Beruflich Dokumente
Kultur Dokumente
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.
APPARATUS 1. Multiple Stirrers – with continuous speed variation from about 20 to 150
rpm. The stirring paddles should be of light gauge, corrosion resistant
material, all of the same configuration and size. An illuminated base to
observe the floc formation.
2. Beakers – glass beakers, 1000 to 1500 ml capacity.
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.
PROCEDURE 1. Place equal volumes (1000 ml) of sample into each beaker (1500 ml
capacity) and record the temperature of the sample.
2. Start the multiple stirrer at flash mix speed (approximately 120 rpm) for
all beakers. Add the test solutions or suspensions at predetermined
dosage levels and sequences. Flash mix for approximately 1 minute
after the addition of chemicals. Record the flash mix time and mixer
speed (rpm).
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. 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.
5. After 15 minutes of settling, record the sample temperature and by
means of a pipet, withdraw supernatent liquor for conducting colour,
turbidity, pH, non-reactive and/or colloidal silica and other required
analysis.
1
NOTES 1. All polyelectrolytes are classified as anionic, cationic, or neutral,
depending upon their composition. A small dosage, under 1 ppm, may
permit a reduction in the dosage or complete elimination of the
coagulant.
2. It is recognized that reproducibility of results is important. To
demonstrate reproducibility, the so-called 3 and 3 procedure is
suggested. In this procedure, duplicate sets of 3 breakers each, are
treated simultaneously with the same chemical dosages in beakers 1 &
4, 2 & 5 and 3 & 6.
3. A suggested format for recording the results is given below:
STATION - DATE -
LOCATION -
SAMPLE -
pH -
TURBIDITY -
COLOUR -
TEMPERATURE -
SAMPLE SIZE (ml) -
2
Beaker No.
S. No.
1 2 3 4 5 6
1. Chemicals, * mg/litre
a.
b.
c.
6. Temperature, oC.
9. Settling rate
a. Turbidity
b. pH
c. Colour
d. Non-reactive/collidal Silica
3
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 1mg
platinum/litre in the form of the chloroplatinate ion.
4
CONDUCTIVITY
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. Measurement of Conductivity
2.1 Conductivity Below 10 microsiemens/cm.
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 oC as
possible. Read the temperature to the nearest 0.5 oC.
2.1.2 If the conductivity meter is provided with a manual temperature
compensator, adjust this to the sample temperature value.
2.1.3 If an automatic temperature compensator is provided, no adjustment is
necessary but sufficient time must be allowed to permit equalization of
temperature.
2.1.4 Read the conductivity.
2.1.5 If the instrument has no means of temperature compensation, determine
a temperature correction to convert readings to 25oC (see notes).
2.2 Conductivity Above 10 microsiemens/cm.
2.2.1 Either a flow-type, dip-type, or piped-type cell may be used. If a flow-
type cell is used, proceed in accordance with 4.2.1.
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 0.5oC) on successive
portions of the sample until a constant value is obtained.
5
2.2.3 Proceed in accordance with 4.2.1.2, 4.2.1.3 and 4.2.1.5.
PRECISION 1. Results obtained should not differ by more than 1% of the conductivity.
6
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.
Apparatus 1. Laboratory pH meter together with its associated glass and reference
electrodes.
CALCULATIONS 1. Most pH meters are calibrated in pH units and the pH of the sample is
obtained directly by reading the meter scale.
2. Report the temperature of measurement to the nearest 1oC.
3. Report the pH of the test solution to the nearest 0.01pH units when the
pH measurement lies between 1.0 and 12.0.
4. Report the pH of the test solution to the nearest 0.1 pH units when the
pH measurement is less than 1.0 and greater than 12.0.
7
INTERFERENCES 1. The true pH of an aqueous solution is affected by the temperature,
which can be compensated automatically in many instruments or can be
manually compensated in most other instruments. The temperature
compensation corrects for the effect of the water temperature on the
instrument, including the electrodes, but does not correct for
temperature effects on the chemical system being monitored. It does not
adjust the measured pH to a common temperature; therefore, the
temperature should be reported for each pH measurement.
2. The glass electrode reliably measures pH is nearly all aqueous solutions
and in general, is not subject to solution interference from colour,
turbidity, colloidal matter, oxidants or reductants.
3. The pH response of most glass electrodes is imperfect at both ends of
the pH scale. The indicated pH value of highly alkaline solutions will be
too low. This is minimized by the selection of proper glass electrode.
4. The indicated pH value of strong aqueous solutions of salts and strong
acids having a pH less than 1, will often be higher than the true pH
value. This is termed the negative error and the pH indicated is
somewhat greater than the true pH.
5. The pH response of the glass electrode may be impaired by a few
coating substances such as oily materials and particulates. The
electrodes can be restored to normal by an appropriate cleaning
procedure recommended by the manufacturer.
NOTES 1. The pH is the negative logarithm to the base ten of the conventional
hydrogen ion activity.
It is derived from the electromotive force (emf) of the cell,
reference electrode solution glass electrode
(E – Er) F
pH = pHr = --------------
2.3026 RT
Where:
pHr = pH of the reference buffer.
E = emf obtained when the electrodes are immersed in the sample.
Er = emf obtained when the electrodes are immersed in a reference
buffer solution.
F = Faraday constant = 96485.3415 sA/mol or 96500 C mol-1
R = Gas constant = 8.314 (J)(K-1)(mol-1)
T = absolute temperature.
2. New glass electrodes and those which have been stored dry, shall be
conditioned and maintained as recommended by the manufacturer. If 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 caped to decrease evaporation. Glass
electrodes should be stored as recommended by the manufacturer and
reference electrodes in saturated potassium chloride solution.
3. Both the saturated Calomel electrode and silver-silver chlorine 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.
4. Where emulsions of free oil and water are to be measured for pH, it is
necessary to clean the glass electrodes thoroughly after each
measurement. The cleaning is done by washing with soap or detergent
and water, followed by several rinse with water, after which, the lower
third of the electrode is immersed in hydrochloric acid (1+9) and finally
washed thoroughly with water.
8
5. If the sample contains sticky soaps or suspended particles, the cleaning
is done with a suitable solvent or by chemical treatment, to dissolve the
deposited coating. After cleaning with solvent the lower third is
immersed in hydrochloric acid (1+9) followed by thorough washing with
water.
6. If glass electrode has failed to respond the treatment as described in
8.4, it is immersed in chromic acid cleaning solution for several minutes.
This drastic treatment, limits the life of electrode and is used only as an
alternative to discarding it. After chromic acid treatment, the electrode is
allowed to stand in water overnight.
