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COS-ISO-00-OIN/OPS/CHEM/017
Rev. No. : 0 April 2006
NTPC Limited
NTPC LIMITED
OPERATION & MAINTENANCE FORMAL DOCUMENTATION SYSTEM
OPERATION INFORMATION NOTE: COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Approved for
Implementation by ..
E. D. (OS)
Date: ..
Enquiries to: Head of Corp. Operation Services
Contents
I) Introduction
II) Superseded Documents
III) Coagulation Flocculation Jar Test
IV) Colour 6
V) Conductivity
VI) Corrosivity of Cooling Water (Coupon Test)
VII)
Crud (Colour Comparison Method)
VIII)
pH 17
IX) Oxidation Reduction Potential (ORP)
X) Turbidity (Nephelometric)
XI) Suspended and Total Dissolved Solids
(25mg/litre or Less of Total Solids)
XII)
Suspended and Total Dissolved Solids
(More than 25mg/litre of Total Solids)
XIII)
Alkalinity (Titration Method, 10 to 500mg/litre)
XIV)
Alkalinity due to Hydroxide
XV)
Aluminium
XVI)
Aluminium Atomic Absorption Method (Direct)
XVII)
Ammonia (Indophenol method, 10 to 500 micrograms/litre)
XVIII)
Ammonia
XIX)
Ammonia by ION Selective Electrode
XX)
Carbon Dioxide (Bicarbonate Titration Method)
XXI)
Carbon Dioxide (Direct Titration of Free Carbon Dioxide)
XXII)
Chloride (Mercuric Thiocyanate Method, 0.05 to 1.4mg/litre)
XXIII)
Chloride (Mercuric Thiocyanate Method, Modified, 2 to 100
micrograms/litre)
XXIV)
Chloride (Silver Nitrate Method, 5mg/litre or more)
XXV)
Chlorine Demand
XXVI)
Chlorine, residual (DPD Method, 0.02 to 4.0mg/litre)
XXVII) Chlorine, Residual (Starch Iodide Thiosulphate Method,
0.04mg/litre or more)
XXVIII) Copper (Neocuprine method, 2 to 1000 micrograms/litre Cu)
XXIX)
Copper (Atomic Absorption Spectrophotometry Method)
XXX)
Equivalent and Free Mineral Acidity
XXXI)
Fluoride (SPANDS DYE Method)
XXXII) Hardness (Total, Calcium and Magnesium)
XXXIII) Hydrazine
XXXIV) Iron (Bathophenanthroline Method)
XXXV) Iron (Ferrozine Method, 500 micrograms/litre and lees)
XXXVI) Atomic Absorption Method (Graphite Furnace)
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Contents
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COS-ISO-00-OIN/OPS/CHEM/017
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Manual on Analytical Test Procedure for Water and Steam in Power Plants
INTRODUCTION
Chemical analysis of water and steam is probably the most important tool for the
Chemist in the power plant. This is frequently required to ascertain the
constituents of water and steam which is working fluid of the unit. Manual on
analytical test procedures for water and steam in thermal power station was issued
in 1983. Based on experience gained in last two decades, some of the earlier
methods have been revised and a couple of new parameters have been included in
this revised manual. It is expected that the revised manual will be handy for the
working personnel of power station laboratories.
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Manual on Analytical Test Procedure for Water and Steam in Power Plants
III)
1.0
SUMMARY OF METHOD
The coagulation - flocculation jar test is carried out to determine chemicals and
their dosages, and conditions required in order to reduce suspended, colloidal, and
non-settleable matter from water by chemical coagulation - flocculation, followed
by gravity settling to achieve optimum results. The variables to be investigated
are (i) chemical additives, (ii) pH, (iii) temperature and (iv) order of addition and
mixing condition.
2.0
APPARATUS
2.1
Multiple Stirrers - with continuous speed variation from about 20 to 150 rpm. The
stirring paddles should be of light gage, corrosion - resistant material, all of the
same configuration and size. An illuminated base is useful to observe the floc
formation.
2.2
2.3
Reagent Racks - for introducing each test solution to all beakers simultaneously.
There should be at least one rack for each test solution or suspension. A typical
configuration is given in Fig-I.
3.0
3.1
REAGENTS
Water - conforming to specifications Type IV conforming to ASTM specification
D-1193.
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3.2
3.2.1
Alum [A12(SO4)3.18H2O].
3.2.2
3.2.3
3.2.4
3.2.5
3.2.6
3.3
3.4
3,5
Alkalis - calcium carbonate (CeC03), dolomitic lime (58% CaO, 40% MgO),
lime-hydrated (Ca(OH)2) magnesium oxide (MgO), sodium carbonate (Na 2CO3),
sodium hydroxide (NaOH).
3.6
Weighting Agents - bentonite, kaolin, Fuller's earth, other clays and minerals.
4.0
PROCEDURE
4.1
Place equal volumes (1000m1) of sample into each beaker (1500m1 capacity) and
record the temperature of the sample. Load the test chemicals in the reagent racks.
Final volume of each tube should be same after required make up.
4.2
Start the multiple stirrers at flash mix speed (approximately 120 rpm). Add the
test solutions or suspensions at predetermined dosage levels and sequence. Flash
mix for approximately 1 minute after the addition of chemicals. Record the flash
mix time and mixer speed (rpm).
4.3
Reduce the speed to the minimum required, to keep floc particles uniformly
suspended throughout the "slow mix" period. Slow mix for 20 minutes. Record
the mixer speed (rpm).
4.4
After the slow mix period, withdraw the paddles and observe settling of floc
particles. Record the time required for the bulk of the particles to settle.
4.5
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5.0
INTERFERENCES
5.1
5.2
Gas release during test - Floatation of coagulated floc may occur due to gas
bubble formation, caused by mechanical agitator, temperature increase or
chemical reaction.
5.3
Testing period - Biological activity or other factors may alter the coagulation
characteristics of water upon prolonged standing. Therefore, the period between
sampling and testing should be kept to a minimum.
6.0
NOTES
6.1
6.2
6.3
LOCATION
SAMPLE
pH
TURBIDITY
COLOUR
TEMPERATURE
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DATE
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S.No.
BEAKER N0.
1
6
1.
Chemicals,* mg/litre
3.
4.
5.
6.
Temperature, C.
7.
8.
9.
Settling rate
10
Supernatent Tests :
a. Turbidity
b. pH
c.
Colour
d.
Non-reactive/colloidal Silica
The preferred sequence of addition of chemical is (a) alum ----- (b) chlorine and
------ (c) lime
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IV)
1.0
COLOUR
SUMMARY OF METHOD
Sample colour is visually compared with a standard Chloroplatinate colour
solution. The unit of colour (Hazen unit) is that produced by l mg
platinum/litre in the form of the chloroplatinate ion.
2.0
APPARATUS
2.1
2.2
pH meter.
3.0
REAGENTS
3:1
3.2
3.3
Colour Standards
Prepare standards having colours of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60
and 70 units by diluting suitable volumes of standard stock solution (3.2) to 50
ml with water in Nessler tubes.
4.0
PROCEDURE
4.1
4.2
Compare the colour of the sample with standard colour by looking vertically
downwards against a white surface.
4.3
If the colour exceeds 70 units, dilute with water until the colour is within the
range of the standards.
4.4
4.5
5.0
CALCULATIONS
5.1
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5.2
Record to Nearest
1 -50
51 -100
101 -250
10
251 -500
20
5.3
6.0
INTERFERENCES
6.1
Even a slight turbidity causes the apparent colour to be noticeably higher than
the true colour; therefore turbidity should be removed before measurement of
true colour.
6.2
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V) CONDUCTIVITY
1.0
SUMMARY OF METHOD
The conductivity cell is dipped in the sample contained in a beaker and the
conductivity is read directly from the conductivity meter.
2.0
APPARATUS
2.1
Conductivity meter.
2.2
2.3
3.0
REAGENTS
3.1
3.2
3.3
3.3
3.4
3.5
4.0
PROCEDURE
4.1
4.1.1
Rinse the conductivity cell with at least three portions of standard potassium
chloride solution.
4.1.2
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Where:
K1
Kx
4.2
Measurement of Conductivity
4.2.1
4.2.1.1
Use a flow type conductivity cell. Adjust the sample stream to a proper flow
rate and bring the temperature to a steady value as near 25 C as possible Read
the temperature to the nearest 0.5oC.
4.2.1.2
4.2.1.3
4.2.1.4
4.2.1.5
4.2.2
4.2.2.1
4.2.2.2
If another type of cell is used, rinse the cell thoroughly several times with
water and then two or more times with the sample. Measure the conductivity
and the temperature (to the nearest 0.5C) on successive portions of the sample
until a constant value is obtained.
4.2.2.3
5.0
CALCULATIONS
5.1
cell constant.
KX
6.0
PRECISION
6.1
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7.0
INTERFERENCES
7.1
7.2
The carbon dioxide, normally present in the air, can drastically change the
conductivity of pure water. Contact with air should be avoided by using flow
through or inline cells.
8.0
NOTES
8.1
8.2
Recommended cell constants for various conductivity ranges are given below:
Range of conductivity,
Cell constant,
(Microsiemens/cm)
(Cm-1 )
0.05 to 10
0.01 to 0.1
10 to 200
0.1 to 1
200 to 5000
1 to 10
5000 to 1000000
10 to 100
8.3
The conductivity of water and aqueous solutions depends strongly upon the
temperature. To avoid making a correction, it is necessary to hold the
temperature of the sample to 25 0.5C. If this cannot be done, the
temperature coefficient is determined by conductivity and temperature
measurements on the sample over the required temperature range. The
conductivity is plotted against temperature and from this curve a table of
temperature correction factors may be prepared, or the ratio of conductivity at
temperature, T, to conductivity at 25C may be plotted against temperature
and this ratio taken from the curve.
8.4
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Manual on Analytical Test Procedure for Water and Steam in Power Plants
VI)
1.0
SUMMARY OF METHOD
Carefully prepared and weighed metal coupons are installed in contact with
flowing cooling water for a specified length of time. After removal from the
system, these coupons are examined, cleaned and reweighed. The corrosivity
and fouling characteristics of the water are determined from the difference in
weight, the depth and distribution of pits and the weight and characteristics of
the foreign matter on the coupons.
2.0
APPARATUS
2.1
2.2
Insulating washer, screw, and nut -for attaching the coupon to the phenolic rod.
The insulating washer has a sleeve that fits into the coupon hole and around the*
screw.
2.3
3.0
REAGENTS
3.1
3.2
Benzene.
3.3
3.4
3.5
3.6
Isopropyl Alcohol.
3.7
3.8
Trichloroethylene.
3.9
3.10
3.11
4.0
COUPON PREPARATION
4.1
4.2
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4.2.1
4.2.2
Drill a 7mm hole with its center about 8mm from one end of the coupon.
4.2.3
Deburr all sharp edges on the coupon specimen using a file or emery belt and
deburr' the hole with an oversize drill.
4.2.4
Stamp identifying numbers on the small coupon area between the edge and the
mounting hole.
4.3
Cleaning of coupons (ferrous, copper, brass and cupronickel coupons) Remove oil by immersion in benzene. Dry. Immerse in hydrochloric acid
(1+4) for 30 minutes at room temperature. Remove acid from the coupon by
three rapid successive rinses in separate water baths; the last rinse water bath
shall contain methyl orange solution and must be kept neutral (yellow).
Rinse successively in isopropyl alcohol and benzene, and dry with a clean
cloth. Store in a desiccator.
5.0
PROCEDURE
5.1
5.2
Attach the coupon to the phenolic rod, using an insulating washer, the screw
and nut assembly.
5.3
5.4
5.4.1
Use short time intervals (4 to 7 days) for the first time series to establish the
rate at which passivity occurs.
5.4.2
Use long time intervals (1 to 3 months) for the second time series to establish
the mean steady state corrosion rate.
5.5
Clean the ferrous coupons, prior to reweighing, with a plastic knife. Remove
oily and greasy deposits by soaking in trichloroethylene. Remove remaining
loose corrosion product by brushing with a soft bristle brush. Immerse in
inhibited hydrochloric acid (1+1.8) for 30 seconds at room temperature.
Remove the specimen from acid bath and rinse with water. Rub with granular
trisodium phosphate and then with tripoli. Rinse with water and then with
isopropyl alcohol. Dry between paper towels followed by warm air drying.
5.6
Clean the copper and copper alloy coupons, prior to reweighing, with a plastic
knife. Remove oily or greasy deposits by soaking in trichloroethylene.
Immerse the coupons in inhibited hydrochloric acid (1+1.8) for 30 seconds.
Rinse with water, then with isopropyl alcohol and finally with benzene. : Dry
between paper towels and place in a desiccator for 1 hour.
5.7
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.
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5.9
6.0
CALCULATIONS
6.1
6.2
W1 =
W2 =
D =
In systems, where all variables are closely controlled, apply the following
equation which gives more precise corrosion rate. Calculate the corrosion rate
for a rectangular coupon as follows:
1
P = --------------------------------------------- x [(W1- W2)/W1.D] x 1.825 x 102
[(1/H) + (1/X) + (1/Y)]
Where:
6.3
W1
W2
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
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7.0
INTERFERENCES
7.1
7.2
7.3
Deviations in the velocity and direction of flow past the coupons may
influence the precision of the results.
7.4
Results are directly comparable only for the water temperature to which the
coupon is exposed.
7.5
8.0
NOTES
8.1
The ferrous metal coupons, until ready for use, should be stored in desiccator
in separate envelopes made from vapour phase inhibitor - impregnated paper.
8.1.1
8.2
Since the corrosion rate will be very high initially and then fall to a lower,
nearly constant rate, two time series are chosen. Short time interval is for 4 to
7 days and long time interval is for 1 to 3 months.
8.3
8.4
8.5
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VII)
1.0
SUMMARY OF METHOD
The sample is filtered through a membrane filter of uniform porosity of 0.45
micron and the coloration produced on the membrane filter is compared with
the standard Babcock & Wilcox Comparison Chart.
2.0
APPARATUS
2.1
2.2
2.3
2.4
3.0
PROCEDURE
3.1
Filter 1-litre of the sample through the membrane filter by applying vacuum.
3.2
Dry the membrane filter at room temperature and compare the coloration on
the membrane filter with the standard Babcock & Wilcox Comparison Chart.
4.0
CALCULATIONS
4.1
Determine the crud level in the sample from the matched colour of the
enclosed Babcock & Wilcox Comparison Chart.
5.0
The method is approximation only. For determining the exact crud level
weighment method to be adopted after passing adequate amount of water
through membrane using in-line filter holder.
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Article I.
1.0
VIII)
pH
SUMMARY OF METHOD
The pH meter and associated electrodes are standardized against two reference
buffer solutions, which are close to the anticipated sample pH. The Sample
measurement is made under specified conditions and prescribed techniques.
2.0
APPARATUS
2.1
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5
3.6
4.0
PROCEDURE
4.1
4.2
Select two reference buffer solutions, the pH values of which are close to the
anticipated sample pH and if possible bracket the sample pH.
4.3
Standardize the pH meter with the above two (4.2) reference buffer solutions
in accordance with the manufacturer's instructions.
4.4
Wash the electrodes with water and fill the beaker (provided with a
thermometer) with water sample. Insert the electrodes into the beaker and
record the pH of the water sample when the drift is less than 0.02 units in 1minute.
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5.0
CALCULATIONS
5.1
5.2
5.3
Report the pH of the test solution to the nearest 0.01 pH units when the pH
measurement lies between 1.0 and 12.0.
5.4
Report the pH of the test solution to the nearest 0.1 pH units when the pH
measurement is less than 1.0 and greater than 12.0.
6.0
PRECISION
6.1
The precision of this method is 0.05 pH units for pH measurements between 1.0
and 12.0.
6.2
When the pH is less than 1.0 and greater than 12.0, the precision is 0.1 pH units.
6.3
In order to attain this precision the condition of the instrumentation and the
technique for standardization and operation is extremely important.
7.0
INTERFERENCES
7.1
7.2
The glass electrode reliably measures pH in nearly all aqueous solutions and in
general, is not subject to solution interference from colour, turbidity, colloidal
matter, oxidants or reductants.
7.3
7.4
7.5
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8.0
NOTES
8.1
The pH is the negative logarithm to the base ten of the conventional hydrogen
ion activity. It is derived from the electromotive force (emf) of the cell,
Reference electrode
pH =
| | solution
pHr
||
glass electrode
(E Er ) F
= --------------2.3026 RT
Where :
pHr
Er
Faraday constant.
Gas constant.
absolute temperature.
8.2
New glass electrodes and those which have been stored dry, shall be
conditioned and maintained as recommended by the manufacturer. It is
necessary to keep the immersible ends of the electrodes in water between
measurements. For prolonged storage, glass electrodes may be allowed to
become dry, but the junction and filling openings of reference electrodes
should be capped to decrease evaporation. Glass electrodes should be stored
as recommended by the manufacturer and reference electrodes in saturated
potassium chloride solution.
