

Transfer a volume of sample (filtered through 0.45 micron membrane filter)


containing not more than 8 micrograms of iron, to a 125m1 separatory funnel.

6.2

Add 1.0m1 of hydroxylamine hydrochloride solution and mix.

6.3

Add 3.0m1 of bathophenanthroline solution and shake for 30 seconds.

6.4

Add ammonium hydroxide (1+1) dropwise with mixing until a distinct


turbidity forms. Add hydrochloric acid (1+9) dropwise with mixing until 1
drop clears the solution. Allow to stand for 1 minute.

6.5

Add 15.0m1 of n-hexyl or isoamyl alcohol and shake vigorously for 1 minute.
Allow to stand for 15 minutes.

6.6

Discard the aqueous layer and transfer the alcohol layer into a 25m1
volumetric flask.

6.7

Add l0ml of methyl, ethyl or isopropyl/alcohol to the funnel and wash the
internal surfaces by rolling and tumbling the funnel. Transfer this alcohol into
the previous alcohol extract (6.6). Dilute to the 25m1 mark with the alcohol
used for extraction (6.6).

6.8

Measure the colour of the alcohol solution at 533nm, adjusting the


spectrophotometer to zero absorbance reading with a reference solution of
15m1 of alcohol used in step 6.5 and l0ml of alcohol used in step 6.7.

6.9

Carry out a blank determination on 50m1 of water, with all reagents and
extracting in the same manner as for the sample.

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7.0

CALCULATIONS

7.1

Calculate the concentration of iron in micrograms per litre in the sample as


follows:
Iron, micrograms/litre =

W x 1000
---------------------------V

Where:
W
V

=
=

micrograms of iron, read from the calibration curve:


milliliters of original sample used.

8.0

PRECISION

8.1

The single operator and overall precision varies with the determined
concentration and may be expressed as follows:
So
=
0.008 X + 0.92
St

0.039 X + 1.47

So

single operator precision, micrograms/ litre.

St
X

=
=

overall precision, micrograms/litre.


determined concentration microgram/litre.

Where:

9.0

INTERFERENCES

9.1

If pH is between 3.3 and 3.7 a l mg/litre concentration of the following ions


does not interfere with the test: copper, manganese, aluminium, zinc,
magnesium, sodium, silica, nitrate and orthophosphate.

10.0

NOTES

10.1

Reagent grade chemicals should be used for preparing the reagents.

10.2

If either dissolved or ferrous iron is to be determined, the sample must be


analyzed as soon as possible after collection. If only total iron is to be
determined, the sample should be immediately acidified with 2m1 of
hydrochloric acid (sp gr 1.19) per 50m1.

10.3

Soak all new glassware in hot hydrochloric acid (1+1) for 2 hours. Drain and
rinse at least 3 times with iron free water. Before and after use, clean all
glassware by making an iron extraction of each piece (without separating the
alcohol - water layers). Drain and flush with iron free methyl alcohol, ethyl
alcohol, or isopropyl alcohol. ,

10.4

If iron content is high in hydrochloric acid (4.5) causing a high blank, distil in
an all glass apparatus, rejecting the first 50m1 and the last 100m1 of distillate.
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10.5

Hydroxylamine hydrochloride solution (4.6) can be purified as follows:


Adjust pH to 3.5 using a pH meter by dropwise addition of ammonium
hydroxide (1+1) and hydrochloric acid (1+9). Transfer to a separatory funnel,
add 6.0m1 of bathophenanthroline solution and shake. Allow to stand for 1
minute. Add 20m1 of n-hexyl or isoamyl alcohol and shake for 1 minute.
Allow to stand for 15 minutes. Remove the aqueous layer and discard
alcoholic layer. Repeat extraction by again adding 3m1 of
bathophenanthroline solution and 20m1 of alcohol. Discard the alcohol. If no
further extractions are indicated make an extraction with alcohol alone and
allow to stand for a long time to remove all of the alcohol layer. Discard the
alcohol layer.

10.6

For total iron determination, heat the sample for 1 hour at 60 0C with 4m1 of
hydrochloric acid (1+1) and 2m1 of hydroxylamine hydrochloride solution.
Thioglycolic acid can also be used for solubilising unreactive iron.

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XXXV) IRON (Ferrozine Method)


1.0

SUMMARY OF METHOD
Soluble iron [both Fe (II) and Fe (III)) is complexed with ferrozine [3-(2pyridyl) - 5,6 bis (4 phenylsulphonic acid) - 1,2,4 triazine, disodium salt) at
pH 4.4 and its concentration, is determined colorimetrically at a wavelength of
562nm.

2.0

RANGE
Upto 500 micrograms/litre Fe.

3.0

APPARATUS

3.1

Spectrophotometer for use at 562nm.

3.2

Matched pair of 50 mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

Combined Reagent and Ammonia/Acetic Acid Buffer Solution - Dissolve


2.00g of ferrozine in approximately 300 m1 of water and add 253m1 of acetic
acid. Add slowly and with stirring 200 m1 of ammonium hydroxide (sp gr
0.90), cool and dilute to 1 litre. Store in a borosilicate glass bottle: The pH of
this solution should be approximately 5.1. This solution is stable for at least 2
months.

4.3

Iron Standard Solution (l ml = 1 microgram Fe) - Dissolve 0.1000g of pure


iron in l0ml of hydrochloric acid (1+1) and l ml of bromine water. Boil to
remove excess bromine. Add 200m1 of hydrochloric acid (1+1), cool, and
dilute to 1 litre with water (Solution A). To l0 ml of solution A add 12 m1 of
hydrochloric acid (1+1) and dilute to 1 litre with water.

5.0

CALIBRATION

5.1

Prepare a series of standards (at least five concentrations) to cover the


expected range of iron concentrations by diluting appropriate volumes of Iron
Standard solution (4.5, l ml =1 microgram Fe) as follows:

5.1.1

Place the required volumes of iron standard solution (4.5) in 50ml volumetric
flasks.

5.1.2

Add enough water to make the volume to 40 ml.

5.1.3

Add 4.0 ml of the combined reagent/ buffer solution and mix

5.1.4

Make up to 50 ml with water.

5.1.5

Measure the absorbance of each standard at 562 nm against the blank prepared
by mixing 46 ml of water and 4 ml of combined reagent/ buffer solution.
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5.1.6

Prepare a calibration curve by plotting the absorbance of the standards against


the iron content in micrograms /litre.

6.0

PROCEDURE

6.1

Place 40 ml of the sample in a 50 ml volumetric flask.

6.2

Add 4.0 ml of the combined reagent / buffer solution and mix and make up to
50ml mark with water.

6.3

Measure the absorbance of the solution at 562nm against water as reference.


Let the absorbance be A1.

6.4

For reagent blank determination, place 40ml of the combined reagent/buffer


solution in a 50ml volumetric flask. Repeat stages 6.3 and 6.4. Let the
absorbance be A2.

7.0

CALCULATIONS

7.1

Calculate the absorbance A3 due to iron in the sample as follows:


A3 = A1 0.1 A2

7.2

From A3 and the calibration curve, calculate the concentration of iron in the
sample.

8.0

INTERFERENCES

8.1

100 micrograms of copper per litre gives rise to a value of iron 1.4
micrograms per litre. None of the other substances, likely to be present, cause
significant interference.

9.0

NOTES

9.1

Reagent grade chemicals should be used fore preparing the reagents.

9.2

If ammonium hydroxide solution (4.2) gives a high blank, purify it as follows:

9.3

Place 600ml of ammonia (sp gr 0.90) in the base of a 25 cm desiccator and


400 ml of water in a polythene beaker supported above the ammonia. (The
polythene beaker should be filled with ammonia and kept for 1 day and then
washed thoroughly with water before use). Replace the lid of the desiccator
and store in a cool place. After several days, the solution in the polythene
beaker will be approximately 9N with respect to ammonia, actual
concentration can be checked by titration with a standard solution of
hydrochloric acid.

9.4

If Acetic acid, glacial, gives a high blank, purify it as follows:

9.5

Distil 800ml of acetic acid in an all glass apparatus. Reject the first 100ml
distillate and the last 100ml remaining in the distillation flask.

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XXXVI) IRON ATOMIC ABSORPRION METHOD (Graphite Furnace)


1.0

Principle
This test method covers the determination of dissolved and total recoverable
iron in most waters and waste waters in the range from 5 to 100 g/L of iron
using a 20 ml L injection. The iron content of the sample is determined by
atomic absorption spectrophotometer used in conjunction with a graphite
furnace. A sample is place in a graphite tube , evaporated to dryness, charred
and atomized. The absorption signal generated during atomization is recorded
and compared to standards.

2.0

Apparatus

3.0

Atomic absorption spectrophotometer for use at 248.3 nm with background


correction. The manufacturers recommendation is to be followed for all
instrumental parameters.
Iron hallow cathode lamp: A single element lamp is preferred but
multielement lamps may be used.
Graphite furnace: It must be capable of reaching temperature s sufficient to
atomize iron.
Graphite tubes: It should be compatible with furnace device .Pyrolytically
coated graphite tubes are recommended to eliminate the possible formation of
carbides.
Data storage and reduction device: It shall be utilized for collection, storage,
reduction and problem recognition. Automatic sampling should be used if
possible.
Reagents

4.0

(a) Iron solution: Stock (1.0 ml = 1000 g of Fe) Dissolve 1.0 g of pure
iron in 100 ml of HCL (1+1) with the aid of heat. Cool and dilute to 1 L
with water.
(b) Iron solution intermediate (1.0 ml = 10 g of Fe): Dilute 10.0 ml of
above stock solution (a) and 1 ml of HNO3 (Sp.Gr. 1.42) to 1 L with
water
(c) Iron solution intermediate (1.0 ml = 0.2 g of Fe): Dilute 20.0 ml of
above stock solution (b) and 1 ml of HNO 3 (Sp.GR 1.42) to 1 L with
water. This standard is used to prepare the working standards at the time
of analysis.
(d) Nitric acid (sp.gr.1.42)
(e) Argon standard, welder grade, commercially available. Nitrogen may
also be used if recommended by the manufacturer.
Inject the measured aliquots of sample into the furnace device following
the directions as provided by the particular instrument manufacturer.
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XXXVII) NICKEL (Glyoxime Method)


1.0

SUMMARY OF METHOD
Nickel is reacted with an ammonical solution of dimethyl glyoxime in the
presence of iodine and the intensity of the wine red complex is measured at
530 nm.

2.0

RANGE
0.01 to 0.1mg/litre with 100 mm cell.
0.1 to 5.0mg/litre with 10 mm cell.

3.0

APPARATUS

3.1

Spectrophotometer for use at 530 nm.

3.2

Matched pairs of 10 mm and 100 mm cells.

4.0

REAGENTS

4.1

Water conforming to specifications Type II.

4.2

Ammonium citrate Solution (575g/litre) Dissolve 500g of citric acid


monohydrate in 675ml of ammonium hydroxide (sp gr 0.90) and dilute to 1
litre with water. Filter.

4.3

Ammonium Hydroxide (1+1) Mix 1 volume of ammonium hydroxide (sp gr


0.90) with 1 volume of water.

4.4

Dimethylglyoxime, ammonical Solution Dissolve1g of dimethylglyoxime in


500 ml of ammonium hydroxide (sp gr 0, 90), add 500 ml of water and filter.
Shelf life of this solution is 2 weeks.

4.5

Iodine Solution (12.7g/litre)- Dissolve 6.35g of iodine in a solution of 75g of


potassium iodide in 60ml of water and dilute to 500 ml with water. Store in a
dark, stoppered bottle.

4.6

Nickel standard Solution (1ml = 0.02mg Ni) place 1.00g of Nickel


(minimum purity 99.9%) in a 250 ml beaker. Add 10ml each of water and
nitric acid (sp gr 1.42) and allow to stand until dissolved. Add 1ml of
sulphuric acid (sp gr 1.84) and evaporate to nearly dryness. Cool, add 5ml
more of sulphuric acid and evaporate to dense white fumes. Dilute to 500ml
with water (solution A). Dilute 50ml of this diluted solution to 250ml.

5.0

CALIBRATION

5.1

Prepare a series of standards (at least five concentrations) to cover the


expected range of Nickel concentrations by diluting kjappropriate volumes of
Nickel standard solution (4.6, 1 ml + 20 microgram of Nickel)

5.1.1

Place the required volumes of nickel standard solution (4.6) in


volumetric flasks.

5.1.2

Add water to make up the volume to 50ml.


NTPC Limited

100ml

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5.1.3

Proceed in accordance with section 6.0 (6.2, 6.3 and 6.5) using 50 ml water as
the reference.

5.1.4

Prepare a calibration curve by plotting the absorbance versus milligrams per


litre of nickel.

6.0

PROCEDURE

6.1

Measure 50 ml portions of the sample into each of two 100ml volumetric


flasks.

6.2

Add 10 ml of ammonium citrate solution and 5ml of iodine solution to each


flask.

6.3

To one flask add 20 ml of ammonical dimethylglyoxime solution. Dilute to


100ml with water and allow to stand for 10 minutes.

6.4

To the other flask add 20ml of ammonium hydroxide (1+1). Dilute to 100ml
with water and allow to stand for minutes. Use this solution as the reference
solution.

6.5

Balance the spectrophotometer at zero absorbance with the reference solution


and read the absorbance at 530nm.

7.0

CALCULATIONS

7.1

Read the nickel concentration, in mg/litre directly from the calibration curve.

8.0

PRECISION

8.1

The overall and within a laboratory precisions are as follows:


ST
SO

=
=

0.06 X
0.04 X

Where:

9.0

ST

overall precision.

SO

precision within one laboratory.

concentration of nickel determined, mg/ litre.

INTERFERENCES
Iron interference is eliminated by the addition of ammonium citrate. Copper
up to 3mg/litre does not interfere with the test.

10.0

NOTES

10.1

Reagent grade chemicals should be used for preparing the reagents.

10.2

Samples shall be preserved with nitric acid (sp gr 1.42) to a pH of 2 or less


immediately at the time of collection, normally about 2 ml/ litre. If only
dissolved nickel is to be determined, the sample shall be filtered through a
0.45 micron membrane filter before acidification.
NTPC Limited

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XXXVIII) NICKEL ATOMIC ABSORPTION METHOD (Direct)


1.0

Principle
The nickel content of the sample is determined by atomic
absorption
spectrophotometry. For dissolved nickel the filtered sample to be directly
aspirated to the atomizer. For total recoverable nickel, HNO3-H2SO4
digestion is to be carried out prior to aspiration of the sample. This method is
applicable in the range from 0.3 to 1.0 mg/L.

2.0

Interference
The presence of high concentration of chromium may increase the nickel
signal. Most interference can be eliminated by the use of nitrous oxide
acetylene flame but nickel sensitivity will be lowered.

3.0

Apparatus
Atomic absorption spectrophotometer with air-acetylene flame. Hallow
cathode lamp or electrodeless discharge lamp for use at 232.0 nm.