7. If the electrode fails to respond to chromic acid cleaning, it is immersed
in a 20% solution of ammonium bifluoride (NH 4HF2) for about 1-minute.
This treatment removes a portion of the bulb glass and should be used
only as a last resort. After the fluoride treatment the electrode is
thoroughly rinsed with water and conditioned, as is recommended for a
new glass electrode.
9
TURBIDITY(Nephelometric)
SUMMARY OF METHOD 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.
PROCEDURE 1. Calibrate the Nephelometer with standard turbidity suspension for each
range, in accordance with the manufacturer’s instructions.
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.
10
SUSPENDED AND TOTAL DISSOLVED SOLIDS
(25 mg/litre or Less of Total Solids)
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.
11
W1 = grams of total solids.
W2 = grams of suspended solids.
W3 = grams of dissolved solids.
V = litres of sample used.
12
SUSPENDED AND TOTAL DISSOLVED SOLIDS
(More than 25 mg/litre of Total Solids)
13
V = litres of sample used.
NOTES 1. Some evaporation residues readily absorb moisture, therefore rapid
weighing should be done.
2. Suspended solids are defined as those solids, exclusive of gases and in
non-liquid state, which are dispersed in water to give a heterogeneous
mixture. Dissolved solids (exclusive of gases) are dispersed in water to
give a homogenous liquid and total solids is the sum of suspended and
dissolved solids.
14
ALKALINITY
(Titration Method, 10 to 500 mg/litre)
SUMMARY OF METHOD The sample is titrated with acid solution to a designated pH and the end
point is determined using internal indicator.
CALCULATIONS
A x N x 50,000
1. Phenolphthalein Alkalinity, mg/litre as CaCO3 = ---------------------
V
B x N x 50,000
2. M-Alkalinity (Total Alkalinity), mg/litre as CaCO3 = ----------------------
V
Where:
A= millilitres of standard hydrochloric acid to reach the
phenolphthalein end point
B= total milliliters of standard hydrochloric acid to reach the mixed
indictor or methyl orange end point.
N= normality of hydrochloric acid.
V= milliliters of sample.
3. Alkalinity Relationship.
15
The following table gives the stoichiometric classification of the three
principal forms of alkalinity present in water.
Where:
P = Phenolphthalein Alkalinity.
M = M-Alkalinity (or total alkalinity).
INTERFERENCES 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.
2. Natural colour or the formation of a precipitate during titration may mask
the colour change.
3. Salts of weak organic and inorganic acids also affect the titration.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
16
ALKALINITY DUE TO HYDROXIDE
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.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. To standardize 0.02 N hydrochloric acid, weigh accurately 0.088 ± 0.001
g of sodium carbonate (previously dried in a platinum crucible at 250 oC
for 4 hours) and transfer to a 500 ml conical flask. Add 50 ml of water to
dissolve the carbonate the add 2 drops 0.1% solution of methyl red in
alcohol. Titrate with hydrochloric acid to the first appearance of a red
colour, and boil the solution carefully until the colour is discharged. Cool
to room temperature and continue the titration. Repeat the process of
boiling and titration until a faint red colour is obtained that is not
discharged on further heating.
17
AMMONIA
(Indophenol Method, 10 to 500 micrograms/litre)
SUMMARY OF The sample is reacted with hypochlorite and phenol in the presence
METHOD of a manganous salt to produce an intense blue compound, the
intensity of which is measured spectrophotometrically at a wavelength of
630 nm.
CALIBRATION 1. Transfer 0.0, 1.0, 5.0, 10.0, 15.0 and 20.0 ml of the standard ammonia
nitrogen solution (1ml = 0.5 microgram N) to 25ml of volumetric flasks.
2. Add 0.05 ml of manganous sulphate solution and mix.
3. Add 0.5 ml of hypochlorous acid solution and add immediately but slowly
0.6 ml of the phenate solution. Dilute to 25ml with water.
4. Measure the absorbance of each standard at 630nm against the zero
standard (blank).
5. Prepare a calibration curve by plotting absorbance versus micrograms of
ammonia nitrogen.
PROCEDURE 1. Place 10 ml (or other suitable volume containing not
more than 10 micrograms ammonia nitrogen) of the sample in a 25 ml
volumetric flask.
2. Proceed in accordance with section 5.0 (5.2 to 5.4).
INTERFERENCES 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.
18
AMMONIA
(Nessler’s Method 0.1 to 2 mg/litre)
SUMMARY OF METHOD The same is reacted with Nessler’s reagent (K2HgI4) to produce a
reddish brown colloidal compound, the intensity of which is measured
spectrophotometrically at a wavelength of 425 nm.
INTERFERENCES 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.
2. Residual chlorine must be removed prior to ammonia determination with
sodium arsenite (NaAsO2) solution (lg/litre). One millilitre of this solution
will remove 1mg/litre of residual chlorine from the 500 ml sample.
3. Turbidity in the sample can be removed as follows:
Add 1 ml of Zinc sulphate solution to 100 ml sample and mix. Add
sodium hydroxide solution to raise the pH to about 10.5 (check with a pH
paper). Allow to settle and filter through whatman No. 40 filter paper. To
prevent cloudiness add 2 drops of sodium potassium tartrate solution or
disodium dihydrogen ethylenediamine tetraacetate.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. The Nessler reagent should give the characteristic colour with ammonia
within 10 minutes after addition, and should not produce a precipitate
with small amounts of ammonia (0.04 mg in 50 ml volume). The solution
may be used without 5 day storage if it is filtered through a 0.45 –
micron membrane filter shortly before use.
19
CARBON DIOXIDE
(Bicarbonate Titration Method)
SUMMARY OF METHOD Carbon dioxide concentration is determined from measured values of pH
and bicarbonate ion.
APPARATUS 1. pH meter.
CALCULATIONS 1. Calculate the bicarbonate ion concentration using the following equation:
2440 x (V2 – V1)
Bicarbonate (HCO3), mg/litre = ----------------------
V
Where:
V= volume of sample is millilitres.
V1 = millilitres of hydrochloric acid required for titration to pH 8.3.
V2 = millilitres of hydrochloric acid required for titrating from pH 8.3 to
4.5
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.
3. Calculate free CO2 concentration in mg/litre as CaCO3 as follows:
Free CO2, mg/litre as CaCO3 = A x 1.14
Where:
A = concentration of CO2, mg/litre as CO2.
20
CARBON DIOXIDE
(Direct Titration of Free Carbon Dioxide)
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.
APPARATUS 1. pH meter.
