Guidelines for Analytical Test Procedures for

The Tata Power Company Ltd Water and Steam System

Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

Core Technology & Diagnostics

POWER PLANT CHEMISTRY

GUIDELINES
FOR
ANALYTICAL TEST PROCEDURES
FOR
WATER AND STEAM SYSTEM

Meant for (Internal Circulation / External – Stakeholders Circulation)

Approved For Issue
Rev Prepared By & Checked By &
Reason for Revision By
No. Date Date
& Date
Knowledge
Subhanjali
Team - Kalyan Panda, Date
R0 First Issue Sanyal, Date
Chemistry, 16/05/2013
05/04/2013
19/04/2013
<<Initials,
R1 <<Reason for revision>> <<Initials, date>> <<Initials, date>>
date>>

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 Guidelines for Analytical Test Procedures for
The Tata Power Company Ltd Water and Steam System

Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

Contents
1 INTRODUCTION ........................................................................................................... 4
2 COAGULATION/ FLOCCULATION JAR TEST ........................................................ 5
3 COLOR.......................................................................................................................... 11
4 CONDUCTIVITY ......................................................................................................... 14
5 CORROSIVITY OF COOLING WATER (Coupon Test)............................................ 19
6 CRUD (Colour Comparison Method) ........................................................................... 25
7 pH .................................................................................................................................. 26
8 OXIDATION – REDUCTION POTENTIAL (ORP) ................................................... 32
9 TURBIDITY (Nephelometric) ...................................................................................... 38
10 SUSPENDED AND TOTAL DISSOLVED SOLIDS .................................................. 41
11 SUSPENDED AND TOTAL DISSOLVED SOLIDS .................................................. 44
12 ALKALINITY (Titration Method, 10 to 500mg/litre) .................................................. 47
13 ALKALINITY DUE TO HYDROXIDE ...................................................................... 52
14 ALUMINIUM ............................................................................................................... 55
15 ALUMINIUM (ATOMIC ABSORPTION METHOD) ................................................ 59
16 AMMONIA (Indophenol method) ................................................................................ 62
17 AMMONIA by Nesseler’s Reagent .............................................................................. 65
18 AMMONIA BY ION SELECTIVE ELECTRODE ...................................................... 69
19 CARBON DIOXIDE (Bicarbonate Titration Method) ................................................. 73
20 CARBON DIOXIDE (Direct Titration of Free Carbon Dioxide) ............................... 75
21 CHLORIDE (Mercuric Thiocyanate Method) ............................................................. 78
22 CHLORIDE (Mercuric Thiocyanate Method, Modified, 2 to 100 micrograms/litre) . 81
23 CHLORIDE (Silver Nitrate Method, 5mg/litre or more) ............................................ 84
24 CHLORINE DEMAND ................................................................................................ 87
25 CHLORINE RESIDUAL (DPD Method, 0.02 to 4.0mg/litre) ..................................... 92
26 CHLORINE, RESIDUAL (Starch Iodide Thiosulphate Method) ................................ 97
27 COPPER (Neocuprine method, 2 to 1000 micrograms/ litre Cu) ............................... 101
28 COPPER (Atomic Absorption Spectrophotometry Method) ...................................... 107
29 EQUIVALENT AND FREE MINERAL ACIDITY .................................................. 109
30 FLUORIDE (SPANDS Dye Method) ......................................................................... 112
31 HARDNESS (TOTAL, CALCIUM AND MAGNESIUM) ....................................... 118
32 HYDRAZINE (p-Dimethylamino Benzaldehyde Method)......................................... 124
33 IRON (Bathophenanthroline Method) ......................................................................... 128
34 IRON (Ferrozine Method) ........................................................................................... 134
35 IRON ATOMIC ABSORPRION METHOD (Graphite Furnace)............................ 137
36 NICKEL (Glyoxime Method) ..................................................................................... 139
37 NICKEL by ATOMIC ABSORPTION METHOD (Direct) ....................................... 143

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 Guidelines for Analytical Test Procedures for
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Date of Issue: 16/05/2013

38 MANGANESE ............................................................................................................ 146

39 NITRATE (Azo dye Method) ..................................................................................... 148
40 NITRATE (PHENOL DISULPHONIC ACID (PDA) METHOD) ............................ 153
41 NITRATE (UV Spectrophotometric Method)............................................................. 156
42 OIL AND GREASE (Solvent Extraction Method) ..................................................... 159
43 ORGANIC MATTER ................................................................................................. 164
44 OXYGEN, DISSOLVED (Indigo Carmine Method) .................................................. 166
45 OXYGEN, DISSOLVED (Iodometric Method) ......................................................... 171
46 OXYGEN DEMAND BIOCHEMICAL (Dissolved Oxygen Loss Method).............. 176
47 OXYGEN DEMAND, CHEMICAL (Potassium Dichromate Method) ..................... 178
48 PHOSPHATE (Amino Reduction Method) ................................................................ 184
49 SILICA, NON REACTIVE (Hydrofluoric Acid method) .......................................... 188
50 SILICA, NON-REACTIVE (Membrane Filtration Method) ...................................... 194
51 SILICA REACTIVE (Amino Reduction Method) ...................................................... 199
52 STEAM PURITY (Sodium Tracer Method) ............................................................... 205
53 SULPHATE (Gravimetric Method) ............................................................................ 207
54 SULPHATE (Volumetric Method) ............................................................................. 210
55 SULPHITE (Titration Method) ................................................................................... 216
56 SILT DENSITY INDEX (SDI) of Water .................................................................... 220
57 SODIUM IN WATER BY AAS ................................................................................. 224
58 POTASSIUM IN WATER BY AAS .......................................................................... 227
59 LEAD IN WATER BY AAS ...................................................................................... 230
60 ARSENIC IN WATER................................................................................................ 237
61 TOTAL MERCURY IN WATER ............................................................................... 247
62 TOC ............................................................................................................................. 259
ANNEXURE – I .................................................................................................................. 269
ATOMIC WEIGHT/ATOMIC NUMBERS OF VARIOUS ELEMENTS ........................ 269
ANNEXURE - II ................................................................................................................. 275
DETERMINATION OF SATURATION INDEX (LANGELIER) AND STABILITY
INDEX (RYZNER) OF COOLING WATER ..................................................................... 275
ANNEXURE - III ................................................................................................................ 277
ANNEXURE - IV................................................................................................................ 282
STANDARD SPECIFICATIONS FOR REAGENT WATER ........................................... 282
ANNEXURE - V ................................................................................................................. 284

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 Guidelines for Analytical Test Procedures for
The Tata Power Company Ltd Water and Steam System

Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

1. INTRODUCTION
Chemical analysis of water and steam is one of the most important tool for the
Chemists in the power plant. The analytical data obtained in power plant by the
combined system of online and offline monitoring system is a very effective
tool to monitor the operating status of the plant and to understand the trend of
operating parameters. Hence, the frequency of offline tests and collection of on-
line data are adequately timed, so as to take timely corrective actions. Each of
our stations do have robust testing facility and system in place, to measure the
chemistry parameters, however inorder to consolidate and bring in uniformity in
approaches, this guideline has been developed to consolidate all the analytical
test procedures adopted in our thermal power plants.

This Guideline has been designed and finalized in consultation with the
Knowledge Team- Chemistry to ensure that all the essential analytical test
procedures are incorporated in this document. These Guidelines shall be
adopted in all Tata Power thermal stations. The Chemistry Head of each
Division shall use this document to decide on the test methods to be used, based
on their plant configuration and comply with the same. The reference is taken
from ASTM/BIS/ISO for making this document. Consequent to issuance of this
Guideline, it is expected that each of the stations shall endeavour to adopt these
and maintain their parametric chemistry regime optimum values.

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 Guidelines for Analytical Test Procedures for
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Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

2. COAGULATION/ FLOCCULATION JAR TEST

2.1 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.

2.2 APPARATUS

2.2.1 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.

2.2.2 Beakers - glass beakers, 1000 to 1500m1 capacity.

2.2.3 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.

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Date of Issue: 16/05/2013

2.3 REAGENTS

2.3.1 Water - conforming to specifications Type IV conforming to ASTM specification

D-1193.
2.3.2 Prime Coagulants (l0g/litre)
2.3.3 Alum [A12(SO4)3.18H2O].
2.3.4 3Ferric Sulphate [Fe2 (SO4)3.XH2O].
2.3.5 Ferric Sulphate (FeSO4.7H2O).
2.3.6 Magnesium Carbonate (MgCO3.3H2O).
2.3.7 Ferric Chloride (FeCl3.6H2O).
2.3.8 Sodium Aluminate (NaA1O2).
2.3.9 Coagulant Aids - activated silica, polyelectrolytes (anionic, cationic and neutral).

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2.3.10 Oxidising Agents - Chlorine (C12), Chlorine dioxide (C1O2), Potassium

permanganate (KMn04), Calcium hypo-chlorite [CaO(C1O).4H20], Sodium
hypochlorite (NaC1O).
2.3.11 Alkalis - calcium carbonate (CeC03), dolomitic lime (58% CaO, 40% MgO), lime-
hydrated (Ca(OH)2) magnesium oxide (MgO), sodium carbonate (Na2CO3), sodium
hydroxide (NaOH).
2.3.12 Weighting Agents - bentonite, kaolin, Fuller's earth, other clays and minerals.

2.4 PROCEDURE

2.4.1 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.

2.4.2 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).

2.4.3 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).

2.4.4 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.

2.4.5 After 15 minutes of settling, record the sample temperature and by means of a
pipette, withdraw supernatant liquor for conducting colour, turbidity, pH, non-
reactive and/or colloidal silica and other required analysis.

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 Guidelines for Analytical Test Procedures for
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Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

2.5 INTERFERENCES

2.5.1 Temperature changes during test - Thermal or convection currents may occur,
interfering with the settling of coagulated particles.

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

2.5.3 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.

2.6 NOTES

2.6.1 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.

2.6.2 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.

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

FORMAT FOR RESULTS RECORDING

STATION – DATE –

LOCATION –

SAMPLE –

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Date of Issue: 16/05/2013

pH –

TURBIDITY –

COLOUR –

TEMPERATURE –

SAMPLE SIZE (ml) –

S.No. BEAKER N0.

1 2 3 4 5 6

1. Chemicals,* mg/litre

2 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

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Date of Issue: 16/05/2013

d. Non-reactive/colloidal Silica

* Indicate order of addition of Chemicals:

The preferred sequence of addition of chemical is (a) alum & or polymer -----
à (b) chlorine and ------à (c) lime (if needed)

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Date of Issue: 16/05/2013

3.0 COLOR
3.1 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.

3.2 APPARATUS

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

3.2.2 pH meter.

3.3 REAGENTS

3.3.1 Water - Conforming to specifications Type II.

3.3.2 Standard Stock Solution (colour of 500 units)

Dissolve 1.246g potassium chloroplatinate, K2PtCl6, (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.
3.3.3 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.
3.4 PROCEDURE
3.4.1 Place 50 ml of sample in a Nessler tube.

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

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

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

3.4.5 Measure the pH of the sample.

3.5 CALCULATIONS

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

Colour unit = A x 50

Where:

A = estimated colour of the diluted sample.

B = milliliters of sample.

3.5.2 Report colour results in whole numbers and record as follows:

Colour Unit Record to Nearest

1 -50 1

51 -100 5

101 -250 10

251 -500 20

3.5.3 Report Sample pH.

3.6 INTERFERENCES

3.6.1 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.

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3.6.2 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.

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4 CONDUCTIVITY
4.1 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.

4.2 APPARATUS

4.2.1 Conductivity meter.

4.2.2 Cells with cell constants from 0.01 to 10 cm-1.

4.2.3 Thermometer, accurate to 0.5°C, when the instrument is not provided with
manual or automatic temperature compensation.

4.3 REAGENTS

4.3.1 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

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

4.3.3 Potassium Chloride Reference Solution A (Conductivity of 97838

microsiemens/cm at 18°C and 111342 microsiemens/cm at 25°C) - Dissolve
74.2460g of potassium chloride in water and dilute to 1 litre at 20°± 2 0 C.
4.3.4 Potassium Chloride Reference Solution B (Conductivity of 11167
microsiemens/cm at 18°C and 12856 microsiemens/cm at 25°C) - Dissolve
7.4365g of potassium chloride in water and dilute to 1 litre at 20±2°0 C.
4.3.5 Potassium Chloride Reference Solution C (Conductivity of 1220.5
microsiemens/cm at 18°0 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.

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4.3.6 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 20±2° 0 C shortly before using.

4.4 PROCEDURE

4.4.1 Determination of Cell Constant

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

4.4.1.2 Thermostat the reference standard at 18 or 25°0 C and measure conductivity in

accordance with the instrument manufacturer instructions.

Cell constant (A) = K1 + K2

Kx

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).

4.4.2 Measurement of Conductivity

4.4.2.1 Conductivity Below 10 microsiemens/cm.

4.4.2.1.1 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.

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

adjust this to the sample temperature value.

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4.4.2.1.3 If an automatic temperature compensator is provided, no adjustment is

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

4.4.2.1.4 Read the conductivity. -

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

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

4.4.2.2 Conductivity Above 10 microsiemens/cm.

4.4.2.2.1 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.

4.4.2.2.2 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 0.5°C) on successive portions of the sample until a
constant value is obtained.

4.4.2.2.3 Proceed in accordance with 4.2.1.2, 4.2.1.3 and 4.2.1.5.

4.5 CALCULATIONS

4.5.1 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.

4.6 PRECISION

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

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4.7 INTERFERENCES

4.7.1 Exposure of a sample to the atmosphere may cause changes in conductivity due
to loss or gain of dissolved gases.

4.7.2 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.

4.8 NOTES

4.8.1 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.

4.8.2 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

4.8.3 The conductivity of water and aqueous solutions depends strongly upon the
temperature. To avoid making a correction, it is necessary to hold the

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temperature of the sample to 25 ± 0.5°C. 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 25°C
may be plotted against temperature and this ratio taken from the curve.

4.8.4 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.

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5 CORROSIVITY OF COOLING WATER (Coupon Test)

5.1 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.

5.2 APPARATUS

5.2.1 Coupon Specimens - prepare coupons in accordance with section 4.0.

5.2.2 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.

5.2.3 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.

5.3 REAGENTS

5.3.1 Water - conforming to specifications Type III.

5.3.2 Benzene.

5.3.3 Corrosion Inhibitor - specific for hydrochloric acid.

5.3.4 Hydrochloric Acid (1+4) - Mix 1 volume of concentrated hydrochloric acid (sp gr
1.19) with 4 volumes of water.

5.3.5 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.

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5.3.6 Isopropyl Alcohol.

5.3.7 Methyl orange Indicator (0.5g/litre) - Dissolve 0.05g of methyl orange in water
and dilute to 100m1.

5.3.8 Trichloroethylene.

5.3.9 Tripoli – finely granulated, porous, of siliceous rock;' amorphous silica, soft,
porous, and free of sharp edges.

5.3.10 Trisodium phosphate (Na3P04.12H20).

5.3.11 Vapour phase Inhibitor paper.

5.4 COUPON PREPARATION

5.4.1 Prepare coupon from sheet metal.

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

5.4.2.1 Shear 20 gage sheet metal of the type desired to the dimensions of 3 by 102mm.

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

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

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

5.4.3 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.

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5.5 PROCEDURE

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

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

5.5.3 Install the holder and coupon assembly in a suitable place.

5.5.4 Remove the coupon from the system at chosen intervals.

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

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

5.5.5 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.

5.5.6 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.

5.5.7 Reweigh each coupon to the nearest 0.lmg.

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5.5.8 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.

5.5.9 Record the appearance of the cleaned, weighed coupon a “protected", 'moderate
localized', moderate pitting" or 'severe pitting'.

5.6 CALCULATIONS

5.6.1 Calculate the corrosion rate for each coupon as follows:

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

Where :

P = corrosion rate, millimeters per year (mmpy).

H = original thickness of the coupon, mm.

W1 = original weight of the coupon, mg.

W2 = final weight of the coupon, mg.

D = exposure time, days.

5.6.2 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:

P = corrosion rate, mmpy.

H = original thickness of coupon, mm.

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X = original length of coupon, mm.

Y = original width of coupon, mm.

W1 = original weight of coupon, mg.

W2 = final weight of coupon, mg.

D = exposure time, days.

5.6.3 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.

5.7 INTERFERENCES

5.7.1 Deviations in metal composition or surface preparation of the coupons may

influence the precision of the results.

5.7.2 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.

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

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

5.7.5 Crevices, deposits or biological growths may affect local corrosivity.

5.8 NOTES

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

5.8.1.1 Non ferrous metal coupons should be stored in sealed plastic envelopes or
wrapped in plastic film.

5.8.2 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.

5.8.3 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.

5.8.4 The specimen can be photographed...

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

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6 CRUD (Colour Comparison Method)

6.1 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.

6.2 APPARATUS

6.2.1 Filter Holder, 47mm diameter.

6.2.2 Filtration Flask, 1 litre capacity.

6.2.3 Laboratory Vacuum pump or Aspirator.

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

6.3 PROCEDURE

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

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

6.4 CALCULATIONS

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

6.4.2 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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7 pH
7.1 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.

7.2 APPARATUS

7.2.1 Laboratory pH meter together with its associated glass and reference electrodes.

7.3 REAGENTS

7.3.1 Water - conforming to specifications Type I.

7.3.2 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 1-litre.

7.3.3 Phosphate Reference Buffer Solution (pH = 6.86 at 25°C) - Dissolve 3.39g of
potassium dihydrogen phosphate (dried at 130°C for 2 hours) (KH2PO4) and
3.53g of anhydrous disodium hydrogen phosphate (dried at 130°C for 2 hours)
(Na2HPO4) in water and dilute to 1-litre.

7.3.4 Phthalate Reference Buffer Solution (pH = 4.00 at 25°C) - Dissolve 10.12g of
potassium hydrogen phthalate (dried at 110°C for 2 hours) (KHC8H4O4) in water
and dilute to 1-litre.

7.3.5 Tetraoxalate Reference Buffer solution (pH = 1.68 at 25°C) - Dissolve 12.61g of
potassium tetroxalate dihydrate (KHC2H4H2C2O4.2H2O) in water and dilute to 1
litre.

7.3.6 Sodium Bicarbonate - Sodium Carbonate Reference Suffer Solution (pH a 10.01
at 25°C) - Dissolve 2.092g of sodium bicarbonate (NaHCO3) and 2.640g of

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sodium carbonate (dried at 275°C for 2 hours) (Na2CO3) in water and dilute to
1-litre.

7.4 PROCEDURE

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

electrical balance with the manufacturer's instructions.

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

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

7.4.4 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 1-minute.

7.5 CALCULATIONS

7.5.1 Most pH meters are calibrated in pH units and the pH of the sample is obtained
directly by reading the meter scale.

7.5.2 Report the temperature of measurement to the nearest 1°C.

7.5.3 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.

7.5.4 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.

7.6 PRECISION

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

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

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

7.7 INTERFERENCES

7.7.1 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.

7.7.2 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.

7.7.3 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.

7.7.4 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.

7.7.5 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.

7.8 NOTES

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7.8.1 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 | | solution || glass electrode

(E – Er ) F
pH = pHr = ---------------
2.3026 RT

Where :

pHr = pH of the reference buffer.

E = emf obtained when the electrodes are immersed in

the sample.

Er = emf obtained when the electrodes are immersed in a

reference buffer solution.

F = Faraday constant.

R = Gas constant.

T = absolute temperature.

7.8.2 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.

7.8.3 Both the saturated Calomel electrode and silver-silver chloride electrode are
satisfactory for measurement at room temperature. The silver-silver chloride

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electrode is recommended for measurement at elevated temperatures where its

potential is more stable than that of the saturated calomel electrode.

7.8.4 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.

7.8.5 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.

7.8.6 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
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.

7.8.6.1 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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8 OXIDATION – REDUCTION POTENTIAL (ORP)

8.1 INTRODUCTION

ORP provides a useful measurement of the oxidizing or reducing nature of a

particular water sample. It finds various applications like chlorination/ de-
chlorination 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.

8.2 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

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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 an
open tank, process pipe line, pressure vessel, or a high pressure sampling line.

8.3 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 (HNO3, 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

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(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 ( HNO3 ,

sp. Gr. 1.42 ) and water

8.4 REDOX STANDARD SOLUTION: FERROUS – FERRIC REFERENCE

SOLUTION:

Dissolve 39.21 g of ferrous ammonium sulphate (Fe(NH4)2(SO4).6H2O ), 48.22

gm of ferric ammonium sulphate ( FeNH4 (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. KCl + 476 mv

Pt,H2 (p=1), H(a=1) + 675 mv

8.5 REDOX REFERENCE QUINHYDRONE SOLUTIONS – Mix 1 Lit of pH 4

buffer solution with 10 g of quinhydrone. Be sure that excess quinhydrone is

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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 4 7

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

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

8.6 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

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8.7 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.

8.8 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.

8.9 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.

8.10 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

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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.

8.11 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.

8.12 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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9 TURBIDITY (Nephelometric)
9.1 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.

9.2 APPARATUS

9.2.1 Nephelometer - covering the range 0 to 1000 NTU.

9.2.2 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.

9.3 REAGENTS

9.3.1 Turbidity free water - water conforming to specifications Type I.

9.3.2 Stock Turbidity Suspension

9.3.3 Solution A - Dissolve 1.000g of Hydrazine Sulphate [(NH2)2H2SO4] in turbidity

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

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

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

9.3.5 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.

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9.3.6 Standard Turbidity Suspension

9.3.6.1 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.

9.3.7 Dilute Turbidity Standard

9.3.7.1 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.)

9.4 PROCEDURE

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

9.4.2 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.

9.4.3 Turbidity less than 40 NTU

Shake the sample thoroughly to disperse the solids. Allow air bubble to
disappear, then proceed.

9.4.4 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.

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9.4.5 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.

9.5 CALCULATIONS

9.5.1 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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10 SUSPENDED AND TOTAL DISSOLVED SOLIDS

(25mg/litre or Less of Total Solids)
10.1 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.

10.2 APPARATUS

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

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

10.2.2 Automatic Evaporation Assembly - A dust shield, constant level device, heater
and evaporation dish.

10.2.3 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).

10.2.4 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.

10.2.5 Glass Petri Dish, 150mm diameter.

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

100 mm diameter and approximately 200 ml capacity.

10.3 REAGENTS

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10.3.1 Chloroform or Benzene, purified.

10.4 PROCEDURE

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

approximately 25mg.

10.4.2 Suspended Solids

10.4.2.1 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.

10.4.2.2 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.

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

10.4.3 Total Solids and Dissolved Solids

10.4.3.1 Weigh a platinum dish that has been dried at 103°C 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).

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

10.5 CALCULATIONS

10.5.1 Calculate the result of each specific determination as follows:

W1

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Total Solids, mg/litre =. --------- x 1000

V

W2
Suspended solids, mg/litre = ---------- x 1000
V

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

W1 = grams of total solids.

W2 = grams of suspended solids.

W3 = grams of dissolved solids.

V = litres of sample used.

10.6 NOTES

10.6.1 Some evaporation residues readily absorb moisture, therefore rapid weighing
should be done.

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 11)

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11 SUSPENDED AND TOTAL DISSOLVED SOLIDS (More

than 25mg/litre of Total Solids)
11.1 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.

11.2 APPARATUS

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

having a valve controlled outlet.

11.2.2 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.

11.2.3 Glass Petri Dish, 150mm diameter.

11.2.4 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.

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

11.3 REAGENTS

11.3.1 Chloroform or Benzene purified.

11.4 PROCEDURE

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

25mg of residue.

11.4.2 Suspended Solids

11.4.2.1 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.

11.4.2.2 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.

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

11.4.3 Total Solids and Dissolved Solids

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

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

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

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

11.5 CALCULATIONS

11.5.1 Calculate the result of each specific determination, as follows:

W1
Total Solids, mg/litre = ---------- x 1000

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W2
Suspended solids, mg/litre = -------- 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.

11.6 NOTES

11.6.1 Some evaporation residues readily absorb moisture, therefore rapid weighing
should be done.

11.6.2 Suspended solids are defined as those solids, exclusive of gases and in non-
liquid 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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12 ALKALINITY (Titration Method, 10 to 500mg/litre)

12.1 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.

