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The Royal Australian Chemical Institute Inc

Chemistry Serving Australia


ABN 69 030 287 244

Qld Branch Chemical Education Group

Secondary-Tertiary Interface
22 August 2009

Techniques for water analysis

Prepared by Elaine Bergmann

With thanks to
Rob Gray and Kathy Gray
for their editorial input.

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Contents

Dissolved oxygen 3

Hardness 7

Alkalinity 11

Chloride ion 14

Hypochlorite in bleach solutions 16

Phosphate 18

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1.0 Dissolved Oxygen (Winkler/iodometric method)
(adapted from Eaton, A, Clesceri, L, Rice, E and Greenberg, A 2005, Standard Methods for the
Examination of Water and Wastewater 21st edition, American Public Health Association, American
Water Works Association and Water Environmental Federation, Washington)

1.1 Introduction
Dissolved oxygen (DO) levels in natural and wastewaters depend on the physical, chemical,
and biochemical activities in the water body. The analysis of DO is a key test in water
pollution and waste treatment process control.
The iodometric method is the most precise and reliable titrimetric procedure for DO analysis.
It is based on the sequence of reactions given below.
Interferences
The presence of oxidising or reducing materials in the sample may cause interference with the
standard method given here. Certain oxidising agents liberate I2 from iodides (positive
interference) and certain reducing agents reduce I2 to iodides (negative interference). Most
organic matter is oxidised partially when the oxidised manganese precipitate is acidified, thus
causing an error.
A number of modifications are available to minimise interference. The azide modification
removes interference due to nitrite (common in effluents and incubated BOD samples). The
permanganate modification is used in the presence of Fe2+.
Reaction sequence of iodometry
In the presence of excess OH-, Mn2+ ions (from MnSO4) form a precipitate of Mn(OH)2. Mn2+
ions (in equilibrium with Mn(OH)2 precipitate), are oxidised by O2 to Mn3+ forming
Mn(OH)3.
O2 + 4 Mn(OH)2 + 2 H2O 4 Mn(OH)3

Addition of acid neutralises OH- and liberates free Mn3+ ions.


Mn(OH)3 + 3H+ Mn3+ + 3 H2 O

I- ions reduce Mn3+ to Mn2+, liberating I2 equivalent to the original DO content.

2 Mn3+ + 2I- 2 Mn2+ + I2

I2 molecules, which are not soluble in water, combine with iodide ions in a reversible reaction
to form the brown, soluble tri-iodide ion.

I2 + I- I3-

In the titration reaction, iodine is then reduced by thiosulfate

I2 + 2 S2O32- 2 I- + S4O62-

As the titration proceeds, the brown colour due to the triiodide ion fades as the iodine is
reduced by the thiosulfate. The disappearance of the triiodide is a difficult endpoint to detect,
so starch is added as the brown colour fades, forming a blue complex with I2. The endpoint is
signalled by the disappearance of the blue colour of the starch-iodine complex.

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1.2 Sampling
The reliability of the results depends heavily upon the sampling method. Since dissolved
oxygen will be measured back in the laboratory, care must be taken to prevent the loss or
addition of oxygen to the sample once it is collected. Because the amount of dissolved O2 is
also temperature dependent, the temperature of the sample should also be maintained (or
stored at a lower temperature). Chemical and biochemical activity may consume O2. Ideally,
Steps 1 - 5 should be performed immediately after sample collection. Once O2 has been
consumed, (after formation of I3-) treated samples can be transported back to the laboratory
for titration.
Collect the sample by gently lowering a bottle (about 1 L and preferably wide-necked) into
the water and filling the bottle completely beneath the surface. Cap the bottle underneath the
water surface so that no bubbles are present in the sample bottle. You need to ensure a smooth
flow of water into the bottle here, to avoid aeration. You should endeavour to collect the
water sample on the same day that you intend to do the DO assay.

1.3 On-site measurements


Record all information regarding the sample (i.e. place, time, temperature, pH, general
description of site). It is most important that you measure the temperature of the water
where you have collected your sample.

1.4 Analysis

1.4.1 Apparatus
1 x 250 mL conical flask with a stopper
1 x 500 mL conical flask
1 x 250 mL measuring cylinder
1 x 10 mL pipette and filler
1 x 50 mL burette
2 x 2mL pipettes

1.4.2 Reagents (The following should be enough to do 4 titrations of a single water sample.)
10 mL 2.2M MnSO4
10 mL alkaline KI reagent (0.9 M KI and 12.5M KOH)
10 mL conc H2SO4
60 mL 0.025M Na2S2O3 (can be standardised with KIO3, see 1.4.5)
10 mL 1% starch suspension
1 L water sample