CALCULATIONS 1. Calculate the free carbon dioxide content of the water in mg/litre using
the following equation:
Free CO2, mg/litre as CO2 = V x N x 440
Where:
V= millilitres of sodium hydroxide required to titrate 100 ml of
sample
N= normality of sodium hydroxide solution.
2. Calculate free CO2 concentration in mg/litre as CaCO3 as follows:
Free CO2, mg/litre as CaCO3 = A x 1.14
Where:
A = concentration of CO2, mg/litre as CO2.
21
CHLORIDE
(Mercuric Thiocyanate Method, 0.05 to 1.4 mg/litre)
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 463 nm.
CALIBRATION 1. Prepare a series of standards by diluting 0, 0.5, 2.5, 5.0, 7.5, 10 and 14
ml of the standard sodium chloride solution (1 ml = 0.01 mg chloride) to
100 ml with water in volumetric flasks.
2. Proceed in accordance with section 6.0.
3. Prepare a calibration curve by plotting absorbance versus the
concentration of chloride in mg/litre.
CALCULATIONS 1. Read the concentration of chloride ion in mg/litre directly from the
calibration curve prepared in accordance with section 5.0.
2. Calculate the chloride concentration in mg/litre as CaCO 3 as follows:
Chloride, mg/litre as CaCO3 – A x 1.41
Where:
A = chloride concentration, mg/litre as Cl.
22
NOTES 1. Reagent grade chemicals should be used for preparing all the reagents.
2. Mercuric salts are very poisonous. Due precautions should be observed
when using these salts.
3. In the preparation of mercuric thiocyanate solution, a slight precipitate
may form and settle out after 24 hours. Only the clear, supernatent liquid
must be used.
4. Soak all new glassware in hot nitric acid (1+19) for several hours and in
water (halide free) between tests. Discard all glassware that appear
etched or scratched.
5. For best results, the temperatures of the standard solutions should be
within 1.0oC of the reagent blank, and the samples.
23
CHLORIDE
(Mercuric Thiocyanate Method, Modified, 2 to 100 micrograms/litre)
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
coprecipitates the Chloride in the sample. The sample is centrifuged and
the supernatent liquid discarded. The precipitate is dissolved in a ferric
iron-mercuric thiocyanate reaction medium and the Chloride is
determined Spectrophotometrically at 463 nm.
CALIBRATION 1. Prepare a series of standards by diluting 0, 1.0, 5.0, 10.0, 15.0, and 25.0
ml of Standard Sodium Chloride Solution (1ml = 1 microgram of
chloride) to 250 ml in 250 ml glass stoppered bottles.
2. Proceed in accordance with Section 6.0 (6.2 to 6.7).
3. Prepare a calibration curve by plotting absorbance versus concentration
of Chloride in mg/litre.
Where:
24
A = chloride concentration, micrograms/litre as Cl.
INTERFERENCES 1. See mercuric thiocyanate method (Section 9.0) for the determination of
Chloride.
NOTES 1. See mercuric thiocyanate method (Section 10.0) for the determination of
Chloride.
2. Lead nitrate is very toxic. Due precautions should be observed when
using this chemical.
3. 2 microgram/litre chloride represents 0.006 absorbance with respect to a
reagent blank when using 50 mm matched cells.
25
CHLORIDE
(Silver Nitrate Method, 5 mg/litre or more)
SUMMARY OF METHOD The sample is adjusted to a pH of 8.3 and titrated with silver nitrate
solution using potassium chromate indicator to a brick red colour.
CALCULATIONS 1. Calculate the chloride ion concentration in the sample, in milligrams per
litre, as follows:
(V1 – V2) x N x 71000
Chloride, mg/litre as Cl = ------------------------------
V
Where:
V1 = millilitres of standard silver nitrate solution for the sample (4.1).
V2 = millilitres of standard silver nitrate solution for the sample (4.6).
N = normality of standard silver nitrate solution.
V = millilitres of sample (4.1).
2. Calculate the chloride concentration in mg/litre as CaCO 3 as follows:
Chloride, mg/litre as CaCO3 = A x 1.41
Where:
A = Chloride concentration, mg/litre as Cl.
26
3. Sulphite and objectionable colour or turbidity must be eliminated.
4. Compounds which precipitate at pH 8.3 may interfere.
NOTES 1. Reagent grade chemicals should be used for preparing all the reagents.
2. If the titration required more than 25ml of silver nitrate in 4.5, use a
smaller sample size.
27
CHLORINE DEMAND
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.
APPARATUS 1. pH meter.
28
CALCULATIONS Calculate the chlorine dosage, in mg/litre, for each increment of
chlorinating solution as follows:
Chlorine dosage, mg/litre = 2AB
Where:
A = millilitres of chlorinating solution added to 500 ml of sample.
B = milligrams of available chlorine per millilitre of the chlorinating
solution.
Determine the chlorine consumed, mg/litre, for each increment of
chlorine application as follows:
On log-log graph paper, plot, for a given chlorine application,
temperature, and pH, the chlorine consumed versus the contact time in
hours. Determine the value of the chlorine consumed at the intercept of
the line with the co-ordinate corresponding to a contact time of 1 hour.
Designate the value of this intercept as K. Determine the slop of the line
and designate as n. The straight lines for each chlorine application at
each temperature and pH are of the general form:
DT = KTtn
Where:
DT = Chlorine consumed at a given temperature .
t = contact time in hours.
KT = Chlorine consumed after 1 hour, mg/litre at a given temperature.
n = Slope of curve.
The chlorine consumed can be interpolated between test values by use
of the above expression.
29
CHLORINE, RESIDUAL
(DPD Method, 0.02 to 4.0 mg/litre)
SUMMARY OF METHOD In the absence of iodide ion, free chlorine reacts with para-amino
diethylaniline (NN-Diethyl-p-Phenylene Diamine abbreviated as DPD) to
produce a red colour. Stepwise colour change is carried out to identify
monochloramine, dichloramine, and nitrogen trichloride. The individual
fractions are determined by titration with ferrous ammonium sulphate.
30
4.1 Place a small crystal of potassium iodide in a 250 ml titration flask, add
100 ml of sample and mix.
4.2 Transfer the contents (4.4.1) to another flask containing 5 ml each of
buffer solution and DPD solution.
4.3 Titrate rapidly with ferrous ammonium sulphate solution.
4.4 Record the volume of ferrous ammonium sulphate in ml as D.
5. Total Available Chlorine
5.1 Place 1 g of potassium iodide in a 250 ml titration flask, add 100ml of
sample and mix.
5.2 Transfer the contents (4.5.1) to another flask containing 5 ml each of
buffer solution and DPD solution and allow to stand for 2 minutes.