12.2 RANGE

10 to 500 mg/litre as CaCO3.

12.3 REAGENTS

12.3.1 Water - conforming to specifications Type I.

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

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

12.3.3 Standard Hydrochloric Acid (0.02N) - Dilute 1.66m1 of hydrochloric acid (sp gr
1.19) to 1 litre with water. For standardization - see notes.

12.3.4 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%).

12.3.5 Methyl Orange Indicator Solution (0.5g/litre) - Dissolve 0.05g of methyl orange
in water and dilute to 100 m1.

12.3.6 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. .

12.4 PROCEDURE

12.4.1 Phenolphthalein Alkalinity (P-Alkalinity)

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

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

12.4.2 Total Alkalinity by Mixed Indicator

12.4.2.1 Add 3 drops of the mixed indicator to the solution in which the phenolphthalein
alkalinity has been determined.

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

Above pH 5.2 - Greenish blue

AT pH 5.0 - Light blue
pH 4.8 - Pink grey with bluish tinge
pH 4.6 - Light Pink

12.4.3 Total Alkalinity (M-Alkalinity) by Methyl Orange

12.4.3.1 Add 2 drops of methyl orange indicator to the solution in which the
phenolphthalein alkalinity has been determined.

12.4.3.2 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).

12.4.4.0 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.

12.5 CALCULATIONS

12.5.1 Phenolphthalein Alkalinity, mg/litre as CaCO3 = A x N x 50,000

12.5.2 M-Alkalinity (Total Alkalinity), mg/litre as CaCO3 = B x N x 50,000

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V
Where:

A = 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.
12.5.3 Alkalinity Relationship.

The following table gives the stoichiometric classification of the three principal
forms of alkalinity present in water.

Results of Hydroxide Carbonate Bicarbonate

Titration Alkalinity Alkalinity Alkalinity
(as CaCO3) (as CaCO3) (as CaCO3)
P=0 0 0 M
P < 1/2 M 0 2P M-2P
P = 1/2 M 0 2P 0
P > 1/2 M 2P-M 2(M-P) 0
P=M M 0 0

Where :

P = Phenolphthalein Alkalinity.

M = M-Alkalinity (or total alkalinity).

12.6 PRECISION

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

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12.7 INTERFERENCES

12.7.1 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.

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

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

12.8 NOTES

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

12.8.2 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.

12.8.3 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.

12.8.3.1 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.

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

sodium carbonate (previously dried in a platinum crucible at 2500C for 4 hours)
and transfer to a 500m1 conical flask. Add 50m1 of water to dissolve the

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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.

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

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13 ALKALINITY DUE TO HYDROXIDE

13.1 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.

13.2 REAGENTS

13.2.1 Water - conforming to specifications type III.

13.2.2 Hydrochloric acid (0.02N) - Dilute 1.66m1 of hydrochloric acid (sp gr 1.19) to
1 litre with water. For standardization - see notes.

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

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

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

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

13.3 PROCEDURE

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

13.3.2 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.

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

13.3.4 Add 4 drops of phenolphthalein indicator solution and quickly titrate with
standard hydrochloric acid to a colourless end-point.

13.4 CALCULATIONS

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

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

N = normality of standard hydrochloric acid.

V1 = milliliters of standard hydrochloric acid.

V = milliliters of sample.

13.4.2 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.

13.5 PRECISION

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

S = 0.05 mg/litre.

Where S = single operator precision.

13.6 INTEREFENCES

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

matter affect the sample titration.

13.6.2 The effects of carbonates and phosphates are eliminated by the addition of
strontium chloride in excess.

13.7 NOTES

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

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

sodium carbonate (previously dried in a platinum crucible at 250°C 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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14 ALUMINIUM
14.1 SUMMARY OF METHOD

14.1.1 Aluminium is complexed with ferron (8-hydroxy-7-iodo-5-quinoline sulphonic

acid) and its concentration is determined colorimetrically at a wave-length of
370nm.

Orthophenanthroline is added to greatly minimize the iron interference and its

simultaneous determination at a wavelength of 520nm.

14.2 RANGE

0.00 to 2.00 mg/litre Al.

14.3 APPARATUS

14.3.1 Spectrophotometer for use at 370 and 520nm.

14.3.2 Matched pair of l0 mm cells.

14.4 REAGENTS

14.4.1 Water - conforming to specifications Type II.

14.4.2 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.

14.4.3 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.

14.4.4 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.

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14.4.5 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 (BeSO4) and dissolve. Dilute to 1 litre
with water.

14.4.6 Sodium Acetate (275g/litre) - Dissolve 275g of sodium acetate trihydrate

(NaC2H3O2.3H2O) in water and dilute to 1 litre with water.

14.5 CALIBRATION

14.5.1 Aluminium Curve

14.5.1.1 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.

14.5.1.2 Using the procedure described in section 6.0, develop the colour and measure
the absorbance of each standard at 370nm.

14.5.1.3 Prepare a calibration curve by plotting the absorbance against the concentration.
14.5.2 Iron Correction Curve

14.5.2.1 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.

14.5.2.2 Using the procedure described in section 6.0 develop the colour and measure the
absorbance of each standard at 370 and 520nm.

14.5.2.3 Prepare calibration curves by plotting absorbance against concentration of iron

at the two specified wavelengths.

14.6 PROCEDURE

14.6.1 Place 25 ml sample into a beaker or flask, and add 2.0 ml of hydroxylamine
hydrochloride solution. Allow to stand for 30 minutes.

14.6.2 Add 5.0 m1 of ferron-orthophenanthroline solution and mix.

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14.6.3 Add 2m1 of sodium acetate solution and allow to stand for 10 minutes.

14.6.4 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.

14.7 CALCULATIONS

14.7.1 Designate the absorbance measurement at 370nm as A.

14.7.2 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.

14.7.3 A minus B is the corrected absorbance. Using the aluminium calibration curve,
find the aluminium concentration corresponding to the corrected absorbance.

14.8 PRECISION

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

So = 0.035

Where So = single operator precision in mg/litre of aluminium.

14.9 INTERFERENCES

14.9.1 Each mg/litre of iron increases the aluminium reading by about 0.01 mg/litre.

14.9.2 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.

14.10 NOTES

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

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14.10.2 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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15 ALUMINIUM (ATOMIC ABSORPTION METHOD)

15.1 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.
15.2 APPARATUS

15.2.1 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 manufacturer’s directions.

Improper sequencing of gas flows at start up and shut down of instrument can
produce explosion from flash back.
15.2.2 Standard Volumetric Glass wares
15.3 REAGENTS
15.3.1 Hydrochloric Acid – concentrated (11 N).

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

15.3.3 Potassium Chloride Solution

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

15.3.4 Stock Aluminium Solution

Dissolve 8.791 g of aluminium potassium sulphate, AlK(SO4)2.12H2O in water

and dilute to 1 000 ml with water in a volumetric flask (1 ml = 500 mg of Al).

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15.3.5 Standard Aluminium Solution

Dilute 10.0 ml of stock aluminium solution to 1000 ml with water in a
volumetric flask (1ml = 5.0 mg of Al)

NOTE – Fresh standard aluminium solution to be prepared after a week.

15.4 PROCEDURE
15.4.1 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
zero63adjustment. Aspirate sequentially the standard solutions and measure the
absorbance at 309.3 nm.

15.4.2 Determination of Aluminium

Add 0.5 ml of concentrated nitric acid to 100 ml of the sample taken in a 250-ml
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
0.45mm 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 HNO3/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.

15.5 Calculations

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Aluminium, mg/l = M
V

Where

M = mass of aluminium present in mg in 100 ml of the final solution, and

V = volume of the sample in ml.

15.6 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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16 AMMONIA (Indophenol method)

16.1 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.

16.2 RANGE

10 to 500 micrograms/litre as N.

16.3 APPARATUS

16.3.1 Spectrophotometer for use at 630nm. .

16.3.2 Matched pair of 10 mm and 50 mm cells.

16.4 REAGENTS

16.4.1 Water - conforming to specifications Type I.

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

phenol in 100 ml of water. Prepare every week.

16.4.3 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.

16.4.4 Manganous Sulphate Solution - Dissolve 0.050 g of manganous sulphate

(MnSO4.H2O) in 100 ml of water.

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

0.3819g of anhydrous ammonium chloride (NH4C1), 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.

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16.5 CALIBRATION

16.5.1 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,

16.5.2 Add 0.05ml of manganous sulphate solution and mix.

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

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

16.5.5 Prepare a calibration curve by plotting absorbance versus micrograms of

ammonia nitrogen.

16.6 PROCEDURE

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

16.7 CALCULATIONS

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

sample, as follows:

A x 1000
Ammonia, micrograms/litre as. NH3 = ------------------------------
V

Where:

A = micrograms of ammonia, nitrogen observed from toe calibration curve.

V = milliliters of sample.

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16.7.2 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.

16.8 INTERFERENCES

16.8.1 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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17 AMMONIA by Nesseler’s Reagent

17.1 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.

17.2 RANGE

0.1 to 2mg/litre as N.

17.3 APPARATUS

17.3.1 Spectrophotometer for use at 425nm.

17.3.2 Matched pair of 10 mm cells.

17.4 REAGENTS

17.4.1 Water - conforming to specifications Type I.

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

ammonium sulphate [(NH4)2SO4] (previously dried at 100°C 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 (HgI2) 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.

17.4.3 Reagents For Sample Turbidity/Cloudiness Removal

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

in water and dilute to 1 litre.

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

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

17.4.3.3 Sodium Potassium Tartarate Solution (300 g/litre) - Dissolve 30g of sodium
potassium tartarate tetrahydrate in 100m1 of water.

17.4.3.4 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.

17.5 CALIBRATION

17.5.1 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.

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

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

17.5.4 Prepare a calibration curve by plotting absorbance versus milligrams of

ammonia nitrogen.

17.6 PROCEDURE

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

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

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17.6.3 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.

17.7 CALCULATIONS

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

follows:

A x 1000
Ammonia nitrogen, mg/litre as N = ------------------------
V
Where:

A = milligrams of ammonia nitrogen observed

from the calibration curve.

V = milliliters of sample.

17.7.2 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.

17.8 PRECISION

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

±0.04.

17.9 INTERFERENCES

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

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17.9.2 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.

17.9.3 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.

17.10 NOTES

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

17.10.2 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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18 AMMONIA BY ION SELECTIVE ELECTRODE

18.1 SCOPE
This test method is applicable to the measurement of ammonia in reagent and
effluent water.
18.2 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.
18.3 INTERFERENCES
18.3.1 Volatile amines are positive interferences.
18.3.2 Mercury, if present, forms ammonia complexes, thus causing negative
interference.
18.3.3 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.
18.4 APPARATUS
18.4.1 Electrode, gas-sensing, ammonia, incorporating and internal reference electrode
and a diffusion-type membrane.
18.4.2 Meter, one of the following:
i. pH Meter, digital or expanded millivolt scale, accurate to±
0.1 mv.

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ii. ISE Meter, with direct-reading concentration scale.

18.4.3 Electrode Holder, for mounting the electrode at 200 to the vertical.
18.4.4 Stirrer, magnetic, with TFE-fluorocarbon-coated stirring bars.
18.4.5 Heat Barrier, 6-mm thick cork board placed underneath the beaker to insulate
the ample solution from heat generated by the magnetic stirrer.

18.5 REAGENTS

18.5.1 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 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.
18.5.2 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.
18.5.3 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.
18.5.4 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.
18.5.5 Sodium Hydroxide Solution (400 g/L) – dissolve 400 g of sodium hydroxide
(NaOH) in water. Cool and dilute to 1 L.
18.6 CALIBRATION
18.6.1 pH Meter – Refer to the manufacturer’s 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.

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18.6.2 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.
18.6.3 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.
18.6.4 Check the Calibration curve every 3 h when analyzing a series of samples.
18.6.5 ISE Meter – Refer to the manufacturer’s 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.
18.6.6 Check the calibration curve every 3 h when analyzing a series of samples;
otherwise, calibrate daily.
18.7 PROCEDURE

18.7.1 Sample Treatment:

18.7.2 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
18.7.3 Add the stirring bar and mix on the magnetic stirrer. Do not mix so rapidly that
air bubbles are drawn into the solution.
18.7.4 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.
18.7.5 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

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18.7.6 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.
18.7.7 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.
18.7.8 Sample Measurement – Determine the ammonia nitrogen concentration by
means of a pH meter of a specific-ion meter.
18.7.9 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).
18.7.10 ISE Meter – Record the concentration reading directly from the logarithmic
scale as milligrams of ammonia nitrogen per litre.

18.8 CALCULATIONS

Report the ammonia nitrogen content in milligrams per litre. If necessary

calculate for dilution of original sample.

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19 CARBON DIOXIDE (Bicarbonate Titration Method)

19.1 SUMMARY OF METHOD

Carbon dioxide concentration is determined from measured values of pH and

bicarbonate ion.

19.2 APPARATUS

pH meter.

19.3 REAGENTS

19.3.1 Water - conforming to specifications Type, I.

19.3.2 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
250°C for 4 hours) using methyl red indicator.

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

19.4 PROCEDURE

19.4.1 Determine the pH of the sample.

19.4.2 Place 50m1 or less of sample water containing no more than 80mg of
bicarbonate ion into a 200m1 beaker.

19.4.3 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.

19.4.4 Continue to titrate to pH 4.5

19.4.5 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.

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19.5 CALCULATIONS

19.5.1 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.

19.5.2 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

19.5.3 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.

19.6 PRECISION

19.6.1 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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20 CARBON DIOXIDE (Direct Titration of Free Carbon Dioxide)

20.1 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.

20.2 APPARATUS

pH meter.

20.3 REAGENTS

20.3.1 Water - conforming to specifications Type I.

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

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

20.3.3 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.

20.3.4 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.

20.3.5 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.

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

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20.4 PROCEDURE

20.4.1 Place 100m1 of sample in a 250m1 beaker and add 5 drops of phenolphthalein
indicator solution.

20.4.2 If the sample remains colourless, titrate rapidly with standard sodium hydroxide
solution until the first faint pink colour is detectable in the solution.

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

20.5 CALCULATIONS

20.5.1 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.

20.5.2 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

20.6 PRECISION

20.6.1 Under the most favourable conditions, precision is approximately 10% of the
indicated carbondioxide content.

20.7 INTERFERENCES

20.7.1 Cations or anions which affect the carbonate equilibrium or precipitate or

consume the reactant preferentially affect the accuracy. Aluminium, iron,

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chromium and copper are examples of metal ions that may yield erroneous
results.

20.7.2 Abnormal results also may be obtained in the presence of ammonia, amines,
phosphate, borate, sulphide and nitrate.

20.7.3 Excessive dissolved solids also, will introduce error.

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21 CHLORIDE (Mercuric Thiocyanate Method)

21.1 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.

21.2 RANGE

0.05 to 1.4mg/litre as C1.

21.3 APPARATUS

21.3.1 Spectrophotometer for use at 463nm.

21.3.2 Matched pair of 50mm cells.

21.4 REAGENTS

21.4.1 Water - conforming to specifications Type II.

21.4.2 Ferric Alum Solution - Dissolve 5.0 g of ferrous ammonium sulphate

[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.

21.4.3 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.

21.4.4 Standard Sodium Chloride Solution (l ml = 0.0l mg chloride) - Dissolve 1.649g

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

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21.5 CALIBRATION

21.5.1 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.

21.5.2 Proceed in accordance with section 6.0.

21.5.3 Prepare a calibration curve by plotting absorbance versus the concentration of

chloride in mg/litre.

21.6 PROCEDURE

21.6.1 Place 25m1 of sample in a 50ml glass stoppered cylinder.

21.6.2 Add 5.0 ml of ferric alum solution and 2.5ml of mercuric thiocyanate solution,
mix thoroughly and allow to stand for 10 minutes.

21.6.3 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.

21.7 CALCULATIONS

21.7.1 Read the concentration of chloride ion in mg/litre directly from the calibration
curve prepared in accordance with section 5.0:

21.7.2 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.

21.8 PRECISION

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

Sr = 0.054 X
So = 0.013 X

Where:

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Sr = overall precision, mg/litre.

So = single operator precision, mg/litre.

X = concentration of chloride ion determined, mg/litre.

21.9 INTERFERENCES

21.9.1 Bromides, iodides, cyanides, thiosulphate, hydrazine and nitrites interfere.

21.9.2 Morpholine concentrations greater than 6mg/litre may interfere.

21.9.3 Colour may also interfere depending upon its spectral absorbance.

21.9.4 Boric acid upto 13000mg / litre does not interfere.

21.10 NOTES

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

21.10.2 Mercuric salts are very poisonous. Due precautions should be observed when
using these salts. -

21.10.3 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.

21.10.4 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.

21.10.5 For best results, the temperatures of the standard solutions should be within 1.0
o
C of the reagent blank, and the samples.

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22 CHLORIDE (Mercuric Thiocyanate Method, Modified, 2 to

100 micrograms/litre)
22.1 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.

22.2 RANGE

2 to 100 micrograms/litre as Cl.

22.3 APPARATUS

22.3.1 Spectrophotometer for use at 463nm

22.3.2. Matched pair of 50mm Cells.

22.4 REAGENTS

22.4.1 Water - conforming to specifications Type II.

22.4.2 Ferric Nitrate Solution - Dissolve 8.09 of ferric nitrate [Fe(NO3)3.9H2O] in

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

22.4.3 Lead Nitrate Solution - Dissolve 20g of lead nitrate [Pb(N03)2] in water and
dilute to 1 litre.

22.4.4 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.

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22.4.5 Standard Sodium Chloride Solution (l ml = 1 microgram of Chloride) - Dissolve

1.649g of sodium chloride (dried at 600°C 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.

22.4.6 Sodium Phosphate Solution - Dissolve 16.7g of sodium dihydrogen phosphate

(NaH2PO4.H2O) and 16.2g of disodium hydrogen phosphate (Na2HPO4.7H2O)
in water and dilute to 1 litre.

22.5 CALIBRATION

22.5.1 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.

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

22.5.3 Prepare a calibration curve by plotting absorbance versus concentration of

Chloride in mg/litre.

22.6 PROCEDURE

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

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

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

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

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

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22.6.6 Add 1.0 m1 of mercuric thiocyanate solution and mix. Dilute to 25 m1 with
water. Allow to stand for 10 minutes.

22.6.7 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.

22.7 CALCULATIONS

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

calibration curve prepared in accordance with Section 5.0.

22.7.2 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.

22.8 INTERFERENCES

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

22.9 NOTES

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

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

22.9.3 2 microgram / litre chloride represents 0.006 absorbance with respect to a

reagent blank when using 50mm matched cells.

22.9.4 For standard method of further low level determination of Cl, PO4 and SO4 in
high purity water, ASTM D-5542 -94 may be referred.

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23 CHLORIDE (Silver Nitrate Method, 5mg/litre or

more)
23.1 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.

23.2 RANGE

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

23.3 REAGENTS

23.3.1 Water - conforming to specifications Type II.

23.3.2 Standard Silver Nitrate Solution (0.025N) - Dissolve 4.247g of silver nitrate
(dried to constant weight at 40°C) in water and dilute to 1 litre. Standardize
against standard sodium chloride solution.
23.3.3 Standard Sodium Chloride Solution (0.025N) - Dissolve 1.461g of sodium
chloride (dried at 600°C for 1 hour) in water and dilute to 1 litre.

23.3.4 Hydrogen Peroxide (30%).

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

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

23.3.6 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.

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

water and dilute to 1 litre.

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

23.4 PROCEDURE

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

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

23.4.3 Adjust the pH to the phenolphthalein endpoint (pH 8.3), using sulphuric acid
solution, or sodium hydroxide solution.

23.4.4 Add 1 ml of potassium chromate indicator and mix.

23.4.5 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.

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

23.5 CALCULATIONS

23.5.1 Calculate the chloride ion concentration in the sample, in milligrams per litre, as
follows:

(V1-V2) x N x 70906
Chloride, mg/litre as Cl = --------------------------------
V
Where:

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).

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

Chloride, mg/litre as CaC03 = A x 1.41

Where:

A = chloride concentration, mg/litre as Cl.

23.6 PRECISION

The precision of this method may be expressed as follows:

ST = 0.013X + 0.70

So = 0.007X + 0.53

Where:

ST = overall precision, mg/litre.

So = Single operator precision, mg/litre.

X = Concentration of Chloride ion determined, mg/litre.

23.7 INTERFERENCES

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

23.7.2 Orthophosphate and polyphosphate interfere, if present, in concentrations

greater than 250 and 25mg/litre, respectively.

23.7.3 Sulphite and objectionable colour or turbidity must be eliminated.

23.7.4 Compounds which precipitate at pH 8.3 may interfere.

23.8 NOTES

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

23.8.2 If the titration requires more than 25m1 of silver nitrate in 4.5, use a smaller
sample size.

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24 CHLORINE DEMAND

24.1 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.

24.2 APPARATUS

24.2.1 pH meter.

24.3 REAGENTS

24.3.1 Water - conforming to specifications Type III.

24.3.2 Calcium Hydroxide Solution (10.7g/litre) - Weigh 10.7g of 100% hydrated lime
[Ca(OH)2] and suspend in water. Dilute to 1 litre.

24.3.3 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.

24.3.4 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

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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.)

24.3.5 Hydrochloric Acid (1+1) - Mix equal volumes of hydrochloric acid (sp gr
1.19) and water.

24.4 PROCEDURE

24.4.1 Establishing Test Conditions

24.4.1.1 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.

24.4.1.2 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.

24.4.1.3 In each of a series of clean 1 litre glass containers, place a 500 ml portion of the
sample.

24.4.2 Trial Chlorination

24.4.2.1 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.

24.4.2.2 Adjust the pH (see notes).

24.4.2.3 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.

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24.4.3 Chlorination

24.4.3.1 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.

24.4.3.2 Adjust the pH (see notes)

24.4.3.3 Allow each portion of chlorinated sample to stand for a predetermined time.
Withdraw a portion of the sample and determine the total residual chlorine.

24.5 CALCULATIONS

24.5.1 Calculate the chlorine dosage, in mg/litre, for each increment of chlorinating
solution as follows:

Chlorine dosage, mg/litre = 2AB

Where:

A = milliliters of chlorinating solution added to 500 m1 of sample.

B = milligrams of available chlorine per milliliter of

the chlorinating solution.

24.5.2 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 co-ordinate
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.

24.6 NOTES

24.6.1 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.

24.6.2 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.

24.6.3 pH Adjustment

24.6.3.1 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.

24.6.3.2 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

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sufficient calcium hydroxide solution to bring the pH of the unchlorinated

sample portion to the midpoint of the desired pH range.

24.6.3.3 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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25 CHLORINE RESIDUAL (DPD Method, 0.02 to

4.0mg/litre)
25.1 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.

25.2 RANGE

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

25.3 REAGENTS

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

chlorine demand (see notes).

25.3.2 DPD Reagent - Dissolve 0.115g DPD sulphate, [NH2C6H4

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.

25.3.3 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).

25.3.4 Sodium Arsenite Solution- Dissolve 0.5 g sodium. arsenite (NaAsO2) in 100 m1
of water.

25.3.5 Potassium Iodide, crystalline.

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25.3.6 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.

25.3.7 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). .

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

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

25.3.9 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.

25.4 PROCEDURE

25.4.1 Free Chlorine

25.4.1.1 Place 5.0 m1 of DPD solution and 5.0m1 of phosphate buffer in a 250m1
titration flask.

25.4.1.2 Add 100 ml of sample and mix.

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

25.4.1.4 Record the volume of ferrous ammonium sulphate in ml used in the titration as
A.

25.4.2 Monochloramine (NH2C1)

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

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25.4.2.2 Record the total volume of ferrous ammonium sulphate in ml as B. For free
chlorine + monochloramine)

25.4.3 Dichloramine (NHC12)

25.4.3.1 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.

25.4.3.2 Continue titration with ferrous ammonium sulphate.

25.4.3.3 Record the total volume of ferrous ammonium sulphate in ml as C (for free
chlorine + monochloramine + dichloramine).