8.3
Both the saturated Calomel electrode and silver-silver chloride electrode are
satisfactory for measurement at room temperature. The silver-silver chloride
electrode is recommended for measurement at elevated temperatures where its
potential is more stable than that of the saturated calomel electrode.
8.4
Where emulsions of free oil and water are to be measured for pH, it is
necessary to clean the glass electrodes thoroughly after each measurement.
The cleaning is done by washing with soap or detergent and water, followed
by several rinse with water, after which, the lower third of the electrode is
immersed in hydrochloric acid (1+9) and finally washed thoroughly with
water.
8.5
8.6
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treatment limits the life of electrode and is used only as an alternative to
discarding it. After chromic acid treatment, the electrode is allowed to stand in
water overnight.
8.6.1
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IX)
1.0
INTRODUCTION
ORP provides a useful measurement of the oxidizing or reducing nature of a
particular water sample. It finds various applications like chlorination/ dechlorination process of water, monitoring cycle chemistry in power plants .
ORP is defined as the electromotive force between a noble metal electrode
and a reference electrode when immersed in a solution. The ORP electrodes
are inert and measure the ratio of the activities of the oxidized to the reduced
species present.
2.0
APPARATUS
Meter Most laboratory pH meters can be used for measurement of ORP by
substitution of an appropriate set of electrodes and meter scale. Readability to
1 mv is adequate. Most process pH meters can be used for ORP measurement
by substitution of an appropriate set of electrodes and meter scale. The choice
of process ORP analyzers is generally based on how closely the characteristics
of the analyzer match the requirement of the application. Typical factors
which may be considered are the types of signals which the analyzer can
produce to drive external devices, and the span range available. For remote
ORP measurements the potential generated can be transmitted to an external
indicating meter. Special shielded cable is required to transmit the signal.
Reference electrode A calomel, silver-silver chloride or other reference
electrode of constant potential shall be used. If a saturated calomel electrode is
used, some potassium chloride crystal shall be contained in the saturated
potassium chloride solution. If the reference electrode is of the flowing
junction type, a slow outward flow of the reference electrode solution is
desired. To achieve this, the solution pressure inside the liquid junction should
be some what in excess of that outside the junction. In non pressurized
applications this requirement can be met by maintaining the inside solution
level higher than that the outside solution level. If the reference electrode is
non flowing junction type, these outward flow and pressurization
considerations shall not apply.
Oxidation-Reduction Electrode A noble metal is used in the construction of
oxidation reduction electrodes. The most common metals employed are
platinum and gold; silver is rarely used. It is important to select a metal that is
not attacked by the test solution. The construction of electrode shall be such
that only the noble metal comes in contact with the test solution. The area of
the noble metal in contact with the test solution should be approximately 1
cm3
Electrode assembly A conventional electrode holder or support can be
employed for laboratory measurements. Many different styles of electrode
holders are suitable for various process applications such as measurements in
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an open tank, process pipe line, pressure vessel, or a high pressure sampling
line.
3.0
4.0
+ 430 mv
+ 439 mv
+ 475 mv
+ 476 mv
KCl
NTPC Limited
+ 675 mv
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5.0
6.0
--------------------
---------------------
Temperature 0 C
20
25
30
20
25
30
Reference electrode
Silver/silver chloride
268
263
258
92
86
79
Calomel
223
218
213
47
41
34
Hydrogen
470
462
454
295
285
275
25 0 C
25 0 C
30 0C
220
221
222
424
420
415
176
176
175
Preparation
7.0
8.0
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9.0
Standardization
Turn on meter according to manufacturers instructions. Check zero on meter
by shorting the input connection. The reading should be less than +/- 0.5 mV.
Checking the response of the electrode to standard redox solutions Wash the
electrodes with three changes of water or by means of a flowing steam from a
wash bottle. Use one or more of the above mentioned reference solutions to
check the response of the electrode. Fill the sample container with fresh redox
standard solution and immerse the electrodes. The reading should be within 30
mV of the value expected for the standard solution. The second reading should
not differ from the first by more than 10 mV.
10.0
Procedure
After the electrode / meter assembly has been standardized, wash the
electrodes with changes of water or by means of flowing water. Place the
sample in a clean glass beaker or sample cup and insert the electrodes. Provide
adequate agitation throughout the measurement period. Read the millivolt
potential of the solution allowing sufficient time for the system to stabilize.
Measure successive portions of the sample until readings on two successive
portions differ by no more than 10 mV. A system that is very slow to stabilize
probably will not yield a meaningful ORP.
Continuous determination of ORP of flowing streams
Process ORP analyzers with their rugged electrodes and electrode chambers
provide continuous measurements which are the basis for fully automatic
control. Make selection of the electrodes and electrode chamber to suit the
physical and chemical characteristics of the process material. Locate the
submersion-style electrode chamber so that fresh solution representative of the
process stream or batch continuously passes across the electrodes. Agitation
may be employed to make the stream/ batch more homogeneous. The ORP
value is usually displayed continuously and can be noted at any specific time.
Frequently the pH value is also recorded yielding a permanent record.
11.0
Report
Report the ORP value to the nearest 1 mV, interpolating the meter scale as
required. When considered appropriate, the temperature at which the ORP and
/ or pH were measured may also be reported.
12.0
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X)
TURBIDITY (Nephelometric)
1.0
SUMMARY OF METHOD
Turbidity is an expression of optical properties of a sample that causes light
rays to be scattered and absorbed rather than transmitted in straight lines
through the sample. The intensity of light scattered by the sample under given
conditions is compared with the intensity of light scattered by a standard
reference suspension under the, same conditions. The higher the intensity of
the scattered light, the higher the turbidity of the sample.
2.0
APPARATUS
2.1
2.2
Sample tubes. It must be clear, colourless glass and clean from both inside
and outside. Index marked so that repeated exact placements into the
instrument cuvette well for measurement can be made.
3.0
REAGENTS
3.1
3.2
3.2.1
3.2.2
3.2..3
3.3
3.3.1
3.4
3.4.1
Dilute portions of the standard turbidity suspension (3.3.1) with turbidity free
water, as required. Prepare weekly. But pl. note that dilution below 4.0 NTU
should be prepared daily. (Standards below 1.0 NTU are difficult to prepare
accurately. Refer to specific manufacture instruction to determine if such a
standard is needed.)
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4.0
PROCEDURE
4.1
Calibrate the Nephelometer with standard turbidity suspension for each range,
in accordance with the manufacturer's instructions.
4.2
Replace the standard by the sample in the same tube after thoroughly washing
the tube with turbidity -free water or in an optically identical tube and record
the reading.
Turbidity less than 40 NTU
Shake the sample thoroughly to disperse the solids. Allow air bubble to
disappear, then proceed.
Turbidity exceeding 40 NTU
Dilute the sample with one or more equal volumes of reagent water until
turbidity is below 40 NTU after mixing and degassing. Then treat this less
than 40 NTU solution as above. The turbidity of the original sample can be
calculated based on dilution data and original sample volume.
After calibration check and adjustment, empty the cell of turbidity standard
and rinse the cell with the water to be tested. The measured NTU value of the
water sample to be determined using the instrument value and the appropriate
calibration curve.
5.0
CALCULATIONS
5.1
1.00 -10.0
0.1
10.0 40.0
1.0
40 100
5.0
100 400
10.0
400 1000
50.0
> 1000
100.0
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XI)
1.0
SUMMARY OF METHOD
Total solids are determined by evaporation, or the suspended and dissolved
solids are separated by filtration and individually determined. The suspended
solids are dried and weighed. The solution of dissolved solids is evaporated to
dryness using a dish provided with a constant level control. The residue is
dried and weighed.
2.0
APPARATUS
2.1
2.2
2.3
Sampling Device - A cooling coil with overflow pipe and solenoid valve
suitable for sampling from a water source to a continuous sample evaporator.
(The cooling coil is necessary, only when, sample is above room temperature).
2.4
2.5
2.6
3.0
REAGENTS
3.1
4.0
PROCEDURE
4.1
4.2
Suspended Solids
4.2.1
Place the membrane filter in a petri dish and dry in an oven at 103 C for 15
minutes or in a vacuum desiccator for 30 minutes. Weigh the filter to the
nearest 0.1 mg.
4.2.2
Filter the sample through membrane filter (4.2.1) using the filtration assembly
and the vacuum pump or water aspirator. Wash the residue with chloroform or
benzene. Place the filter in the petri dish.
4.2.3
Place the petri dish in the oven at 103C for 30 minutes. Reweigh the filter and
record the weight of the residue on the filter.
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4.3
4.3.1
Weigh a platinum dish that has been dried at 103C for 1 hour and cooled in a
desiccator. Using evaporation assembly start the evaporation of the selected
volume of the sample for total solids (4.1) or the filtrate from the suspended
solids determination (4.2).
4.3.2
When the evaporation is almost complete remove the dish from the assembly
and dry at 103C for 1 hour in an oven: Cool in a desiccator and weigh.
Record the weight of the residue.
5.0
CALCULATIONS
5.1
W1
=. --------- x 1000
V
W2
---------- x 1000
V
W3
------------- x 1000
V
Where:
W1 =
W2
W3
6.0
NOTES
6.1
6.2
Samples containing 25mg/litre or less of total solids on which only the total solids
content is, to be determined shall be immediately acidified with 0.2ml of
hydrochloric acid (sp gr 1.19) per litre of water. If suspended solids is to be
separately determined, the sample, regardless of total solids content, shall be
filtered, as soon as possible and then acidified
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XII)
1.0
SUMMARY OF METHOD
Total solids are determined by evaporation of an appropriate portion of the
sample and weighing the residue obtained. The suspended and dissolved
solids can be separated by filtration and then determined individually. The
suspended solids are dried and weighed and dissolved solids are determined
by weighing the residue, obtained by evaporating the filtered sample.
2.0
APPARATUS
2.1
2.2
2.3
2.4
2.4
Heater - Hot plate or steam bath for maintaining the temperature of the
evaporating sample near the boiling point.
3.0
REAGENTS
3.1
4.0
PROCEDURE
4.1
4.2
Suspended Solids
4.2.1
Place the membrane filter in a petri dish and dry in an oven at 103 C for 15
minutes or in a vacuum desiccator for 30 minutes. Weigh the filter to the
nearest 0.1 mg.
4.2.2
Filter the sample through the membrane filter (4.2.1) using the filtration
assembly and the vacuum pump or water aspirator. Place the filter in the petri
dish.
4.2.3
Place the petri dish in the oven at 103C for 30 minutes. Reweigh the filter and
record the weight of the residue on the filter,
4.3
4.3.1
Transfer the sample for total solids determination (4.1) or the filtrate from
suspended solid determination (4.2) to a sample reservoir.
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4.3.2.
Fill an evaporating dish (previously dried at 103 C for 1 hour and weighed) to
within 6.3mm of the top, with sample.
4.3.3
Evaporate the sample on a hot plate or steam bath. Periodically, add sample
from the reservoir to the dish until the reservoir is empty.
4.3.4
Dry the dish at 103C for 1 hour. Cool in a desiccator and weigh. Record the
weight of the residue in the dish.
5.0
CALCULATIONS
5.1
W2
-------- x 1000
V
W3
Total dissolved solids, mg/litre = --------- x 1000
V
Where :
W1
W2
6.0
NOTES
6.1
6.2
Suspended solids are defined as those solids, exclusive of gases and in nonliquid state, which are dispersed in water to give a heterogeneous mixture.
Dissolved solids (exclusive of gases) are dispersed in water to give a
homogeneous liquid and total solids is the sum of suspended and dissolved
solids.
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XIII)
1.0
SUMMARY 0F METHOD
The sample is titrated with a standard acid solution to a designated pH and the
end point is determined using internal indicator.
2.0
RANGE
10 to 500 mg/litre as CaCO3.
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5
3.6
4.0
PROCEDURE
4.1
4.1.1
4.1.2
Titrate over a white surface with 0.02N standard hydrochloric acid from a
pink colour to a colourless end point.
4.2
4.2.1
4.2.2
Titrate over a white surface with 0.02N standard hydrochloric acid to the
required end point.
Above
pH 5.2
AT pH 5.0
pH 4.8
pH 4.6
Greenish blue
Light blue
Pink grey with bluish tinge
Light Pink
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4.3
4.3.1
4.3.2
Titrate over a white surface with 0.02 N standard hydrochloric acid to the
required end point. (At pH 4.6 the colour changes to orange and at pH 4.0 to
pink).
4.4.0
5.0
CALCULATIONS
5.1
A x N x 50,000
V
5.2
B x N x 50,000
V
Where:
A
5.3
Hydroxide
Carbonate
Bicarbonate
Alkalinity
(as Alkalinity
(as Alkalinity
(as
CaCO3)
CaCO3)
CaCO3)
P=0
P < 1/2 M
P = 1/2 M
P > 1/2 M
P=M
0
0
2P-M
M
2P
2P
2(M-P)
0
M-2P
0
0
0
Where :
P
Phenolphthalein Alkalinity.
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6.0
PRECISION
6.1
7.0
INTERFERENCES
7.1
Free residual chlorine markedly affects the indicator colour response in some
water samples through its bleaching action. It can be removed by the addition
of sodium thiosulphate.
7.2
Natural colour or the formation of a precipitate during titration may mask the
colour change.
7.3
Salts of weak organic and inorganic acids also affect the titration.
8.0
NOTES
8.1
8.2
8.3
The following pH values are suggested as the equivalence points for the
corresponding alkalinity concentration as calcium carbonate:
pH of 5.1 for total Alkalinities of about 30mg/litre, pH of 4.8 for 150mg/litre,
and pH of 4.5 for 500 mg/litre.
8.3.1
Indicators effective in these ranges which give the most reliable results are
mixed indicator for higher pH values and methyl orange for pH values below
4.6.
8.4
8.5
Sulphuric acid can also be used in place of hydrochloric acid for titration.
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XIV)
1.0
SUMMARY OF METHOD
The sample is treated with a solution of strontium chloride to precipitate
dissolved carbonates and phosphates and the hydroxide ion is titrated with a
standard hydrochloric acid solution using phenolphthalein indicator.
2.0
REAGENTS
2.1
2.2
2.3
2.4
3.0
PROCEDURE
3.1
3.2
Add quickly, while swirling the flask, 1 ml of strontium chloride solution for
each milligram of carbonate or phosphate ion in the sample aliquot, plus a 4ml
excess.
3.3
Stopper the flask loosely, boil the contents for a few seconds, and then cool to
room temperature.
3.4
4.0
CALCULATIONS
4.1
4.2
V1
milliliters of sample.
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5.0
PRECISION
5.1
0.05 mg/litre.
INTEREFENCES
6.1
6.2
7.0
NOTES
7.1
7.2
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XV)
ALUMINIUM
1.0
1.1
SUMMARY OF METHOD
Aluminium is complexed with ferron (8-hydroxy-7-iodo-5-quinoline
sulphonic acid) and its concentration is determined colorimetrically at a wavelength of 370nm.
Orthophenanthroline is added to greatly minimize the iron interference and its
simultaneous determination at a wavelength of 520nm.
RANGE
0.00 to 2.00 mg/litre Al.
APPARATUS
Spectrophotometer for use at 370 and 520nm.
Matched pair of l0 mm cells.
REAGENTS
Water - conforming to specifications Type II.
Aluminium Standard
Solution (l ml = 0.010mg A1) - Dissolve 1.769g of
aluminium potassium sulphate [AlK(SO4)2.12H20] in water. Add 10 ml of
hydrochloric acid (sp gr 1.19) and dilute to 1 litre with water (solution A).
Dilute 100m1 of solution A to 1 litre with water.
Iron Standard Solution (l ml = 0.010mg Fe) - Dissolve 0.7022g of ferrous
ammonium sulphate [FeSO4(NH4)2 SO4.6 H2O] in 50m1 of water and 20m1 of
Sulphuric acid (sp gr 1.84). Dilute to 1 litre with water (solution B). Dilute
100 ml of Solution B to 1 litre with water.
Ferron- orthophenanthroline Reagent - Add 0.5g of ferron and 1.0g
orthophenanthroline to 1 litre of water. Stir for at least 2 hours. If any solids
settle out, decant the clear supernatent liquid for use.
Hydroxylamine Hydrochloride Solution (10%) - Dissolve 100g of
hydroxylamine hydrochloride in 500m1 water. Add 40m1 of hydrochloric acid
(sp gr 1.19) and l g of beryllium sulphate (BeSO 4) and dissolve. Dilute to 1
litre with water.
Sodium Acetate (275g/litre) - Dissolve 275g of sodium acetate trihydrate
(NaC2H3O2.3H2O) in water and dilute to 1 litre with water.
CALIBRATION
Aluminium Curve
To eleven 100m1 volumetric flasks, add respectively 0.0, 2.0, 4.0, 6.0, 8.0,
10.0, 12.0, 14.0, 16.0, 18.0 and 20.Om1 of standard aluminium solution (4.2, l
ml = 0.010 mg A1). Dilute to 100m1 with water.