5.3 Titrate with ferrous ammonium sulphate solution and record the volume
in ml as V1.
CALCULATIONS
V1 x 100
1. Total available chlorine, mg/litre as Cl = -------------
V
Where:
V1 = millilitres of ferrous ammonium sulphate used for total available
chlorine.
V = millilitres of sample.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. For preparing chlorine demand free water, approximately 20 mg/litre of
available chlorine to III reagent grade water. Allow the chlorinated to
stand about 1 week in the absence of sunlight no residual chlorine
remains.
3. For standardizing ferrous ammonium sulphate (1 litre), place 25 ml of
0.003 N potassium dichromate 500 ml titration flask and dilute to about
250 ml and 20 ml of sulphuric acid (sp gr 1.84) and allow solution to
31
cool. Titrate with ferrous ammonia sulphate, using phenanthroline-
ferrous sulphate indicator.
Calculate the strength of ferrous ammonium sulphate solution as
follows:
Strength of ferrous ammonium sulphate solution g/litre
V1 x N1 x 392
= -------------------
V
Where:
V1 = millilitres of potassium dichromate solution
N1 = normality of potassium dichromate solution
V = millilitres of ferrous ammonium sulphate soluion.
32
COPPER
(Neocuproine Method, 2 to 1000 micrograms/litre Cu)
SUMMARY OF METHOD The copper is reduced with hydroxylamine-hydrochloride. The pH of the
aqueous phase is adjusted to 4.0-6.0 with sodium acetate buffer. The
cuprous ion is then reacted with neocuproine (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 457 nm and at 454 nm when extracted with
isoamyl alcohol.
CALIBRATION 1. Prepare a series of standards (at least five concentrations) to cover the
expected range of copper concentrations by diluting appropriate
volumes of copper standard solution (4.3, 1 ml = 2 micrograms Cu) as
follows:
1.1 Place the required volumes of copper standard solution (4.3) in 250 ml
separatory funnels.
1.2 Add 0.4 ml hydrochloric acid (sp gr 1.19) to each funnel and add water
to make 200 ml.
1.3 Prepare a blank (zero standard) by diluting 0.4 ml hydrochloric acid (sp
gr 1.19) to 200 ml with water.
1.4 Proceed in accordance with section 6.0 (6.2 to 6.7) and measure the
absorbance of each individual standard.
1.5 Use the organic liquid from the bland as a reference solution for the
initial spectrophotometer setting.
1.6 Prepare a calibration curve by plotting the absorbance of the standards
against the copper content in micrograms.
33
PROCEDURE 1. Transfer 200 ml of acidified (with 0.4 ml hydrochloric acid, sp gr 1.19)
and unfiltered sample (for total copper) or 200 ml of filtered (through
0.45 micron filter) and acidified sample (for dissolved copper) into a 250
ml separatory funnel.
2. Add 1 ml of hydroxylamine hydrochloride solution and mix.
3. Add 10 ml of sodium acetate solution and mix.
4. Add 2 to 4 ml of neocuproine solution and shake the funnel and contents
for 1 minute.
5. Add 25 ml of chloroform solvent or isoamyl alcohol, shake vigorously for
at least 1 minute and allow to stand for 5 minutes.
6. Transfer the organic layer into a dry 50 ml Erlenmeyer flask and add 10
ml of isopropyl alcohol to clear the solution. Make upto 35 ml with
chloroform solvent or isoamyl alcohol depending on the extractant used.
7. Measure the absorbance of the organic solution (6.6) at 457 nm (when
chloroform solvent is the extractant) using a mixture of 25 ml of
chloroform solvent and 10 ml of isopropyl alcohol as a reference solution
for initial spectrophotometer setting or at 454 nm (when isoamyl alcohol
is the extractant) using a mixture of 25 ml of isoamyl alcohol and 10 ml
of isopropyl alcohol as a reference solution.
8. Carry out a blank determination on 200 ml of water with all reagents and
extracting in the same manner as for the sample.
INTERFERENCES 1. None of the ions commonly found in low solids water interfere with the
test.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. A polythene bottle must be used for sample collection. Hydrochloric acid
(sp gr 1.19) should be added to the filtered sample for total recoverable
copper immediately at the time of collection. The volume of acid should
be sufficient to neutralize the sample to pH 4 (using narrow range pH
paper) and then add 2.0 ml for each litre of sample.
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.
4. If the sample contains more than maximum concentration of copper
specified in the range, a smaller size sample should be diluted to 200 ml
with copper free water containing 0.4 ml of hydrochloric acid (sp gr 1.19)
per 200 ml of solution.
34
5. Normally, 2 ml of neocuproine solution is sufficient in a test. 4 ml of the
reagent should be used when the sample contains more than 100
micrograms of copper or when it is high in heavy metal ions.
6. The blank determination made for calibration in section 5.0
compensates for copper in both the reagents and 200 ml 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 ml
aliquots of copper free water. In aliquot the normal values of reagents in
hydrochloric acid, hydroxylamine hydrochloride, sodium acetate and
neocuproine solution are used and in the other aliquot twice the normal
values of reagents are used. The organic extract from the normal blank
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.
35
HARDNESS – TOTAL, CALCIUM AND MAGNESIUM
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 Erichrome 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.
CALCULATIONS
V1 x M x 10,000
1. Total hardness, mg/litre as CaCO3 = -----------------------
V
V2 x M x 10,000
36
2. Calcium hardness, mg.litre as CaCO3 = -----------------------
V
3. Magnesium hardness, mg/litre as CaCO 3 = Total hardness, mg/litre as
CaCO3 minus calcium hardness, mg/litre as CaCO3.
Where:
V1 = millilitres of standard EDTA solution required for magnesium
plus calcium (4.1.5) minus the blank determination (4.1.6).
V2 = millilitres of standard EDTA solution required for calcium (4.2.4)
minus the blank determination (4.2.5).
V = millilitres of sample taken.
M = molarity of standard EDTA solution.
PRECISION 1. The precision of this method for calcium (13 to 88 mg/ litre as Ca) may
be expressed as follows:
Sr = 0.006 X + 0.62
So = 0.006 X + 0.51
Where:
Sr = overall precision.
So = single operator precision.
X = determined concentration of calcium, mg/litre as Ca.
2. The precision of this method for magnesium (2.5 to 36 mg/litre, as Mg)
may be expressed as follows:
ST = 0.017 X + 0.85
SO = 0.002 X + 0.70
Where:
ST = overall precision.
SO = single operator precision.