25.4.4 Nitrogen Trichloride (NC13)

25.4.4.1 Place a small crystal of potassium iodide in a 250m1 titration flask, add 100m1
of sample and mix.

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

25.4.4.3 Titrate rapidly with ferrous ammonium sulphate solution.

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

25.4.5 Total Available Chlorine

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

25.4.5.2 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.

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

ST = 0.008 X + 0.9

Where:

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ST = overall precision.

X = determined concentration of copper, micrograms/litre.

25.5 INTERFERENCES

25.5.1 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.HNO3. 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.

25.6 NOTES

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

25.6.2 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 to
neutralize the sample to pH 4 (using narrow range pH paper) and then add 2.0
m1 for each litre of sample.

25.6.3 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

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acid (1+9) until used again. Discard any glassware that appears etched or
scratched.

25.6.4 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.

25.6.5 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.

25.6.6 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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26 CHLORINE, RESIDUAL (Starch Iodide Thiosulphate

Method)

26.1 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.

26.2 RANGE

0.04mg/litre or more, as Cl

26.3 REAGENTS

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

chlorine demand (see notes).

26.3.2 Acetic Acid, glacial (99.5%).

26.3.3 Potassium Iodide, crystalline.

26.3.4 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).

26.3.5 Sodium Thiosulphate Standard solution (0.01N)- Dilute 25m1 of 0.1N sodium
thiosulphate solution (3.4) to 250 m1 in a volumetric flask.

26.3.6 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

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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.

26.4 PROCEDURE

26.4.1 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.

26.4.2 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)

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

titrated. Mix well.

26.4.4 Titrate with sodium thiosulphate solution using starch as indicator.

26.4.5 Carry out a blank determination using water instead of sample:

26.5 CALCULATIONS

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

(V1- V2) X N X 35.45

Residual Chlorine, mg/litre as C1 = ----------------------------------------
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.

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V= milliliters of sample.

26.6 INTERFERENCES

26.6.1 Free available chlorine cannot be determined quantitatively when organic matter
is present that rapidly and continuously consume free available chlorine.

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

from iodide at a pH of 4.0.

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

not interfere at a pH of 4.0.

26.6.4 Excessive colour and turbidity also interfere.

26.7 NOTES

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

26.7.2 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.

26.7.3 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.

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

potassium dichromate, transfer to a platinum dish, and dry at 120°C 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

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3 g of potassium iodide, 2g of sodium bicarbonate add 5 m1 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:

W
N= ---------------------
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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27 COPPER (Neocuprine method, 2 to 1000 micrograms/

litre Cu)

27.1 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.

27.2 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).

27.3 APARATUS

27.3.1 Spectrophotometer for use at 454 and 457nm.

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

27.4 REAGENTS

27.4.1 Water - conforming to specifications Type I.

27.4.2 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.

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27.4.3 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.

27.4.4 Hydrochloric Acid (sp gr 1.19).

27.4.5 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.

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

isopropyl alcohol. Dilute to 100 m1 with water.

27.4.7 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.

27.4.8 Chloroform Solvent - Mix 9 volumes of chloroform (CHCl3) with one volume
of isopropyl alcohol.

27.4.9 Isoamyl Alcohol, copper free.

27.4.10 Isopropyl Alcohol, copper free.

27.5 CALIBRATION

27.5.1 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:

27.5.1.1 Place the required volumes of copper standard solution (4.3) in 250m1
separatory funnels.

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

27.5.1.3 Prepare a blank (zero standard) by diluting 0.4 m1 hydrochloric acid (sp gr
1.19) to 200 m1 with water.

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

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

27.5.1.6 Prepare a calibration curve by plotting the absorbance of the standards against
the copper' content in micrograms.

27.6 PROCEDURE

27.6.1 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.

27.6.2 Add l ml of hydroxylamine hydrochloride solution and mix.

27.6.3 Add l0 ml of sodium citrate solution and mix.

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

27.6.5 Add 20 m1 of chloroform solvent shake vigorously for at least 1 minute and
allow to stand for 5 minutes.

27.6.6 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.

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27.6.7 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
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.

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

27.7 CALCULATIONS

27.7.1 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.

27.8 PRECISION

27.8.1 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.

27.9 INTERFERENCES

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27.9.1 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.HNO3. 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.

27.10 NOTES

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

27.10.2 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 to
neutralize the sample to pH 4 (using narrow range pH paper) and then add 2.0
m1 for each litre of sample.

27.10.3 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.

27.10.4 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

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water containing 0.4m1 of hydrochloric acid (sp gr 1.19) per 200 m1 of

solution.

27.10.5 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.

27.10.6 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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28 COPPER (Atomic Absorption Spectrophotometry Method)

28.1 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.

28.2 APPARATUS

Atomic Absorption Spectrophotometer , for use at 324.7nm with background

correction. The manufacturer’s 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.

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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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29 EQUIVALENT AND FREE MINERAL ACIDITY

29.1 SUMMARY OF METHOD

29.1.1 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.

29.1.2 Free Mineral Acidity - The sample is titrated with a standard solution of sodium
hydroxide using screened methyl orange as indicator.

29.2 REAGENTS

29.2.1 Water - conforming to specifications Type II.

29.2.2 Strong Acid cation Resin, Bead Type.

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

litre with water.

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

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

29.2.5 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.

29.3 PROCEDURE

29.3.1 Equivalent Mineral Acidity (EMA)

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29.3.1.1 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.

29.3.1.2 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.

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

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

29.3.2 Free Mineral Acidity (FMA)

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

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

29.4 CALCULATIONS

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

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

V1 = milliliters of standard sodium hydroxide solution.

N = normality of sodium hydroxide solution.

V = milliliters of sample.

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

V2 X N X 50,000

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FMA, mg/litre as CaCO3 = -----------------------

V
Where:

V2 = milliliters of standard sodium hydroxide solution.

N = normality of sodium hydroxide solution.

V = milliliters of sample.

29.5 NOTES

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

29.5.2 For standardization of 0.02N sodium hydroxide solution place 0.19 + 0.005g of
potassium hydrogen phthalate (dried at 120°C 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:

W
N = -----------------
(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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30 FLUORIDE (SPANDS Dye Method)

30.1 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.

30.2 RANGE

0.00 to 1.40 mg/litre as F.

30.3 APPARATUS

30.3.1 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 200°C.

30.3.2 Spectrophotometer for use at 570 nm.

30.3.3 Matched pair of l0mm cells.

30.4 REAGENTS

30.4.1 Water - conforming to specifications Type I.

30.4.2 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.

30.4.3 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.

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30.4.4 Acid Zirconyl - SPANDS Reagent - Mix equal volumes of Zirconyl acid
reagent and SPANDS solution.

30.4.5 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.

30.4.6 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.

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

and dilute to 1 litre.

30.4.8 Sulphuric Acid (sp gr 1.84).

30.5 CALIBRATION

30.5.1 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.

30.5.2 If the sample to be analyzed contains free chlorine, add 2 drops of sodium
arsenite solution to each standard.

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

30.5.4 Prepare a calibration curve by plotting absorbance versus the concentration of

fluoride in mg/litre.

30.6 PROCEDURE

30.6.1 Distillation

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30.6.1.1 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 180°C. Discard the
distillate.

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

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

30.6.2 Analysis

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

30.6.2.2 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.

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

30.6.2.4 Measure the absorbance against reference solution (4.5) at 510 nm using l0 mm
matched absorption cells.

30.7 CALCULATIONS

30.7.1 Calculate the concentration of fluoride in the sample, in mg/litre, directly from
the calibration curve prepared in accordance with section 5.0.

30.7.2 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:

30.8 PRECISION

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

0.81mg/litre of F.

30.9 INTFRFERENCES

30.9.1 In sample distillation, the following interferences may be experienced:

30.9.1.1 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.

30.9.1.2 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.

30.9.1.3 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.

30.9.1.4 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.

30.9.2 The Table 1 lists the interferences of various constituents on the SPANDS
procedure.

TABLE 1

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.

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No. Constituent Concentration (mg/litre) Type of Error

Alkalinity (as CaCO3)
Aluminium (A1+3)
Chloride (CI-)
Iron (Fe+3)
Hexametaphosphate(NaPO3)6
Phosphate (PO4-3)

Sulphate (SO4-2)

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

30.10 NOTES

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

30.10.2 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).

30.10.3 The SPANDS solution (4.3) is stable indefinitely if stored in a well sealed bottle
protected from sunlight.

30.10.4 A new standard curve (5.0) should be prepared whenever a new batch of
SPANDS reagent is prepared.

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

30.10.6 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.

30.10.7 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.

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30.10.8 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.

30.10.9 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.

30.10.9.1 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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31 HARDNESS (TOTAL, CALCIUM AND MAGNESIUM)

31.1 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.

31.2 RANGE

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

31.3 REAGENTS

31.3.1 Water - conforming to specifications Type II.

31.3.2 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.

31.3.3 Sodium Hydroxide Solution (8% w/v).

31.3.4 Ammonium Purpurate - Mix thoroughly 1.0g of ammonium purpurate with 200
g of sucrose.

31.3.5 Eriochrome Black-T - Dissolve 0.4g of Eriochrome Black-T in 100m1

of water. This solution has a shelf life of 1 week.

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.

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

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

31.3.7 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).

31.4 PROCEDURE

31.4.1 Total Hardness (Ca plus Mg)

31.4.1.1 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).

31.4.1.2 Add l ml of buffer solution.

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

powdered indicator.

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

31.4.1.5 Record the volume of EDTA solution required in the titration.

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

including all added reagents.

31.4.2 Calcium Hardness

31.4.2.1 Pipet 50.0 m1 of sample into a titration flask and add l ml of sodium hydroxide
solution.

31.4.2.2 Add 0.2 g ammonium purpurate indicator and mix.

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

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

31.4.2.5 Determine a reagent blank correction by similarly 50.0m1 of water including all
added reagents.

31.5 CALCULATIONS

V1 x M
31.5.1 Total hardness, mg/litre as CaCO3 = ------------------------- x 10,000

V2 x M
31.5.2 Calcium hardness, mg/litre as CaCO3 = ------------------------- x 10,000

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).

V = milliliters of sample taken.

M = molarity of standard EDTA solution.

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31.6 PRECISION

31.6.1 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:

Sr = overall precision.
So = single operator precision.

X = determined concentration of calcium, mg/litre

as Ca.

31.6.2 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.

31.7 INTERFERENCES

31.7.1 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.

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31.7.2 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.

31.7.3 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.

31.7.4 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.

31.8 NOTES

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

31.8.2 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.

31.8.3 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.

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

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31.8.5 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.

31.8.6 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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32 HYDRAZINE (p-Dimethylamino Benzaldehyde Method)

32.1 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.

32.2 RANGE

4 to 100 micrograms/litre N2H4.

32.3 APPARATUS

32.3.1 Spectrophotometer suitable for measurement at 458nm.

32.3.2 Matched pairs of l0 mm and 50 mm cells.

32.4 REAGENTS

32.4.1 Water - conforming to specifications Type II.

32.4.2 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.

32.4.3 Hydrochloric Acid (sp gr 1.19).

32.4.4 Hydrochloric Acid (1+9) - Mix 1 volume of hydrochloric acid (sp gr 1.19) with
9 volumes of water.

32.4.5 Hydrochloric Acid (1+99) – Mix 1volume of hydrochloric acid (sp gr 1.19) with
99 volumes of water.

32.4.6 Para Dimethylaminobenzaldehyde Solution - Dissolve 4.0 g of p-

dimethylaminobenzaldehyde in 200m1 of methyl alcohol and 20m1 of
hydrochloric acid (sp gr 1.19). Store in a dark bottle, out of direct sunlight.

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32.5 CALIBRATION

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

hydrazine solution. (1 ml = 100 micrograms N2H4) 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).

32.5.2 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 (6.3-6.4).

32.5.3 Prepare a calibration curve by plotting transmittance against micrograms of

hydrazine.

32.6 PROCEDURE

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

32.6.2 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.

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

for 10 minutes.

32.6.4 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.

32.7 CALCULATIONS

32.7.1 Calculate the hydrazine concentration in micrograms per litre as follows:

W x 1000
Hydrazine, micrograms/litre = ----------------------------------

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Where:

W = micrograms of hydrazine found in accordance with section 6.0.

V = milliliters of sample.

32.8 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.

32.9 INTERFERENCES

32.9.1 The hydrazine content may be diminished by oxidising agents collected with the
sample or absorbed by it prior to testing.

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

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32.10 NOTES

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

32.10.2 The purity of hydrazine dihydrochloride may be checked by iodimetric

methods.

32.10.3 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.

32.10.4 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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33 IRON (Bathophenanthroline Method)

33.1 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.

33.2 RANGE

4 to 80 micrograms/litre Fe with 100mm cell.

10 to 160 micrograms/litre Fe with 50mm cell.

33.3 APPARATUS

33.3.1 Spectrophotometer for use at 533nm.

33.3.2 Matched pair of 50mm and 100mm cells.

33.4 REAGENTS

33.4.1 Water - conforming to specifications Type II.

33.4.2 Alcohol, n-Hexyl or Isoamyl.

33.4.3 Alcohol, Methyl, ethyl or Isopropyl.

33.4.4 Bathophenanthroline Solution (0.835g/litre)- Dissolve 0.0835g of

bathophenanthroline in 100m1 of ethyl alcohol.

33.4.5 Hydrochloric Acid (1+1) - Mix equal volumes of hydrochloric acid (sp gr 1.19)
and water.

33.4.6 Hydroxylamine Hydrochloride Solution (10%)

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33.4.7 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.

33.4.8 Hydrochloric Acid (1+9) - Mix 1 volume of hydrochloric acid (sp gr 1.19) with
9 volumes of water.

33.4.9 Ammonium Hydroxide (1+1) - Mix equal volumes of ammonium

hydroxide (sp gr 0.90) and water.

33.5 CALIBRATION

33.5.1 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:

33.5.1.1 Place the required volumes of Iron standard solution (4.7) in 125m1 separatory
funnels.

33.5.1.2 Add water to make 50m1.

33.5.1.3 Add 2.0 m1 of hydroxylamine hydrochloride solution and mix.

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

33.5.1.5. 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.

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

33.5.1.7 Simultaneously carry out a blank determination containing no added iron using
50m1 of water and all reagents.

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33.6 PROCEDURE

33.6.1 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.

33.6.2 Add 1.0m1 of hydroxylamine hydrochloride solution and mix.

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

33.6.4 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.

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

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

33.6.7 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).

33.6.8 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.

33.6.9 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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33.7 CALCULATIONS

33.7.1 Calculate the concentration of iron in micrograms per litre in the sample as
follows:

W x 1000
Iron, micrograms/litre = ----------------------------
V
Where:
W = micrograms of iron, read from the calibration curve:

V = milliliters of original sample used.

33.8 PRECISION

33.8.1 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

Where:

So = single operator precision, micrograms/ litre.

St = overall precision, micrograms/litre.

X = determined concentration microgram/litre.

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33.9 INTERFERENCES

33.9.1 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.

33.10 NOTES

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

33.10.2 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.

33.10.3 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. ,

33.10.4 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.

33.10.5 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

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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.

33.10.6 For total iron determination, heat the sample for 1 hour at 60 0°C 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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34 IRON (Ferrozine Method)

34.1 SUMMARY OF METHOD

Soluble iron [both Fe (II) and Fe (III)) is complexed with ferrozine [3-(2-
pyridyl) - 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.

34.2 RANGE

Upto 500 micrograms/litre Fe.

34.3 APPARATUS

34.3.1 Spectrophotometer for use at 562nm.

34.3.2 Matched pair of 50 mm cells.

34.4 REAGENTS

34.4.1 Water - conforming to specifications Type II.

34.4.2 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.

34.4.3 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.

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34.5 CALIBRATION

34.5.1 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:

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

34.5.1.2 Add enough water to make the volume to 40 ml.

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

34.5.1.4 Make up to 50 ml with water.

34.5.1.5 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.

34.5.1.6 Prepare a calibration curve by plotting the absorbance of the standards against
the iron content in micrograms /litre.

34.6 PROCEDURE

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

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

34.6.3 Measure the absorbance of the solution at 562nm against water as reference. Let
the absorbance be A1.

34.6.4 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.

34.7 CALCULATIONS

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

A3 = A1 – 0.1 A2

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

34.8 INTERFERENCES

34.8.1 100 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.

34.9 NOTES

34.9.1 Reagent grade chemicals should be used fore preparing the reagents.

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

34.9.3 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.

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

34.9.5 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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35 IRON ATOMIC ABSORPRION METHOD (Graphite

Furnace)

35.1 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 µg/L of iron
using a 20 ml µL 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.
35.2 APPARATUS
Atomic absorption spectrophotometer for use at 248.3 nm with background
correction. The manufacturer’s 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.

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35.3 REAGENTS

(a) Iron solution: Stock (1.0 ml = 1000 µg 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 µg 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 µg of Fe): Dilute 20.0 ml of above stock
solution (b) and 1 ml of HNO3 (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.

35.4 Inject the measured aliquots of sample into the furnace device following the
directions as provided by the particular instrument manufacturer.

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36 NICKEL (Glyoxime Method)

36.1 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.

36.2 RANGE

0.01 to 0.1mg/litre with 100 mm cell.

0.1 to 5.0mg/litre with 10 mm cell.

36.3 APPARATUS

36.3.1 Spectrophotometer for use at 530 nm.

36.3.2 Matched pairs of 10 mm and 100 mm cells.

36.4 REAGENTS

36.4.1 Water – conforming to specifications Type II.

36.4.2 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.

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

0.90) with 1 volume of water.

36.4.4 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.

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36.4.5 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.

36.4.6 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.

36.5 CALIBRATION

36.5.1 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)

36.5.1.1 Place the required volumes of nickel standard solution (4.6) in 100ml
volumetric flasks.

36.5.1.2 Add water to make up the volume to 50ml.

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

36.5.1.4 Prepare a calibration curve by plotting the absorbance versus milligrams per
litre of nickel.

36.6 PROCEDURE

36.6.1 Measure 50 ml portions of the sample into each of two 100ml volumetric flasks.

36.6.2 Add 10 ml of ammonium citrate solution and 5ml of iodine solution to each
flask.

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36.6.3 To one flask add 20 ml of ammonical dimethylglyoxime solution. Dilute to

100ml with water and allow to stand for 10 minutes.

36.6.4 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.

36.6.5 Balance the spectrophotometer at zero absorbance with the reference solution
and read the absorbance at 530nm.

36.7 CALCULATIONS

36.7.1 Read the nickel concentration, in mg/litre directly from the calibration curve.

36.8 PRECISION

36.8.1 The overall and within a laboratory precisions are as follows:

ST = 0.06 X

SO = 0.04 X

Where:

ST = overall precision.

SO = precision within one laboratory.

X = concentration of nickel determined, mg/ litre.

36.9 INTERFERENCES

Iron interference is eliminated by the addition of ammonium citrate. Copper up

to 3mg/litre does not interfere with the test.

36.10 NOTES

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

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36.10.2 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.

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37 NICKEL by ATOMIC ABSORPTION METHOD (Direct)

37.1 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.

37.2 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.

37.3 APPARATUS

Atomic absorption spectrophotometer with air-acetylene flame. Hallow –

cathode lamp or electrodeless discharge lamp for use at 232.0 nm.

37.4 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

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Pipette out 10.0 ml of stock nickel solution into a 1000 ml volumetric flask and
make upto mark with water ( 1.0 ml = 10µg of Ni )

37.5 PROCEDURE

Calibration curve

Prepare standard solution containing 0 to 60 µg /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. 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.

37.6 CALCULATION

Soluble Ni (direct determination without digestion)

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µg of Ni (in 100 ml of the final solution)

Ni mg/l = ---------------------------------------------------------------- x 100

Where V = volume in ml of the sample used

Soluble Ni (direct determination with digestion)

µg of Ni (in 100 ml of the final solution)

Ni mg/l = ---------------------------------------------------------------- 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

37.7 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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38 MANGANESE
38.1 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.
38.2 INTERFERENCE:
Chlorides, organic matter, iron, colour and turbidity interfere in the estimation
of Mn.
38.3 APPARATUS
Colorimeter to operate at 525 nm.
Nessler’s tube cap. 100 ml.
Water bath.
38.4 REAGENTS
H2SO4 conc.
HNO3 conc.
H3PO4 85%.
KIO4 A.R. grade
AgNO3 salt
H2O2 30%
38.5 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.

38.6 PROCEDURE

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(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.

(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 10m 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.

Prepare a calibration curve using standard solution containing 50 to 1500m g of

mn/1.

Calculate the conc. Of Manganese in the sample from calibration curve and
express in mg/1 as Mn.

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39 NITRATE (Azo dye Method)

39.1 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.

39.2 RANGE

0.05 to l mg/litre as N but reliable upto 0.01mg/litre.

39.3 APPARATUS

39.3.1 Reduction column - consisting of the following:

39.3.1.1 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.

39.3.1.2 Tubing glass or vinyl 1mm inside diameter and about 350mm in length.

39.3.2 Cylinders, graduated, 50 ml capacity.

39.3.3 Test tubes, 15 ml capacity.

39.3.4 Spectrophotometer for use at 543 nm.

39.3.5 Matched pair of 10 mm cells.

39.3.6 Pipettes, serological 1 and 10ml capacity, calibrated to 0.1ml to deliver with
ejection.

39.4 REAGENTS

39.4.1 Water - Conforming to specifications Type II.

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39.4.2 Ammonium chloride solution – dissolve 85g of ammonium chloride (NH4 Cl)
in water and dilute to 1litre.

39.4.3 Cadmium, 250 to 425 micron size, granulated.

39.4.4 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.

39.4.5 Copper Sulphate Solution – dissolve 20g of copper sulphate (CuSO4.5H2O )

in 500ml of water and dilute to 1litre.

39.4.6 1,1,2 – Trichloro – 1,2,2 trifluoroethane.

39.4.7 Hydrochloric Acid (1+1) - Mix equal volumes of hydrochloric acid (sp gr 1.19)
and water.

39.4.8 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.

39.4.9 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.

39.5 PREPARATON OF REDUCTION COLUMN

39.5.1 Cadmium Granules Treatment

39.5.1.1 Clean about 10g of cadmium granules with hydrochloric acid (1+1) and then
rinse with water.

39.5.1.2 Swirl the clean cadmium granules in 100ml of copper sulphate solution for
5minutess or until the blue colour partially fades.

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39.5.1.3 Decant and repeat with a fresh 100m1 copper sulphate solution solution until
the first trace of a brown colloidal precipitate appears.

39.5.1.4 Wash the granules with water at least ten times to remove all the precipitated
copper.

39.5.2 Filling the Reduction Column

39.5.2.1 Insert a small plug of glass wool in the tip of the pipette.

39.5.2.2 Fill the column with water.

39.5.2.3 Pour sufficient cadmium granules into the apparatus to produce a column
300mm in length.

39.5.2.4 1 Wash the column thoroughly with ammonium chloride solution. .

39.6 CALIBRATION

39.6.1 Prepare a series of standards by diluting appropriate volumes of standard nitrate

solution (l ml = 0.01 mg N) to 100m1 in volumetric flasks.

39.6.2 Proceed in accordance with section 7.0 (7.1 to 7.6).

39.6.3 Prepare a calibration curve by plotting the absorbance versus concentration of

nitrate as N in milligrams per litre.

39.7 PROCEDURE

39.7.1 Mix 20m1 of sample (pH between 6 to 8) with 80m1 of ammonium chloride
solution.

39.7.2 Pour about 60m1 of mixed sample (7.1) into the reservoir of the reduction
column.

39.7.3 Discard initial 30 m1 of effluent.

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39.7.4 Place a clean 50m1 graduated cylinder under the siphon outlet and collect 25m1
of effluent.

39.7.5 Place l0 ml of the collected effluent (7.3) into a 15m1 test tube.

39.7.6 Add 3.0 m1 of colour reagent, mix, and allow to stand for 15 minutes.

39.7.7 Measure the absorbance of solution against water as reference at 543nm using l0
mm matched absorption cells.

39.8 CALCULATIONS

39.8.1 Calculate the concentration of nitrate, in mg/litre as N, directly from the

calibration curve prepared in accordance with section 6.0.