1.4.3 Safety
Latex gloves, safety glasses, remember that the KI reagent and conc. H2SO4
are both extremely corrosive.

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1.4.4 Method
1. Carefully fill a 250 mL conical flask (with a stopper) to nearly full with water from your
sampling site. Pour the sample water down the side of the flask in order to minimise bubbles.
You should leave a space at the top that will accommodate about 5 mL of reagents. (Check
with tap water before you start. Ideally you should not have any air bubbles after adding the
first 2 reagents and capping the solution.)
2. Using a 2 mL pipette, quickly add 2.0 mL MnSO4 solution, mix and then add 2.0 mL of the
alkaline KI reagent.
3. A precipitate of manganese(II) hydroxide will form. Stopper the flask and invert several
times to mix and bring about the reaction with the O2(aq). When the precipitate settles,
leaving about 100 mL of clear supernatant, repeat the inversions.
4. Allow the precipitate to settle so that about 100 mL of clear solution is produced.
5. Add 2.0 mL of conc H2SO4 (wearing latex gloves) by allowing the acid to run down the
neck of the flask. Stopper the flask and invert/mix several times until all the precipitate
dissolves.
6. Using a 250 mL measuring cylinder, take 203 mL from the flask and transfer to a 500 mL
conical flask. (The 203 mL allows for the addition of the other reagents and is equivalent to
200 mL of the original water sample.) It does not matter that the solution is now open to the
air (why not?)
7. Record the initial volume of sodium thiosulfate in the burette. Titrate with this thiosulfate
to a pale straw yellow colour. THEN add starch indicator (~0.5 mL). (The starch reacts with
iodine to give a deep blue colour.) Continue the titration to the first disappearance of blue
colour. Record the final volume of sodium thiosulfate in the burette. Calculate volume of
thiosulfate used.
8. Repeat steps 1 – 7 for further aliquots.

1.4.5 Standardisation of thiosulfate solutions


Thiosulfate solutions can be standardised by reaction with iodate. Molarity of iodate solution
should be about one-sixth that of the thiosulfate being used.
The overall reaction is as follows:
2 IO3- + 12 H+ + 12 S2O32- 2 I- + 6 S4O62- + 6 H2O
Method
1. Accurately weigh approximately 0.1 g KIO3 (dried at 120˚C for at least 2 hours prior to
weighing) and make up to 100 mL in a volumetric flask.
2. Pipette out 25 mL of this solution and add 10 mL of 10% sulfuric acid solution and 2 g of
KI.
3. Titrate with thiosulfate solution, adding starch as colour fades to straw yellow.

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1.4.6 Calculations and Discussion
1. Calculate the molarity of the thiosulfate from the solution standardisation procedure.
2. Calculate the Dissolved Oxygen (check your notes for some help) for your sample.
Shortcut (if thiosulfate concentration is accurate): When a 200 mL water sample is used,
1mL of sodium thiosulfate solution (0.025 M) is equivalent to 1 mg/L (1ppm) dissolved
oxygen in the sample. (If 8.7 mL of sodium thiosulfate was used, then the DO of the sample is
8.7mg/L i.e. 8.7 ppm.

3. Compare your results with the Oxygen Solubility Data (Table 1).
(a) Calculate the percentage saturation of your sample.
(b) Make some suggestions about any differences between your results and the
saturation values given in the table.

Table 1. Oxygen Solubility Reference Table

The following values refer to the solubility of oxygen in chloride-free water at various
concentrations. The water is in equilibrium with water-saturated air at a total pressure of
1.013 x 103 kPa and a partial pressure of oxygen of 0.213 x 103kPa.

Temp DO Temp DO Temp DO Temp DO


(˚C) (ppm) (˚C) (ppm) (˚C) (ppm) (˚C) (ppm)
0 14.62 11 11.08 22 8.83 33 7.3
1 14.23 12 10.83 23 8.68 34 7.2
2 13.84 13 10.60 24 8.53 35 7.1
3 13.48 14 10.37 25 8.38 36 7.0
4 13.13 15 10.15 26 8.22 37 6.9
5 12.80 16 9.95 27 8.07 38 6.8
6 12.48 17 9.74 28 7.92 39 6.7
7 12.17 18 9.54 29 7.77 40 6.6
8 11.87 19 9.35 30 7.7 41 6.5
9 11.59 20 9.17 31 7.5 42 6.4
10 11.33 21 8.99 32 7.4 43 6.3

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2. 0 Water Hardness by Complexation Titration
(Adapted from Greenberg, A.E. et al, 1975 Standard methods for the examination of water and
wastewater 14th edition, American Public Health Association, Washington)

2.1 Introduction
In the past, water hardness was defined as a measure of the capacity of water to precipitate
soap. Current laboratory practices, however, define total hardness as the sum of divalent ion
concentrations, especially those of calcium and magnesium, expressed in terms of
mgCaCO3/L. There are no known adverse health effects of hard or soft water, but the
presence of hard waters results in two economic considerations:
(1) hard waters require considerably larger amounts of soap to foam and clean
materials and
(2) hard waters readily precipitate carbonates (known as boiler scale) in piping
systems at high temperatures.