X = determined concentration of magnesium, mg/litre as Mg.
INTERFERENCES 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 5 mg/litre Fe, 10 mg/litre Mn, 10 mg/litre Cu,
10 mg/litre Zn and 10 mg/litre Pb can be tolerated when hydroxylamine
and cyanide are added.
2. In the titration of total hardness the higher oxidation states of
manganese above 2 reacts rapidly with the indicator to form discoloured
oxidation products. Hydroxylamine hydrochloride reagent is used to
reduce manganese to divalent state. The divalent manganese
interference can be eliminated by addition of one or two small crystals of
potassium ferrocyanide.
3. In the presence of aluminium concentrations in excess of 10 mg/litre, the
blue colour which indicates that the end point has been reached will
appear and then on short standing will revert to red.
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.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. If total recoverable calcium and magnesium concentration are being
determined, acidify the sample with nitric acid (sp gr 1.42) to a pH of 2 or
less (check with the help of narrow range pH paper) immediately at the
time of collection; normally about 2 ml/litre is required.
3. If dissolved calcium and magnesium concentrations are being
determined, filter the samples through a 0.45 micron membrane filter
and acidify the filtrate with nitric acid (sp gr 1.42), 2 ml/litre.
4. The upper and lower limits of concentration given in range (3.0) may be
extended either by dilution or use of micro apparatus.
37
5. The titration of the sample with EDTA should be completed within 5
minutes of the buffer addition. If more than 15 ml titrant is required, take
a smaller sample aliquot and repeat the test.
6. Fluorescein methylene iminodiacetic acid indicator can be used in place
of ammonium purpurate used in the titration of calcium. The end point
will be indicated by a colour change from deep green to purple.
This indicator is prepared by grinding 0.2g of fluorescein methylene
iminodiacetic acid and 0.12g of thymol-phthalein with 20 g of potassium
chloride to 300 to 425 micron size.
38
HYDRAZINE
(p-Dimethylamino Benaldehyde Method, 4 to 100 micrograms/litre).
SUMMARY OF METHOD The sample is reacted with a solution of para-dimethyl
aminobenzaldehyde to produce a yellow colour. The intensity of the
colour is measured colorimetrically at a wavelength of 458 nm.
PROCEDURE 1. Place 5.0 ml of hydrochloric acid (1+9) into a 100 ml measuring flask.
Collect that sample upto the mark.
2. Transfer the sample, to the cylinder that will contain approximately 0.20
to 5.0 micrograms of hydrazine and make the final volume to 50 ml with
water.
3. Add 10.0 ml of p-dimethylaminobenzaldehyde solution, mix and allow to
stand for 10 minutes.
4. Measure the transmittance of the solution of 458 nm by adjusting the
spectrophotometer at 100% transmittance with the blank, prepared by
adding 10.0 ml of p-dimethylaminobenzaldehyde to 50 ml of water.
CALCULATIONS 1. Calculate the hydrazine concentration in micrograms per litre as follows:
W x 1000
2. Hydrazine, micrograms/litre = --------------
V
Where:
W= micrograms of hydrazine found in accordance with section 6.0.
V = millilitres of sample.
PRECISION The precision of this method may be expressed as follows:
SO = (0.99 X + 0.041) / V
St = (1.08 X + 0.081) / V
Where:
SO = single operator precision expressed in mg/litre of hydrazine.
St = overall precision expressed in mg/litre. of hydrazine.
X = concentration of hydrazine determined in mg/litre.
39
V = millilitres of sample taken for test.
INTERFERENCES 1. The hydrazine content may be diminished by oxidizing agents collected
with the sample or absorbed by it prior to testing.
2. Colours, that absorb in the prescribed wavelength, also, interfere.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. The purity of hydrazine dihydrochloride may be checked by iodimetric
methods.
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.
4. The sample should be analyzed as quickly as possible after collection
since hydrazine undergoes auto-oxidation, as well as, oxidation by
oxidizing agents. Such agents may be in the sample or may enter the
sample from the atmosphere. If it is suspected that oxidation of the
hydrazine in the sample is occurring in the interval between collection
and analysis or if the sample is not to be analyzed immediately then the
sample is to be collected under acid by placing 5.0 ml of hydrochloric
acid (1+9) in a 50 ml volumetric flask, and collecting sufficient sample to
make total volume to 50 ml.
When the sample is collected under acid, the step 6.1 of section 6.0
should be deleted and in step 6.2 hydrochloric acid (1+99) to be used,
instead of water for dilution.
40
IRON
(Bathophenanthroline Method, 200 micrograms/litre and less)
SUMMARY OF METHOD Iron is reduced with hydroxylamine hydrochloride and then reacted with
bathophenanthroline (4, 7-diphenyl – 1, 10 phenanthroline). The red
ferrous complex is extracted with n-hexyl or isoamyl alcohol and the
intensity of the colour is measured at 533 nm.
CALIBRATION 1. Prepare a series of standards (at least five concentrations) to cover the
expected range of iron concentrations by diluting appropriate volumes of
Iron standard solution (4.7, 1 ml = 1 microgram Fe) as follows:
1.1 Place the required volumes of Iron standard solution (4.7) in 125 ml
separatory funnels.
1.2 Add water to make 50 ml.
1.3 Add 2.0 ml of hydroxylamine hydrochloride solution and mix.
1.4 Add 3.0 ml of bathophenanthroline solution and shake for 30 seconds.
1.5 Add ammonium hydroxide (1+1) dropwise with mixing until a distinct
turbidity forms. Add hydrochloric acid (1+9) dropwise with mixing until 1
drop clears the solution. Allow to stand for 1 minute.
1.6 Proceed in accordance with section 6.0 (6.5 to 6.8).
1.7 Simultaneously carry out a blank determination containing no added iron
using 50 ml of water and all reagents.
41
alcohol into the previous alcohol extract (6.6). Dilute to the 25 ml mark
with the alcohol used for extraction (6.6).
8. Measure the colour of the alcohol solution at 533 nm, adjusting the
spectrophotometer to zero absorbance reading with a reference solution
of 15 ml of alcohol used in step 6.5 and 10 ml of alcohol used in step
6.7.
9. Carry out a blank determination on 50 ml of water, with all reagents and
extracting in the same manner as for the sample.
CALCULATIONS 1. Calculate the concentration of iron in micrograms per litre in the sample
as follows:
W x 1000
Iron, micrograms/litre = -------------
V
Where:
W= micrograms of iron, read from the calibration curve.
V = millilitres of original sample used.