39.8.2 Calculate the nitrate concentration in mg/litre as NO3 as follows:

Nitrate concentration, mg/litre as NO3 = A x 4.43

Where:

A = nitrate concentration, mg/litre as N.

39.8.3 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

39.9 INTERFERENCES

39.9.1 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.

39.9.2 Sample colour that absorbs at wavelengths between 520 and 540nm interferes
with the absorbance measurement. When colour is suspected, analyze a sample

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blank, omitting the N-(1-naphthyl) ethylenediamine dihydro-chloride from the

colour reagent.

39.9.3 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.

39.9.4 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.

39.9.5 Certain metal ions such as mercury, copper, iron and manganese, in
concentrations above 35mg/litre, may cause interference.

39.10 NOTES

39.10.1 Reagent grade chemicals should be used in preparing all the reagents.

39.10.2 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.

39.10.3 If nitrite is present in the sample, it can be determined separately by carrying out
the procedure and omitting the cadmium reduction step.

39.10.4 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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40 NITRATE (PHENOL DISULPHONIC ACID (PDA) METHOD)

40.1 PRINCIPLE
Nitrate reacts with phenol disulphonic acid and produces a nitro-derivative
which in alkaline solution develops yellow colour due to rearrangement of its
structure. The colour produced follows Beer’s law and is proportional to the
concentration of NO3 present in the sample.
40.2 INTERFERENCE
Chlorides and nitrate, are the two main sources of interference. Pretreatment of
sample is necessary when the interfering radicals are present.
40.3 APPARATUS
a. Colorimeter or spectrophotometer having a range of 300-700 nm.
b. Nessler’s tubes capacity 100 ml.
c. Beakers capacity 100 ml.
d. Water bath capacity 100 ml.
40.4 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.

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1 ml = 100m 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 = 10m 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 NH4OH and allowed to
stand for 1 hr. Decant the supernatant and wash the precipitate a number of
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.

40.5 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

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i. Neutralize the clarified sample to pH 7.0.

ii. Take suitable aliquot of the sample in a beaker and evaporate to dryness
on water bath.
iii. Dissolve the residue using glass rod with 2 ml phenol disulfonic acid
reagent. Dilute
and transfer to Nessler tubes.
iv. 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 100ml. To avoid this add
10ml conc. NH4OH instead of KOH.
v. Prepare blank in the same way using distilled water instead of sample.
vi. Read the colour developed at 410 nm with a light path of 1 cm. Record
NO3 as N in mg/l.
vii. Prepare calibration curve using suitable aliquots of standard NO3 in the
range of 5 to 500 g N/1 following the above procedure.

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41 NITRATE (UV Spectrophotometric Method)

41.1 PRINCIPLE

Measurement of the ultraviolet absorption at 220 nm enables rapid

determination of nitrate. The nitrate calibration curve follows Beer’s 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 CaCO3.
Chloride has no affect on the determination. Minimum detectable concentration
is 40 g/l nitrate N.

41.2 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.

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Treat coloured samples with aluminium aluminum hydroxide suspension

or dilute to minimize colour interference.

41.3 APPARATUS

a. Sepectrophotometer, for use at 220 nm and 275 nm with matched silica

cells of 1 cm or longer light path.

b. Filter: 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 filter paper

sufficiently retentive for fine precipitates.

c. Nessler tubes, 50 ml, short form.

41.4 REAGENTS

a Redistilled water: Use redistilled water for the preparation of all

solutions and dilutions.

b Stock nitrate solution: Prepare as described in PDA method 1.00 ml =

100 mg N=443 mg NO3.

c Standard nitrate solution: Dilute 100.0 ml with stock nitrate solution to

1000 ml with distilled water : 1.00ml =10.0 mg N = 443.3 mg NO3.

d Hydrochloric acid solution, HCl, 1.N.

e Aluminum hydroxide suspension: Prepare as directed in PDA Method.

41.5 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

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0.45m 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 350m 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.

41.6 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 m g nitrate N ml of Sample.

NO3 mg/l = Nitrate N mg/l x 4.43.

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42 OIL AND GREASE (Solvent Extraction Method)

42.1 OIL AND GREASE

Any material recovered as a substance soluble in hexane

42.2 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.

42.3 PARTITION GRAVIMETRIC METHOD

42.3.1 Principle

Dissolved or emulsified oil and grease is extracted from water by hexane and
estimation is made gravimetrically.

42.3.2 Interferences

The solvent extracts are not only oil and grease but other organic substances
also.

42.3.3 Apparatus

42.3.3.1 Separating funnel – 1 litre capacity with teflon or equivalent stopcock.

42.3.3.2 Distillation flask – 250 –ml capacity.

42.3.3.3 Water Bath

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42.3.3.4 Filter Paper – Whatman No. 40 or equivalent, 11cm diameter.

42.3.4 Reagents

42.3.4.1 Hydrochloric acid – 1:1.

42.3.4.2 Hexane

42.3.4.3 Sodium Sulphate – anhydrous.

42.3.5 Procedure

42.3.5.1 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
obtained, add 1g of sodium sulphate (Na2 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.

42.3.6 CALCULATION
Oil and grease, mg/l = M/V x1000

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Where

M = mass, in mg, of the residue; and

V = volume, in ml, of the sample taken.

42.4 SOXHLET EXTRACTION METHOD

42.4.1 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.

42.4.2 APPARATUS

Soxhlet Apparatus

Vacuum Pump

Buchner Funnel – 12 cm diameter.

Electric Heating Device

Paper Extraction Thimble

Filter Paper – Whatman No. 40 or equivalent 11 cm diameter.

Muslin cloth discs – 11 cm diameter.

42.4.3 REAGENTS

Hydrochloric Acid – 1:1.

Hexane – See 5.4.2

Diatomaceous Silica Filter aid suspension – 10 g/l, distilled water.

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42.4.4 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 103°C 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 70°C.
Place the flask on a water bath at 70°C for lb minutes and draw air through it by
vacuum for the final 1 minute. Cool in a desiccator for 30 minutes and weigh.

42.4.5 CALCULATION
Oil and grease, mg/l = Mx1000
V
Where

M = mass, in mg, of the residue; and

V = volume in ml, of the sample.

42.5 MODIFIED METHOD FOR HYDROCARBON

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42.5.1 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.

42.5.2 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

42.5.3 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 110°C
for 24 hours and stored in tightly sealed container is required.

42.5.4 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.

42.5.5 CALCULATION

Hydrocarbons, mg / l = Mx1000
V
Where
M = mass, in mg, of residue; and

V = volume, in ml, of sample

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43 ORGANIC MATTER (Potassium Permanganate

Consumption Method)

43.1 SUMMARY OF METHOD

The sample is reacted with a standard solution of potassium permanganate at

27°C for 4 hours and the residual permanganate is determined iodometrically.

43.2 REAGENTS

43.2.1 Water - conforming to specifications Type III.

43.2.2 Potassium Permanganate Stock Solution - Dissolve 3.951g of potassium

permanganate (previously dried at 105°C) in water and dilute to 1 - litre.
Standardize with sodium oxalate. (see notes).

43.2.3 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.

43.2.4 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.

43.2.5 Potassium Iodide.

43.2.6 Sodium Thiosulphate Stock Solution - Dissolve 31.2 g of sodium thiosulphate

and 6g of sodium bicarbonate in water and dilute to 1-litre.

43.2.7 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.

43.2.8 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

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to adjust the pH to 4.0 (Check with a narrow range PH paper). This has a shelf
life of 'l year.

43.3 PROCEDURE

43.3.1 Place 100m1 of the sample into a clean, glass stoppered bottle of 250 m1
capacity and place in a thermostat at 27°C. .

43.3.2 When the temperature of the sample becomes 27°C, 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 27°C protected from sunlight.

43.3.3 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.

43.3.4 Run a blank on 100m1 of water under the same conditions.

43.4 CALCULATIONS

43.4.1 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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44 OXYGEN, DISSOLVED (Indigo Carmine Method)

44.1 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.

44.2 RANGE

Less than 60 micrograms/litre.

44.3 APPARATUS

44.3.1 Burette, 25 or 50 m1.

44.3.2 Sampling Bucket, with an overflow at least 20mm above the top of the sampling
vessel.

44.3.3 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.

44.4 REAGENTS

44.4.1 Water-conforming to specifications Type II.

44.4.2 Colour standards, stock solutions.

44.4.2.1 Red Colour Standard-Dissolve 59.29g of cobaltous chloride (CoC12.6H2O) in

hydrochloric acid (1+99) and dilute to 1 litre.

44.4.2.2 Yellow Colour Standard-Dissolve 45.05g of ferric chloride (FeC13.6H2O) in

hydrochloric acid (1+99) and dilute to 1 litre.

44.4.2.3 Blue Colour Standard - Dissolve 62.45g of cupric sulphate (CuSO4.5H2O) in

hydrochloric acid (1+99) and dilute to 1-litre.

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44.4.2.4 Hydrochloric Acid (sp gr 1.19)

44.4.2.5 Hydrochloric Acid (1+99)-Mix 1 volume of hydrochloric acid (sp gr 1.19) with
99 volumes of water.

44.4.2.6 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.

44.4.2.7 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.

44.4.2.8 Potassium Hydroxide Solution (530g/litre)- Dissolve 530g of potassium

hydroxide in water and dilute to 1 litre.

44.5 CALIBRATION

44.5.1 Prepare a series of colour standards as listed below:

Equivalent Dissolved Milliliters of Colour

Oxygen(micrograms/litre) Standards
RED YELLOW BLUE

0 0.75 05.0 -

5 5.0 20.0 -

10 6.25 12.5 -

15 9.4 10.0 -

20 13.0 5.4 -

25 14.4 5.5 -

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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

44.5.2 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.

44.6 PROCEDURE

44.6.1 Place a clean sampling vessel in the sampling bucket and collect the sample
under water. Allow the sample to overflow for several minutes.

44.6.2 Fix a burette such that its tip dips into the overflowing sample to a depth of 10
to 15mm.

44.6.3 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.

44.6.4 Remove the sample tubing from the sampling vessel.

44.6.5 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.

44.6.6 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,

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44.7 PRECISION

44.7.1 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.

44.8 INTFRFERENCES

44.8.1 Tannin, hydrazine, and sulphite do not interfere up to l mg/litre.

44.8.2 Ferric iron, cyclohexylamine, and morpholine up to 4mg/litre can be tolerated.

44.8.3 Ferrous iron will produce low results and copper will cause high results.

44.8.4 In samples, where ferrous iron and copper are present, their combined effect is
frequently zero.

44.8.5 Nitrate is a possible interference.

44.9 NOTES

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

44.9.2 All colour stock solutions should be stored in coloured bottles to prevent fading.

44.9.3 Indigo carmine solution (4.2.6) is stable for 30 days if stored in a refrigerator.

44.9.4 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.

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44.9.5 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.

44.9.6 The sample should be analysed as soon as possible after the collection.

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45 OXYGEN, DISSOLVED (Iodometric Method)

45.1 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.

45.2 RANGE

1.0 mg/litre or more.

45.3 APPARATUS

45.3.1 Sample bottles, 300m1 capacity, with tapered ground glass stoppers.

45.3.2 Pipettes, l0ml capacity, graduated in 0.lml divisions.

45.4 REAGENTS

45.4.1 Water - conforming to specifications Type II.

45.4.2 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.

45.4.3 Manganous Sulphate Solution (364g/litre) - Dissolve 364g of manganous

sulphate (MnSO4.H2O) in water, filter, and dilute to 1 litre.

45.4.4 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 (Na2CO3). Dilute to 1-litre and allow to stand for
24 hours. Standardize against potassium dichromate (See Notes).

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45.4.5 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.

45.4.6 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.

45.4.7 Sulphuric Acid (sp gr 1.84).

45.4.8 Potassium Fluoride Solution (400g/litre) - Dissolve 40g of potassium fluoride

(KF.2H2O) in water and dilute to 100 m1. Store in a plastic bottle.

45.4.9 Potassium Oxalate solution (20g/litre) - Dissolve 2g of potassium oxalate

(K2C2O4.H20) in 100m1 of water.

45.4.10 Potassium Permanganate solution (6.3g/litre) Dissolve 6.3g of potassium

permanaganate (KMnO4) water and dilute to 1 litre.

45.5 PROCEDURE

45.5.1 Collect the sample in the sample bottle (300m1 capacity).

45.5.2 Add 2.0 m1 of manganous sulphate solution and 2.0 m1 of alkaline iodide-
sodium azide solution well below the surface of the sample. Replace the stopper
and mix by inversion.

45.5.3 When the floc has settled, add 2.0 m1 of sulphuric acid (sp gr 1.84). Restopper,
and mix by inversion.

45.5.4 Titrate 203 m1 of solution (equivalent to 200m1 sample) with standard solution
of sodium thiosulphate using starch indicator.

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45.6 CALCULATIONS

45.6.1 Calculate the dissolved oxygen content of the sample as follows:

V1 X 0.2
Dissolved oxygen, mg/litre = -------------------------- x 100
200

Where:

V1 = militaries of 0:025N sodium thiosulphate solution required for

titration of sample.

45.7 PRECISION
45.7.1 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.

45.8 INTERFERENCES

45.8.1 Nitrite interferences are eliminated by routine use of sodium azide.

45.8.2 Ferric iron interferes unless l ml of potassium fluoride solution is used, in which
case 100 to 200mg/litre can be tolerated.

45.8.3 Ferrous iron interference can be removed by potassium permanganate.

45.9 NOTES

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

45.9.2 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

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Hence 200m1 of original sample = 200 X -----------

(300 - 4)
=203.3 ml
45.9.3 If it is necessary to eliminate ferrous iron, interference it is done before step 5.2
of the procedure. Following method is followed:

45.9.3.1 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.

45.9.3.2 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.

45.9.4 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.

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

potassium dichromate, transfers to platinum dish, and dry at 120°C 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:

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W
N = ------------------------------------------
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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46 OXYGEN DEMAND BIOCHEMICAL (Dissolved Oxygen

Loss Method)
46.1 SUMMARY OF METHOD

The sample is incubated at 20°C 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).

46.2 APPARATUS

46.2.1 Incubation Bottles - 250 to 300m1 capacity with ground glass stoppers.

46.2.2 Air Incubator - thermostatically controlled at 20+1°C. All light should be

excluded to prevent possibility of photosynthetic production of DO.

46.3 REAGENTS

46.3.1 Dilution Water - Add 0.3g of sodium bicarbonate per litre of Type II water.

46.4 PROCEDURE

46.4.1 Adjust the temperature of a suitable portion of the well mixed sample to 20°C.
Remove the oxygen or excess air by maintaining the sample under vacuum for
10 minutes using laboratory vacuum pump.

46.4.2 Fill completely two incubation bottles (250 or 300m1 capacity) with the sample
as treated above (4.1). Allow to stand for 15 minutes.

46.4.3 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.

46.5 CALCULATIONS

46.5.1 Calculate the BOD of the sample as follows: Biochemical oxygen demand
(BOD), mg/litre = Dl - D2 (5 days at 20°C).

Where:

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Dl = initial dissolved oxygen content, mg/litre.

D2 = dissolved oxygen content after 5 days incubation, mg/litre.

46.6 INTERFERENCES

46.6.1 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 4°C or below.

Analysis should be done before 24 hours after grab sample collection.

46.7 NOTES

46.7.1 The dissolved oxygen content of the sample before incubation shall be
approximately 9mg/litre or preferably less.

46.7.2 For samples of doubtful purity, the sample should be mixed with dilution water
in the ratio 1:1 at 20°C. 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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47 OXYGEN DEMAND, CHEMICAL (Potassium Dichromate

Method)
47.1 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.

47.2 RANGE

Upto 800mg/litre.

Samples with higher COD concentrations may be analyzed by appropriate

dilution of the sample.

47.3 APPARATUS

47.3.1 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.

47.3.2 Heating mantle or hot plate.

47.3.3 Apparatus for Blending or Homogenising Samples - A household blender is

satisfactory.

47.4 REAGENTS

47.4.1 Water - conforming to specifications Type III.

47.4.2 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).

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47.4.3 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.

47.4.4 Mercuric Sulphate (Hg SO4), powdered.

47.4.5 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.

47.4.6 Potassium Acid Phthalate Solution, Standard (1m1=1mg COD) - Dissolve

0.851g of potassium hydrogen phthalate (KC8H5O4) in water and dilute to 1
litre.

47.4.7 Potassium Dichromate Standard Solution (0.25N) - Dissolve 12.259g of

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

47.4.8 Potassium Dichromate Standard Solution (0.025N) - Dilute 100m1 of 0.25N

potassium dichromate solution (4.7) to 1 litre.

47.4.9 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).

47.5 PROCEDURE

47.5.1 Homogenize the sample by blending, if necessary. Place 50 m1 of the sample in

a reflux flask.

47.5.2 Place 50m1 of water in a separate reflux flask for blank determination,

47.5.3 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.

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47.5.4 Add 70m1 of sulphuric acid - silver sulphate solution slowly such that the
solution temperature is maintained as low as possible (below 400C).

47.5.5 Reflux for 2 hours.

47.5.6 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.

47.5.7 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).

47.5.8 For waters of low COD (10 to 50 mg/litre) use 0.025N potassium dichromate
and 0.025N ferrous ammonium sulphate solutions.

47.6 CALCULATIONS

47.6.1 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.

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V = milliliters of sample used for the test.

47.7 INTERFERENCES

47.7.1 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 40°C) 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.

47.7.2 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.

47.7.3 Oxidizable inorganic ions, such as ferrous, nitrite, sulphites, and sulphides are
oxidised and measured also as organic constituents.

47.8 NOTES

47.8.1 Potassium acid phthalate and potassium dichromate should be of primary

standard grade. All other reagents should be prepared from reagent grade
chemicals.

47.8.2 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.

47.8.3 Calculate the normality (N) of ferrous ammonium sulphate solution as follows:

V1 X N1
Normality, N = ------------------------------

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Where :
N = normality of ferrous sulphate solution.
V1 = milliliters of potassium solution.

N1 = normality of potassium solution.

V = 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 precisely
with water and 50m1 of the diluted sample are placed in the reflux flask.

47.8.4 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.

47.8.5 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.

47.8.6 Preserve samples by cooling to 4°C if analyzed within 24 hours after sampling
or preserve for up to 7 days at pH < 2 at 4°C.

47.8.7 Silver sulphate acts as a catalyst in the reaction to facilitate the oxidation of
organics which are difficult to oxidise.

47.8.8 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.

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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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48 PHOSPHATE (Amino Reduction Method)

48.1 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.

48.2 RANGE

0.5 to l0mg/litre P04

0.1 to 2.5mg/litre P04 (when bismuth salt is added)

48.3 APPARATUS

48.3.1 Spectrophotometer for use at 650nm.

48.3.2 Matched pair of 25mm cells.

48.4 REAGENTS

48.4.1 Water - conforming to specifications Type II.

48.4.2 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-2-
naphthol-4 sulphonic acid, and 6.2g of sodium metabisulphite (Na2S2O5). Store
in an amber coloured bottle and make fresh every two weeks.

48.4.3 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.

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48.4.4 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.

48.4.5 Phosphate Standard Solution (l0mg/litre PO4) - Dilute 10.0m1 of the stock
solution (4.4) to 100m1 with water.

48.4.6 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.

48.4.7 Sulphuric Acid Solution (B) - Dissolve 1.200g of bismuth nitrate

[Bi(NO3)3.5H2O] in 250m1 of sulphuric acid solution (A) (4.6).

48.5 CALIBRATION

48.5.1 Range from 0.5 to l0mg/litre PO4

48.5.1.1 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 PO4) to 100m1 with
water in a volumetric flask.

48.5.1.2 Proceed in accordance with Section 6.0.

485.1.3 Measure the absorbance of the each standard against reagent blank (zero
standard) at 650nm using 25mm matched absorption cells.

48.5.1.4 Prepare a calibration curve by plotting absorbance versus milligrams per litre of
phosphate.

48.5.2 Range from 0.1 to 2.5 mg/litre PO4

48.5.2.1 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 PO4) to 100m1 water in a
volumetric flask.

48.5.2.2 Proceed in accordance with section 6.0

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48.5.2.3 Proceed in accordance with 5.1.3 and 5.1.4.

48.6 PROCEDURE

48.6.1 Orthophosphate, Range 0.5 to l0.0 mg/litre PO4

48.6.1.1 Transfer 100 m1 of the clear sample into a 250m1 flask.

48.6.1.2 Add 5.0m1 of sulphuric acid solution (A) and mix.

48.6.1.3 Add 5.0m1 of ammonium molybdate solution and mix.

48.6.1.4 Add 5.0m1 of ANSA solution, mix, and allow to stand for 10 minutes.

48.6.1.5 Measure the absorbance against reagent blank (prepared by adding all the
reagents to 100 m1 water) at 650nm using 25mm matched absorption cells.

48.6.2 Orthophosphate, Range 0.1 to 2.5mg/litre PO4

48.6.2.1 Proceed in accordance with 6.1, substituting sulphuric acid solution (B) in place
of sulphuric acid solution (A) in step 6.1.2.

48.7 CALCULATIONS

48.7.1 Read the concentration of phosphate in mg/litre directly from the calibration
curve prepared in accordance with section 5.0.

48.7.2 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.

48.8 INTERFERENCES

48.8.1 A silica concentration fifty times that of the phosphate will cause an error of
less than 2 percent.

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48.8.2 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.

48.8.3 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.

48.8.4 Nitrite interference can be eliminated by addition of 0.lg of sulphamic acid

before adding ammonium molybdate.

48.8.5 Sulphide upto several mg/litre will not interfere.

48.9 NOTES

48.9.1 Reagent grade chemicals should be used in preparing all the reagents.

48.9.2 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.

48.9.3 All glassware and sampling bottles should be soaked in hydrochloric acid (1+3)
and rinsed with water before use.

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49 SILICA, NON REACTIVE (Hydrofluoric Acid method)

49.1 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.

49.2 RANGE

0 to 500 micrograms/litre SiO2.

49.3 APPARATUS

49.3.1 Spectrophotometer for use at 815nm.

49.3.2 Matched pair of 50mm cells.

49.4 REAGENTS

49.4.1 Water - conforming to specifications Type II and filtered through 0.2/0.1 micron
membrane fitter.

49.4.2 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.

49.4.3 Hydrochloric Acid (1+2) - Dilute 50m1 of hydrochloric acid (sp gr 1.19) with
100 m1 of water.

49.4.4 Zirconium Solution - Dissolve 25g of zirconium oxychloride (ZrOC12.8H2O) in

100m1 of water.

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49.4.5 Ammonium Molybdate Solution (10$) - Dissolve l0g of ammonium molybdate

[(NH4)6 Mo7O24.4H2O ] in water and dilute to 100m1 with water.

49.4.6 Oxalic Acid Solution (10%) - Dissolve l0g of oxalic acid (H2C2O4.H2O) in
water and dilute to 100m1.

49.4.7 Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino -2-
naphthol -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.

49.4.8 Silica Stock Solution (lml = 1mg SiO2) - 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).

49.4.9 Standard Silica Solution A (l ml = 10 micrograms Si02)-Dilute l0ml of silica

stock solution (4.8) to 1 litre with water.

49.4.10 Standard silica solution B (l ml = 1 microgram SiO2) .-Dilute 100m1 of standard

silica solution A (4.9) to 1 litre with water,

49.5 CALIBRATION

49.5.1 Range from 0 to 500 micrograms, SiO2 per Litre

49.5.1.1 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.

49.5.1.2 Transfer each solution (5.1.1) to 200m1 polythene conical flasks.

49.5.1.3 Proceed in accordance with section 6.1 (6.1.2 to 6.1.5).

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49.5.1.4 Prepare a calibration curve by plotting absorbance versus micrograms of Si02

per litre.

49.5.2 Range from 0 to 50 micrograms Si02 per Litre

49.5.2.1 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.

49.5.2.2 Transfer each solution (5.2.1) to 200 ml polythene conical flasks.

49.5.2.3 Proceed in accordance with Section 6.1 (6.1.2 to 6.1.5)

49.5.2.4 Prepare a calibration curve by plotting absorbance versus micrograms of SiO2

per litre.