Using the procedure described in section 6.0, develop the colour and measure
the absorbance of each standard at 370nm.
Prepare a calibration curve by plotting the absorbance against the
concentration.
2.0
3.0
3.1
3.2
4.0
4.1
4.2
4.3
1.4
4.5
4.6
5.0
5.1
5.1.1
5.1.2
5.1.3
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5.2
5.2.1
5.2.2
5.2.3
6.0
6.1
6.2
6.3
6.4
7.0
7.1
7.2
7.3
8.0
8.1
PRECISION
The precision of this method may be expressed as follows:
So
=
0.035
Where
So = single operator precision in mg/litre of aluminium.
9.0
9.1
9.2
INTERFERENCES
Each mg/litre of iron increases the aluminium reading by about 0.01 mg/litre.
Several other metals and anions cause interference, but only manganese, lead,
cobalt and fluoride show sufficiently pronounced effects to require correction.
Orthophosphate upto 5mg/litre and residual chlorine up to 5mg/litre do not
interfere. Natural colour and turbidity interfere and a correction is usually
required.
10.0
NOTES
10.1
10.2
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XVI)
1.1
Principle
The aluminium content of the sample is determined by atomic absorption
spectrophotometers. For dissolved aluminium the filtered sample may be
directly aspirated to the atomizer. For total recoverable aluminum, a
pretreatment with conc. HCl is carried out, prior to aspiration of the sample.
This method is applicable in the range from 5 to 100 mg/l of aluminium.
However, the concentration range will vary with the sensitivity of the
instrument used.
1.2
Apparatus
1.2.1
1.2.2
1.3
Reagents
1.3.1
1.3.2
1.3.3
1.3.4
1.3.5
1.4
1.4.1
Procedure
Calibration
Prepare a reagent blank and sufficient standards containing 0 to 60 mg/l of
aluminium by diluting suitable volumes of standard aluminium solution with
nitric acid (1:499) to 100 ml in volumetric flasks. Add 2 ml of KCl solution to
each of the volumetric flasks. Aspirate the reagent blank and carry out zero
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63adjustment. Aspirate sequentially the standard solutions and measure the
absorbance at 309.3 nm.
1.4.2
Determination of Aluminium
Add 0.5 ml of concentrated nitric acid to 100 ml of the sample taken in a 250ml beaker. (If total recoverable aluminium is to be determined, use 100 ml of
the sample obtained after a pretreatment as given below. Add 5 ml of
concentrated hydrochloric acid to 100ml of the sample taken in a 250-ml
beaker. Heat on a hot plate to reduce the volume to about 50 ml and filter the
sample through 0.45m membrane. Transfer quantitatively the contents of the
beaker to a 100ml volumetric flask. Make up to the mark in volumetric flask.)
Add 2ml of KCl solution to this. Prepare a reagent blank with 100ml of water.
Rinse the atomizer by aspirating water containing 1.5 ml conc HNO 3/l.
Aspirate the reagent blank and carry out zero adjustment. Aspirate the sample
solution and measure the absorbance at 309.3 nm. From the absorbance data,
determine the micrograms of aluminium present in 100 ml of the final
solution.
1.5
Calculations
Aluminium, g/l = M
V
Where
M = mass of aluminium present in g in 100 ml of the final solution, and
V = volume of the sample in ml.
1.6
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XVII)
1.0
SUMMARY OF METHOD
The sample is reacted with hypochlorite and phenol in the presence of a
manganous salt to produce an intense blue compound, the intensity of which
is measured spectrophotometrically at a wavelength of 630nm.
2.0
RANGE
10 to 500 micrograms/litre as N.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
5.0
CALIBRATION
5.1
Transfer 0.0, 1.0, 5.0, 10.0, 15.0 and 20.0ml of the standard ammonia nitrogen
solution. (1ml =0.5 microgram N) to 25ml volumetric flasks,
5.2
5.3
Add 0.5ml of hypochlorous acid. solution and add immediately but slowly
0.6m1 of Phenolate solution. Dilute to 25m1 with water.
5.4
Measure the absorbance of each standard at 630nm against the zero standard
(blank).
5.5
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6.0
PROCEDURE
6.1
6.2
Place 10ml (or other suitable volume containing not more than 10 micrograms
ammonia nitrogen) of the sample in a 25m1 volumetric flask.
Proceed in accordance with section 5.0 .(5.2 to 5.4).
7.0
CALCULATIONS
7.1
A x 1000
-----------------------------V
Where:
A = micrograms of ammonia, nitrogen observed from toe calibration curve.
V =
7.2
milliliters of sample.
8.0
INTERFERENCES
8.1
More than 500 mg/litre of alkalinity, more than 100 mg / litre of acidity,
colour and turbidity interfere.
These interferences can be removed by distillation prior to analysis.
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SUMMARY OF METHOD
The sample is reacted with Nessler's reagent (KZHgI4) to produce a reddish
brown colloidal compound, the intensity of which is measured
spectrophotometrically at a wavelength of 425nm.
2.0
RANGE
0.1 to 2mg/litre as N.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.4
4.4.1
4.4.2
4.4.3
4.4.4
Disodium Dihydrogen Ethylenediamine tetraacetate solution (500g/litre) Dissolve 50g of disodium dihydrogen ethylenediamine tetraacetate dihydrate
in water containing 10g of sodium hydroxide. Gently heat to complete
dissolution. Cool and dilute to 100m1.
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5.0
CALIBRATION
5.1
Prepare a series of standards by diluting 0.0, 1.0, 3.0, 5.0, 8.0 and l0.0m1 of
standard ammonia nitrogen solution (l ml = 0.01 mg N) to 50m1 in Nessler
cylinders.
5.2
5.3
Measure the absorbance of each standard (5.1) at 425nm against the zero
standard (blank) using l0mm matched pair of cells.
5.4
6.0
PROCEDURE
6.1
Place 50ml sample (or other suitable volume diluted to 50ml) containing not
more than 0.lmg of ammonia nitrogen in a Nessler cylinder.
6.2
6.3
Measure the absorbance of the sample at 425nm against the reagent blank
prepared by taking 50 ml of water in a Nessler cylinder and following the step
6.2.
7.0
CALCULATIONS
7.1
A x 1000
-----------------------V
Where:
7.2
milliliters of sample.
8.0
PRECISION
8.1
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9.0
INTERFERENCES
9.1
Glycerine, hydrazine, and some amines will react with Nessler's reagent to
give the characteristic yellow colour in the time required for the test.
9.2
9.3
10.0
NOTES
10.1
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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Scope
This test method is applicable to the measurement of ammonia in reagent and
effluent water.
2.0
3.0
Interferences
1
4.0
5.0
Heat Barrier, 6-mm thick cork board placed underneath the beaker to
insulate the ample solution from heat generated by the magnetic stirrer.
Reagents
1
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2
3
4
5
6.0
Calibration
1
7.0
Sample Treatment:
Transfer 100 ml of the sample (or an aliquot diluted to 100 ml) to 150-ml
beaker. The sample temperature must be the same as that of the standards
used in calibration
Add the stirring bar and mix on the magnetic stirrer. Do not mix so rapidly
that air bubbles are drawn into the solution.
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4
5.
6
7.
8.
9.
10
8.0
Immerse the electrode into the sample, positioning it at an angle 200 to the
vertical, making sure that no air bubbles are trapped on the membrane of
the electrode. All precautions recommended by the manufacturer should
be observed to ensure accurate measurements.
Add 1.0 ml of NaOH solution (see 15.5) to the sample. The NaOH
solution should be added just prior to measurement because ammonia may
be lost to the atmosphere from a stirred alkaline solution
Check the pH of the sample with pH paper. The pH must be greater than
11.0. If less than 11.0, add additional NaOH solution (see 15.5) in 0.1-ml
increments until the pH of the solution exceeds 11.0.
When the electrode comes to equilibrium, measure the electrode potential
of the ammonia nitrogen concentration as directed below.
Note 3 The time required for the electrode to come to equilibrium is
dependent on the ammonia content of the sample. For concentrations
above 0.5 mg/L, the response time is about 30 s.
Sample Measurement Determine the ammonia nitrogen concentration by
means of a pH meter of a specific-ion meter.
pH Meter Record the observed potential in millivolts and convert to
milligrams per litre of ammonia nitrogen by means of the calibration curve
(see 17.2).
ISE Meter Record the concentration reading directly from the
logarithmic scale as milligrams of ammonia nitrogen per litre.
Calculations
Report the ammonia nitrogen content in milligrams per litre. If necessary
calculate for dilution of original sample.
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XX)
1.0
SUMMARY OF METHOD
Carbon dioxide concentration is determined from measured values of pH and
bicarbonate ion.
2.0
APPARATUS
2.1
pH meter.
3.0
REAGENTS
3.1
3.2
3.3
Methyl Red Indicator Solution (5g/litre) - Dissolve 0.5g of methyl red in 100
m1 of 95 % ethanol.
4.0
PROCEDURE
4.1
4.2
4.3
If the pH of the sample is above 8.3, titrate with 0.04N hydrochloric acid to
this pH value using the pH meter for end-point detection.
4.4
4.5
5.0
CALCULATIONS
5.1
V2
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5.2
Calculate the free carbon dioxide concentration in mg/ litre by using the
following equation for waters with pH values from 6 to 9:
Free CO2, mg/litre as CO2 = 1.60 X 10 (6 .0-pH) X mg HCO3 / litre
5.3
6.0
PRECISION
6.1
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XXI)
1.0
SUMMARY OF METHOD
Free carbon dioxide is reacted with sodium hydroxide to form sodium
bicarbonate. The end point of the reaction is detected electrometrically or by
means of a pH colour indicator.
2.0
APPARATUS
2.1
pH meter.
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5
3.6
Methyl Red Indicator solution (5g/litre) - Dissolve 0.5g of methyl red in 100
m1 of 95% ethanol.
4.0
PROCEDURE
4.1
4.2
4.2.1
Alternatively, titrate the sample to pH 8.3 using a pH meter to detect the end
point.
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5.0
CALCULATIONS
5.1
Calculate the free carbondioxide content of the water in mg/litre using the
following equation:
Free CO2, mg/litre as CO2 = V x N x 440
Where V = milliliters of sodium hydroxide required to titrate 100 ml of
sample.
N = normality of sodium hydroxide solution.
5.2
6.0
PRECISION
6.1
7.0
INTERFERENCES
7.1
7.2
7.3
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XXII)
1.0
SUMMARY OF METHOD
The sample is treated with ferric ammonium sulphate and mercuric
thiocyanate solutions. The chloride ion reacts with mercuric thiocyanate to
release the thiocyanate ion which combines with ferric ion to form red ferric
thiocyanate. The intensity of the colour is measured at a wavelength of
463nm.
2.0
RANGE
0.05 to 1.4mg/litre as C1.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
Water -
4.2
[Fe (NH4)2 (SO4)2.6H20] in 20m1 of water. Add 38m1 of nitric acid (sp gr
1.42) and boil to oxidise the iron and remove the oxides of nitrogen. Dilute to
100 ml with water.
4.3
4.3
5.0
CALIBRATION
5.1
Prepare a series of standards by diluting 0, 0.5, 2.5, 5.0, 7.5, 10 and 14m1 of
the standard sodium chloride solution (1ml = 0.01mg chloride) to 100 ml with
water in volumetric flasks.
Proceed in accordance with section 6.0.
Prepare a calibration curve by plotting absorbance versus the concentration of
chloride in mg/litre.
PROCEDURE
Place 25m1 of sample in a 50ml glass stoppered cylinder.
Add 5.0 ml of ferric alum solution and 2.5ml of mercuric thiocyanate solution,
mix thoroughly and allow to stand for 10 minutes.
5.2
5.3
6.0
6.1
6.2
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6.3
7.0
7.1
7.2
8.0
8.1
9.0
9.1
9.2
9.3
9.4
10.0
10.1
10.2
10.3
10.4
10.5
Measure the intensity of colour at 463m, against the reagent blank, prepared
by using 25 m1 of water and following step 6.2, using 50 mm matched
absorption cells.
CALCULATIONS
Read the concentration of chloride ion in mg/litre directly from the calibration
curve prepared in accordance with section 5.0:
Calculate the chloride concentration in mg/litre as CaC03 as follows:
Chloride, mg/litre as CaCO3, = A x 1.41
Where A =
chloride concentration, mg/litre as Cl.
PRECISION
The precision of this method may be expressed as follows:
Sr = 0.054 X
So = 0.013 X
Where:
Sr =
overall precision, mg/litre.
So =
single operator precision, mg/litre.
X =
concentration of chloride ion determined, mg/litre.
INTERFERENCES
Bromides, iodides, cyanides, thiosulphate, hydrazine and nitrites interfere.
Morpholine concentrations greater than 6mg/litre may interfere.
Colour may also interfere depending upon its spectral absorbance.
Boric acid upto 13000mg / litre does not interfere.
NOTES
Reagent grade chemicals should be used for preparing all the reagents.
Mercuric salts are very poisonous. Due precautions should be observed when
using these salts. In the preparation of mercuric thiocyanate solution, a slight precipitate may
form and settle out after 24 hours. Only the clear, supernatent liquid must be
used.
Soak all new glassware in hot nitric acid (1+19) for several hours and in water
(halide free) between tests. Discard all glassware that appear etched or
scratched.
For best results, the temperatures of the standard solutions should be within
1.0 oC of the reagent blank, and the samples.
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XXIII)
1.0
SUMMARY OF METHOD
A solution of lead nitrate is added to the sample followed by addition of
phosphate buffer. The resulting precipitation of lead phosphate co precipitates
the Chloride in the sample. The sample resulting precipitation of lead
phosphate is centrifuged and the supernatant liquid discarded. The precipitate
is dissolved in a ferric iron-mercuric thiocyanate reaction medium and the
Chloride is determined spectrophotometrically at 463nm.
2.0
RANGE
2 to 100 micrograms/litre as Cl.
3.0
APPARATUS
3.1
3.2.
4.0
REAGENTS
4.1
4.2
4.3
Lead Nitrate Solution - Dissolve 20g of lead nitrate [Pb(N0 3)2] in water and
dilute to 1 litre.
4.4
4.5
Standard Sodium Chloride Solution (l ml = 1 microgram of Chloride) Dissolve 1.649g of sodium chloride (dried at 600C for 1 hour) in water and
dilute to 1- litre (Solution A). Dilute 100m1 of Solution A to 1 litre (Solution
B). Finally dilute 10.0 m1 of Solution B to 1 litre. This solution should be
prepared fresh before use.
4.6
5.0
CALIBRATION
5.1
Prepare a series of standards by diluting 0, 1.0, 5.0, 10.0, 15.0, and 25.0 m1 of
Standard Sodium Chloride Solution (l ml = 1 microgram of chloride) to 250
m1 in 250 ml glass stoppered bottles.
5.2
5.3
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6.0
PROCEDURE
6.1
6.2
Add 5.0 ml of the lead nitrate solution to the bottle. Cap the bottle and mix.
Allow to stand for 2 minutes.
6.3
Add 5.0m1 of sodium phosphate solution and mix. Allow to stand for 5
minutes.
6.4
Centrifuge the capped bottle solution at 1500 rpm for 6 minutes. Decant the
supernatent liquid immediately after centrifuging.
6.5
Add 15.0 m1 of ferric nitrate solution and mix to dissolve the precipitate.
6.6
6.7
7.0
CALCULATIONS
7.1
7.2
8.0
INTERFERENCES
8.1
9.0
NOTES
9.1
9.2
Lead nitrate is very toxic. Due precautions should be observed when using
this chemical.
9.3
9.4
For standard method of further low level determination of Cl, PO 4 and SO4 in
high purity water, ASTM D-5542 -94 may be referred.
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XXIV)
1.0
2.0
RANGE
Validated for a concentration range of 8.0 to 250 ppm of Cl.
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
Sulphuric Acid Solution (1+19) - Mix 1 volume of sulphuric acid (sp gr 1.84)
with 19 volumes of water.
4.0
PROCEDURE
4.1
4.2
If Sulphite is present, add 0.5 ml of hydrogen peroxide solution and mix for 1
minute,
4.3
4.4
4.5
Titrate with standard silver nitrate solution to a brick red (or pink) colour
which persisted through out the sample when illuminated with a yellow light.
4.6
Repeat 4.1 to 4.5 using 25m1 of sample diluted to 50ml with water.
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5.0
CALCULATIONS
5.1
Calculate the chloride ion concentration in the sample, in milligrams per litre,
as follows:
Chloride, mg/litre as Cl =
(V1-V2) x N x 70906
-------------------------------V
Where:
5.2
V1 =
V2 =
N =
V =
6.0
PRECISION
The precision of this method may be expressed as follows:
ST =
So =
Where:
ST =
So =
X =
0.013X + 0.70
0.007X + 0.53
overall precision, mg/litre.
Single operator precision, mg/litre.