PRECISION 1. The single operator and overall precision varies with the determined
concentration and may be expressed as follows:
SO = 0.008 X + 0.92
St = 0.039 X + 1.47
Where:
SO = single operator precision, micrograms/litre.
St = overall precision, micrograms/litre.
X = determined concentration micrograms/litre.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. If either dissolved or ferrous iron is to be determined, the sample must
be analyzed as soon as possible after collection. If only total iron is to be
determined, the sample should be immediately acidified with 2 ml of
hydrochloric acid (sp gr 1.19) per 50 ml.
3. Soak all new glassware is 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.
4. If iron content is high in hydrochloric acid (4.5) causing a high blank,
distil in an all glass apparatus, rejecting the first 50 ml and the last
100 ml of distillate.
5. Hydroxylamine hydrochloride solution (4.6) can be purified as follows:
Adjust pH to 3.5 using a pH meter by dropwise addition of ammonium
hydroxide (1+1) and hydrochloric acid (1+9). Transfer to a separatory
funnel, add 6.0 ml of bathophenanthroline solution and shake. Allow to
stand for 1 minute. Add 20 ml of n-hexyl or isoamyl alcohol and shake
for 1 minute. Allow to stand for 15 minutes. Remove the aqueous layer
and discard alcoholic layer. Repeat extraction by again adding 3 ml of
bathophenanthroline solution and 20 ml of alcohol. Discard the alcohol.
If no further extractions are indicated make an extraction with alcohol
alone and allow to stand for a long time to remove all of the alcohol
layer. Discard the alcohol layer.
6. For total iron determination, heat the sample for 1 hour at 60 oC with
4 ml of hydrochloric acid (1+1) and 2 ml of hydroxylamine hydrochloride
solution. Thioglycolic acid can also be used for solubilising unreactive
iron.
42
ORGANIC MATTER
(Potassium Permanganate Consumption Method)
SUMMARY OF METHOD The sample is reached with a standard solution of potassium
permanganate at 27oC for 4 hours and the residual permanganate is
determined iodometrically.
PROCEDURE 1. Place 100 ml of the sample into a clean, glass stoppered bottle of 250
ml capacity and place in a thermostat at 27oC.
2. When the temperature of the sample becomes 27 oC, add 4ml of
Sulphuric acid (1+3) and 10ml of potassium permanganate solution
(N/80). Mix well and allow to stand for 4 hours at 27 oC protected from
sunlight.
3. Add few crystals of potassium iodide (0.2-0.3g) and titrate the librated
iodine with standard sodium thiosulphate solution (N/80) using starch
indicator.
4. Run a blank of 100ml of water under the same conditions.
43
OXYGEN, DISSOLVED
(Indigo Carmine Method, less than 60 micrograms/litre)
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 the
sample is compared with colour standards representing different
concentrations of dissolved oxygen.
44
2. Place the amounts of stock solutions listed above in 300 ml borosilicate
glass stoppered reagent bottles. Add 3.0 ml of hydrochloric acid (sp gr
1.19) to each. Dilute to neck of the bottle with water. Stopper and mix by
inversion. Store in a dark place.
PROCEDURE 1. Place a clean sampling vessel in the sampling bucket and collect the
sample under water. Allow the sample to overflow for several minutes.
2. Fix a burette such that its tip dips into the overflowing sample to a depth
of 10 to 15 mm.
3. Fill the burrette with indigo carmine-potassium hydroxide reagent. Drain
about 1ml of reagent into the overflowing sample, and allow the sample
to flush for 1 minute.
4. Remove the sample tubing from the sampling vessel.
5. Quickly introduce 0.8ml of the reagent if 60 ml tube is used or 4ml of
reagent if a BOD bottle is used, stopper the vessel and mix by inversion.
6. Place the vessel on a white surface and match its colour with the
standard by viewing at a 45 o angle using a ‘Cool’ white fluorescent lamp
for illumination.
NOTES 1. Reagent grade chemicals should be used for preparing the reagents.
2. All colour stock solutions should be stock in coloured bottles to prevent
fading.
3. Indigo carmine solution (4.2.6) is stable for 30 days if stored in a
refrigerator.
4. In the procedure (6.1), the sample flow should be between 500 to 1000
ml/minute when using 300 ml bottle, or 100 to 200 ml/minute when using
60 ml sample tubes.
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.
6. The sample should be analysed as soon as possible after the collection.
45
OXYGEN DEMAND, BIOCHEMICAL
(Dissolved Oxygen Loss Method)
SUMMARY OF METHOD The sample is incubated at 20 oC 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).
APPARATUS 1. Incubation Bottles - 250 to 300 ml capacity with ground glass stoppers.
2. Air Incubator – thermostatically controlled at 20+1 0C. All light should be
excluded to prevent possibility of photosynthetic production of DO.
REAGENTS 1. Dilution Water – Add 0.3 g of sodium bicarbonate per litre of Type II
water.
PROCEDURE 1. Adjust the temperature of a suitable portion of the well mixed sample to
20oC. Remove the oxygen or excess air by maintaining the sample
under vacuum for 10 minutes using laboratory vacuum pump.
2. Fill completely two incubation bottles (250 or 300 ml capacity) with the
sample as treated above (4.1). Allow to stand for 15 minutes.
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.
INTERFERENCES 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 4oC or below.
Analysis should be done before 24 hours after grab sample collection.
NOTES 1. The dissolved oxygen content of the sample before incubation shall be
approximately 9 mg/litre or preferably less.
2. For samples of doubtful purity, the sample should be mixed with dilution
water in the ratio 1:1 at 20oC. 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.
46
OXYGEN DEMAND, CHEMICAL
(Potassium Dichromate Method, upto 800 mg/litre)
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 orthophenan-
throline-ferrous complex as an internal indicator.
47
8. For waters of low COD (10 to 50 mg/litre) use 0.025N potassium
dichromate and 0.025 N ferrous ammonium sulphate solutions.
INTERFERENCES 1. The method does not uniformly oxidize all organic materials. Volatile
organic materials. Volatile organics which are difficult to oxidize may be
partially lost before oxidation is achieved. Care in maintaining a low
solution temperature (about 40oC) 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.
2. Chloride ion is quantitatively oxidized by dichromate in acid solution,
with each mg/litre chloride exerting the equivalent of 0.226 mg/litre COD.
Reaction of chloride ion (up to 1000 mg/litre) is inhibited by addition of
mercuric sulphate.
3. Oxidizable inorganic ions, such as ferrous, nitrite, sulphites, and
sulphides are oxidized and measured also a organic constituents.
48
6. Preserve sample by cooling to 4 oC if analyzed within 24 hours
after sampling or preserve for up to 7 days at pH < 2 at 4 oC.