Calcium and magnesium carbonates are two of the few common salts whose solubility
decreases with increasing temperature. This is due to the removal of dissolved CO2 as
temperature increases. The advent of synthetic detergents has significantly reduced the
problems associated with hard water and the “lack of foaming”. However, scale formation
continues to be a problem.

The method described below relies on a “competition” between EDTA and an indicator
(Eriochrome Black T). Both are organic compounds which can form a complex with divalent
metal ions. The chemical structure of EDTA is shown below. Note the lone pairs of electrons
on the two nitrogens. These, combined with the dissociated carboxyl groups, create a 1:1
hexadentate complex with each divalent ion in solution. However, the complexation constant
is a function of pH. Virtually all common divalent ions will be complexed at pH values
greater than 10, the pH used in this titration experiment and in most hardness tests. Thus, the
value reported for hardness includes all divalent ions in a water sample.

A simplified representation of the neutral The tetra-anion form of EDTA exists


form of EDTA. In fact, N atoms are at high pH and is able to form 6
protonated and two of the carbonyl bonds to a central metal ion, forming
groups are deprotonated, as in the an octahedral complex.
zwitter-ion of amino acids.

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At high pH (>10), each of the 4 carboxyl groups will be deprotonated as will the N atoms
(being in a basic solution), so the EDTA will exist in this solution as a tetra-anion.
EDTA is supplied as the disodium salt, (Na+)2H2EDTA2-, in which 2 protons have been
removed, forming a di-anion.
In solution, the ions dissociate, so H2EDTA2- ions are free in solution. In the presence of
excess OH- ions, the remaining H+ ions are removed from the carboxyl groups, to form the
tetra-anion. This has lone pairs on the 2 N atoms of the amino groups, as well as on O of each
carboxylate anion. These are able to form co-ordinate covalent bonds with empty valence
orbitals of metal ions. The EDTA is said to act as a ligand or chelate, and one EDTA forms 6
bonds to each divalent metal ion – hence it’s said to be a hexadentate ligand.
In this analysis you will be titrating Ca2+ in a standard solution and water samples with
EDTA. Both Ca2+ solutions and EDTA are colourless so an indicator is needed to signal the
reaction completion. The indicator of choice is Eriochrome Black T (EBT) which forms a
wine-red complex with Mg2+. A very small amount of Mg2+ will be bound to the indicator
through most of the titration. When all of the Ca2+ (and any other divalent metal ions present)
has been removed from solution by reaction with EDTA, the Mg2+ originally bound to the
indicator will combine with the EDTA. The indicator then returns to a sky-blue form
signaling the end-point. (Calcium ions are “better” at bonding to EDTA than magnesium, and
when there are no free calcium ions left, the EDTA is “better” at bonding with magnesium
ions than the indicator is. So at the end point the indicator is not bound to any metal ion. This
can be related to the K values (stability constants) for the formation of each complex with
EDTA and with EBT given below.

Stability constants for the formation of each complex ion are as follows:
[CaEDTA]2- log K = 10.65 K = 4.5 x 1010
[CaEBT]2+ log K = 5.4 K = 2.5 x 105
[MgEDTA]2- log K = 8.85 K = 7.1 x 108
[MgEBT]2+ log K = 7 K = 1.0 x 107
(Aylward, G. and Findlay, T. SI Chemical Data 5th edition (pp. 132 - 133), John Wiley and
Sons, Australia Limited)

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2.2 Analysis
2.2.1 Apparatus
20 mL pipette and filler
50 mL burette
250 mL conical flask
pH meter or indicator strips to give pH 10 – 10.5
50 mL pipette (or measuring cylinder)

2.2.2 Reagents
250 mL 0.01M CaCl2 solution (see Section 2.2.3.1)
250 mL 0.01M EDTA solution
(Weigh approximately 0.9 g of AR grade disodium ethylenediamine tetraacetate
dihydrate (Na2H2C10H12O8N2.2H2O), dissolve in distilled water, and dilute to 250 mL.
Store in a labelled plastic bottle.)
pH 10 buffer containing Mg2+
(Dissolve 16.9 g NH4Cl in 143 mL conc NH4OH, to which has been added 1.25 g of the Mg salt
of EDTA. (If Mg salt of EDTA is not available, dissolve 1.18g of MgSO4.7H2O or 645mg of
MgCl2.6H2O in 50 mL H2O and add to buffer solution. Make up to 250 mL with distilled water.
Store in a plastic bottle, tightly stoppered.)
Eriochrome Black T indicator
(For a powder: mix 0.5 g of the dye and 100 g NaCl
For a solution: mix 0.5 g of the dye with 4.5 g of hydroxylamine hydrochloride, then dissolve in
100 mL of 95% ethyl or isopropyl alcohol.)