Concentration of Chloride ion determined, mg/litre.
7.0
INTERFERENCES
7.1
7.2
7.3
7.4
8.0
NOTES
8.1
8.2
Reagent grade chemicals should be used for preparing all the reagents.
If the titration requires more than 25m1 of silver nitrate in 4.5, use a smaller
sample size.
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XXV)
CHLORINE DEMAND
1.0
SUMMARY OF METHOD
A chlorinating solution of known concentration is applied in increasing
increments of chlorine concentration to a series of portions of the individual
sample of water to be tested. The residual chlorine is determined at succeeding
intervals of time.
2.0
APPARATUS
2.1
pH meter.
3.0
REAGENTS
3.1
3.2
3.3
Calcium Hypochlorite Solution (l ml = 0.5 to 100mg available Chlorine) Dissolve 145g of calcium hypochlorite (70% available chlorine, by weight) in
water and make up to 1 litre. Allow to settle and decant the supernatent
solution containing approximately 100 mg available chlorine per ml. Dilute
with water to give 0.5 to 100 mg of available chlorine per ml. Standardize
prior to use in accordance with 3.4.
3.4
3.5
4.0
PROCEDURE
4.1
4.1.1
Ascertain the range of pH, time of chlorine contact, and the chlorine
application concentration to achieve the objective of Chlorination from past
experience, from literature survey, by experimentation, or from plant
conditions.
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4.1.2
Determine the pH of each test and additions of chlorinating solutions such that
there is not less than five equal increments of the chlorine application
concentrations.
4.1.3
4.2
Trial Chlorination
4.2.1
To the first of the series of 500 ml portions of the samples, add the maximum
anticipated amount of chlorinating solution. Determine the pH of the solution.
4.2.2
4.2.3
4.3
Chlorination
4.3.1
4.3.2
4.3.3
5.0
CALCULATIONS
5.1
5.2
A =
B =
milligrams
of
available
of the chlorinating solution.
chlorine
per
milliliter
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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.
NOTES
6.1
6.2
When the anticipated chlorine requirement is less than 600mg/litre, use the
chlorinating solution which is to be used in ultimate plant treatment. When the
anticipated chlorine requirement is 600 mg/litre or more, use the appropriate
hypochlorite solution.
6.3
pH Adjustment
6.3.1
If the pH of the chlorinated sample is higher than the desired range, add
hydrochloric acid (1+1) to the chlorinated sample until the pH of sample
reaches the upper limit of the desired range.
6.3.2
If the pH of the chlorinated sample is lower than the desired range, discard
the sample and proceed with another series of sample portions, as follows: add
sufficient calcium hydroxide solution to bring the pH of the unchlorinated
sample portion to the midpoint of the desired pH range.
6.3.3
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XXVI)
1.0
2.0
RANGE
Upto 4 mg/litre with minimum detection limit of 18 micrograms/litre.
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
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4.0
PROCEDURE
4.1
Free Chlorine
4.1.1
4.1.2
4.1.3
Titrate with ferrous ammonium sulphate solution until the red colour is
discharged.
4.1.4
4.2
Monochloramine (NH2C1)
4.2.1
To the solution after titration for free chlorine (4.1) add 2 drops of potassium
iodide solution (5g/litre) and continue the titration.
4.2.2
4.3
Dichloramine (NHC12)
4.3.1
4.3.2
4.3.3
4.4
4.4.1
4.4.2
Transfer the contents (4.4.1) to another flask containing 5m1 each of buffer
solution and DPD solution.
4.4.3
4.4.4
4.5
4.5.1
4.5.2
4.5.3
Titrate with ferrous ammonium sulphate solution and record the volume in ml
as V1.
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5.0
5.1
CALCULATIONS
Total available, chlorine, mg/litre as Cl =
Where:
V1 =
V =
5.2
V1
------------- x 100
V
C-D
TITRE VALUE
NC1 3 -ABSENT
NC1 3 -PRESENT
Free Chlorine
Free Chlorine
B-A
NH 2 C1
NH 2 C1
C-B
NHC1 2
2 (D-A)
NC1 3
NHC1 2
C-D
6.0
INTERFERENCES
6.1
6.2
6.3
6.3.1
The titration should be carried out as soon as the red colour is formed in each
step.
6.3.2
Too low a pH in the first step will tend to make the monochloramine show in
the free-chlorine step and the dichloramine in the monochloramine step.
6.3.3
6.4
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ferrous ammonium sulphate until red colour is discharged. Subtract the
reading from 'A' as given in the procedure or from 4.5 as the case may be.
7.0
NOTES
7.1
7.2
7.3
V1 X N1
--------------V
x 392
Where:
V1 =
N1 =
V =
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SUMMARY OF METHOD
The sample is treated with potassium iodide at a pH between 3.0 and 4.0. The
librated iodine which is stoichiometrically proportional to the total chlorine
present is titrated with standard solution of sodium thiosulphate.
2.0
RANGE
0.04mg/litre or more, as Cl
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5
3.6
Starch Indicator Solution - Make a paste of l g of soluble starch and mix into 1
litre of boiling water. Add 20 g of potassium hydroxide, mix, and allow to
stand for 2 hours. Add 6 m1 glacial acetic acid, mix, and add sufficient
hydrochloric acid (sp gr 1.19) to adjust the pH to 4.0 (check. with a narrow
range pH paper). This has a shelf life of 1 year.
4.0
PROCEDURE
4.1
4.2
4.3
4.4
4.5
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5.0
CALCULATIONS
5.1
Where:
V1 =
V2 =
N =
V=
milliliters of sample.
6.0
INTERFERENCES
6.1
6.2
6.3
6.4
7.0
NOTES
7.1
7.2
7.3
Test should be made as soon as possible after collection of the sample (not
more than 5 minutes) because the residual chlorine may diminish with time,
due to chlorine demand of the-sample.
7.4
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quickly. and allow to stand for 10 minutes in dark. Titrate with sodium
thiosulphate solution until the solution is yellowish-green. Add 2m1 of starch
solution (10g/litre) and continue the titration to the disappearance of the blue
colour.
Calculate the normality of the sodium thiosulphate solution, as follows:
N=
W
--------------------0.04904 x V
Where:
N =
W =
V =
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SUMMARY OF METHOD
The copper (II) is reduced to Cu (I) with hydroxylamine-hydrochloride. The
pH of the aqueous phase is adjusted to 5 with sodium acetate buffer. The
cuprous ion is then reacted with neocuprine (2, 9 - dimethyl -1, 10 phenanthroline) and the yellow complex extracted either with chloroform or
isoamyl alcohol. The intensity of colour, when extracted with chloroform, is
measured at 457nm and at 454nm when extracted with isoamyl alcohol.
2.0
RANGE
20 to 1,000
APARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
4.6
4.7
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4.8
4.9
4.10
5.0
CALIBRATION
5.1
5.1.1
5.1.2
Add 0.4 ml hydrochloric acid (sp gr 1.19) to each funnel and add water to
make 200m1.
5.1.3
5.1.4
Proceed in accordance with section 6.0 (6.2 to 6.7) and measure the
absorbance of each individual standard.
5.1.5
Use the organic liquid from the blank as a reference solution for the initial
spectrophotometer setting.
5.1.6
6.0
PROCEDURE
6.1
6.2
6.3
6.4
Add 10 m1 of neocuprine solution and shake the funnel and contents for 1
minute.
6.5
6.6
Transfer the organic layer into a dry 50 m1 Erlenmeyer flask and add 20 ml of
isopropyl alcohol to clear the solution. Make upto 50 m1 with chloroform
solvent or isolamyl alcohol depending on the extractant used.
6.7
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spectrophotometer setting or at 454 nm (when isoamyl alcohol is the
extractant) using a mixture of 25 m1 of isoamyl alcohol and l0 ml of isopropyl
alcohol as a reference solution.
6.8
Carry out a blank determination on 200m1 of water, with all reagents and
extracting in the same manner as for the sample.
7.0
CALCULATIONS
7.1
V =
8.0
PRECISION
8.1
0.008 X + 0.9
Where:
ST =
overall precision.
X =
9.0
INTERFERENCES
9.1
Cr interferes when its conc. exceeds 5 times of Cu. The interference from
organic matter, sulphide, cyanide and chromium can be eliminated by as
follows:
If the interfering substances are present add 1 ml of con.HNO 3. Evaporate the
sample to dense white sulphur trioxide fumes on a hot plate. Repeat the
treatment with 5 ml of con.HNO3 and 5 ml of H2O2 and evaporate the solution
to complete dryness. Dissolve the residue with 80 ml of water, boil, cool and
filter. Adjust the pH within 4 to 6 with dropwise addition of ammonium
hydroxide. Add 0.2 ml of hydrochloric acid and dilute to 100 ml. If no
interfering substance is present, just boil the acidified sample and cool.
10.0
NOTES
10.1
10.2
A polythene bottle must be used for sample collection. Hydrochloric acid (sp
gr 1.19) should be added to the filtered sample for total recoverable copper
immediately at the time of collection. The volume of acid should be sufficient
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to neutralize the sample to pH 4 (using narrow range pH paper) and then add
2.0 m1 for each litre of sample.
10.3
Soak all new glassware in hot nitric acid (1+9) for several hours. To ensure the
conditioning of glassware, rinse it with water and run a copper determination
(blank) on copper free water. Repeat until the copper value is less than 4
micrograms per litre. After carrying out the test, always rinse the glassware
with organic solvent, followed by water. Always keep the glassware soaked in
nitric acid (1+9) until used again. Discard any glassware that appears etched
or scratched.
10.4
10.5
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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2.0
APPARATUS
Atomic Absorption Spectrophotometer , for use at 324.7nm with background
correction. The manufacturers instruction should be followed for all
instrumental parameters.
Copper cathode lamp: A single element lamp is preferred but multielement
lamps may be used.
Graphite furnace : It must be capable of reaching temperatures sufficient to
atomize the element of interest.
Graphite tubes : It should be compatible with the furnace device. Pyrolytically
coated graphite tubes are recommended.
Data storage and reduction device: This shall be utilized for collection,
storage, reduction and problem recognition. Automatic sampling is
recommended.
Inject a measured aliquot of sample into the furnace device following the
direction as provided by the particular instrument manufacturer.
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XXX)
1.0
SUMMARY OF METHOD
1.1
1.2
2.0
REAGENTS
2.1
2.2
2.3
2.4
2.5
3.0
PROCEDURE
3.1
3.1.1
Transfer 50m1 of strong acid cation resin into a cation column. Backwash
with water maintaining 50 percent expansion of the bed. Continue
backwashing until the effluent is clear.
3.1.2
3.1.3
Pass sample through the column. Reject first 50m1 and collect 100m1 sample
in a 500 m1 conical flask.
3.1.4
Add 2-3 drops of screened methyl orange indicator and titrate with standard
sodium hydroxide solution till the sample turns smoky grey.
3.2
3.2.1
3.2.2
Add 2-3 drops of screened methyl orange indicator and titrate with standard
sodium hydroxide solution till the sample turns smoky grey.
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4.0
CALCULATIONS
4.1
4.2
V1
milliliters of sample.
V2 X N X 50,000
----------------------V
Where:
V2 =
N =
V =
milliliters of sample.
5.0
NOTES
5.1
5.2
W
----------------(0.20423xV)
Where:
N =
W =
V =
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SUMMARY OF METHOD
The fluoride is distilled from the sample as hydrofluorosilicic acid which is
then treated with SPANDS dye. Decrease in the color-intensity of SPANDS
dye which is proportional to the concentration of fluoride is measured at a
wavelength of 570nm.
2.0
RANGE
0.00 to 1.40 mg/litre as F.
3.0
APPARATUS
3.1
3.2
3.3
4.0
REAGENTS
4.1
4.2
4.3
SPANDS solution - Dissolve 0.958 g of SPANDS reagent (Sodium 2 (Parasulphophenylazo) - 1,8 - dihydroxy - 3,6 - naphthalene disulphonate] in
water and dilute to 500 m1.
4.4
4.5
4.6
4.7
4.8
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5.0
CALIBRATION
5.1
5.2
5.3
5.4
6.0
PROCEDURE
6.1
Distillation
6.1.1
Place 400 m1 of water in the distillation flask and add 200 m1 of sulphuric
acid (sp gr 1.84). Assemble the apparatus and heat the solution to 180C.
Discard the distillate.
6.1.2
Cool the solution to below 100 oC, add slowly 300 m1 of sample, mix
thoroughly and distill at 180C.
6.1.3
6.2
Analysis
6.2.1
6.2.2
If the sample contains free chlorine, add 1 drop of sodium arsenite solution for
each 0.l mg of chlorine present. Add 2 drops of sodium arsenite solution in
excess.
6.2.3
6.2.4
7.0
CALCULATIONS
7.1
7.2
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8.0
PRECISION
8.1
9.0
INTFRFERENCES
9.1
9.1.1
9.1.2
9.1.3
9.1.4
9.2
Constituent
Concentration (mg/litre)
Type of Error
1.
5000
Negative
2.2
Aluminium (A1+3)
0.1*
Negative
3.33 3
Chloride (CI-)
7000
Positive
4.44 4
Iron (Fe+3)
10
Negative
Positive
16
Positive
200
Positive
5.5 5
6.66
7.7
Hexametaphosphate(NaPO3)6
.
Phosphate (PO4-3)
Sulphate (SO4-2)
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10.0
NOTES
10.1
Reagent grade chemicals should be used for preparing all the reagents.
10.2
10.3
10.4
10.5
10.6
The acid water distillation solution (6.1.1) may be used repeatedly until the
build up of interfering materials equal the concentration given in section 9.0.
10.7
The 50m1 distillate or sample (6.2.1) should contain less than 0.028 mg of
fluoride. If fluoride is more than 0.028 mg, a smaller aliquot diluted to 50 m1
should be used.
10.8
10.9
The use of reference solution (4.5) permits the analyst to adjust the instrument
so that the meter reading of the blank may be used on the optimum portion of
the meter scale, 0.0 to 0.8 absorbance units.
10.9.1
Instrument can also be adjusted to some convenient point using the 0.00 mg F
standard. The fixed reading of 0.80 absorbance is suggested.
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SUMMARY OF METHOD
For the determination of total hardness the sample pH is adjusted to 10 with
ammonium chloride - ammonium hydroxide buffer solution and then titrated
with EDTA (ethylene diamine tetraacetic acid or its sodium salt) using
Eriochrome Black-T as indicator. For calcium hardness determination, the
sample pH is adjusted to 12 to 13 with sodium hydroxide and then titrated
with EDTA using ammonium purpurate as indicator. Magnesium is
determined by difference.
2.0
RANGE
1 to 1000mg/litre of Ca plus Mg expressed as Ca.
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5
Black-T
in
3.7
4.0
PROCEDURE
4.1
4.1.1
Pipet 50.0 m1 of sample into a titration flask and adjust the pH to 7-10 by the
dropwise addition of ammonium hydroxide (sp gr 0.90).
4.1.2
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4.1.3
4.1.4
Titrate with EDTA standard solution. The end point will be indicated by
colour change from pink to clear blue.
4.1.5
4.1.6
4.2
Calcium Hardness
4.2.1
4.2.2
4.2.3
Titrate with EDTA standard solution. The endpoint will be indicated by colour
change from pink to purple.
4.2.4
4.2.5
5.0
CALCULATIONS
V1 x M
------------------------- x 10,000
V
5.1
5.2
V2 x M
Calcium hardness, mg/litre as CaCO3 = ------------------------- x 10,000
V
Magnesium hardness, mg/litre as CaCO3 = Total hardness, mg/litre as CaC03
minus calcium hardness, mg/ litre as CaCO3.
Where:
V1
V2
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6.0
PRECISION
6.1
The precision of this method for calcium (13 to 88 mg/ litre as Ca) may be
expressed as follows:
Sr =
0.006 X +0.62
So =
0.006 X +0.51
Where:
6.2
Sr
overall precision.
So
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 =
X =
7.0
INTERFERENCES
7.1
EDTA reacts with several metallic ions. The interference due to these ions can
be minimized by addition of hydroxylamine and cyanide. Metal
concentrations as high as 5mg/litre Fe, l0mg/ litre Mn, l0 mg/litre Cu, l0
mg/litre Zn and l0 mg/litre Pb can be tolerated when hydroxylamine and
cyanide are added.
7.2
7.3
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7.4
In the titration of calcium, ammonium purpurate reacts with strontium but not
with magnesium or barium. In the presence of strontium, the endpoint is slow
and the titration is not strictly stoichiometric. Barium does not titrate as
calcium, but affects the indicator in some unknown way so that no endpoint or
a poor endpoint is obtained. Barium can be removed by precipitation with
sulphuric acid.
8.0
NOTES
8.1
8.2
8.3
8.4
The upper and lower limits of concentration given in range (3.0) may be
extended either by dilution or use of micro apparatus.
8.5
The titration of the sample with EDTA should be completed within 5 minutes
of the buffer addition. If more than 15 m1 titrant is required, take a smaller
sample aliquot and repeat the test.