4.0

Reagents
Hydrochloric acid Concentrated (11 N), 1:1 and 10 % v/v
Nitric acid

Concentrated (16 N) and dilute to (1: 499)

Sulphuric acid -

Concentrated (36 N)

Stock Nickel solution


Dissolve 1.273 g of nickel oxide in a minimum quantity of 10 % ( v/v) HCl
and transfer quantitatively into a 1000 volumetric flask. Dilute upto the mark
with water. (1 ml = 1.0 mg of Ni)
Standard nickel solution
Pipette out 10.0 ml of stock nickel solution into a 1000 ml volumetric flask
and make upto mark with water ( 1.0 ml = 10g of Ni )
5.0

Procedure
Calibration curve
Prepare standard solution containing 0 to 60 g /l of nickel by diluting
suitable volumes of standard nickel solution with nitric acid (1:499) to 100 ml
in the volumetric flasks. Prepare a reagent blank in an identical manner using
10 ml of water. Aspirate the reagent blank and carryout zero adjustment.
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Aspirate sequentially the standard solutions and measure the absorbance at
232 nm.
Construct a calibration curve by plotting absorbance values against
micrograms of Ni in 100 ml of the final volume. Ensure that the calibration
curve is linear by making necessary changes in the volume of the standard
solution used.
Determination of Nickel
For the determination of dissolved nickel content, filtration through 0.45
micron membrane filter, at the time of sampling is required. For total
recoverable nickel, HNO3 H2SO4 digestion is to be carried out.
Add 0.5 ml of nitric acid to a suitable volume of the sample taken in a 100 ml
volumetric flask. Make upto the mark. Rinse the nebulizer by aspirating water
containing 1.5 ml of con.HNO3/l. Aspirate the sample solution and measure
the absorbance at 232 nm. Determine microgram of nickel in the solution
from the absorbance reading, by referring to the calibration curve.
6.0

Calculation
Soluble Ni (direct determination without digestion)
Ni mg/l

g of Ni (in 100 ml of the final solution)


= ---------------------------------------------------------------- x 100
V

Where V = volume in ml of the sample used


Soluble Ni (direct determination with digestion)
Ni mg/l

g of Ni (in 100 ml of the final solution)


= ---------------------------------------------------------------- x 100
V1 x V2

Where V1 = volume in ml of the sample used


V2 = total volume in ml of digested solution used for Ni estimation
7.0

Precision and accuracy


The relative standard deviation reported in the literature for the nickel at 4.0
mg/l concentration level is 9.8%.

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XXXIX)
1.0

MANGANESE
Principle
Manganese is oxidized to higher valence state (permanganic state) giving
permanganic colour by boiling with potassium periodate in acid condition and
in the presence of silver nitrate catalyst. The colour is proportional to the
manganese concentration.
Periodate method is more sensitive than persulphate in lower concentrations
and colour produced is stable for longer time.

2.0

Interference:
Chlorides, organic matter, iron, colour and turbidity
interfere in the estimation of Mn.

3.0

Apparatus
1.
2.
3.

4.0

Colorimeter to operate at 525 nm.


Nesslers tube cap. 100 ml.
Water bath.

Reagents
1.
2.
3.
4.
5.
6.

H2SO4 conc.
HNO3 conc.
H3PO4 85%.
KIO4 A.R. grade
AgNO3 salt
H2O2 30%

5.0

Standard Mn solution: Prepare 0.1 N KmnO4 solution by dissolving 3.2 gm


KmnO4 in distilled water and making up to litre. Age for several weeks, filter
and standardize against sodium oxalate.

6.0

Procedure
(a) In case, pretreatment is required take suitable aliquot of sample and add 5
ml conc. H2SO4 followed by 5 ml conc. HNO3 evaporate till SO3 fumes
disappear. This will remove interfering radicals such as organization
qatter, Chlorides and other oxidizable substances. This result in
dehydration of silica and production of turbidity, cool it and filter.
(b) Take filtrate add 85 ml distilled water, 5 ml HNO3 and 5 H3 PO4 85%. Mix
well. Addition of H3PO4 decolorizes Fe +++ion and prevent precipitation
of iodates or periodates of Mn.
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(c) If pretreatment is not required add 5 ml conc. H2SO4 5 ml conc. HNO3
and 5 ml H3PO4 85%. Mix well.
(d) Boil till sample concentrates to about 90 ml and cool.
(e) Add 0.3 g KIO4. If Mn concentration is 10 g or less add 20 mg AgNO3.
(f) Heat till boiling for 1 hr. Cool immediately and dilute to 100 ml.
(g) Measure colour intensity at 525 nm.
8.0

Prepare a calibration curve using standard solution containing 50 to 1500 g


of mn/1.

9.0

Calculate the conc. Of Manganese in the sample from calibration curve and
express in mg/1 as Mn.

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XL)
1.0

NITRATE (Azo dye Method)


SUMMARY OF METHOD
A filtered sample is passed through a column containing copper coated
cadmium granules to reduce nitrate to nitrite ion which is diazotized with
sulphanilamide and coupled with
N- (1-naphthyl) ethylenediamine
dihydrochloride to form a highly coloured azodye that is measured
spectrophotometrically at a wavelength of 543nm.

2.0

RANGE
0.05 to l mg/litre as N but reliable upto 0.01mg/litre.

3.0

APPARATUS

3.1

Reduction column - consisting of the following:

3.1.1

Pipet volumetric, 100 ml capacity, with 200 mm delivery stem. The top of the
bulb shall be cut off and the delivery tip curved to form a shallow hook.

3.1.2

Tubing glass or vinyl 1mm inside diameter and about 350mm in length.

3.2

Cylinders, graduated, 50 ml capacity.

3.3

Test tubes, 15 ml capacity.

3.4

Spectrophotometer for use at 543 nm.

3.5

Matched pair of 10 mm cells.

3.6

Pipettes, serological 1 and 10ml capacity, calibrated to 0.1ml to deliver with


ejection.

4.0

REAGENTS

4.1

Water - Conforming to specifications Type II.

4.2

Ammonium chloride solution dissolve


Cl) in water and dilute to 1litre.

4.3

Cadmium, 250 to 425 micron size, granulated.

4.4

Colour Reagent Add 100ml of concentrated phosphoric acid, 10g of


sulphanilamide, and 0.5g of N- (1- naphthyl) ethylenediamine dihydrochloride
to 800ml of water . Stir until dissolved. Dilute to 1 litre with water and store in
a brown bottle in a dark cool place.

4.5

Copper Sulphate Solution dissolve 20g of copper sulphate (CuSO4.5H2O )


in 500ml of water and dilute to 1litre.

4.6

1,1,2 Trichloro 1,2,2 trifluoroethane.

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85g of ammonium chloride (NH4

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4.7

Hydrochloric Acid (1+1) - Mix equal volumes of hydrochloric acid (sp gr


1.19) and water.

4.8

Nitrate Stock Solution (l ml = 1mg N) dissolve 7.218g of potassium nitrate


(dried in an oven at 105oc for 24 hours) in water and dilute to 1litre with
water. Add 2 ml of chloroform as a preservative and store in a dark bottle.

4.9

Standard Nitrate Solution (l ml = 0.01mg N) Dilute 10 ml of nitrate stock


solution (4.8) to 1 litre with water. Add 2 ml of chloroform and store in a dark
bottle. Prepare fresh.

5.0

PREPARATON OF REDUCTION COLUMN

5.1

Cadmium Granules Treatment

5.1.1

Clean about 10g of cadmium granules with hydrochloric acid (1+1) and then
rinse with water.

5.1.2

Swirl the clean cadmium granules in 100ml of copper sulphate solution for
5minutess or until the blue colour partially fades.

5.1.3

Decant and repeat with a fresh 100m1 copper sulphate solution solution until
the first trace of a brown colloidal precipitate appears.

5.1.4

Wash the granules with water at least ten times to remove all the precipitated
copper.

5.2

Filling the Reduction Column

5.2.1

Insert a small plug of glass wool in the tip of the pipette.

5.2.2

Fill the column with water.

5.2.3

Pour sufficient cadmium granules into the apparatus to produce a column


300mm in length.

5.2.4 1

Wash the column thoroughly with ammonium chloride solution. .

6.0

CALIBRATION

6.1

Prepare a series of standards by diluting appropriate volumes of standard


nitrate solution (l ml = 0.01 mg N) to 100m1 in volumetric flasks.

6.2

Proceed in accordance with section 7.0 (7.1 to 7.6).

6.3

Prepare a calibration curve by plotting the absorbance versus concentration of


nitrate as N in milligrams per litre.

7.0

PROCEDURE

7.1

Mix 20m1 of sample (pH between 6 to 8) with 80m1 of ammonium chloride


solution.

7.2

Pour about 60m1 of mixed sample (7.1) into the reservoir of the reduction
column.
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7.3

Discard initial 30 m1 of effluent.

7.4

Place a clean 50m1 graduated cylinder under the siphon outlet and collect
25m1 of effluent.

7.5

Place l0 ml of the collected effluent (7.3) into a 15m1 test tube.

7.6

Add 3.0 m1 of colour reagent, mix, and allow to stand for 15 minutes.

7.7

Measure the absorbance of solution against water as reference at 543nm using


l0 mm matched absorption cells.

8.0

CALCULATIONS

8.1

Calculate the concentration of nitrate, in mg/litre as N, directly from the


calibration curve prepared in accordance with section 6.0.

8.2

Calculate the nitrate concentration in mg/litre as NO3 as follows:


Nitrate concentration, mg/litre as NO3 = A x 4.43
Where:
A =

8.3

nitrate concentration, mg/litre as N.

Calculate the nitrate concentration in mg/litre as CaCO3 as follows:


Nitrate concentration, mg/litre as CaCO3 - B x 0.81
Where:
B =

Nitrate concentration, mg/litre as NO3

9.0

INTERFERENCES

9.1

Turbidity of sample results in a buildup on the reduction column that restricts


sample flow. For turbidity removal the sample is filtered through 0.45 micron
membrane filter.

9.2

Sample colour that absorbs at wavelengths between 520 and 540nm interferes
with the absorbance measurement. When colour is suspected, analyze a
sample blank, omitting the N-(1-naphthyl) ethylenediamine dihydro-chloride
from the colour reagent.

9.3

Oil and grease in the sample coat the surface of the cadmium and prevent
complete reduction of nitrate to nitrite.
For oil and grease removal, adjust the pH of the sample to 2 with hydrochloric
acid. Extract with two 25 m1 portion of trichlorotrifluoroethane and discard
the organic layer.

9.4

In acidic samples (pH less than 4.5) nitrate is not reduced in the cadmium
column. The pH is adjusted between 6 to 8 with hydrochloric acid or
ammonium hydroxide.

9.5

Certain metal ions such as mercury, copper, iron and manganese, in


concentrations above 35mg/litre, may cause interference.
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10.0

NOTES

10.1

Reagent grade chemicals should be used in preparing all the reagents.

10.2

When not in use, the cadmium column should be covered with ammonium
chloride solution. If air enters the packing or it is dried out, prepare another
column.

10.3

If nitrite is present in the sample, it can be determined separately by carrying


out the procedure and omitting the cadmium reduction step.

10.4

Prepare at least one calibration standard from potassium nitrite at the same
concentration as one of the nitrate standards to verify the efficiency of the
reduction column. The nitrite standard will fall on the nitrate standard curve if
the reduction of nitrate was complete. If the nitrite standard is 5% higher,
prepare a fresh reduction column and repeat the analysis of the nitrate
standards.

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XLI)

NITRATE (PHENOL DISULPHONIC ACID (PDA) METHOD)

1.0

Principle: Nitrate reacts with phenol disulphonic acid and produces a nitroderivative which in alkaline solution develops yellow colour due to
rearrangement of its structure. The colour produced follows Beers law and is
proportional to the concentration of NO3 present in the sample.

2.0

Interference:
Chlorides and nitrate, are the two main sources of
interference. Pretreatment of sample is necessary when the interfering radicals
are present.

3.0

Apparatus:
a.
b.
c.
d.

4.0

Colorimeter or spectrophotometer having a range of 300-700 nm.


Nesslers tubes capacity 100 ml.
Beakers
capacity 100 ml.
Water bath
capacity 100 ml.

Reagents:
a) Standard silver sulfate: Dissolve 4.40 g Ag2SO4 in distilled water and
dilute to 1000 ml, 1 ml = 1mg Cl.
b) Phenol disulfonic acid (PDA): Dissolve 25 g white phenol in 150 ml
conc. H2SO4. Add 75 ml fuming H2SO4 (15% free SO3) stir well and heat
for 2 hr on waterbath. If fuming sulfuric acid is not available add
additional 85 ml conc. H2SO4 to the 150 ml H2SO4 stir well and heat for 2
hr.
c) Ammonium hydroxide concentrated.
d) Potassium hydroxide 12N: Dissolve 673 g KOH in distilled water and
make up to 1000 ml with distilled water for hard waters use liquid
ammonia.
e) Stock nitrate solution: Dissolve 721.8 mg anhydrous potassium nitrate
and dilute to 1000 ml with distilled water.
1 ml = 100 g N.
f) Standard nitrate solution: Evaporate 50 ml stock NO3 to dryness on
water bath. Dissolve residue in 2 ml PDA reagent and dilute to 500 ml.
1 ml = 10 g N.
g) EDTA: Rub 50 g EDTA with 20 ml distilled water to form a paste. Add 60
ml NH4OH and mix well.
h) Aluminium hydroxide:
Dissolve 125 g potash alum in 1000 ml
distilled water. Warm to 600C and add 55-60 ml NH 4OH and allowed to
stand for 1 hr. Decant the supernatant and wash the precipitate a number of
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times till it is free from C1, NO2 and NO3. Finally after settling, decant off
as much clean liquid as possible, leaving only the concentrated
suspension.
5.0

Procedure:
a) Pretreatment of sample
1.

Colour removal: If the sample has a colour in excess of 10 units; add


3 ml aluminium hydroxide to 150 ml sample. Stir well and allow to
settle for a few min. Filter and use the filtrate discarding the first portion
of the filtrate.

2.

Nitrite removal:
(1) Generally NO2 occurs along with NH3 and gets eliminated in the
routine test due to decomposition of NO2 and NH3 to N2,
(ii) Oxidize NO2 to NO3 under acid condition using KMnO4, (iii) Add
sulfamic acid to the sample to suppress NO2 interference.

3.

Chloride removal: determine the Cl contents of the sample and


precipitate out as AgCl. One should be very careful while adding Ag2SO4
because excess Ag will precipitate out as silver oxide when alkali is
added to sample.

b) Colour Development
1.

Neutralize the clarified sample to pH 7.0.

2.

Take suitable aliquot of the sample in a beaker and evaporate to


dryness on water bath.

3.

Dissolve the residue using glass rod with 2 ml phenol disulfonic acid
reagent. Dilute and transfer to Nessler tubes.

4.

Add 8-10 ml 12 N KOH. If turbidity is developed add the EDTA


reagent drop wise till it dissolves. Filter and make up to 100 ml. To
avoid this add 10 ml conc. NH4OH instead of KOH.

5.

Prepare blank in the same way using distilled water instead of


sample.

6.

6 Read the colour developed at 410 nm with a light path of 1 cm.


Record NO3 as N in mg/1.

7.

Prepare calibration curve using suitable aliquots of standard NO 3 in


the range of 5 to 500 g N/1 following the above procedure.

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XLII)
1.0

NITRATE (UV Spectrophotometric Method)


Principle:
Measurement of the ultraviolet absorption at 220 nm enables rapid
determination of nitrate. The nitrate calibration curve follows Beers law up to
11 mg/l N. Because dissolved organic matter may also absorb at 320 nm and
nitrate does not absorb at 275 nm a second measurement can be made at 275
nm to correct the nitrate value. The extent of this empirical is related to the
nature and concentration of the organic matter to the nature and concentration
of the organic mater and may vary from one water to another. Filtration of the
sample is intended to remove possible interference from suspended particles.
Acidification with 1 N hydrochloric acid is designed to prevent interference
from hydroxide or carbonate concentrations up to 1,000 mg/l as CaCO 3.
Chloride has no affect on the determination. Minimum detectable
concentration is 40 g/l nitrate N.

2.0

Interference:
Dissolved organic matter, nitrate, hexavalent chromium, and surfactants
interfere. The latter three substances may be compensated for by the
preparation of individual correction curves.
Organic matter can cause a positive but variable interference, the degree
depending on the nature and concentration of the organic material.
Note: Clean all glassware thoroughly and rinse to reduce the error that might
result from streaks or particles on the outside of the cuvettes, as well as
traces of surfactants or dichromate cleaning solution that might adhere
on the interior glass surfaces.
Treat coloured samples with aluminium aluminum hydroxide
suspension or dilute to minimize colour interference.

3.0

Apparatus
a.

Sepectrophotometer, for use at 220 nm and 275 nm with matched silica


cells of 1 cm or longer light path.

b.

Filter:

c.
4.0

One of the following is required.

i)

Membrane filter: 0.45 nm membrane filter, and appropriate


filter assembly.

ii)

Paper: Acid-washed, ashless hard-finish


sufficiently retentive for fine precipitates.

filter

paper

Nessler tubes, 50 ml, short form.