2.2.3 Standardisation of EDTA Solution

2.2.3.1 Preparation of a standard solution of 0.01M CaCl2


1. Accurately weigh approximately 0.2500 g of dried anhydrous CaCO3, record its mass and
quantitatively transfer to a 250 mL Erlenmeyer flask.
2. Place a funnel in the neck of the flask and add approximately 25 mL of distilled water, then
2 mL of 6M HCl. Mix, and if the mixture remains cloudy, add another drop of HCl. Continue
adding HCl dropwise until the solution is clear.
3. Add 50 mL distilled water and boil for a few minutes to expel CO2.
4. Cool, add a few drops of methyl red indicator, and adjust to the intermediate orange colour
(approx pH 5) by adding 3M NH4OH or 6M HCl, as required.
5. Transfer quantitatively to a 250 mL volumetric flask and fill to the mark with distilled
water. Stopper, invert 10 – 15 times to mix thoroughly.
If 0.2500 g of CaCO3 is used, this standard is equivalent to 1.00 mg CaCO3/1.00 mL. (1000
ppm) If a slightly different amount of CaCO3 is used, then a factor must be applied e.g.
0.2432/0.2500)

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2.2.3.2 Standardisation of 0.01M EDTA solution
1. Rinse a 50 mL burette with distilled water then with the EDTA solution. Fill with EDTA.
2. Rinse a pipette with distilled water then with CaCl2. Pipette 20 mL of the CaCl2 solution
into a rinsed 250 mL Erlenmeyer flask.
3. Add pH 10 buffer solution to give a pH of 10 – 10.1, and 2 drops of Eriochrome Black T
indicator. Mix well. What colour should the solution be at this point?
4. Titrate the sample in the flask with the EDTA, slowing additions (as red becomes more
purple) as you near the sky-blue endpoint (wait 3–5 seconds between additions, as the blue
colour does not develop immediately). Record the volume required to titrate the CaCl2
sample. Keep the first sample as a colour reference. Your titration should not take longer than
5 minutes, from the time the buffer is added to endpoint.
5. Prepare a second portion of CaCl2 in the same way as above (steps 2 - 3) and repeat the
titration, recording all data. If the volumes of EDTA agree to within 0.4 mL, proceed to the
next section. If not, repeat the titration until 2 or more titres agree within 0.4 mL.

2.2.4 Determination of water hardness


1. Measure100 mL of tap water into a 250mL flask. Add pH 10 buffer (about 5 times the
volume you added to the standard, to bring pH to 10 – 10.1 as above) and 5 drops of
Eriochrome Black T. Mix well. Titrate with the standardised EDTA solution. (100 mL of
SEQ water should give a titre of around 10 mL; the volume of water can be varied for water
with more or less calcium. If your water is very hard, then reduce the volume of water in the
flask.)
2. Repeat until you have 2 titres which are in agreement as Step 5 above.

2.2.5 Calculations
1. Determine the moles of CaCO3 (moles Ca2+) in the 250 mL of standard solution, and in
each 20.00mL aliquot.

2. EDTA and Ca2+ react in a 1:1 ratio. Calculate the average volume of EDTA which reacted
with the standard solution, and hence calculate EDTA concentration.

3. Calculate the average volume of EDTA which reacted completely with the tap water
sample, and hence calculate the concentration of calcium (and other divalent ions) in the
water. Express this result both as a molarity and as mg CaCO3 per litre (ppm).

4. The Brisbane City Council website states that the average total hardness of Brisbane tap
water is 100mg as sCaCO3/L. How closely does your result agree with this value? If it does
not, suggest possible reasons for the difference. Consider both your laboratory procedures and
other factors.

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3.0 Alkalinity
(adapted from Eaton, A, Clesceri, L, Rice, E and Greenberg, A 2005, Standard Methods for the
Examination of Water and Wastewater 21st edition, American Public Health Association, American
Water Works Association and Water Environmental Federation, Washington)

3.1.1 Introduction
This procedure could be taught in conjunction with work on equilibrium and buffers with
specific reference to the carbonate/bicarbonate equilibrium.
Alkalinity is a measure of the acid neutralising capacity of a water or wastewater and is a
useful component in the interpretation of water quality for various uses.
As neutralising capacity depends mainly on carbonate, bicarbonate and hydroxide, it can be
used as an indicator of the concentrations of these components.
For groundwaters, the main source of carbonate and bicarbonate is rocks through which the
water has passed.

3.1.2 Summary of Test Method


The total alkalinity is determined by titrating a portion of sample with standardised sulfuric
acid to pH 4.5 end point using bromocresol green-methyl red indicator solution, or for
samples with pH greater than 8.3, “Phenolphthalein Alkalinity” to pH 8.3 end point using
phenolphthalein indicator.