8.6
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XXXIII)
1.0
2.0
RANGE
4 to 100 micrograms/litre N2H4.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
4.6
Para Dimethylaminobenzaldehyde Solution - Dissolve 4.0 g of pdimethylaminobenzaldehyde in 200m1 of methyl alcohol and 20m1 of
hydrochloric acid (sp gr 1.19). Store in a dark bottle, out of direct sunlight.
5.0
CALIBRATION
5.1
5.2
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5.3
6.0
PROCEDURE
6.1
6.2
Transfer a portion of the sample, to the above cylinder (6.1) that will contain
approximately 0.20 to 5.0 micrograms of hydrazine and make the final
volume to 50m1 with water.
6.3
6.4
7.0
CALCULATIONS
7.1
8.0
W =
V =
milliliters of sample.
PRECISION
The precision of this method may be expressed as follows;
So =
(0.99 X + 0.041)/ V
St =
(1.08 X + 0.081)/V
Where:
So =
St =
X =
V =
9.0
INTERFERENCES
9.1
9.2
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10.0
NOTES
10.1
10.2
10.3
Para-dimethylaminobenzaldehyde
reagent
obtained
from
different
manufacturers produce different intensities of colour in solution. It is
necessary that each new supply of reagent be tested on standard solutions
before using with previously determined calibration curves.
10.4
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XXXIV)
1.0
2.0
RANGE
4 to 80 micrograms/litre Fe with 100mm cell.
10 to 160 micrograms/litre Fe with 50mm cell.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
Ammonium
Hydroxide (1+1) - Mix equal volumes of ammonium
hydroxide (sp gr 0.90) and water.
5.0
CALIBRATION
5.1
Dissolve
0.0835g
of
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5.1.1
5.1.2
5.1.3
5.1.4
5.1.5.
5.1.6
5.1.7
6.0
PROCEDURE
6.1
6.2
6.3
6.4
6.5
Add 15.0m1 of n-hexyl or isoamyl alcohol and shake vigorously for 1 minute.
Allow to stand for 15 minutes.
6.6
Discard the aqueous layer and transfer the alcohol layer into a 25m1
volumetric flask.
6.7
Add l0ml of methyl, ethyl or isopropyl/alcohol to the funnel and wash the
internal surfaces by rolling and tumbling the funnel. Transfer this alcohol into
the previous alcohol extract (6.6). Dilute to the 25m1 mark with the alcohol
used for extraction (6.6).
6.8
6.9
Carry out a blank determination on 50m1 of water, with all reagents and
extracting in the same manner as for the sample.
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7.0
CALCULATIONS
7.1
W x 1000
---------------------------V
Where:
W
V
=
=
8.0
PRECISION
8.1
The single operator and overall precision varies with the determined
concentration and may be expressed as follows:
So
=
0.008 X + 0.92
St
0.039 X + 1.47
So
St
X
=
=
Where:
9.0
INTERFERENCES
9.1
10.0
NOTES
10.1
10.2
10.3
Soak all new glassware in hot hydrochloric acid (1+1) for 2 hours. Drain and
rinse at least 3 times with iron free water. Before and after use, clean all
glassware by making an iron extraction of each piece (without separating the
alcohol - water layers). Drain and flush with iron free methyl alcohol, ethyl
alcohol, or isopropyl alcohol. ,
10.4
If iron content is high in hydrochloric acid (4.5) causing a high blank, distil in
an all glass apparatus, rejecting the first 50m1 and the last 100m1 of distillate.
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10.5
10.6
For total iron determination, heat the sample for 1 hour at 60 0C with 4m1 of
hydrochloric acid (1+1) and 2m1 of hydroxylamine hydrochloride solution.
Thioglycolic acid can also be used for solubilising unreactive iron.
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SUMMARY OF METHOD
Soluble iron [both Fe (II) and Fe (III)) is complexed with ferrozine [3-(2pyridyl) - 5,6 bis (4 phenylsulphonic acid) - 1,2,4 triazine, disodium salt) at
pH 4.4 and its concentration, is determined colorimetrically at a wavelength of
562nm.
2.0
RANGE
Upto 500 micrograms/litre Fe.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
5.0
CALIBRATION
5.1
5.1.1
Place the required volumes of iron standard solution (4.5) in 50ml volumetric
flasks.
5.1.2
5.1.3
5.1.4
5.1.5
Measure the absorbance of each standard at 562 nm against the blank prepared
by mixing 46 ml of water and 4 ml of combined reagent/ buffer solution.
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5.1.6
6.0
PROCEDURE
6.1
6.2
Add 4.0 ml of the combined reagent / buffer solution and mix and make up to
50ml mark with water.
6.3
6.4
7.0
CALCULATIONS
7.1
7.2
From A3 and the calibration curve, calculate the concentration of iron in the
sample.
8.0
INTERFERENCES
8.1
100 micrograms of copper per litre gives rise to a value of iron 1.4
micrograms per litre. None of the other substances, likely to be present, cause
significant interference.
9.0
NOTES
9.1
9.2
9.3
9.4
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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Principle
This test method covers the determination of dissolved and total recoverable
iron in most waters and waste waters in the range from 5 to 100 g/L of iron
using a 20 ml L injection. The iron content of the sample is determined by
atomic absorption spectrophotometer used in conjunction with a graphite
furnace. A sample is place in a graphite tube , evaporated to dryness, charred
and atomized. The absorption signal generated during atomization is recorded
and compared to standards.
2.0
Apparatus
3.0
4.0
(a) Iron solution: Stock (1.0 ml = 1000 g of Fe) Dissolve 1.0 g of pure
iron in 100 ml of HCL (1+1) with the aid of heat. Cool and dilute to 1 L
with water.
(b) Iron solution intermediate (1.0 ml = 10 g of Fe): Dilute 10.0 ml of
above stock solution (a) and 1 ml of HNO3 (Sp.Gr. 1.42) to 1 L with
water
(c) Iron solution intermediate (1.0 ml = 0.2 g of Fe): Dilute 20.0 ml of
above stock solution (b) and 1 ml of HNO 3 (Sp.GR 1.42) to 1 L with
water. This standard is used to prepare the working standards at the time
of analysis.
(d) Nitric acid (sp.gr.1.42)
(e) Argon standard, welder grade, commercially available. Nitrogen may
also be used if recommended by the manufacturer.
Inject the measured aliquots of sample into the furnace device following
the directions as provided by the particular instrument manufacturer.
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SUMMARY OF METHOD
Nickel is reacted with an ammonical solution of dimethyl glyoxime in the
presence of iodine and the intensity of the wine red complex is measured at
530 nm.
2.0
RANGE
0.01 to 0.1mg/litre with 100 mm cell.
0.1 to 5.0mg/litre with 10 mm cell.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
4.6
5.0
CALIBRATION
5.1
5.1.1
5.1.2
100ml
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5.1.3
Proceed in accordance with section 6.0 (6.2, 6.3 and 6.5) using 50 ml water as
the reference.
5.1.4
6.0
PROCEDURE
6.1
6.2
6.3
6.4
To the other flask add 20ml of ammonium hydroxide (1+1). Dilute to 100ml
with water and allow to stand for minutes. Use this solution as the reference
solution.
6.5
7.0
CALCULATIONS
7.1
Read the nickel concentration, in mg/litre directly from the calibration curve.
8.0
PRECISION
8.1
=
=
0.06 X
0.04 X
Where:
9.0
ST
overall precision.
SO
INTERFERENCES
Iron interference is eliminated by the addition of ammonium citrate. Copper
up to 3mg/litre does not interfere with the test.
10.0
NOTES
10.1
10.2
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Principle
The nickel content of the sample is determined by atomic
absorption
spectrophotometry. For dissolved nickel the filtered sample to be directly
aspirated to the atomizer. For total recoverable nickel, HNO3-H2SO4
digestion is to be carried out prior to aspiration of the sample. This method is
applicable in the range from 0.3 to 1.0 mg/L.
2.0
Interference
The presence of high concentration of chromium may increase the nickel
signal. Most interference can be eliminated by the use of nitrous oxide
acetylene flame but nickel sensitivity will be lowered.
3.0
Apparatus
Atomic absorption spectrophotometer with air-acetylene flame. Hallow
cathode lamp or electrodeless discharge lamp for use at 232.0 nm.
4.0
Reagents
Hydrochloric acid Concentrated (11 N), 1:1 and 10 % v/v
Nitric acid
Sulphuric acid -
Concentrated (36 N)
Procedure
Calibration curve
Prepare standard solution containing 0 to 60 g /l of nickel by diluting
suitable volumes of standard nickel solution with nitric acid (1:499) to 100 ml
in the volumetric flasks. Prepare a reagent blank in an identical manner using
10 ml of water. Aspirate the reagent blank and carryout zero adjustment.
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Aspirate sequentially the standard solutions and measure the absorbance at
232 nm.
Construct a calibration curve by plotting absorbance values against
micrograms of Ni in 100 ml of the final volume. Ensure that the calibration
curve is linear by making necessary changes in the volume of the standard
solution used.
Determination of Nickel
For the determination of dissolved nickel content, filtration through 0.45
micron membrane filter, at the time of sampling is required. For total
recoverable nickel, HNO3 H2SO4 digestion is to be carried out.
Add 0.5 ml of nitric acid to a suitable volume of the sample taken in a 100 ml
volumetric flask. Make upto the mark. Rinse the nebulizer by aspirating water
containing 1.5 ml of con.HNO3/l. Aspirate the sample solution and measure
the absorbance at 232 nm. Determine microgram of nickel in the solution
from the absorbance reading, by referring to the calibration curve.
6.0
Calculation
Soluble Ni (direct determination without digestion)
Ni mg/l
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XXXIX)
1.0
MANGANESE
Principle
Manganese is oxidized to higher valence state (permanganic state) giving
permanganic colour by boiling with potassium periodate in acid condition and
in the presence of silver nitrate catalyst. The colour is proportional to the
manganese concentration.
Periodate method is more sensitive than persulphate in lower concentrations
and colour produced is stable for longer time.
2.0
Interference:
Chlorides, organic matter, iron, colour and turbidity
interfere in the estimation of Mn.
3.0
Apparatus
1.
2.
3.
4.0
Reagents
1.
2.
3.
4.
5.
6.
H2SO4 conc.
HNO3 conc.
H3PO4 85%.
KIO4 A.R. grade
AgNO3 salt
H2O2 30%
5.0
6.0
Procedure
(a) In case, pretreatment is required take suitable aliquot of sample and add 5
ml conc. H2SO4 followed by 5 ml conc. HNO3 evaporate till SO3 fumes
disappear. This will remove interfering radicals such as organization
qatter, Chlorides and other oxidizable substances. This result in
dehydration of silica and production of turbidity, cool it and filter.
(b) Take filtrate add 85 ml distilled water, 5 ml HNO3 and 5 H3 PO4 85%. Mix
well. Addition of H3PO4 decolorizes Fe +++ion and prevent precipitation
of iodates or periodates of Mn.
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(c) If pretreatment is not required add 5 ml conc. H2SO4 5 ml conc. HNO3
and 5 ml H3PO4 85%. Mix well.
(d) Boil till sample concentrates to about 90 ml and cool.
(e) Add 0.3 g KIO4. If Mn concentration is 10 g or less add 20 mg AgNO3.
(f) Heat till boiling for 1 hr. Cool immediately and dilute to 100 ml.
(g) Measure colour intensity at 525 nm.
8.0
9.0
Calculate the conc. Of Manganese in the sample from calibration curve and
express in mg/1 as Mn.
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XL)
1.0
2.0
RANGE
0.05 to l mg/litre as N but reliable upto 0.01mg/litre.
3.0
APPARATUS
3.1
3.1.1
Pipet volumetric, 100 ml capacity, with 200 mm delivery stem. The top of the
bulb shall be cut off and the delivery tip curved to form a shallow hook.
3.1.2
Tubing glass or vinyl 1mm inside diameter and about 350mm in length.
3.2
3.3
3.4
3.5
3.6
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
4.6
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4.7
4.8
4.9
5.0
5.1
5.1.1
Clean about 10g of cadmium granules with hydrochloric acid (1+1) and then
rinse with water.
5.1.2
Swirl the clean cadmium granules in 100ml of copper sulphate solution for
5minutess or until the blue colour partially fades.
5.1.3
Decant and repeat with a fresh 100m1 copper sulphate solution solution until
the first trace of a brown colloidal precipitate appears.
5.1.4
Wash the granules with water at least ten times to remove all the precipitated
copper.
5.2
5.2.1
5.2.2
5.2.3
5.2.4 1
6.0
CALIBRATION
6.1
6.2
6.3
7.0
PROCEDURE
7.1
7.2
Pour about 60m1 of mixed sample (7.1) into the reservoir of the reduction
column.
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7.3
7.4
Place a clean 50m1 graduated cylinder under the siphon outlet and collect
25m1 of effluent.
7.5
7.6
Add 3.0 m1 of colour reagent, mix, and allow to stand for 15 minutes.
7.7
8.0
CALCULATIONS
8.1
8.2
8.3
9.0
INTERFERENCES
9.1
9.2
Sample colour that absorbs at wavelengths between 520 and 540nm interferes
with the absorbance measurement. When colour is suspected, analyze a
sample blank, omitting the N-(1-naphthyl) ethylenediamine dihydro-chloride
from the colour reagent.
9.3
Oil and grease in the sample coat the surface of the cadmium and prevent
complete reduction of nitrate to nitrite.
For oil and grease removal, adjust the pH of the sample to 2 with hydrochloric
acid. Extract with two 25 m1 portion of trichlorotrifluoroethane and discard
the organic layer.
9.4
In acidic samples (pH less than 4.5) nitrate is not reduced in the cadmium
column. The pH is adjusted between 6 to 8 with hydrochloric acid or
ammonium hydroxide.
9.5
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10.0
NOTES
10.1
10.2
When not in use, the cadmium column should be covered with ammonium
chloride solution. If air enters the packing or it is dried out, prepare another
column.
10.3
10.4
Prepare at least one calibration standard from potassium nitrite at the same
concentration as one of the nitrate standards to verify the efficiency of the
reduction column. The nitrite standard will fall on the nitrate standard curve if
the reduction of nitrate was complete. If the nitrite standard is 5% higher,
prepare a fresh reduction column and repeat the analysis of the nitrate
standards.
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XLI)
1.0
Principle: Nitrate reacts with phenol disulphonic acid and produces a nitroderivative which in alkaline solution develops yellow colour due to
rearrangement of its structure. The colour produced follows Beers law and is
proportional to the concentration of NO3 present in the sample.
2.0
Interference:
Chlorides and nitrate, are the two main sources of
interference. Pretreatment of sample is necessary when the interfering radicals
are present.
3.0
Apparatus:
a.
b.
c.
d.
4.0
Reagents:
a) Standard silver sulfate: Dissolve 4.40 g Ag2SO4 in distilled water and
dilute to 1000 ml, 1 ml = 1mg Cl.
b) Phenol disulfonic acid (PDA): Dissolve 25 g white phenol in 150 ml
conc. H2SO4. Add 75 ml fuming H2SO4 (15% free SO3) stir well and heat
for 2 hr on waterbath. If fuming sulfuric acid is not available add
additional 85 ml conc. H2SO4 to the 150 ml H2SO4 stir well and heat for 2
hr.
c) Ammonium hydroxide concentrated.
d) Potassium hydroxide 12N: Dissolve 673 g KOH in distilled water and
make up to 1000 ml with distilled water for hard waters use liquid
ammonia.
e) Stock nitrate solution: Dissolve 721.8 mg anhydrous potassium nitrate
and dilute to 1000 ml with distilled water.
1 ml = 100 g N.
f) Standard nitrate solution: Evaporate 50 ml stock NO3 to dryness on
water bath. Dissolve residue in 2 ml PDA reagent and dilute to 500 ml.
1 ml = 10 g N.
g) EDTA: Rub 50 g EDTA with 20 ml distilled water to form a paste. Add 60
ml NH4OH and mix well.
h) Aluminium hydroxide:
Dissolve 125 g potash alum in 1000 ml
distilled water. Warm to 600C and add 55-60 ml NH 4OH and allowed to
stand for 1 hr. Decant the supernatant and wash the precipitate a number of
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times till it is free from C1, NO2 and NO3. Finally after settling, decant off
as much clean liquid as possible, leaving only the concentrated
suspension.
5.0
Procedure:
a) Pretreatment of sample
1.
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.
b) Colour Development
1.
2.
3.
Dissolve the residue using glass rod with 2 ml phenol disulfonic acid
reagent. Dilute and transfer to Nessler tubes.
4.
5.
6.
7.
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XLII)
1.0
2.0
Interference:
Dissolved organic matter, nitrate, hexavalent chromium, and surfactants
interfere. The latter three substances may be compensated for by the
preparation of individual correction curves.
Organic matter can cause a positive but variable interference, the degree
depending on the nature and concentration of the organic material.