49.6 PROCEDURE

49.6.1 For Reactive Silica

49.6.1.1 Place 100m1 of sample in a 200m1 polythene conical flask.

49.6.1.2 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.

49.6.1.3 Add 3 m1 of oxalic acid solution and mix. Allow to stand for 10 minutes.

49.6.1.4 Add 2 m1 of amino naphthol sulphonic acid solution and allow to stand for 10
minutes.

49.6.1.5 Measure the absorbance of the sample against the zero standard (blank) (E1) at
815nm.

49.6.1.6 For blank, place 100m1 of water in a 200m1 polythene conical flask and
proceed in accordance with 6.1.2 to 6:2.4

49.6.2 For Non-Reactive Silica plus Reactive Silica

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49.6.2.1 Place 100m1 of sample in a 200m1 polythene conical flask.

49.6.2.2 Add l ml of hydrochloric acid and 2m1 of hydrofluoric acid and mix
thoroughly. Allow to stand for 10 minutes.

49.6.2.3 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.

49.6.2.4 Add 3m1 of oxalic acid solution and mix thoroughly. Allow to stand for 10
minutes.

49.6.2.5 Add 2m1 of amino-naphthol-sulphonic acid solution and allow to stand for 10
minutes.

49.6.2.6 Measure the absorbance of sample against the blank solution (E2) at 815nm.

49.6.2.7 For blank, place 100m1 of water in a 200m1 polythene conical flask and
proceed in accordance with 6.2.2 to 6.2.5.

49.7 CALCULATIONS

49.7.1 From the value E2 using the calibration curve, calculate the, concentration of
reactive plus non reactive silica in the sample.

49.7.2 From the value (E2-El), using the calibration curve, calculate the concentration
of non reactive silica in the sample.

49.7.3 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.

49.8 INTERFERENCES

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49.8.1 See method for the determination of soluble silica (section 9.0). ,

49.9 NOTES

49.9.1 See method for the determination of soluble silica (Section 10.0).

49.9.2 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.

49.9.2.1 The strength of hydrofluoric acid is determined by titration with a standard

alkali solution.

49.9.2.2 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 1000°C 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:

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W1 = weight of zirconium oxide.

W = weight of zirconium oxychloride.

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50 SILICA, NON-REACTIVE (Membrane Filtration Method)

50.1 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.

50.2 RANGE

0 to 100 micrograms /litre SiO2

(Higher concentrations can be determined by proper dilution of the sample with

water):

50.3 APPARATUS

50.3.1 Membrane Filter, 0.2 micron pore size and 47mm diameter.

50.3.2 Membrane Filter Holder, preferably of stainless steel.

50.3.3 Laboratory vacuum pump.

50.3.4 Polythene Beakers, 150m1 capacity with polythene covers.

50.3.5 Polythene Discs, 50mm diameter.

50.3.6 Water Bath to accommodate at least 6 beakers and with a temperature control
between 35 - 50°C.

50.3.7 Spectrophotometer for use at 420 and 815nm.

50.3.8 Matched pair of l0 mm and 50 mm cells.

50.4 REAGENTS

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50.4.1 Water- conforming to specification Type II and filtered through 0.2/0.1

membrane filter.

50.4.2 Boric Acid Solution (5%) - Dissolve 100g of boric acid (H3BO3) in 2 litres of
warm water.

50.4.3 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.

50.4.4 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. .

50.4.5 Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino-2-

naphthol-4- sulphonic acid in 50m1 of a solution containing l g of sodium
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.

50.4.6 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).

50.4.7 Standard Silica Solution A (l ml = 10 micrograms SiO2) - Dilute l0ml of silica

stock solution (4.6) to 1 litre with water.

50.4.8 Standard silica solution B (l ml = 1 microgram SiO2) --Dilute 100m1 of

standard silica solution A (4:7) to, 1 litre with water.

50.5 CALIBRATION

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50.5.1 Range from 0 to 500 micrograms SiO2 per Litre

50.5.1.1 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.

50.5.1.2 Add 4.0m1 of ammonium molybdate reagent and mix. Allow to stand for 20
minutes at 35-40°C in a water bath.

50.5.1.3 Remove the flasks from the water bath and add 20m1 of sulphuric acid (10 N)
rapidly while stirring.

50.5.1.4 Measure the absorbance of each standard at 420nm against zero standard
(blank) using l0mm absorption cells,

50.5.1.5 Prepare a calibration curve by plotting absorbance versus concentration of silica

in micrograms.

50.5.2 Range from 0 to 100 micrograms Si02 per Litre

50.5.2.1 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.

50.5.2.2 Add 4.Om1 of ammonium molybdate reagent and mix. Allow to stand for 20
minutes at 35-40°C in a water bath.

50.5.2.3 Remove the flasks from the water bath and add 20m1 of sulphuric acid (10 N)
rapidly while stirring. Allow to stand for 5 minutes.

50.5.2.4 Add l ml of amino-naphthol-sulphonic acid solution and mix. Allow to stand

for 20 minutes.

50.5.2.5 Measure the absorbance of each standard at 815nm against zero standard
(blank) using 50mm absorption cells.

50.5.2.6 Prepare a calibration curve by plotting absorbance versus concentration of silica

in micrograms.

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50.6 PROCEDURE

50.6.1 Filter 500 m1 of the water sample through a 0.2 micron membrane filter by
applying vacuum.

50.6.2 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.

50.6.3 Add 25m1 of water and 50m1 of boric acid solution. Mix well and place the
beaker in a water bath controlled at 40-50°C. Allow to stand for 15 minutes.

50.6.4 Add 40m1 of ammonium molybdate reagent while stirring. Allow to stand for
20 minutes at 35-40°C in a water bath.

50.6.5 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.

50.6.6 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.

50.6.7 Measure the absorbance at 815nm using 50mm absorption cell.

50.6.8 Run a blank alongwith the sample, using a 0.2 micron membrane filter and
proceeding in accordance with 6.2 to 6.6.

50.7 CALCULATIONS

50.7.1 Calculate the concentration of non-reactive silica in micrograms per litre as

follows:
Non-reactive silica, micrograms/litre = 2A.
where:

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A = Silica concentration read from the calibration curve in micrograms.

50.7.2 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.

50.8 NOTES

50.8.1 See method for the determination of soluble silica (section 10.0).
50.8.2 Reagent grade chemicals should be used for preparing all the reagents.
50.8.3 Hydrofluoric acid used should contain least possible amount of fluorosilicic
acid.
50.8.4 0.1 micron membrane filters should be preferred.
50.8.5 Presence of boric acid up to a concentration of 16,200 mg/litre does not interfere
significantly.

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51 SILICA REACTIVE (Amino Reduction Method)

51.1 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.

51.2 RANGE

5 to 140 micrograms/litre SiO2.

51.3 APPARATUS

51.3.1 Spectrophotometer for use at 815nm.

51.3.2 Matched pair of 50mm cells.

51.4 REAGENTS

51.4.1 Water - conforming to specifications Type II.

51.4.2 Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino -2-
naphthol-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.

51.4.3 Ammonium Molybdate Solution - Dissolve 10.0g of ammonium molybdate

[(NH4)6.Mo7O24.4H2O] in water and dilute to 100m1 with water.

51.4.4 Hydrochloric Acid (1+1) - Mix equal volumes hydrochloric acid (sp gr
1.19) and water.

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51.4.5 Oxalic Acid Solution (10%) - Dissolve l0g of oxalic acid (H2C2O4.2H2O) in
water and dilute to 100m1.

51.4.6 Silica Stock Solution (l ml = l mg SiO2) - 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).

51.4.7 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.

51.5 CALIBRATION

51.5.1 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.

51.5.2 Proceed in accordance with section 6.0 (6.2 to 6.6)

51.5.3 Prepare a calibration curve by plotting absorbance versus micrograms of

Si02/litre.

51.6 PROCEDURE

51.6.1 Transfer 50m1 of sample into a 100m1 polythene bottle.

51.6.2 Add 1.0 m1 of hydrochloric acid (1+1) and mix, then add 2.0ml of ammonium
molybdate solution and mix well.

51.6.3 After 5 minutes, add 1.5m1 of oxalic acid solution and mix well.

51.6.4 After 1 minute, add 2.0m1 of amino-naphthol-sulphonic-acid solution. Mix well

and allow to stand for 10 minutes.

51.6.5 Prepare a reagent blank by treating 50.0m1 of water as directed in 6.2 through
6.4.

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Measure the absorbance at 815nm against the reagent blank using 50mm
matched absorption cells.

51.7 CALCULATIONS

Read the concentration of silica in micrograms/ litre as SiO2 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

51.8 PRECISION

51.8.1 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.

51.9 INTEREFERENCES

51.9.1 Samples containing less than 1.Omg/litre of Si02 do not normally contain a
significant concentration of interfering substances.

51.9.2 Colour and turbidity will interfere if not removed by filtration or dilution.

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51.9.3 Phosphate interference is eliminated by the addition of oxalic acid.

51.9.4 No significant interference due to the presence of boric acid up to

16,200mg/litre has been observed.

51.9.5 Strong oxidising and reducing agents may interfere in the reduction step.

51.9.6 Organic compounds may interfere in the colour formation.

51.10 NOTES

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

51.10.2 Samples should be collected in plastic or stainless steel sample bottles provided
with rubber or plastic stoppers.

51.10.3 All reagents to be used in this method should be stored in polythene or other
suitable plastic bottles.

51.10.4 The amino-naphthol-sulphonic acid solution should be discarded when its

colour darkens or a precipitate forms.

51.10.5 The ammonium molybdate solution should be discarded when a white

precipitate develops.

51.10.6 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.

51.10.7 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

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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 110°C 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 two
5m1 increments of hydrochloric acid (sp gr 1.19). Dry the evaporated residue in
an oven at 110°C 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 1200°C. 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
1200°C 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.

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Calculate the concentration of silica, in milligrams per litre, in silica stock

solution, as follows:

(Wl-W3) - (W2-W4)
Si02, mg/litre = -----------------------------------------
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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52 STEAM PURITY (Sodium Tracer Method)

52.1 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.

52.2 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.

52.3 APPARATUS

52.3.1 Flame photometer or sodium ion electrode assembly.

52.4 TEST CONDITION AND PROCEDURE

52.4.1 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.

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5 samples to be collected for analysis at the end of the steady state of boiler
operation.

52.4.2 Determine total solids in the boiler water sample by evaporation method.

52.5 CALCULATIONS

52.5.1 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 (µs/cm) / 1.8}
WS = Concentration of sodium in boiler water, mg/litre

Steam purity (% Dryness factor) = 100 -TDS in steam

52.6 NOTES

52.6.1 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.

52.6.2 A continuously flowing sample must be employed for the sodium ion electrode
method. (By on-line analyzer)

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53 SULPHATE (Gravimetric Method)

53.1 SUMMARY OF METHOD

Sulphate ion is precipitated and weighed as barium sulphate after removal of

silica and other insoluble matter.

53.2 RANGE

20 to 100mg/litre as SO4.

It can be extended to higher or lower ranges by adjusting the sample size.

53.3 REAGENTS

53.3.1 Water - conforming to specifications Type II.

53.3.2 Barium Chloride Solution (118g/litre) - Dissolve 118g of barium chloride

(BaC12.2H2O) in water and dilute to 1 litre.

53.3.3 Hydrochloric Acid (1+9) - Mix 1 volume of hydrochloric acid (sp gr 1.19) with
9 volumes of water.

53.3.4 Hydrofluoric Acid (48 to 51%).

53.3.5. Methyl Orange Indicator Solution (0.5g/litre) - Dissolve 0.05g of methyl orange
in water and dilute to 100m1.

53.3.6 Silver Nitrate Solution (100g/litre) - Dissolve l0 g of silver nitrate (AgNO3) in

water and dilute to 100m1.

53.3.7 Sulphuric Acid (sp gr 1.84).

53.4 PROCEDURE

53.4.1 Place clear sample, containing sulphate ion equivalent to 10 to 50mg of barium
sulphate into a 500m1 beaker.

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53.4.2 Adjust the volume of sample to approximately 200m1 by evaporation or

dilution.

53.4.3 Adjust the acidity of the sample to methyl orange end point and add l0 ml
excess of hydrochloric acid (1+9).

53.4.4 Boil the solution and add slowly 5m1 of hot barium chloride solution while
stirring vigorously. Keep for 2 hours on a .steam bath.

53.4.5 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).

53.4.6 Place the filter paper and its contents in a weighed platinum crucible and ignite
at 800°C for 1 hour.

53.4.7 Add a drop of sulphuric acid and a few drops of hydrofluoric acid, and
evaporate under a hood to expel silica.

53.4.8 Reignite at 800°C, cool in a desiccator, and weigh as barium sulphate.

53.5 CALCULATIONS

53.5.1 Calculate the concentration of sulphate in mg/litre as follows:

W X 411,500
Sulphate, mg/litre as SO4 = --------------------------
V

Where:

W = weight of barium sulphate, g.

V = volume of sample, ml.

53.5.2 Calculate the sulphate concentration in mg/litre as CaCO3, as follows:

Sulphate concentration, mg/litre as CaCO3 = A x 1.04

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Where:

A = sulphate concentration, mg/litre as SO4.

53.6 PRECISION

53.6.1 Results of this method are precise to 1.0% of the amount of sulphate ion
present.

53.7 INTERFERENCES

53.7.1 Sulphites and sulphides may oxidise and precipitate with sulphate.

53.7.2 Turbidity caused by silica or other insoluble material .would interfere if allowed
to be present.

53.8 NOTES

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

53.8.2 Turbidity may be removed by filtration 'through a fine filter paper (eg.,
Whatman No.42).

53.8.3 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.

53.8.4 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.

53.8.5 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.

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54 SULPHATE (Volumetric Method)

54.1 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.

54.2 RANGE

5 to 1000mg/litre as S04.

54.3 APPARATUS

54.3.1 Microburette, reading to 0.01ml.

54.3.2 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.

54.4 REAGENTS

54.4.1 Water - conforming to specifications Type II.

54.4.2 Alcohol - Ethyl alcohol (95%), isopropyl alcohol, or methyl alcohol.

54.4.3 Ammonium Hydroxide (1+99) - Mix 1 Volume of ammonium hydroxide (sp gr

0.90) with 99 volumes of water.

54.4.4 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

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3.8 to 4.0 with dilute hydrochloric acid. Standardize in accordance with section
5.0.

54.4.5 Hydrochloric Acid (1+99) - Mix 1 volume of hydrochloric acid (sp gr 1.19)
with 99 volumes of water.

54.4.6 Hydrogen Peroxide (30%).

54.4.7 Standard Iodine Solution (1 ml = 0.480mg SO4) - 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.

54.4.8 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).

54.4.9 Magnesium Carbonate (MgC03).

54.4.10 Phenolphthalein Indicator Solution (5g/litre) = Dissolve 0.5g of phenolphthalein

in 50m1 of ethyl alcohol. Dilute to 100m1 with water.

54.4.11 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.

54.4.12 Standard Sulphate Solution (l ml = 0.l00mg SO4) - Dissolve 0.1479g of

anhydrous sodium sulphate, in water and dilute to 1 litre with water.
Standardize by the gravimetric method.

54.4.13 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.

54.5 STANDARDIZATION OF BARIUM CHLORIDE SOLUTION

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54.5.1 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.

54.5.2 Determine the blank and sulphate equivalent of barium chloride solution (note
12:2) in accordance with 6.3, 6.4 and 6.5.

54.6 PROCEDURE IN THE PRESENCE OF SULPHITE, PHOSPHATE AND

CHROMIUM

54.6.1 Place 25m1 of filtered sample into a 100m1 beaker. Add 0.5 m1 of starch
indicator and titrate the sulphite with iodine solution.

54.6.2 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 10°C 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 10°C. Add few drops of hydrogen peroxide, shake, and adjust the volume to
50 m1 with water.

54.6.3 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).

54.6.4 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.

54.6.5 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

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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.

54.7 PROCEDURE IN THE ABSENCE OF SULPHITE, PHOSPHATE AND

CHROMIUM

54.7.1 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.

54.8 PROCEDURE IN THE PRESENCE OF NEGLIGIBLE

INTERFERENCES

54.8.1 Directly titrate l0.0m1 of the filtered sample in accordance with 6.4 and 6.5.

54.9 CALCULATIONS

Calculate the sulphate concentration in the original sample, in milligrams per

litre, as follows:

[(V1-B1) X 500] [(V2 -B2) X 480]

Sulphate, mg/litre SO4 = --------------------- - -----------------------
V3 V4

Where:

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.

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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: A = sulphate concentration, mg/litre as SO4.

54.10 PRECISION

54.10.1 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.

54.11 INTERFERENCES

54.11.1 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.

54.11.2 Interference by cations is eliminated by ion exchange.

54.11.3 Fluorides and nitrates cause no interference up to concentrations of 2 and

50mg/litre respectively.

54.11.4 Ortho and metaphosphate interfere when present in excess of 2mg/litre.

Phosphate is removed by precipitation with magnesium carbonate and filtration
in cold.

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54.11.5 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.

54.11.6 Chloride masks the pink endpoint if present in concentration more than
1000mg/litre when the sulphate present is low (about 5mg/litre).

54.11.7 Chromium present as chromates and dichromates is converted to Cr+3 with

hydrogen peroxide and then removed by ion exchange.

54.12 NOTES

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

54.12.2 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.

54.12.3 Phosphate ion is almost completely precipitated (step 6.2) at or below 10°C, but
solubility increases with increasing temperature.

54.12.4 If the ammonium hydroxide--(step 6.4) is added too fast, it is possible to over-
run 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.

54.12.5 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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55 SULPHITE (Titration Method)

55.1 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.

55.2 RANGE

3mg/litre or more as Na2SO3.

55.3 REAGENTS

55.3.1 Water - conforming to specifications Type II.

55.3.2 Hydrochloric Acid Solution (1+3) - Mix one volume of hydrochloric acid (sp gr
1.19) with three volumes of water.

55.3.3 Potassium Iodate Solution (l ml = l mg Na2SO3) -Dissolve 0.566g of potassium

iodate (KIO3, dried at 120°C) and 0.5g of sodium bicarbonate (NaHCO3) in
water and dilute to 1 litre.

55.3.4 Potassium Iodide Solution (5%) - Dissolve 50 g of potassium iodide (KI) in 1

litre of water.

55.3.5 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.

55.3.6 Sulphamic Acid (NH2SO3H), Crystalline.

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55.4 PROCEDURE

55.4.1 No Nitrite Interference Suspected

55.4.1.1 Add 5m1 of hydrochloric acid solution and 5 m1 of potassium iodide solution to
a 250 m1 conical flask.

55.4.1.2 Add 100 m1 of sample and mix.

55.4.1.3 Add 2 to 3m1 of starch indicator solution and titrate with potassium iodate
solution to the first persistent blue colour.

55.4.1.4 Record the volume (ml) of potassium iodate solution used as ‘ V1’ .

55.4.1.5 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’

55.4.2 Nitrite Interference Suspected

55.4.2.1 Place 100 m1 of sample in a 250m1 conical flask.

55.4.2.2 Add about 0.lg of sulphamic acid and stir until crystals are completely dissolved
and no further gas evolution is noted.

55.4.2.3 Add 5m1 of hydrochloric acid solution and stir again until no further gas
evolution is noted.

55.4.2.4 Add 5m1 of potassium iodide solution.

55.4.2.5 Repeat steps 4.1.3 to 4.1.5.

55.5 CALCULATIONS

55.5.1 Calculate the concentration of sulphite in mg/litre, as follows:

(V1-V2) X N X 1000
Sulphite, mg/litre as Na2S03 = -----------------------------------------

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V
Where:

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.

55.5.2 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.

55.5.3 Calculate the sulphite concentration in mg/litre as CaCO3, as follows:

Sulphite concentration, mg/litre as CaCO3 = B X 1.25

Where:

B = sulphite concentration, mg/litre as 503.

55.6 PRECISION

The precision of this method may be expressed as follows:

SO = 1

Where:

SO = single operator precision, mg/litre of Na2SO3.

55.7 INTERFERENCES

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55.7.1 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.

55.7.2 Other reducing agents, such as sulphides and ferrous-iron, will react like
sulphite.

55.7.3 Nitrite, if present, will oxidise sulphite when the sample is acidified. Nitrite,
interference can be eliminated by the addition of sulphamic acid.

55.8 NOTES

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

55.8.2 To avoid premature oxidation of sulphite, the titration should be carried out
immediately after collection.

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56 Silt Density Index (SDI) of Water

56.1 SUMMARY OF METHOD

Water is passed through a0.45μm membrane filter at constant pressure of 30psi,

and the rate of pligging of filter is measured.

SDI is calculated from rate of plugging.

56.2 SIGNIFICANCE & USE

The SDI of water can serve as a useful indication of the quantity of particulate
matter in water.The index can be used to determine the effectiveness of
various processes such as filteration or clarification to remove the particulate
matter.The index is also used to correlate the fouling tendency of reverse
osmosis plants.

56.3 APPARATUS

56.5.11 SDI assembly is schematically shown in fig.1. All the wetted part shall be made
up of high quality SS or plastic to prevent the contamination by
corrosion.Suitable filter holders (SS or plastic) to withstand pressure of 30psi
shall be used.

56.3.2 Membrane filter of 47 mm diameter with mean pore size of 0.45 μm ±0.02 μm.

56.3.3 Graduated cylinder of capacity 500 ml.

56.3.4 Stopwatch with graduation of one hundredths of a minute.

56.3.5 Thermometer, liquid in glass, capable of being read to within ± 1°C

56.4 PROCEDURE

56.4.1. Assemble apparatus as shown in fig.1

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56.4.2. Flush the apparatus with the water to be tested to remove entrained
contaminants.
56.4.3. Measure the temperature of water.
56.4.4. Open the membrane holder & place a47mm dia membrane filter on support
plate.Handle filter membrane with dull tweezers to avoid damage.touching
with finger must be avoided. (Record the manufacturer indentification for the
membrane filter)
56.4.5. Replace the top half of the holder assembly and close loosely.
56.4.6. Crack open the valve to remove the air from filter. Close valve and tighten filter
holder.
56.4.7. Open ball valve, and simultaneously start stopwatch to record time required for
the flow of 500ml. Record time (tᵢ). Leave the valve open for continued flow.
(The time to collect the 500 ml should be within ±10% of the time required to
collect 500ml of reference nonplugging water.Nonplugging reference water can
be obtained from filtering distilled or DM water through 0.2 μm membrane
filter. If time (tᵢ) is less than 90% of nonplugging time membrane might be
cracked; and if it is more than 110% then smaller sample size (250 or 100 ml)
can be used.
56.4.8. Measure and record the time to collect additional 500 ml volume of sample,
starting the collection time at5, 10 and 15 min of total elapsed flow
time.Measure the water temperature and check the pressure as each sample is
collected.(pressure must remain 30 ± 1 psi throughout the test and temperature
should reamin constant ± 1°C.)
56.4.9. After completion of the test membrane can be retain for future reference.

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5. Calculation
56.4.10. Calculate silt density index (SDIT)

% P30 [1- ti/tf] 100

SDIT = ---------------- = ---------------------
T T
where
% P30 = percent at 30 psi (207kPa) feed pressure

ti = Initial time reqired to collecte 500 ml sample.

tf = Time required to collect 500 ml sample after test time T (usually 15
min)

(For this test method, % P30 should not exceed 75%. If exceed use shorter time
for T (i.e.5 or 10 min); If % P30 exceed 75% after 5 min other test method to be
used)

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56.5 REPORT

56.5.1. Report SDI with subscript indicating the total elapsed flow time (T) in minutes.
56.5.2. Water temperature before and after test.
56.5.3. Manufacturer of membrane and manufacturer identification for membrane filter.

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57 Sodium in water by AAS

57.1 SUMMARY OF METHOD

The sodium in water can be determined by flame atomic absorption

spectrophotometery.The applicable range of this test method is from 0,20 to 3.0
mg/Lwhen using the 589.6 nm resonance line.It is found that this method is
reliable for determining sodium level to 0.005 mg/L.the low level determination
depend upon the configuration of aspirator and nebulizer system and the skill of
the analyst.