Reagents
a

Redistilled water: Use redistilled water for the preparation of all


solutions and dilutions.
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5.0

6.0

Stock nitrate solution: Prepare as described in PDA method 1.00 ml =


100 g N=443 g NO3.

Standard nitrate solution: Dilute 100.0 ml with stock nitrate solution


to 1000 ml with distilled water : 1.00ml =10.0 g N = 443.3 g NO3.

Hydrochloric acid solution, HCl, 1.N.

Aluminum hydroxide suspension: Prepare as directed in PDA Method.

Procedure
a.

Colour removal: If the sample has a high colour or is known to contain


organic interference, add 4 ml Al (OH) 3 suspension/100 ml sample in an
Erlenmeyer flask. Swirl to mix and let settle for 5 min. Filter through a
0.45 m membrane filter previously washed with about 200 ml distilled
water.

b.

Treatment of sample: To 50 ml clear sample, filtered if necessary, or to


50 ml sample filtered after colour removal, add 1 ml 1N, HCl and mix
thoroughly.

c.

.Preparation of standard curve: Prepare nitrate calibration standards in


the range 0 to 350 g N by diluting to 50 ml the following volumes of
the standard nitrate solution: 0.1.00, 2.00, 4.00, 7.0 35.0 ml. Breathe
nitrate standards in the same manner as the samples.

d.

Spectrophotometric measurement: Read


the
absorbance
or
transmittance against redistilled water set at zero absorbance or 100%
transmittance. Use a wavelength of f220 nm to obtain the nitrate reading
and, if necessary, a wavelength of 275 nm to obtain the interference due
to dissolved organic matter.

Calculation
For correction for dissolved organic matter, subtract 2 times the reading at 275
at 275 nm from the reading at 220 nm to obtain the absorbance due to nitrate.
Convert this absorbance value into equivalent nitrate by reading the nitrate.
Value from a standard calibration curve obtained at 220 nm.
Calculate as follows:
Nitrate N mg/l = Net g nitrate N ml of Sample.
NO3 mg/l = Nitrate N mg/l x 4.43.

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XLIII)

OIL AND GREASE (Solvent Extraction Method)

1.0

OIL AND GREASE


Any material recovered as a substance soluble in hexane

2.0

SAMPLING AND STORAGE


Collects about 1 litre of a representative sample in a wide mouth glass bottle
that has been rinsed with the solvent (hexane). Mark the sample level in the
bottle. Acidify to pH 2 by adding concentrated hydrochloric acid. Collect a
separate sample for oil and grease determination and do not subdivide in the
laboratory. Loss of grease will occur on composite sampling equipment hence
collection of a composite sample is not practical. Individual sample collected
at prescribed time intervals should be analysed separately to obtain average
concentration over an extended period.

3.0

PARTITION GRAVIMETRIC METHOD

3.1

Principle
Dissolved or emulsified oil and grease is extracted from water by hexane and
estimation is made gravimetrically.

3.2

Interferences
The solvent extracts are not only oil and grease but other organic substances
also.

3.3

Apparatus

3.3.1

Separating funnel 1 litre capacity with teflon or equivalent stopcock.

3.3.2

Distillation flask 250 ml capacity.

3.3.3

Water Bath

3.3.4

Filter Paper Whatman No. 40 or equivalent, 11cm diameter.

3.4

Reagents

3.4.1

Hydrochloric acid 1:1.

3.4.2

Hexane

3.4.3

Sodium Sulphate anhydrous.

3.5

Procedure

3.5.1

Transfer the acidified sample to a separating funnel. Carefully rinse the


sample bottle with 30ml of hexane and add the solvent washings to the
separating funnel.
Shake vigorously for about 2 minutes. However, if it is suspected that a stable
emulsion will form, shake gently for 5 to 10 minutes. Let the layers separate.
Drain the solvent layer through a funnel containing solvent moistened filter
paper into a clean, tared distillation flask. If a clear solvent layer cannot be
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obtained, add 1g of sodium sulphate (Na 2 SO4) crystals to the filter paper cone
and slowly drain emulsified solvent on to the crystals. Add more sodium
sulphate, if necessary. Extract two more times with 30 ml of solvent each
time, but first rinse the sample container with the solvent. Collect the extracts
in a tared distillation flask and wash filter paper with an additional 10 to20 ml
of the solvent. Distil solvent from distillation flask over a water bath at 700 C.
Quantitatively transfer the residue using a minimum quantity of solvent into a
clean, tared, dried beaker. Place the beaker on water bath for 15 minutes at
700 C and evaporate off all the solvents. Cool the beaker in a desiccator for 30
minutes and weigh.
3.6

Calculation
Oil and grease, mg/l = M/V x1000
Where
M = mass, in mg, of the residue; and
V = volume, in ml, of the sample taken.

4.0

SOXHLET EXTRACTION METHOD

4.1

Principle
The material is subjected to extraction in a Soxhlet apparatus with hexane.
The residue left after the evaporation of solvent is weighed. Compounds
volatilized at or below 103 0 C will be lost when filter is dried. The method is
empirical and reproducible results can be obtained only by adherence to all the
details.

4.2

Apparatus

4.2.1

Soxhlet Apparatus

4.2.2

Vacuum Pump

4.2.3

Buchner Funnel 12 cm diameter.

4.2.4

Electric Heating Device

4.2.5

Paper Extraction Thimble

4.2.6

Filter Paper Whatman No. 40 or equivalent 11 cm diameter.

4.2.7

Muslin cloth discs 11 cm diameter.

4.3

Reagents

4.3.1

Hydrochloric Acid 1:1.

4.3.2

Hexane See 5.4.2

4.3.3

Diatomaceous Silica Filter aid suspension 10 g/l, distilled water.

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4.4

Procedure
Prepare a filter consisting of a muslin cloth disc overlaid with filter paper. Wet
the cloth and paper. Pass 100 ml of filter aid suspension through the prepared
filter using vacuum and wash with 1 litre of distilled water. Filter the acidified
sample (pH<52). Apply vacuum until no more liquid sample passes through
filter paper. Using forceps transfer the filter paper to a watch glass. Add
material adhering to edges of muslin cloth disc. Wipe sides and bottom of
collecting vessel and Buchner funnel with filter paper soaked in solvent,
taking care to remove all films caused by grease and collect all the solid
material. Add pieces of filter paper to filter paper on watch glass. Roll all filter
papers containing sample and put into a paper extraction thimble. Add any
pieces of material remaining on watch glass. Wipe the watch glass with a filter
paper soaked in solvent and place it in the thimble. Dry the filled thimble at
103C for 30 minutes in an oven. Fill the thimble with glass wool or small
glass beads. Weigh the extraction flask and extract oil and grease in a Soxhlet
apparatus, using hexane at a rate of 20 cycles per hour for four hours counting
from first cycle. Distil solvent from extraction flask over a water bath
maintained at 70C. Place the flask on a water bath at 70C for lb minutes and
draw air through it by vacuum for the final 1 minute. Cool in a desiccator for
30 minutes and weigh.

4.4

Calculation
Oil and grease, mg/l = Mx1000
V
Where
M = mass, in mg, of the residue; and
V = volume in ml, of the sample.

5.0

MODIFIED METHOD FOR HYDROCARBON

5.1

Principle
To estimate the petroleum hydrocarbon content of oil and grease this modified
method is used. Silica gel has the ability to adsorb all constituents of oil and
grease except hydrocarbons. The material not adsorbed by silica gel is
designated as hydrocarbons by this method.

5.2

Interference
The method is not accurate for the reason that any compound other than
hydrocarbon and fatty matter recovered by the solvent interfere by coming
either in hydrocarbon part or in fatty matter.

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5.3

Reagents
All reagents required for partition gravimetric method shall be applicable for
this method also. In addition, silica gel of 75 to 150 micron size, dried at
110C for 24 hours and stored in tightly sealed container is required.

5.4

Procedure
Follow the extraction procedure as given in 5.5. To the extracted solution, add
3 to 4 g of silica gel. Stopper the container and stir gently 5or 10 minutes.
Filter the solution through filter paper and wash silica gel and filter paper with
10 ml of solvent. Collect the filtrate. Distil off the solvent from the filtrate and
weigh the residue as hydrocarbons.

5.5

Calculation
Hydrocarbons, mg / l = Mx1000
V
Where
M = mass, in mg, of residue; and
V = volume, in ml, of sample

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XLIV)

ORGANIC MATTER (Potassium Permanganate Consumption


Method)

1.0

SUMMARY OF METHOD
The sample is reacted with a standard solution of potassium permanganate at
27C for 4 hours and the residual permanganate is determined iodometrically.

2.0

REAGENTS

2.1

Water - conforming to specifications Type III.

2.2

Potassium Permanganate Stock Solution - Dissolve 3.951g of potassium


permanganate (previously dried at 105C) in water and dilute to 1 - litre.
Standardize with sodium oxalate. (see notes).

2.3

Potassium Permanganate Standard Solution (N/80) (l ml = 0.l mg oxygen) Dilute 100 m1 of potassium permanganate stock solution (2.2) to 1 litre.

2.4

Sulphuric Acid (1+3) - Mix 1 volume of sulphuric acid (sp gr 1.84) with 3
volumes of water. Add standard permanganate solution until a very faint pink
colour persists after 4 hours.

2.5

Potassium Iodide.

2.6

Sodium Thiosulphate Stock Solution - Dissolve 31.2 g of sodium thiosulphate


and 6g of sodium bicarbonate in water and dilute to 1-litre.

2.7

Sodium Thiosulphate Standard Solution (N/80) - Dilute 100 m1 of sodium


thiosulphate stock solution (2.6) to 1-litre. Standardize with N/80 potassium
permanganate solution.

2.8

Indicator Solution - Make a paste of l g of soluble starch and mix into 1 litre
of boiling water. Add 20g of potassium hydroxide, mix, and allow to stand for
2 hours. Add 6m1 of glacial acetic acid, mix and, add sufficient hydrochloric
acid to adjust the pH to 4.0 (Check with a narrow range PH paper). This has a
shelf life of 'l year.

3.0

PROCEDURE

3.1

Place 100m1 of the sample into a clean, glass stoppered bottle of 250 m1
capacity and place in a thermostat at 27C.
.

3.2

When the temperature of the sample becomes 27C, add 4ml of sulphuric acid
(1+3) and l0 ml of potassium permanganate solution (N/80). Mix well and
allow to stand for 4 hours at 27C protected from sunlight.

3.3

Add few crystals of potassium iodide (0.2-0.3 g) and titrate the librated iodine
with standard sodium thiosulphate solution (N/80) using starch indicator.

3.4

Run a blank on 100m1 of water under the same conditions.

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4.0

CALCULATIONS

4.1

Calculate the milligrams of oxygen consumed per litre of sample as follows:


Oxygen consumed, mg/litre = V2 - V1
Where:
V2 =

milliliters of standard sodium thiosulphate used for blank titration.

V1 =

milliliters of standard sodium thiosulphate used for sample


titration.

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XLV)

OXYGEN, DISSOLVED (Indigo Carmine Method)

1.0

SUMMARY OF METHOD
Dissolved oxygen reacts, under alkaline conditions, with the indigo carmine
solution to produce a progressive colour change from yellow-green through
red to blue and blue-green. The colour developed in standards dissolved the
sample is compared with colour representing different concentrations of
oxygen.

2.0

RANGE
Less than 60 micrograms/litre.

3.0

APPARATUS

3.1

Burette, 25 or 50 m1.

3.2

Sampling Bucket, with an overflow at least 20mm above the top of the
sampling vessel.

3.3

Sampling Vessels - Nessler type 60 m1 tubes or 300 m1 BOD bottles having a


raised lip around the neck and glass stoppers ground to a conical lower tip.

4.0

REAGENTS

4.1

Water-conforming to specifications Type II.

4.2

Colour standards, stock solutions.

4.2.1

Red Colour Standard-Dissolve 59.29g of cobaltous chloride (CoC12.6H2O) in


hydrochloric acid (1+99) and dilute to 1 litre.

4.2.2

Yellow Colour Standard-Dissolve 45.05g of ferric chloride (FeC13.6H2O) in


hydrochloric acid (1+99) and dilute to 1 litre.

4.2.3

Blue Colour Standard - Dissolve 62.45g of cupric sulphate (CuSO 4.5H2O) in


hydrochloric acid (1+99) and dilute to 1-litre.

4.2.4

Hydrochloric Acid (sp gr 1.19)

4.2.5

Hydrochloric Acid (1+99)-Mix 1 volume of hydrochloric acid (sp gr 1.19)


with 99 volumes of water.

4.2.6

Indigo Carmine Solution- Dissolve 0.18 g of indigo carmine and 2.0 g of


dextrose (or glucose) in 50 m1 of water. Add 750 m1 of glycerin and mix
thoroughly.

4.2.7

Indigo Carmine-Potassium Hydroxide Reagent- In a small bottle mix 4 parts


by volume of indigo carmine solution (4.2.6) with 1 part of potassium
hydroxide solution (4.2.8). Allow to stand until the initial red colour changes
to lemon yellow. Prepare fresh solution daily.

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4.2.8

Potassium Hydroxide Solution (530g/litre)- Dissolve 530g of potassium


hydroxide in water and dilute to 1 litre.

5.0

CALIBRATION

5.1

Prepare a series of colour standards as listed below:


Equivalent Dissolved
Oxygen(micrograms/litre)

Milliliters of Colour
Standards
RED

YELLOW

BLUE

0.75

05.0

5.0

20.0

10

6.25

12.5

15

9.4

10.0

20

13.0

5.4

25

14.4

5.5

30

14.5

3.3

0.2

35

15.1

2.9

1.1

40

15.5

2.4

2.2

45

16.1

2.0

2.5

50

18.3

1.7

3.1

55

21.7

1.4

13.1

60

25.0

1.0

15.0

5:2

Place the amounts of stock solutions listed above in 300 m1 borosilicate glass
stoppered reagent bottles. Add 3.0 m1 of hydrochloric acid (sp gr 1.19) to
each. Dilute to the neck of the bottle with water. Stopper and mix by
inversion. Store in a dark place.

6.0

PROCEDURE

6.1

Place a clean sampling vessel in the sampling bucket and collect the sample
under water. Allow the sample to overflow for several minutes.

6.2

Fix a burette such that its tip dips into the overflowing sample to a depth of 10
to 15mm.

6.3

Fill the burette with indigo carmine-potassium hydroxide reagent.


Drain
about l ml of reagent into the overflowing sample, and allow the sample to
flush for 1 minute.

6.4

Remove the sample tubing from the sampling vessel.


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6.5

Quickly introduce 0.8m1 of the reagent if 60m1 tube is used or 4m1 of


reagent if a BOD bottle is used, stopper the vessel and mix by inversion.

6.6

Place the vessel on a white surface and match its colour with the standard by
viewing at a 45 angle using a 'Cool" white fluorescent lamp for illumination,

7.0
7.1

PRECISION
The single operator precision of this method may be expressed as follows:
So = 0.052 X + 0.7
Where:
So =

single operator precision

X =

concentration of dissolved oxygen determined, micrograms/litre.

8.0

INTFRFERENCES

8.1

Tannin, hydrazine, and sulphite do not interfere up to l mg/litre.

8.2

Ferric iron, cyclohexylamine, and morpholine up to 4mg/litre can be tolerated.

8.3

Ferrous iron will produce low results and copper will cause high results.

8.4

In samples, where ferrous iron and copper are present, their combined effect is
frequently zero.

8.5

Nitrate is a possible interference.

9.0

NOTES

9.1

Reagent grade chemicals should be used for preparing the reagents.

9.2

All colour stock solutions should be stored in coloured bottles to prevent


fading.

9.3

Indigo carmine solution (4.2.6) is stable for 30 days if stored in a refrigerator.

9.4

In the procedure (6.1), the sample flow should be between 500 to


1000m1/minute when using 300m1 bottle, or 100 to 200m1/minute when
using 60m1 sample tubes.