Note: Clean all glassware thoroughly and rinse to reduce the error that might
result from streaks or particles on the outside of the cuvettes, as well as
traces of surfactants or dichromate cleaning solution that might adhere
on the interior glass surfaces.
Treat coloured samples with aluminium aluminum hydroxide
suspension or dilute to minimize colour interference.
3.0
Apparatus
a.
b.
Filter:
c.
4.0
i)
ii)
filter
paper
Reagents
a
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5.0
6.0
Procedure
a.
b.
c.
d.
Calculation
For correction for dissolved organic matter, subtract 2 times the reading at 275
at 275 nm from the reading at 220 nm to obtain the absorbance due to nitrate.
Convert this absorbance value into equivalent nitrate by reading the nitrate.
Value from a standard calibration curve obtained at 220 nm.
Calculate as follows:
Nitrate N mg/l = Net g nitrate N ml of Sample.
NO3 mg/l = Nitrate N mg/l x 4.43.
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XLIII)
1.0
2.0
3.0
3.1
Principle
Dissolved or emulsified oil and grease is extracted from water by hexane and
estimation is made gravimetrically.
3.2
Interferences
The solvent extracts are not only oil and grease but other organic substances
also.
3.3
Apparatus
3.3.1
3.3.2
3.3.3
Water Bath
3.3.4
3.4
Reagents
3.4.1
3.4.2
Hexane
3.4.3
3.5
Procedure
3.5.1
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obtained, add 1g of sodium sulphate (Na 2 SO4) crystals to the filter paper cone
and slowly drain emulsified solvent on to the crystals. Add more sodium
sulphate, if necessary. Extract two more times with 30 ml of solvent each
time, but first rinse the sample container with the solvent. Collect the extracts
in a tared distillation flask and wash filter paper with an additional 10 to20 ml
of the solvent. Distil solvent from distillation flask over a water bath at 700 C.
Quantitatively transfer the residue using a minimum quantity of solvent into a
clean, tared, dried beaker. Place the beaker on water bath for 15 minutes at
700 C and evaporate off all the solvents. Cool the beaker in a desiccator for 30
minutes and weigh.
3.6
Calculation
Oil and grease, mg/l = M/V x1000
Where
M = mass, in mg, of the residue; and
V = volume, in ml, of the sample taken.
4.0
4.1
Principle
The material is subjected to extraction in a Soxhlet apparatus with hexane.
The residue left after the evaporation of solvent is weighed. Compounds
volatilized at or below 103 0 C will be lost when filter is dried. The method is
empirical and reproducible results can be obtained only by adherence to all the
details.
4.2
Apparatus
4.2.1
Soxhlet Apparatus
4.2.2
Vacuum Pump
4.2.3
4.2.4
4.2.5
4.2.6
4.2.7
4.3
Reagents
4.3.1
4.3.2
4.3.3
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4.4
Procedure
Prepare a filter consisting of a muslin cloth disc overlaid with filter paper. Wet
the cloth and paper. Pass 100 ml of filter aid suspension through the prepared
filter using vacuum and wash with 1 litre of distilled water. Filter the acidified
sample (pH<52). Apply vacuum until no more liquid sample passes through
filter paper. Using forceps transfer the filter paper to a watch glass. Add
material adhering to edges of muslin cloth disc. Wipe sides and bottom of
collecting vessel and Buchner funnel with filter paper soaked in solvent,
taking care to remove all films caused by grease and collect all the solid
material. Add pieces of filter paper to filter paper on watch glass. Roll all filter
papers containing sample and put into a paper extraction thimble. Add any
pieces of material remaining on watch glass. Wipe the watch glass with a filter
paper soaked in solvent and place it in the thimble. Dry the filled thimble at
103C for 30 minutes in an oven. Fill the thimble with glass wool or small
glass beads. Weigh the extraction flask and extract oil and grease in a Soxhlet
apparatus, using hexane at a rate of 20 cycles per hour for four hours counting
from first cycle. Distil solvent from extraction flask over a water bath
maintained at 70C. Place the flask on a water bath at 70C for lb minutes and
draw air through it by vacuum for the final 1 minute. Cool in a desiccator for
30 minutes and weigh.
4.4
Calculation
Oil and grease, mg/l = Mx1000
V
Where
M = mass, in mg, of the residue; and
V = volume in ml, of the sample.
5.0
5.1
Principle
To estimate the petroleum hydrocarbon content of oil and grease this modified
method is used. Silica gel has the ability to adsorb all constituents of oil and
grease except hydrocarbons. The material not adsorbed by silica gel is
designated as hydrocarbons by this method.
5.2
Interference
The method is not accurate for the reason that any compound other than
hydrocarbon and fatty matter recovered by the solvent interfere by coming
either in hydrocarbon part or in fatty matter.
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5.3
Reagents
All reagents required for partition gravimetric method shall be applicable for
this method also. In addition, silica gel of 75 to 150 micron size, dried at
110C for 24 hours and stored in tightly sealed container is required.
5.4
Procedure
Follow the extraction procedure as given in 5.5. To the extracted solution, add
3 to 4 g of silica gel. Stopper the container and stir gently 5or 10 minutes.
Filter the solution through filter paper and wash silica gel and filter paper with
10 ml of solvent. Collect the filtrate. Distil off the solvent from the filtrate and
weigh the residue as hydrocarbons.
5.5
Calculation
Hydrocarbons, mg / l = Mx1000
V
Where
M = mass, in mg, of residue; and
V = volume, in ml, of sample
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XLIV)
1.0
SUMMARY OF METHOD
The sample is reacted with a standard solution of potassium permanganate at
27C for 4 hours and the residual permanganate is determined iodometrically.
2.0
REAGENTS
2.1
2.2
2.3
Potassium Permanganate Standard Solution (N/80) (l ml = 0.l mg oxygen) Dilute 100 m1 of potassium permanganate stock solution (2.2) to 1 litre.
2.4
Sulphuric Acid (1+3) - Mix 1 volume of sulphuric acid (sp gr 1.84) with 3
volumes of water. Add standard permanganate solution until a very faint pink
colour persists after 4 hours.
2.5
Potassium Iodide.
2.6
2.7
2.8
Indicator Solution - Make a paste of l g of soluble starch and mix into 1 litre
of boiling water. Add 20g of potassium hydroxide, mix, and allow to stand for
2 hours. Add 6m1 of glacial acetic acid, mix and, add sufficient hydrochloric
acid to adjust the pH to 4.0 (Check with a narrow range PH paper). This has a
shelf life of 'l year.
3.0
PROCEDURE
3.1
Place 100m1 of the sample into a clean, glass stoppered bottle of 250 m1
capacity and place in a thermostat at 27C.
.
3.2
When the temperature of the sample becomes 27C, add 4ml of sulphuric acid
(1+3) and l0 ml of potassium permanganate solution (N/80). Mix well and
allow to stand for 4 hours at 27C protected from sunlight.
3.3
Add few crystals of potassium iodide (0.2-0.3 g) and titrate the librated iodine
with standard sodium thiosulphate solution (N/80) using starch indicator.
3.4
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4.0
CALCULATIONS
4.1
V1 =
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XLV)
1.0
SUMMARY OF METHOD
Dissolved oxygen reacts, under alkaline conditions, with the indigo carmine
solution to produce a progressive colour change from yellow-green through
red to blue and blue-green. The colour developed in standards dissolved the
sample is compared with colour representing different concentrations of
oxygen.
2.0
RANGE
Less than 60 micrograms/litre.
3.0
APPARATUS
3.1
Burette, 25 or 50 m1.
3.2
Sampling Bucket, with an overflow at least 20mm above the top of the
sampling vessel.
3.3
4.0
REAGENTS
4.1
4.2
4.2.1
4.2.2
4.2.3
4.2.4
4.2.5
4.2.6
4.2.7
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4.2.8
5.0
CALIBRATION
5.1
Milliliters of Colour
Standards
RED
YELLOW
BLUE
0.75
05.0
5.0
20.0
10
6.25
12.5
15
9.4
10.0
20
13.0
5.4
25
14.4
5.5
30
14.5
3.3
0.2
35
15.1
2.9
1.1
40
15.5
2.4
2.2
45
16.1
2.0
2.5
50
18.3
1.7
3.1
55
21.7
1.4
13.1
60
25.0
1.0
15.0
5:2
Place the amounts of stock solutions listed above in 300 m1 borosilicate glass
stoppered reagent bottles. Add 3.0 m1 of hydrochloric acid (sp gr 1.19) to
each. Dilute to the neck of the bottle with water. Stopper and mix by
inversion. Store in a dark place.
6.0
PROCEDURE
6.1
Place a clean sampling vessel in the sampling bucket and collect the sample
under water. Allow the sample to overflow for several minutes.
6.2
Fix a burette such that its tip dips into the overflowing sample to a depth of 10
to 15mm.
6.3
6.4
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6.5
6.6
Place the vessel on a white surface and match its colour with the standard by
viewing at a 45 angle using a 'Cool" white fluorescent lamp for illumination,
7.0
7.1
PRECISION
The single operator precision of this method may be expressed as follows:
So = 0.052 X + 0.7
Where:
So =
X =
8.0
INTFRFERENCES
8.1
8.2
8.3
Ferrous iron will produce low results and copper will cause high results.
8.4
In samples, where ferrous iron and copper are present, their combined effect is
frequently zero.
8.5
9.0
NOTES
9.1
9.2
9.3
9.4
9.5
In the procedure (6.6), the colours should be matched as soon as possible after
mixing the reagents and sample, since the colours are not stable for more than
30 minutes and air leakage may cause a change in colour.
9.6
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XLVI)
1.0
SUMMARY OF METHOD
Free iodine is librated equivalent to Oxygen concentration in the sample by
manganese sulphate solution. The librated iodine is titrated with standard
sodium thiosulphate solution using starch indicator.
2.0
RANGE
1.0 mg/litre or more.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
Sodium Thiosulphate Standard Solution (0.025N) (l ml = 0.2mg oxygen) Dilute 125 m1 of 0.1N sodium thiosulphate solution to 500 m1 in a volumetric
flask.
4.6
Starch Solution - Make a paste of l g of soluble starch and mix into 1-litre of
boiling water. Add 20 g potassium hydroxide, mix, and allow to stand for 2
hours. Add 6m1 of glacial acetic acid, mix, and add sufficient hydrochloric
acid (sp gr. 1.19) to adjust the pH to 4.0 (check with a narrow range pH
paper). This has a shelf life of 1-year.
4.7
4.8
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4.9
4.10
5.0
PROCEDURE
5.1
5.2
Add 2.0 m1 of manganous sulphate solution and 2.0 m1 of alkaline iodidesodium azide solution well below the surface of the sample. Replace the
stopper and mix by inversion.
5.3
When the floc has settled, add 2.0 m1 of sulphuric acid (sp gr 1.84).
Restopper, and mix by inversion.
5.4
6.0
CALCULATIONS
6.1
V1 X 0.2
-------------------------200
x 100
Where:
V1 =
7.0
7.1
PRECISION
The precision of this method was determined by six operators in three
laboratories using a saturated sample of reagent water. The mean
concentration was 9.0 m1/litre and the pooled single operator precision in
these samples was 0.052 mg/litre.
8.0
INTERFERENCES
8.1
8.2
8.3
9.0
NOTES
9.1
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9.2
9.3
In the procedure (5.4), 203m1 of the solution is titrated to take care of the
displaced sample by 2m1 each of manganous sulphate solution and alkaline
iodide-solution.
300
Hence 200m1 of original sample = 200 X ----------(300 - 4)
=203.3 ml
If it is necessary to eliminate ferrous iron, interference it is done before step
5.2 of the procedure. Following method is followed:
9.3.1
9.3.2
After 5 minutes, destroy the violet colour by adding 0.5 to 1.0m1 of potassium
oxalate solution. Mix and allow to stand in dark. Complete decolorization
should be obtained in 2 to 10 minutes.
9.4
9.5
W
-----------------------------------------0.04904 X V
Where:
N =
W =
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SUMMARY OF METHOD
The sample is incubated at 20C for 5 days. Dissolved oxygen is measured
initially and after incubation. The BOD is computed from the difference
between initial and final dissolved oxygen (DO).
2.0
APPARATUS
2.1
2.2
3.0
REAGENTS
3.1
Dilution Water - Add 0.3g of sodium bicarbonate per litre of Type II water.
4.0
PROCEDURE
4.1
Adjust the temperature of a suitable portion of the well mixed sample to 20C.
Remove the oxygen or excess air by maintaining the sample under vacuum for
10 minutes using laboratory vacuum pump.
4.2
Fill completely two incubation bottles (250 or 300m1 capacity) with the
sample as treated above (4.1). Allow to stand for 15 minutes.
4.3
Determine the dissolved oxygen in one bottle by the Iodometric method and in
the other after 5 days" incubation in darkness in the stoppered bottle at 20oC.
5.0
CALCULATIONS
5.1
D2 =
6.0
INTERFERENCES
6.1
Samples for BOD analysis may degrade significantly during storage, resulting
in low BOD values. This can be minimized by analyzing the sample promptly
or cooling it to 4C or below.
Analysis should be done before 24 hours after grab sample collection.
7.0
NOTES
7.1
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7.2
For samples of doubtful purity, the sample should be mixed with dilution
water in the ratio 1:1 at 20C. Further dilutions shall be used if necessary to
ensure that not more than half the oxygen is consumed during the incubation.
Determine the dissolved oxygen before and after incubation and calculate the
result using the appropriate dilution factor.
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SUMMARY OF METHOD
The sample is treated with a standard potassium dichromate solution in 50%
sulphuric acid solution. The excess dichromate is titrated with a standard
ferrous ammonium sulphate solution, using orthoprenan-throline-ferrous
complex as an internal indicator.
2.0
RANGE
Upto 800mg/litre.
Samples with higher COD concentrations may be analyzed by appropriate
dilution of the sample.
3.0
APPARATUS
3.1
3.2
3.3
4.0
REAGENTS
4.1
Water
4.2
4.3
4.4
4.5
4.6
4.7
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4.8
4.9
5.0
PROCEDURE
5.1
5.2
5.3
Place the reflux flasks in an ice bath and add l g of powdered mercuric
sulphate, 5.0 m1 of sulphuric acid (sp gr 1.84) and several glass beads or
boiling stones to each flask and mix well to complete dissolution.
5.4
Add 70m1 of sulphuric acid - silver sulphate solution slowly such that the
solution temperature is maintained as low as possible (below 400C).
5.5
5.6
Allow the flasks to cool and wash down the condensers with about 25m1 of
water. Dilute the solution to about 300 m1 with water and allow to cool to
room temperature.
5.7
5.8
For waters of low COD (10 to 50 mg/litre) use 0.025N potassium dichromate
and 0.025N ferrous ammonium sulphate solutions.
6.0
CALCULATIONS
6.1
V2 =
N =
V =
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7.0
INTERFERENCES
7.1
The method does not uniformly oxidise all organic materials. Volatile
organics which are difficult to oxidise may be partially lost before oxidation is
achieved. Care .in maintaining a low solution temperature (about 40C) and
permitting oxidation to proceed at the lower temperature for a period of time
before reflux is initiated will result in higher recoveries of theoretical COD.
7.2
7.3
Oxidizable inorganic ions, such as ferrous, nitrite, sulphites, and sulphides are
oxidised and measured also as organic constituents.
8.0
NOTES
8.1
8.2
8.3
V1 X N1
-----------------------------V
Where :
N
V1
N1
If less than 50m1 of the sample is used (procedure, 5.1) add necessary amount
of dilution water to the reflux flask, then add the sample aliquot and mix.
Samples containing more than 800mg/litre COD are diluted and mixed
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precisely with water and 50m1 of the diluted sample are placed in the reflux
flask.
8.4
To check the validity of the test (procedure, 5.0) results, make a standard
determination using potassium acid phthalate solution (4.6). A COD of 500
mg/litre should be obtained on a 25m1 aliquot of the standard solution diluted
to 50m1.
8.5
In the procedure (5.8) if the COD determined is higher than 50mg/litre after
using 0.025N potassium dichromate and 0.025N ferrous ammonium sulphate
solutions, reanalyze the sample using more concentrated reagents.
8.6
8.7
8.8
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SUMMARY OF METHOD
The sample containing orthophosphate, is reacted with ammonium molybdate
in an acidic medium and the resulting phosphomolybdate is reduced to
molybdenum blue complex with amino-naphthol-sulphonic-acid. The
intensity of the blue colour is measured at a wavelength of 650nm. When a
bismuth salt is added the intensity of the blue colour increases by four times.
2.0
RANGE
0.5 to l0mg/litre P04
0.1 to 2.5mg/litre P04 (when bismuth salt is added)
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
ANSA Solution - Dissolve the following chemicals (in the given order) in
100m1 of water: 3.7g of sodium sulphite (Na2SO3), 0.100g of 1-amino-2naphthol-4 sulphonic acid, and 6.2g of sodium metabisulphite (Na2S2O5).