57.2 SIGNIFICANCE & USE

The determination of low level of sodium in high pressure boiler feed and steam
is important.Generally no other method is available to cross check the on-line
analyser (sodium sensitive electrode) results.

57.3 INTERFERENCE

In analysis of lo-solid water, interferences are usually negligible.

57.4 APPARATUS

57.4.1. Atomic absorption spectrophotometer for use at 589.6 nm. (Manufacturer’s

instruction should be followed for all instrumental parameters.)
57.4.2. Sodium hollow cathode lamps: multielements hollow cathode lamps are also
suitable for analysis.
57.4.3. Oxidant: Air free from oil and foreign substance is suitable.
57.4.4. Fuel: Acetylene- Standard, commercial available acetylene is usual fuel.Acetone
is always present in acetylene therefore the cylinder must be replaced at 50 psig
to avoid carryover of acetone.

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57.4.5. Pressure reducing valves: The supplies pressure of fuel and oxidant shall be
maintained somewhat higher than operating pressure of instrument.

57.5 APPARATUS

57.5.1. Purity of Reagents: All reagent grade chemicals should be used in all tests.
57.5.2. Purity of water: The reference water must conforming to specification
D1193,Type I (ASTM)
57.5.3. Sodium stock solution: Dry sodium chloride (AR grade) to constant weight at
105 °C.Dissolved 2.5418 grams in water (Type I) and dilute to1L.(1.00 mL= 1.0
mg Na)
(Certified stock sodium solution available in market is better option.)
Standard Sodium solution (1.00mL= 0.1mg Na) : Dilute 100.00mL of stock
solution to 1L with water.
57.5 STANDARDIZATION
57.5.1. Preapre a blank and at least four standard solutions to bracket the expected
sodium range of unknown sample by diluting the Standard sodium solution with
water. Preapre standard each time of the test is to be performed. Select standards
to give zero,middle and maximum points for an analytical curve.
57.5.2. Aspirate the balnk and the standards and record the instrument readings.
(Computerised recording is also available). Aspirate water between standards.
57.6.1. Prepare analytical curve by plotting absorbance versus concentration for each
standard on linear graph. Alternatively store the readings in data system of
instrument if this capability is available.

57.6 PROCEDURE

57.6.2. Aspirate each sample and determine the absorbance or concentration. Aspirate
water between samples. Calculate the concentration of sodium in samle from
curve or direct reading from the instrument.

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57.8 PRECISION & BIAS (conforming to ASTM D2777-98)

The overall and single-operator precision of this test method for eight
laboratories, which include a total of twelve operators analyzing each sample on
three consecutive days, within its range for reagent water varies with the
quantity being measured according to Table 1.

(Only reagent water was used to obtain the precision statement since this test
method is designated for the determination of low amounts of sodium in low-
solids water.)
Recoveries of known amounts of sodium (from sodium chloride) in the series of
prepared standards for the same laboratories and operators were as given in
Table 1.

Table 1 Determination of Bias for sodium in reagent water by Atomic

absorption
Amount added Amount found
mg/l mg/L St So Bias %
0.20 0.184 0.053 0.024 -8.0
1.20 1.25 0.094 0.028 +4.17
2.70 2.81 0.129 0.081 +4.07

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58 POTASSIUM IN WATER BY AAS

58.1 SUMMARY OF METHOD

The potassium in water can be determined by flame atomic absorption

spectrophotometery.The applicable range of this test method is from 0.20 to 4.0
mg/Lwhen using the 766.5 nm resonance line.It is also found that this method is
reliable for determining sodium level to 0.02 mg/L.The low level determination
depend upon the configuration of aspirator and nebulizer system and the skill of
the analyst.

58.2 INTERFERENCE

In the analysis of low solid water, interference is usally neligible

58.3 APPARATUS

58.3.1 Atomic absorption spectrophometer for use at 766.5 nm. (The manufacturer’s
instructions should be followed for all instrumental parameters)
58.3.2 Potassium hollow cathode lamp: Multi elements hollow cathode lamps can be
utilized for analysis.

58.3.3 Pressure reducing valves: The supply of oxidant and fuel shall be maintained
somewhat higher than operating pressure of the instrument by suitable valve.

58.4 REAGENTS

58.4.1 Purity: Reagent grade chemicals to be used for all testing

58.4.2 Purity of water: Water conforming to ASTM D1193 Type I utilized for all test
and standard preparation.

58.4.3 Potassium Stock solution : (1.00 mL= 1.0 mg K):Dry potassium chloride
(reagent grade) to constant weight at 105 °C. Dissolve 1.907 gm of dry KCl in

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water (type I) dilute to 1L. (Certified potassium stock solution is commercially

available is better option)

58.4.5 Potassium standard solution : (1.00mL=0.1 mg K)- Dilute 100mL stock solution
to 1 L with water.

58.4.6 Oxidant: Air, which has been passed through a suitable filter to remove oil,
water, and other foreign substances, is the usual oxidant.

58.4.7 Fuel: Acetylene—Standard, commercially available acetylene is the usual fuel.

Acetone, always present in acetylene cylinders can affect analytical results. The
cylinder should be replaced at 50 psig (345 kPa) to avoid acetone carry over.

58.5 STANDARDIZATION

58.5.1 Prepare 100 mL each of a blank and at least four standard solutions to bracket
the expected potassium concentrationrange of the samples to be analyzed by
diluting the potassium standard solution with water.Prepare the standard each
time the test is performed. Select the standards to give zero, middle, and
maximum points for an analytical curve.
58.5.2 Aspirate the blank and the standards and record the instrument readings.Aspirate
water between standards.
58.5.3 Prepare an analytical curve by plotting the absorbance versus concentration for
each standard on linear graph paper.Alternatively, read directly in
concentration if this capability is provided with the instrument.

58.6 PROCEDURE

Aspirate each sample and determine its absorbance or concentration. Aspirate

water between samles.

58.7 PRECISION AND BIAS (conforming to ASTM D2777-98)

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The overall and single-operator precision of this test method for eight
laboratories, which include a total of twelve operators analyzing each sample on
three consecutive days, within its range for reagent water varies with the
quantity being measured according to Table 1.
(Only reagent water was used to obtain the precision statement since this test
method is designated for the determination of trace amounts of potassium in
low-solids water.)

Table 1Determination of Bias for Potassium in Reagent water by Atomic Absorption

Amount added Amount found
mg/L mg/L St So Bias %
0.15 0.164 0.037 0.014 +9.33
1.50 1.62 0.085 0.044 +8.00
3.00 3.03 0.179 0.062 +1.13

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59 Lead in Water by AAS

59.1 SCOPE

These test methods cover the determination of dissolved and total recoverable
lead in water and waste water by atomic-absorption spectrophotometry:

Test method A- AAS, direct: 1.0 to 10 mg/L

Test method B- AAS, Graphite furnace: 5 to 100 μg/L

These methods are used to determine lead content if water and waste water.

59.2 TEST METHOD A – ATOMIC ABSORPTION DIRECT

59.2.1 SUMMARY OF METHOD

Lead is determined by atomic absorption spectrophotometry.Dissolved lead is

determined by aspirating the filtered and preserved sample directly with no
pretreatment. Total recoverable lead is determined by aspirating the sample
following hydrochloric-nitric acid digestion and filtration.

59.2.2 INTERFERENCE

59.2.2.1 Other metals usually do not interfere in the determination of lead by increasing
or decreasing the amount of absorbed radiation. The most common interference
is caused by a chemical reaction in the flame that prevents conversion of the
lead to the atomic state.

High concentrations of calcium, such as those connected with the coal industry,
will give lead concentrations higher than which actually exist.

The equipment manufacturer’s instructions for use of specific correction

technique shall be followed.

59.2.3. APPARATUS

59.2.3.1. Atomic Absorption Spectrophotometer, for use at 283.3 nm.

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(The manufacturer’s instructions shall be followed for all instrumental

parameters.Wavelengths other than 283.3 nm may be used if they have been
determined to be equally suitable.)
59.2.3.2. Lead Light Source, hollow-cathode lamps or electrodeless-discharge lamps have
Been found satisfactory.
59.2.3.3. Oxidant: Air, which has been passed through a suitable filter to remove oil,
water, and other foreign substances, is the usual oxidant.
59.2.3.4. Fuel: Acetylene—Standard, commercially available acetylene is the usual fuel.
Acetone, always present in acetylene cylinders, can affect analytical results. The
cylinder should be replaced at 50 psig (345 kPa).
59.2.3.5. Pressure-Reducing Valves—The supplies of fuel and oxidant shall be
maintained at pressures somewhat higher than the controlled operating pressure
of the instrument by suitable valves.

59.2.4. REAGENTS

59.2.4.1. Hydrochloric Acid (sp gr 1.19)—Concentrated hydrochloric acid (HCl).

(If the reagent blank concentration is greater than the method detection limit,
distill the HCl or use a spectrograde acid. Caution—When HCl is distilled, an
azeotropic mixture is formed (approximately 6 N HCl is formed). Therefore,
whenever concentrated HCl is used in the preparationof a reagent or in the
procedure, use double the volume specified if distilled HCl is used.)
59.2.4.2. Lead Solution, Stock (1 mL = 1 mg lead)—Dissolve 1.5999 g of lead nitrate (Pb
(NO3)2) in a mixture of 10 mL of HNO3(sp gr 1.42) and 100 mL of water.
Dilute to 1 L with water. Warning—Lead salts are toxic. Handle with care and
avoid personal contamination.
59.2.4.3. Lead Solution, Standard (1 mL = 0.1 mg lead)—Dilute 100.0 mL of stock lead
solution to 1 L with HNO3(1 + 499). Store all solutions in polyethylene bottles.
Warning—Lead salts are toxic. Never pipet by mouth. Pipet with the end of a

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suction device or employ other conventional means of quantitative

measurement.
59.2.4.4. Nitric Acid (sp gr 1.42)—Concentrated nitric acid (HNO3).(If the reagent blank
concentration is greater than the method detection limit, distill the HNO3 or use
a trace metal grade acid.)
59.2.4.5. Nitric Acid (1 + 499)—Add 1 volume of HNO3 (sp gr 1.42) to 499 volumes of
water.

59.2.5. STANDARDIZATION
59.2.5.1. Prepare 100 mL each of a blank and at least four standard solutions to bracket
the expected lead concentration range to be analyzed by diluting the lead
standard solution with HNO3 (1 + 499). Prepare the standards each time the test
is to be performed.
59.2.5.2. When determining total recoverable lead, add 0.5 mL of HNO3(sp gr 1.42) to
each blank and standard solution and proceed as directed in 6.2 through 6.4.
After the digestion of the blank and standard solutions has been completed in
6.4, return to 5.3 to complete the standardization for total recoverable
determinations. When determining dissolved lead, proceed with 5.3.
59.2.5.3. Aspirate the blank and standards and record the instrument readings. Aspirate
HNO3 (1 + 499) between standards.
59.2.5.4. Prepare an analytical curve by plotting the absorbance versus the concentration
for each standard on linear graph paper. Alternatively, read directly in
concentration if this capability is provided with an instrument.

59.2.6. PROCEDURE
59.2.6.1. Measure 100.0 mL of a well-mixed acidified sample into a 125-mL beaker or
flask. (If only dissolved lead is to be determined, start with 6.5.)
59.2.6.2. Add 5 mL of HCl (sp gr 1.19) to each sample.

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59.2.6.3. Heat the samples on a steam bath or hot plate in a well-ventilated hood until the
volume has been reduced to 15 to 20 mL, making certain that the samples do
not boil.
(For samples having appreciable amounts of suspended matter or dissolved
matter, the amount of reduction in volume is left to the discretion of the
analyst.)
59.2.6.4. Cool and filter the samples through a suitable filter such as fine-textured, acid
washed, ashless paper, into 100-mL volumetric flasks. Wash the filter paper two
or three times with water and adjust to volume.
59.2.6.5. Aspirate each filtered and acidified sample and determine its absorbance or
concentration at 283.3 nm. Aspirate HNO3(1 + 499) between samples.

59.2.7. CALCULATION
Calculate the concentration of lead in each sample, in milligrams per litre, using
the calibration curve established in 5.4.

59.3 Test Method B – Atomic Absorption Graphite furnace

59.3.1 SUMMARY OF METHOD

59.3.2.1. Lead 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 (pyrolyzed or ashed) and atomized. The
absorption signal generated during atomization is recorded and compared to
standards.
59.3.2.2. Dissolved lead is determined on a filtered and preserved sample with no
pretreatment.
59.3.2.3. Total recoverable lead is determined following acid digestion and filtration.
Because chlorides interfere with furnace procedures for some metals, the use of

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hydrochloric acid in any digestion or solubilization step is to be avoided. If

suspended material is not present, this digestion and filtration may be omitted.

59.3.3 APPARATUS
59.3.3.1. Atomic Absorption Spectrophotometer, for use at 283.3 nm with background
correction.(The manufacturer’s instructions should be followed for all
instrumental parameters.)
59.3.3.2. Lead Electrodeless Discharge Lamps are satisfactory.
59.3.3.3. Graphite Furnace, capable of reaching temperatures sufficient to atomize the
element of interest.
59.3.3.4. Graphite Tubes, compatible with furnace device.
59.3.3.5. Pipets, microlitre with disposable tips. Sizes may range from 5 μL to 100 μL, as
required.
59.3.3.6. Argon, standard, welder’s grade, commercially available. Nitrogen may also be
used if recommended by the instrument manufacturer.
59.3.3.7. Data Storage and Reduction Devices—Computer- and microprocessor-
controlled devices, or strip chart recorder, should be utilized for data collection,
storage, reduction, and problem recognition (drift, incomplete atomization,
changes in sensitivity, etc.). Strip chart recorders shall have a full-scale
deflection time of 0.2 s or less to ensure accuracy.

59.3.4 REAGENTS
59.3.4.1. Lanthanum Nitrate Solution, (1 mL = 50 mg La)— Dissolve 58.64 g of ACS
reagent grade La2O3 in 100 mL of concentrated HNO3 and dilute to 1000 mL
with water. This solution is added to the lead calibration standard and to the
sample solution as well at a rate of 10 mL per 100 mL of standard or sample
solution.
59.3.4.2. Lead Solution, Stock (1.0 mL = 200 μg Pb)

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59.3.4.3. Lead Solution, Standard (1.0 mL = 1.0 μg Pb)—Dilute 5.0 mL of lead solution,
stock and 1 mL of HNO3 (sp gr 1.42) to 1 L with water.
59.3.4.4. Lead Solution, Working—Prepare the working standards at the time of analysis
by adding various volumes of standard lead solution to 50 mL of water
containing 0.5 mL of HNO3(sp gr 1.42) adding 10 mL of lanthanum nitrate
solution (40.1) and diluting to 100 mL with water in a volumetric flask.
59.3.4.5. Nitric Acid (sp gr 1.42)—Concentrated nitric acid (HNO3).
59.3.4.6. Nitric Acid (1 + 1)—cautiously dilute 50 mL of nitric acid (sp gr 1.42) to 100
mL with water.

59.3.5 STANDARDIZATION
Initially, set the instrument according to the manufacturer’sspecifications.
59.3.6 PROCEDURE
59.3.6.1. Clean all glassware to be used for preparation of standard solutions or in the
solubilization step, or both, by rinsing first with HNO3(1 + 1) and then with
water.
59.3.6.2. Measure 100.0 mL of a well-mixed sample into a 125-mL beaker or flask. For
total recoverable lead add HNO3 (sp gr 1.42) to each sample at a rate of 5 mL/L
and proceed as directed in 4 through 6 (below).
59.3.6.3. If only dissolved lead is to be determined, filter the sample through a 0.45 μm
membrane filter prior to acidification, add 10 mL of lanthanum nitrate solution
per 100 mL of sample and proceed to 6.
59.3.6.4. Heat the samples at 95°C on a steam bath or hotplatein a well ventilated fume
hood until the volume has beenreduced to 15 to 20 mL, making certain that the
samples do not boil.
59.3.6.5. Cool and filter the sample through a suitable filter (such as fine texture, acid
washed, ashless paper) into a 100-mL volumetric flask. Wash the filter paper 2
or 3 times with water, add 10 mL of lanthanum nitrate solution and bring to
volume.

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59.3.6.6. Inject a measured aliquot of sample into the furnace device following the
directions as provided by the particular instrument manufacturer.
59.3.7 CALCULATION
The dissolved lead results obtained from a graph or instrument readout must be
multiplied by 1.1 to compensate for dilution made by the addition of lanthanum
nitrate solution in 3 (at 3.5)

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60 Arsenic in Water
60.1 SCOPE
These test methods cover the photometric and atomic absorption determination
of arsenic in most waters and wastewaters.Three test methods are given as
follows:
Concentration
Range

Test Method A—Silver Diethyldithiocarbamate

Colorimetric 5 to 250 μg/L
Test Method B—Atomic Absorption,
Hydride Generation 1 to 20 μg/L
Test Method C—Atomic Absorption,
Graphite Furnace 5 to 100 μg/L
(Only two methods (A and C) are described here)
60.2. SIGNIFICANCE AND USE
Herbicides, insecticides, and many industrial effluents contain arsenic and are
potential sources of water pollution. Arsenic is significant because of its adverse
physiological effects on humans.
60.3 PURITY OF REAGENTS
60.3.1 Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it
is intended that all reagents shall conform to the specifications of the Committee
on Analytical Reagents of the American Chemical Society, where such
specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.

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60.3.2 Purity of Water— Unless otherwise indicated, references to water shall be

understood to mean reagent water conforming to Specification D 1193 Type I.
Other reagent water types may be used provided it is first ascertained that
thewater is of sufficiently high purity to permit its use without adversely
affecting the bias and precision of the test method.
60.4 SAMPLING
60.4.1. Collect the sample in accordance with Practices D 3370.
60.4.2. Preserve the samples with HNO3 (sp gr 1.42) to a pH of 2 or less immediately
at the time of collection; normally about 2 mL/L is required. If only dissolved
arsenic is to be determined, filter the sample through a 0.45-μm membrane filter
before acidification. The holding times for the samples may be calculated in
accordance with Practice D 4841.

60.5 TEST METHOD A – SILVER DIETHYLDITHIOCARBAMATE

COLORIMETRIC
60.5.1 SUMMARY
Organic arsenic-containing compounds are decomposed by adding sulfuric and
nitric acids and repeatedly evaporating the sample to fumes of sulfur trioxide.
The arsenic (V) soproduced, together with inorganic arsenic originally present,
is subsequently reduced to arsenic (III) by potassium iodide and stannous
chloride, and finally to gaseous arsine by zinc in hydrochloric acid solution. The
resulting mixture of gases is passed through a scrubber containing borosilicate
wool impregnated with lead acetate solution and then into an absorption tube
containing a solution of silver diethyldithiocarbamatein pyridine. Arsine reacts
with this reagent to form a redcolored silver sol having maximum absorbance at
about 540 nm. The absorbance of the solution is measured photometrically and
the arsenic determined by reference to an analytical curve prepared from
standards.

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60.5.2 INTERFERENCES
60.5.2.1. Although many samples are relatively free of interferences, several metals,
notably cobalt, nickel, mercury, silver, platinum, copper, chromium, and
molybdenum, may interfere with the evolution of arsine and with the recovery
of arsenic. The presence of any or all of these metals in a sample being analyzed
must be considered as a potential source of interference, and the analyst must
fully determine the extent of actua linterference, if any. This could be
accomplished by spiking.
60.5.2.2. Hydrogen sulfide and other sulfides interfere, but commonly encountered
quantities are effectively removed by the lead acetate scrubber and the
digestion.
60.5.2.3. Antimony interferes by forming stibine, which distills along with the arsine.
Stibine reacts with the color-forming reagent to form a somewhat similar red sol
having maximum absorbance near 510 nm. The sensitivity for antimony at 540
nm is only about 8 % that of arsenic (1 mg/L of antimony will show an apparent
presence of 0.08 mg/L of arsenic).
60.5.2.4. Nitric acid interferes with the test and must be completely eliminated during the
digestion
60.5.3 APPARATUS
60.5.3.1 Arsine Generator, Scrubber, and Absorber, assembled as shown in Fig. 1.

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60.5.3.2 Spectrophotometer or Filter Photometer, suitable for use at 540 nm and

providing a light path of at least 10 mm.
60.5.4 REAGENTS
60.5.4.1. Arsenic Solution, Stock (1.00 mL = 1.00 mg As)— Dissolve 1.320 g of arsenic
trioxide (As2O3), dried for at least 1 h at 110°C, in 10 mL of NaOH solution
(420 g/L) and dilute to 1 L with water. This solution is stable.
(Warning: Arsenic trioxide is extremely toxic. Avoid ingestion or inhalation of
dry powder during standard preparation. Wash hands thoroughly immediately
after handling arsenic trioxide. Under no circumstances pipet any arsenic
solutions by mouth.)
60.5.4.2. Arsenic Solution, Intermediate (1.00 mL = 10.0 μg As)— Dilute 5.00 mL of
arsenic stock solution to 500 mL with water.
60.5.4.3. Arsenic Solution, Standard (1.00 mL = 1.00 μg As)— Dilute 10.0 mL of arsenic
intermediate solution to 100 mL with water. Prepare fresh before each use.

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60.5.4.4. Hydrochloric Acid (sp gr 1.19)—Concentrated hydrochloric acid (HCl). Use

analytical grade acid with an arsenic content not greater than 1 x 10 ⁻⁶ % .
60.5.4.5. Lead Acetate Solution (100 g/L)—Dissolve 10 g of lead acetate (Pb(C
2H3O2)2·3H2O) in 100 mL of water. Store reagent in a tightly stoppered
container.
60.5.4.6. Nitric Acid (sp gr 1.42)—Concentrated nitric acid (HNO3). Use analytical grade
acid with an arsenic content not greater than 1x 10⁻⁶ % .
60.5.4.7. Nitric Acid (1 + 1)—Add 250 mL of concentrated nitric acid (sp gr 1.42) to 250
mL of water.
60.5.4.8. Potassium Iodide Solution (150 g/L)—Dissolve 15 g of potassium iodide (KI) in
100 mL of water. Store in an amber bottle.
60.5.4.9. Silver Diethyldithiocarbamate Solution—Dissolve 1 g of silver
diethyldithiocarbamate (AgDDC) in 200 mL of pyridine. This solution is stable
for at least several months when stored in an amber bottle.
60.5.4.10. Sodium Hydroxide Solution (420 g/L)—Dissolve 42 g of sodium hydroxide
(NaOH) pellets in 100 mL of water.
60.5.4.11. Stannous Chloride Solution—Dissolve 40 g of arsenic-free stannous chloride
(SnCl 2·2H2O) in 100 mL of HCl (sp gr 1.19). Add a few small pieces of mossy
tin.
60.5.4.12. Sulfuric Acid (1 + 1)—cautiously, and with constant stirring and cooling, add
250 mL of concentrated H2SO4 (sp gr1.84) to 250 mL of water.
60.5.4.13. Zinc, Granular, 20-mesh. Arsenic content must notexceed 1x 10⁻⁶ % .
60.5.5 STANDARIZATION
60.5.5.1. Clean all glassware before use by rinsing first with hot HNO3 (1 + 1) and then
with water. The absorbers must be additionally rinsed with acetone and then air-
dried.