9.5

In the procedure (6.6), the colours should be matched as soon as possible after
mixing the reagents and sample, since the colours are not stable for more than
30 minutes and air leakage may cause a change in colour.

9.6

The sample should be analysed as soon as possible after the collection.

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XLVI)

OXYGEN, DISSOLVED (Iodometric Method)

1.0

SUMMARY OF METHOD
Free iodine is librated equivalent to Oxygen concentration in the sample by
manganese sulphate solution. The librated iodine is titrated with standard
sodium thiosulphate solution using starch indicator.

2.0

RANGE
1.0 mg/litre or more.

3.0

APPARATUS

3.1

Sample bottles, 300m1 capacity, with tapered ground glass stoppers.

3.2

Pipettes, l0ml capacity, graduated in 0.lml divisions.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

Alkaline Iodide-Sodium Azide solution -Dissolve 500gm


of sodium
hydroxide (or 700g of potassium hydroxide) and 135g of sodium iodide (or
150g of potassium iodide) in water and dilute to 950m1. To this solution add
10g of sodium-azide (NaN3) dissolved in 40 m1 of water. Store the solution in
a dark, rubber stoppered bottle.

4.3

Manganous Sulphate Solution (364g/litre) - Dissolve 364g of manganous


sulphate (MnSO4.H2O) in water, filter, and dilute to 1 litre.

4.4

Sodium Thiosulphate Standard Solution (0.1N) - Dissolve 25g of Sodium


thiosulphate (Na2S2O3.5H2O) in 500m1 of freshly boiled and cooled water,
and add 0.llg of sodium carbonate (Na 2CO3). Dilute to 1-litre and allow to
stand for 24 hours. Standardize against potassium dichromate (See Notes).

4.5

Sodium Thiosulphate Standard Solution (0.025N) (l ml = 0.2mg oxygen) Dilute 125 m1 of 0.1N sodium thiosulphate solution to 500 m1 in a volumetric
flask.

4.6

Starch Solution - Make a paste of l g of soluble starch and mix into 1-litre of
boiling water. Add 20 g potassium hydroxide, mix, and allow to stand for 2
hours. Add 6m1 of glacial acetic acid, mix, and add sufficient hydrochloric
acid (sp gr. 1.19) to adjust the pH to 4.0 (check with a narrow range pH
paper). This has a shelf life of 1-year.

4.7

Sulphuric Acid (sp gr 1.84).

4.8

Potassium Fluoride Solution (400g/litre) - Dissolve 40g of potassium fluoride


(KF.2H2O) in water and dilute to 100 m1. Store in a plastic bottle.
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4.9

Potassium Oxalate solution (20g/litre) - Dissolve 2g of potassium oxalate


(K2C2O4.H20) in 100m1 of water.

4.10

Potassium Permanganate solution (6.3g/litre) Dissolve 6.3g of potassium


permanaganate (KMnO4) water and dilute to 1 litre.

5.0

PROCEDURE

5.1

Collect the sample in the sample bottle (300m1 capacity).

5.2

Add 2.0 m1 of manganous sulphate solution and 2.0 m1 of alkaline iodidesodium azide solution well below the surface of the sample. Replace the
stopper and mix by inversion.

5.3

When the floc has settled, add 2.0 m1 of sulphuric acid (sp gr 1.84).
Restopper, and mix by inversion.

5.4

Titrate 203 m1 of solution (equivalent to 200m1 sample) with standard


solution of sodium thiosulphate using starch indicator.

6.0

CALCULATIONS

6.1

Calculate the dissolved oxygen content of the sample as follows:


Dissolved oxygen, mg/litre =

V1 X 0.2
-------------------------200

x 100

Where:
V1 =

militaries of 0:025N sodium thiosulphate solution required for


titration of sample.

7.0
7.1

PRECISION
The precision of this method was determined by six operators in three
laboratories using a saturated sample of reagent water. The mean
concentration was 9.0 m1/litre and the pooled single operator precision in
these samples was 0.052 mg/litre.

8.0

INTERFERENCES

8.1

Nitrite interferences are eliminated by routine use of sodium azide.

8.2

Ferric iron interferes unless l ml of potassium fluoride solution is used, in


which case 100 to 200mg/litre can be tolerated.

8.3

Ferrous iron interference can be removed by potassium permanganate.

9.0

NOTES

9.1

Reagent grade chemicals should be used for preparing the reagents.

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9.2

9.3

In the procedure (5.4), 203m1 of the solution is titrated to take care of the
displaced sample by 2m1 each of manganous sulphate solution and alkaline
iodide-solution.
300
Hence 200m1 of original sample = 200 X ----------(300 - 4)
=203.3 ml
If it is necessary to eliminate ferrous iron, interference it is done before step
5.2 of the procedure. Following method is followed:

9.3.1

Add 0.7m1 of sulphuric acid (sp gr 1.84) and 1.0m1 of potassium


permanganate to the sample. When high iron is present, also add 1.0ml of
potassium fluoride solution. Stopper and mix by inversion. Add sufficient
potassium permanganate to maintain a violet tinge for 5 - minutes.

9.3.2

After 5 minutes, destroy the violet colour by adding 0.5 to 1.0m1 of potassium
oxalate solution. Mix and allow to stand in dark. Complete decolorization
should be obtained in 2 to 10 minutes.

9.4

Do not delay the determination of dissolved oxygen. Samples may be


preserved 4 to 8 hours by adding 0.7m1 of sulphuric acid (sp gr 1.84) and l ml
of sodium azide solution (20g/litre) to the sample.

9.5

For standardizing sodium thiosulphate solution (0.1N), pulverize 2g of


potassium dichromate, transfers to platinum dish, and dry at 120C for 4
hours. Cool in a desiccator. Weigh accurately 0.21 0.0lg of the dried
potassium dichromate, and transfer to a 500m1 glass stoppered conical flask.
Add 100m1 of water, swirl to dissolve, remove the stopper, and quickly add
3g of potassium iodide, 2g of sodium bicarbonate and 5m1 of hydrochloric
acid (sp gr 1.19). Stopper the flask quickly and allow to stand for 10 minutes
in dark. Titrate with sodium thiosulphate solution until the solution is
yellowish-green. Add 2m1 of starch solution (10g/litre) and continue the
titration to the disappearance of the blue colour.
Calculate the normality of the sodium thiosulphate solution, as follows:
N

W
-----------------------------------------0.04904 X V

Where:
N =

normality of sodium thiosulphate solution.

W =

grams of potassium dichromate used.

milliliters of sodium thiosulphate solution required for titration of


the solution.

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XLVII) OXYGEN DEMAND BIOCHEMICAL (Dissolved Oxygen Loss


Method)
1.0

SUMMARY OF METHOD
The sample is incubated at 20C for 5 days. Dissolved oxygen is measured
initially and after incubation. The BOD is computed from the difference
between initial and final dissolved oxygen (DO).

2.0

APPARATUS

2.1

Incubation Bottles - 250 to 300m1 capacity with ground glass stoppers.

2.2

Air Incubator - thermostatically controlled at 20+1C. All light should be


excluded to prevent possibility of photosynthetic production of DO.

3.0

REAGENTS

3.1

Dilution Water - Add 0.3g of sodium bicarbonate per litre of Type II water.

4.0

PROCEDURE

4.1

Adjust the temperature of a suitable portion of the well mixed sample to 20C.
Remove the oxygen or excess air by maintaining the sample under vacuum for
10 minutes using laboratory vacuum pump.

4.2

Fill completely two incubation bottles (250 or 300m1 capacity) with the
sample as treated above (4.1). Allow to stand for 15 minutes.

4.3

Determine the dissolved oxygen in one bottle by the Iodometric method and in
the other after 5 days" incubation in darkness in the stoppered bottle at 20oC.

5.0

CALCULATIONS

5.1

Calculate the BOD of the sample as follows: Biochemical oxygen demand


(BOD), mg/litre = Dl - D2 (5 days at 20C).
Where:
Dl =

initial dissolved oxygen content, mg/litre.

D2 =

dissolved oxygen content after 5 days incubation, mg/litre.

6.0

INTERFERENCES

6.1

Samples for BOD analysis may degrade significantly during storage, resulting
in low BOD values. This can be minimized by analyzing the sample promptly
or cooling it to 4C or below.
Analysis should be done before 24 hours after grab sample collection.

7.0

NOTES

7.1

The dissolved oxygen content of the sample before incubation shall be


approximately 9mg/litre or preferably less.
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7.2

For samples of doubtful purity, the sample should be mixed with dilution
water in the ratio 1:1 at 20C. Further dilutions shall be used if necessary to
ensure that not more than half the oxygen is consumed during the incubation.
Determine the dissolved oxygen before and after incubation and calculate the
result using the appropriate dilution factor.

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XLVIII) OXYGEN DEMAND, CHEMICAL (Potassium Dichromate Method)


1.0

SUMMARY OF METHOD
The sample is treated with a standard potassium dichromate solution in 50%
sulphuric acid solution. The excess dichromate is titrated with a standard
ferrous ammonium sulphate solution, using orthoprenan-throline-ferrous
complex as an internal indicator.

2.0

RANGE
Upto 800mg/litre.
Samples with higher COD concentrations may be analyzed by appropriate
dilution of the sample.

3.0

APPARATUS

3.1

Reflux Apparatus - A 500ml Erlenmeyer or a 300m1 round bottomed flask,


made of heat resistant glass, connected to a 300mm Allihn condenser by
means of a ground glass joint.

3.2

Heating mantle or hot plate.

3.3

Apparatus for Blending or Homogenising Samples - A household blender is


satisfactory.

4.0

REAGENTS

4.1

Water

4.2

Ferrous Ammonium sulphate solution, Standard (0.25N) - Dissolve 98.Og of


ferrous ammonium sulphate, [FeSO4(NH4)2SO4.6H20] in water. Add 20m1 of
sulphuric acid (sp gr 1.84). Cool and dilute to 1litre. Standardize with
potassium dichromate (0.25N) (see notes).

4.3

Ferrous Ammonium Sulphate Solution, Standard (0.025N) - Dilute 100m1 of


0.25N ferrous ammonium sulphate solution (4.2) to 1 litre. Standardize
against 0.025N potassium dichromate.

4.4

Mercuric Sulphate (Hg SO4), powdered.

4.5

Phenanthroline - Ferrous Sulphate Indicator Solution - Dissolve 1.48g of 1,10


- pherianthroline monohydrate, and 0.70g of ferrous sulphate (FeSO4. 7H2O)
in 100mI of water.

4.6

Potassium Acid Phthalate Solution, Standard (1m1=1mg COD) - Dissolve


0.851g of potassium hydrogen phthalate (KC8H5O4) in water and dilute to 1
litre.

4.7

Potassium Dichromate Standard Solution (0.25N) - Dissolve 12.259g of


potassium dichromate, (K2Cr2O7) previously dried at 103C for 2 hours, in
water and dilute to 1 litre.

- conforming to specifications Type III.

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4.8

Potassium Dichromate Standard Solution (0.025N) - Dilute 100m1 of 0.25N


potassium dichromate solution (4.7) to 1 litre.

4.9

Sulphuric Acid - Silver Sulphate Solution - Dissolve 15g of powdered silver


sulphate (Ag2SO4) in 300m1 of Sulphuric acid (sp gr 1.84) and dilute to 1 litre
with sulphuric acid (sp gr 1.84).

5.0

PROCEDURE

5.1

Homogenize the sample by blending, if necessary. Place 50 m1 of the sample


in a reflux flask.

5.2

Place 50m1 of water in a separate reflux flask for blank determination,

5.3

Place the reflux flasks in an ice bath and add l g of powdered mercuric
sulphate, 5.0 m1 of sulphuric acid (sp gr 1.84) and several glass beads or
boiling stones to each flask and mix well to complete dissolution.

5.4

Add 70m1 of sulphuric acid - silver sulphate solution slowly such that the
solution temperature is maintained as low as possible (below 400C).

5.5

Reflux for 2 hours.

5.6

Allow the flasks to cool and wash down the condensers with about 25m1 of
water. Dilute the solution to about 300 m1 with water and allow to cool to
room temperature.

5.7

Add 8 to 10 drops of phenanthroline ferrous sulphate indicator solution and


titrate the excess dichromate with 0.25N ferrous ammonium sulphate solution.
The colour change is from a blue-green to a reddish-hue. (If the solution
immediately turns reddish brown upon addition of the indicator, repeat the
analysis on a smaller sample aliquot).

5.8

For waters of low COD (10 to 50 mg/litre) use 0.025N potassium dichromate
and 0.025N ferrous ammonium sulphate solutions.

6.0

CALCULATIONS

6.1

Calculate the COD in the sample in mg/litre as follows:


COD, mg/litre = (V1 - V2) x N x 8000
--------------------------V
Where:
V1 =

milliliters of ferrous ammonium sulphate solution required for


titration of blank.

V2 =

milliliters of ferrous ammonium sulphate solution required for


titration of the sample.

N =

normality of ferrous ammonium sulphate.

V =

milliliters of sample used for the test.


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7.0

INTERFERENCES

7.1

The method does not uniformly oxidise all organic materials. Volatile
organics which are difficult to oxidise may be partially lost before oxidation is
achieved. Care .in maintaining a low solution temperature (about 40C) and
permitting oxidation to proceed at the lower temperature for a period of time
before reflux is initiated will result in higher recoveries of theoretical COD.

7.2

Chloride ion is quantitatively oxidised by dichromate in acid solution, with


each mg/litre chloride exerting the equivalent of 0.226mg/litre COD. Reaction
of chloride ion (up to 1000mg/litre) is inhibited by addition of mercuric
sulphate.

7.3

Oxidizable inorganic ions, such as ferrous, nitrite, sulphites, and sulphides are
oxidised and measured also as organic constituents.

8.0

NOTES

8.1

Potassium acid phthalate and potassium dichromate should be of primary


standard grade. All other reagents should be prepared from reagent grade
chemicals.

8.2

For standardizing ferrous ammonium sulphate (0.25N), place 25m1 of 0.25N


potassium dichromate in a 500m1 titration flask and dilute to about 250m1.
Add 20m1 of sulphuric acid (sp gr 1.84) and allow the solution to cool. Titrate
with ferrous ammonium sulphate, using phenanthroline-ferrous sulphate
indicator.

8.3

Calculate the normality (N) of ferrous ammonium sulphate solution as


follows:
Normality, N =

V1 X N1
-----------------------------V

Where :
N

normality of ferrous sulphate solution.

V1

milliliters of potassium solution.

N1

normality of potassium solution.

milliliters of ferrous sulphate solution.

If less than 50m1 of the sample is used (procedure, 5.1) add necessary amount
of dilution water to the reflux flask, then add the sample aliquot and mix.
Samples containing more than 800mg/litre COD are diluted and mixed
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precisely with water and 50m1 of the diluted sample are placed in the reflux
flask.
8.4

To check the validity of the test (procedure, 5.0) results, make a standard
determination using potassium acid phthalate solution (4.6). A COD of 500
mg/litre should be obtained on a 25m1 aliquot of the standard solution diluted
to 50m1.

8.5

In the procedure (5.8) if the COD determined is higher than 50mg/litre after
using 0.025N potassium dichromate and 0.025N ferrous ammonium sulphate
solutions, reanalyze the sample using more concentrated reagents.

8.6

Preserve samples by cooling to 4C if analyzed within 24 hours after sampling


or preserve for up to 7 days at pH < 2 at 4C.

8.7

Silver sulphate acts as a catalyst in the reaction to facilitate the oxidation of


organics which are difficult to oxidise.

8.8

The chemical reaction involved in oxidation of materials by dichromate is


illustrated by the following reaction with potassium acid phthalate (KC8H504):
41H2SO4+l0K2Cr2O7+2KC8H5O4 = l0 Cr2(SO4)3+11K2SO4+16CO2 +46H2O.
Since 10 mol of K2Cr2O7 have the same oxidative power as 15 mol of O2, the
equivalent reaction is:
2 KC8H5O4 + 15 O2 + H2SO4 = 16 Co2 + 6 H2O + K2SO4.
Thus 2 mol of potassium acid phthalate consume 15 mol of oxygen. The
theoretical COD for KC8H5O4 is 1.175 g of O2/g of KC8 H5O4.