Store in an amber coloured bottle and make fresh every two weeks.
4.3
4.4
4.5
4.6
Sulphuric Acid Solution (A) - Add 370m1 of sulphuric acid (sp gr 1.84),
slowly and with stirring, to 600m1 of water. Cool and dilute to 1 litre with
water.
4.7
5.0
CALIBRATION
5.1
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5.1.1
Prepare a series of phosphate standards by diluting 0.0, 0.5, 1.0, 2.0, 5.0 and
l0.0m1 of phosphate stock solution (4.4, l m1 = 0.lmg PO 4) to 100m1 with
water in a volumetric flask.
5.1.2
5.1.3
Measure the absorbance of the each standard against reagent blank (zero
standard) at 650nm using 25mm matched absorption cells.
5.1.4
5.2
5.2.1
5.2.2
5.2.3
6.0
PROCEDURE
6.1
6.1.1
6.1.2
6.1.3
6.1.4
Add 5.0m1 of ANSA solution, mix, and allow to stand for 10 minutes.
6.1.5
Measure the absorbance against reagent blank (prepared by adding all the
reagents to 100 m1 water) at 650nm using 25mm matched absorption cells.
6.2
6.2.1
7.0
CALCULATIONS
7.1
7.2
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8.0
INTERFERENCES
8.1
A silica concentration fifty times that of the phosphate will cause an error of
less than 2 percent.
8.2
8.3
8.4
8.5
9.0
NOTES
9.1
9.2
9.3
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L)
1.0
SUMMARY OF METHOD
Non reactive silica is dissolved in hydrofluoric acid and the resulting
fluorosilicic acid in the presence of zirconium ions releases soluble silicic
acid. The latter is reacted with molybdate ion and the resulting green yellow
coloured complex is reduced to a blue complex, the intensity of which is
measured at a wavelength of 815nm.
2.0
RANGE
0 to 500 micrograms/litre SiO2.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4,2
4.3
Hydrochloric Acid (1+2) - Dilute 50m1 of hydrochloric acid (sp gr 1.19) with
100 m1 of water.
4.4
4.5
4.6
4.7
Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino -2naphthol -4- sulphonic acid in 50 m1 of a solution containing 1g of sodium
sulphite (Na2SO3). Add the solution to 100m1 of a solution containing 30g of
sodium hydrogen sulphite (NaHSO3). Make up to 200m1 and store in a dark,
plastic bottle. Prepare fresh solution every 2 weeks.
4.8
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4.9
4.10
5.0
CALIBRATION
5.1
5.1.1
Place 0, 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0m1 of standard silica solution A (l ml
=10 micrograms SiO2) in 100m1 volumetric flasks and make up to 100m1
with water.
5.1.2
5.1.3
5.1.4
5.2
5.2.1
Place 0.0, 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0m1 of standard silica solution B (l ml =
1 microgram Si02) in 100m1 volumetric flasks and make up to 100 m1 with
water.
5.2.2
5.2.3
5:2.4
6.0
PROCEDURE
6.1
6.1.1
6.1.2
6.1.3
Add 3 m1 of oxalic acid solution and mix. Allow to stand for 10 minutes.
6.1.4
Add 2 m1 of amino naphthol sulphonic acid solution and allow to stand for
10 minutes.
6.1.5
Measure the absorbance of the sample against the zero standard (blank) (E1)
at 815nm.
6.1.6
For blank, place 100m1 of water in a 200m1 polythene conical flask and
proceed in accordance with 6.1.2 to 6:2.4
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6.2
6.2.1
6.2.2
6.2.3
Add 3.5m1 of zirconium solution and, drop by drop with stirring, 2m1 of
ammonium - molybdate solution. Mix thoroughly. Allow to stand for 10
minutes.
6.2.4
Add 3m1 of oxalic acid solution and mix thoroughly. Allow to stand for 10
minutes.
6.2.5
6.2.6
Measure the absorbance of sample against the blank solution (E2) at 815nm.
6.2.7
For blank, place 100m1 of water in a 200m1 polythene conical flask and
proceed in accordance with 6.2.2 to 6.2.5.
7.0
CALCULATIONS
7.1
From the value E2 using the calibration curve, calculate the, concentration of
reactive plus non reactive silica in the sample.
7.2
From the value (E2-El), using the calibration curve, calculate the
concentration of non reactive silica in the sample.
7.3
8.0
INTERFERENCES
8.1
9.0
NOTES
9.1
9.2
In the analytical procedure the HF/Zr ratio must be kept constant and should
be equal to 6/1. Values greater than this ratio correspond to an excess of
hydrofluric acid which then again reacts with silicic acid to form fluorosilicic
acid and thus introducing error. Values lower than this ratio corresponds to an
excess of Zr+4 ions that give rise to a white precipitate in the presence of
silico-molybdic complex. Hence, it is very important to know precisely, the
zirconium content in the ZrOCl2.8H20 reagent and the HF titre in 40%
hydrofluoric acid to adjust the amount of zirconium and HF solutions.
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9.2.1
9.2.2
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LI)
1.0
SUMMARY OF METHOD
The sample is filtered through a 0.2 micron membrane filter and the residue
left on the membrane filter is treated with 48% hydrofluoric acid. The soluble
silica thus produced is reacted with ammonium molybdate and the
concentration of resulting complex is determined calorimetrically.
2.0
RANGE
0 to 100 micrograms /litre SiO2
(Higher concentrations can be determined by proper dilution of the sample
with water):
3.0
APPARATUS
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
4.0
REAGENTS
4.1
4.2
Boric Acid Solution (5%) - Dissolve 100g of boric acid (H3BO3) in 2 litres of
warm water.
4.3
4.4
4.5
Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino-2naphthol-4- sulphonic acid in 50m1 of a solution containing l g of sodium
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sulphite (Na2S3). Add the solution to 100m1 of a solution containing 30g of
sodium bisulphite (NaHSO3). Make up to 200m1 with water and store in a
dark, plastic bottle.
4.6
4.7
4.8
5.0
CALIBRATION
5.1
5.1.1
Place 0.0, 0.5, 1.0, 2:0, 3.0, 4.0 and 5.0 m1 of standard silica solution A (l ml
= 10 micrograms Si02) in 200m1 polythene flasks. Add water to make 75m1.
5.1.2
Add 4.0m1 of ammonium molybdate reagent and mix. Allow to stand for 20
minutes at 35-40C in a water bath.
5.1.3
Remove the flasks from the water bath and add 20m1 of sulphuric acid (10 N)
rapidly while stirring.
5.1.4
5.1.5
5.2
5.2.1
Place 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 and l0.0 m1 of standard silica solution B (l ml
= 1 microgram Si02) in 200m1 polythene flasks. Add water to make 75m1.
5.2.2
Add 4.Om1 of ammonium molybdate reagent and mix. Allow to stand for 20
minutes at 35-40C in a water bath.
5.2.3
Remove the flasks from the water bath and add 20m1 of sulphuric acid (10 N)
rapidly while stirring. Allow to stand for 5 minutes.
5.2.4
5.2.5
5.2.6
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6.0
PROCEDURE
6.1
Filter 500 m1 of the water sample through a 0.2 micron membrane filter by
applying vacuum.
6.2
Place the membrane filter in the bottom of a 150m1 polythene beaker and add
0.5 ml of 48% hydrofluoric acid with the help of a long and thin, calibrated
polythene dropper. Place a polythene disc on the membrane filter and cover
the beaker with a polythene cover. Allow to stand for 30 minutes.
6.3
Add 25m1 of water and 50m1 of boric acid solution. Mix well and place the
beaker in a water bath controlled at 40-50C. Allow to stand for 15 minutes.
6.4
Add 40m1 of ammonium molybdate reagent while stirring. Allow to stand for
20 minutes at 35-40C in a water bath.
6.5
Remove the beaker from the water bath and add 20m1 of sulphuric acid
(10 N) rapidly while stirring. If a pronounced yellow colour remains, measure
the absorbance at 420nm using l0 mm absorption cell.
6.6
6.7
6:8
Run a blank alongwith the sample, using a 0.2 micron membrane filter and
proceeding in accordance with 6.2 to 6.6.
7.0
CALCULATIONS
7.1
7.2
8.0
NOTES
8.1
8.2
8.3
8.4
8.5
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LII)
1.0
SUMMARY OF METHOD
The sample containing reactive silica is reacted with molybdate ion in an
acidic medium (pH 1.2 to 1.5) and the resulting green-yellow coloured
complex is reduced to a blue complex with 1-amino-2- naphthol-4-sulphonic
acid the intensity of which is measured at a wavelength of 815nm.
2.0
RANGE
5 to 140 micrograms/litre SiO2.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
Amino - Naphthol - Sulphonic Acid Solution - Dissolve 0.5g of 1-amino -2naphthol-4-sulphonic acid in 50m1 of a solution containing l g of sodium
sulphite (Na2SO3). Add the solution to 100 ml of a solution containing 30g of
sodium hydrogen sulphite (NaHSO3). Make up, to 200m1 and store in a dark
plastic bottle. Prepare fresh solution every 2 weeks.
4.3
4.4
Hydrochloric
1.19) and water.
4.5
4.6
4.7
5.0
CALIBRATION
5.1
Prepare a series of standards (at least five concentrations) to cover the range 5
to 140 micrograms Si02/litre by diluting appropriate volumes of silica standard
solution (4.7, l ml = 1 microgram SiO2) to 50 m1 in 100 m1 polythene bottles.
5.2
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5.3
6.0
PROCEDURE
6.1
6.2
Add 1.0 m1 of hydrochloric acid (1+1) and mix, then add 2.0ml of ammonium
molybdate solution and mix well.
6.3
After 5 minutes, add 1.5m1 of oxalic acid solution and mix well.
6.4
6.5
7.0
CALCULATIONS
Read the concentration of silica in micrograms/ litre as SiO 2 directly from the
calibration curve prepared in section 5.0.
Calculate the concentration of silica in micrograms/litre as CaCO3, as follows:
Silica, micrograms/litre as CaCO3 = A x 0.83.
Where:
A = Silica concentration, micrograms/litre as SiO2
8.0
PRECISION
8.1
0.005 X + 0.7
St =
0.03 X + 1.3
Where:
= single operator precision, micrograms
SiO2/litre.
St =
X =
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9.0
INTEREFERENCES
9.1
9.2
9.3
9.4
9.5
Strong oxidising and reducing agents may interfere in the reduction step.
9.6
10.0
NOTES
10.1
Reagent grade chemicals should be used for preparing all the reagents.
10.2
10.3
10.4
10.5
10.6
10.7
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two 5m1 increments of hydrochloric acid (sp gr 1.19). Dry the evaporated
residue in an oven at 110C for 1 hour. Add 5m1 of hydrochloric acid (sp gr
1.19) and then 50m1 of water to the beaker, warm the beaker and its contents
and stir the mixture. Filter the warm solution through an ashless, medium
texture filter paper. Wash the residue. on the paper 15 times with hydrochloric
acid (1+19) and then with several small increments of water.
Place both filter papers with their residues in a weighed platinum crucible, dry
and char the paper without flaming it, and then ignite the charred residue for
30 minutes at 1000 to 1200C. Cool in a desiccator and weigh. Repeat the
ignition, cooling, and weighing until a constant weight is obtained.
Add several drops of sulphuric acid (sp yr 1.84) and about 5m1 of
hydrofluoric acid (48%) to the weighed residue in, the crucible and evaporate
to dryness on a low temperature hot plate under a fume hood. Reignite the
residue at 1000 to 1200C and weigh. Repeat the ignition, cooling, and
weighing until a constant weight is obtained.
Determine a reagent blank by making an identical silica determination on the
quantity of water required for the washing of the residue plus 100m1.
Calculate the concentration of silica, in milligrams per litre, in silica stock
solution, as follows:
Si02, mg/litre
(Wl-W3) - (W2-W4)
----------------------------------------V
Where:
W1 = weight of crucible and residue, mg, after first ignition.
W2 = weight of crucible and residue, mg, after treatment with hydrofluoric
acid and reignite it.
W3 = weight of crucible and blank residue, mg, after first ignition.
W4 = weight of crucible and blank residue, mg, after treatment with
hydrofluoric acid and reignition.
V = volume of sample used, litres.
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Manual on Analytical Test Procedure for Water and Steam in Power Plants
LIII)
1.0
SUMMARY OF METHOD
Sodium is determined both in steam and boiler water by flame photometer or
sodium ion electrode method. Then total solids are determined in boiler water,
and concentration of impurities in steam is calculated based on the assumption
that concentration of sodium-to-impurities in steam is equal to the
corresponding ratio in boiler water.
2.0
RANGE
If the impurities are principally sodium compounds, impurity concentrations
as low as 0.6 microgram/ litre may be detected by the flame photometry
method and as low as 0.05 microgram/litre by the sodium ion electrode
method.
3.0
APPARATUS
3.1
4.0
4.1
4.2
5.0
CALCULATIONS
5.1
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NOTES
6.1
6.2
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LIV)
1.0
SUMMARY OF METHOD
Sulphate ion is precipitated and weighed as barium sulphate after removal of
silica and other insoluble matter.
2.0
RANGE
20 to 100mg/litre as SO4.
It can be extended to higher or lower ranges by adjusting the sample size.
3.0
REAGENTS
3.1
3.2
3.3
3.4
3.5.
3.6
3.7
4.0
PROCEDURE
4.1
4.2
4.3
Adjust the acidity of the sample to methyl orange end point and add l0 ml
excess of hydrochloric acid (1+9).
4.4
Boil the solution and add slowly 5m1 of hot barium chloride solution while
stirring vigorously. Keep for 2 hours on a .steam bath.
4.5
Filter through Whatman No.42 or equivalent filter paper and wash the
precipitate with hot water until the washings are substantially free of chloride
(check with silver nitrate solution).
4.6
Place the filter paper and its contents in a weighed platinum crucible and
ignite at 800C for 1 hour.
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4.7
Add a drop of sulphuric acid and a few drops of hydrofluoric acid, and
evaporate under a hood to expel silica.
4.8
5.0
CALCULATIONS
5.1
W X 411,500
-------------------------V
Where:
W = weight of barium sulphate, g.
V = volume of sample, ml.
5.2
6.0
PRECISION
6.1
Results of this method are precise to 1.0% of the amount of sulphate ion
present.
7.0
INTERFERENCES
7.1
7.2
8.0
NOTES
8.1.
8.2
Reagent grade chemicals should be used for preparing all the reagents.
Turbidity may be removed by filtration 'through a fine filter paper (eg.,
Whatman No.42).
Silica may be removed, prior to analysis, by acid dehydration procedure (see
method for the determination of soluble silica, Note 10.7). In this case, the
ignition described in 4.6 need not be done in a platinum crucible.
Faster precipitation and a coarser precipitate can be obtained by adding l0ml
of saturated picric acid solution and boiling the sample for.5 minutes before
adding barium chloride.
Do not attempt to obtain a complete removal for chloride. Discontinue
washing, when not more than a faint opalescence is produced in the test for
chloride.
8.3
8.4
8.5
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LV)
1.0
2.0
RANGE
5 to 1000mg/litre as S04.
3.0
APPARATUS
3.1
3.2
4.0
REAGENTS
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
Ion Exchange Resin - Strong acid cation exchange resin, 710 to 850 micron.
(IR 120 or equivalent). Regeneration is to be done with hydrochloric acid
(I+4).
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4.9
4.10
4.11
Starch Indicator - Make a paste of l g of starch with cold water. Pour the paste
into 100m1 of boiling water and boil for several minutes. This is stable for 2
to 3 days.
4.12
4.13
Thorin solution (2.0g/litre) - Dissolve 0.2g of thorin [2 (2-hydroxy-3, 6 disulpho - 1-naphthylazo) benzene arsenic acid] in 100 m1 of water.
5.0
5.1
Prepare a series of standard sulphate solution: by diluting with water 0.0, 2.0,
5.0, 10.0, 15.0,25.0, 35.0 and 50.0m1 of the standard sulphate solution (l ml=
0.l00mg SO4) to 50m1 in volumetric flasks.
5.2
Determine the blank and sulphate equivalent of barium chloride solution (note
12:2) in accordance with 6.3, 6.4 and 6.5.
6.0
6.1
Place 25m1 of filtered sample into a 100m1 beaker. Add 0.5 m1 of starch
indicator and titrate the sulphite with iodine solution.
6.2
6.3
Pass the solution through the ion exchange column and discard the first 25 to
30m1 of effluent. Place l0.0m1 of the next effluent into a small white
porcelain dish (100 to 125m1 capacity).
6.4
Add 40m1 of alcohol and 2 drops of thorin indicator. Adjust the pH to 3.8 to
4.0 by dropwise addition of ammonium hydroxide (1+99) until the- solution
just turns pink. Add hydrochloric acid (1+99) dropwise until the pink colour
disappears.