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60.5.5.2. Prepare, in a 250-mL generator flask, a blank and sufficient standards

containing from 0.0 to 25.0 μg of arsenic by diluting 0.0 to 25.0-mL portions of
the arsenic standard solution to approximately 100 mL with water.
60.5.5.3. Proceed as described in 6.3 to 6.9 (Procedure)
60.5.5.4. Construct an analytical curve by plotting the absorbances of standards versus
micrograms of arsenic.
(The response is linear up to 15 μg of arsenic; however, because the curve is
nonlinear above 15 μg, it is necessary to have sufficient standards above 15 μg
to permit constructing an accurate curve.)
60.5.6 PROCEDURE
60.5.6.1. Clean all glassware before use by rinsing first with hot HNO3 (1 + 1) and
then with water. The absorbers must be additionally rinsed with acetone and
then air-dried.
60.5.6.2. Pipet a volume of well-mixed acidified sample containing less than 25 μg of
arsenic (100 mL maximum) into a generating flask and dilute to approximately
100 mL.
(If only dissolved arsenic is to be determined use a filtered and acidified
sample)
60.5.6.3. To each flask, add 7 mL of H2SO 4(1 + 1) and 5 mL of concentrated HNO3.
Add a small boiling chip and carefully evaporate to dense fumes of SO3,
maintaining an excess of HNO3 until all organic matter is destroyed. This
prevents darkening of the solution and possible reduction and loss of arsenic.
Cool, add 25 mL of water, and again evaporate to dense fumes of SO 3.
Maintain heating for 15 min to expel oxides of nitrogen.
60.5.6.4. Cool, and adjust the volume in each flask to approximately 100 mL with water.
60.5.6.5. To each flask add successively, with thorough mixing after each addition, 8 mL
of concentrated HCl, 4 mL of KI solution, and 1 mL of SnCl2 solution. Allow
about 15 min for complete reduction of the arsenic to the trivalent state.

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60.5.6.6. Place in each scrubber a plug of borosilicate wool that has been impregnated
with lead acetate solution. Assemble the generator, scrubber, and absorber,
making certain that all parts fit and are correctly adjusted. Add 3.00 mL of
silver diethyldithiocarbamate-pyridine solution to each absorber. Add glass
beads to the absorbers until the liquid just covers them.
(Four millilitres of silver diethyldithiocarbamate-pyridine solution may be used
with some loss of sensitivity.)
60.5.6.7. Disconnect each generator, add 6 g of zinc, and reconnect immediately.
60.5.6.8. Allow 30 min for complete evolution of arsine. Warm the generator flasks for a
few minutes to make sure that all arsine is released.
60.5.6.9. Pour the solutions from the absorbers directly into clean spectrophotometer cells
and within 30 min measure the absorbance of each at 540 nm.
60.5.7 CALCULATIONS
Determine the weight of arsenic in each sample by referring to the analytical
curve. Calculate the concentration of arsenic in the sample in micrograms per
litre:-
Arsenic μg/L = 1000 W/ V
Where : W- volume of sample in mL
V- weight of arsenic in sample, μg.

TEST METHOD C- ATOMIC ABSORPTION, GRAPHITE FURNACE

60.6.1 SCOPE
This test method covers the determination of dissolved and total recoverable
arsenic in most waters and wastewaters.
60.6.2 SUMMARY
60.6.2.1. Arsenic 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 (pyrolyzed or ashed), and atomized. Since the

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graphite furnace uses the sample much more efficiently than flame atomization,
the detection of low concentrations of elements in small sample volumes is
possible. Finally, the absorption signal generated during atomization is recorded
and compared to standards.
60.6.2.2. Dissolved arsenic is determined on a filtered and acidified sample with no
pretreatment.
60.6.2.3. Total recoverable arsenic is determined following acid digestion and
centrifugation. Because chlorides interfere with furnace procedures for some
metals, the use of hydrochloric acid in the digestion or solubilization step is to
be avoided.
60.6.3 APPARATUS
60.6.3.1. Atomic-Absorption Spectrophotometer, for use at 193.7 nm with background
correction.
(The manufacturer’s instructions should be followed for all instrumental
parameters.)
60.6.3.2. Centrifuge, capable of holding centrifuge tubes of 15-mL volume.
60.6.3.3. Centrifuge Tubes, graduated centrifuge tubes of 15-mL capacity with stoppers.
60.6.3.4. Graphite Furnace, capable of reaching temperatures sufficient to atomize
arsenic.
60.6.3.5. Graphite Tubes, compatible with the furnace device. Standard graphite tubes are
recommended for the determination of arsenic.
60.6.3.6. Light Source— Arsenic electrodeless discharge lamps are recommended, but
hollow-cathode lamps may be used.
60.6.3.7. Pipets—Microlitre with disposable tips. Sizes may range from 1 to 100 μL, as
required.
60.6.3.8. Strip-Chart Recorder
60.6.3.9. Automatic Sampling, is recommended if available.
60.6.4 REAGENTS

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60.6.4.1. Arsenic Solution, Intermediate (1.00 mL = 10.0 μg As).Dilute 5.00 mL of

arsenic stock solution to 500 mL with water.
60.6.4.2. Arsenic Solution, Standard (1.00 mL = 1.00 μg As) — Dilute 10.0 mL of
arsenic intermediate solution and 1 mL of HNO3 (sp gr 1.42) to 100 mL. This
standard is used to prepare working standards at the time of analysis.
60.6.4.3. Hydrogen Peroxide (30 %)—Hydrogen peroxide (H2O2).
60.6.4.4. Nickel Nitrate Solution (1.0 mL = 10 mg Ni)- Dissolve 5.0 g of nickel nitrate
[Ni(NO3)2·6H2O] in water and dilute to 100 mL.
60.6.4.5. Nitric Acid (sp gr 1.42)—Concentrated nitric acid (HNO3).
60.6.4.6. Nitric Acid (1 + 9)—Add 1 mL of HNO3 (sp gr 1.42) to 9 mL of water.
60.6.4.7. Support Gas— Prepurified argon is the usual support gas. Nitrogen may be used
if recommended by the instrument manufacturer.
60.6.5 STANDARIZATION
60.6.5.1 Set the instrumental parameters to the manufacturer’s specifications.
60.6.5.2 Prepare a calibration curve using a blank and a series of standards.
(It is essential that the concentrations of the nickel nitrate and the nitric acid be
equal for both standards and samples.)
60.6.6 PROCEDURE
60.6.6.1. Clean all glassware to be used for preparation of standard solutions or in the
digestion step, or both, by rinsing first with HNO3(1 + 1) and then with water.
If possible, soak the glassware overnight in HNO3(1 + 1).
60.6.6.2. If only dissolved arsenic is to be determined, add 8.0mL of a filtered and
acidified sample to a beaker or flask. Then add 1.0 mL of HNO3(1 + 9) and 1.0
mL of nickel nitrate solution. Mix the solution thoroughly and proceed to 6.6.
60.6.6.3. For total arsenic, measure 30 mL of each standard and well-mixed sample to a
150-mL beaker. Add 0.25 mL of HNO3 (sp gr 1.42) and 2 mL of hydrogen
peroxide (30 %) to the sample and mix thoroughly. Heat the samples at 95°C on

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a hot-plate or steam bath, in a well-ventilated fume hood, until the volume has
been reduced to approximately 10 mL.
60.6.6.4. Cool and quantitatively transfer the sample to a 15-mL centrifuge tube. Dilute
to volume with water, cap the tube, and mix the solution thoroughly. If
undissolved material is present, centrifuge the sample for a few minutes to
obtain a clear solution.
60.6.6.5. Pipet 5.0 mL of the supernatant liquid into a 10-mL volumetric flask. Add 1 mL
of nickel solution and dilute to volume.
60.6.6.6. Inject a measured aliquot of sample into the furnace device following the
directions as provided by the particular instrument manufacturer.
60.6.7 CALCULATION
Use curves to determine arsenic in each sample.

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61 Total Mercury in Water (ASTM 3223-2002)

61.1 SCOPE
This test method2 covers the determination of total mercury in water in the
range from 0.5 to 10.0 μg Hg/L. The test method is applicable to fresh waters,
saline waters, and some industrial and sewage effluents.
61.1.1 The analyst should recognize that the precision and bias of this standard may be
affected by the other constituents in all waters, as tap, industrial, river, and
wastewaters. The cold vapor atomic absorption measurement portion of this
method is applicable to the analysis of materials other than water (sediments,
biological materials, tissues, etc.) if, and only if, an initial procedure for
digesting and oxidizing the sample is carried out, ensuring that the mercury in
the sample is converted to the mercuric ion, and is dissolved in aqueous media.
61.1.2 Both organic and inorganic mercury compounds may be analyzed by this
procedure if they are first converted to mercuric ions. Using potassium
persulfate and potassium permanganate as oxidants, and a digestion temperature
of 95°C, approximately 100 % recovery of organomercury compoundscan be
obtained.
61.1.3 The range of the test method may be changed by instrument or recorder
expansion or both, and by using a larger volume of sample
61.2 SUMMARY
61.2.1 The test method consists of a wet chemical oxidation which converts all
mercury to the mercuric ion; reduction of mercuric ions to metallic mercury,
followed by a cold vapor atomic absorption analysis.
61.2.2 Cold vapor atomic absorption analysis is a physical method based on the
absorption of ultraviolet radiation at a wavelength of 253.7 nm by mercury
vapor. The mercury is reduced to the elemental state and aerated from solution
ineither a closed recirculating system or an open one-pass system. The mercury

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vapor passes through a cell positioned in the light path of an atomic absorption
spectrophotometer. Absorbance is measured as a function of mercury
concentration.
61.3 SIGNIFICANCE & USE
The presence of mercury in industrial discharge, domestic discharge, and
potable water is of concern to the public because of its toxicity. Regulations and
standards have been established that require the monitoring of mercury in water.
This test method provides an analytical procedure to measure total mercury in
water.
61.4 INTERFERENCES
61.4.1 Possible interference from sulfide is eliminated by the addition of potassium
permanganate. Concentrations as high as 20 mg/L of sulfide as sodium sulfide
do not interfere with the recovery of added inorganic mercury from distilled
water.
61.4.2 Copper has also been reported to interfere; however, copper concentrations as
high as 10 mg/L have no effect on the recovery of mercury from spiked
samples.
61.4.3 Seawaters, brines, and industrial effluents high in chlorides require additional
permanganate (as much as 25 mL).
61.4.4 During the oxidation step chlorides are converted to free chlorine which will
also absorb radiation at 253.7 nm. Care must be taken to assure that free
chlorine is absent before mercury is reduced and swept into the cell. This may
be accomplished by using an excess of hydroxylamine sulfate reagent (25 mL).
The dead air space in the reaction flask must also be purged before the addition
of stannous sulfate. Both inorganic and organic mercury spikes have been
quantitatively recovered from sea water using this technique.
61.4.5 Volatile organic materials that could interfere will be removed with sample
digestion as described in 9.2 through 9.4.

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61.5 APPARARTUS
61.5.1 The schematic arrangement of the closed recirculating system is shown in Fig. 1
and the schematic arrangement of the open one-pass system is shown in Fig. 2.
(Take care to avoid contamination of the apparatus with mercury. Soak all glass
apparatus, pipets, beakers, aeration tubes, and reaction flasks in nitric acid
(HNO3) (1 + 1), and rinse with mercury-free water before use.)
61.5.2 Atomic Absorption Spectrophotometer—A commercial atomic absorption
instrument is suitable if it has an openburner head area in which to mount an
absorption cell, and if it provides the sensitivity and stability for the analyses.
Also instruments designed specifically for the measurement of mercury using
the cold vapor technique in the working range specified may be used.
61.5.3 Mercury Hollow Cathode Lamp.
61.5.4 Simultaneous Background Correction—Background correction may be
necessary to compensate for molecular absorption that can occur at this mercury
wavelength.
Recorder—Any multirange variable speed recorder that is compatible with the
ultraviolet (UV) detection system is suitable.
61.5.5 Absorption Cell—The cell (Fig. 3) is constructed from glass 25.4-mm outside
diameter by 114 mm (Note below). The ends are ground perpendicular to the
longitudinal axis and quartz windows (25.4-mm diameter by 1.6 mm thickness)
are cemented in place. Gas inlet and outlet ports (6.4-mm diameter) are attached
approximately 12 mm from each end. The cell is strapped to a support and
aligned in the light beam to give maximum transmittance.
(An all-glass absorption cell, 18 mm in outside diameter by 200 mm, with inlet
12 mm from the end, 18-mm outside diameter outlet in the center, and with
quartz windows has been found suitable. Methyl methacrylate tubing may also
be used.)

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61.5.6 Air Pump—A peristaltic pump, with electronic speed control, capable of
delivering 1 L of air per minute may be used. Regulated compressed air can be
used in the open one-pass system.
61.5.7 Flowmeter, capable of measuring an air flow of 1 L/min.
61.5.8 Aeration Tubing—A straight glass frit having a coarse porosity is used in the
reaction flask. Clear flexible vinyl plastic tubing is used for passage of the
mercury vapor from the reaction flask to the absorption cell.
61.5.9 Lamp—Asmall reading lamp containing a 60-W bulb is used to prevent
condensation of moisture inside the cell. The lamp shall be positioned to shine
on the absorption cell maintaining the air temperature in the cell about 10°C
above ambient. Alternatively, a drying tube, 150 by 18 mm in diameter,
containing 20 g of magnesium perchlorate, may be placed in the line to prevent
moisture in the absorption cell.
(Warning—If the presence of organic vapors is expected, the purity of the
drying agent should be determined to establish the absence of traces of free
perchloric acid in the salt. This is to prevent the formation of perchloric esters,
some of which are known to be violently explosive compounds.)
61.5.10 Reaction Flask—A250 to 300-mL glass container fitted with a rubber stopper
may be used.

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61.6 REAGENTS
61.6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Other
grades may be used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the accuracy of the
determination.
61.6.2 Purity of Water—Unless otherwise indicated, references to water shall be
understood to mean reagent water conforming to Specification D 1193 Type I.
Other reagent water types may be used, provided it is first ascertained that the
water is of sufficiently high purity to permit its use without adversely affecting
the bias and precision of the test method. Type II water was specified at the time
of round-robin testing of this test method.
61.6.3 Mercury Solution, Stock (1 mL = 1 mg Hg)—Dissolve 0.1354 g of mercuric
chloride (HgCl2) in a mixture of 75 mL of water and 10 mL of HNO3(sp gr
1.42) and dilute to 100 mL with water.
Mercury Solution, Intermediate (1 mL = 10 μg Hg)— Pipet 10.0 mL of the
stock mercury solution into a mixture of 500 mL of water and 2 mL of
HNO3(sp gr 1.42) and dilute to 1 L with water. Prepare fresh daily.

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Mercury Solution, Standard (1 mL = 0.1 μg Hg)—Pipet 10.0 mL of the

intermediate mercury standard into a mixture of 500 mL of water and 2 mL of
HNO3(sp gr 1.42) and dilute to 1 L with water. Prepare fresh daily.
61.6.4 Nitric Acid (sp gr 1.42)—Concentrated nitric acid (HNO3).
61.6.5 Potassium Permanganate Solution (50 g/L)—Dissolve 50 g of potassium
permanganate (KMnO4) in water and dilute to 1 L.
61.6.6 Potassium Persulfate Solution (50 g/L)—Dissolve 50 g of potassium persulfate
(K2S2O8) in water and dilute to 1 L.
61.6.7 Sodium Chloride-Hydroxylamine Sulfate Solution (120 g/L)—Dissolve 120 g
of sodium chloride (NaCl) and 120 g of hydroxylamine sulfate
[(NH2OH)2H2SO4] in water and dilute to 1 L.
(The analyst may wish to use hydroxylamine hydrochloride instead of
hydroxylamine sulfate. The analyst should dissolve 12 g of hydroxylamine
hydrochloride in 100 mL of Type I water.)
61.6.8 Stannous Sulfate Solution (100 g/L)—Dissolve 100 g of stannous sulfate
(SnSO4) in water containing 14 mL of H2SO4 (sp gr 1.84) and dilute to 1 L.
This mixture is a suspension and should be mixed continuously when being
applied as a reagent.
(The analyst may wish to use stannous chloride instead of stannous sulfate.
Stannous chloride crystal (100 g in 50 mL) should be dissolved in concentrated
HCl. The solution is heated and cooled until dissolved and diluted to 1 L.)
61.6.9 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid (H2SO4).
61.7 SAMPLING
61.7.1 Collect samples in acid-washed glass or high densityhard polyethylene bottles.
Samples shall be analyzed within 38 days if collected in glass bottles, and
within 13 days if collected in polyethylene bottles.
61.7.2 Samples shall be preserved with HNO3 (sp gr 1.42) to a pH of 2 or less
immediately at the time of collection, normally about 2 mL/L of HNO3. If only

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dissolved mercury is to be determined, the sample, before acidification shall be

filtered through a 0.45-μm membrane filters using an all-glass filtering
apparatus.
61.8. CALIBRATION
61.8.1 Transfer 0, 1.0, 2.0, 5.0, and 10.0 mL-aliquots of the standard mercury solution
containing 0 to 1.0 μg of mercury to a series of reaction flasks. Add enough
water to each flask to make a total volume of 100 mL.
61.8.2 Mix thoroughly and add cautiously 5 mL of H2SO4 (sp gr 1.84) and 2.5 mL of
HNO3(sp gr 1.42) to each flask.
(Loss of mercury may occur at elevated temperatures. However, with the stated
amounts of acid the temperature rise is only about 13°C (25–38°C) and no
losses of mercury will occur.)
61.8.3 Add 15 mL of KMnO4 solution to each bottle and allow to stand at least 15
min.
61.8.4 Add 8 mL of K2S2O8 solution to each flask, heat for 2 h in a water bath at
95°C, and cool to room temperature. 10.5 Turn on the circulating pump and
adjust its rate to 1 L/min. The pump may be allowed to run continuously
throughout the entire series of samples.
61.8.5 Add 6 mL of sodium chloride-hydroxylamine sulfate solution to reduce the
excess permanganate, as evident by loss of solution color.
61.8.6 After waiting 30 s treat each flask individually by adding 5 mL of the SnSO4
solution and immediately attach the bottle to the aeration apparatus forming a
closed system.
61.8.7 *After the absorbance has reached a maximum and the recorder pen has leveled
off, prepare the system for the next standard by one of the following procedures:
61.8.8 Closed Recirculating System—Open the by-pass valve and continue aeration
until the absorbance returns to its minimum value. Close the by-pass valve,
remove the stopper and frit from the reaction flask, and continue the aeration.

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61.8.9 Open One-Pass System—Remove the stopper and frit from the reaction flask,
open the valve, and evacuate the system with vacuum until the absorbance
returns to its minimum value. Close the valve and continue aeration.
(Warning—Because of the toxic nature of mercury vapor, precaution must be
taken to avoid its inhalation. Therefore, a bypass has been included in the
system to either vent the mercury vapor into an exhaust hood or pass the vapor
through some absorbing media such as: (a) equal volumes of 0.1 N KMnO4
solution and 10 % H2SO4, or (b) 0.25 % iodine in 3 % KI solution.)
61.8.10 Proceed with the standards and construct a standard curve by plotting peak
height versus micrograms of mercury.
61.9 PROCEDURE
61.9.1 Transfer 100 mL or an aliquot diluted to 100 mL containing not more than 1.0
μg of mercury to a reaction flask.
61.9.2 Add cautiously 5 mL of H2SO4 (sp gr 1.84) and 2.5 mL of HNO3 (sp sr 1.42)
mixing after each addition.(Refer open one-pass system above)
61.9.3 Add 15 mL of KMnO4 solution to each sample bottle. Shake and add additional
portions of KMnO4 solution until the purple color persists for at least 15 min.
61.9.4 Add 8 mL of K2S2O8 solution to each flask and heat for 2 h in a water bath at
95°C and cool to room temperature.
61.9.5 Turn on the circulating system and adjust its rate to 1 L/min. The pump may be
allowed to run continuously throughout the entire series of samples.
61.9.6 Add 6 mL of sodium chloride-hydroxylamine sulfate solution to reduce the
excess permanganate as evident by loss of solution color.
61.9.7 Wait 30 s and add 5 mL of SnSO4 solution to each flask individually and
immediately attach it to the aeration apparatus.
61.9.8 Continued as describe in * above.
61.10 CALCULATION

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61.10.1 Determine the peak height of the unknown from the recorder chart and read the
micrograms of mercury from the standard curve.
61.10.2 Calculate the mercury concentration in the sample as follows:

Mercury Total, μg/L = (Wx10000)/S

Where W- mercury in aliquot determined from calibration curve
S- aliquot used for analysis, mL
61.11 PRECISION & BIAS
61.11.1 ASTM and the U. S. Environmental Protection Agency conducted a joint study
of this test method in October 1972. One hundred and one laboratories from the
United States and Canada, including federal, state and local agencies,
universities and private and industrial groups, participated in the interlaboratory
study.
(If the analyst uses hydroxylamine hydrochloride instead of hydroxylamine
sulfate and stannous chloride instead of stannous sulfate, then it is the analyst’s
responsibility to determine the precision and bias of this test method.)
61.11.2 Eight water sample concentrates were prepared in sealed glass ampules by
dissolving weighed amounts of reagent grade chemicals in reagent water, Type
II, to produce accurately known concentrations of inorganic and organic
mercury. All eight samples contained the same ratio of inorganic to organic
mercury, 40 to 60, as mercuric chloride and methyl mercury chloride,
respectively.
61.11.3 Each laboratory was instructed to dilute a separate 5.0-mL aliquot of each
concentrate to 1 L with reagent water and to 1L with a natural water or
wastewater of their choice. Then, the laboratory was instructed to perform a
single analysis on each of the resulting sixteen samples. The natural water was
also analyzed without a spike to determine the background level of mercury.

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61.11.4 The precision of this test method within the range from 0.2 to 10 μg/L mercury
may be expressed as follows:
In reagent water, Type II:
St = 0.307X 1 0.183
S0 = 0.076X 1 0.293
In natural waters:
St = 0.386X 1 0.107
S0 = 0.145X 1 0.023
where:
St = overall precision,
S0 = single-operator precision, and
X = determined concentration of mercury, μg/L.
61.11.5 Bias—Recoveries of known amounts of mercury are shown in Table 1.
61.11.6 These data apply to fresh water, saline waters, and some industrial and sewage
effluents. It is the analyst’s responsibility to ensure the validity of the test
method to waters of other matrices or to a particular matrix.

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62 Total Orgainic Carbon in Water (ASTM D-6317-98)

62.1 SCOPE
62.1.1 This test method covers the determination of total carbon (TC), inorganic
carbon (IC), and total organic carbon (TOC) in water in the range from 10 to
1000 μg/L of carbon.
62.1.2 The test method utilizes persulfate or ultraviolet oxidation of organic carbon, or
both coupled with a CO2 selective membrane to recover the CO2 into deionized
water. The change in conductivity of the deionized water is measured and
related to carbon concentration in the oxidized sample. Inorganic carbon is
determined in a similar manner without the oxidation step.
62.2 SUMMARY
Carbon can occur in water as inorganic and organic compounds. This test
method can be used to make independent measurements of IC and TC and can
also determine TOC as the difference of TC and IC. If IC is high relative to
TOC it is desirable to use a vacuum degassing unit to reduce the IC
concentration as part of the measurement. Alternatively, the IC can be removed
by acidifying and sparging the sample prior to injection into the instrument. The
basic steps of the procedure are as follows:
62.2.1 Removal of IC, if desired, by vacuum degassing;
62.2.2 Conversion of remaining inorganic carbon to CO2 by action of acid in both
channels and oxidation of total carbon to CO2 by action of ultraviolet (UV)
radiation in the TC channel. (Acid-persulfate can be added but is usually not
required at TOC levels below 1 ppm).
62.2.3 Detection of CO2 that is swept out of the U.V. reactor and delay coil by the
liquid stream and passed through membranes that allow the specific passage of
CO2 to high purity water where change in conductivity is measured and;

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62.2.4 Conversion of the conductivity detector signal to a display of carbon

concentration in parts per million (ppm=mg/L) or parts per billion (ppb=μg/L).
The IC channel reading is subtracted from the TC channel to give a TOC
reading. A diagram of suitable apparatus is given in Fig. 1.
62.3 INTERFERENCES & LIMITATIONS
62.3.1 The oxidation of dissolved carbon to CO2 is brought about at relatively low
temperatures by the chemical action of reactive species produced by UV-
irradiated persulfate ions and water. Not all suspended or refractory material
may be oxidized under these conditions; analysts should take steps todetermine
what recovery is being obtained. This may be done by several methods: by
rerunning the sample under more vigorous reaction conditions or by spiking
samples with known refractories and determining recovery.
62.3.2 Chloride ion above 250 mg/L tends to interfere with oxidative reaction
mechanisms in this test method. Follow manufacturer’s instructions for dealing
with this problem. Other interferences have been investigated and found to be
minimal under most conditions.
62.3.3 Note that error will be introduced when the method of difference is used to
derive a relatively small level from two large levels. In this case the vacuum
degassing unit on the instrument should be used to reduce the concentration of
IC prior to measurement. Alternatively, the sample can be acidified and sparged
prior to introduction into the instrument.
62.3.4 Use of the vacuum degassing unit or sparging the sample may cause loss of
volatile organic compounds, thus yielding a value lower than the true TOC
level. At low TOC levels, the degassing unit may introduce a measurable TOC
and IC background. The user should characterize the background and
performance of the degassing module for their application. Table 1 provides
typical IC removal performance and background levels of the vacuum degassing
unit.