3.1.3 Interferences
Strongly coloured or turbid samples may hinder end point detection. To overcome this, a
smaller aliquot of sample may be used or the procedure for low alkalinity may be followed.
Sample alkalinity less than 20 mg CaCO3/L can only be reported if the low alkalinity
procedure is used.

3.1.4 Sample preservation


Samples should be collected in glass or plastic bottles with no entrapped air if possible. If
stored at 0-4˚C immediately upon receipt, samples can be kept for up to 24 hours prior to
analysis. Do not filter samples. Samples may be subject to microbial action and to loss or gain
of gases when exposed to air, so they should be analysed without delay. Avoid sample
agitation and prolonged exposure to air.

3.2 Analysis
3.2.1 Apparatus
150 or 250 mL Erlenmeyer Flasks
50 mL burette
10 mL pipette.
50 mL pipette

For low alkalinity procedure.


20 mL microburette
pH meter
250 mL beaker
magnetic stirrer

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3.2.2 Reagents
• 0.01M sulfuric acid
(see 3.2.3.1 for standardisation procedure)
• mixed bromocresol green - methyl red indicator solution
(Dissolve 100 mg bromocresol green and 20 mg methyl red into 100 mL 95% ethyl or isopropyl alcohol; or
100mg bromocresol green sodium salt and 20mg methyl red sodium salt in 100 mL water.)
• phenolphthalein solution
(Dissolve 1 g phenolphthalein in 100 mL 95% ethyl or isopropyl alcohol and add 100 mL
distilled water.)

Note: The colour response of the mixed bromocresol green-methyl red is approximately as
follows: above pH 5.2, greenish blue; pH 5.0, light blue with lavender grey; pH 4.8, light
pink grey with bluish cast; pH 4.5, light pink; and below pH 4.0, strong pink.

3.2.3 Method
3.2.3.1 Standardisation of 0.01M H2SO4
Make up a 0.025M Na2CO3 solution.
1. Dry 3 to 5 g of primary standard Na2CO3 at 250C for 4 hours and cool in a desiccator.
2. Weigh 2.5 +/- 0.2g (to the nearest mg), transfer to a 1L volumetric flask, fill flask to the
mark with distilled water, and dissolve and mix reagent. Do not keep longer than a week.
3. Titrate 10 mL of this solution with the 0.01M H2SO4 using 5 drops of the bromocresol
green–methyl red indicator.
4. Repeat the titration as necessary.
5. An indicator blank should be titrated as well, to ensure that this result is not being affected
by residual alkalinity of the distilled water used to make up the standard solution. Add 5 drops
of indicator to 10mL of the water, and titrate as above. If this value is significant, then the
volume should be subtracted from the volume used in the standardization titration before
determining concentration of sulfuric acid.

Calculations
1. Write the balanced equation for the reaction between Na2CO3 and H2SO4.
2. Find the number of moles of Na2CO3 (nNa2CO3) weighed out to make up the standard
solution.
3. Calculate the molarity of the Na2CO3 solution (M Na2CO3).
4. Subtract the value for the indicator blank from the average volume of acid that was added
to the Na2CO3 solution. (VH2SO4)
5. Use this value to calculate the molarity of the H2SO4 solution.

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3.2.3.2 Total alkalinity
•Test the pH of the sample before beginning titration. If it is above 8.3, then you must use the
phenolphthalein procedure. If below 8.3, then proceed as follows:
1. Pipette 50 mL of sample (or less if alkalinity is high) into an Erlenmeyer flask.
2. Add approximately 5 drops of mixed indicator to the sample.
3. Over a white surface, titrate with 0.01M H2SO4 to a persistent colour change characteristic
of the equivalence point (this can be found by making a pH buffer solution to pH 4.5 and
adding 5 drops of mixed indicator).
4. Repeat steps 1 – 3 as required.

3.2.3.3 Phenolphthalein alkalinity


If solution pH is greater than 8.3 proceed as in Total Alkalinity above, substituting
phenolphthalein for the mixed indicator.

3.2.3.4 Low alkalinity samples


Use a 200 mL sample volume, and titrate using a 20 mL microburette and the pH 4.5 endpoint
procedure.

3.2.4 Calculations
As alkalinity is reported as the equivalent mass of CaCO3, calculations are based on the
reaction between CaCO3 and H2SO4.
As the stoichiometric ratio is 1:1, at the end point, n(CaCO3) = n(H2SO4).
M(CaCO3)= M(H2SO4) x V(H2SO4)/V(water sample)
Alkalinity (as mg/L CaCO3) = M(CaCO3) x Molar Mass (CaCO3) x 103mg/g
(n = no. of moles; M = molarity; V = volume of solution or sample)

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4. 0 Chloride ion titration by Mohr (argentometric) method
(adapted from Eaton, A, Clesceri, L, Rice, E and Greenberg, A 2005, Standard Methods for the
Examination of Water and Wastewater 21st edition, American Public Health Association, American
Water Works Association and Water Environmental Federation, Washington)

4.1 Introduction
The method is suitable for the analysis of chloride ion concentrations in relatively clean water
when 0.15 to 10 mg of Cl- is present in the portion titrated.