6.5
Prepare a blank using water and reagents described in 6.1 to 6.4 and record the
iodine solution used for the sulphite correction of the blank. Titrate the sample
with barium chloride solution, using the untitrated yellow blank as a colour
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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.
7.0
7.1
Pass 50m1 of the filtered sample directly through the ion exchange column.
Collect l0.0ml of effluent and proceed in accordance with 6.3, 6.4 and 6.5.
8.0
PROCEDURE
IN
INTERFERENCES
8.1
Directly titrate l0.0m1 of the filtered sample in accordance with 6.4 and 6.5.
9.0
CALCULATIONS
THE
PRESENCE
OF
NEGLIGIBLE
[(V1-B1) X 500]
--------------------- V3
Where:
9.2
V1 =
V2 =
B1 =
B2 =
V3 =
V4 =
10.0
PRECISION
10.1
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11.0
INTERFERENCES
11.1
Both cations and anions may cause co-precipitation errors with barium
sulphate precipitate. Most metallic ions also interfere by forming coloured
complexes with the thorin indicator, especially in alcohol water mixtures.
11.2
11.3
11.4
11.5
11.6
11.7
12.0
NOTES
12:1
Reagent grade chemicals should be used for preparing all the reagents.
12.2
12.3
12.4
If the ammonium hydroxide--(step 6.4) is added too fast, it is possible to overrun the colour change from yellow to pink and the sample continues to be
yellow.
It is then impossible to develop the pink colour by addition of
ammonium-hydroxide.
12.5
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LVI)
1.0
SUMMARY OF METHOD
The sample is mixed with hydrochloric acid and potassium iodide and titrated
against potassium iodate solution in presence of starch indicator. The iodine
liberated reacts with sulphite and the endpoint is indicated by the formation of
blue colour.
2.0
RANGE
3mg/litre or more as Na2SO3.
3.0
REAGENTS
3.1
3.2
Hydrochloric Acid Solution (1+3) - Mix one volume of hydrochloric acid (sp
gr 1.19) with three volumes of water.
3.3
3.4
3.5
Starch Indicator - Make a paste of 6g of starch with cold water. Pour the paste
into 1 litre boiling water add 20g of potassium hydroxide, mix, and allow to
stand for 2 hours. Add 6m1 of glacial acetic acid (sp gr 1.05) and mix. Add
hydrochloric acid (sp gr 1.19) to adjust the pH value of the solution to 4.0
(check with the help of pH-paper). This has a shelf life of 1 year.
3:6
4.0
PROCEDURE
4.1
4.1.1
4.1.2
4.1.3
Add 2 to 3m1 of starch indicator solution and titrate with potassium iodate
solution to the first persistent blue colour.
4.1.4
4.1.5
Carry out a blank determination using 100 m1 of water instead of sample and
repeating the steps 4.1.1 to 4.1.3. Record the volume of potassium iodate
solution used as 'V2
4.2
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4.2.1
4.2.2
Add about 0.lg of sulphamic acid and stir until crystals are completely
dissolved and no further gas evolution is noted.
4.2.3
Add 5m1 of hydrochloric acid solution and stir again until no further gas
evolution is noted.
4.2.4
4.2.5
5.0
CALCULATIONS
5.1
(V1-V2) X N X 1000
----------------------------------------V
Where:
5.2
VL
V2 =
N =
V =
5.3
6.0
PRECISION
The precision of this method may be expressed as follows:
SO =
Where:
SO =
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7.0
INTERFERENCES
7.1
Catalysts, such as copper, cause rapid oxidation of the sulphite when the
sample is exposed to air. This reaction is accelerated by an increase in
temperature. EDTA may be added to the sample to complex such metallic
ions.
7.2
Other reducing agents, such as sulphides and ferrous-iron, will react like
sulphite.
7.3
Nitrite, if present, will oxidise sulphite when the sample is acidified. Nitrite,
interference can be eliminated by the addition of sulphamic acid.
8.0
NOTES
8.1
Reagent grade chemicals should be used for preparing all the reagents.
8.2
LVII)
REVIEW
The Head of Corporate Operation Services will be responsible for reviewing
this document on a 2 yearly basis, or as and when required.
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Annexure - I
ATOMIC WEIGHT/ATOMIC NUMBERS OF VARIOUS ELEMENTS
S.NO.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16
17.
18.
19.
20.
21.
22.
23.
24
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
NAME
Actinium
Aluminium
Americium
Antimony
Argon
Arsenic
Astanine
Barium
Berkelium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Caesium
Calcium
Californium
Carbon
Cerium
Chlorine
Chromium
Cobalt
Copper
Curium
Dysprosium
Einsteinium
Erbium
Europium
Fermium
Fluorine
Francium
Gadolinium
Gallium
Germanium
Gold
Hafnium
Helium
Holmium
Hydrogen
Indium
SYMBOL
Ac
Al
Am
Sb
Ar
As
At
Ba
Bk
Be
Bi
B
Br
Cd
Cs
Ca
Cf
C
Ce
Cl
Cr
Co
Cu
Cm
Dy
Es
Er
Eu
Fm
F
Fr
Gd
Ga
Ge
Au
Hf
He
Ho
H
In
ATOMIC
NUMBER
89
13
95
51
18
33
85
56
97
4
83
5
35
48
55
20
98
6
58
17
24
27
29
96
66
99
68
63
100
9
87
64
31
32
79
72
2
67
1
49
NTPC Limited
ATOMIC
WEIGHT
227
26.98154
243.13
121.75
39.948
74.9216
---137.34
--9.0122
208.9808
10.811 0.003
79.904
112.40
132.9054
40.08
---12.01
140.12
35.453
51.996
58.9331
63.546
---162.50
---167.28
151.96
--18.99840
---157.25
69.72
72.59
196.967
178.49
4.0026
164.930
1.00797
114.82
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COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
S.NO.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
NAME
Iodine
Iridium
Iron
Krypton
Lanthanum
Lawrencium
Lead
Lithium
Lutetium
Magnesium
Manganese
Mendeleevium
Mercury
Molybdenum
Neodymium
Neon
Neptunium
Nickel
Niobium
Nitrogen
Nobelium
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Plutonium
Polonium
Potassium
Praseodymium
Promethium
Protoactinium
Radium
Radon
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
SYMBOL
I
Ir
Fe
Kr
La
Lw
Pb
Li
Lu
Mg
Mn
Md
Hg
Mo
Nd
Ne
Np
Ni
Nb
N
No
Os
O
pd
p
Pt
Pu
Po
K
Pr
Pm
Pa
Ra
Rn
Re
Rh
Rb
Ru
Sm
Sc
Se
Si
Ag
ATOMIC
NUMBER
53
77
26
36
57
103
82
3
71
12
25
101
80
42
60
10
93
28
41
7
102
76
8
46
15
78
94
84
19
59
61
91
88
86
75
45
37
44
62
21
34
14
47
NTPC Limited
ATOMIC
WEIGHT
126.9044
192.20
55.847
83.80
138.91
----207.19
6.939
174.97
24.312
54.938
-200.59
95.94
144.24
20.183
237.00
58.71
92.906
14.0067
---190.20
15.9994
106.40
30.97376
195.09
242
210.05
39.09
140.907
---231.10
226.0254
222.00
186.2
102.905
85.47
101.07
150.35
44.956
78.96
28.086
107.868
Page - 152
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
S.NO.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
NAME
Sodium
Strontium
Sulphur
Tantalum
Technetium
Tellurium
Terbium
thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Xenon
Ytterbium
Yttrium
Zinc
Zirconium
SYMBOL
Na
Sr
S
Ta
Tc
Te
Tb
Tl
Th
Tm
Sn
Ti
W
U
V
Xe
Yb
Y
Zn
Zr
ATOMIC
NUMBER
11
38
16
73
43
52
65
81
90
69
50
22
74
92
23
54
70
39
30
40
NTPC Limited
ATOMIC
WEIGHT
22.9898
87.62
32.064
180.948
-----127.60
158.924
204.37
232.038
168.934
118.69
47.90
183.85
238.03
50.942
131.30
173.04
88.905
65.38
91.22
Page - 153
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
ANNEXURE - II
DETERMINATION OF SATURATION INDEX (LANGELIER) AND
STABILITY INDEX (RYZNER) OF COOLING WATER
1.0
SUMMARY OF METHOD
The saturation index and the stability index are calculated from the total
alkalinity, calcium hardness, pH, approximate concentration of total dissolved
solids and the temperature of the water.
2.0
PROCEDURE
2.1
Determine the total alkalinity, calcium hardness, pH, total dissolved solids and
the temperature of the water.
To determine the saturation Index (Langelier Index), obtain the values of
A,B,C and D from table 1 (Section 3.0) and calculate the saturation pH as
follows:
pHs = (9.3 + A+B) - (C+D)
Then, using the actual pH of the water, calculate the index as follows:
Saturation Index (Langelier Index) = pH - pHs
Calculate the stability Index (Ryzner Index) as follows:
Stability Index (Ryzner Index) = 2 pHs - pH
2.2
2.3
TABLE 1
A
0.1
0.2
Temperature
(0C)
0
2
7
10
14
18
22
28
32
38
44
51
57
64
72
82
B
2.6
2.5
2.4
2.3
2.2
2.1
2.0
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
Calcium Hardness
(mg/litre CaCO3)
10
12
14
18
23
28
35
44
56
70
88
11
139
1175
30
280
350
440
560
700
870
1050
NTPC Limited
C
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
Total Alkalinity
(mg/litre CaCO3)
10
12
14
18
23
28
36
45
56
70
88
111
140
177
230
280
360
450
560
700
800
D
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
Page - 154
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
4.0
NOTES
4.1
4.2
4.3
4.4
NTPC Limited
Min.
0.5
6.0
6.0
20
-
Max.
1.5
6.0
8.0
300
2,500
Page - 155
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
ANNEXURE - III
SHELF LIFE AND STORAGE OF REAGENTS AND STANDARDS
REAGENT
SHELF LIFE
CONTAINER
1.
2.
3.
4.
Acetic Acid
Aluminium Chloride
Aluminium Sulphate
Amine Solution
1 Year
1 Year
1 Year
1 week
5.
1 month
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
Glass
Glass
Glass
Amber coloured
bottle.
dark glass bottle.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31
32.
33.
34.
Barium Chloride
Barium Nitrate
Baryta water
Benzene
Bromine water
Cadmium Acetate
Cadmium Sulphate
Calcium Chloride
Ceric Sulphate
Calcium Nitrate
Calcium Sulphate
Carbon Tetrachloride
Chlorine water
2 weeks
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 Year
1 month
1 month
1 year
1 month
a. To be
prepared fresh
b. One week if
stored at 40 C
1 year
1 year
1 month
1 year
1 week
1 year
1 year
1 year
1 month
1 year
1 year
1 year
1 week
NTPC Limited
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Page - 156
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
REAGENT
SHELF LIFE
CONTAINER
1 year
1 year
1 year
1 year
1 month
1month
1 week:
4 month:
1 month:
1 month
1 year
1 month
1 month
Glass
Glass
Glass
Glass
Glass
Glass
Glass
42.
43.
44.
45.
Chromic Acid
Cobalt Chloride
Cobalt Nitrate
Copper Sulphate
Dimethyl Glyoxime Solution
Diphaenyl Amine
diphenyl Carbazide
(3.32g/1)
(2.89g/1)
Diphenyl Thiocarbzone
Disodium Hydrogen phosphate
disodium salt of EDTA
Eriochrome Black T
46.
1 year
47.
48.
49.
Formaldehyde
Hydrazine Sulphate
Hydrochloric Acid (standardization
every month)
Hydrogen peroxide
1 month
1 month
1 year
Freshly
prepared
1 month
1 month
1 month
1 month
1 year
1 month
1 week
1 year
1 year
1 week
1 month
1 year
1 year
1 year
1 month
6 month
1 year
Indefinite
Indefinite
35.
36.
37.
38.
39.
40.
41.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
1 month
NTPC Limited
Glass
Glass
Polyethylene,plastic.
dark coloured
stoppered bottle
Dark Coloured
stoppered bottle.
Glass
Glass
Glass (tightly
closed)
Glass (dark
coloured)
Glass
Glass
Glass
Dark bottle at 40 C
Amber Glass
Dark bottle
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Amber bottle
Glass
Glass
Glass
Glass
Page - 157
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
REAGENT
SHELF LIFE
CONTAINER
1 year
Amber bottle
1 year
1 year
1 year
1 month
1 year
1 year
1 year
1 year
1 year
1 year
1 month
1 year
Glass
Glass
Glass
Dark bottle
glass
glass
glass
glass
glass
glass
Glass
Polyethylene
1 year
Fresh
1 year
1 year
Fresh
1 year
glass
Amber bottle
glass
Glass
Amber Bottle
Sodium chloride
Sodium Hydrogen Carbonate
Sodium Hydroxide (standardize
monthly)
1 year
1 year
1 year
1 month
1 year
1 year
1 year
1 year
1 year
NTPC Limited
Glass
Amber Bottle
Glass
Glass
Glass
Dark coloured Glass
Bottle.
Glass
Glass
polythene Bottle
Page - 158
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
ANNEXURE - IV
STANDARD SPECIFICATIONS FOR REAGNT WATER
1.0
This specification covers requirements for water suitable for use in methods of
chemical analysis. Three grades of reagent water are given below:
1.1
1.2
1.3
2.0
SPECIFICATIONS
S.NO. PARAMETER
1.
Total solids, max, mg/ litre
2.
Electrical conductivity, max, micro
siemens /cm at 250C
3.
pH at 250C
4.
Minimum colour retention time of
potassium permangnate, minutes.
5.
Maximum soluble silica
6.
TYPE I
0.1
0.06
TYPE II
0.1
1.0
TYPE III
0.1
1.0
*
60
*
60
6.2 to 7.5
10
not
detectable
not
10 micro
detectable gm/ ltr.
Microbiological classification **
Maximum total
bacteria count
Type A
TypeB
Type C
0/ml
10/ml
100/ml
3.0
3.1
3.2
water
. Ion
initial
single
Page - 159
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
3.3
Type III grade of reagent water shall be prepared by distillation, ion exchange,
reverse osmosis, or a combination thereof, followed by polishing with a 0.45
micron membrane filter.
4.0
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
5.2
5.3
5.4
5.5
NTPC Limited
Page - 160
COS-ISO-00-OIN/OPS/CHEM/017
Rev. No.: 0
Manual on Analytical Test Procedure for Water and Steam in Power Plants
ANNEXURE - V
CONVERSON FACIOR OF FREQUENTLY USED CHEMICALS TO CaCO3
EQUIVALENT
S.NO.
SUBSTANCE
FORMULA
ATOMIC/MOLEC
ULAR WEIGHT
EQUIVALENT
WEIGHT
SUBSTENCE
TO CaCo3
Equivalent
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
Calcium
Carbondioxide
Chloride
Fluorine
Hydrogen
Hydroxide
Magnesium
Nitrate
Oxygen
Phosphate
Silica
Sulphate
Sulphite
Ca
CO2
Cl
F
H
OH
Mg
NO3
O
PO4
SiO2
SO4
SO3
40.1
44.0
35.5
19.0
1.01
17.0
24.3
126.9
16.0
95.0
60.1
96.1
80.1
20.0
44.0
35.5
19.0
1.01
17.0
12.2
126.9
8.0
31.7
30.0
48.0
40.0
2.50
1.14
1.41
2.63
50
2.94
4.10
0.39
6.25
1.58
0.83
1.04
1.25
NTPC Limited
UNCONTROLLED
II Regional Head Quarters
21. Executive Director (NR), Lucknow
22. Executive Director (SR), Hyderabad
23. Executive Director (WR), Mumbai
24. Executive Director (ER), Patna
25. Executive Director (NCR), Noida
Rihand
Vindhyachal
Kahalgaon
Farakka
Dadri (Coal & Gas)
Unchahar
Korba
Ramagundam
Badarpur
Talcher Kaniha
Kayamkulam
Kawas
Simhadri
Singrauli
Tanda
Talcher Thermal
Auraiya
Jhanor Gandhar
Faridabad
Anta
IV Head of O&M
37. Singrauli
41. Vindhyachal
45. Unchahar
49. Simhadri
53. Jhanor Gandhar
57. Tanda
38. Korba
42. Rihand
46. Talcher Kaniha
50. Auraiya
54. Dadri (Gas)
39. Ramagundam
43. Kahalgaon
47.Talcher Thermal
51. Anta
55. Kayamkulam
40. Farakka
44. Dadri(Coal)
48. Badarpur
52. Kawas
56. Faridabad
60. Ramagundam
64. Kahalgaon
68.Talcher Thermal
72. Anta
76. Kayamkulam
61. Farakka
65. Dadri(Coal)
69. Badarpur
73. Kawas
77. Faridabad
Head of Chemistry
58. Singrauli
62. Vindhyachal
66. Unchahar
70. Simhadri
74. Jhanor Gandhar
78. Tanda
59. Korba
63. Rihand
67. Talcher Kaniha
71. Auraiya
75. Dadri (Gas)