Beruflich Dokumente
Kultur Dokumente
Secondary-Tertiary Interface
22 August 2009
With thanks to
Rob Gray and Kathy Gray
for their editorial input.
Dissolved oxygen 3
Hardness 7
Alkalinity 11
Chloride ion 14
Phosphate 18
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
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-
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.
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.
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.
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.
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.
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)
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.)
2.2.5 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.
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.
3.1.3 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.
3.2 Analysis
3.2.1 Apparatus
150 or 250 mL Erlenmeyer Flasks
50 mL burette
10 mL pipette.
50 mL pipette
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.
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)
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.
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
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.
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.
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.
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
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.
5.2.3.3 Calculations
1. Use the stoichiometric information given above to find the molarity of your diluted bleach
solution.
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.
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.)
6.2.3.1 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.
• To prepare each standard solution for colorimetric measurement, apply the persulfate
digestion and colorimetric development procedures as given above.
• Prepare the calibration curve.