The titrant is a standardised solution of AgNO3. Chloride ions are quantitatively precipitated
as AgCl before the red silver chromate precipitate is formed.

Ag+(aq) + Cl- (aq) AgCl(s) (Ksp = 1.8 x 10-10; s = 1.34 x 10-5 M)

2Ag+(aq) + CrO42- (aq) Ag2CrO4(s) (Ksp = 2.6 x 10-12; s = 8.66 x 10-5 M)

4.2 Sample collection


Collect samples in clean chemically resistant glass or plastic bottles. Maximum sample
portion required for a single titration is 100 mL.

4.3 Analysis

4.3.1 Apparatus
250 mL flask
50 mL burette
pH probe or indicator strips for pH range 7 - 10
1 mL pipette
100 mL pipette or measuring cylinder

4.3.2 Reagents
K2CrO4 indicator solution
(Dissolve 50 g K2CrO4 in a little distilled water. Add AgNO3 solution until a definite red
precipitate is formed. Let stand for 12 hours, filter (Whatman No. 42) and dilute to 1 L with
distilled water.)
standard silver nitrate titrant, 0.0141 M
(Dissolve 2.395 g AgNO3 in distilled water and dilute to 1000 mL. Standardise against NaCl by
the procedure described below. Store in a brown bottle.)
standard NaCl solution, 0.0141 M.
(Dissolve 824.0 mg NaCl (dried at 140˚C) in distilled water and dilute to 1000 mL
0.5 M H2SO4
1.0M NaOH

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4.3.3 Method
4.3.3.1 Standardisation of AgNO3 titrant
1. Establish a reagent blank value by titrating 100mL of distilled water plus 1.0 mL of K2CrO4
indicator with the AgNO3 titrant.
2. Titrate 20 mL of the standard NaCl solution with the AgNO3 to a pinkish yellow end point.
Be consistent in end point recognition.
3. Subtract the reagent blank value from the titre and use the difference to calculate the
concentration of the AgNO3.

4.3.3.2 Sample preparation


1. Use a 100 mL sample or a suitable portion diluted to 100mL if chloride ion concentration is
high.
2. Test pH of sample. Adjust sample pH to 7 - 10 with 0.5M H2SO4 or 1M NaOH as
necessary.

4.3.3.3 Titration
1. Add1.0 mL K2CrO4 indicator solution.
2. Titrate with standard AgNO3 solution to a pinkish yellow end point as for the
standardisation above.

Chloride ion concentration of sample is reported as mg Cl- per L (ppm).

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5.0 Sodium hypochlorite (free chlorine) levels in Bleach
5.1 Introduction
Note: Standard titrimetric methods for determination of free chlorine (hypochlorite ion,
hypochlorous acid and chlorine) are not sensitive enough for the analysis of municipal water
supplies. This method is suitable for the analysis of pool water, or to investigate the effect of
factors such as UV light or addition of organic materials to pool water.
A redox titration is used to determine the concentration of free chlorine in a sample of bleach.
A diluted sample of commercial bleach is firstly reacted in a flask with a solution containing
an excess of acidified iodide ion. This reaction produces I2. (This in turn combines with
iodide ion to form the very visible soluble brown triiodide ion I3-.)

ClO- + 2I- + 2 H+ I2 + Cl- + H2O (1)


(faint yellow) (colourless) (brown)

We can’t detect an end-point for the reaction above, so the I2 product is titrated with
thiosulfate. As the iodine is used, the brown colour due to the triiodide ion fades to yellow,
and then disappears. This is a hard endpoint to detect, so when the brown starts to fade to
yellow, starch can be added. Starch forms a blue complex with I2, and this colour disappears
when the stoichiometric amount of thiosulfate has been added to the flask.

2 S2O32- + I2 2 I- + S4O62- (2)

From equations (1) and (2), it can be seen that 1 mole of ClO- reacts to form 1 mole I2, which
consumes 2 moles of S2O32-. Hence, 1 mole of hypochlorite is equivalent to 2 moles of
thiosulfate.

Typical bleach concentrations are quoted as 35 g/L available Cl as sodium hypochlorite


(approx 1M) or approximately 5.25% NaClO by mass (approx 0.7M), so it is advisable to
dilute the bleach by a factor of 1 in 10.