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XLIX) PHOSPHATE (Amino Reduction Method)


1.0

SUMMARY OF METHOD
The sample containing orthophosphate, is reacted with ammonium molybdate
in an acidic medium and the resulting phosphomolybdate is reduced to
molybdenum blue complex with amino-naphthol-sulphonic-acid. The
intensity of the blue colour is measured at a wavelength of 650nm. When a
bismuth salt is added the intensity of the blue colour increases by four times.

2.0

RANGE
0.5 to l0mg/litre P04
0.1 to 2.5mg/litre P04 (when bismuth salt is added)

3.0

APPARATUS

3.1

Spectrophotometer for use at 650nm.

3.2

Matched pair of 25mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

ANSA Solution - Dissolve the following chemicals (in the given order) in
100m1 of water: 3.7g of sodium sulphite (Na2SO3), 0.100g of 1-amino-2naphthol-4 sulphonic acid, and 6.2g of sodium metabisulphite (Na2S2O5).
Store in an amber coloured bottle and make fresh every two weeks.

4.3

Ammonium Molybdate solution (48g/litre)


- Dissolve 48g of ammonium
molybdate [(NH4)6Mo7O24.4H20] in 800m1 of water. Add 25m1 of ammonium
hydroxide (sp gr 0.90) and dilute to 1 litre with water.

4.4

Phosphate Stock Solution (100mg/litre P04) - Dissolve 0.1433g of potassium


dihydrogen phosphate (KH2PO4), dried at 105oC for 1 hour, in water and dilute
to 1 litre.

4.5

Phosphate Standard Solution (l0mg/litre PO4) - Dilute 10.0m1 of the stock


solution (4.4) to 100m1 with water.

4.6

Sulphuric Acid Solution (A) - Add 370m1 of sulphuric acid (sp gr 1.84),
slowly and with stirring, to 600m1 of water. Cool and dilute to 1 litre with
water.

4.7

Sulphuric Acid Solution (B) - Dissolve 1.200g of bismuth nitrate


[Bi(NO3)3.5H2O] in 250m1 of sulphuric acid solution (A) (4.6).

5.0

CALIBRATION

5.1

Range from 0.5 to l0mg/litre PO4


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5.1.1

Prepare a series of phosphate standards by diluting 0.0, 0.5, 1.0, 2.0, 5.0 and
l0.0m1 of phosphate stock solution (4.4, l m1 = 0.lmg PO 4) to 100m1 with
water in a volumetric flask.

5.1.2

Proceed in accordance with Section 6.0.

5.1.3

Measure the absorbance of the each standard against reagent blank (zero
standard) at 650nm using 25mm matched absorption cells.

5.1.4

Prepare a calibration curve by plotting absorbance versus milligrams per litre


of phosphate.

5.2

Range from 0.1 to 2.5 mg/litre PO4

5.2.1

Prepare a series of phosphate standards by diluting 0, 1, 5, 10, 15, 20 and 25


m1 of the phosphate standard solution (4.5, l ml = 0.0l mg PO 4) to 100m1
water in a volumetric flask.

5.2.2

Proceed in accordance with section 6.0

5.2.3

Proceed in accordance with 5.1.3 and 5.1.4.

6.0

PROCEDURE

6.1

Orthophosphate, Range 0.5 to l0.0 mg/litre PO4

6.1.1

Transfer 100 m1 of the clear sample into a 250m1 flask.

6.1.2

Add 5.0m1 of sulphuric acid solution (A) and mix.

6.1.3

Add 5.0m1 of ammonium molybdate solution and mix.

6.1.4

Add 5.0m1 of ANSA solution, mix, and allow to stand for 10 minutes.

6.1.5

Measure the absorbance against reagent blank (prepared by adding all the
reagents to 100 m1 water) at 650nm using 25mm matched absorption cells.

6.2

Orthophosphate, Range 0.1 to 2.5mg/litre PO4

6.2.1

Proceed in accordance with 6.1, substituting sulphuric acid solution (B) in


place of sulphuric acid solution (A) in step 6.1.2.

7.0

CALCULATIONS

7.1

Read the concentration of phosphate in mg/litre directly from the calibration


curve prepared in accordance with section 5.0.

7.2

Calculate phosphate concentration in mg/litre as CaCO3, as follows:


Phosphate concentration, mg/litre as CaCO3 = A x 1.58
Where:
A =

phosphate concentration, mg/litre as PO4.

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8.0

INTERFERENCES

8.1

A silica concentration fifty times that of the phosphate will cause an error of
less than 2 percent.

8.2

Up to 40mg/litre iron, 75 mg/litre chromate, and 50,000 mg/litre chloride will


not interfere with the test. Not more than 1500 mg/litre chloride should be
present when the bismuth salt modification is used.

8.3

To prevent formation of calcium sulphate, 7 m1 of hydrochloric acid (sp gr


1.19) should be used in place of sulphuric acid when the calcium
concentration in the sample exceeds 200mg/litre.

8.4

Nitrite interference can be eliminated by addition of 0.lg of sulphamic acid


before adding ammonium molybdate.

8.5

Sulphide upto several mg/litre will not interfere.

9.0

NOTES

9.1

Reagent grade chemicals should be used in preparing all the reagents.

9.2

Only orthophosphate forms a blue colour in the test. Other forms of


phosphorus such as polyphosphate and organic phosphorus can be converted
to orthophosphate, if present in the sample, before applying above mentioned
methods.

9.3

All glassware and sampling bottles should be soaked in hydrochloric acid


(1+3) and rinsed with water before use.

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L)

SILICA, NON REACTIVE (Hydrofluoric Acid method)

1.0

SUMMARY OF METHOD
Non reactive silica is dissolved in hydrofluoric acid and the resulting
fluorosilicic acid in the presence of zirconium ions releases soluble silicic
acid. The latter is reacted with molybdate ion and the resulting green yellow
coloured complex is reduced to a blue complex, the intensity of which is
measured at a wavelength of 815nm.

2.0

RANGE
0 to 500 micrograms/litre SiO2.

3.0

APPARATUS

3.1

Spectrophotometer for use at 815nm.

3.2

Matched pair of 50mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II and filtered through 0.2/0.1


micron membrane fitter.

4,2

Hydrofluoric Acid (1+4) - Dilute 50m1 of 40 % hydrofluoric acid with 200m1


of water. If the hydrofluoric acid is not exactly 40 % adjust the dilution
accordingly.

4.3

Hydrochloric Acid (1+2) - Dilute 50m1 of hydrochloric acid (sp gr 1.19) with
100 m1 of water.

4.4

Zirconium Solution - Dissolve 25g of zirconium oxychloride (ZrOC1 2.8H2O)


in 100m1 of water.

4.5

Ammonium Molybdate Solution (10$) - Dissolve l0g of ammonium


molybdate [(NH4)6 Mo7O24.4H2O ] in water and dilute to 100m1 with water.

4.6

Oxalic Acid Solution (10%) - Dissolve l0g of oxalic acid (H 2C2O4.H2O) in


water and dilute to 100m1.

4.7

Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino -2naphthol -4- sulphonic acid in 50 m1 of a solution containing 1g of sodium
sulphite (Na2SO3). Add the solution to 100m1 of a solution containing 30g of
sodium hydrogen sulphite (NaHSO3). Make up to 200m1 and store in a dark,
plastic bottle. Prepare fresh solution every 2 weeks.

4.8

Silica Stock Solution (lml = 1mg SiO 2) - Dissolve 4.732g of sodium


metasilicate (Na2SiO3.9H20) in water and dilute to 1 litre. Standardize the
solution by acid dehydration procedure (see method for the determination of
soluble silica, Note 10.7).
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4.9

Standard Silica Solution A (l ml = 10 micrograms Si02)-Dilute l0ml of silica


stock solution (4.8) to 1 litre with water.

4.10

Standard silica solution B (l ml = 1 microgram SiO2) .-Dilute 100m1 of


standard silica solution A (4.9) to 1 litre with water,

5.0

CALIBRATION

5.1

Range from 0 to 500 micrograms, SiO2 per Litre

5.1.1

Place 0, 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0m1 of standard silica solution A (l ml
=10 micrograms SiO2) in 100m1 volumetric flasks and make up to 100m1
with water.

5.1.2

Transfer each solution (5.1.1) to 200m1 polythene conical flasks.

5.1.3

Proceed in accordance with section 6.1 (6.1.2 to 6.1.5).

5.1.4

Prepare a calibration curve by plotting absorbance versus micrograms of Si02


per litre.

5.2

Range from 0 to 50 micrograms Si02 per Litre

5.2.1

Place 0.0, 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0m1 of standard silica solution B (l ml =
1 microgram Si02) in 100m1 volumetric flasks and make up to 100 m1 with
water.

5.2.2

Transfer each solution (5.2.1) to 200 ml polythene conical flasks.

5.2.3

Proceed in accordance with Section 6.1 (6.1.2 to 6.1.5)

5:2.4

Prepare a calibration curve by plotting absorbance versus micrograms of SiO 2


per litre.

6.0

PROCEDURE

6.1

For Reactive Silica

6.1.1

Place 100m1 of sample in a 200m1 polythene conical flask.

6.1.2

Add 2m1 of hydrochloric acid solution, 4.5m1 of water and 2m1 of


ammonium molybdate solution. Mix thoroughly and allow to stand for 10
minutes.

6.1.3

Add 3 m1 of oxalic acid solution and mix. Allow to stand for 10 minutes.

6.1.4

Add 2 m1 of amino naphthol sulphonic acid solution and allow to stand for
10 minutes.

6.1.5

Measure the absorbance of the sample against the zero standard (blank) (E1)
at 815nm.

6.1.6

For blank, place 100m1 of water in a 200m1 polythene conical flask and
proceed in accordance with 6.1.2 to 6:2.4

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6.2

For Non-Reactive Silica plus Reactive Silica

6.2.1

Place 100m1 of sample in a 200m1 polythene conical flask.

6.2.2

Add l ml of hydrochloric acid and 2m1 of hydrofluoric acid and mix


thoroughly. Allow to stand for 10 minutes.

6.2.3

Add 3.5m1 of zirconium solution and, drop by drop with stirring, 2m1 of
ammonium - molybdate solution. Mix thoroughly. Allow to stand for 10
minutes.

6.2.4

Add 3m1 of oxalic acid solution and mix thoroughly. Allow to stand for 10
minutes.

6.2.5

Add 2m1 of amino-naphthol-sulphonic acid solution and allow to stand for 10


minutes.

6.2.6

Measure the absorbance of sample against the blank solution (E2) at 815nm.

6.2.7

For blank, place 100m1 of water in a 200m1 polythene conical flask and
proceed in accordance with 6.2.2 to 6.2.5.

7.0

CALCULATIONS

7.1

From the value E2 using the calibration curve, calculate the, concentration of
reactive plus non reactive silica in the sample.

7.2

From the value (E2-El), using the calibration curve, calculate the
concentration of non reactive silica in the sample.

7.3

Calculate the non-reactive silica concentration in micrograms/litre as CaCO3,


as follows:
Non reactive silica concentration, micrograms/litre as CaCO3 = Ax 0.83.
Where:
A=

non-reactive silica concentration, micrograms/ litre as SiO2.

8.0

INTERFERENCES

8.1

See method for the determination of soluble silica (section 9.0).,

9.0

NOTES

9.1

See method for the determination of soluble silica (Section 10.0).

9.2

In the analytical procedure the HF/Zr ratio must be kept constant and should
be equal to 6/1. Values greater than this ratio correspond to an excess of
hydrofluric acid which then again reacts with silicic acid to form fluorosilicic
acid and thus introducing error. Values lower than this ratio corresponds to an
excess of Zr+4 ions that give rise to a white precipitate in the presence of
silico-molybdic complex. Hence, it is very important to know precisely, the
zirconium content in the ZrOCl2.8H20 reagent and the HF titre in 40%
hydrofluoric acid to adjust the amount of zirconium and HF solutions.
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9.2.1

The strength of hydrofluoric acid is determined by titration with a standard


alkali solution.

9.2.2

For the determination of zirconium in zirconyl oxychloride weigh 0.25g of


zirconyl oxychloride, dissolve it in about 60m1 of water and add 20m1 of
hydrochloric acid (sp gr 1.19). Precipitate by addition of 20m1 of 10 % phenyl
arsenic acid solution. Bring to boil. Filter through a slow filter paper (e.g.,
Whatman No.42) and wash the precipitate with a 1% hydrochloric acid
solution. Ignite the precipitate in a porcelain crucible at a temperature of
1000C for 3 hours. Cool in a desiccator and weigh as zirconium oxide.
Calculate the zirconium content in zirconium oxychloride as follows:
W1 x 7403
Zr content (% w/w in zirconium oxychloride) = ---------------W x 28.317
Where:
W1

weight of zirconium oxide.

weight of zirconium oxychloride.

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LI)

SILICA, NON-REACTIVE (Membrane Filtration Method)

1.0

SUMMARY OF METHOD
The sample is filtered through a 0.2 micron membrane filter and the residue
left on the membrane filter is treated with 48% hydrofluoric acid. The soluble
silica thus produced is reacted with ammonium molybdate and the
concentration of resulting complex is determined calorimetrically.

2.0

RANGE
0 to 100 micrograms /litre SiO2
(Higher concentrations can be determined by proper dilution of the sample
with water):

3.0

APPARATUS

3.1

Membrane Filter, 0.2 micron pore size and 47mm diameter.

3.2

Membrane Filter Holder, preferably of stainless steel.

3.3

Laboratory vacuum pump.

3.4

Polythene Beakers, 150m1 capacity with polythene covers.

3.5

Polythene Discs, 50mm diameter.

3.6

Water Bath to accommodate at least 6 beakers and with a temperature control


between 35 - 50C.

3.7

Spectrophotometer for use at 420 and 815nm.

3.8

Matched pair of l0 mm and 50 mm cells.

4.0

REAGENTS

4.1

Water- conforming to specification Type II and filtered through 0.2/0.1


membrane filter.

4.2

Boric Acid Solution (5%) - Dissolve 100g of boric acid (H3BO3) in 2 litres of
warm water.

4.3

Ammonium Molybdate Reagent - Dissolve 50g of ammonium molybdate


[(NH4)6Mo7O24:4H2O) about 400m1 of water. Add slowly with constant
stirring, 40m1 of sulphuric acid '(sp gr 1.84). Cool to room temperature and
dilute to 500m1 with water.

4.4

Sulphuric Acid (l0 N) - Cautiously add, with constant stirring, 555m1 of


sulphuric acid (sp gr 1.84) to 1.4 litres of water. Cool to room temperature and
dilute to 2 litres with water.
.

4.5

Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino-2naphthol-4- sulphonic acid in 50m1 of a solution containing l g of sodium
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sulphite (Na2S3). Add the solution to 100m1 of a solution containing 30g of
sodium bisulphite (NaHSO3). Make up to 200m1 with water and store in a
dark, plastic bottle.
4.6

Silica Stock Solution (l ml = l mg SiO2) - Dissolve 4.732g of sodium


metasilicate (Na2SiO3.9H2O) in water and dilute to 1 litre. Standardize the
solution by acid dehydration procedure (see method for the determination of
soluble silica, Note 10.7).

4.7

Standard Silica Solution A (l ml = 10 micrograms SiO2) - Dilute l0ml of silica


stock solution (4.6) to 1 litre with water.

4.8

Standard silica solution B (l ml = 1 microgram SiO 2) --Dilute 100m1 of


standard silica solution A (4:7) to, 1 litre with water.

5.0

CALIBRATION

5.1

Range from 0 to 500 micrograms SiO2 per Litre

5.1.1

Place 0.0, 0.5, 1.0, 2:0, 3.0, 4.0 and 5.0 m1 of standard silica solution A (l ml
= 10 micrograms Si02) in 200m1 polythene flasks. Add water to make 75m1.