7. Silver sulphate acts as a catalyst in the reaction to facilitate the
oxidation of organics which are difficult to oxidize.
8. The chemical reaction involved in oxidation of materials by
dichromate is illustrated by the following reaction with potassium
acid phthalate (KC8H5O4):
41H2SO4 + 10K2Cr2O7 + 2KC8H5O4 = 10Cr2(SO4)3 + 11K2SO4 +
16CO2 + 46H2O.
Since 10 mol of K2Cr2O7 have the same oxidative power as 15
mol of O2, the equivalent reaction is:
2 KC8H5O4 + 15O2 + H2SO4 = 16 CO2 + 6 H2O + K2SO4.
Thus 2 mol of potassium acid phthalate consume 15 mol of
oxygen. The theoretical COD for KC 8H5O4 is 1.175g of O2/g of
KC8H5O4.
49
PHOSPHATE
(Amino Reduction Method, 0.1 to 10 mg/litre)
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 650
nm. When a bismuth salt is added the intensity of the blue colour
increases by four times.
50
2.1 Proceed in accordance with 6.1, substituting sulphuric acid solution (B)
in place of sulphuric acid solution (A) in step 6.1.2.
INTERFERENCES 1. A silica concentration fifty times that of the phosphate will cause an error
of less than 2 percent.
2. Up to 40 mg/litre iron, 75 mg/litre chromate, and 50,000 mg/litre chloride
will not interfere with the test. Not more than 1500 mg/litre chloride
should be present when the bismuth salt modification is used.
3. To prevent formation of calcium sulphate, 7 ml of hydrochloric acid (sp
gr 1.19) should be used in place of Sulphuric acid when the calcium
concentration in the sample exceeds 200 mg/litre.
4. Nitrite interference can be eliminated by addition of 0.1 g of sulphamic
acid before adding ammonium molybdate.
5. Sulphide upto several mg/litre will not interfere.
NOTES 1. Reagent grade chemicals should be used in preparing all the reagents.
2. Only orthophosphate forms a blue colour in the test. Other forms of
phosphorous such as polyphosphate and organic phosphorous can be
converted orthophosphate, if present in the sample, before applying
above mentioned methods.
3. All glassware and sampling bottles should be soaked in hydrochloric
acid (1+3) and rinsed with water before use.
51
SILICA, NON-REACTIVE
(Membrane Filtration Method, 0 to 100 micrograms/litre)
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.
52
2.1 Place 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 and 10.0 ml of standard silica solution B
(1ml = 1microgram SiO2) in 200 ml polythene flasks. Add water to make
75 ml.
2.2 Add 4.0 ml of ammonium molybdate reagent and mix. Allow to stand for
20 minutes at 35-40oC in a water bath.
2.3 Remove the flasks from the water bath and add 20 ml of Sulphuric acid
(10 N) rapidly while stirring. Allow to stand for 5 minutes.
2.4 Add 1 ml of amino-naphthol-sulphonic acid solution and mix. Allow to
stand for 20 minutes.
2.5 Measure the absorbance of each standard at 815 nm against zero
standard (blank) using 50 mm absorption cells.
2.6 Prepare a calibration curve by plotting absorbance versus concentration
of silica in micrograms.
PROCEDURE 1. Filer 500 ml of the water sample through a 0.2 micron membrance filter
by applying vacuum.
2. Place the membrane filter in the bottom of a 150 ml 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.
3. Add 25 ml of water and 50 ml of boric acid solution. Mix well and place
the beaker in a water bath controlled at 40-50 oC. Allow to stand for 15
minutes.
4. Add 40 ml of ammonium molybdate reagent while stirring. Allow to stand
for 20 minutes at 35-40oC in a water bath.
5. Remove the beaker from the water bath and add 20ml of Sulphuric acid
(10N) rapidly while stirring. If a pronounced yellow colour remains,
measure the absorbance at 420 nm using 10 mm absorption cell.
6. If the yellow colour is not pronounced, add 1ml of amino-naphthol-
sulphonic acid solution 5 minutes after the addition of Sulphuric acid.
Allow to stand for 20 minutes.
7. Measure the absorbance at 815 nm using 50 mm absorption cell.
8. Run a blank alongwith the sample, using a 0.2 micron membrane filter
and proceeding in accordance with 6.2 to 6.6.
NOTES 1. See method for the determination of soluble silica (section 10.0).
2. Reagent grade chemicals should be used for preparing all the reagents.
3. Hydrofluoric acid used should contain least possible amount of
fluorosilicic acid.
4. 0.1 micron membrane filters should be preferred.
5. Presence of boric acid up to a concentration of 16,200 mg/litre does not
interfere significantly.
53
SILICA, REACTIVE
(Amino Reduction Method, 5 to 140 micrograms/litre)
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
compled is reduced to a blue complex with 1-amino-2-naphthol-4-
sulphonic acid the intensity of which is measured at wavelength of 815
nm.
CALIBRATION 1. Prepare a series of standards (at least five concentrations) to cover the
range 5 to 140 micrograms SiO 2/litre by diluting appropriate volumes of
silica Standard solution (4.7, 1ml = 1 microgram SiO 2) to 50 ml in 100 ml
polythene bottles.
2. Proceed in accordance with section 6.0 (6.2 to 6.6).
3. Prepare a calibration curve by plotting absorbance versus micrograms of
SiO2/litre.
54
8.0 PRECISION
SO = 0.005 X + 0.7
St = 0.03 X + 1.3
Where:
9.0 INTERFERENCES
9.1 Samples containing less than 1.0 mg/litre of SiO 2 do not normally contain a significant
concentration of interfering substances.
9.2 Colour and turbidity will interfere if not removed by filtration or dilution.
9.4 No significant interference due to the present of boric acid up to 16,200 mg/litre has been
observed.
9.5 Strong oxidizing and reducing agents may interfere in the reduction step.
10.0 NOTES
10.1 Reagent grade chemicals should be used for preparing all the reagents.
10.2 Samples should be collected in plastic or stainless steel sample bottles provided with
rubber or plastic stoppers.
10.3 All reagents to be used in this method should be stored in polythene or other suitable
plastic bottles.
10.4 The amino-naphthol-sulphonic acid solution should be discarded when its colour darkens
or a precipitate forms.
10.5 The ammonium molybdate solution should be discarded when a white precipitate
developes.