5.2 Analysis
5.2.1 Apparatus
pipettes 10 mL, 20 mL and 25 mL and filler
burette (50 mL)
100 mL volumetric flask
250 mL conical flasks

5.2.2 Reagents
bleach (freshly purchased)
0.2 M Na2S2O3 solution
acidified NaI or KI solution
(12.6 g NaI or 14.0 g KI + 40 mL glacial acetic acid in 1 L)
1% starch suspension

E.Bergmann 16 Sec/Tert Interface 2009


5.2.3 Method
5.2.3.1 Part A standardisation of thiosulfate
Thiosulfate solutions can be standardised by reaction with iodate. Molarity of iodate solution
should be about one-sixth that of the thiosulfate being used.
The overall reaction is as follows:
2 IO3- + 12 H+ + 12 S2O32- 2 I- + 6 S4O62- + 6 H2O

1. Accurately weigh approximately 0.7 g KIO3 (dried at 120˚C for at least 2 hours prior to
weighing) and make up to 100 mL in a volumetric flask.
2. Pipette out 25 mL of this solution and add 10 mL of 10% sulfuric acid solution and 2 g of
KI.
3. Titrate with thiosulfate solution, adding starch as colour fades to straw yellow.

5.2.3.2 Part B titration of bleach solution


1. Prepare the diluted bleach solution by pipetting 10 mL into a 100 mL volumetric flask and
filling to the mark with distilled water. Stopper and invert several times to mix.
2. Rinse a 20 mL (or 25 mL) pipette with the bleach solution, and transfer an aliquot to a
conical flask.
3. Add 50 mL of the acidified iodide solution to the bleach in the flask. It should go brown. If
it does not, check the bleach – it decomposes over time.
4. Rinse and fill the burette with Na2S2O3 solution, and titrate until the brown colour fades to a
straw yellow. Add a few drops of starch indicator. A blue starch-iodine complex should form.
5. Continue adding Na2S2O3 to the flask until the blue colour disappears.
6. Repeat titrations.

5.2.3.3 Calculations

1. Use the stoichiometric information given above to find the molarity of your diluted bleach
solution.

2. Calculate the molarity of the neat bleach.

E.Bergmann 17 Sec/Tert Interface 2009


6.0 Colorimetric Phosphate Determination (stannous chloride method)
(adapted from Eaton, A, Clesceri, L, Rice, E and Greenberg, A 2005, Standard Methods for the
Examination of Water and Wastewater 21st edition, American Public Health Association, American
Water Works Association and Water Environmental Federation, Washington)

6.1 Introduction
Phosphorus occurs in natural waters and in wastewaters almost solely as phosphates. These
are classified as orthophosphates (phosphate PO43-), condensed phosphates (polyphosphates)
and organically bound phosphates. They occur in solution, in particles or detritus, or in the
bodies of aquatic organisms.

These forms of phosphate arise from a variety of sources. Small amounts of orthophosphate
or certain condensed phosphates are added to some water supplies during treatment. Larger
quantities of the same compounds may be added during laundering or other cleaning, because
these materials are major constituents of many commercial cleaning preparations.
Orthophosphates applied to agricultural or residential cultivated land as fertilisers are carried
into surface waters with storm runoff. Organic phosphates are formed primarily by biological
processes. They are contributed to sewage by body wastes and food residues.

Phosphorus is essential to the growth of organisms and can be the nutrient that limits the
primary productivity of a body of water. In instances where phosphate is a growth-limiting
nutrient, the discharge of raw or treated wastewater, agricultural drainage, or certain industrial
wastes to that water may stimulate the growth of photosynthetic aquatic micro- and macro-
organisms in nuisance quantities. Phosphates also occur in bottom sediments and in biological
sludges, both as precipitated inorganic forms and incorporated into organic compounds.

Analysis of phosphorus involves 2 steps: (i) digestion or conversion of the phosphorus to


dissolved orthophosphate; (ii) colorimetric determination of dissolved orthophosphate. The
digestion can be accomplished in 3 ways: (i) perchloric acid recommended only for difficult
samples such as sediments; (ii) nitric acid-sulfuric acid can be used for most samples, but the
simplest is (iii) persulfate oxidation. This method oxidises all nitrogen compounds to nitrate
and all phosphorus compounds to orthophosphate.

In this colorimetric determination of phosphate concentration, ammonium molybdate reacts


under acid conditions to form a heteropoly acid, molybdophosphoric acid. This is then
reduced by stannous chloride to intensely coloured moleybdenum blue. The concentration of
the orthophosphate is then determined colorimetrically.