5.1.2

Add 4.0m1 of ammonium molybdate reagent and mix. Allow to stand for 20
minutes at 35-40C in a water bath.

5.1.3

Remove the flasks from the water bath and add 20m1 of sulphuric acid (10 N)
rapidly while stirring.

5.1.4

Measure the absorbance of each standard at 420nm against zero standard


(blank) using l0mm absorption cells,

5.1.5

Prepare a calibration curve by plotting absorbance versus concentration of


silica in micrograms.

5.2

Range from 0 to 100 micrograms Si02 per Litre

5.2.1

Place 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 and l0.0 m1 of standard silica solution B (l ml
= 1 microgram Si02) in 200m1 polythene flasks. Add water to make 75m1.

5.2.2

Add 4.Om1 of ammonium molybdate reagent and mix. Allow to stand for 20
minutes at 35-40C in a water bath.

5.2.3

Remove the flasks from the water bath and add 20m1 of sulphuric acid (10 N)
rapidly while stirring. Allow to stand for 5 minutes.

5.2.4

Add l ml of amino-naphthol-sulphonic acid solution and mix. Allow to stand


for 20 minutes.

5.2.5

Measure the absorbance of each standard at 815nm against zero standard


(blank) using 50mm absorption cells.

5.2.6

Prepare a calibration curve by plotting absorbance versus concentration of


silica in micrograms.

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6.0

PROCEDURE

6.1

Filter 500 m1 of the water sample through a 0.2 micron membrane filter by
applying vacuum.

6.2

Place the membrane filter in the bottom of a 150m1 polythene beaker and add
0.5 ml of 48% hydrofluoric acid with the help of a long and thin, calibrated
polythene dropper. Place a polythene disc on the membrane filter and cover
the beaker with a polythene cover. Allow to stand for 30 minutes.

6.3

Add 25m1 of water and 50m1 of boric acid solution. Mix well and place the
beaker in a water bath controlled at 40-50C. Allow to stand for 15 minutes.

6.4

Add 40m1 of ammonium molybdate reagent while stirring. Allow to stand for
20 minutes at 35-40C in a water bath.

6.5

Remove the beaker from the water bath and add 20m1 of sulphuric acid
(10 N) rapidly while stirring. If a pronounced yellow colour remains, measure
the absorbance at 420nm using l0 mm absorption cell.

6.6

If the yellow colour is not pronounced, add l ml of amino-naphthol-sulphonic


acid solution 5 minutes after the addition of sulphuric acid. Allow to stand for
20 minutes.

6.7

Measure the absorbance at 815nm using 50mm absorption cell.

6:8

Run a blank alongwith the sample, using a 0.2 micron membrane filter and
proceeding in accordance with 6.2 to 6.6.

7.0

CALCULATIONS

7.1

Calculate the concentration of non-reactive silica in micrograms per litre as


follows:
Non-reactive silica, micrograms/litre = 2A.
where:
A = Silica concentration read from the calibration curve in micrograms.

7.2

Calculate the non-reactive silica concentration in micrograms/litre as CaCO3,


as follows:
Non-reactive silica concentration, micrograms/litre as CaCO3 = B x 0.83.
Where:
B = non-reactive silica concentration, micrograms/ litre as SiO2.

8.0

NOTES

8.1
8.2
8.3

See method for the determination of soluble silica (section 10.0).


Reagent grade chemicals should be used for preparing all the reagents.
Hydrofluoric acid used should contain least possible amount of fluorosilicic
acid.
0.1 micron membrane filters should be preferred.
Presence of boric acid up to a concentration of 16,200 mg/litre does not
interfere significantly.

8.4
8.5

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LII)

SILICA REACTIVE (Amino Reduction Method)

1.0

SUMMARY OF METHOD
The sample containing reactive silica is reacted with molybdate ion in an
acidic medium (pH 1.2 to 1.5) and the resulting green-yellow coloured
complex is reduced to a blue complex with 1-amino-2- naphthol-4-sulphonic
acid the intensity of which is measured at a wavelength of 815nm.

2.0

RANGE
5 to 140 micrograms/litre SiO2.

3.0

APPARATUS

3.1

Spectrophotometer for use at 815nm.

3.2

Matched pair of 50mm cells.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino -2naphthol-4-sulphonic acid in 50m1 of a solution containing l g of sodium
sulphite (Na2SO3). Add the solution to 100 ml of a solution containing 30g of
sodium hydrogen sulphite (NaHSO3). Make up, to 200m1 and store in a dark
plastic bottle. Prepare fresh solution every 2 weeks.

4.3

Ammonium Molybdate Solution - Dissolve 10.0g of ammonium molybdate


[(NH4)6.Mo7O24.4H2O] in water and dilute to 100m1 with water.

4.4

Hydrochloric
1.19) and water.

4.5

Oxalic Acid Solution (10%) - Dissolve l0g of oxalic acid (H2C2O4.2H2O) in


water and dilute to 100m1.

4.6

Silica Stock Solution (l ml = l mg SiO 2) - Dissolve 4.732g of sodium meta


silicate (Na2SO3-9H20) in water and dilute to 1 litre. Standardize the solution
by acid dehydration procedure (Note 10.7).

4.7

Silica Standard Solution (l ml = 1 microgram SiO2) - Dilute l0.0m1 of silica


stock solution (4.6) to 1 litre with water. Again dilute 100m1 of this diluted
solution to 1 litre.

5.0

CALIBRATION

5.1

Prepare a series of standards (at least five concentrations) to cover the range 5
to 140 micrograms Si02/litre by diluting appropriate volumes of silica standard
solution (4.7, l ml = 1 microgram SiO2) to 50 m1 in 100 m1 polythene bottles.

5.2

Proceed in accordance with section 6.0 (6.2 to 6.6)

Acid (1+1) - Mix equal volumes hydrochloric acid (sp gr

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5.3

Prepare a calibration curve by plotting absorbance versus micrograms of


Si02/litre.

6.0

PROCEDURE

6.1

Transfer 50m1 of sample into a 100m1 polythene bottle.

6.2

Add 1.0 m1 of hydrochloric acid (1+1) and mix, then add 2.0ml of ammonium
molybdate solution and mix well.

6.3

After 5 minutes, add 1.5m1 of oxalic acid solution and mix well.

6.4

After 1 minute, add 2.0m1 of amino-naphthol-sulphonic-acid solution. Mix


well and allow to stand for 10 minutes.

6.5

Prepare a reagent blank by treating 50.0m1 of water as directed in 6.2 through


6.4.
Measure the absorbance at 815nm against the reagent blank using 50mm
matched absorption cells.

7.0

CALCULATIONS
Read the concentration of silica in micrograms/ litre as SiO 2 directly from the
calibration curve prepared in section 5.0.
Calculate the concentration of silica in micrograms/litre as CaCO3, as follows:
Silica, micrograms/litre as CaCO3 = A x 0.83.
Where:
A = Silica concentration, micrograms/litre as SiO2

8.0

PRECISION

8.1

The precision of this method may be expressed as follows:


So =

0.005 X + 0.7

St =

0.03 X + 1.3

Where:
= single operator precision, micrograms
SiO2/litre.
St =

overall precision, micrograms Si02/litre.

X =

concentration of silica determined, micrograms SiO2/litre.

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9.0

INTEREFERENCES

9.1

Samples containing less than 1.Omg/litre of Si02 do not normally contain a


significant concentration of interfering substances.

9.2

Colour and turbidity will interfere if not removed by filtration or dilution.

9.3

Phosphate interference is eliminated by the addition of oxalic acid.

9.4

No significant interference due to the presence of boric acid up to


16,200mg/litre has been observed.

9.5

Strong oxidising and reducing agents may interfere in the reduction step.

9.6

Organic compounds may interfere in the colour formation.

10.0

NOTES

10.1

Reagent grade chemicals should be used for preparing all the reagents.

10.2

Samples should be collected in plastic or stainless steel sample bottles


provided with rubber or plastic stoppers.

10.3

All reagents to be used in this method should be stored in polythene or other


suitable plastic bottles.

10.4

The amino-naphthol-sulphonic acid solution should be discarded when its


colour darkens or a precipitate forms.

10.5

The ammonium molybdate solution should be discarded when a white


precipitate develops.

10.6

An alternate method of standard silica solution preparation is from transparent


spectrosil rod. This rod is made of Si02 containing less than l mg/litre of
impurities and 30cm of this rod weighs about 5g. Procedure is as follows:
Weigh 1.000g of spectrosil rod into a, platinum crucible and place 5g of
anhydrous sodium carbonate on the top of rod. Heat to bright red and continue
heating for 10 minutes. Cool, dissolve the melt in water and make up to 1 litre.

10.7

The strength of silica stock solution (4.6) may be checked as follows:


Place 100m1 of Silica stock solution (4.6) in a 400m1 scratch-free glass
beaker. Neutralize with hydro-chloric acid (sp gr 1.19) to methyl orange end
point and add 5m1 in excess. Evaporate the solution to dry-ness on a water
bath, with periodic additions of three more 5m1 increments of hydrochloric
acid (sp gr 1.19). Dry the evaporated residue in an oven at 110C for 1 hour.
Add 5ml of hydrochloric acid (sp gr: 1.19) and then 50m1 of water to the
beaker, warm the beaker and its contents. Stir the mixture. Filter the warm
solution through an ashless, medium texture filter paper. Wash the residue on
the paper 15 times with hydrochloric acid (1+19) and then with several small
increments of water. Reserve the paper and its residue for later ignition,
Return the filtrate and washings obtained above to the original evaporating
beaker, and evaporate to dryness on a water bath with periodic addition of
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two 5m1 increments of hydrochloric acid (sp gr 1.19). Dry the evaporated
residue in an oven at 110C for 1 hour. Add 5m1 of hydrochloric acid (sp gr
1.19) and then 50m1 of water to the beaker, warm the beaker and its contents
and stir the mixture. Filter the warm solution through an ashless, medium
texture filter paper. Wash the residue. on the paper 15 times with hydrochloric
acid (1+19) and then with several small increments of water.
Place both filter papers with their residues in a weighed platinum crucible, dry
and char the paper without flaming it, and then ignite the charred residue for
30 minutes at 1000 to 1200C. Cool in a desiccator and weigh. Repeat the
ignition, cooling, and weighing until a constant weight is obtained.
Add several drops of sulphuric acid (sp yr 1.84) and about 5m1 of
hydrofluoric acid (48%) to the weighed residue in, the crucible and evaporate
to dryness on a low temperature hot plate under a fume hood. Reignite the
residue at 1000 to 1200C and weigh. Repeat the ignition, cooling, and
weighing until a constant weight is obtained.
Determine a reagent blank by making an identical silica determination on the
quantity of water required for the washing of the residue plus 100m1.
Calculate the concentration of silica, in milligrams per litre, in silica stock
solution, as follows:
Si02, mg/litre

(Wl-W3) - (W2-W4)
----------------------------------------V

Where:
W1 = weight of crucible and residue, mg, after first ignition.
W2 = weight of crucible and residue, mg, after treatment with hydrofluoric
acid and reignite it.
W3 = weight of crucible and blank residue, mg, after first ignition.
W4 = weight of crucible and blank residue, mg, after treatment with
hydrofluoric acid and reignition.
V = volume of sample used, litres.

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LIII)

STEAM PURITY (Sodium Tracer Method)

1.0

SUMMARY OF METHOD
Sodium is determined both in steam and boiler water by flame photometer or
sodium ion electrode method. Then total solids are determined in boiler water,
and concentration of impurities in steam is calculated based on the assumption
that concentration of sodium-to-impurities in steam is equal to the
corresponding ratio in boiler water.

2.0

RANGE
If the impurities are principally sodium compounds, impurity concentrations
as low as 0.6 microgram/ litre may be detected by the flame photometry
method and as low as 0.05 microgram/litre by the sodium ion electrode
method.

3.0

APPARATUS

3.1

Flame photometer or sodium ion electrode assembly.

4.0

TEST CONDITION AND PROCEDURE

4.1

4.2

Test to conducted at full load ( around 90 % MCR )


Steady operating conditions of load, drum water level, steaming rate and
boiler water chemistry
The operating parameters of load, steam flow, drum pressure and drum level
are to be maintained for a minimum 4 hours.
Maximum permissible phosphate to be dosed in the boiler and CBD to remain
in closed condition.
Determine the sodium content of both steam and boiler water samples.
5 samples to be collected for analysis at the end of the steady state of boiler
operation.
Determine total solids in the boiler water sample by evaporation method.

5.0

CALCULATIONS

5.1

Calculate the impurity concentration of the steam sample as follows:


WT
St = Ss x --------------------WS
Where:
St =
Concentration of total dissolved solid (TDS) in steam, mg/litre
Ss =
Concentration of Sodium in steam, mg/ litre
WT =
Concentration of total dissolved solids (TDS) in boiler water,
mg/litre. {Coductivity (s/cm) / 1.8}
WS =
Concentration of sodium in boiler water, mg/litre
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Steam purity (% Dryness factor) = 100 -TDS in steam


6.0

NOTES

6.1

When flame photometric method is employed, determine the sodium


concentration of steam either from a continuously flowing sample or from at
least 10 separately collected samples taken under steady state conditions.
Samples having sodium contents considerably higher than other samples are
generally assumed to be contaminated and should be discarded.

6.2

A continuously flowing sample must be employed for the sodium ion


electrode method. (By on-line analyzer)

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LIV)

SULPHATE (Gravimetric Method)

1.0

SUMMARY OF METHOD
Sulphate ion is precipitated and weighed as barium sulphate after removal of
silica and other insoluble matter.

2.0

RANGE
20 to 100mg/litre as SO4.
It can be extended to higher or lower ranges by adjusting the sample size.

3.0

REAGENTS

3.1

Water - conforming to specifications Type II.

3.2

Barium Chloride Solution (118g/litre) - Dissolve 118g of barium chloride


(BaC12.2H2O) in water and dilute to 1 litre.

3.3

Hydrochloric Acid (1+9) - Mix 1 volume of hydrochloric acid (sp gr 1.19)


with 9 volumes of water.

3.4

Hydrofluoric Acid (48 to 51%).

3.5.

Methyl Orange Indicator Solution (0.5g/litre) - Dissolve 0.05g of methyl


orange in water and dilute to 100m1.

3.6

Silver Nitrate Solution (100g/litre) - Dissolve l0 g of silver nitrate (AgNO 3) in


water and dilute to 100m1.

3.7

Sulphuric Acid (sp gr 1.84).

4.0

PROCEDURE

4.1

Place clear sample, containing sulphate ion equivalent to 10 to 50mg of


barium sulphate into a 500m1 beaker.

4.2

Adjust the volume of sample to approximately 200m1 by evaporation or


dilution.

4.3

Adjust the acidity of the sample to methyl orange end point and add l0 ml
excess of hydrochloric acid (1+9).

4.4

Boil the solution and add slowly 5m1 of hot barium chloride solution while
stirring vigorously. Keep for 2 hours on a .steam bath.

4.5

Filter through Whatman No.42 or equivalent filter paper and wash the
precipitate with hot water until the washings are substantially free of chloride
(check with silver nitrate solution).

4.6

Place the filter paper and its contents in a weighed platinum crucible and
ignite at 800C for 1 hour.
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4.7

Add a drop of sulphuric acid and a few drops of hydrofluoric acid, and
evaporate under a hood to expel silica.

4.8

Reignite at 800C, cool in a desiccator, and weigh as barium sulphate.

5.0

CALCULATIONS

5.1

Calculate the concentration of sulphate in mg/litre as follows:


Sulphate, mg/litre as SO4

W X 411,500
-------------------------V

Where:
W = weight of barium sulphate, g.
V = volume of sample, ml.
5.2

Calculate the sulphate concentration in mg/litre as CaCO3, as follows:


Sulphate concentration, mg/litre as CaCO3 = A x 1.04
Where:
A =

sulphate concentration, mg/litre as SO4.

6.0

PRECISION

6.1

Results of this method are precise to 1.0% of the amount of sulphate ion
present.