10.6 An alternate method of standard silica solution preparation is from transparent spectrosil
rod. This rod is made of SiO 2 containing less than 1mg/litre of impurities and 30 cm of
this rod weighs about 5g. Procedure is as follows:
Weigh 1.000g of spectrosil rod into a platinum crucible and place 5g of anhydrous
sodium carbonate on the top of rod. Heat to bright red and continue heating for 10
minutes. Cool, dissolve the melt in water and make up to 1litre.
10.7 The strength of silica stock solution (4.6) may be checked as follows:
Place 100ml of Silica stock solution (4.6) in a 400ml scratch-free glass beaker.
Neutralize with hydrochloric acid (sp gr 1.19) to methyl orange end point and add 5 ml in
excess. Evaporate the solution to dryness on a water bath, with periodic additions of
three more 5 ml increments of hydrochloric acid (sp gr 1.19). Dry to evaporated residue
in an oven at 110oC for 1 hour. Add 5 ml of hydrochloric acid (sp gr 1.19) and then 50 ml
of water to the beaker, warm the beaker and its contents. Stir the mixture. Filter the
warm solution through an ashless, medium texture filter paper. Wash the residue on the
55
paper 15 times with hydrochloric acid (1+19) and then with several small increments of
water. Reserve the paper and its residue for later ignition.
Return the filtrate and washings obtained above to the original evaporating beaker, the
evaporate to dryness on a water bath with periodic addition of two 5 ml increments of
hydrochloric acid (sp gr 1.19). Dry the evaporated residue in a oven at 110 oC for 1 hour.
Add 5 ml of hydrochloric acid (sp gr 1.19) and then 50 ml 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
1200oC. 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 gr 1.84) and about 5 ml of hydrofluoric acid
(48%) to the weighed residue in the crucible and evaporate to dryness on a low
temperature hot plate under a fume hood. Reignite the residue at 1000 to 1200 oC and
weigh. Repeat the ignition, cooling, and weighing until a constant weight is obtained.
Calculate the concentration of silica, in milligrams per litre, in silica stock solution, as
follows:
(W1 – W3) – (W2 – W4)
SiO2, mg/litre = --------------------------
V
Where:
56
SULPHATE
(Gravimetric Method, 20-100 mg/litre)
SUMMARY OF METHOD Sulphate ion is precipitated and weighed as barium sulphate after
removal of silica and other insoluble matter.
RECISION 1. Results of this method are precise to 1.0 % of the amount of sulphate
ion present.
INTERFERENCES 1. Sulphites and sulphides may oxidize and precipitate with sulphate.
2. Turbidity caused by silica or other insoluble material would interfere if
allowed to be present.
NOTES 1. Reagent grade chemicals should be used for preparing all the reagents.
57
2. Turbidity may be removed by filtration through a fine filter paper (eg.
Whatman No. 42).
58
SULPHATE
(Volumetric Method, 5-1000 mg/litre)
SUMMARY OF METHOD The sample is titrated in an alcoholic solution under controlled acid
conditions with a standard barium chloride solution using thorium as
indicator. The endpoint is indicated by a change in colour from a yellow
to a stable pink colour.
PROCEDURE IN THE 1. Place 25 ml of filtered sample into a 100 ml beaker. Add 0.5 ml of starch
PRESENCE OF indicator and titrate the sulphite with iodine solution.
SULPHITE, 2. Add 2 to 3 drops of phenolphthalein indicator and adjust the pH to about
PHOSPHATE 10.3 with hydrochloric acid (1+99) using narrow range pH paper. Add
AND CHROMIUM 0.3 to 0.5g magnesium carbonate and boil for 5 minutes. Cool to 10 oC
59
and filter through Whatman No. 41 or equivalent filter paper into a 50 ml
volumetric flask. Wash the precipitate with three 5 ml portions of water at
10oC. Add few drops of hydrogen peroxide, shake, and adjust the
volume to 50 ml with water.
3. Pass the solution through the ion exchange column and discard the first
25 to 30ml of effluent. Place 10.0 ml of the next effluent into a small
white porcelain dish (100 to 125 ml capacity).
4. Add 40 ml of alcohol and 2 drops and 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.
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 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.
PROCEDURE IN THE 1. Pass 50 ml of the filtered sample directly through the ion exchange
ABSENCE OF column. Collect 10.0 ml of effluent and proceed in accordance with 6.3,
SULPHITE, PHOSPHATE 6.4 and 6.5.
AND CHROMIUM
PROCEDURE IN THE 1. Directly titrate 10.0 ml of the filtered sample in accordance with 6.4 and
PRESENCE OF 6.5.
NEGLIGIBLE INTERFERENCES
PRECISION 1. Titration of Sulphate in the range 5 to 100 mg/litre , after ion exchange
treatment is accurate to 1.5mg/litre. The precision of this method upto
100 mg/litre is 0.7 mg/litre. Single operator precision may be expected to
be 0.5 mg/litre.
INTERFERENCES 1. Both cations and anions may cause coprecipitation errors with barium
sulphate precipitate. Most metallic ions also interfere by forming
coloured complexes with the thorin indicator, especially in alcohol water
mixtures.
2. Interference by cations is eliminated by ion exchange.
3. Fluorides and nitrates cause no interference up to concentrations of 2
and 50 mg/litre respectively.
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4. Ortho and metaphosphate interfere when present in excess of 2 mg/litre.
Phosphate is removed by precipitation with magnesium carbonate and
filtration in cold.
5. Sulphite interference is eliminated by determining the sulphate
equivalent of the sulphite and subtraction of this sulphate from the
determined sulphate content. Sulphides can be removed by precipitation
as zinc sulphide.
6. Chloride mask the pink endpoint if present in concentration more than
1000 mg/litre when the sulphate present is low (about 5mg/litre).
7. Chromium present as chromates and dichromates is converted to Cr +3
with hydrogen peroxide and then removed by ion exchange.
NOTES 1. Reagent grade chemicals should be used for preparing all the reagents.
2. A solution of known sulphate concentration should be run with each
series of tests or new reagents to check the standardization curve. The
blank used to determine sulphate content is preferably that determined
from the standardization curve extrapolated to zero.
3. Phosphate ion is almost completely precipitated (step 6.2) at or below
10oC, but solubility increases with increasing temperature.
4. If the ammonium hydroxide (step 6.4) is added too fast, it is possible to
over-run the colour change from yellow to pink and the sample
continues to be yellow. It is then impossible to develop the pink colour
by addition of ammonium-hydroxide.
5. For very low sulphate concentrations a less concentrated barium
chloride solution (1 ml = 0.200 mg sulphate) should be used. A standard
sulphate solution may be added to the sample to raise the total sulphate
concentration to 10 to 15 mg/litre. This added sulphate must be
subtracted from the final result.
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