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62.3.5 Contamination of the sample with both CO2 and organic carbon is a severe
problem as lower levels of analyte are attempted. Throughout this method the
analyst must be vigilant for all potential sources of contamination and must
monitor blanks and adjust operations to prevent contamination.
62.4 APPARATUS
62.4.1 Apparatus for Carbon Determination—A typical instrument consists of reagent
and sample introduction mechanism, reaction vessel, detector, control system,
and a display. Fig. 1 shows a diagram of such an arrangement.

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62.4.2 Sampling Needle— A double chambered needle capable of piercing the sample
bottle septum and pulling sample from the bottom of the bottle is used. The
second chamber vents the top of the bottle to prevent vacuum build up as the
sample is withdrawn. Typically this needle is mounted on an autosampler to
provide unattended analysis of several samples.
62.4.3 I.C. Removal—Vacuum degassing requires the manufacturer’s module5 which
includes a vacuum pump and a hollow fiber membrane assembly. Use of this
vacuum degasser will remove essentially all IC as part of the analysis. The
membrane module consists of a tube and shell arrangement of microporous
polypropylene hollow fibers. Sample flows along the inside of the fibers, while
air is passed on the shell side-counterflow to the sample flow. The shell side
pressure is reduced by means of a vacuum pump on the air outlet. The sample is
acidified before introduction into the degasser to facilitate CO2 transport
through the hollow fibers. Sparging requires an inert vessel with provision for
sparging the acidified sample with 50 to 100 mL/min of carbon free gas. This
procedure will remove essentially all IC in 2 to 10 min, depending on design.
62.4.4 Reactor—The sample flow is split after the addition of reagents. Half of the
flow passes to the delay coil while the other half passes into the oxidation
reactor. The effluent from both streams passes over individual membranes that
allow CO2 to pas through the membrane into prepurified water for detection.
62.4.5 Membrane—The membrane is a CO2 selective fluoropolymer which is
hydrophobic and non-porous. Refer to the bibliography for additional details.
62.4.6 Detector—The CO2 that has passed through the membrane into the purified
water is measured by conductivity sensors. The temperature of the conductivity
cell is also automatically monitored so the readings can be corrected for changes
in temperature.
62.4.7 Data Display— The conductivity detector output is related to stored calibration
data and then displayed as parts per million, (ppm = mg of carbon per litre) or

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parts per billion, (ppb = μg of carbon per L). Values are given for TC, IC, and
TOC by difference.
62.5 REAGENTS
62.5.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society,
where such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficient purity to permit its use without
lessening the accuracy of the determination.
62.5.2 Purity of Water— Unless otherwise indicated, references to water shall be
understood to mean reagent water conforming to Type I or Type II in
Specification D 1193. The indicated specification does not actually specify
inorganic carbon or organic carbon levels. These levels can affect the results of
this test method, especially at progressively lower levels of the carbon content
in the samples to be measured.
Where inorganic carbon in reagent water is significant, CO2- free water may be
prepared from reagent water by acidifying to pH 2, then sparging with fritted-
glass sparger using CO2-free gas (time will depend on volume and gas flow
rate, and should be determined by test). The carbon contribution of the reagent
water should be determined and its effect allowed for in preparation of standards
and other solutions. CO2-free water should be protected from atmospheric
contamination. Glass containers are required for storage of water and standard
solutions. Continuous U.V. treatment of water with recycling through
appropriate mixed bed ion exchange resins may be necessary to maintain
adequately low TOC reagent water.
62.5.3 Persulfate Reagent (15 % w/v)—Prepare ammonium persulfate solution to a
concentration of 15 % w/v by dissolving 15 g of ammonium peroxydisulfate in
water and diluting to 100 mL. Verify that it contains less than 2000 μg/L

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organic carbon contamination. Certification of reagent assay should be

available. Reagents in prepackaged containers from the instrument manufacturer
have been found to be acceptable.
62.5.4 Acid Reagent (6M)—Prepare acid solution to a concentration of 6M and verify
that it contains less than 600 μg/L organic carbon contamination. Since halogens
are potential interferences, use only sulfuric or phosphoric acid for reagents.
Sulfuric acid is prepared by diluting 336 mL of 95 % reagent (sp gr 1.84) to 1 L
with reagent water. Phosphoric acid is prepared by diluting 410 mL of 85 %
reagent (sp gr 1.69) to 1 L with water. Certification of reagent assay should be
available. Reagents in prepackaged containers from the instrument manufacturer
have been found to be acceptable.
62.5.5 Organic Carbon, Standard Solution (1000 mg/L)— Choose a water-soluble,
stable reagent grade compound, such as benzoic acid or anhydrous potassium
hydrogen phthalate (KHC8H4O4). Calculate the weight of compound required
to make 1 L of organic carbon standard solution; for example, KHC8 H 4O4 =
0.471 g of carbon per g, so one L of 1 g/L ofstandard requires 1/0.471, or 2.12,
grams of KHP. Dissolve the required amount of standard in some CO2-free
water in a 1-L volumetric flask, add 1 mL of sulfuric acid, and dilute to volume.
Dilutions of this stock solution are to be used tocalibrate and test performance
of the carbon analyzer.
62.6 SAMPLING & PRESERVATION
62.6.1 Samples must be collected in contamination free bottles sealed with a
fluoropolymer lined septa. Specially cleaned (for TOC) 40 ml bottles are
commercially available. The sample bottle should be rinsed several times with
the sample, filled, and then tightly sealed.
62.6.2 To preserve samples for this analysis, store samples in glass at 4 °C. To aid
preservation, acidify the samples to a pH of 2. It should be noted that
acidification will enhance loss of inorganic carbon. If the purgeable organic

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fraction is important, fill the sample bottles to overflowing with a minimum of

turbulence and cap them using a fluoropolymer-lined cap, without headspace.
62.6.3 For accurate measurements of samples containing < 0.5 mg/L stringent
measures must be taken to minimize contamination. Low level samples exposed
to ambient air will generally increase in both inorganic and organic carbon.
Sample container and all sampling devices must be clean and exposure of the
sample to the atmosphere must be minimized. Blanks should be carried through
all steps of the sampling and analysis procedure to check for contamination.
62.7 INSTRUMENT OPERATION
Follow the manufacturer’s instructions for setting up the instrument and
adjusting reagent flows. Ensure that the pH of the waste stream is below four (4)
in all cases. Additional acid is required if a vacuum degassing unit is used for IC
removal. Follow manufacturer’s instructions for reagent flows when using a
degassing unit.
62.8 CALIBRATION
Use appropriate dilutions of the standard solution of 1000 mg/L of carbon to
check the instrument calibration.
62.8.1 Calibration protocols may vary with equipment manufacturers. However, in
general, calibrate the instrument in accordance with the manufacturer’s
instructions, and use standards to verify such calibration in the specific range of
interest for actual measurements. Plots of standard concentration versus
instrument reading may be used for calibration or to verify linearity of response.
62.8.2 Below 500 μg/L, contamination of reagents is a severe problem. Because of this
it is recommended that the general calibration check of the instrument be carried
out with standards above 500 μg/L. The response of the instrument is extremely
linear, allowing calibration at higher levels without loss of accuracy at low
levels. See Precision & Bias for data regarding linearity of the response.
62.9 PROCEDURE

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62.9.1 The sample is introduced into the instrument by piercing the septum with a
double chambered needle. The analyzer in either the grab sample or autosampler
mode will pull sample out of the sample bottle, into the analyzer.
62.9.2 If inorganic carbon is to be removed by vacuum degassing, or if I. C. removal is
unnecessary, no additional sample preparation is required. If inorganic carbon is
to be removed by sparging prior to sample introduction, acidify to
approximately pH 2 with concentrated acid (if not already done) inject through
the needle and sparge through the needle with an appropriate flow of gas. Use of
the double chambered needle prevents contamination of the sample during
sparging.
Other configurations that prevent sample contamination are acceptable. Samples
with high alkali content or buffer capacity may require larger amounts of acid.
In such cases, incorporate this dilution into the calculation of results. If
incomplete sparging of CO2 from IC is suspected, sparge and analyze the
sample and then repeat the procedure until appropriate conditions are
established.
62.9.3 Follow manufacturers’ instructions for introducing the sample into the analyzer.
The sample may be directly aspirated, sampled from an auto sampler, or
connected directly into a source for continuous on-line monitoring.
62.10 CALCULATION
62.10.1 Read carbon values directly from the digital display, printer, or computer
connected to a suitable data interface on the instrument.
62.10.2 Blank correction should be applied to samples that have been prepared or
diluted with reagent water. In the case of materials prepared in reagent water,
the entire blank value obtained in the reagent water should be subtracted. In the
case of dilution, the blank should be corrected for the dilution factor and
subtracted from the obtained value.
62.11 PRECISION & BIAS

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Linearity of the response over the entire measurement range allows calibration
at a single higher level concentration. This facilitates preparation of accurate
standards minimizing the effect of contamination. Fig. 2 shows instrument
response for carbon versus carbon concentration over five orders of magnitude
from 0.25 μg/L C to 25 000 μg/L C for two instruments calibrated at 25 000
μg/L C. As stated in Section Calibration, the user should confirm proper
operation of the instrument by running check samples in the range of test
samples.

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Annexure – I
ATOMIC WEIGHT/ATOMIC NUMBERS OF VARIOUS ELEMENTS

S.NO. NAME SYMBOL ATOMIC ATOMIC

NUMBER WEIGHT
1. Actinium Ac 89 227
2. Aluminium Al 13 26.98154
3. Americium Am 95 243.13
4. Antimony Sb 51 121.75
5. Argon Ar 18 39.948
6. Arsenic As 33 74.9216
7. Astanine At 85 ----
8. Barium Ba 56 137.34
9. Berkelium Bk 97 ---
10. Beryllium Be 4 9.0122
11. Bismuth Bi 83 208.9808
12. Boron B 5 10.811 ± 0.003
13. Bromine Br 35 79.904
14. Cadmium Cd 48 112.40
15. Caesium Cs 55 132.9054
16 Calcium Ca 20 40.08
17. Californium Cf 98 ----
18. Carbon C 6 12.01
19. Cerium Ce 58 140.12
20. Chlorine Cl 17 35.453
21. Chromium Cr 24 51.996
22. Cobalt Co 27 58.9331
23. Copper Cu 29 63.546

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S.NO. NAME SYMBOL ATOMIC ATOMIC

NUMBER WEIGHT
24 Curium Cm 96 ----
25. Dysprosium Dy 66 162.50
26. Einsteinium Es 99 ----
27. Erbium Er 68 167.28
28. Europium Eu 63 151.96
29. Fermium Fm 100 ---
30. Fluorine F 9 18.99840
31. Francium Fr 87 ----
32. Gadolinium Gd 64 157.25
33. Gallium Ga 31 69.72
34. Germanium Ge 32 72.59
35. Gold Au 79 196.967
36. Hafnium Hf 72 178.49
37. Helium He 2 4.0026
38. Holmium Ho 67 164.930
39. Hydrogen H 1 1.00797
40. Indium In 49 114.82
41. Iodine I 53 126.9044
42. Iridium Ir 77 192.20
43. Iron Fe 26 55.847
44. Krypton Kr 36 83.80
45. Lanthanum La 57 138.91
46. Lawrencium Lw 103 -----
47. Lead Pb 82 207.19
48. Lithium Li 3 6.939
49. Lutetium Lu 71 174.97

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S.NO. NAME SYMBOL ATOMIC ATOMIC

NUMBER WEIGHT
50. Magnesium Mg 12 24.312
51. Manganese Mn 25 54.938
52. Mendeleevium Md 101 --
53. Mercury Hg 80 200.59
54. Molybdenum Mo 42 95.94
55. Neodymium Nd 60 144.24
56. Neon Ne 10 20.183
57. Neptunium Np 93 237.00
58. Nickel Ni 28 58.71
59. Niobium Nb 41 92.906
60. Nitrogen N 7 14.0067
61. Nobelium No 102 ----
62. Osmium Os 76 190.20
63. Oxygen O 8 15.9994
64 Palladium pd 46 106.40
65. Phosphorus p 15 30.97376
66. Platinum Pt 78 195.09
67. Plutonium Pu 94 242
68. Polonium Po 84 210.05
69. Potassium K 19 39.09
70. Praseodymium Pr 59 140.907
71. Promethium Pm 61 ----
72. Protoactinium Pa 91 231.10
73. Radium Ra 88 226.0254
74. Radon Rn 86 222.00
75. Rhenium Re 75 186.2

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S.NO. NAME SYMBOL ATOMIC ATOMIC

NUMBER WEIGHT
76. Rhodium Rh 45 102.905
77. Rubidium Rb 37 85.47
78. Ruthenium Ru 44 101.07
79. Samarium Sm 62 150.35
80. Scandium Sc 21 44.956
81. Selenium Se 34 78.96
82. Silicon Si 14 28.086
83. Silver Ag 47 107.868
84. Sodium Na 11 22.9898
85. Strontium Sr 38 87.62
86. Sulphur S 16 32.064
87. Tantalum Ta 73 180.948
88. Technetium Tc 43 ------
89. Tellurium Te 52 127.60
90. Terbium Tb 65 158.924
91. thallium Tl 81 204.37
92. Thorium Th 90 232.038
93. Thulium Tm 69 168.934
94. Tin Sn 50 118.69
95. Titanium Ti 22 47.90
96. Tungsten W 74 183.85
97. Uranium U 92 238.03
98. Vanadium V 23 50.942
99. Xenon Xe 54 131.30
100. Ytterbium Yb 70 173.04
101. Yttrium Y 39 88.905

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S.NO. NAME SYMBOL ATOMIC ATOMIC

NUMBER WEIGHT
102. Zinc Zn 30 65.38
103. Zirconium Zr 40 91.22

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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.
2.2 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
2.3 Calculate the stability Index (Ryzner Index) as follows:
Stability Index (Ryzner Index) = 2 pHs - pH
TABLE 1

DATA FOR CALCULATION OF SATURATION AND STABILITY INDEX

Total Solids A Temperature B Calcium Hardness C Total Alkalinity D

0
(mg/litre) ( C) (mg/litre CaCO3) (mg/litre CaCO3)
50-350 0.1 0 2.6 10 0.6 10 1.0
400-1100 0.2 2 2.5 12 0.7 12 1.1
7 2.4 14 0.8 14 1.2
10 2.3 18 0.9 18 1.3
14 2.2 23 1.0 23 1.4
18 2.1 28 1.1 28 1.5
22 2.0 35 1.2 36 1.6
28 1.9 44 1.3 45 1.7
32 1.8 56 1.4 56 1.8

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Total Solids A Temperature B Calcium Hardness C Total Alkalinity D

0
(mg/litre) ( C) (mg/litre CaCO3) (mg/litre CaCO3)
38 1.7 70 1.5 70 1.9
44 1.6 88 1.6 88 2.0
51 1.5 11 1.7 111 2.1
57 1.4 139 1.8 140 2.2
64 1.3 1175 1.9 177 2.3
72 1.2 30 2.0 230 2.4
82 1.1 280 2.1 280 2.5
350 2.2 360 2.6
440 2.3 450 2.7
560 2.4 560 2.8
700 2.5 700 2.9
870 2.6 800 3.0
1050 2.7

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:

Min. Max.
Langelier saturation index 0.5 1.5
Ryzner stability index 6.0 6.0
pH 6.0 8.0
Calcium hardness, mg/litre as CaCO3. 20 300
Total dissolved solids mg /litre - 2,500

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ANNEXURE - III

SHELF LIFE AND STORAGE OF REAGENTS AND STANDARDS

REAGENT SHELF LIFE CONTAINER

1. Acetic Acid 1 Year Glass

2. Aluminium Chloride 1 Year Glass
3. Aluminium Sulphate 1 Year Glass
4. Amine Solution 1 week Amber coloured
bottle.
5. p-amino dimethyl aniline 1 month dark glass bottle.
hydrochloride.
6. Amino naphthol Sulphonic acid. 2 weeks plastic, dark place.
7. Ammonia Solution 1 Year Glass
8. Ammonium Acetate 1 Year Glass
9. Ammonium Carbonate 1 Year Glass
10. Ammonium chloride 1 Year Glass
11. Ammonium Fluoride 1 Year Glass
12. Ammonium Iodide 1 Year Glass
13. Ammonium Molybdate 1 Year Glass
14. Ammonium Nitrate 1 Year Glass
15. Ammonium Oxalate 1 Year Glass
16. Ammonium Sulphate 1 Year Glass
17. Ammonium Sulphide Solution 1 month Glass
18. Ammonium Thiocyanate 1 month Glass
19. Aniline 1 year Glass
20. Aniline Sulphate 1 month Glass
21. Ascorbic Acid a. To be Glass

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REAGENT SHELF LIFE CONTAINER

prepared fresh
b. One week i
stored at 40 C
22. Barium Chloride 1 year Glass
23. Barium Nitrate 1 year Glass
24. Baryta water 1 month Glass
25. Benzene 1 year Glass
26. Bromine water 1 week Glass
27. Cadmium Acetate 1 year Glass
28. Cadmium Sulphate 1 year Glass
29. Calcium Chloride 1 year Glass
30. Ceric Sulphate 1 month Glass
31 Calcium Nitrate 1 year Glass
32. Calcium Sulphate 1 year Glass
33. Carbon Tetrachloride 1 year Glass
34. Chlorine water 1 week Glass
35. Chromic Acid 1 year Glass
36. Cobalt Chloride 1 year Glass
37. Cobalt Nitrate 1 year Glass
38. Copper Sulphate 1 year Glass
39. Dimethyl Glyoxime Solution 1 month Glass
40. Diphaenyl Amine 1month Glass
41. diphenyl Carbazide 1 week: Glass
4 month:
(3.32g/1)
1 month:
(2.89g/1)
42. Diphenyl Thiocarbzone 1 month Glass

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REAGENT SHELF LIFE CONTAINER

43. Disodium Hydrogen phosphate 1 year Glass

44. disodium salt of EDTA 1 month Polyethylene,plastic.
45. Eriochrome Black T 1 month dark coloured
stoppered bottle
46. Eriochrome Black T (solid) 1 year Dark Coloured
stoppered bottle.
47. Formaldehyde 1 month Glass
48. Hydrazine Sulphate 1 month Glass
49. Hydrochloric Acid (standardization 1 year Glass (tightly
every month) closed)
50. Hydrogen peroxide 1 month Glass (dark
coloured)
51. Hydrogen Sulphide (saturated Freshly Glass
solution) prepared
52. Hydroxylamine Hydrochloride 1 month Glass
53. 8 – hydroxyquinoline 1 month Glass
54. Indigo Carmine 1 month Dark bottle at 40 C
55. Iodine (standardize before use) 1 month Amber Glass
56. Iron (III) Chloride 1 year Dark bottle
57. Iron (III) per iodate 1 month Glass
58. Iron (III) sulphate (saturated) 1 week Glass
59. Iron (III) sulphate 1 year Glass
60. Lead Acetate 1 year Glass
61. Lime water 1 week Glass
62. Magnesia mixture 1 month Glass
63. Magnesium Chloride 1 year Glass
64. Magnesium Sulphate 1 year Glass
65. Manganese (II) sulphate Solution 1 year Glass

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REAGENT SHELF LIFE CONTAINER

66. Mercuric Thiocyanate 1 month Amber bottle

67. Mercapto succinic Acid Solution 6 month Glass
68. Methyl Alcohol 1 year Glass
69. Methylene blue Indefinite Glass
70. Methyl Orange Indefinite Glass
71. Nessler's Reagent (if kept in 1 year Amber bottle
chemically resistant bottle and in
complete darkness)
72. Nitric Acid 1 year Glass
73. Oxalic Acid 1 year Glass
74. O - phenanthroline 1 year Glass
75. O – Toludine (avoid rubber contact) 1 month Dark bottle
76. phenolphthalein 1 year glass
77. Potassium Bromate 1 year glass
78. Potassium bromide 1 year glass
79. Potassium chlorate 1 year glass
80. Potassium Chloride 1 year glass
81. Potassium Chromate 1 year glass
82. Potassium dichromate 1 month Glass
83 Potassium Hydroxide ( Standardize 1 year Polyethylene
monthly)
84. Potassium Iodate 1 year
85. Potassium Iodide (6m) Fresh glass
86. Potassium Iodide (10%) 1 year Amber bottle
87. Potassium Nitrate 1 year glass
88. Potassium Nitrite Fresh Glass
89. Potassium Permanganate 1 year Amber Bottle

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Date of Issue: 16/05/2013

REAGENT SHELF LIFE CONTAINER

( Satndardize weekly )
90. Pyrogallol 1 month Glass
91. Silver Nitrate (standardize monthly) 1 year Amber Bottle
92. Silver sulphate 1 year Glass
93. Sodium Acetate 1 year Glass
94. Sodium Carbonate 1 year Glass
95. Sodium Arsenite 1 year Dark coloured Glass
Bottle.
96. Sodium chloride 1 year Glass
97. Sodium Hydrogen Carbonate 1 year Glass
98. Sodium Hydroxide (standardize 1 year polythene Bottle
monthly)

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Form No: TPC-CTDS-GUID Page 281 of 284

 Guidelines for Analytical Test Procedures for
The Tata Power Company Ltd Water and Steam System

Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

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 TYPE I TYPE II TYPE III

1. Total solids, max, mg/ litre 0.1 0.1 0.1
2. Electrical conductivity, max, micro 0.06 1.0 1.0
siemens /cm at 250C
3. pH at 250C * * 6.2 to 7.5
4. Minimum colour retention time of 60 60 10
potassium permangnate, minutes.
5. Maximum soluble silica not not 10 micro
detectable detectable gm/ ltr.
6. 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:
Type A TypeB Type C

Maximum total
bacteria count 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 250C followed by

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Form No: TPC-CTDS-GUID Page 282 of 284

 Guidelines for Analytical Test Procedures for
The Tata Power Company Ltd Water and Steam System

Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

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 water having a
conductivity of less than 1.0 microsiemens/cm at 250C . Ion exchange,
distillation, or reverse osmosis may be required as an initial treatment prior to
distillation if the purity cannot be attained by single distillation.
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.

Confidential & Proprietary – The Tata Power Company Limited

Form No: TPC-CTDS-GUID Page 283 of 284

 Guidelines for Analytical Test Procedures for
The Tata Power Company Ltd Water and Steam System

Document Ref No.:

CTDS/COMM/GUID-021/2013/014
Date of Issue: 16/05/2013

ANNEXURE - V

CONVERSON FACIOR OF FREQUENTLY USED CHEMICALS TO CaCO3

EQUIVALENT

S.N SUBSTANCE FORMU ATOMIC/MOL EQUIVALENT SUBSTEN

O. LA ECULAR CE
WEIGHT
WEIGHT TO CaCo3
Equivalent
1. Calcium Ca 40.1 20.0 2.50
2. Carbondioxide CO2 44.0 44.0 1.14
3. Chloride Cl 35.5 35.5 1.41
4. Fluorine F 19.0 19.0 2.63
5. Hydrogen H 1.01 1.01 50
6. Hydroxide OH 17.0 17.0 2.94
7. Magnesium Mg 24.3 12.2 4.10
8. Nitrate NO3 126.9 126.9 0.39
9. Oxygen O 16.0 8.0 6.25
10. Phosphate PO4 95.0 31.7 1.58
11. Silica SiO2 60.1 30.0 0.83
12. Sulphate SO4 96.1 48.0 1.04
13. Sulphite SO3 80.1 40.0 1.25

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Form No: TPC-CTDS-GUID Page 284 of 284