7.0

INTERFERENCES

7.1

Sulphites and sulphides may oxidise and precipitate with sulphate.

7.2

Turbidity caused by silica or other insoluble material .would interfere if


allowed to be present.

8.0

NOTES

8.1.
8.2

Reagent grade chemicals should be used for preparing all the reagents.
Turbidity may be removed by filtration 'through a fine filter paper (eg.,
Whatman No.42).
Silica may be removed, prior to analysis, by acid dehydration procedure (see
method for the determination of soluble silica, Note 10.7). In this case, the
ignition described in 4.6 need not be done in a platinum crucible.
Faster precipitation and a coarser precipitate can be obtained by adding l0ml
of saturated picric acid solution and boiling the sample for.5 minutes before
adding barium chloride.
Do not attempt to obtain a complete removal for chloride. Discontinue
washing, when not more than a faint opalescence is produced in the test for
chloride.

8.3

8.4

8.5

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

LV)
1.0

SULPHATE (Volumetric Method)


SUMMARY OF METHOD
The sample is titrated in an alcoholic solution under controlled acid conditions
with a standard barium chloride solution using thorin as indicator. The
endpoint is indicated by a change in colour from a yellow to a stable pink
colour.

2.0

RANGE
5 to 1000mg/litre as S04.

3.0

APPARATUS

3.1

Microburette, reading to 0.01ml.

3.2

Ion Exchange Column - Glass column, 500 5mm long and 9 to l0 mm


inside diameter. The top of column widens to a reservoir of 50 to 55mm inside
diameter and 100 5mm in length. 30cm of wet strong acid cation resin is
poured into the column which is held by a filter plug. The flow is controlled
by a length- of 2mm bore capillary tubing joined to the bottom of the column.
This tubing is bent into a U-shape and rises to about 13mm above the resin
bed and then makes a U-bend downward for about 50 to 70mm.

4.0

REAGENTS

4.1

Water - conforming to specifications Type II.

4.2

Alcohol - Ethyl alcohol (95%), isopropyl alcohol, or methyl alcohol.

4.3

Ammonium Hydroxide (1+99) - Mix 1 Volume of ammonium hydroxide (sp


gr 0.90) with 99 volumes of water.

4.4

Barium chloride standard solution (l ml = 0.500mg S04) - Dissolve 1.221g of


barium chloride (BaC12.2H20) in 1 litre of water that has been adjusted to pH
3.8 to 4.0 with dilute hydrochloric acid. Standardize in accordance with
section 5.0.

4.5

Hydrochloric Acid (1+99) - Mix 1 volume of hydrochloric acid (sp gr 1.19)


with 99 volumes of water.

4.6

Hydrogen Peroxide (30%).

4.7

Standard Iodine Solution (1 ml = 0.480mg SO 4) - Dissolve 10g of potassium


iodide (KI) in 100m1 of water, add 1.27g of iodine crystals, and stir to
dissolve. Dilute to 1 litre. Standardize against 0.01N sodium thiosulphate
solution.

4.8

Ion Exchange Resin - Strong acid cation exchange resin, 710 to 850 micron.
(IR 120 or equivalent). Regeneration is to be done with hydrochloric acid
(I+4).
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Manual on Analytical Test Procedure for Water and Steam in Power Plants
4.9

Magnesium Carbonate (MgC03).

4.10

Phenolphthalein Indicator Solution (5g/litre) = Dissolve 0.5g


phenolphthalein in 50m1 of ethyl alcohol. Dilute to 100m1 with water.

4.11

Starch Indicator - Make a paste of l g of starch with cold water. Pour the paste
into 100m1 of boiling water and boil for several minutes. This is stable for 2
to 3 days.

4.12

Standard Sulphate Solution (l ml = 0.l00mg SO 4) - Dissolve 0.1479g of


anhydrous sodium sulphate, in water and dilute to 1 litre with water.
Standardize by the gravimetric method.

4.13

Thorin solution (2.0g/litre) - Dissolve 0.2g of thorin [2 (2-hydroxy-3, 6 disulpho - 1-naphthylazo) benzene arsenic acid] in 100 m1 of water.

5.0

STANDARDIZATION OF BARIUM CHLORIDE SOLUTION

5.1

Prepare a series of standard sulphate solution: by diluting with water 0.0, 2.0,
5.0, 10.0, 15.0,25.0, 35.0 and 50.0m1 of the standard sulphate solution (l ml=
0.l00mg SO4) to 50m1 in volumetric flasks.

5.2

Determine the blank and sulphate equivalent of barium chloride solution (note
12:2) in accordance with 6.3, 6.4 and 6.5.

6.0

PROCEDURE IN THE PRESENCE OF SULPHITE, PHOSPHATE AND


CHROMIUM

6.1

Place 25m1 of filtered sample into a 100m1 beaker. Add 0.5 m1 of starch
indicator and titrate the sulphite with iodine solution.

6.2

Add 2 to 3 drops of phenolphthalein indicator and adjust the pH to about 10.3


with hydrochloric acid (1+99) or ammonium hydroxide (1+99) using narrow
range pH paper. Add 0.3 to 0.5g magnesium carbonate and boil for 5 minutes.
Cool to 10C and filter through Whatman No.41 or equivalent filter paper into
a 50 m1 volumetric flask. Wash the precipitate with three 5 m1 portions of
water at 10C. Add few drops of hydrogen peroxide, shake, and adjust the
volume to 50 m1 with water.

6.3

Pass the solution through the ion exchange column and discard the first 25 to
30m1 of effluent. Place l0.0m1 of the next effluent into a small white
porcelain dish (100 to 125m1 capacity).

6.4

Add 40m1 of alcohol and 2 drops of thorin indicator. Adjust the pH to 3.8 to
4.0 by dropwise addition of ammonium hydroxide (1+99) until the- solution
just turns pink. Add hydrochloric acid (1+99) dropwise until the pink colour
disappears.

6.5

Prepare a blank using water and reagents described in 6.1 to 6.4 and record the
iodine solution used for the sulphite correction of the blank. Titrate the sample
with barium chloride solution, using the untitrated yellow blank as a colour
NTPC Limited

of

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
reference, to a stable pink colour -which deepens to a reddish pink on over
titration. Then titrate the blank to the same colour, reached in the sample.
7.0

PROCEDURE IN THE ABSENCE OF SULPHITE, PHOSPHATE AND


CHROMIUM

7.1

Pass 50m1 of the filtered sample directly through the ion exchange column.
Collect l0.0ml of effluent and proceed in accordance with 6.3, 6.4 and 6.5.

8.0

PROCEDURE
IN
INTERFERENCES

8.1

Directly titrate l0.0m1 of the filtered sample in accordance with 6.4 and 6.5.

9.0

CALCULATIONS

THE

PRESENCE

OF

NEGLIGIBLE

Calculate the sulphate concentration in the original sample, in milligrams per


litre, as follows:
Sulphate, mg/litre SO4 =

[(V1-B1) X 500]
--------------------- V3

[(V2 -B2) X 480]


----------------------V4

Where:

9.2

V1 =

milliliters of barium chloride solution required for titration of the


sample.

V2 =

milliliter of iodine solution required for titration of the sample for


sulphite correction.

B1 =

milliliters of barium chloride solution required for titration of the


blank.

B2 =

milliliters of iodine solution required for titration of the blank for


sulphite correction.

V3 =

milliliters of original sample titrated.

V4 =

milliliters of original sample titrated for the sulphite correction.

Calculate the sulphate concentration in mg/litre as CaC03, as follows:


Sulphate concentration, mg/litre as CaCO3 = Ax1.04
Where:

sulphate concentration, mg/litre as SO4.

10.0

PRECISION

10.1

Titration of Sulphate in the range 5 to 100mg/litre, after ion exchange


treatment is accurate to 1.5mg/ litre. The precision of this method upto
100mg/litre is 0.7mg/litre. Single operator precision may be expected to be
0.5mg/litre.
NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
11.0

INTERFERENCES

11.1

Both cations and anions may cause co-precipitation errors with barium
sulphate precipitate. Most metallic ions also interfere by forming coloured
complexes with the thorin indicator, especially in alcohol water mixtures.

11.2

Interference by cations is eliminated by ion exchange.

11.3

Fluorides and nitrates cause no interference up to concentrations of 2 and


50mg/litre respectively.

11.4

Ortho and metaphosphate interfere when present in excess of 2mg/litre.


Phosphate is removed by precipitation with magnesium carbonate and
filtration in cold.

11.5

Sulphite interference is eliminated by determining the sulphate equivalent of


the sulphite and subtraction of this sulphate from the determined sulphate
content. Sulphides can be removed by precipitation as zinc sulphide.

11.6

Chloride masks the pink endpoint if present in concentration more than


1000mg/litre when the sulphate present is low (about 5mg/litre).

11.7

Chromium present as chromates and dichromates is converted to Cr +3 with


hydrogen peroxide and then removed by ion exchange.

12.0

NOTES

12:1

Reagent grade chemicals should be used for preparing all the reagents.

12.2

A solution of known sulphate concentration should be run with each series of


tests or new reagents to check the standardization curve. The blank used to
determine sulphate content is preferably that determined from the
standardization curve extrapolated to zero.

12.3

Phosphate ion is almost completely precipitated (step 6.2) at or below 10C,


but solubility increases with increasing temperature.

12.4

If the ammonium hydroxide--(step 6.4) is added too fast, it is possible to overrun the colour change from yellow to pink and the sample continues to be
yellow.
It is then impossible to develop the pink colour by addition of
ammonium-hydroxide.

12.5

For very low sulphate concentrations a less concentrated barium chloride


solution (l ml = 0.200mg sulphate) should be used. A standard sulphate
solution may be added to the sample to raise the total sulphate concentration
to 10 to 15mg/litre. This added sulphate must be subtracted from the final
result.

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

LVI)

SULPHITE (Titration Method)

1.0

SUMMARY OF METHOD
The sample is mixed with hydrochloric acid and potassium iodide and titrated
against potassium iodate solution in presence of starch indicator. The iodine
liberated reacts with sulphite and the endpoint is indicated by the formation of
blue colour.

2.0

RANGE
3mg/litre or more as Na2SO3.

3.0

REAGENTS

3.1

Water - conforming to specifications Type II.

3.2

Hydrochloric Acid Solution (1+3) - Mix one volume of hydrochloric acid (sp
gr 1.19) with three volumes of water.

3.3

Potassium Iodate Solution (l ml = l mg Na2SO3) -Dissolve 0.566g of


potassium iodate (KIO3, dried at 120C) and 0.5g of sodium bicarbonate
(NaHCO3) in water and dilute to 1 litre.

3.4

Potassium Iodide Solution (5%) - Dissolve 50 g of potassium iodide (KI) in 1


litre of water.

3.5

Starch Indicator - Make a paste of 6g of starch with cold water. Pour the paste
into 1 litre boiling water add 20g of potassium hydroxide, mix, and allow to
stand for 2 hours. Add 6m1 of glacial acetic acid (sp gr 1.05) and mix. Add
hydrochloric acid (sp gr 1.19) to adjust the pH value of the solution to 4.0
(check with the help of pH-paper). This has a shelf life of 1 year.

3:6

Sulphamic Acid (NH2SO3H), Crystalline.

4.0

PROCEDURE

4.1

No Nitrite Interference Suspected

4.1.1

Add 5m1 of hydrochloric acid solution and 5 m1 of potassium iodide solution


to a 250 m1 conical flask.

4.1.2

Add 100 m1 of sample and mix.

4.1.3

Add 2 to 3m1 of starch indicator solution and titrate with potassium iodate
solution to the first persistent blue colour.

4.1.4

Record the volume (ml) of potassium iodate solution used as V1 .

4.1.5

Carry out a blank determination using 100 m1 of water instead of sample and
repeating the steps 4.1.1 to 4.1.3. Record the volume of potassium iodate
solution used as 'V2

4.2

Nitrite Interference Suspected


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Manual on Analytical Test Procedure for Water and Steam in Power Plants
4.2.1

Place 100 m1 of sample in a 250m1 conical flask.

4.2.2

Add about 0.lg of sulphamic acid and stir until crystals are completely
dissolved and no further gas evolution is noted.

4.2.3

Add 5m1 of hydrochloric acid solution and stir again until no further gas
evolution is noted.

4.2.4

Add 5m1 of potassium iodide solution.

4.2.5

Repeat steps 4.1.3 to 4.1.5.

5.0

CALCULATIONS

5.1

Calculate the concentration of sulphite in mg/litre, as follows:


Sulphite, mg/litre as Na2S03 =

(V1-V2) X N X 1000
----------------------------------------V

Where:

5.2

VL

volume of potassium-iodate required for sample, ml.

V2 =

volume of potassium iodate required for water (blank), ml.

N =

sodium sulphite equivalent of standard potassium iodate solution in


mg/ml.

V =

volume of sample, ml.

Calculate the sulphite concentration in mg/litre as SO3 as follows:


Sulphite concentration, mg/litre as S03 = A x 0.64
Where:
A = sulphite concentration, mg/litre as Na2S03.

5.3

Calculate the sulphite concentration in mg/litre as CaCO3, as follows:


Sulphite concentration, mg/litre as CaCO3 = B X 1.25
Where:
B =

6.0

sulphite concentration, mg/litre as 503.

PRECISION
The precision of this method may be expressed as follows:
SO =

Where:
SO =

single operator precision, mg/litre of Na2SO3.

NTPC Limited

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Manual on Analytical Test Procedure for Water and Steam in Power Plants
7.0

INTERFERENCES

7.1

Catalysts, such as copper, cause rapid oxidation of the sulphite when the
sample is exposed to air. This reaction is accelerated by an increase in
temperature. EDTA may be added to the sample to complex such metallic
ions.

7.2

Other reducing agents, such as sulphides and ferrous-iron, will react like
sulphite.

7.3

Nitrite, if present, will oxidise sulphite when the sample is acidified. Nitrite,
interference can be eliminated by the addition of sulphamic acid.

8.0

NOTES

8.1

Reagent grade chemicals should be used for preparing all the reagents.

8.2

To avoid premature oxidation of sulphite, the titration should be carried out


immediately after collection.

LVII)

REVIEW
The Head of Corporate Operation Services will be responsible for reviewing
this document on a 2 yearly basis, or as and when required.

NTPC Limited

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Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants

Annexure - I
ATOMIC WEIGHT/ATOMIC NUMBERS OF VARIOUS ELEMENTS
S.NO.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16
17.
18.
19.
20.
21.
22.
23.
24
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.

NAME
Actinium
Aluminium
Americium
Antimony
Argon
Arsenic
Astanine
Barium
Berkelium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Caesium
Calcium
Californium
Carbon
Cerium
Chlorine
Chromium
Cobalt
Copper
Curium
Dysprosium
Einsteinium
Erbium
Europium
Fermium
Fluorine
Francium
Gadolinium
Gallium
Germanium
Gold
Hafnium
Helium
Holmium
Hydrogen
Indium

SYMBOL
Ac
Al
Am
Sb
Ar
As
At
Ba
Bk
Be
Bi
B
Br
Cd
Cs
Ca
Cf
C
Ce
Cl
Cr
Co
Cu
Cm
Dy
Es
Er
Eu
Fm
F
Fr
Gd
Ga
Ge
Au
Hf
He
Ho
H
In

ATOMIC
NUMBER
89
13
95
51
18
33
85
56
97
4
83
5
35
48
55
20
98
6
58
17
24
27
29
96
66
99
68
63
100
9
87
64
31
32
79
72
2
67
1
49

NTPC Limited

ATOMIC
WEIGHT
227
26.98154
243.13
121.75
39.948
74.9216
---137.34
--9.0122
208.9808
10.811 0.003
79.904
112.40
132.9054
40.08
---12.01
140.12
35.453
51.996
58.9331
63.546
---162.50
---167.28
151.96
--18.99840
---157.25
69.72
72.59
196.967
178.49
4.0026
164.930
1.00797
114.82

Page - 151
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Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
S.NO.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.