E.Bergmann 18 Sec/Tert Interface 2009


6.2 Analysis
6.2.1 Apparatus
hotplate
10 mL pipette
25 mL pipette
50 mL conical flask x 4
100 mL volumetric flask
25 mL volumetric flask x 6
80 mL conical flask x 10
spectrophotometer

6.2.2 Reagents
6.2.2.1 Part A persulfate digestion
• phenolphthalein indicator solution
• strong acid solution
(slowly add 300 mL conc H2SO4 to 600 mL distilled water. When cool, add 4.0 mL conc HNO3
and dilute to 1L.)
• sulfuric acid solution
(Carefully add 300mL conc H2SO4 solution to approx 600 mL distilled water and dilute to 1L
with distilled water.)
• potassium persulfate, K2S2O8, solid or ammonium persulfate, (NH4)2S2O8 , solid
• 1.0M sodium hydroxide
6.2.2.2 Part B Colour development
• phenolphthalein indicator solution
• strong acid solution (as above)
• ammonium molybdate reagent
(Dissolve 25 g of (NH4)6Mo7O24.4H2O in 175 mL of distilled water. Cautiously add 280 mL conc.
H2SO4 to 400 mL distilled water. Cool, add molybdate solution, and dilute to 1 L.)
• stannous chloride reagent
(Dissolve 2.5 g fresh SnCl2.2H2O in 100 mL of glycerol. Heat in a water bath and stir with a glass
rod to hasten dissolution. This reagent is stable and requires neither preservative nor special
storage.)

6.2.2.3 Part C Standard curve


• standard phosphate solution
(Dissolve in distilled water 219.5 mg anhydrous KH2PO4 and dilute to 1 L (1.00 mL = 50.0 µg
phosphorus; or P concentration is 50.0 ppm.)

E.Bergmann 19 Sec/Tert Interface 2009


6.2.3Method
Acid washing of all glassware
All glassware should be rinsed with hot dilute (5%) HCl solution to remove traces of
phosphates left by detergents. Rinse with distilled water.

6.2.3.1 Part A - Acid persulfate digestion (for each water sample and for the calibration
curve standards)
1. Use 50 mL or a suitable portion of a thoroughly mixed sample. Add 0.05 mL (1 drop) of
phenolphthalein indicator. If sample turns pink, add strong acid solution dropwise to just
discharge the colour. Then add 1 mL H2SO4 solution and either 0.4 g solid (NH4)2S2O8 or
0.5g of solid K2S2O8.
2. Boil gently on a preheated hotplate for 30 to 40 minutes or until a final volume of 10 mL is
reached. Cool, dilute to 30 mL with distilled water, add 0.05 mL (1 drop) of phenolphthalein
indicator solution, and neutralise to a faint pink colour with NaOH.
3. Make up to 100 mL with distilled water. In some samples, a precipitate may form at this
stage, but do not filter. For any subsequent subdividing of the sample, shake well. The
precipitate (which is possibly a calcium phosphate) redissolves under the acidic conditions of
the colorimetric reactive phosphorus test.

6.2.3.2 Part B Colorimetric development


• Preliminary sample treatment To 100 mL of digested sample containing not more than
200µg of phosphate and free from colour and turbidity, add 0.05 mL (1 drop) of
phenolphthalein indicator. If sample turns pink, add strong acid solution dropwise to
discharge the colour. If more than 0.25 mL (5 drops) is required, take a smaller sample and
dilute to 100 mL with distilled water after first discharging the pink colour with acid.
• Colour development Add, with thorough mixing after each addition, 4.0 mL molybdate
reagent and 0.5 mL (10 drops) of stannous chloride reagent. Rate of colour development and
intensity of colour depend on temperature of the final solution, each 1˚C increase producing
about 1% increase in colour. Hence, hold samples, standards and reagents within 2˚C of one
another and the temperature range between 20 and 30˚C.
• Colour measurement After 10 minutes, but before 12 minutes, using the same specific
interval for all determinations, measure colour photometrically at 690 nm, using a distilled
water blank. Use a calibration curve prepared as described in Part C below to find the
concentration of P.
Always run a blank on reagents and distilled water. Because the colour at first develops
progressively and later fades, maintain equal timing conditions for samples and standards.
Prepare at least one standard with each set of samples or once each day that tests are made.
The calibration curve may deviate from a straight line at the upper concentrations of the 0.3 to
2.0 mg/L range.

E.Bergmann 20 Sec/Tert Interface 2009


6.2.3.3 Part C Preparation of calibration curve
• Prepare a 5 ppm P standard solution by pipetting 10.0 mL of the stock (50ppm P) solution
into a 100 mL volumetric flask and making up to 100 mL.
• From this, prepare a range of standards from 0 - 5 ppm according to the volumes given
below.
Concentration of P Volume of 5ppm Volume of water
(ppm, mg/L or µg/mL) solution (mL)
(mL)
5 25 0
4 20 5
3 15 10
2 10 15
1 5 20
0 0 25

• To prepare each standard solution for colorimetric measurement, apply the persulfate
digestion and colorimetric development procedures as given above.
• Prepare the calibration curve.

E.Bergmann 21 Sec/Tert Interface 2009