NAME
Iodine
Iridium
Iron
Krypton
Lanthanum
Lawrencium
Lead
Lithium
Lutetium
Magnesium
Manganese
Mendeleevium
Mercury
Molybdenum
Neodymium
Neon
Neptunium
Nickel
Niobium
Nitrogen
Nobelium
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Plutonium
Polonium
Potassium
Praseodymium
Promethium
Protoactinium
Radium
Radon
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver

SYMBOL
I
Ir
Fe
Kr
La
Lw
Pb
Li
Lu
Mg
Mn
Md
Hg
Mo
Nd
Ne
Np
Ni
Nb
N
No
Os
O
pd
p
Pt
Pu
Po
K
Pr
Pm
Pa
Ra
Rn
Re
Rh
Rb
Ru
Sm
Sc
Se
Si
Ag

ATOMIC
NUMBER
53
77
26
36
57
103
82
3
71
12
25
101
80
42
60
10
93
28
41
7
102
76
8
46
15
78
94
84
19
59
61
91
88
86
75
45
37
44
62
21
34
14
47

NTPC Limited

ATOMIC
WEIGHT
126.9044
192.20
55.847
83.80
138.91
----207.19
6.939
174.97
24.312
54.938
-200.59
95.94
144.24
20.183
237.00
58.71
92.906
14.0067
---190.20
15.9994
106.40
30.97376
195.09
242
210.05
39.09
140.907
---231.10
226.0254
222.00
186.2
102.905
85.47
101.07
150.35
44.956
78.96
28.086
107.868

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Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
S.NO.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.

NAME
Sodium
Strontium
Sulphur
Tantalum
Technetium
Tellurium
Terbium
thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Xenon
Ytterbium
Yttrium
Zinc
Zirconium

SYMBOL
Na
Sr
S
Ta
Tc
Te
Tb
Tl
Th
Tm
Sn
Ti
W
U
V
Xe
Yb
Y
Zn
Zr

ATOMIC
NUMBER
11
38
16
73
43
52
65
81
90
69
50
22
74
92
23
54
70
39
30
40

NTPC Limited

ATOMIC
WEIGHT
22.9898
87.62
32.064
180.948
-----127.60
158.924
204.37
232.038
168.934
118.69
47.90
183.85
238.03
50.942
131.30
173.04
88.905
65.38
91.22

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Manual on Analytical Test Procedure for Water and Steam in Power Plants

ANNEXURE - II
DETERMINATION OF SATURATION INDEX (LANGELIER) AND
STABILITY INDEX (RYZNER) OF COOLING WATER
1.0

SUMMARY OF METHOD
The saturation index and the stability index are calculated from the total
alkalinity, calcium hardness, pH, approximate concentration of total dissolved
solids and the temperature of the water.

2.0

PROCEDURE

2.1

Determine the total alkalinity, calcium hardness, pH, total dissolved solids and
the temperature of the water.
To determine the saturation Index (Langelier Index), obtain the values of
A,B,C and D from table 1 (Section 3.0) and calculate the saturation pH as
follows:
pHs = (9.3 + A+B) - (C+D)
Then, using the actual pH of the water, calculate the index as follows:
Saturation Index (Langelier Index) = pH - pHs
Calculate the stability Index (Ryzner Index) as follows:
Stability Index (Ryzner Index) = 2 pHs - pH

2.2

2.3

TABLE 1

DATA FOR CALCULATION OF SATURATION AND STABILITY INDEX


Total Solids
(mg/litre)
50-350
400-1100

A
0.1
0.2

Temperature
(0C)
0
2
7
10
14
18
22
28
32
38
44
51
57
64
72
82

B
2.6
2.5
2.4
2.3
2.2
2.1
2.0
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1

Calcium Hardness
(mg/litre CaCO3)
10
12
14
18
23
28
35
44
56
70
88
11
139
1175
30
280
350
440
560
700
870
1050

NTPC Limited

C
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7

Total Alkalinity
(mg/litre CaCO3)
10
12
14
18
23
28
36
45
56
70
88
111
140
177
230
280
360
450
560
700
800

D
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0

Page - 154
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Manual on Analytical Test Procedure for Water and Steam in Power Plants
4.0

NOTES

4.1

The Langelier index or calcium carbonate saturation index of cooling water is


used in prediction the scaling of corrosive tendency of the water.

4.2

If the saturation index (Langelier index) is zero, water is in chemical balance.


If the index is positive, scaling tendencies are indicated. If the index is
negative corrosive tendencies are indicated.

4.3

The Ryzner stability index is a modification of the Langelier saturation index.


All values of this index will be positive and values above 6.0 indicate a
corrosive tendency while values below 6.0 indicate a tendency to form scale.

4.4

The control limits of cooling water are given below:

Langelier saturation index


Ryzner stability index
pH
Calcium hardness, mg/litre as CaCO3.
Total dissolved solids mg /litre

NTPC Limited

Min.
0.5
6.0
6.0
20
-

Max.
1.5
6.0
8.0
300
2,500

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ANNEXURE - III
SHELF LIFE AND STORAGE OF REAGENTS AND STANDARDS
REAGENT

SHELF LIFE

CONTAINER

1.
2.
3.
4.

Acetic Acid
Aluminium Chloride
Aluminium Sulphate
Amine Solution

1 Year
1 Year
1 Year
1 week

5.

1 month

6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.

p-amino dimethyl aniline


hydrochloride.
Amino naphthol Sulphonic acid.
Ammonia Solution
Ammonium Acetate
Ammonium Carbonate
Ammonium chloride
Ammonium Fluoride
Ammonium Iodide
Ammonium Molybdate
Ammonium Nitrate
Ammonium Oxalate
Ammonium Sulphate
Ammonium Sulphide Solution
Ammonium Thiocyanate
Aniline
Aniline Sulphate
Ascorbic Acid

Glass
Glass
Glass
Amber coloured
bottle.
dark glass bottle.

22.
23.
24.
25.
26.
27.
28.
29.
30.
31
32.
33.
34.

Barium Chloride
Barium Nitrate
Baryta water
Benzene
Bromine water
Cadmium Acetate
Cadmium Sulphate
Calcium Chloride
Ceric Sulphate
Calcium Nitrate
Calcium Sulphate
Carbon Tetrachloride
Chlorine water

2 weeks
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 month
1 month
1 year
1 month
a. To be
prepared fresh
b. One week if
stored at 40 C
1 year
1 year
1 month
1 year
1 week
1 year
1 year
1 year
1 month
1 year
1 year
1 year
1 week

NTPC Limited

plastic, dark place.


Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass

Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass

Page - 156
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
REAGENT

SHELF LIFE

CONTAINER

1 year
1 year
1 year
1 year
1 month
1month
1 week:
4 month:
1 month:
1 month
1 year
1 month
1 month

Glass
Glass
Glass
Glass
Glass
Glass
Glass

42.
43.
44.
45.

Chromic Acid
Cobalt Chloride
Cobalt Nitrate
Copper Sulphate
Dimethyl Glyoxime Solution
Diphaenyl Amine
diphenyl Carbazide
(3.32g/1)
(2.89g/1)
Diphenyl Thiocarbzone
Disodium Hydrogen phosphate
disodium salt of EDTA
Eriochrome Black T

46.

Eriochrome Black T (solid)

1 year

47.
48.
49.

Formaldehyde
Hydrazine Sulphate
Hydrochloric Acid (standardization
every month)
Hydrogen peroxide

1 month
1 month
1 year

Hydrogen Sulphide (saturated


solution)
Hydroxylamine Hydrochloride
8 hydroxyquinoline
Indigo Carmine
Iodine (standardize before use)
Iron (III) Chloride
Iron (III) per iodate
Iron (III) sulphate (saturated)
Iron (III) sulphate
Lead Acetate
Lime water
Magnesia mixture
Magnesium Chloride
Magnesium Sulphate
Manganese (II) sulphate Solution
Mercuric Thiocyanate
Mercapto succinic Acid Solution
Methyl Alcohol
Methylene blue
Methyl Orange

Freshly
prepared
1 month
1 month
1 month
1 month
1 year
1 month
1 week
1 year
1 year
1 week
1 month
1 year
1 year
1 year
1 month
6 month
1 year
Indefinite
Indefinite

35.
36.
37.
38.
39.
40.
41.

50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.

1 month

NTPC Limited

Glass
Glass
Polyethylene,plastic.
dark coloured
stoppered bottle
Dark Coloured
stoppered bottle.
Glass
Glass
Glass (tightly
closed)
Glass (dark
coloured)
Glass
Glass
Glass
Dark bottle at 40 C
Amber Glass
Dark bottle
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Amber bottle
Glass
Glass
Glass
Glass

Page - 157
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants

71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.

REAGENT

SHELF LIFE

CONTAINER

Nessler's Reagent (if kept in


chemically resistant bottle and in
complete darkness)
Nitric Acid
Oxalic Acid
O - phenanthroline
O Toludine (avoid rubber contact)
phenolphthalein
Potassium Bromate
Potassium bromide
Potassium chlorate
Potassium Chloride
Potassium Chromate
Potassium dichromate
Potassium Hydroxide ( Standardize
monthly)
Potassium Iodate
Potassium Iodide (6m)
Potassium Iodide (10%)
Potassium Nitrate
Potassium Nitrite
Potassium Permanganate
( Satndardize weekly )
Pyrogallol
Silver Nitrate (standardize monthly)
Silver sulphate
Sodium Acetate
Sodium Carbonate
Sodium Arsenite

1 year

Amber bottle

1 year
1 year
1 year
1 month
1 year
1 year
1 year
1 year
1 year
1 year
1 month
1 year

Glass
Glass
Glass
Dark bottle
glass
glass
glass
glass
glass
glass
Glass
Polyethylene

1 year
Fresh
1 year
1 year
Fresh
1 year

glass
Amber bottle
glass
Glass
Amber Bottle

Sodium chloride
Sodium Hydrogen Carbonate
Sodium Hydroxide (standardize
monthly)

1 year
1 year
1 year

1 month
1 year
1 year
1 year
1 year
1 year

NTPC Limited

Glass
Amber Bottle
Glass
Glass
Glass
Dark coloured Glass
Bottle.
Glass
Glass
polythene Bottle

Page - 158
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants

ANNEXURE - IV
STANDARD SPECIFICATIONS FOR REAGNT WATER
1.0

This specification covers requirements for water suitable for use in methods of
chemical analysis. Three grades of reagent water are given below:

1.1

Type I Reagent water.

1.2

Type II Reagent Water.

1.3

Type III Reagent Water.

2.0

SPECIFICATIONS

S.NO. PARAMETER
1.
Total solids, max, mg/ litre
2.
Electrical conductivity, max, micro
siemens /cm at 250C
3.
pH at 250C
4.
Minimum colour retention time of
potassium permangnate, minutes.
5.
Maximum soluble silica
6.

TYPE I
0.1
0.06

TYPE II
0.1
1.0

TYPE III
0.1
1.0

*
60

*
60

6.2 to 7.5
10

not
detectable

not
10 micro
detectable gm/ ltr.

Microbiological classification **

* The measurement of pH in Type I and Type II reagent waters is


meaningless,
since electrodes used in this test may contaminate the water
** When bacterial levels need to be controlled, reagent grade types should be
further classified as follows:

Maximum total
bacteria count

Type A

TypeB

Type C

0/ml

10/ml

100/ml

3.0

PREPATATION OF REAGENT WATER

3.1

Type I grade of reagent water shall be prepared by the distillation of feed


water having a maximum conductivity of 20 microsiemens /cm at 25 0C
followed by polishing with a mixed bed of ion exchange materials and a 0.2
micron membrane filter.

3.2

Type II grade of reagent water shall be prepared by distillation of


having a conductivity of less than 1.0 microsiemens/cm at 25 0C
exchange, distillation, or reverse osmosis may be required as an
treatment prior to distillation if the purity cannot be attained by
distillation.
NTPC Limited

water
. Ion
initial
single

Page - 159
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
3.3

Type III grade of reagent water shall be prepared by distillation, ion exchange,
reverse osmosis, or a combination thereof, followed by polishing with a 0.45
micron membrane filter.

4.0

USE OF REAGENT WATER

4.1

Type I grade of reagent water shall be used where maximum accuracy and
precision is indicated, provided dissolved organic matter is not a possible
interference.

4.2

Type II grade of reagent water shall be used for most analytical procedures
and all procedures requiring water low in organics.

4.3

Type III grade of reagent water shall be recommended for general laboratory
testing.

5.0

TEST METHODS

5.1

Total Solids see method B; the determination of suspended and total


dissolved solids.

5.2

Electrical Conductivity see method for the determination of conductivity.

5.3

pH see method for the determination of pH.

5.4

Consumption of potassium per magnate add 0.20ml of potassium


permanganate (0.316g/litre) to a mixture of 500ml of the reagent water and
1 ml of sulphuric acid (sp gr 1.84) in a stoppered bottle of chemically resistant
glass. Consider the reagent water as having passed the test if the
permanganate colour does not disappear completely after standing for the
indicated period of time at room temperature. This test should be run against a
blank using water known to be free of organic substances.

5.5

Silica see the method for the determination of soluble silica.

NTPC Limited

Page - 160
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants

ANNEXURE - V
CONVERSON FACIOR OF FREQUENTLY USED CHEMICALS TO CaCO3
EQUIVALENT
S.NO.

SUBSTANCE

FORMULA

ATOMIC/MOLEC
ULAR WEIGHT

EQUIVALENT
WEIGHT

SUBSTENCE
TO CaCo3
Equivalent

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.

Calcium
Carbondioxide
Chloride
Fluorine
Hydrogen
Hydroxide
Magnesium
Nitrate
Oxygen
Phosphate
Silica
Sulphate
Sulphite

Ca
CO2
Cl
F
H
OH
Mg
NO3
O
PO4
SiO2
SO4
SO3

40.1
44.0
35.5
19.0
1.01
17.0
24.3
126.9
16.0
95.0
60.1
96.1
80.1

20.0
44.0
35.5
19.0
1.01
17.0
12.2
126.9
8.0
31.7
30.0
48.0
40.0

2.50
1.14
1.41
2.63
50
2.94
4.10
0.39
6.25
1.58
0.83
1.04
1.25

NTPC Limited

Document for Distribution to:


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Farakka
Dadri (Coal & Gas)
Unchahar
Korba
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Badarpur
Talcher Kaniha
Kayamkulam
Kawas
Simhadri
Singrauli
Tanda
Talcher Thermal
Auraiya
Jhanor Gandhar
Faridabad
Anta

26. STA to Chairman & Managing Director, SCOPE, New Delhi


27. STA to Director (Technical), SCOPE, New Delhi
28. STA to Director (Operations) , SCOPE, New Delhi
29. STA to Director (Commercial), SCOPE, New Delhi
30. STA to Director (Projects) , SCOPE, New Delhi
31. Executive Director, PMI, Noida
32. Executive Director (Engg.), EOC, Noida
33. Executive Director (OS),EOC, Noida
34. General Manager (R&D), Noida
35. General Manager (CENPEEP), Noida
36. Concerned Group Heads in Operation Services, CC

IV Head of O&M
37. Singrauli
41. Vindhyachal
45. Unchahar
49. Simhadri
53. Jhanor Gandhar
57. Tanda

38. Korba
42. Rihand
46. Talcher Kaniha
50. Auraiya
54. Dadri (Gas)

39. Ramagundam
43. Kahalgaon
47.Talcher Thermal
51. Anta
55. Kayamkulam

40. Farakka
44. Dadri(Coal)
48. Badarpur
52. Kawas
56. Faridabad

60. Ramagundam
64. Kahalgaon
68.Talcher Thermal
72. Anta
76. Kayamkulam

61. Farakka
65. Dadri(Coal)
69. Badarpur
73. Kawas
77. Faridabad

Head of Chemistry

58. Singrauli
62. Vindhyachal
66. Unchahar
70. Simhadri
74. Jhanor Gandhar
78. Tanda

59. Korba
63. Rihand
67. Talcher Kaniha
71. Auraiya
75. Dadri (Gas)